Structure of the ion-rich phase in DVB cross-linked graft-copolymer proton-exchange membranes

We report on correlations between the proton conductivity, the water swelling and the dry-state morphology of ETFE-g-poly(sulfonated styrene-co-DVB) proton-exchange membranes (PEMs). We focus on the influence of the systematically varied monomer composition. Especially, the impact of the DVB cross-linker on the ion-rich phase aggregated in the dry PEM is studied by small-angle X-ray scattering. A modified hard-sphere fluid model describing the ion-rich phase is applied to interpret the observed scattering function. We find hereby that the size and number density of the ion-rich domains decrease with increasing cross-link level. Consequently, the distance between the ion-rich domains is proportional to the cross-link level. The total volume fraction of water in the hydrated membrane is proportional to the overall volume fraction of the ion-rich phase, and the number of water molecules per ion-rich aggregate is inversely proportional to the level of cross-linking. We show that there is a clear correlation between the structure of the ion-rich phase formed in the dry state and the proton conductivity of the hydrated membrane: beyond a threshold, indicating the onset of percolation of the aqueous network, the conductivity is proportional to the hydration level and inversely proportional to the mean distance between the ion-rich domains.     

Relaxation processes and intermolecular interactions in PVME hydrogels in sub-zero temperatures: Glass transition and pre-melting of ice

The phase transition observed by various methods in poly(vinyl methyl ether)/water systems at around 18 °C has been assigned by some investigators to the pre-melting of water and by others to a glass transition of the polymer. In this study, broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry were used to identify this transition in radiationally crosslinked poly(vinyl methyl ether) hydrogels, as well as to analyse sub-zero relaxation processes in such a three-phase (polymer/ice/liquid water) system. The process at 18 °C was related to the pre-melting of water induced by the segmental motions of the polymer; however, it was seen to be one transition due to the cooperative motions of both compounds. The atypical (two regimes) temperature dependence of the segmental motion process was observed and was related to confinement of the polymer chains between ice clusters below approximately ?24 °C; furthermore, the main dielectric process of hexagonal ice was identified and a Maxwell-Wagner effect was observed.     

Effect of high temperature annealing on scratch behavior of acrylonitrile styrene acrylate copolymers

The scratch behavior of butyl-acrylate rubber-modified styrene-acrylonitrile (ASA) upon high temperature annealing is investigated following the ASTM D7027/ISO 19252 linearly increasing normal load test methodology. The critical normal loads at the onset of the major deformation transitions along the scratch path, such as groove formation, scratch visibility, microcrack formation, and plowing, are reported and quantitatively analyzed. It is found that the scratch resistance improves with high temperature annealing, i.e., 30 °C above T_g, as compared to annealing below or around T_g. Microscopic investigation suggests that the increase in scratch resistance is related to the changes in surface morphology of the polymer. It is concluded that performing high temperature annealing enhances the scratch performance without compromising ASA bulk properties. Implication of the present study for improving scratch resistance of polymers is discussed.     

Deformation-mediated superstructures and cavitation of poly (l-lactide): In-situ small-angle X-ray scattering study

Cavitation and superstructure evolution of polymers during stretching play crucial roles to influence the mechanical properties of materials. In this study, we investigated deformation-mediated superstructures and cavitation of poly (l-lactide) (PLA) as well as their dependence on stretching temperatures by in-situ small-angle X-ray (SAXS) analysis coupled with mechanical testing. It is found that the cavitation and crystalline deformation are strongly influenced by stretching stress during deformation, which significantly depends on the stretching temperature. At lower stretching temperature (70 °C), the cavitation is initiated before the yielding and then stimulates the crystallite shearing. At higher stretching temperature (90 °C), however, the crystallites shear firstly and then crystalline deformation promotes the formation of cavities orientated along the stretching direction. High stretching temperature benefits the formation of relatively perfect crystals with high orientation. The results provide the basic knowledge of how to adjust the mechanical properties of polymer materials by controlling their superstructure in the deformation process.     

Microgel/SiO2 hybrid colloids prepared using a water soluble silica precursor

In the present work we demonstrate that functional polymer microgels may act as smart self-catalyzing system inducing controlled formation of silica nanoparticles inside the polymer network and formation of hybrid colloids. We synthesized a water soluble silica precursor PEG-PEOS via post-modification of hyperbranched poly(ethoxysiloxane) (PEOS) with poly(ethylene glycol) monomethyl ether. We used poly(N-vinylcaprolactam)-based microgel functionalized with imidazole and β-diketone groups as a matrix for biomimetic deposition of silica. Composite microgel particles containing silica nanoparticles (up to 20 wt.-%) have been prepared by simultaneous PEG-PEOS conversion and silica deposition in the microgels. TEM studies indicate the infiltration of silica nanoparticles (～10 nm) inside the corona region of the microgels due to the strong acid–base interaction between the acidic silica and basic imidazole groups. The resulting composite particles were found to be colloidally stable and no aggregation was observed even after months of storage. The incorporation of silica nanoparticles increased the rigidity of the microgel particles and reduced their thermal sensitivity.     

