TY - JOUR A1 - Sentker, K. A1 - Zantop, A. W. A1 - Lippmann, M. A1 - Hofmann, T. A1 - Seeck, O. H. A1 - Kityk, A. V. A1 - Yildirim, Arda A1 - Schönhals, Andreas A1 - Mazza, M. G. A1 - Huber, P. T1 - Quantized self-assembly of discotic rings in a liquid crystal confined in nanopores N2 - Disklike molecules with aromatic cores spontaneously stack up in linear columns with high, onedimensional charge carrier mobilities along the columnar axes, making them prominent model systems for functional, self-organized matter.We show by high-resolution optical birefringence and synchrotron-based x-ray diffraction that confining a thermotropic discotic liquid crystal in cylindrical nanopores induces a quantized formation of annular layers consisting of concentric circular bent columns, unknown in the bulk state. Starting from the walls this ring self-assembly propagates layer by layer towards the pore center in the supercooled domain of the bulk isotropic-columnar transition and thus allows one to switch on and off reversibly single, nanosized rings through small temperature variations. By establishing a Gibbs free energy phase diagram we trace the phase transition quantization to the discreteness of the layers’ excess bend deformation energies in comparison to the thermal energy, even for this near room-temperature system. Monte Carlo simulations yielding spatially resolved nematic order parameters, density maps, and bondorientational order parameters corroborate the universality and robustness of the confinement-induced columnar ring formation as well as its quantized nature. KW - Discotic liquid crystals KW - Nanopores PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-440253 DO - https://doi.org/10.1103/PhysRevLett.120.067801 SN - ‎0031-9007 SN - 1079-7114 VL - 120 IS - 6 SP - 067801-1 EP - 067801-7 PB - American Physical Society AN - OPUS4-44025 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yildirim, Arda A1 - Szymoniak, Paulina A1 - Sentker, K. A1 - Butschies, M. A1 - Bühlmeyer, A. A1 - Huber, P. A1 - Laschat, S. A1 - Schönhals, Andreas T1 - Dynamics and ionic conductivity of ionic liquid crystals forming a hexagonal columnar mesophase N2 - For the first time, the molecular mobility of two linear-shaped tetramethylated guanidinium triflate ionic liquid crystals (ILCs) having different length of alkyl chains were investigated by a combination of broadband dielectric spectroscopy (BDS) and specific heat spectroscopy (SHS). By self-assembly, these ILCs can form a hexagonal ordered mesophase besides plastic crystalline phases and the isotropic state. Three dielectric active processes were found by BDS for both samples. At low temperatures, a γ-process in the plastic crystalline state is observed which is assigned to localized fluctuations of methyl groups including nitrogen atoms in the guanidinium head. At higher temperatures but still in the plastic crystalline state, an α1-process takes place. An α2 process was detected by SHS but with a completely different temperature dependence of the relaxation times than that of the α1-relaxation. This result is discussed in detail, and different molecular assignments of the processes are suggested. At even higher temperatures, electrical conductivity is detected and an increase in the DC conductivity by four orders of magnitude at the phase transition from the plastic crystalline to the hexagonal columnar mesophase is found. This result is traced to a change in the charge transport mechanism from a delocalized electron hopping in the stacked aromatic systems (in the plastic phase) to one dominated by an ionic conduction in the quasi-1D ion channels formed along the supermolecular columns in the ILCs hexagonal mesophases. KW - Ionic liquid crystalls PY - 2018 DO - https://doi.org/10.1039/c7cp08186c SN - 1463-9084 SN - 1463-9076 VL - 20 IS - 8 SP - 5626 EP - 5635 PB - Royal Society of Chemistry AN - OPUS4-44254 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Unraveling the dynamics of thin films of a miscible PVME/PS blend N2 - Dielectric spectroscopy (BDS) was employed to investigate the dynamics of thin films (7 – 200 nm) of a Poly (vinyl methyl ether) (PVME) / Polystyrene (PS) blend (50:50 wt%). For the BDS measurements Nano-Structured Capacitors (NSC) were employed, where films have a free surface. This method was applied for film thicknesses up to 36 nm. Thicker films were prepared between Crossed Electrodes Capacitors (CEC). The spectra of the films showed multiple processes. The first process was assigned to the -relaxation of a bulk-like layer. For films measured by NSC, its rates were higher compared to that of the bulk blend. This behavior was related to a PVME-rich free-surface layer. A second process was observed for films measured by CEC (process X) and the 36 nm film measured by NSC (process X2). This process was assigned to fluctuations of PVME constraint by PS. Its activation energy was found to be thickness dependent, due to the evidenced thickness dependency of the compositional heterogeneity. Finally, a third process with an activated temperature-dependence was observed for all films measured by NSC (process X1). It resembled the molecular fluctuations in an adsorbed layer found for films of pure PVME. T2 - Anual Meeting of the American Physical Society CY - Los Angeles, CA, USA DA - 05.03.2018 KW - Thin polymeric films PY - 2018 AN - OPUS4-44414 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dong, S. A1 - Leng, J. A1 - Feng, Y. A1 - Liu, M. A1 - Stackhouse, C. J. A1 - Schönhals, Andreas A1 - Chiappisi, L. A1 - Gao, L. A1 - Chen, W. A1 - Shang, J. A1 - Jin, L. A1 - Qi, Z. A1 - Schalley, C. A. T1 - Structural water as an essential comonomer in supramolecular polymerization N2 - Although the concept of structural water that is bound inside hydrophobic pockets and helps to stabilize protein structures is well established, water has rarely found a similar role in supramolecular polymers. Water is often used as a solvent for supramolecular polymerization, however without taking the role of a comonomer for the supramolecular polymer structure. We report a low–molecular weight monomer whose supramolecular polymerization is triggered by the incorporation of water. The presence of water molecules as comonomers is essential to the polymerization process. The supramolecular polymeric material exhibits strong adhesion to surfaces, such as glass and paper. It can be used as a water-activated glue, which can be released at higher temperatures and reused many times without losing its performance. KW - Supra molecular polymerization PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-432728 DO - https://doi.org/10.1126/sciadv.aao0900 SN - 2375-2548 VL - 3 IS - 11 SP - eaao0900, 1 EP - eaao0900, 8 PB - American Association for the Advancement of Science AN - OPUS4-43272 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Structure-property relationships of nanocomposite based on polylactide and layered double hydroxides as nanofiller N2 - Polymer-based nanocomposites attracted recently a lot of attention from both the applicative and fundamental point of research. While the former point of view is due to the properties improvement compared to the corresponding matrix polymers the latter aspect is related to interaction of polymers with solid surfaces and confinement effects. Here, nanocomposites based on poly(L-lactide) (PLA), which is a semi-crystalline polymer, and organically modified Layered Double Hydroxides (LDH) were prepared by melt blending, and investigated by a combination of Differential Scanning Calorimetry (DSC), Small- and Wide-Angle X-ray Scattering (SAXS, WAXS), and dielectric spectroscopy (BDS). Two different LDH materials were considered, which results in different morphologies of the nanocomposites. The influence of these different morphologies on the properties of the nanocomposites especially on the molecular mobility is discussed in detail. In general the structure of semi-crystalline polymers has to be described by a three phase model, consisting of a mobile amorphous (MAF), a crystalline (CF), and a rigid amorphous fraction (RAF). For nanocomposites based on semi-crystalline polymers the RAF is due to both the crystallites (RAFcrystal) and the filler (RAFfiller). The considered nanocomposites were further investigated by hyper and temperature modulated differential scanning calorimetry. For the first time the different phase fractions CF, MAF, RAFcrystal, and RAFfiller could be estimated independently from each other. T2 - Soft Matter Seminar Universität Halle CY - Halle, Germany DA - 21.11.2017 KW - Polymer based nanocomposites PY - 2017 AN - OPUS4-43098 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Broadband dielectric spectroscopy to study soft matter systems N2 - The basics of broadband dielectric spectroscopy were introduced in detail. The analysis of the data was discussed. As application of broadband dielectric spectroscopy the alpha-relaxation (dynamic glass transition) and the chain dynamics of polymers were ilustrated. Further the application of dielectric spectroscopy to polymerbased nanocomposites and high preformance polymers was discussed in detail. T2 - Kolloquiumsvotrag am Karlsruher Instiut of Technology CY - Karlsruhe, Germany DA - 05.12.2018 KW - Broadband dielectric spectroscopy PY - 2018 AN - OPUS4-46910 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Schönhals, Andreas A1 - Frick, B. A1 - Zorn, R. ED - Kremer, Friedrich ED - Loidl, Alois T1 - The scaling of the molecular dynamics of liquid crystals as revealed by broadband dielectric, specific heat, and neutron spectroscopy N2 - A combination of different complementary methods is employed to investigate scaling of the molecular dynamics of two different liquid crystals. Each method is sensitive to different kind of fluctuations and provides therefore a different window to look at the molecular dynamics. In detail, broadband dielectric spectroscopy is combined with specific heat spectroscopy and neutron scattering. As systems the nematic liquid crystal E7 and a discotic liquid crystalline pyrene are considered. First of all it was proven that both systems show all peculiarities which are characteristic for glassy dynamics and the glassy state. Especially for the nematic liquid crystal E7 it could be unambiguously shown by a combination of dielectric and specific heat spectroscopy that the tumbling mode is the underlying motional process responsible for glassy dynamics. Dielectric investigations on the discotic liquid crystalline pyrene reveal that at the phase transition from the plastic crystalline to the hexagonal columnar liquid crystalline phase the molecular dynamics changes from a more strong to fragile temperature dependence of the relaxation rates. Moreover a combination of results obtained by specific heat spectroscopy with structural methods allows an estimation of the length scale relevant for the glass transition. KW - Broadband dielectric spectroscopy KW - Specific heat spectroscopy KW - Rod-like liquid crystals KW - Discotic liquid crystals PY - 2018 UR - https://link.springer.com/content/pdf/10.1007%2F978-3-319-72706-6.pdf SN - 978-3-319-72705-9 SN - 978-3-319-72706-6 DO - https://doi.org/10.1007/978-3-319-72706-6_9 SN - 2190-930X SN - 2190-9318 SP - 279 EP - 306 PB - Springer International publishing AG CY - Cham, Switzerland ET - 1. AN - OPUS4-45624 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Thin polymer films as model systems for polymer nanocomposites N2 - Polymers at interfaces play a major role in a broad variety of applications ranging from engineering purposes (for instance polymer based nanocomposites) to high tech implications (for instance light emitting diodes). Here, thin films with thicknesses down to few nanometers are prepared on different substrates as model systems for polymer composites. The thin films are investigated by a combination of surface analytical and volume sensitive methods. As surface analytical methods atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and contact angle measurements (CAM) are employed. As volume sensitive broadband dielectric spectroscopy (BDS), specific heat spectroscopy (SHS), and ellipsometry are used. Especially attention is paid to understand the glass transition behavior of thin films because the glass transition is the key phenomenon determines the application of polymers also in thin films. To understand the glass transition behavior of thin films, which is controversially discussed in literature, a three layer model is discussed. Firstly, a mobile surface layer is assumed at polymer air interface of the film due to missing of segment/segment interactions. Secondly, in the middle of the film a bulk-like layer should be expected. Thirdly, for polymers having non-repulsive interactions with the substrate an irreversibly adsorbed layer is expected to be formed. Due the adsorption the molecular mobility of the segments in this layer is slowed down. What is measured for the glass transition of thin films is a complicated average of all of these effects. The different layers are hardly to address separately. Therefore, in the presentation especially model systems are selected and investigated to verify the layer model. T2 - Kolloquiumsvortrag and der Universität des Saarlandes CY - Saarbrücken, Gemany DA - 20.11.2018 KW - Thin polymer films PY - 2018 AN - OPUS4-46692 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Schönhals, Andreas A1 - Zorn, R. T1 - Quasi-elastic scattering of high free volume polymers by neutron time-of-flight spectroscopy N2 - Experimental report to proposal 13562 Quasi-elastic scattering of the polymer with intrinsic microporoasity PIM-1 is measured by neutron time-of-flight spectroscopy and discussed. KW - Neutron scattering KW - PIM-1 PY - 2018 SP - 1 EP - 2 CY - Garching AN - OPUS4-46693 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Nano-sized Relaxation Spectroscopy of Miscible PVME/PS Blend Thin Films N2 - The moleculat dynamics of ultra thin films of polystyrene/poly(vinyl methyl ether) blends as revealed by nanosized specific heat and dielectric spectroscopy is discussed. T2 - Viscous liquids and the glass transition XV CY - Søminestationen, Holbæk, Denmark DA - 21.06.2018 KW - Thin polymeric films KW - Dielectric spectroscopy KW - Specific heat spectroscopx PY - 2018 AN - OPUS4-45280 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Glass transition of thin polymeric films as revealed by calorimetric and dielectric techniques N2 - The structure and dynamics of thin polymeric films is reviewed and discussed in the frame work of novel theoretical approaches T2 - Lähnwitzseminar on Calorimetry CY - Rostock-Warnemünde, Germany DA - 03.06.2018 KW - Thin polymeric films KW - Dielectric spectroscopy KW - Thermal süectroscopy PY - 2018 AN - OPUS4-45164 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Growth kinetics and molecular mobility of irreversibly adsorbed layers in thin polymer films N2 - In well-annealed thin polymer films, with non-repulsive polymer/substrate interactions, an irreversibly adsorbed layer is expected to from. These adsorbed layers have shown greate potential for technological applications. However, their growth kinetics and molecular dynamics are still not fully understood. This is partly due to the hard accessibility of these layers in thin films. Here, the irreversibly adsorbed layers of homopolymer thin films are revealed by solvent-leaching experiments. First, the growth kinetics of these layers is investigated as a function of annealing time, annealing temperature, leaching time and the original filme thickness. The film thickness, topography and the quality of the adsorbed layer is controlled by Atomic Force Microscopy (AFM). Secondly, the molecular mobility of the adsorbed layer is investigated by Broadband Dielectric Spectroscopy (BDS). A recently developed nanostructured capacitor arrangement is employed to measure the layer with a free surface. The results are quantitatively compared and discussed with respect to recently published work. T2 - 10th Conference on Broadband Dielectric Spectroscopy and its Applications