TY - CONF A1 - Madkour, Sherif Aly Hassan Aly A1 - Yin, Huajie A1 - Schönhals, Andreas A1 - Füllbrandt, Marieke T1 - Specific heat spectroscopy characterization of dynamic glass transition in ultrathin poly-2-vinyl pyridine films T2 - Polydays 2014 T2 - Polydays 2014 CY - Berlin, Germany DA - 2014-09-30 PY - 2014 AN - OPUS4-31692 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Madkour, Sherif A1 - Szymoniak, Paulina A1 - Schönhals, Andreas T1 - Evidence of a Three-Layred Structure in Ultrathin PVME and PVME-PS Blend Films by Nanosized Relaxation Spectroscopy N2 - In the course of miniaturizing modern technology down to the molecular scale, much remain unknown about the materials behavior and the deviations from the bulk that might arises from confinement effects. Here, a combination of nano-sized relaxation spectroscopies (Broadband dielectric spectroscopy (BDS) and Specific heat spectroscopy (SHS); employing AC nanochip calorimetry) were utilized to investigate the glassy dynamics of ultra-thin films of Poly (vinyl methyl ether) (PVME) and of blends PVME / Polystyrene (PS) 50:50 wt-%,, which are miscible in bulk (thicknesses: ca. 8 nm – 160 nm, film thickness was controlled by ellipsometry, film topography by AFM). Both methods are sensitive to different probes; where SHS senses entropy fluctuations while BDS measures dipole fluctuations. For BDS measurements, a recently developed nano-structured electrode sample arrangement is employed, where ultra-thin films are spin-coated on an ultra-flat highly conductive silicon wafer, sandwiched between a wafer with nanostructured SiO2 nano-spacers with heights between 35 nm and 70 nm. For PVME films, two thickness independent processes were observed and interpreted to be the α-processes of a bulk-like layer and a process due to an absorbed layer to the substrate. This adsorbed layer further undergoes a confinement effect that results in the localization of the segmental dynamics, which results in an Arrhenius-like temperature dependence. A detailed analysis of the dielectric strengths of both processes reveals that the thickness of the adsorbed layer decreases with increasing temperature, while that of the bulk-like layer increases. For the blend system, by measuring the dynamic Tg in dependence of the film thickness, SHS showed that the Tg of the whole film was strongly influenced by a nanometer-thick surface layer at the polymer/air interface due to a self-assembling process. The dynamic Tg obtained from the SHS measurements decreased with decreasing film thickness. On the other hand, BDS measurements showed a completely different behavior. At high temperatures, the temperature dependence of the relaxation times of the films follows that of bulk-like PS/PVME; obeying the VFT-law. With decreasing temperature, the temperature dependence deviates from the VFT to an Arrhenius law; where the apparent activation energy decreases with decreasing film thickness. This is the first example where confinement induced changes were observed by BDS for ultra-thin films. All results were analyzed in detail in a comprehensive discussion. T2 - 14. Lähnwitzseminar on Calorimetry CY - Rostock-Warnemünde, Germany DA - 05.05.2016 KW - Ultra-Thin films PY - 2016 AN - OPUS4-36477 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Madkour, Sherif A1 - Szymoniak, Paulina A1 - Schönhals, Andreas T1 - Evidence of a three-layred structure in ultrathin PVME and PVME-PS blend films by nanosized relaxation spectroscopy N2 - In the course of miniaturizing modern technology down to the molecular scale, much remain unknown about the materials behavior and the deviations from the bulk that might arises from confinement effects. Here, a combination of nano-sized relaxation spectroscopies (Broadband dielectric spectroscopy (BDS) and Specific heat spectroscopy (SHS); employing AC nanochip calorimetry) were utilized to investigate the glassy dynamics of ultra-thin films of Poly (vinyl methyl ether) (PVME) and of blends PVME / Polystyrene (PS) 50:50 wt-%,, which are miscible in bulk (thicknesses: ca. 8 nm – 160 nm, film thickness was controlled by ellipsometry, film topography by AFM). Both methods are sensitive to different probes; where SHS senses entropy fluctuations while BDS measures dipole fluctuations. For BDS measurements, a recently developed nano-structured electrode sample arrangement is employed, where ultra-thin films are spin-coated on an ultra-flat highly conductive silicon wafer, sandwiched between a wafer with nanostructured SiO2 nano-spacers with heights between 35 nm and 70 nm. For PVME films, two thickness independent