Anthracene-Containing Conjugated Polymer Showing Four Optical Transitions Upon Doping: A Spectroscopic Study

An anthracene-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) (PAE-PAV) of general constitutional unit (PhCCAnthrCCPhCHCHAnthrCHCH)(n) bearing two 2-ethylhexyloxy solubilizing side chains on each phenylene (Ph) unit has been synthesized and characterized. The basic electrochemical characterization was done, showing the existence of two non-reversible oxidation and one reversible reduction peaks. The optical properties, the real and imaginary part of the dielectric function, were probed using spectroscopic ellipsometry (SE). The vibrational structure of the undoped/doped polymer was investigated using Fourier transformed infrared spectroscopy. A strong change in the polaronic absorption was observed during the doping, which after modeling revealed the existence of two separated transitions. The optical changes upon doping were additionally recorded using the SE technique. Similar to the results from FT-IR spectroscopy, two new in-the-gap absorptions were found. Moreover, the electrical conductivity as well as the mobility of positive carriers were measured. In the undoped state, the conductivity of the polymer was found to be below the detection limit (

Fabrication of Zinc Oxide Nanowires/Polymer Composites by Two-Photon Polymerization

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Theoretical investigation of the interaction of a polymer film with a nanoparticle

The fundamental aim in our investigation of the interaction of a polymer film with a nanoparticle is the extraction of information on the dynamics of the liquid using a single tracking particle. In this work two theoretical methods were used: one passive, where the motion of the particle measures the dynamics of the liquid, one active, where perturbations in the system are introduced through the particle. In the first part of this investigation a thin polymeric film on a substrate is studied using molecular dynamics simulations. The polymer is modeled via a 'bead spring' model. The particle is spheric and non structured and is able to interact with the monomers via a Lennard Jones potential. The system is micro-canonical and simulations were performed for average temperatures between the glass transition temperature of the film and its dewetting temperature. It is shown that the stability of the nanoparticle on the polymer film in the absence of gravity depends strongly on the form of the chosen interaction potential between nanoparticle and polymer. The relative position of the tracking particle to the liquid vapor interface of the polymer film shows the glass transition of the latter. The velocity correlation function and the mean square displacement of the particle has shown that it is caged when the temperature is close to the glass transition temperature. The analysis of the dynamics at long times shows the coupling of the nanoparticle to the center of mass of the polymer chains. The use of the Stokes-Einstein formula, which relates the diffusion coefficient to the viscosity, permits to use the nanoparticle as a probe for the determination of the bulk viscosity of the melt, the so called 'microrheology'. It is shown that for low frequencies the result obtained using microrheology coincides with the results of the Rouse model applied to the polymer dynamics. In the second part of this investigation the equations of Linear Hydrodynamics are solved for a nanoparticle oscillating above the film. It is shown that compressible liquids have mechanical response to external perturbations induced with the nanoparticle. These solutions show strong velocity and pressure profiles of the liquid near the interface, as well as a mechanical response of the liquid-vapor interface. The results obtained with this calculations can be employed for the interpretation of experimental results of non contact AFM microscopy

Networking - a statistical physics perspective

Networking encompasses a variety of tasks related to the communication of information on networks; it has a substantial economic and societal impact on a broad range of areas including transportation systems, wired and wireless communications and a range of Internet applications. As transportation and communication networks become increasingly more complex, the ever increasing demand for congestion control, higher traffic capacity, quality of service, robustness and reduced energy consumption requires new tools and methods to meet these conflicting requirements. The new methodology should serve for gaining better understanding of the properties of networking systems at the macroscopic level, as well as for the development of new principled optimization and management algorithms at the microscopic level. Methods of statistical physics seem best placed to provide new approaches as they have been developed specifically to deal with nonlinear large-scale systems. This review aims at presenting an overview of tools and methods that have been developed within the statistical physics community and that can be readily applied to address the emerging problems in networking. These include diffusion processes, methods from disordered systems and polymer physics, probabilistic inference, which have direct relevance to network routing, file and frequency distribution, the exploration of network structures and vulnerability, and various other practical networking applications. © 2013 IOP Publishing Ltd.