CY - Brussles, Belgium DA - 26.08.2018 KW - Thin polymer films PY - 2018 AN - OPUS4-45837 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Schönhals, Andreas A1 - Zorn, R. T1 - Elastic scans on highly permeable glassy polynorbornenes N2 - Experimantal Report to proposal 13603: Elastic Scans on Highly Permeable Glassy Polynorbornenes are measured by neutron backscatering and discuused KW - Neutron backscattering KW - Glassy polynorbornenes PY - 2018 SP - 1 EP - 2 CY - Garching (MLZ) AN - OPUS4-45436 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yin, Huajie A1 - Napolitano, S. A1 - Schönhals, Andreas T1 - Molecular mobility and glass transition of thin films of poly(bisphenol A carbonate) N2 - Glass transition behavior of thin poly(bisphenol A carbonate) (PBAC) films capped between two aluminum (Al) layers is investigated by means of dielectric expansion dilatometry and dielectric relaxation spectroscopy accompanied by contact angle measurements. The thermal glass transition temperature is more or less independent of the film thickness down to 20 nm. For thickness below 20 nm, an increase of Tg is observed. Meanwhile, an increase of the relaxation time at a fixed temperature is observed for the film with the thickness of 19 nm on the basis of a careful analysis of the temperature dependence of the relaxation rates. A more detailed analysis of the relaxation map reveals that the Vogel temperature increases and the fragility decreases systematically with decreasing film thickness. These properties are discussed in terms of the formation of a boundary layer with PBAC segments adsorbed onto the Al electrode due to the strong interaction between the Al and PBAC layers (2.51 mJ/m²), which results in a reduced molecular mobility with regard to bulk PBAC behavior. As the dielectric strength is proportional to the number of segments fluctuating on the time and length scale of the dynamic glass transition, it is used as a unique probe of the deviations from bulk behavior. The temperature dependence of the penetration depth of the interfacial interactions on the structural relaxation is further quantitatively determined. The dynamic length scale of the perturbations into the chain conformations responsible for the deviation from bulk behavior is estimated to be smaller than 9 nm. PY - 2012 DO - https://doi.org/10.1021/ma202127p SN - 0024-9297 SN - 1520-5835 VL - 45 IS - 3 SP - 1652 EP - 1662 PB - American Chemical Society CY - Washington, DC AN - OPUS4-25472 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yin, Huajie A1 - Schönhals, Andreas T1 - Calorimetric glass transition of ultrathin poly(bisphenol A carbonate) films N2 - Specific heat spectroscopy in the frequency range from 1 Hz to 10³ Hz with a sensitivity of pJ K-1 was employed to study the glass transition behavior of ultrathin poly(bisphenol A carbonate) (PBAC) films with thicknesses ranging from 192 nm down to 10 nm. The amplitude and the phase angle of the complex differential voltage as a measure of the complex heat capacity were obtained as a function of temperature at a given frequency simultaneously. Both spectra are used to determine the dynamic glass transition temperature as a function of both the frequency and the film thickness. As the main result no thickness dependence of the dynamic glass transition temperature was observed down to a film thickness of 10 nm within the experimental uncertainty of ±3 K. The obtained data were compared with literature results in detail. PY - 2012 DO - https://doi.org/10.1039/c2sm26174j SN - 1744-683X VL - 8 IS - 35 SP - 9132 EP - 9139 PB - RSC Publ. CY - Cambridge AN - OPUS4-26379 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Boucher, V.M. A1 - Cangialosi, D. A1 - Yin, Huajie A1 - Schönhals, Andreas A1 - Alegría, A. A1 - Colmenero, J. T1 - Tg depression and invariant segmental dynamics in polystyrene thin films N2 - We investigate the segmental dynamics and glass transition temperature (Tg) of polystyrene (PS) thin films. The former is investigated by alternating current (AC) calorimetry and dielectric spectroscopy (BDS). The Tg, underlying the equilibrium to out-of-equilibrium crossover from the supercooled liquid to the glass, is obtained by differential scanning calorimetry (DSC) and capacitive dilatometry (CD). We show that the intrinsic molecular dynamics of PS are independent of the film thickness both for the freestanding and supported films, whereas Tg decreases with film thickness from several microns down to 15 nm. This result is found for complementary methods and in a simultaneous measurement in BDS and CD. This questions the widespread notion that segmental mobility and the equilibrium to out-of-equilibrium transition are, under any experimental conditions, fully interrelated. For thin films, it appears that the molecular mobility and Tg are affected differently by geometrical factors. PY - 2012 DO - https://doi.org/10.1039/c2sm25419k SN - 1744-683X VL - 8 IS - 19 SP - 5119 EP - 5122 PB - RSC Publ. CY - Cambridge AN - OPUS4-25805 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Yin, Huajie A1 - Schönhals, Andreas T1 - Glass transition and segmental dynamics of ultrathin poly(bisphenol A carbonate) films N2 - Broadband dielectric spectroscopy (BDS), capacitive scanning dilatometry (CSD) and differential ac-chip calorimetry (DACC) were used to examine the glass transition and segmental dynamics of ultrathin poly(bisphenol A carbonate) (PBAC) films. An increase of Vogel temperature (T0) as well as glass transition temperature (Tg) with decreasing film thickness was observed when the thickness is less than 20 nm. Moreover, the segmental relaxation time at a fixed temperature was found to increase for the aluminium (Al) capped PBAC films (<20 nm) in the BDS measurements, whereas in the DACC measurements no thickness dependency of the segmental dynamics was detected within the experimental error limit for the supported PBAC films (10-55 nm). These properties are discussed in terms of the thin film geometry and the relevant interfacial interaction between the polymer and the substrate. T2 - 6th International conference on times of polymers (TOP) and composites CY - Ischia, Italy DA - 10.06.2012 KW - Ultrathin film KW - Poly(bisphenol A carbonate) KW - Glass transition KW - Aluminium KW - Dielectric thin films KW - Differential scanning calorimetry KW - Permittivity KW - Polymer films PY - 2012 SN - 978-0-7354-1061-9 DO - https://doi.org/10.1063/1.4738399 N1 - Serientitel: AIP conference proceedings – Series title: AIP conference proceedings IS - 1459 SP - 64 EP - 67 AN - OPUS4-26349 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Omar, Hassan A1 - Ahmadi, Shayan A1 - Szymoniak, Paulina A1 - Schönhals, Andreas T1 - Molecular Mobility of Thin Films of Poly (bisphenol-A carbonate) Capped and with one Free Surface: From Bulk-like Samples down to the Adsorbed Layer N2 - The molecular mobility of thin films of poly(bisphenol A carbonate) (PBAC) was systematically investigated using broadband dielectric spectroscopy, employing two distinct electrode configurations. First, films were prepared in a capped geometry between aluminum electrodes employing a crossed electrode capacitor (CEC) configuration, down to film thicknesses of 40 nm. The Vogel temperature, derived from the temperature dependence of relaxation rate of the α-relaxation, increases with decreasing film thickness characterized by an onset thickness. The onset thickness depends on the annealing conditions, with less intense annealing yielding a lower onset thickness. Additionally, a broadening of the β-relaxation peak was observed with decreasing thickness, attributed to the interaction of phenyl groups with thermally evaporated aluminum, resulting in a shift of certain relaxation modes to higher temperatures relative to the bulk material. A novel phenomenon, termed the slow Arrhenius process (SAP), was also identified in proximity to the α-relaxation temperature. For films with thicknesses below 40 nm, nanostructured electrodes (NSE) were utilized, incorporating nanostructured