Optical, Structural, and Dielectric Properties of Composites Based on Thermoplastic Polymers of the Polyolefin and Polyurethane Type and BaTiO3 Nanoparticles.

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.

Azathioprine Electrochemical Adsorption onto the Reduced Graphene Oxide Sheets in Absence and in the Presence of Polyaniline.

The azathioprine (AZA) electrochemical adsorption onto the screen-printed carbon electrodes (SPCE) modified with the reduced graphene oxide (RGO) sheets in the absence and in the presence of polyaniline-emeraldine salt (PANI-ES) is reported in this work. Using cyclic voltammetry (CV), in the case of the SPCE modified with the RGO sheets non-functionalized and functionalized with PANI-ES, respectively, an irreversible process at the electrode/electrolyte interface is highlighted to take place. In the case of the SPCE modified with the non-functionalized RGO sheets (SPCERGO), the oxidation-reduction processes induce an up-shift of the AZA Raman lines from 856 and 1011 cm-1 to 863 and 1020 cm-1, respectively. These variations indicate an AZA adsorption onto the surface of the SPCE modified with the RGO sheets that takes place throught the imidazole and pyrimidine cycles of mercaptopurine, when the generation of the π-π* bonds between the mercaptopurine structure and hexagonal carbon cycles of RGO occurs. The electrochemical functionalization of the RGO sheets with PANI-ES is proved by the appearance of the Raman lines at 1165, 1332-1371, 1496 and 1585 and 1616 cm-1. The oxidation-reduction processes induced at the interface of the SPCE modified with PANI-ES functionalized RGO sheets and the electrolyte consisting into a phosphate buffer (PB) and AZA lead to the generation of new positive charges onto the PANI macromolecular chain and the adsorption of the drug on the working electrode surface that takes place via the π-π* bonds established between the benzene/quinoide rings of PANI and the imidazole/ purine cycles of AZA. These results indicate that the SPCE modified with the PANI-ES functionalized RGO sheets shows potential applications in the field of sensors for AZA detection.

Mixture of Graphene Oxide/Phosphoric Acid/Melamine as Coating for Improved Fire Protective Performance and Enhancement of Surface Electrical Properties on Wood Chipboard.

Looking for multifunctional materials, an assessment of the performances both as fire retardant and generator of electrically conductive surfaces for a three component mixture of graphene oxide, phosphoric acid and melamine applied on wood chipboard was performed. A simple approach was used to investigate the intumescent char formation and quantify the loss mass during vertical burning tests, in which the prepared samples were exposed for a certain time interval to a flame generated by an ethanol lamp in ambient conditions. Moreover, mass loss evolution and structural changes that occur during the burning process were more comprehensive investigated by differential thermal and thermogravimetric (DTA/TGA) techniques. By comparing the performances between the wood chipboard samples without any coverage and those covered with one or multiple component mixture, an increase of protection against the fire action was noticed when the three component mixture was used. Also, an improvement of the electrical properties was observed, after flame exposure of the samples covered with multiple layers (i.e., two and three), when the three component mixture was used. Morphological and structural investigations by microscopy (optical and electronic-SEMEDX), X-ray diffraction (XRD) and spectral (Raman, FTIR) methods are described. An assessment of market potential is also discussed.

Vibrational and Photoluminescence Properties of Composites Based on Double-Walled Carbon Nanotubes, Poly(o-phenylenediamine) and Poly(ethylene oxide).

Chemical polymerization of o-phenylenediamine (OPD) in the presence of poly(ethylene oxide), double-wall carbon nanotubes (DWNTs) and ferric chloride is carried out in order to obtain composites based on the poly(o-phenylenediamine)-poly(ethylene oxide) (POPD-PEO) fibres covered and interconnected with DWNTs. Vibrational and photoluminescence properties of these composite materials as well as their morphologies are shown by infrared (IR) spectroscopy, Raman scattering, photoluminescence (PL) and scanning electron microscopy (SEM). An adsorption of DWNTs onto the POPD rods surface in the absence and in the presence of PEO is highlighted by SEM. The vibrational changes reported by Raman scattering and IR spectroscopy prove a covalent functionalization of DWNTs with the macromolecular compound POPD which is doped with FeCl-4 ions. New hydrogen bonds are generated between POPD covalently functionalized DWNTs and hydroxyl groups of PEO according to IR spectroscopic studies. The two macromolecular compounds, POPD and POPD-PEO, show a complex emission band with maxima at 572 and 566 nm, having a shoulder at 667 nm. A significant change in the profile of the PL bands of POPD and POPD-PEO is induced in the DWNTs presence. We show that DWNTs induce (i) a diminution in the POPD PL band intensity peaked between 525-600 nm simultaneous with the increase in the intensity of the PL band situated in the 600-800 nm spectral range and (ii) an enhancement process of the emission band localized in the 475-800 nm spectral range in the case of POPD-PEO.

Screen-Printed Carbon Electrodes Modified with Double-Walled Carbon Nanotubes Functionalized with Polypyrrole and Their Electrochemical Processes in the Presence of Folic Acid.