Direct observation of morphological development during the spin-coating of polystyrene-poly(methyl methacrylate) polymer blends

We present results of the direct observation, in real-space, of the phase separation of high molecular weight polystyrene and poly(methyl methacrylate) from ortho-xylene using our newly developed technique of high speed stroboscopic interference microscopy. Taking a fixed concentration (3 wt % in o-xylene) at a fixed composition (1:4 by weight) and by varying the rotational rate during the spin-coating process, we are able to observe the formation of a range of phase separated bicontinuous morphologies of differing length-scales. Importantly, we are able to show that the mechanism by which the final phase separated structure is formed is through domain coarsening when rich in solvent, before vitrification occurs and fixes the phase separated structure. The ability to directly observe morphological development offers a route toward controlling the length-scale of the final morphology through process control and in situ feedback, from a single stock solution. © 2013 Wiley Periodicals, Inc.

Evaluation of piezoelectric PVDF polymers for use in space environments. III. Comparison of the effects of vacuum UV and gamma radiation

Films of piezoelectric PVDF and P(VDF-TrFE) were exposed to vacuum UV (115-300 nm VUV) and -radiation to investigate how these two forms of radiation affect the chemical, morphological, and piezoelectric properties of the polymers. The extent of crosslinking was almost identical in both polymers after -irradiation, but surprisingly, was significantly higher for the TrFE copolymer after VUV-irradiation. Changes in the melting behavior were also more significant in the TrFE copolymer after VUV-irradiation due to both surface and bulk crosslinking, compared with only surface crosslinking for the PVDF films. The piezoelectric properties (measured using d33 piezoelectric coefficients and D-E hysteresis loops) were unchanged in the PVDF homopolymer, while the TrFE copolymer exhibited more narrow D-E loops after exposure to either - or VUV-radiation. The more severe damage to the TrFE copolymer in comparison with the PVDF homopolymer after VUV-irradiation is explained by different energy deposition characteristics. The short wavelength, highly energetic photons are undoubtedly absorbed in the surface layers of both polymers, and we propose that while the longer wavelength components of the VUV-radiation are absorbed by the bulk of the TrFE copolymer causing crosslinking, they are transmitted harmlessly in the PVDF homopolymer.

Evaluation of piezoelectric PVDF polymers for use in space environments. II. Effects of atomic oxygen and vacuum UV exposure

The effects of atomic oxygen (AO) and vacuum UV radiation simulating low Earth orbit conditions on two commercially available piezoelectric polymer films, poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE), have been studied. Surface erosion and pattern development are significant for both polymers. Erosion yields were determined as 2.8 � 10�24 cm3/atom for PVDF and 2.5 � 10�24 cm3/atom for P(VDF-TrFE). The piezoelectric properties of the residual material of both polymers were largely unchanged after exposure, although a slight shift in the Curie transition of the P(VDF-TrFE) was observed. A lightly cross-linked network was formed in the copolymer presumably because of penetrating vacuum ultraviolet (VUV) radiation, while the homopolymer remained uncross-linked. These differences were attributed to varying degrees of crystallinity and potentially greater absorption, and hence damage, of VUV radiation in P(VDFTrFE) compared with PVDF.

Evaluation of piezoelectric poly(vinylidene fluoride) polymers for use in space environments. I. Temperature limitations

Smart materials, such as thin-film piezoelectric polymers, are interesting for potential applications on Gossamer spacecraft. This investigation aims to predict the performance and long-term stability of the piezoelectric properties of poly(vinylidene fluoride) (PVDF) and its copolymers under conditions simulating the low-Earthorbit environment. To examine the effects of temperature on the piezoelectric properties of PVDF, poly(vinylidenefluoride-co-trifluoroethylene), and poly(vinylidenefluoride-cohexafluoropropylene), the d33 piezoelectric coefficients were measured up to 160 8C, and the electric displacement/electric field (D–E) hysteresis loops were measured from �80 to þ110 8C. The room-temperature d33 coefficient of PVDF homopolymer films, annealed at 50, 80, and 125 8C, dropped rapidly within a few days of thermal exposure and then remained unchanged. In contrast, the TrFE copolymer exhibited greater thermal stability than the homopolymer, with d33 remaining almost unchanged up to 125 8C. The HFP copolymer exhibited poor retention of d33 at temperatures above 80 8C. In situ D–E loop measurements from �80 to þ110 8C showed that the remanent polarization of the TrFE copolymer was more stable than that of the PVDF homopolymer. D–E hysteresis loop and d33 results were also compared with the deflection of the PVDF homopolymer and TrFE copolymer bimorphs tested over a wide temperature range.