silica spacers to establish a free surface with air. This free surface causes an enhancement in the molecular mobility for the 40 nm sample, preserving the β-relaxation as a distinct peak. The α-relaxation was detectable in the dielectric loss down to 18 nm, shifting to higher temperatures as film thickness is decreased. Notably, the onset thickness for the increase in Vogel temperature was lower in the NSE configuration compared to the CEC setup, attributed to the presence of the polymer-air interface. KW - Thin polymer films PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-623422 DO - https://doi.org/10.1039/d4sm01238k SN - 1744-6848 VL - 21 IS - 2 SP - 241 EP - 254 PB - RSC AN - OPUS4-62342 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kimiaei, E. A1 - Farooq, M. A1 - Szymoniak, Paulina A1 - Ahmadi, Shayan A1 - Babaeipour, S. A1 - Schönhals, Andreas A1 - Österberg, M. T1 - The role of lignin as interfacial compatibilizer in designing lignocellulosic-polyester composite films N2 - Advancing nanocomposites requires a deep understanding and careful design of nanoscale interfaces, as interfacial interactions and adhesion significantly influence the physical and mechanical properties of these materials. This study demonstrates the effectiveness of lignin nanoparticles (LNPs) as interfacial compatibilizer between hydrophilic cellulose nanofibrils (CNF) and a hydrophobic polyester, polycaprolactone (PCL). In this context, we conducted a detailed analysis of surface-to-bulk interactions in both wet and dry conditions using advanced techniques such as quartz crystal microbalance with dissipation (QCM-D), atomic force microscopy (AFM), water contact angle (WCA) measurements, broadband dielectric spectroscopy (BDS), and inverse gas chromatography (IGC). QCM-D was employed to quantify the adsorption behavior of LNPs on CNF and PCL surfaces, demonstrating LNPs’ capability to interact with both hydrophilic and hydrophobic phases, thereby enhancing composite material properties. LNPs showed extensive adsorption on a CNF model film (1186 ± 178 ng.cm−2) and a lower but still significant adsorption on a PCL model film (270 ± 64 ng.cm−2). In contrast, CNF adsorption on a PCL model film was the lowest, with a sensed mass of only 136 ± 35 ng.cm−2. These findings were further supported by comparing the morphology and wettability of the films before and after adsorption, using AFM and WCA analyses. Then, to gain insights into the molecular-level interactions and molecular mobility within the composite in dry state, BDS was employed. The BDS results showed that LNPs improved the dispersion of PCL within the CNF network. To further investigate the impact of LNPs on the composites’ interfacial properties, IGC was employed. This analysis showed that the composite films containing LNPs exhibited lower surface energy compared to those composed of only CNF and PCL. The presence of LNPs likely reduced the availability of surface hydroxyl groups, thus modifying the physicochemical properties of the interface. These changes were particularly evident in the heterogeneity of the surface energy profile, indicating that LNPs significantly altered the interfacial characteristics of the composite materials. Overall, these findings emphasize the necessity to control the interfaces between components for next-generation nanocomposite materials across diverse applications. KW - Lignin KW - Nanocomposites PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-615098 DO - https://doi.org/10.1016/j.jcis.2024.10.083 SN - 0021-9797 VL - 679 SP - 263 EP - 275 PB - Elsevier Inc. AN - OPUS4-61509 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xu, Q. A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed A. A1 - Yang, Z. A1 - Wang, S. A1 - Gao, Y. A1 - Shang, J. A1 - Hunger, J. A1 - Aldiyarov, A. A1 - Schönhals, Andreas A1 - Ge, Y. A1 - Qi, Z. T1 - Molecular engineering of supramolecular polymer adhesive with confined water and a single crown ether N2 - Here, we report a water-induced supramolecular polymer built from confined structural water and an intrinsic amphiphilic macrocyclic self-assembly in a nanophase separated structure. The newly designed crown ether macrocycle, featuring strong hydrophilic hydrogen bonding receptor selenoxide and a synergistical hydrophobic selenium-substituted crown core, confines the structural water in a segregated, interdigitated architecture. Although water molecules typically freeze around 0 °C, the confined structural water in this supramolecular polymer remains in a liquid-like state down to 80 °C. Previous studies suggest that multiple crown ether units are needed to generate structural water. However, here, one unit is sufficient to control the formation and disappearance of structural water and consequent supramolecular polymerization. Typically, the DC conductivity of water shows Arrhenius temperature dependency (lnσDC ∝ 1/T). In contrast, this new crown unit maintains water in confined states, which exhibit a Vogel/Fulcher/Tammann behavior (lnσDC ∝ 1/(T-T0)) at temperatures above the glass transition temperature. Moreover, this water-induced supramolecular polymer exhibits remarkable adhesion properties to hydrophilic surfaces and maintains tough adhesion at low temperatures. These findings show how a single small macrocycle can govern the complex structure and functionality of water in supramolecular systems. KW - Supramolecular polymerization PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-623631 DO - https://doi.org/10.1039/D4SC06771A SN - 2041-6539 VL - 16 SP - 1 EP - 9 PB - RSC AN - OPUS4-62363 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Li, Z. A1 - Raab, A. A1 - Kolmangadi, Mohamed Aejaz A1 - Busch, M. A1 - Grunwald, M. A1 - Demel, F. A1 - Bertram, F. A1 - Kityk, A. V. A1 - Schönhals, Andreas A1 - Laschat, S. A1 - Huber, P. T1 - Self-Assembly of Ionic Superdiscs in Nanopores N2 - Discotic ionic liquid crystals (DILCs) consist of self-assembled superdiscs of cations and anions that spontaneously stack in linear columns with high one-dimensional ionic and electronic charge mobility, making them prominent model systems for functional soft matter. Compared to classical nonionic discotic liquid crystals, many liquid crystalline structures with a combination of electronic and ionic conductivity have been reported, which are of interest for separation membranes, artificial ion/proton conducting membranes, and optoelectronics. Unfortunately, a homogeneous alignment of the DILCs on the macroscale is often not achievable, which significantly limits the applicability of DILCs. Infiltration into nanoporous solid scaffolds can, in principle, overcome this drawback. However, due to the experimental challenges to scrutinize liquid crystalline order in extreme spatial confinement, little is known about the structures of DILCs in nanopores. Here, we present temperaturedependent high-resolution optical birefringence measurement and 3D reciprocal space mapping based on synchrotron X-ray scattering to investigate the thermotropic phase behavior of dopamine-based ionic liquid crystals confined in cylindrical channels of 180 nm diameter in macroscopic anodic aluminum oxide membranes. As a function of the membranes’ hydrophilicity and thus the molecular anchoring to the pore walls (edge-on or face-on) and the variation of the hydrophilic−hydrophobic balance between the aromatic cores and the alkyl side chain motifs of the superdiscs by tailored chemical synthesis, we find a particularly rich phase behavior, which is not present in the bulk state. It is governed by a complex interplay of liquid crystalline elastic energies (bending and splay deformations), polar interactions, and pure geometric confinement and includes textural transitions between radial and axial alignment of the columns with respect to the long nanochannel axis. Furthermore, confinement-induced continuous order formation is observed in contrast to discontinuous first-order phase transitions, which can be quantitatively described by Landau-de Gennes free energy models for liquid crystalline