Fabrication and nanoscale properties of PEDOT:PSS conducting polymer nanospheres.

Electrically conducting nanospheres of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) with tailored size were prepared using a solvent displacement technique. To fabricate these nanostructures, dried PEDOT:PSS was dissolved in ethylene glycol (EG) and the solution was precipitated in deionized water. The proposed fabrication route allowed obtaining a water-based dispersion of PEDOT:PSS nanospheres with good optical properties. To determine the physical properties of the nanospheres, we followed a nanoscale approach, using atomic force microscopy. Our nanoscale mechanical and electrical investigations showed that the nanospheres retained good physical and conductivity properties, compared to the commercial product. Moreover, the local studies indicated that the reprecipitation process and the spherical shape lead to a different arrangement of the PSS and PEDOT phases.

Triggering Forces at the Nanoscale: Technologies for Single-Chain Mechanical Activation and Manipulation.

Over the past decades, polymer mechanochemistry has focused on the development and application of advanced force application methods to better understand the mechanochemical response of mechanophores. In this regard, techniques such as ultrasonication and single-molecule force spectroscopy (SMFS) are used to activate and detect up to thousands of chemical events within a polymer single chain, allowing the researchers to probe the mechanochemical reactivity of these stress-responsive motifs. Here, the most recent contributions of the single-molecule force spectroscopy technique to this field are presented, putting emphasis on the fundamental parameters of the technique for triggering specific force responses and on the description of force-extension curves measured for single- and multi-mechanophore polymers. Moreover, new contributions of microscopy-based techniques in the field of polymer mechanochemistry, as well as the potential application of single-chain nanoparticles as mechanoresponsive materials, are highlighted.

Effect of environmental humidity on the ionic transport of poly(ethylene oxide) thin films, investigated by local dielectric spectroscopy.

The effect of humidity on the ionic transport in the amorphous phase of poly(ethylene oxide) thin films has been studied by local dielectric spectroscopy. We explored a controlled humidity range between 15% RH and 50% RH. AFM-based local dielectric imaging allowed the thin film topography and the corresponding dielectric contrast maps to be obtained simultaneously. No humidity effect on the film topography was observed whereas large variation of the dielectric signal could be detected. In addition, we observed a clear dielectric contrast in different locations on the thin film surface. At selected regions with high contrast in the dielectric maps, we performed nanoDielectric Spectroscopy (nDS) measurements covering the frequency range from 5 Hz to 100 kHz. By modeling these spectroscopy results, we quantified the conductivity of the amorphous phase of the semicrystalline poly(ethylene oxide) films. The crystalline fraction of the PEO thin films was extracted and found to be about 36%, independently of humidity. However, the average conductivity increased by a factor of 25 from 2 × 10-10 to 5 × 10-9 S cm-1, by changing environmental humidity in the explored % RH range.

Broadband dielectric spectroscopy to validate architectural features in Type-A polymers: Revisiting the poly(glycidyl phenyl ether) case.

Broadband dielectric spectroscopy (BDS) is a powerful technique that allows studying the molecular dynamics of materials containing polar entities. Among a vast set of different applications, BDS can be used as a complementary tool in polymer synthesis. In this work, we will show how BDS can be used to validate architectural features in Type-A polymers, those having a net dipole moment component along the chain contour. Specifically, we will focus on the evaluation of the dielectric relaxation of poly(glycidyl phenyl ether) (PGPE) samples designed and synthesized with a variety of topologies and regio-orders: linear regio-regular chains synthesized from monofunctional and bifunctional initiators, macrocyclic regio-regular chains, and linear and macrocyclic regio-irregular chains. Our study highlights the impact of using BDS as a complementary characterization technique for providing topological details of polymers, which are otherwise not possible with many traditional techniques (e.g., NMR and mass spectrometry).

Ionic transport in the amorphous phase of semicrystalline polyethylene oxide thin films.

We present a detailed study on the ionic transport properties of polyethylene oxide (PEO) thin films prepared under different conditions. Using a state-of-the-art Atomic Force Microscopy (AFM) methodology, we simultaneously acquired the nanostructured topography of these semicrystalline polymer films as well as the corresponding dielectric function; in the latter case by probing the frequency-dependent tip-sample electrical interactions. By means of this AFM protocol, we studied the ionic conductivity in the PEO amorphous phase and its dependence on film preparation conditions. In general, for any preparation method, we found a distribution of conductivities ranging from 10-14 to 10-6 S cm-1. Specifically, PEO thin films crystallized from the melt presented relatively high conductivity values, which decreased in the PEO films prepared from solutions at room temperature depending on solvent polarity. We discuss our results by considering the molecular arrangement of the polymer segments in the complex amorphous phase, which is strongly influenced by the PEO crystallization route.

Structural Evolution of an Organic Semiconducting Molecule onto a Soft Substrate.

The structural organization and evolution of the organic semiconducting molecule 2,7-dioctyloxy[1]benzothieno[3,2-b]-benzothiophene on a soft matrix is studied. Thin films of a blend formed from polystyrene and the molecule were prepared by spin-coating onto silicon substrates, which were subsequently studied by using a combination of microscopy and scattering techniques. The organic semiconducting molecule segregated to the surface and developed a phase with a different structure to the bulk, as in the case of a substrate induced phase observed previously. Under a solvent vapor annealing procedure, the growth of micrometer-sized tetragonal crystals onto the polymer surface was observed, which was not evidenced for the silicon substrates.

