Enhanced mechanical properties and morphological characterizations of poly(vinyl alcohol)-carbon nanotube composite films

Tensile tests were carried out on free-standing composite films of poly(vinyl alcohol) (PVA) and multiwall carbon nanotubes (MWNTs) for different loading levels. Results show that overall mechanical properties of the composite were greatly improved as compared to the neat PVA film. For PVA-based materials at significant high loading level such as 9.1 wt.% MWNTs, considerable increases in Young's modulus, tensile strength and toughness by factors of 4.5, 2.7 and 4.1, respectively, were achieved. Raman, SEM, TEM, and DSC techniques were used to evaluate the PVA/MWNTs composite system. Strong acid-modification of the pristine MWNTs and the subsequent ultrasonication processing allowed good distribution of the nanotubes in the matrix. SEM together with DSC result shows apparent good wetting of the nanotubes by the PVA matrix, which are supportive of good interfacial bonding between the modified carbon nanotubes and the hosting polymer matrix.     

Magnetic properties of poly(3-hexylthiophene)

A room temperature ferromagnetic phase is observed in samples of poly(3-hexylthiophene) partially doped with ClO₄⁻. The magnetic behavior presents a strong dependence on the sample preparation conditions, in particular, a dependence with the final potential of the sample after reduction. The origin of the ferromagnetism is proposed to be associated with interactions between spin 1/2 polarons formed in the polymeric chain upon doping. The dependence of saturation and spontaneous magnetization as the function of the final potential after reduction shows a way to control the magnetic properties of this polymer.     

Photoluminescence properties of europium-doped porous silicon nanocomposites

We present new results concerning the photoluminescence properties of europium (Eu³⁺) incorporated in porous silicon (PS) matrix. Eu³⁺ ions were embedded in the matrix by simple impregnation of PS layers in chloride solution of europium. Complete and uniform penetration of Eu³⁺ into the pores is proved from RBS study.The PL spectrum shows the existence of several peaks superposed to the PL band of PS. These peaks are related to level transitions in Eu³⁺. The effect of the ray excitation on the PL shows that energy transfer is not the principal route for radiative recombination.A systematic study of the PL versus annealing temperature was performed. It was found that the optimised PL spectrum is found after annealing at 1000°C. Low-temperature study of the PL shows an important increase of the intensity and a broadness of the peaks due to the appearance of a second crystallographic site.     

Upon a magnetic composite preparation based on magnetite and poly(succinimide)-b-poly(ethylene glycol) shell

Taking into account that magnetic particles with suitable surface characteristics have a high potential for the use in a lot of in vitro and in vivo applications, in the study is presented the in situ preparation of a core-shell magnetic composite based on the magnetite core and the shell composed from the poly(succinimide)-b-poly(ethylene glycol) copolymer. The average particle size of the synthesized magnetic microspheres is in the range of 6.5-8.8 μm with a magnetite content of around 11%. The saturation magnetization of the microspheres was found 26.8 emu/g, the magnetic microspheres being characterized by superparamagnetic properties. The particles have combined properties of high magnetic saturation and biocompatibility and interactive functions at the surface through the block copolymer shell. The surface of the magnetic particles has also the possibility for further functionalization or the attachment of various bioactive molecules after the hydrolysis of the succinimide cycle and the resulting carboxylic group.     

Photoluminescence properties of heat-treated porous alumina films formed in oxalic acid

Photoluminescence and optical properties of as-anodized and heat-treated at 500 °C porous alumina films formed in a 0.3 M oxalic acid at 40 V have been studied. The FTIR indicates that the oxalate ions are embedded in the anodic alumina as chelating bidentate structures and further heating up to 500 °C does not cause any change in ion coordination. The results of time-resolved spectroscopy show the presence of two luminescence centers both in the as-anodized and heat-treated anodic alumina films with lifetimes of about 0.25 and 4.0 ns. The F⁺-centers in anodic alumina are responsible for the luminescence peak at about 420 nm, with a lifetime of about 4.0 ns. The luminescence peak at about 480 nm, with lifetime of about 0.25 ns, can be attributed to the luminescence of carboxylate ions existing in bulk of anodic alumina.     

Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.     

π-electron density dependence of third-order optical nonlinearities in poly(1,4-phenylene vinylene) derivatives

The third-order nonlinear optical properties of poly(1,4-phenylene vinylene) (PPV), poly(2-bromo-1,4-phenylene vinylene) (BrPPV) and poly(2-chloro-1,4-phenylene vinylene) (ClPPV) were studied by forward degenerate four-wave mixing (DFWM). They have large and ultrafast third-order optical nonlinear responses, which mainly arise from the distortion of the large π-conjugated electronic charge distribution in the backbone. It was found that there was a significant contribution to π-electron density and thus χ⁽³⁾ values from the substituents at the phenylene ring.     

Optical properties and color generation mechanism of porous anodic alumina films

Porous anodic alumina thin films with iridescent colors were fabricated electrochemically in phosphoric acid electrolyte. Compared to the color saturation of alumina films fabricated in oxalic acid electrolyte, the saturation obtained using phosphoric acid was enhanced dramatically. The mechanisms behind this observation are discussed, and the microstructure and optical characteristics of the films are characterized. Multicolor patterns were obtained by an organics-assisted process for which details are given.     

Rheological,thermal, and mechanical properties of poly(ethylene naphthalate)/poly(ethylene terephthalate) blends

Structural, Theological, thermal, and mechanical properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) obtained by melt blending were investigated using capillary rheometry, differential scanning calorimetry (DSC), scanning electron microscopic (SEM) observation, tensile testing. X-ray diffraction, and ¹H nuclear magnetic resonance (NMR) measurements. The melt Theological behavior of the PEN/PET blends was very similar to that of the two parent polymers. The melt viscosity of the blends was between that of PEN and that of PET. Thermal properties and NMR measurement of the blends revealed that PEN is partially miscible with PET in the as molded blends, indicating that an interchange reaction occurs to some extent on melt processing. The blend of 50/50 PEN/PET was more difficult to crystallize compared with blends of other PEN/PET ratios. The blends, once melted during DSC measurements, almost never showed cold crystallization and subsequent melting and definitely exhibited a single glass transition temperature between those of PEN and PET during a reheating run. Improvement of the miscibility between PEN and PET with melting is mostly due to an increase in transesterification. The tensile modulus of the PEN/PET blend strands had a low value, reflecting amorphous structures of the blends, while tensile strength at the yield point increased linearly with increasing PEN content.     

Tip-surface interactions at redox responsive poly(ferrocenylsilane) (PFS) interface by AFM-based force spectroscopy

Poly(ferrocenylsilanes) (PFS) belong to the class of redox responsive organometallic polymers. Atomic force microscopy (AFM)-based single molecule force spectroscopy (SMFS) was used earlier to study single chain PFS response and redox energy driven single chain PFS molecular motors. Here we present further AFM investigations of force interactions between tip and a grafted PFS surface under potential control in electrochemical redox cycles. Typical tip-Au interaction is considered as reference in the force measurements. First the electrostatic component in the diffused double layer (DL) in NaClO₄ electrolyte environment was considered for a “grafted to” PFS, which dominated the interplay between the tip and sample surface. The DL forces can also hinder the physisorption of PFS chain onto the tip when the voltage was applied at −0.1 V. On the other hand, if the tip contacted the PFS surface prior to the electrochemical process, physisorption of PFS chains governed the overall interaction regardless of subsequently applied surface potential. In addition, prolonged contact time, t_c, may also contribute to the stability of tip-PFS bridging and detection of electrostatic forces between the tip-PFS interface. The results showed that tip-substrate interaction forces without PFS grafts have negligibly small force contributions under similar, electrochemically controlled, conditions used in single PFS chain based molecular motors.     

Effect of relative humidity on the electrical transport properties of poly(thionaphtheneindole)

Poly(thionaphtheneindole) (pTNI) conducting polymer has previously been observed to undergo a large variation in the electrical conductivity as a function of relative humidity. In this paper the electrical characteristics of this material as a function of the adsorbed water are studied. Isothermal current-time and current-voltage plots can be understood in terms of an ionic charge transfer inside the polymer, controlled by a diffusion limited electrodic process. The charge transfer at the electrodes is probably due to proton reduction at the cathode and water oxidation at the anode.     