order transitions in confinement. Our observations suggest that the infiltration of DILCs into nanoporous solids allows tailoring their nanoscale texture and ion channel formation and thus their electrical and optical functionalities over an even wider range than in the bulk state in a homogeneous manner on the centimeter scale as controlled by the monolithic nanoporous scaffolds. KW - Ionic Liquid Crystals KW - Nanopropous materials KW - Landau de-Gennes analysis KW - X-ray scattering KW - Optical birefringence PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600797 DO - https://doi.org/10.1021/acsnano.4c01062 SN - 1936-0851 VL - 18 IS - 22 SP - 14414 EP - 14426 PB - ACS AN - OPUS4-60079 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krause, Christina A1 - Zorn, R. A1 - Frick, B. A1 - Schönhals, Andreas T1 - Quasi- and inelastic neutron scattering to investigate the molecular dynamics of discotic molecules in the bulk N2 - In- and quasielastic neutron scattering is employed to investigate both the vibrational density of states and the molecular dynamics of two homologous discotic liquid crystals (DLC) with different length of the alkyl side chain based on a triphenylene derivate. For both compounds characteristic low frequency excess contributions to the vibrational density of states are found. Therefore it is concluded that these liquid crystals show a glass-like behaviour. Elastic scans further show that in these materials a rich molecular dynamics takes place. T2 - QENS/WINS 2014 - 11th International Conference on Quasielastic Neutron Scattering and 6th International Workshop on Inelastic Neutron Spectrometers CY - Autrans, France DA - 2014-05-11 PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-325477 DO - https://doi.org/10.1051/epjconf/20158302017 SN - 2100-014X VL - 83 SP - 02017-1 EP - 02017-4 PB - EDP Sciences CY - Les Ulis AN - OPUS4-32547 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Yin, Huajie A1 - Schönhals, Andreas ED - Utracki, L.A. ED - Wilkie, C. A. T1 - Broadband dielectric spectroscopy on polymer blends N2 - In this chapter broadband dielectric spectroscopy (BDS) is employed to polymeric blend systems. In its modern form BDS can cover an extraordinary broad frequency range from 10-4 to 1012 Hz. Therefore, molecular and collective dipolar fluctuations, charge transport, and polarization effects at inner phase boundaries can be investigated in detail including its temperature dependence. In the first part of the chapter, the theoretical basics of dielectric spectroscopy are briefly introduced covering both static and dynamic aspects. This section is followed by short description of the various experimental techniques to cover this broad frequency range. To provide the knowledge to understand the dielectric behavior of polymeric blend systems, the dielectric features of amorphous homopolymers are discussed in some detail. This concerns an introduction of the most important relaxation processes observed for these polymers (localized fluctuations, segmental dynamics related to the dynamic glass transition, chain relaxation), a brief introduction to the conductivity of disordered systems as well as polarization effects at phase boundaries. Theoretical models for each process are shortly discussed. In the last paragraph the dielectric behavior of polymer blends is reviewed where special attention is paid to binary systems for the sake of simplicity. In detail the dielectric behavior of binary miscible blends is described. The two most important experimental facts like the broadening of the dielectric relaxation spectra and the dynamic heterogeneity of the segmental dynamics are addressed in depth. Appropriate theoretical approaches like the temperature-driven concentration fluctuation model and the self-concentration idea are introduced. PY - 2014 SN - 978-94-007-6063-9 SN - 978-94-007-6064-6 SN - 978-94-007-6065-3 DO - https://doi.org/10.1007/978-94-007-6064-6_14 SP - Chapter 12, 1299 EP - 1356 PB - Springer Science + Business Media AN - OPUS4-32087 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular Dynamics of linear poly(n-isopropylacrylamide) in water below and above the phase transition: A broadband dielectric relaxation spectroscopy study T2 - Polydays 2014 CY - Berlin, Germany DA - 2014-09-30 PY - 2014 AN - OPUS4-32279 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fahmy, A. A1 - Mohamed, T.A. A1 - Schönhals, Andreas T1 - Structure of plasma poly(acrylic acid): Influence of pressure and dielectric properties N2 - Thin poly(acrylic acid) PAA films were deposited by pulsed plasma polymerization on different organic and inorganic substrates. The structure–property relationships of the deposited acrylic acid polymers were studied in dependence on the monomer pressure by various techniques and probes. The surface and bulk properties of the plasma deposited films were investigated by X-ray photoelectron spectroscopy, attenuated total reflection infrared, and broad band dielectric spectroscopy. The experimental infrared frequencies of PAA films are compared with those predicted from quantum mechanical calculation. The concentration of the COOH groups in the film (stored in ambient air) decreased by about 15 % compared to the as-prepared sample. The plasma deposited PAA probably form a highly branched product. However, the dielectric measurements show that in addition to the hydrogen bonds, self condensation process was able to hinder the localized fluctuation as well. These processes lead to form a cross-linked network polymer film. Nevertheless, a low energy is sufficient to break these processes during heating at atmospheric pressure. Therefore, homogenized samples with free branches (functional group) were obtained after a first heating with structures close to conventional polymerized acrylic acid. Thus, a thermally stable product was obtained. KW - Acrylic acid KW - Plasma polymerization KW - Dielectric properties KW - Thermal stability KW - Aging KW - Monomer pressure PY - 2015 DO - https://doi.org/10.1007/s11090-014-9603-8 SN - 0272-4324 VL - 35 IS - 2 SP - 303 EP - 320 PB - Plenum Publ. Corp. CY - New York, NY, USA AN - OPUS4-32711 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dhotel, A. A1 - Chen, Z. A1 - Sun, J. A1 - Youssef, B. A1 - Saiter, J.-M. A1 - Schönhals, Andreas A1 - Tan, L. A1 - Delbreilh, L. T1 - From monomers to self-assembled monolayers: the evolution of molecular mobility with structural confinements N2 - The effect of structural constriction on molecular mobility is investigated by broadband dielectric spectroscopy (BDS) within three types of molecular arrangements: monomers, oligomers and self-assembled monolayers (SAMs). While disordered monomers exhibit a variety of cooperative and local relaxation processes, the constrained nanodomains of oligomers and highly ordered structure of monolayers exhibit much hindered local molecular fluctuations. Particularly, in SAMs, motions of the silane headgroups are totally prevented whereas the polar endgroups forming the monolayer canopy show only one cooperative relaxation process. This latter molecular fluctuation is, for the first time, observed independently from other overlapping dielectric signals. Numerous electrostatic interactions among those dipolar endgroups are responsible for the strong cooperativity and heterogeneity of the canopy relaxation process. Our data analyses also revealed that the bulkiness of dipolar endgroups can disrupt the organization of the monolayer canopy thus increasing their ability to fluctuate as temperature is increased. PY - 2015 DO - https://doi.org/10.1039/c4sm01893a SN - 1744-683X VL - 11 IS - 4 SP - 719 EP - 731 PB - RSC Publ. CY - Cambridge AN - OPUS4-32378 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Behavior of Ultra-Thin Polymerich Films as Investigated by a Combination of Complementary Methods T2 - Kolloquiumsvortrag Universität Bielefeld, Fakultät für Physik CY - Bielefeld, Germany DA - 2014-12-12 PY - 2014 AN - OPUS4-32354 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brás, A.R. A1 - Fonseca, I.M. A1 - Dionísio, M. A1 - Schönhals, Andreas A1 - Affouard, F. A1 - Correia, N.T. T1 - Influence of nanoscale confinement on the molecular mobility of ibuprofen N2 - The molecular mobility of ibuprofen confined to a mesoporous silica host (MCM-41) of 3.6 nm pore diameter is investigated by dielectric relaxation spectroscopy. It is confirmed that crystallization is suppressed; therefore, depending on the temperature, the guest exists in the glassy and supercooled state inside of the pores. A detailed relaxation map is provided where multiple processes are dynamically characterized, comprised of three processes that are also found for the bulk and two additional ones. The bulk-like processes include two secondary processes, a simple thermally activated one, a γ process and a Johari–Goldstein βJG process, and the one associated with the dynamic glass transition of molecules located in the pore center (α process). In confinement, all of these processes display deviations in its dynamical behavior relative to the bulk, the most dramatic one undergone by the α process, which exhibits Arrhenius-like temperature dependence upon approaching the glass transition instead of Vogel/Fulcher/Tammann/Hesse (VFTH) scaling as obeyed by the bulk. The two additional relaxations are associated with the dynamical behavior of hydrogen-bonded ibuprofen molecules lying in an interfacial layer near the pore wall, an S process for which the mobility is strongly reduced relative to the α process and a Debye-like D process for which the dynamics is closely correlated to the dynamics of the interfacial process, both exhibiting VFTH temperature dependencies. The comparison with the behavior of the same guest in the analogous host, SBA-15, with a higher pore diameter (8.6 nm) leads to the conclusion that the bulk-like mobility associated with the dynamic glass transition undergoes finite size effects being accelerated upon a decrease of the pore size with a concomitant reduction of the glass transition temperature relative to the bulk, 22 and 32 K, respectively, for the 8.6 and 3.6 nm pore diameters. The continuous decrease in the separation between the α- and βJG-trace with pore size decrease allows one to conclude that confined ibuprofen is a suitable guest molecule to test the Coupling Model that predicts a transformation of the α process into a βJG-mode under conditions of an extreme nanoconfinement. The overall behavior inside of pores is consistent with the existence of two distinct dynamical domains, originated by ibuprofen molecules in the core of the pore cavity and adjacent to the pore wall, from which a clear picture is given by molecular dynamics simulation. PY - 2014 DO - https://doi.org/10.1021/jp500630m SN - 1932-7447 SN - 1089-5639 VL - 118 IS - 25 SP - 13857 EP - 13868 PB - Soc. CY - Washington, DC AN - OPUS4-31170 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular Dynamics of Discotic Liquid Crystals in the Bulk and embedded in Nanochannels T2 - 8th International Conference on Broadband Dielectric Spectroscopy and its Applications CY - Wisla, Poland DA - 2014-09-15 PY - 2014 AN - OPUS4-31464 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular Dynamics of Linear Poly(N-isopropylacrylamide) in Water below and above the Phase Transition: A Broadband Dielectric Relaxation Spectroscopy Study T2 - 8th International Conference on Broadband Dielectric Spectroscopy and its Applications CY - Wisla, Poland DA - 2014-09-15 PY - 2014 AN - OPUS4-31465 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kityk, A.V. A1 - Busch, M. A1 - Rau, D. A1 - Calus, S. A1 - Cerclier, C.V. A1 - Lefort, R. A1 - Morineau, D. A1 - Grelet, E. A1 - Krause, Christina A1 - Schönhals, Andreas A1 - Frick, B. A1 - Huber, P. T1 - Thermotropic orientational order of discotic liquid crystals in nanochannels: an optical polarimetry study and a Landau-de Gennes analysis N2 - Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3–22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau–de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter. PY - 2014 DO - https://doi.org/10.1039/c4sm00211c SN - 1744-683X VL - 10 IS - 25 SP - 4522 EP - 4534 PB - RSC Publ. CY - Cambridge AN - OPUS4-30866 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Papadakis, C.M. T1 - Editorial - Special issue in honor of Friedrich Kremer N2 - Prof. Dr. Friedrich Kremer is celebrating his 65th birthday this year. Furthermore, also for this reason, he resigned from the position as an Editor-in-Chief of the journal Colloid and Polymer Science. In his more than 20 years of successful editorship, he has substantially contributed to develop Colloid and Polymer Science to become a leading international journal in the field of polymers and colloids including their manifold connections with other branches of science. He will remain in a close connection to the journal as the new Chief Advisory Editor. To appreciate both his 65th birthday and his prosperous engagement for this journal, Springer is pleased to launch the present special issue of Colloid and Polymer Science dedicated to Prof. Dr. Friedrich Kremer. Friends, editors, and colleagues, as well as coworkers and former students contribute to this special issue with their own selected original scientific work in order to honor Prof. Dr. Friedrich Kremer not only as a leading scientist but also as a person with an outstanding personality. PY - 2014 DO - https://doi.org/10.1007/s00396-014-3292-y SN - 0303-402X SN - 1435-1536 VL - 292 IS - 8 SP - 1735 EP - 1736 PB - Springer CY - Berlin AN - OPUS4-31185 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krause, Christina A1 - Zorn, R. A1 - Frick, B. A1 - Schönhals, Andreas T1 - Thermal properties and vibrational density of states of a nanoconfined discotic liquid crystal N2 - Neutron scattering is employed to investigate the vibrational density of states (VDOS) of the discotic liquid crystal 2,3,6,7,10,11-hexakis[hexyloxy] triphenylene (HAT6) confined to the pores of alumina oxide membranes with different pore sizes. Additionally, the phase transitions were studied by differential scanning calorimetry. The transitions were observed down to the smallest pore size. The decrease of the transition enthalpies versus inverse pore size for both transitions implies an increase of the amount of disordered amorphous material. By extrapolation of its pore size dependence, a critical pore diameter for structure formation of 17 nm is estimated. Similar to the bulk, excess contributions to the VDOS (Boson peak) are also observed for confined HAT6. The Boson peak gains in intensity and shifts to lower frequencies with decreasing pore diameter. This is discussed in the framework of a softening of HAT6 induced by the confinement due to a less-developed plastic crystalline state inside the pores compared to the bulk. KW - Discotic liquid crystals KW - Confinement KW - Neutron scattering KW - Boson peak PY - 2014 DO - https://doi.org/10.1007/s00396-014-3247-3 SN - 0303-402X SN - 1435-1536 VL - 292 IS - 8 SP - 1949 EP - 1960 PB - Springer CY - Berlin AN - OPUS4-31254 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecules in Nanometer Confinement investigated by Dieletric, Thermal and Neutron Spectroscopy T2 - Kolloquiumsvortrag Universität Rouen CY - Rouen, France DA - 2013-12-10 PY - 2013 AN - OPUS4-30020 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Crystallization behavior of nanocomposites based on poly(L-lactide) and layered doubled hydroxides – Unbiased determination of the rigid amorphous phase due to the crystals and the nanofiller N2 - Semicrystalline polymers have to be described by a three phase model consisting of a mobile amorphous (MAF), a crystalline (CF), and a rigid amorphous fraction (RAF). For nanocomposites based on a semicrystalline polymer the RAF is due to both the crystallites (RAFcrystal) and the filler (RAFfiller). In most cases a separation of both contributions is not possible without further assumptions. Polymer nanocomposite based on poly(L-lactide) and MgAl layered double hydroxide nanofiller were