Are polymers glassier upon confinement?

Glass forming systems are characterized by a stability against crystallization upon heating and by the easiness with which their liquid phase can be transformed into a solid lacking of long-range order upon cooling (glass forming ability). Here, we report the thickness dependence of the thermal phase transition temperatures of poly(l-lactide acid) thin films supported onto solid substrates. The determination of the glass transition, cold crystallization and melting temperatures down to a thickness of 6 nm, permitted us to build up parameters describing glass stability and glass forming ability. We observed a strong influence of the film thickness on the latter, while the former is not affected by 1D confinement. Further experiments permitted us to highlight key structural morphology features giving insights to our ellipsometric results via a physical picture based on the changes in the free volume content in proximity of the supporting interfaces.

Self-assembled three-dimensional hydrogels based on graphene derivatives and cerium oxide nanoparticles: scaffolds for co-culture of oligodendrocytes and neurons derived from neural stem cells.

Stem cell-based therapies have shown promising results for the regeneration of the nervous system. However, the survival and integration of the stem cells in the neural circuitry is suboptimal and might compromise the therapeutic outcomes of this approach. The development of functional scaffolds capable of actively interacting with stem cells may overcome the current limitations of stem cell-based therapies. In this study, three-dimensional hydrogels based on graphene derivatives and cerium oxide (CeO2) nanoparticles are presented as prospective supports allowing neural stem cell adhesion, migration and differentiation. The morphological, mechanical and electrical properties of the resulting hydrogels can be finely tuned by controlling several parameters of the self-assembly of graphene oxide sheets, namely the amount of incorporated reducing agent (ascorbic acid) and CeO2 nanoparticles. The intrinsic properties of the hydrogels, as well as the presence of CeO2 nanoparticles, clearly influence the cell fate. Thus, stiffer adhesion substrates promote differentiation to glial cell lineages, while softer substrates enhance mature neuronal differentiation. Remarkably, CeO2 nanoparticle-containing hydrogels support the differentiation of neural stem cells to neuronal, astroglial and oligodendroglial lineage cells, promoting the in vitro generation of nerve tissue grafts that might be employed in neuroregenerative cell therapies.

Preparation, Physical Properties, and Applications of Water-Based Functional Polymer Inks.

In this study, water-based functional polymer inks are prepared using different solvent displacement methods, in particular, polymer functional inks based on semiconducting polymer poly(3-hexylthiophene) and the ferroelectric polymer poly(vinylidene fluoride) and its copolymers with trifluoroethylene. The nanoparticles that are included in the inks are prepared by miniemulsion, as well as flash and dialysis nanoprecipitation techniques and we discuss the properties of the inks obtained by each technique. Finally, an example of the functionality of a semiconducting/ferroelectric polymer coating prepared from water-based inks is presented.

Phase Transitions in Poly(vinylidene fluoride)/Polymethylene-Based Diblock Copolymers and Blends.

The crystallization and morphology of two linear diblock copolymers based on polymethylene (PM) and poly(vinylidene fluoride) (PVDF) with compositions PM23-b-PVDF77 and PM38-b-PVDF62 (where the subscripts indicate the relative compositions in wt%) were compared with blends of neat components with identical compositions. The samples were studied by SAXS (Small Angle X-ray Scattering), WAXS (Wide Angle X-ray Scattering), PLOM (Polarized Light Optical Microscopy), TEM (Transmission Electron Microscopy), DSC (Differential Scanning Calorimetry), BDS (broadband dielectric spectroscopy), and FTIR (Fourier Transform Infrared Spectroscopy). The results showed that the blends are immiscible, while the diblock copolymers are miscible in the melt state (or very weakly segregated). The PVDF component crystallization was studied in detail. It was found that the polymorphic structure of PVDF was a strong function of its environment. The number of polymorphs and their amount depended on whether it was on its own as a homopolymer, as a block component in the diblock copolymers or as an immiscible phase in the blends. The cooling rate in non-isothermal crystallization or the crystallization temperature in isothermal tests also induced different polymorphic compositions in the PVDF crystals. As a result, we were able to produce samples with exclusive ferroelectric phases at specific preparation conditions, while others with mixtures of paraelectric and ferroelectric phases.

Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s' Molecular Dynamics.

Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure-property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s.

Laser Fabrication of Polymer Ferroelectric Nanostructures for Nonvolatile Organic Memory Devices.

Polymer ferroelectric laser-induced periodic surface structures (LIPSS) have been prepared on ferroelectric thin films of a poly(vinylidene fluoride-trifluoroethylene) copolymer. Although this copolymer does not absorb light at the laser wavelength, LIPSS on the copolymer can be obtained by forming a bilayer with other light-absorbing polymers. The ferroelectric nature of the structured bilayer was proven by piezoresponse force microscopy measurements. Ferroelectric hysteresis was found on both the bilayer and the laser-structured bilayer. We show that it is possible to write ferroelectric information at the nanoscale. The laser-structured ferroelectric bilayer showed an increase in the information storage density of an order of magnitude, in comparison to the original bilayer.