In this work, the electrochemical polymerization of pyrrole in the presence of H3PMo12O40 onto the screen-printed carbon electrodes (SPCE) modified with double-walled carbon nanotubes (DWNTs) is reported. The influence of the pyrrole and H3PMo12O40 concentration as well as a scan rate used to recording of cyclic voltammograms that describe the electrochemical synthesis of polypyrrole (PPY) onto the DWNTs surface is assessed. Using scanning electron microscopy (SEM) we demonstrate that the electrosynthesis of PPY doped with H3PMo12O40 heteropolyanions (PPY-PMo12) results in the generation of a globular morphology. Considering the variations induced of DWNTs in the IR and Raman spectra of PPY doped with H3PMo12O40 heteropolyanions, a functionalization process of carbon nanotubes with macromolecular compound is invoked. According to SEM investigations, DWNTs allow the realization of connections between the globular structures of the macromolecular compound. The changes induced of folic acid (FA) during the oxidation-reduction processes at the interface of the DWNTs functionalized with PPY doped with H3PMo12O40 heteropolyanions (SPCE-DWNT/PPY-PMo12) with electrolyte solution are reported.

Adsorption of 1,4-phenylene diisothiocyanate onto the graphene oxide sheets functionalized with polydiphenylamine in doped state.

Adsorption processes of 1,4-phenylene diisothiocyanate (PDITC) on two new platforms of the type graphene oxide (GO) sheets and GO layers functionalization with polydiphenylamine (PDPA) are studied by Raman scattering and photoluminescence (PL). An interaction in solid state phase of the two constituents, i.e. PDITC and GO sheets, and a deposition of PDITC onto the PDPA functionalized GO layers, respectively, by the drop casting method, were performed. In the first case, it is shown that interaction in solid state phase of GO with PDITC leads to an intercalation of the organic compound between GO sheets simultaneously with the appearance of the o-thiocarbamate groups, that induces: (i) an enhancement of the PDITC Raman lines situated in the 400-800 and 1000-1300 cm-1 spectral ranges, (ii) a change in the ratio between the relative intensities of the two Raman lines peaked at 1585 and 1602 cm-1 accompanied by an up-shift in the case of the second line and (iii) a down-shift of the PDTIC PL band from 502 to 491 nm. Using cyclic voltammetry, an electrochemical functionalization of the GO layers with PDPA doped with H3PMo12O40 heteropolyanions takes place, as demonstrated by Raman scattering and FTIR spectroscopy. The presence of the amine groups in the molecular structure of the doped PDPA functionalized GO layers induces a chemical adsorption of PDITC on this platform, when the thiourea groups appear simultaneously with o-thiocarbamate groups. A chemical mechanism is proposed to take place at the interface of the GO sheets and the doped PDPA functionalized GO layers, respectively, with PDITC.

Influence of TiO2 and Si on the exciton-phonon interaction in PbI2 and CdS semiconductors evidenced by Raman spectroscopy.

The exciton-phonon interaction, considered as a stimulated Raman scattering process, is studied in different semiconductor mixtures: PbI2/TiO2, PbI2/Si and CdS/Si. Raman spectra recorded at excitation wavelengths of 514.5 and 488 nm for PbI2 and CdS, respectively, reveal a strong enhancement of the Raman lines peaked at 97 and 305 cm-1, evaluated by the ratio I TK/I 300 K between the relative intensities of the spectra recorded in the temperature range of 88-300 K. It is found that PbI2 and CdS exhibit a decrease in the Raman intensity modes with decreasing temperature, while in TiO2 and Si an increase in the Raman lines intensities peaked at 138 and 520 cm-1 is observed. This behavior can be explained by an energy transfer process from PbI2 or CdS towards TiO2 and Si. This explanation is supported by the schematic potential energy levels diagram obtained from the density of states, which is calculated using the density functional theory. According to this energy levels diagram, the electrons are expected to migrate directly from the conduction band (CB) energetic levels of the PbI2 and CdS towards the CB levels of TiO2 and Si.

Electropolymerization of N-ethylcarbazole on single walled carbon nanotubes-cyclic voltammetry, raman and FTIR studies.

The electrochemical polymerization of N-ethyl carbazole (EK) on carbon nanotubes (CNs) films immersed in a LiClO4/acetonitrile solution was studied by cyclic voltammetry. Cyclic voltammograms recorded on a blank Pt electrode were compared with those obtained when CNs films were deposited on a Pt plate. In the latter case, the oxidation maximum is not clearly observed. Using the Raman scattering studies, oligomers of poly(N-ethyl carbazole) (PEK) on CNs are shown to be formed. A covalent functionalization of CNs with the PEK oligomers is demonstrated by FTIR spectroscopy studies. The formation of new C-C covalent bonds between CNs and the benzene ring of PEK induces steric hindrance effects that are shown in FTIR spectra by the increase in the intensity of the absorption band at 1072 cm(-1) attributed to the vibration of C-H in plane deformation of aromatic ring. The influence of the monomer and the supporting electrolyte concentration as well as the sweep rate on the polymerization conditions in the case of the composites based on the PEK oligomers and CNs were also investigated.