Compaction of poly(dimethylsiloxane) (PDMS) due to proton beam irradiation

This work is about the detailed investigation of the changes of the surface topography, the degree of compaction/shrinkage and its relation to the irradiation fluence and the structure spacing in poly(dimethylsiloxane) (PDMS) patterned with 2 MeV proton microbeam. The irradiated periodic structures consisted of parallel lines with different widths and spacing. To achieve different degrees of compaction, each structure was irradiated with more different fluences. At the irradiated areas the surface topography, the adhesion, the wettability and the rigidity of the surface also changes due to the chemical/structural change of the basic poly(dimethylsiloxane) polymer. The surface topography, the phase modification of the surface, and the connection between them was revealed with using an atomic force microscope (AFM).     

Hole-transporting property of a chemically hybridized poly(vinylcarbazole)-fullerene

We synthesized a star copolymer of poly(vinylcarbazole) (PVK) branched from a fullerene (C₆₀) center, and investigated its optical absorption and photoluminescence properties. The chemically hybridized PVK-C₆₀ was then employed as a hole-transporting layer of the electroluminescent device with a poly(9,9^′-dihexylfluorene-2,7-divinylene-m-phenylenevinylene-stat-p-phenylenevinylene) (CPDHFPV) emitting layer. The ITO/PVK-C₆₀/CPDHFPV/LiF/Al device showed a strong electroluminescence quenching due to a direct contact of the PVK-C₆₀ and the CPDHFPV layers. In contrast, when an additional PVK layer was introduced between the two layers, the electroluminescence was largely enhanced. The emitted light power of the ITO/PVK-C₆₀/PVK/CPDHFPV/LiF/Al device was improved by 3 times compared with the device without the PVK-C₆₀ layer.     

Stability of centrosome numbers in poly(ADP-ribose) polymerase-1- and poly(ADP-ribose) glycohydrolase-deficient mouse ES cells

Poly(ADP-ribose) polymerase-1 (Parp-1) localizes mainly in the nucleus and functions in DNA repair, genome stability and cell death regulation. Meanwhile, it also localizes in centrosomes and is involved in the regulation of centrosome duplication. An abnormal increase in centrosome numbers is frequently observed in Parp-1-deficient (Parp-1^−/−) mouse embryonic fibroblasts (MEFs) (Kanai et al. (2003) Mol. Cell. Biol. 23, 2451–2462). However, there are no studies on whether the centrosome abnormality occurs also in other cell types under Parp-1 deficiency. In this study, we report that Parp-1^−/− mouse embryonic stem (ES) cell lines did not show an abnormally increased number of centrosomes compared to wild-type ES cells. Recently, poly(ADP-ribose) glycohydrolase (Parg) has also been shown to localize in centrosomes (Ohashi et al. (2003) Biochem. Biophys. Res. Commun. 307, 915–921). The number of centrosomes of Parg-deficient (Parg^−/−) ES cells was also analyzed in this study and was found to be stable under Parg deficiency. We also examined centrosome numbers in wild-type, Parp-1^−/− and Parg^−/− ES cell lines after treatment with methylmethanesulfonate (MMS) or γ-irradiation. Although a slight increase in the number of centrosomes is observed in each genotype twenty-four hours after treatment with MMS at 50 μM or with γ-irradiation at 1.4 Gy, there was no difference among the genotypes. These results suggest that loss of Parp-1 and Parg is insufficient to induce abnormality in centrosome numbers in ES cells and that ES cells possibly possess a strict mechanism for the maintenance of a normal number of centrosomes.     

Difference of optical properties between porous alumina and sapphire using two-substrate method at elevated temperature

We report on simultaneous measurements of the emittance, transmittance and reflectance of a porous alumina under same environment at 573 K, which has not been obtained. It is demonstrated that the correction of substrate radiation and multiple reflections is important for the accurate measurement of infrared (IR) optical properties of porous materials in a two-substrate method. We deduced the extinction, absorption and scattering coefficients of the alumina from the measured three quantities, based on the classical geometry model. The coefficients explain the difference of the IR optical properties between the alumina and the sapphire. The increasing reflectance of the alumina with thickness, unlike the sapphire, is attributed to the relatively high scattering coefficient at short wavelengths.     