prepared. Due to the low crystallization rate of PLA its crystallization can be suppressed by a high enough cooling rate, and the RAF is due only to the nanofiller. The MAF, CF, and RAF were estimated by Temperature Modulated DSC. For the first time CF, MAF, RAFcrystal, and RAFfiller could be estimated. It was found, that RAFfiller increases linearly with the concentration of the nanofiller. Furthermore, RAFcrystal is only slightly influenced by the presence of the nanofiller. T2 - Marchmetting American Physical Society CY - New Orleans, USA DA - 13.03.2017 KW - Nanocomposites PY - 2017 AN - OPUS4-39554 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Asadujjaman, Asad A1 - Bertin, Annabelle A1 - Schönhals, Andreas T1 - Dielectric analysis of the upper critical solution temperature behaviour of a poly(acrylamide-coacrylonitrile) copolymer system in water N2 - A copolymer consisting of acrylamide (AAm) and acrylonitrile (AN) in aqueous solution was investigated using broadband dielectric spectroscopy at frequencies between 10⁻¹ Hz and 10⁶ Hz in the temperature range from 2 °C to 60 °C. This system shows an UCST phase behavior. The phase transition and aggregation behavior is monitored by both the temperature and frequency dependence of the complex conductivity σ*(f, T), where the AN fraction and the concentration of the solution were varied. Additionally, the dielectric data are compared with the results obtained from dynamic light scattering measurements. The temperature dependence of the DC conductivity (σDC) of the copolymer solution is monitored and the phase transition temperature (PTT) of the poly(AAm-co-AN) copolymer is deduced from a change in the T-dependence of the DC conductivity. The change in σDC can be explained by decreased effective charge carrier mobility and a reduction of the effective charge number density at temperatures below the phase Transition temperature of the poly(AAm-co-AN) solution. A pronounced interfacial polarization effect on the frequency dependence of the real part of the conductivity (σ') is observed at temperatures below the phase Transition temperature. The charge carriers are blocked at the formed aggregates giving rise to this interfacial polarization. The dependence of the interfacial polarization on the acrylonitrile fraction in the copolymer and the concentration of the solution is studied in detail and conclusions concerning the internal structures of the copolymer aggregates are drawn. KW - Thermoresponsive polymres PY - 2017 DO - https://doi.org/10.1039/c6sm02684b SN - 1744-6848 SN - 1744-683X VL - 13 IS - 12 SP - 2384 EP - 2393 PB - Royl Society of Chemistry Publishing AN - OPUS4-39556 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Madkour, Sherif A1 - Szymoniak, Paulina A1 - Schick, Ch. A1 - Schönhals, Andreas T1 - Unexpected behavior of ultra-thin films of blends of polystyrene/poly(vinyl methyl ether) studied by specific heat spectroscopy N2 - Specific heat spectroscopy (SHS) employing AC nanochip calorimetry was used to investigate the glassy dynamics of ultra-thin films (thicknesses: 10 nm–340 nm) of a polymer blend, which is miscible in the bulk. In detail, a Poly(vinyl methyl ether) (PVME)/Polystyrene (PS) blend with the composition of 25/75 wt. % was studied. The film thickness was controlled by ellipsometry while the film topography was checked by atomic force microscopy. The results are discussed in the framework of the balance between an adsorbed and a free surface layer on the glassy dynamics. By a self-assembling process, a layer with a reduced mobility is irreversibly adsorbed at the polymer/substrate interface. This layer is discussed employing two different scenarios. In the first approach, it is assumed that a PS-rich layer is adsorbed at the substrate. Whereas in the second approach, a PVME-rich layer is suggested to be formed at the SiO2 substrate. Further, due to the lower surface tension of PVME, with respect to air, a nanometer thick PVME-rich surface layer, with higher molecular mobility, is formed at the polymer/air interface. By measuring the glassy dynamics of the thin films of PVME/PS in dependence on the film thickness, it was shown that down to 30 nm thicknesses, the dynamic Tg of the whole film was strongly influenced by the adsorbed layer yielding a systematic increase in the dynamic Tg with decreasing the film thickness. However, at a thickness of ca. 30 nm, the influence of the mobile surface layer becomes more pronounced. This results in a systematic decrease in Tg with the further decrease of the film thickness, below 30 nm. These results were discussed with respect to thin films of PVME/PS blend with a composition of 50/50 wt.%as well as literature results. KW - Ultra thin polymer films PY - 2017 DO - https://doi.org/10.1063/1.4978505 SN - 0021-9606 SN - 1089-7690 VL - 146 IS - 20 SP - 203321-1 EP - 203321-9 PB - AIP Publishing AN - OPUS4-39558 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Madkour, Sherif A1 - Szymoniak, Paulina A1 - Heídari, M. A1 - von Klitzing, R. A1 - Schönhals, Andreas T1 - Unveiling the dynamics of self-assembled layers of thin films of poly(vinyl methyl ether) (PVME) by nanosized relaxation spectroscopy N2 - A combination of nanosized dielectric relaxation (BDS) and thermal spectroscopy (SHS) was utilized to characterize the dynamics of thin films of Poly(vinyl methyl ether) (PVME) (thicknesses: 7 nm – 160 nm). For the BDS measurements, a recently designed nano-structured electrode system is employed. A thin film is spin-coated on an ultra-flat highly conductive silicon wafer serving as the bottom electrode. As top electrode, a highly conductive wafer with non-conducting nanostructured SiO2 nano-spacers with heights of 35 nm or 70 nm is assembled on the bottom electrode. This procedure results in thin supported films with a free polymer/air interface. The BDS measurements show two relaxation processes, which are analyzed unambiguously for thicknesses smaller than 50 nm. The relaxation rates of both processes have different temperature dependencies. One process coincidences in its position and temperature dependence with the glassy dynamics of bulk PVME and is ascribed to the dynamic glass transition of a bulk-like layer in the middle of the film. The relaxation rates were found to be thickness independent as confirmed by SHS. Unexpectedly, the relaxation rates of the second process obey an Arrhenius-like temperature dependence. This process was not observed by SHS and was related to the constrained fluctuations in a layer, which is irreversibly adsorbed at the substrate with a heterogeneous structure. Its molecular fluctuations undergo a confinement effect resulting in the localization of the segmental dynamics. To our knowledge, this is the first report on the molecular dynamics of an adsorbed layer in thin films. KW - Broadband dielectric spectroscopy KW - AC-nanochip calorimetry KW - Nanostructured capacitors KW - Thin films PY - 2017 UR - http://pubs.acs.org/doi/pdf/10.1021/acsami.6b14404 DO - https://doi.org/10.1021/acsami.6b14404 SN - 1944-8244 VL - 9 IS - 8 SP - 7535 EP - 7546 PB - ACS Publications CY - Washington DC AN - OPUS4-39291 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Behavior of Ultra-Thin POLYMER Films investigated by Nanosized Relaxation Spectroscopy N2 - The glass transition behavior of ultra-thin polymer films is discussed in detail. Further nanosized relxation spectroscopy is introduced in the form of AC chip calorimetry and dielectric spectroscopy employing nanostructured electrodes. These methods arre applied to ultra-thin films. T2 - Soft Matter Seminar Jülich CY - Jülich, Germany DA - 15.12.2016 KW - Ultra-thin polymer films PY - 2016 AN - OPUS4-38714 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Neutron and dielectric spectroscopy - taking advantage of the strengths of each technique in confinement studies: Vibrational and molecular dynamics of nanoconfined liquid crystals N2 - The effect of a nanometre confinement on the molecular dynamics of liquid crystals was studied by broadband dielectric and