Electrospraying a reproducible method for production of polymeric microspheres for biomedical applications

The ability to reproducibly load bioactive molecules into polymeric microspheres is a challenge. Traditional microsphere fabrication methods typically provide inhomogeneous release profiles and suffer from lack of batch to batch reproducibility, hindering their potential to up-scale and their translation to the clinic. This deficit in homogeneity is in part attributed to broad size distributions and variability in the morphology of particles. It is thus desirable to control morphology and size of non-loaded particles in the first instance, in preparation for obtaining desired release profiles of loaded particles in the later stage. This is achieved by identifying the key parameters involved in particle production and understanding how adapting these parameters affects the final characteristics of particles. In this study, electrospraying was presented as a promising technique for generating reproducible particles made of polycaprolactone, a biodegradable, FDA-approved polymer. Narrow size distributions were obtained by the control of electrospraying flow rate and polymer concentration, with average particle sizes ranging from 10 to 20 um. Particles were shown to be spherical with a homogenous embossed texture, determined by the polymer entanglement regime taking place during electrospraying. No toxic residue was detected by this process based on preliminary cell work using DNA quantification assays, validating this method as suitable for further loading of bioactive components.

The influence of variant PE-b-PEO segments on physical properties of LLDPE graft copolymers

A method was adopted to fix a series of polymers of PE-b-PEO with different PEO/PE segments on the chains of LLDPE. Maleic anhydride (MA) reacting with hydroxyl group of PE-b-PEO (mPE-b-PEO) was used as the intermediate. The structures of intermediates and graft copolymers were approved by H-1 NMR and FTIR. XPS analysis revealed a great amount of oxygen on the surface of grafted copolymers although the end group of PEO was fixed on the LLDPE chains through MA. Thermal properties of the graft copolymers as determined by differential scanning calorimetry (DSC) showed that PE segments in the grafted monomers could promote the heterogeneous nucleation of the polymer, increase T., and crystal growth rate.

Synthesis and Aqueous Solution Properties of Hydrophobically Modified Anionic Acrylamide Copolymers

In this investigation, hydrophobically modified polyacrylamide with low amounts of anionic long-chain alkyl was synthesized by the free radical polymerization in deionized water. This water-soluble copolymerization method is more convenient compared with the traditional micellar copolymerization methods. The copolymers were characterized using Fourier transform infrared, H-1 NMR, and the molecular weight and polydispersity were determined using gel permeation chromatography. The solution behavior of the copolymers was studied as a function of composition, pH, and added electrolytes. As NaCl was added to solutions of AM/C(11)AM copolymers or pH was lowered, the shielding or elimination of electrostatic repulsions between carboxylate groups of the C(11)AM unit lead to coil shrinkage.

Crystallization and morphology of poly(ethylene oxide-b-lactide) crystalline-crystalline diblock copolymers

The crystallization behaviors and morphology of asymmetric crystalline-crystalline diblock copolymers poly(ethylene oxide-lactide) (PEO-b-PLLA) were investigated using differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and microscopic techniques (polarized optical microscopy (POM) and atomic force microscopy (AFM)). Both blocks of PEO5-b-PLLA(16) can be crystallized, which was confirmed by WAXD, while PEO block in PEO5-b-PLLA(30) is difficult to crystallize because of the confinement induced by the high glass transition temperature and crystallization of PLLA block with the microphase separation of the block copolymer.

Molecular weight dependence of phase Behavior of PEO/P(EO-b-DMS) blends: Application of Sanchez-Lacombe lattice fluid theory

Molecular weight dependence of phase separation behavior of the Poly (ethylene oxide) (PEO)/Poly(ethylene oxide-block-dimethylsiloxane) (P(EO-b-DMS)) blends was investigated by both experimental and theoretical methods. The cloud point curves of PEO/P(EO-b-DMS) blends were obtained by turbidity method. Based on Sanchez-Lacombe lattice fluid theory (SLLFT), the adjustable parameter, epsilon*(12)/k (quantifying the interaction energy between different components), was evaluated by fitting the experimental data in phase diagrams. To calculate the spinodals, binodals, and the volume changes of mixing for these blends, three modified combining rules of the scaling parameters for the block copolymer were introduced.

Layer-by-layer assembly of gelatin

Electrostatic assembly of one species can be realized using gelatin as a polyampholyte. Under suitable conditions where the electrostatic attraction and repulsion were both significant and in balance, linear growth of multilayers driven by electrostatic interactions was sustained over many successive assembly steps, and the maximum amount of adsorption of each layer was reached when the solution pH was around the isoelectric point. The rearrangement of the adsorbed chains after drying was confirmed by contact angle analysis. In addition with only one species involved, the assembled thin films should be chemically uniform rather than layered.