Clustering of magnetic nanoparticles using a double hydrophilic block copolymer, poly(ethylene oxide)-b-poly(acrylic acid)

The use of a double hydrophilic block copolymer (DHBC), poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) to prepare magnetic nanoparticle (MNP) clusters was investigated. In this one-pot synthesis method, the DHBC controlled the particle growth and served as both stabilizer and clustering agent. Depending on the iron-to-polymer ratio, the synthesized particles can be in the form of colonies of small iron oxide particles or clusters of these particles with size larger than 100 nm. Compared to the previous reported result using random copolymers, the clusters prepared with DHBC were more compact and homogeneous. The yield of clusters increased when the amount of polymer added was limiting. Insufficient amounts of polymer resulted in the formation of bare patches on the magnetite surface, and the strong van der Waals attraction induced cluster formation.     

Synthesis and properties of the nanocomposite of zink oxide and poly(amic acid)

The composite comprised of zinc oxide quantum dots and poly(amic acid) (PAAc) was prepared and studied by X-rays diffraction, X-ray photoelectron spectroscopy, light scattering, UV absorbance and UV fluorescence. The UV absorbance of the ZnO/PAAc composite was found to be much larger than that of its components taken separately. The fluorescence of the ZnO/PAAc composite was found to be shifted to longer wavelengthes in comparison with pure ZnO. The presence of the dopant dodecylbenzenesulfonic acid was found to affect the observed fluorescence.     

Effect of PMMA on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in semi-dilute solutions

Films of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend were derived from a special procedure of casting semi-dilute solutions. Hydrophilic character and crystallization of PVDF were optimized by variation of PMMA concentration in PVDF/PMMA blends. It was found that a PVDF/PMMA blend containing 70 wt% PMMA has a good performance for the potential application of hydrophilic membranes via thermally induced phase separation. The films presented β crystalline phase regardless of PMMA content existed in the blends. Thermal analysis of the blends showed a promotion of crystallization of PVDF with small addition of PMMA which induced larger lamellar thickness of PVDF, leading to the largest spherulitic crystal of PVDF (10 wt% PMMA) is about 8 μm. SEM micrographs illustrated no phase separation occurred in blends, due to the high compatibility between PVDF and PMMA.     

Measurement of speed of sound in poly(lactic acid)-clay composite

We measured longitudinal speed of sound for matrix[poly(lactic acid)]-additive(clay particles) composite rectangular-solid specimen prepared by injection molding. It was found that the speed of sound measured in the direction along the longer side of the specimen was the highest at the middle of the specimen. This trend corresponded with that for crystallinity determined through differential scanning calorimetry (DSC). A cross section view of the specimen parallel to its longer side showed that there was a transverse flow trace of resin in the vicinity of the injection gate while the flow trace along the direction of the longer side spread wider as getting far from the gate toward the middle of the specimen. The high crystallinity appeared in the middle of the specimen was inferred to come from the promotion of crystallization by molecular orientation induced with the above flow trace parallel to the direction along the longer side of the specimen.     

Thermal transitions and degradative processes in Fe(III)-tetracarboxyphthalocyanine-grafted poly(N-vinylcarbazole)

The introduction of 2,9,16,23-tetracarboxy-Fe(III)phthalocyanine [Fe(III)tcPc] units onto fractions of poly(N-vinylcarbazole) (PVK) by Friedel-Crafts reaction leads to amorphous PVK-based grafted compounds that show major interchain distances by the wide-angle x-ray scattering (WAXS) technique. Glass transition temperatures of the products are lower than the main glass transition temperature of PVK and are attributed to local movements of the voluminous added groups. Dynamic thermogravimetric experiments show decarboxylation processes within the 250°C-500°C range and little weight loss. The large remaining residue, up to 70% of the sample at 800°C, is suggested to be the consequence of successive cross-linking reactions. The Fourier transform infrared (FTIR) spectrum of the residue is similar to that of the grafted sample before degradation.