neutron spectroscopy. As confining host the molecular sieve Al-MCM-41 (Si/Al=60) with a mean pore diameter of 3 nm was selected. As guest the liquid crystals 8CB and E7 were chosen where the latter does not crystallize but undergoes a glass transition forming a nematic glass. Dielectric spectroscopy shows that for the confined systems one relaxation process is observed. Ist characteristic relaxation time is much lower compared to that of the bulk. No signature of the Phase transition characteristics of the bulk liquid crystal is detected. The temperature dependence of the relaxation time of this relaxation process has to be described by the Vogel-Fulcher-Tammann equation and thus shows similarities to glassy dynamics. The vibrational density of states measured by neutron spectroscopy (IN6, ILL; TOFTOF, MLZ) Shows excess contributions with respect to the Debye density of states (boson peak). For the confined systems the low frequency contributions of the boson peak are suppressed, an effect which is also found for conventional glass forming systems. In addition elastic scans were carried out at the backscattering spectrometer (BS) IN10 at ILL. Such measurements provide an overview about the temperature dependence of the microscopic dynamics. Assuming a Gaussian form for the elastically scattered intensities the effective mean square displacement was calculated. For the nanoconfined samples the mean square displacement is strongly reduced in comparison to the bulk. Also these measurements show the signature of a glass Transition indicated by a change in the temperature dependence of the mean square displacement. For confined E7 the extracted glass transition temperature is shifted by more than 20 K to higher temperatures. Broadband inelastic neutron scattering was carried out by combining time-of-flight (IN6, ILL; TOFTOF, MLZ) and backscattering (IN10, ILL; SPHERES, MLZ) experiments in the time domain. The time dependence of the incoherent intermediate scattering function Sinc(q,t) shows two Relaxation processes which were quantitatively analyzed by fitting the KWW function to the data. The process at shorter times shows a close similarity the methyl group rotation found for polymeric systems. The process at longer times was assigned to glassy dynamics. The obtained data are compared in detail in their temperature dependence to the dielectric results. T2 - Deutsche Neutronenstreutagung 2016 CY - Kiel, Germany DA - 20.09.2016 KW - Neutron scattering KW - Broadband dielectric spectroscopy PY - 2016 AN - OPUS4-37516 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Calus, S. A1 - Kityk, A.V. A1 - Borowik, L. A1 - Lefort, R. A1 - Morineau, D. A1 - Krause, Christina A1 - Schönhals, Andreas A1 - Busch, M. A1 - Huber, P. T1 - High-resolution dielectric study reveals pore-size-dependent orientational order of a discotic liquid crystal confined in tubular nanopores N2 - We report a high-resolution dielectric study on a pyrene-based discotic liquid crystal (DLC) in the bulk state and confined in parallel tubular nanopores of monolithic silica and alumina membranes. The positive dielectric anisotropy of the DLC molecule at low frequencies (in the quasistatic case) allows us to explore the thermotropic collective orientational order. A face-on arrangement of the molecular discs on the pore walls and a corresponding radial arrangement of the molecules is found. In contrast to the bulk, the isotropic-to-columnar transition of the confined DLC is continuous, shifts with decreasing pore diameter to lower temperatures, and exhibits a pronounced hysteresis between cooling and heating. These findings corroborate conclusions from previous neutron and x-ray-scattering experiments as well as optical birefringence measurements. Our study also indicates that the relative simple dielectric technique presented here is a quite efficient method in order to study the thermotropic orientational order of DLC-based nanocomposites. PY - 2015 DO - https://doi.org/10.1103/PhysRevE.92.012503 SN - 1539-3755 SN - 1063-651X VL - 92 IS - 1 SP - 012503-1 EP - 012503-6 PB - American Institute of Physics CY - Melville, NY AN - OPUS4-33813 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rijal, B. A1 - Delbreilh, L. A1 - Saiter, J.-M. A1 - Schönhals, Andreas A1 - Saiter, A. T1 - Quasi-isothermal and heat-cool protocols from MT-DSC - Influence on the values extracted for the cooperativity length calculation N2 - Understanding the evolution of the cooperative molecular mobility as a function of time and temperature remains an unsolved question in condensed matter physics. Many recent works concern the question of the molecular dynamic slowdown in a temperature domain ranging from the crossover temperature T c (beginning of cooperative relaxation) down to the calorimetric glass transition temperature T g. Recent studies have shown that the estimation of cooperativity length based on calorimetric investigations using Donth's approach can be extended to a wider temperature range from T g to T c. To describe the relaxation time evolution and the characteristic length evolution of cooperative motions, besides the Donth's fluctuation approach other models exist in the literature such as '4 points correlation function' model. Whatever the model used, calorimetric investigations are needed to estimate the heat capacity as a function of the temperature. In this work, we have focused our attention on the modulated temperature differential scanning calorimetry (MT-DSC) experiments and we have tested different MT-DSC protocols allowing the heat capacity determination. For this goal we decided to work on different amorphous glass formers in order to cover a large range of glass transition temperature. The influence of the protocol used on the cooperativity length calculation is discussed in detail. Lissajous figures were constructed to verify whether the steady state is reached. KW - Glass transition KW - MT-DSC KW - Heat capacity KW - Cooperative rearranging region (CRR) PY - 2015 DO - https://doi.org/10.1007/s10973-015-4671-4 SN - 1388-6150 SN - 1418-2874 SN - 0368-4466 SN - 1572-8943 VL - 121 IS - 1 SP - 381 EP - 388 PB - Kluwer Academic Publ. CY - Dordrecht AN - OPUS4-33670 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yin, Huajie A1 - Dittrich, Bettina A1 - Farooq, Muhammad A1 - Kerling, S. A1 - Wartig, K.-A. A1 - Hofmann, D. A1 - Huth, Christian A1 - Okolieocha, C. A1 - Altstädt, V. A1 - Schönhals, Andreas A1 - Schartel, Bernhard T1 - Carbon-based nanofillers/poly(butylene terephthalate): thermal, dielectric, electrical and rheological properties N2 - The influence of distinct carbon based nanofillers: expanded graphite (EG), conducting carbon black (CB), thermally reduced graphene oxide (TRGO) and multi-walled carbon nanotubes (CNT) on the thermal, dielectric, electrical and rheological properties of polybutylene terephthalate (PBT) was examined. The glass transition temperature (Tg) of PBT nanocomposites is independent of the filler type and content. The carbon particles act as nucleation agents and significantly affect the melting temperature (Tm), the crystallization temperature (Tc) and the degree of crystallinity of PBT composites. PBT composites with EG show insulating behaviour over the tested concentration range of 0.5 to 2 wt.-% and hardly changed rheological behaviour. CB, CNT and TRGO induce electrical conductivity to their particular PBT composites by forming a conducting particle network within the polymer matrix. CNT reached the percolation threshold at the lowest concentration (<0.5 wt.-%), followed by TRGO (<1 wt.-%) and CB (<2 wt.-%). With the formation of a particle network, the flow behaviour of composites with CB, CNT and TRGO is affected, i.e., a flow limit occurs and the melt viscosity increases. The degree of influence of the carbon nanofillers on the rheological properties of PBT composites follows the same order as for electrical conductivity. Electrical and rheological results suggest an influence attributed to the particle dispersion, which is proposed to follow the order of EG<< CB