Surface enhanced Raman scattering studies on poly(3,4-ethylene dioxythiophene)/single-walled carbon nanotubes composites and their application to rechargeable lithium batteries.

In this paper, surface enhanced Raman scattering (SERS) studies on the chemical polymerization of 3,4-ethylene dioxythiophene (EDOT) in the presence of single-walled carbon nanotubes (SWNTs) are reported. Both a non-covalent and covalent functionalization of SWNTs with poly(3,4-ethylene dioxythiophene) (PEDOT) is invoked as a result of the following variations induced in the SERS spectra of PEDOT and SWNTs: (i) the appearance of a Raman line at 140 cm(-1) indicating the formation of a new covalent bond between PEDOT and SWNTs; (ii) an increase in the intensity of the Raman line at 705 cm(-1), associated with the deformation vibration mode of C-S-C bond, the result of a steric hindrance effect induced by the bonding of PEDOT on SWNTs; and (iii) the enhancement of the Raman band with maximum at 1540 cm(-1) (G- component) in SWNTs when the PEDOT weight in the PEDOT/SWNTs composite increases. Using the PEDOT/SWNTs composite as a positive electrode and an electrolytic solution containing LiPF6, the charge-discharge characteristics of the rechargeable lithium cells are determined. High specific discharge capacity are reported for the PEDOT/SWNTs composite (ca. 218 mAh g(-1)) in comparison with PEDOT doped with FeCl4- ions (ca. 25 mAh g(-1)).

ZnO particles of wurtzite structure as a component in ZnO/carbon nanotube composite.

Composites based on carbon nanotubes and ZnO particles with needle shapes were prepared for applications in energy storage. Depending on the temperature (85 or 25 °C) at which the reaction between NaOH and ZnCl(2) was carried out, particles with two different morphologies: needle-shaped (NS) and double-pyramid-shaped (DPS), respectively, are obtained. Scanning electron microscopy, photoluminescence, UV-Vis absorption spectroscopy, x-ray diffraction and Raman light scattering studies reveal that the NS and DPS particles belong to ZnO with wurtzite (WZ) structure and ε-Zn (OH)(2) as precursors of ZnO, respectively. Using the ZnO/carbon nanotube composite as a negative electrode and an electrolytic solution containing LiPF(6), the charge-discharge characteristics of rechargeable lithium ions cells were determined. Additional information concerning the electrochemical reactions at the interface of the two electrodes was obtained by cyclic voltammetry.

Quantum well effect in bulk PbI(2) crystals revealed by the anisotropy of photoluminescence and Raman spectra.

On subjecting a bulk 2H-PbI(2) crystal to vacuum annealing at 500 K followed by a sudden cooling at liquid nitrogen temperature stacking faults are generated that separate distinct layers of nanometric thickness in which different numbers of I-Pb-I atomic layers are bundled together. Such structures, containing two, three, four, five etc I-Pb-I atomic layers, behave as quantum wells of different widths. The signature of such a transformation is given by a shift towards higher energies of the fundamental absorption edge, which is experimentally revealed by specific anisotropies in the photoluminescence and Raman spectra. The quantum confining effect is made visible by specific variations of a wide extra-excitonic band (G) at 2.06 eV that originates in the radiative recombination of carriers (electrons and holes), trapped on the surface defects. The excitation spectrum of the G band, with p polarized exciting light, reveals a fine structure comprised of narrow bands at 2.75, 2.64, 2.59 and 2.56 eV, which are associated with the PbI(2) quantum wells formed from two, three, four and five I-Pb-I atomic layers of 0.7 nm thickness. Regardless of the polarization state of the laser exciting light of 514.5 nm (2.41 eV), which is close to the band gap energy of PbI(2) (2.52 eV), the Raman scattering on bulk as-grown PbI(2) crystals has the character of a resonant process. For p polarized exciting light, the Raman scattering process on vacuum annealed PbI(2) becomes non-resonant. This originates from the quantum well structures generated inside the crystal, whose band gap energies are higher than the energy of the exciting light.

Optical cooling of single-walled carbon nanotubes as revealed by their anti-Stokes Raman spectra.

Semiconducting single-walled carbon nanotubes resonantly excited by the interband E(22)(S) electronic transitions (at 1064 nm) display for the two components of the radial Raman band-one associated with the isolated tubes and the other associated with the bundled tubes-an anti-Stokes/Stokes Raman intensity ratio (I(aS)/I(S)) which deviates oppositely from the predictions of the Maxwell-Boltzmann formula. A cooling and heating vibration process, evidenced by an enhancement and diminishment of (I(aS)/I(S)), appears in the isolated and bundled nanotubes, respectively. Here we confirm a cooling process, observed only for semiconducting nanotubes, which emerges from the relaxation of the E(22)(S) excited state by the electronic relaxation from E(22)(S) to E(11)(S) that precedes the spontaneous luminescence emission at E(11)(S). Metallic nanotubes do not exhibit luminescence and no cooling effect is observed. Both semiconducting and metallic nanotubes show for the bundled component of the radial Raman band an enhancement of (I(aS)/I(S)) such as is frequently observed in a coherent anti-Stokes Raman scattering process.