Influence of a compatibilizer on the morphology development in polymer blends under elongation

Compatibilization is the modification of the interface in immiscible polymer blends in order to refine and stabilize their phase structure. The presence of a compatibilizer at the interface markedly affects the deformation behaviour of the dispersed droplets during and after cessation of flow. In this work the morphology development in blends of polystyrene and linear low-density polyethylene compatibilized with styrene-butadiene-styrene triblock copolymer during and after uniaxial elongation was investigated by means of electron microscopy and small-angle X-ray scattering. The incorporation of only 1 wt.-% of the compatibilizer led to a pronounced increase of the stationary elongational viscosity of the blend. It was found, that at moderate capillary number (Ca ≈ Ca_CR) the compatibilizer stabilises the droplets against break-ups during the flow. When Ca >> Ca_CR no differences in the deformation of uncompatibilized and compatibilized droplets were observed. After cessation of the flow, the presence of the compatibilizer prevented the droplet break-up and supported and accelerated the shape recovery of the elongated particles.     

Synthesis and characterization of polyphenols derived from 4-fluorobenzaldeyde: The effect of electron-donating group on some physical properties

In this study, we proposed to investigate how the effect of electron-donating methyl ( CH₃) group at p-position of amin ( NH₂) group in aminophenol (AP) compound affected thermal stability, optical, electrochemical properties, and conductivity measurement. For this reason, we choice 2-AP and 2-amino-4-methylphenol compounds and synthesized phenolic monomers by condensation reactions 4-fluorobenzaldehyde with aromatic amino phenols. Then, these monomers were converted to their polyphenol derivatives by oxidative polycondensation reactions in an aqueous alkaline medium. Structural characterizations were carried out by FTIR, NMR, and size exclusion chromatography. Cyclic voltammetry was used to determine the electrochemical oxidation-reduction characteristics. Optical properties were investigated by UV–vis and fluorescence analyses. Solid state electrical conductivities were measured on polymer films by four-point probe technique using an electrometer. Thermal data of monomer/polymer and polymers were obtained by TG-DTA and DSC techniques, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effects of temperature,radiation, and illumination on current–voltage characteristics of Au/PVA(Co,Zn-doped)/n-Si Schottky diodes

Polyvinyl alcohol (PVA)/(Co-Ni) nanofiber film was fabricated on silicon wafer using electrospinning technique. The topography of the produced PVA/(Co-Ni) nanofiber film was examined by scanning electron microscopy (SEM). The Au/Poly (vinyl alcohol) (Co, Ni-doped)/n-Si Schottky diode (SD) was thermally formed in evaporating system after the spinning process. At first, the current–voltage (I–V) characteristics of Au/PVA (Co, Zn-doped)/n-Si SD was measured at the room temperature (300 K). For the investigating the effect of temperature, illumination and radiation on Au/PVA (Co, Zn-doped)/n-Si SD comparatively, the measurement was performed under the illumination intensity of 200 W, at 380K, and finally the radiation dose of 22 kGy respectively. The diode characteristics such as the zero-bias barrier height (ϕ_Bo), ideality factor (n) and series resistance (R_s) were calculated at room temperature and under the condition of high temperature, illumination, and radiation. It was found that these characteristics were affected by the illumination and radiation as well as the temperature. The density of interface states (N_ss) distribution profiles as a function of (E_c - E_ss) extracted from the forward I–V measurements were also affected by illumination and radiation even if just a bit. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The production of large bilayer hexagonal graphene domains by a two-step growth process of segregation and surface-catalytic chemical vapor deposition

A novel two-step process combining surface catalyzed process with segregation growth was used to prepare single crystal hexagonal bilayer graphene domains on Cu metal substrates by ambient pressure chemical vapor deposition. Carbon atoms are first dissolved into the quasi-melting Cu metal at 1080 °C and then segregated on the Cu surface to form nucleation centers of single-layer graphene during cooling. The graphene crystallites spontaneously act as templates to induce the carbon atoms to form hexagonal bilayer graphene domains. The bilayer graphene domains are size-tunable by controlling the growth conditions. The yield of the bilayer graphene is over 90% and the defect-free domains reach ～100 μm in size, greater than the reported single-layer domains.     

Porous concrete as a template for the synthesis of porous carbon materials

The potential of industrial porous concrete for using as a template for the synthesis of porous carbon materials has been investigated. Carbon replicas of porous concrete have been prepared by carbonization of sucrose. The pores of the resulting carbon materials range from the macropore to the micropore region, pointing to a hierarchy.