processes were observed and interpreted to be the α-processes of a bulk-like layer and a process due to an absorbed layer to the substrate. This adsorbed layer further undergoes a confinement effect that results in the localization of the segmental dynamics, which results in an Arrhenius-like temperature dependence. A detailed analysis of the dielectric strengths of both processes reveals that the thickness of the adsorbed layer decreases with increasing temperature, while that of the bulk-like layer increases. For the blend system, by measuring the dynamic Tg in dependence of the film thickness, SHS showed that the Tg of the whole film was strongly influenced by a nanometer-thick surface layer at the polymer/air interface due to a self-assembling process. The dynamic Tg obtained from the SHS measurements decreased with decreasing film thickness. On the other hand, BDS measurements showed a completely different behavior. At high temperatures, the temperature dependence of the relaxation times of the films follows that of bulk-like PS/PVME; obeying the VFT-law. With decreasing temperature, the temperature dependence deviates from the VFT to an Arrhenius law; where the apparent activation energy decreases with decreasing film thickness. This is the first example where confinement induced changes were observed by BDS for ultra-thin films. All results were analyzed in detail in a comprehensive discussion. T2 - Polydays 2016 CY - Potsdam, Germany DA - 28.09.2016 KW - Ultra-Thin films PY - 2016 AN - OPUS4-38188 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Madkour, Sherif A1 - Penner, P. A1 - Zhang, X. A1 - Gölzhäuser, A. A1 - Schönhals, Andreas T1 - Dielectric investigations on carbon nanomembranes N2 - Multilayer carbon nanomembrances (CNMs) could pave the way for a new ultrathin functional conductive coatings with tunable electrical, optical, and chemical properties. Due to their molecular thickness, they can also be regarded as “interfaces without bulk” separating regions of different gaseous, liquid, or solid components and controlling the materials exchange between them, making them optimal materials for membranes applications. Furthermore, their physical and chemical properties depend strongly on their structure, molecular composition, and the surroundings of either sides, thus allowing for tailored properties. Here, nanolayers of Aromatic p-terphenylthiol (TPT) self-assembled into 2D carbon monolayers (thickness - 1.6 nm) were synthesized and further crosslinked by ion bombardment, forming CNMs. Here, though a recently developed multilayer nanosheets routine, stacks of 5, 10, 15 and 20 TPT sheets where transferred on top of each other forming a multilayered CNMs. However, this transfer routine could introduce some intrinsic defects to the sheets, which would alter the molecular composition and / or structure, thus consequently the CNMs properties. Therefore, it is essential to characterize defects in “pure” TPT nanomembranes, before tailoring the molecular compositions, e.g. adding functional groups. For this reason, broadband dielectric spectroscopy (BDS) was utilized to characterize any defects that could be rasied during preparation. Due the structure of pure TPT membranes, no dipole moment should exsist. However, the presence of other elements, e.g. water or sulphur, would result in a dipole moment that could be probed by BDS. As a main result, for all different stacked-layer numbers, a clear relaxation process is seen, which moves to higher frequencies with increasing the temperature. The temperature dependence of the relaxation rate of this process is independent of film thickness and can be well described by a common VFT function, hence a corporative motion. This relaxation process was assigned to intrinisic defects in the membranes, introduced during preparation, which was further confimed by a detailed anaylsis of the dielectric strength. This is the first BDS measurment on TPT CNMs. T2 - 9th International Conference on Broadband Dielectric Spectroscopy and its Applications CY - Pisa, Italy DA - 11.09.2016 KW - Carbon nanomembranes PY - 2016 AN - OPUS4-37527 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Madkour, Sherif Aly Hassan Aly A1 - Yin, Huajie A1 - Schönhals, Andreas A1 - Füllbrandt, Marieke T1 - Calorimetric glass transition of ultrathin poly-2-vinyl pyridine films T2 - 8th International Conference of Broadband Dielectric Spectroscopy T2 - 8th International Conference of Broadband Dielectric Spectroscopy CY - Wisla, Poland DA - 2014-09-14 PY - 2014 AN - OPUS4-31693 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -