TY - JOUR A1 - Szymoniak, Paulina A1 - Madkour, Sherif A1 - Schönhals, Andreas T1 - Molecular dynamics of the asymmetric blend PVME/PS revisited by broadband dielectric and specific heat spectroscopy: Evidence of multiple glassy dynamics N2 - The molecular mobility of the highly asymmetric miscible blend poly(vinyl methyl ether)/polystyrene was investigated by broadband dielectric (frequency range 10^-1 Hz – 10^9 Hz) and specific heat spectroscopy (frequency range 10^1 Hz – 10^4 Hz). The dielectric spectra revealed a complex molecular dynamic behavior, where three different relaxation processes were observed. At temperatures below the glass transition temperature an α´-relaxation was found, with an Arrhenius-like temperature dependence of its relaxation rates. It is assigned to localized fluctuations of the confined PVME segments within a frozen glassy matrix dominated by PS. Above the thermal glass transition temperature two processes with a VFT behavior of their relaxation rates were detected called α1- and α2-relaxation, both originating from PVME dipoles fluctuating in PS-rich environments, however with diverse PS concentrations. The relevant length scales for the processes are assumed to be different, corresponding to the Kuhn segment length for the former relaxation and to the CRR for the latter one. The observed multiple glassy dynamics result from spatial local compositional heterogeneities on a microscopic level. Additionally, SHS investigations were performed for the first time for this system, proving an existence of a fourth relaxation process (α3-relaxation) due to the cooperative fluctuations of both PS and PVME segments. The separation between the thermal α3- and dielectric α2-relaxation increases dramatically with increasing polystyrene concentration, proving that the thermal response is dominated by PS. KW - Polymer blends KW - Dynamic heterogeneity KW - Broadband dielectric spectroscopy KW - Specific heat spectroscopy PY - 2019 U6 - https://doi.org/10.1021/acs.macromol.8b02697 SN - 0024-9297 VL - 52 IS - 4 SP - 1620 EP - 1631 PB - ACS Publications AN - OPUS4-47516 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nikitin, D. A1 - Madkour, Sherif A1 - Pleskunov, P A1 - Tafiichuk, R A1 - Shelemin, A A1 - Hanus, J A1 - Gordeev, I A1 - Sysolyatina, E A1 - Ermolaeva, S A1 - Titov, V A1 - Schönhals, Andreas A1 - Choukourov, A T1 - Cu nanoparticles constrain segmental dynamics of crosslinked polyethers: a trade -off between non-fouling and antibacterial properties N2 - Copper has a strong bactericidal effect against multi-drug resistant pathogens and polyethers are known for their resistance to biofilm formation. Herein, we combined Cu nanoparticles (NPs) and a polyether Plasma polymer in the form of nanocomposite thin films and studied whether both effects can be coupled. Cu NPs were produced by magnetron sputtering via the aggregation in a cool buffer gas whereasolyether layers were synthesized by Plasma-Assisted Vapor Phase Deposition with poly(ethylene oxide) (PEO) used as a precursor. In situ specific heat spectroscopy and XPS analysis revealed the formation of a modified polymer layer around the NPs which propagates on the scale of a few nanometers from the Cu NP/polymer interface and then transforms into a bulk polymer phase. The chemical composition of the modified layer is found to be ether-deficient due to the catalytic influence of copper whereas the bulk polymer Phase exhibits the chemical composition close to the original PEO. Two cooperative glass transition phenomena are revealed that belong to the modified polymer layer and the bulk phase. The former is characterized by constrained mobility of polymer segments which manifests itself via a 30 K increase of dynamic glass transition temperature. Furthermore, the modified layer is characterized by the heterogeneous structure which results in higher fragility of this layer as compared to the bulk phase. The Cu NPs/polyether thin films exhibit reduced Protein adsorption; however, the constrained segmental dynamics leads to the Deterioration of the non-fouling properties for ultra-thin polyether coatings. The films are found to have a bactericidal effect against multi-drug resistant Gram-positive Methicillin-Resistant Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa. KW - Nanocomposites KW - Specific heat spectroscopy PY - 2019 U6 - https://doi.org/10.1039/c8sm02413h VL - 15 IS - 13 SP - 2884 EP - 2896 PB - RSC AN - OPUS4-47765 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -