TY - JOUR A1 - Schönhals, Andreas A1 - Goering, Harald A1 - Brzezinka, Klaus-Werner A1 - Schick, C. T1 - Molecular dynamics of polymers in random nanometer confinements investigated by relaxational scattering techniques N2 - Dielectric spectroscopy and temperature-modulated differential scanning calorimetry are employed to study the molecular dynamics of oligomeric poly(propylene glycol) (PPG) melts of different molecular weights confined to nanoporous glasses (pore sizes 2.5, 5.0, 7.5 and 20 nm). Moreover, the results obtained for the polymers are compared with those for the corresponding monomer. The experimental results are discussed in the framework of the interplay of confinement and adsorption effects. For large pore sizes (> 5 nm) a speeding up of the molecular dynamics is observed (the confinement effect), whereas for small pore sizes (< 5 nm) a slowing down of the segmental fluctuations is found (the adsorption effect). In addition, a minimal length scale for the glass transition of 1.6 nm is estimated for PPG confined in nanoporous glasses. This supports the idea that the molecular motions responsible for the glassy dynamics must be describable by a characteristic length scale. Polarized Raman scattering investigations are carried out to investigate the conformations of the macromolecules inside the pores. These experiments show that the confined polymer chains are locally stretched. This effect increases with decreasing pore size. T2 - 3rd Workshop on Non-Equilibrium Phenomena in Supercooled Fluids, Glasses and Amorphous Materials CY - Pisa, Italy DA - 2003-09-22 PY - 2003 DO - https://doi.org/10.1088/0953-8984/15/11/334 SN - 0953-8984 SN - 1361-648X VL - 15 IS - 11 SP - S1139 EP - S1148 PB - IOP Publ. Ltd. CY - Bristol AN - OPUS4-2041 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polar Molecules in Nanoporous Confinements T2 - Workshop "Glasübergang" CY - Rostock, Germany DA - 2002-12-16 PY - 2002 AN - OPUS4-2042 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Goering, Harald A1 - Brzezinka, Klaus-Werner A1 - Schick, Ch. T1 - The molecular dynamics of polymers in random nanometre confined spaces investigated by relaxational and scattering techniques PY - 2003 SN - 0953-8984 SN - 1361-648X VL - 15 SP - S1139 EP - S1148 PB - IOP Publ. Ltd. CY - Bristol AN - OPUS4-2463 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frunza, L. A1 - Kosslick, H. A1 - Bentrup, U. A1 - Pitsch, I. A1 - Fricke, R. A1 - Frunza, S. A1 - Schönhals, Andreas T1 - Surface layer in composites containing 4-n-octyl-4'-cyanobiphenyl. FTIR spectroscopic characterization N2 - Composites containing 4-n-octyl-4?-cyanobiphenyl (8CB) either confined to nanopores of molecular sieves with very large pores or coating silica nanoparticles of aerosil type at high silica-to-8CB ratios are investigated by IR spectroscopy. Band shape analysis was performed in wavenumber regions in which the peaks due to CN stretching, CH stretching and CH out-of-plane vibrations appear. Some of molecules confined to molecular sieves show spectroscopic features characteristic to a bulk-like 8CB matter located in the centre of the pores or in the inter-grain space. Other features of the IR spectra are due to 8CB molecules located in the surface layer, mostly forming hydrogen bonds between their CN groups and surface OH groups. Another part of the 8CB molecules in the surface layer may also interact by ? electrons of the aromatic rings. Hydrogen bonding is less hindered for the molecules of the surface layers onto aerosil particles than inside pores of the molecular sieves. Comparison is also made with the case of composites based on molecular sieves with small pores. KW - Surface layer KW - Cyanobiphenyls KW - Infrared spectroscopy KW - Band shape analysis PY - 2003 DO - https://doi.org/10.1016/S0022-2860(03)00110-8 SN - 0022-2860 SN - 1872-8014 SN - 0377-046X VL - 651-653 SP - 341 EP - 347 PB - Elsevier CY - Amsterdam AN - OPUS4-2795 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frunza, S. A1 - Kosslick, H. A1 - Schönhals, Andreas A1 - Frunza, L. A1 - Enache, I. A1 - Beica, T. T1 - Study of the surface layer of aerosil-8CB composites by TG/DTA/DSC measurements N2 - Thermal analysis measurements were applied to study the behavior of composite systems containing a nematic liquid crystal (LC), 4-n-octyl-4?-cyanobiphenyl (8CB) and aerosil particles. The silica density ?s (g of silica per 1 cm3 of LC) was varied from 0.20 to 12 g/cm3 in order to approach the monomolecular structure of the surface layer. Thus, thermogravimetric (TG) measurements were performed to get information on the LC content of the samples. Moreover, they allowed an unusual application, to characterize the interaction of 8CB molecules with aerosil surface because the corresponding curves show multistep processes the temperatures of which depend on the silica density. Differential thermal analysis (DTA) also indicates several processes. Some of them, mostly due to desorption, are endothermal. Other processes are exothermal, and these are assigned to chemical transformations. The sample with silica density of 12 g/cm3 has no endothermal desorption peak at low temperatures, and has the highest shift for the DTA peaks. It was supposed that its surface layer has a monomolecular structure. For representative samples, TG–DTA studies were supported by FTIR investigations. Thus conventional TG–DTA techniques have provided new tools to characterize the nanocomposites. Differential scanning calorimetry gives the behavior of the phase transitions. Samples with low silica density exhibit a depression of the phase transition temperatures characteristic for the bulk 8CB while those with high silica densities do not show any phase transitions. PY - 2003 DO - https://doi.org/10.1016/S0022-3093(03)00319-3 SN - 0022-3093 VL - 325 IS - 1-3 SP - 103 EP - 112 PB - North-Holland Publ. Co. CY - Amsterdam AN - OPUS4-2796 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Floudas, G. A1 - Mierzwa, M. T1 - Temperature and pressure dependence of the dynamics in a poly(methyl acrylate) side-chain liquid-crystalline polymer N2 - The molecular dynamics of a side-chain polymer liquid crystal with a poly(methyl acrylate) backbone and a (p-alkoxy-phenyl)-benzoate mesogenic group have been studied in the unaligned state as a function of temperature and pressure using dielectric spectroscopy. Polarizing optical microscopy, differential scanning calorimetry, and pressure-volume-temperature (PVT) measurements revealed three transition temperatures separating four phases (glass, smectic, nematic, and isotropic). Different dynamic processes have been identified reflecting librational modes (? process), local relaxation of the mesogenic group (? process), the segmental mode (? process) associated with the dynamic glass transition, and a slower process (? process) reflecting the side-chain dynamics within the liquid crystal order. Pressure exerts a stronger influence on the ? as compared to the ? process. Starting from the nematic phase, pressure was found to induce the nematic-to-smectic transformation. The associated dynamic changes were in excellent agreement with the PVT results implying that the dynamics are directly coupled to the thermodynamic state. Pressure was found to enhance the stability of the smectic order within the P-T phase diagram. PY - 2003 DO - https://doi.org/10.1103/PhysRevE.67.031705 SN - 1539-3755 SN - 1063-651X VL - 67 IS - 3 SP - 031705-1-031705-8 PB - American Institute of Physics CY - Melville, NY AN - OPUS4-2800 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Frunza, Ligia A1 - Kosslick, H. A1 - Frunza, Stefan A1 - Fricke, R. T1 - On the mobility of sodium ions and of confined liquid crystals in faujasite T2 - Frühjahrstagung des Arbeitskreises Festkörperphysik bei der DPG CY - Regensburg, Germany DA - 2002-03-11 PY - 2002 SN - 0420-0195 SN - 0372-5448 SN - 0343-9216 IS - CPP 15.12 SP - 438 CY - Bad Honnef AN - OPUS4-2262 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Frunza, Ligia A1 - Frunza, Stefan A1 - Bentrup, U. A1 - Fricke, R. A1 - Pitsch, I. A1 - Kosslick, H. T1 - Confinement of nematic liquid crystals in SBA mesoporous materials N2 - This work presents some results obtained by confining octylcyanobiphenyl (8CB) to the pores of two SBA-15 type host materials: a silica SBA-15 (pores of 10.2 nm) and an aluminum containing AlSBA-15 (pores of 7.5 nm). The LC molecules were loaded inside the pores from a solution in acetone, in a percentage higher than 70% from the maximum possible loading. It was observed that the 8CB molecules confined to molecular sieves may preserve the phase transitions characteristic for the bulk LC provided that the confining pores are sufficiently large, as offered by SBA materials. However, present guest-host interactions play an important role in these phase transitions. Such a behavior is at variance with the 8CB confined to Controlled Porous Glass with the same pore dimensions, for which the bulk-like phase transitions can be always observed. T2 - 2nd International FEZA conference CY - Taormina, Italy DA - 2002-09-01 PY - 2002 DO - https://doi.org/10.1016/S0167-2991(02)80296-8 SN - 0167-2991 VL - 142 IS - 2 SP - 1323 EP - 1329 PB - Elsevier CY - Amsterdam AN - OPUS4-2263 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Frunza, Ligia A1 - Kosslick, H. A1 - Pitsch, I. A1 - Frunza, Stefan T1 - Molecular dynamics of 4n-octylcyanobiphenyl confined to nanoporous molecular sieves of SBA-type T2 - International Conference of Dielectric Spectroscopy CY - Leipzig, Germany DA - 2002-09-01 PY - 2002 SP - 1(?) AN - OPUS4-2264 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Frunza, Ligia A1 - Frunza, Stefan A1 - Kosslick, H. T1 - Unusual relaxation behavior of water inside the sodalite cages of faujasite-type molecular sieves T2 - International Conference of Dielectric Spectroscopy CY - Leipzig, Germany DA - 2002-09-01 PY - 2002 SP - 1(?) AN - OPUS4-2265 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Frunza, Stefan A1 - Frunza, Ligia T1 - Dinamica compozitelor aerosil - 8CB prin spectroscopie dielectrica; On the dynamics of aerosil - 8CB composites by dielectric spectroscopy T2 - Romanian Annual Conference 2002 CY - Târgu Mure¸s, Romania DA - 2002-09-01 PY - 2002 SP - 1(?) AN - OPUS4-2266 LA - ron AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Frunza, Stefan A1 - Kosslick, H. A1 - Frunza, Ligia A1 - Enache, I. A1 - Beica, T. T1 - Studiul stratului de suprafata pe compozite aerosil - 8CB prin analiza termica / Study of surface layer in 8CB-aerosil composites by TG/DTA/TG measurements T2 - Annual Session of Romanian Research Program CERES CY - Bucharest, Romania DA - 2002-11-28 PY - 2002 AN - OPUS4-2267 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Frunza, Ligia A1 - Kosslick, H. A1 - Pitsch, I. A1 - Fricke, R. A1 - Bentrup, U. A1 - Frunza, Stefan T1 - Nanoporous materials as hosts for liquid crystals T2 - DFG-Workshop on Key Program "Nanoporous Crystals" CY - Berlin, Germany DA - 2002-10-21 PY - 2002 SP - 1(?) AN - OPUS4-2268 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Frunza, S. A1 - Frunza, L. A1 - Goering, Harald T1 - On the dynamics of the surface layer in octylcynobiphenyl-aerosil nanocomposites T2 - Frühjahrstagung des Arbeitskreises Festkörperphysik bei der DPG CY - Regensburg, Germany DA - 2002-03-11 PY - 2002 SN - 0420-0195 SN - 0372-5448 SN - 0343-9216 IS - CPP 15.11 SP - 438 CY - Bad Honnef AN - OPUS4-2269 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Frunza, Ligia A1 - Kosslick, H. A1 - Bentrup, U. A1 - Pitsch, I. A1 - Fricke, R. A1 - Frunza, Stefan ED - Barnes, A. J. T1 - First spectroscopic characterization of the surface layer in composites containing liquid crystals confined to nanopores T2 - 26th European Congress on Molecular Spectroscopy (EUCMOS) CY - Villeneuve-d'Ascq, France DA - 2002-09-01 KW - Liquid crystals KW - Confinement KW - Surface layer KW - Infrared spectroscopy KW - Band shape analysis PY - 2002 SN - 0022-2860 VL - 651-653 SP - 1(?) EP - 14(?) PB - Elsevier CY - Amsterdam AN - OPUS4-2270 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Goering, Harald A1 - Schick, C. A1 - Frick, B. A1 - Zorn, R. T1 - Glassy dynamics of polymers confined to nanoporous glasses revealed by relaxational and scattering experiments N2 - The glassy dynamics of poly(propylene glycol) (PPG) and poly(dimethyl siloxane) (PDMS) confined to a nanoporous host system revealed by dielectric spectroscopy, temperature-modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature-modulated DSC agree quantitatively indicating that both experiments sense the glass transition. For PPG the segmental dynamics is determined by a counterbalance of adsorption and confinement effect. The former results form an interaction of the confined macromolecules with the internal surfaces. A confinement effect originates from an inherent length scale on which the underlying molecular motions take place. The increment of the specific-heat capacity at the glass transition vanishes at a finite length scale of 1.8 nm. Both results support the conception that a characteristic length scale is relevant for glassy dynamics. For PDMS only a confinement effect is observed which is much stronger than that for PPG. Down to a pore size of 7.5 nm, the temperature dependence of the relaxation times follows the Vogel-Fulcher-Tammann dependence. At a pore size of 5 nm this changes to an Arrhenius-like behaviour with a low activation energy. At the same pore size vanishes for PDMS. Quasielastic neutron scattering experiments reveal that also the diffusive character of the relevant molecular motions --found to be characteristic above the glass transition-- seems to disappear at this length scale. These results gives further strong support that the glass transition has to be characterised by an inherent length scale of the relevant molecular motions. KW - Glass transitions KW - Dielectric loss and relaxation KW - Macromolecular and polymer solutions KW - Polymer melts KW - Swelling PY - 2003 DO - https://doi.org/10.1140/epje/i2003-10036-4 SN - 1292-8941 SN - 1292-895X VL - 12 IS - 1 SP - 173 EP - 178 PB - EDP Sciences CY - Orsay AN - OPUS4-2866 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Turky, Gamal A1 - Schönhals, Andreas T1 - Influence of azobenzene concentration on the dielectric behavior of amorphous comb-like copolymers with photochromic side groups N2 - Dielectric spectroscopy in the frequency range from 10-2 to 106 Hz and in the temperature range from 190 to 440 K is employed to study the effect of azobenzene concentration on the dielectric relaxation processes of an amorphous comb-like copolymethacrylate. Four concentrations (x=29, 45.5, 54, and 74.5 mol%) of photochromic group 4-amino-azobenzene were investigated, where as comonomer a methacrylate unit having a derivative of benzanilide in the side group is used. Two prominent processes, the ?-relaxation at low temperatures which is related to rotational fluctuations of the mesogenic unit around its long axes and the dynamic glass transition (?-relaxation, segmental dynamics) at higher temperatures are observed for all azobenzene concentrations. In addition in between the ?- and the ?-relaxation a ??-process is observed for the polymers with the two lowest azobenzene concentrations, which seems to be related to the azobenzene unit. The dependence of the dielectric strength and the relaxation rate of the relaxation processes on the azobenzene concentration is discussed and interpreted in a simple phenomenological model, where also data obtained by semi empirical quantum chemical calculations are used. KW - Azobenzene KW - comb-like copolymer KW - Dielectric relaxation KW - Mesogenic unit PY - 2004 DO - https://doi.org/10.1016/j.polymer.2003.10.063 SN - 0032-3861 SN - 1873-2291 VL - 45 IS - 1 SP - 255 EP - 262 PB - Springer CY - Berlin AN - OPUS4-2867 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - The behavior of polymers confined to nanoporous glasses investigated by dielectric, thermal and neutron spectroscopy T2 - Vortrag an der Universität Toulouse "Paul Sabatier" CY - Toulouse, France DA - 2004-07-21 PY - 2004 AN - OPUS4-3900 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Dynamics of surface layer in cyanobiphenyl-aerosil nanocompositeswith a high silica density T2 - 3th International Conference on Broadband Dielectric Spectroscopy and its Applications CY - Delft, Netherlands DA - 2004-08-23 PY - 2004 AN - OPUS4-3902 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers in Nanoconfinements - What can we learn from relaxation and scattering experiments? T2 - 3th International Conference on Broadband Dielectric Spectroscopy and its Applications CY - Delft, Netherlands DA - 2004-08-23 PY - 2004 AN - OPUS4-3904 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers in Random Nanoporous Glasses: Molecular dynamics and Structure T2 - Fall Meeting Material Research Society of America CY - Boston, MA, USA DA - 2003-12-01 PY - 2003 AN - OPUS4-4061 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular Dynamics and Structure of Polymers in Confining Space Revealed by Relaxation and Scattering Techniques T2 - International Workshop on Dynamics in Confinement CY - Grenoble, France DA - 2003-01-23 PY - 2003 AN - OPUS4-4108 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Broadband Dielectric Spetroskopy and its Application to Dynamic Glass Transition: From the Bulk to the Confined State T2 - International Discussion Seminar on Inelastic x-Ray Scattering (eingeladener Vortrag) CY - Grenoble, France DA - 2003-02-10 PY - 2003 AN - OPUS4-4109 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Broadband Dielectric Spetroskopy and its Application to Dynamic Glass Transition T2 - Frühjahrsschule "Festkörperphysik" der Universität Karlsruhe (eingeladene Vortrag) CY - Karlsruhe, Germany DA - 2003-02-17 PY - 2003 AN - OPUS4-4110 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polar Molecules in Nanoconfinements T2 - Vortrag Universität Lyon CY - Lyon, France DA - 2003-03-31 PY - 2003 AN - OPUS4-4111 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymere in Nano-Confinements: Vergleich von Relaxationsexperimenten und (Neutronen) streuung T2 - Kolloquium der Abteilung VI CY - Berlin, Germany DA - 2003-06-05 PY - 2003 AN - OPUS4-4113 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Inverse Nanocomposites: Structure and Dynamics of Polymers Confined to Nanopores T2 - 7th International Symposium Polymers for Advanced Technologies CY - Fort Lauderdale, FL, USA DA - 2003-09-21 PY - 2003 AN - OPUS4-4191 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers confined to nanoporous glasses: What can we leam from relaxation and scattering experiments? T2 - Softmatter Seminar des Forschungszentrums Jülich CY - Jülich, Germany DA - 2003-11-13 PY - 2003 AN - OPUS4-4192 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers in Random Nanoporous glasses: Molecular Dynamics and Structure T2 - Fall meeting Material Researsh Society of America CY - Boston, MA, USA DA - 2003-12-01 PY - 2003 AN - OPUS4-4193 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymere in nanoporösen Gläsern: Was können wir von Relaxations- und Streuexperimenten lernen? T2 - Workshop Glasübergang CY - Berlin, Germany DA - 2003-12-14 PY - 2003 AN - OPUS4-4196 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Rotational fluctuations of water inside nanopores/nanocavities of molecular sieves T2 - Workshop Confit 2006 CY - Grenoble, France DA - 2006-03-23 PY - 2006 AN - OPUS4-12015 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers confined to nanoporous glasses investigated by quasielastic and inelastic neutron scattering T2 - Workshop Confit 2006 CY - Grenoble, France DA - 2006-03-23 PY - 2006 AN - OPUS4-12000 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular fluctuations of 4-n-octyl-4'cyanobiphenyl confined to nanoporous SBA-type molecular sieves with different filling degrees T2 - Workshop Confit 2006 CY - Grenoble, France DA - 2006-03-23 PY - 2006 AN - OPUS4-12005 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Neutron spectroscopy on polymers confined to nanoporous glasses T2 - Frühjahrstagung der Deutschen Physikalischen Gesellschaft CY - Dresden, Germany DA - 2006-03-21 PY - 2006 AN - OPUS4-12032 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frunza, Ligia A1 - Kosslick, H. A1 - Frunza, Stefan A1 - Schönhals, Andreas T1 - Molecular dynamics of 4-n-octyl-4'-cyanobiphenyl in partially filled nanoporous SBA-type molecular sieves N2 - The molecular dynamics of 4-n-octyl-4'-cyanobiphenyl (8CB) confined to the nanopores of new SBA-type molecular sieves was investigated in a wide temperature range using broadband dielectric spectroscopy (10-2–109 Hz). One molecular sieve has a hexagonal structure of the pores while the other is a cellular nanoporous material. To explore the extent of surface interaction effects a high and a low filling degree were considered. For the molecular sieves with a high filling degree two relaxation regions were observed: a bulk-like relaxation process related to molecules, which behave as mesophase, located in the centre of the pores. The second relaxation process has a much lower relaxation rate than the former and is assigned to molecules located in a surface layer. The temperature dependence of its relaxation rates follows the Vogel–Fulcher–Tammann law, characteristic for glassy dynamics. For samples with a low filling degree only one relaxation process due to the surface layer was observed. Moreover, especially at the temperatures lower than the melting point of bulk 8CB, its relaxation rate is situated between the characteristic frequencies of the two relaxation processes observed for the pores with a high filling degree. This behaviour gives a measure of the extension of the influence of the wall on the neighbouring 8CB molecules. In addition, the differences revealed by the molecule dynamics inside the two types of nanoporous materials are related to both surface interactions and geometrical constraints. KW - Confined liquid crystals KW - Molecular sieves KW - Dielectric measurements KW - Relaxation processes KW - Glassy dynamics PY - 2006 DO - https://doi.org/10.1016/j.micromeso.2005.10.025 SN - 1387-1811 SN - 1873-3093 VL - 90 IS - 1-3 SP - 259 EP - 270 PB - Elsevier CY - Amsterdam AN - OPUS4-12118 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Goering, Harald A1 - Schick, C. T1 - Poly(methyl phenyl siloxane) in Random Nanoporous Glasses - Comparison of coated and uncoated confining surfaces T2 - Poly(methyl phenyl siloxane) in Random Nanoporous Glasses: Comparison of coated and uncoated confining surfaces CY - Boston, MA, USA DA - 2006-11-28 PY - 2006 VL - 899E SP - 0899-N09-05.1-0899-N09-05.6 CY - Boston AN - OPUS4-12214 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Structure property relationships of different polymer based nanocomposites as investigated by dieletric spectroscopy and gas transport measurements T2 - 2nd International Symposium on Nanostructured and Functional Polymer-based Materials and Nanocomposites (NANOFUN-POLY) CY - Lyon, France DA - 2006-05-29 PY - 2006 AN - OPUS4-12393 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymer based nanocomposites as investigated by dielectric spectroscopy, gas transport measurements and related techniques T2 - NoE Nanofun Polymer, 6. FP der EU CY - Poznan, Poland DA - 2006-09-01 PY - 2006 AN - OPUS4-12625 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers confined to Nanoporous Glasses T2 - Vortrag am National Research Center, Kairo CY - Cairo, Egypt DA - 2005-10-16 PY - 2005 AN - OPUS4-11669 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers in Random Nanoporous Glasses Investigated by Dielectric, Thermal and Neutron Spectroscopy T2 - Herbst Meeting der Amerikanischen Gesellschaft für Materialforschung, 01.12. CY - Boston, MA, USA DA - 2005-11-27 PY - 2005 AN - OPUS4-11708 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecules in nanometre confinement investigated by dieletric spectroscopy and related techniques T2 - 4. Conference of the International Dieletric Society CY - Poznan, Poland DA - 2006-09-03 PY - 2006 AN - OPUS4-13042 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schick, C. A1 - Sukhorukov, D. A1 - Schönhals, Andreas T1 - Comparison of the Molecular Dynamics of a Liquid Crystalline Side Group Polymer Revealed from Temperature Modulated DSC and Dielectric Experiments in the Glass Transition Region N2 - Temperature modulated DSC (TMDSC) in the frequency range from 10-3 Hz to 3.4 10-2 Hz and dielectric spectroscopy in the frequency range from 10-2 Hz to 106 Hz is employed to analyze the temperature dependence of the relaxation rates of the - and of the -relaxation of a liquid crystalline polymethacrylate having a derivative of (p-alkoxy-phenyl)-benzoate as mesogenic unit in the side group. Especially the molecular assignment of the -relaxation was discussed controversial in the literature up to now. By applying a temperature derivative method it was found that the temperature dependencies of the relaxation rates of the dielectric -relaxation and of the dynamic glass transition measured by TMDSC can be described by Vogel/Fulcher/Tammann laws with the same Vogel temperature. Therefore it is argued that the dielectric -relaxation of liquid crystalline polymers is rather due to the dynamic glass transition related to the segmental dynamics of the backbone than to the transverse dipole component of the mesogenic unit. PY - 2001 DO - https://doi.org/10.1002/1521-3935(20010501)202:8<1398::AID-MACP1398>3.0.CO;2-C SN - 1022-1352 SN - 1521-3935 VL - 202 IS - 8 SP - 1398 EP - 1404 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-13693 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers confined to nanoporous glasses investigated by quasielastic and inelastic neutron scattering T2 - Soft Matter User Meeting CY - Grenoble, France DA - 2006-11-22 PY - 2006 AN - OPUS4-13881 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymers in nanoconfinements investigated by various spectroscopic methods T2 - Department of Physics and Astronomy, Universität Leuven CY - Leuven, Belgium DA - 2006-11-30 PY - 2006 AN - OPUS4-14203 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular Dynamics of polar molecules in nanometre confinement T2 - Vortrag an der Universität Lissabon, Fakultät für Chemie CY - Lisbon, Portugal DA - 2007-01-17 PY - 2007 AN - OPUS4-14503 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Neutron Spectroscopy on nano-confined polymers in comparison with dielectric and thermal results T2 - Jahrestagung der Deutschen Physikalischen Gesellschaft, AK Chemische Physik/Polymerphysik CY - Regensburg, Germany DA - 2007-03-26 PY - 2007 AN - OPUS4-14566 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Goering, Harald A1 - Schick, C. A1 - Frick, B. A1 - Mayorova, M. T1 - Segmental dynamics of poly(methyl phenyl siloxane) confined to nanoporous glasses N2 - The effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). Nanoporous glasses with pore sizes of 2.5–20 nm have been used. DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. For high temperatures the temperature dependence of the relaxation rates for confined PMPS crosses that of the bulk state. Besides finite states effects also the thermodynamic state of nano-confined PMPS is different from that of the bulk. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel/Fulcher/Tammann like to an Arrhenius behavior where the activation energy depends on pore size. This is in agreement with the results obtained by NS. The increment of the specific heat capacity at the glass transition depends strongly on pore size and vanishes at a finite length scale between 3 and 5 nm which can be regarded as minimal length scale for glass transition to appear in PMPS. PY - 2007 SN - 1951-6355 SN - 1951-6401 VL - 141 IS - 1 SP - 255 EP - 259 PB - Springer CY - Berlin AN - OPUS4-14602 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Dielectric and neutron spectroscopy on nano-confined liquid crystals T2 - Jahrestagung der Deutschen Physikalischen Gesellschaft, AK Chemische Physik/Polymerphysik CY - Regensburg, Germany DA - 2007-03-26 PY - 2007 AN - OPUS4-14590 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular dynamics in glass-forming liquid crystal as studied by broadband dielectric and thermal spectroscopy T2 - Jahrestagung der Deutschen Physikalischen Gesellschaft, AK Chemische Physik/Polymerphysik CY - Regensburg, Germany DA - 2007-03-26 PY - 2007 AN - OPUS4-14592 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hao, Ning A1 - Böhning, Martin A1 - Goering, Harald A1 - Schönhals, Andreas T1 - Nanocomposites of Polyhedral Oligomeric Phenethylsilsesquioxanes and Poly(bisphenol A carbonate) as Investigated by Dielectric Spectroscopy N2 - Nanocomposites were prepared by solution blending of polyhedral oligomeric silsesquioxane with phenethyl substituents (PhenethylPOSS) into poly(bisphenol A carbonate) (PBAC). The nanocomposites were investigated by dielectric spectroscopy, differential scanning calorimetry (DSC) and density measurements. PhenethylPOSS shows one relaxation process, the α-relaxation, confirmed by DSC investigations. PBAC shows a β-relaxation at lower and an α-relaxation at higher temperatures. With increasing PhenethylPOSS content the α-relaxation of the composites shifts to lower temperatures. Thus, incorporation of PhenethylPOSS leads to a plasticization of PBAC due to a decrease of the packing density which is rationalized by density measurements. For higher concentrations of PhenethylPOSS (>10 wt %) the α-relaxation of the polycarbonate matrix splits into two peaks. Moreover, close to the α-relaxation of PhenethylPOSS a third process is observed. These results indicate a phase separation into a PBAC matrix with a few percents of molecularly solved POSS and POSS-rich domains. These POSS-rich domains are surrounded by an interfacial layer of PBAC having a higher concentration of POSS than the matrix. A phase diagram is deduced providing a miscibility criterion. For the phase separated nanocomposites an interfacial polarization phenomena is observed. Using a simplified model the time constant of this process is correlated with the size of the PhenethylPOSS-rich domains and theire increasing size with the increase of the concentration of POSS. KW - Polyhedral oligomeric silsesquioxane (POSS) KW - Polymer-based nanocomposites KW - Broadband dielectric spectroscopy KW - Interfacial polarisation PY - 2007 SN - 0024-9297 SN - 1520-5835 VL - 40 IS - 8 SP - 2955 EP - 2964 PB - American Chemical Society CY - Washington, DC AN - OPUS4-14768 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brás, A. R. A1 - Dionísio, M. A1 - Huth, H. A1 - Schick, C. A1 - Schönhals, Andreas T1 - Origin of glassy dynamics in a liquid crystal studied by broadband dielectric and specific heat spectroscopy N2 - A combination of broadband dielectric (10-2 Hz–109 Hz) and specific heat (10-3 Hz–2×103 Hz) spectroscopy is employed to study the molecular dynamics of the glass-forming nematic liquid crystal E7 in a wide temperature range. In the region of the nematic phase the dielectric spectra show two relaxation processes which are expected theoretically: The δ relaxation which corresponds to rotational fluctuations of the molecules around its short axis and the tumbling mode at higher frequencies than the former one. For both processes the temperature dependence of the relaxation rates follows the Vogel-Fulcher-Tammann formula which is characteristic for glassy dynamics. By applying a detailed data analysis, it is shown that close to the glass transition the tumbling mode has a much steeper temperature dependence than the δ process. The former has a Vogel temperature which is by 30 K higher than that of the δ relaxation. Specific heat spectroscopy gives one relaxation process in its temperature and frequency dependence which has to be assigned to the α relaxation (dynamic glass transition). The unique and detailed comparison of the temperature dependence of the dielectric and the thermal relaxation rates delivers unambiguously that the dielectric tumbling mode has to be related to the dynamic glass transition. PY - 2007 DO - https://doi.org/10.1103/PhysRevE.75.061708 SN - 1539-3755 SN - 1063-651X VL - 75 IS - 6 SP - 061708-1-061708-8 PB - American Institute of Physics CY - Melville, NY AN - OPUS4-15041 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Structure property relationships of polymeric nanocomposites based on polyhedral oligomeric silsesquioxanes T2 - Meeting American Chemical Society CY - Boston, MA, USA DA - 2007-07-19 PY - 2007 AN - OPUS4-15457 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hao, Ning A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Gas Transport Properties of Polymeric Nanocomposites Based on Polyhedral Oligomeric Silsesquioxanes PY - 2007 SN - 0743-0515 VL - 97 SP - 444 EP - 445 PB - Division of Polymeric Materials Science and Engineering, American Chemical Society CY - Washington, DC AN - OPUS4-15846 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Schick, C. A1 - Huth, H. A1 - Frick, B. A1 - Mayorova, M. A1 - Zorn, R. T1 - Molecular dynamics in glass-forming poly(phenyl methyl siloxane) as investigated by broadband thermal, dielectric and neutron spectroscopy KW - Neutron diffraction/scattering KW - Dielectric properties KW - Relaxation KW - Electric modulus KW - Glass transition PY - 2007 SN - 0022-3093 VL - 353 IS - 41-43 SP - 3853 EP - 3861 PB - North-Holland Publ. Co. CY - Amsterdam AN - OPUS4-15898 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular mobility poly(phenyl methyl siloxane) invesstigated by thermal, dielectric and neutron spectroscopy T2 - Meeting of the American Chemical Society, PMSE CY - Boston, MA, USA DA - 2007-08-19 PY - 2007 AN - OPUS4-15463 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frunza, L. A1 - Schönhals, Andreas A1 - Frunza, S. A1 - Parvulescu, V.I. A1 - Cojocaru, B. A1 - Carriazo, D. A1 - Martín, C. A1 - Rives, V. T1 - Rotational Fluctuations of Water Confined to Layered Oxide Materials - Nonmonotonous Temperature Dependence of Relaxation Times N2 - The rotational molecular dynamics of water confined to layered oxide materials with brucite structure was studied by dielectric spectroscopy in the frequency range from 10-2 to 107 Hz and in a broad temperature interval. The layered double hydroxide samples show one relaxation process, which was assigned to fluctuations of water molecules forming a layer, strongly adsorbed to the oxide surface. The temperature dependence of the relaxation rates has an unusual saddlelike shape characterized by a maximum. The model of Ryabov et al. (J. Phys. Chem. B 2001, 105, 1845) recently applied to describe the dynamics of water molecules in porous glasses is employed also for the layered materials. This model assumes two competing effects: rotational fluctuations of water molecules that take place simultaneously with defect formation, allowing the creation of free volume necessary for reorientation. The activation energy of rotational fluctuations, the energy of defect formation, a pre-exponential factor, and the defect concentration are obtained as main parameters from a fit of this model to the data. The values of these parameters were compared with those found for water confined to nanoporous molecular sieves, porous glasses, or bulk ice. Several correlations were discussed in detail, such as the lower the value of the energy of defect formation, the higher the number of defects. The pre-exponential factor increases with increasing activation energy, as an expression of the compensation law, and indicates the cooperative nature of the motional process. The involvement of the surface OH groups and of the oxygen atoms of the interlayer anions in the formation of hydrogen bonds was further discussed. For the birnessite sample, the relaxation processes are probably overlaid by a dominating conductivity contribution, which is analyzed in its frequency and temperature dependence. It is found that the conductivity of birnessite obeys the characteristics of semiconducting disordered materials. Especially the Barton/Nakajima/Namikawa relationship is fulfilled. Analyzing the temperature dependence of the direct current (dc) conductivity σ0 in detail gives some hint that σ0(T) has also an unusual saddlelike form. PY - 2007 DO - https://doi.org/10.1021/jp0717140 SN - 1089-5639 SN - 1520-5215 VL - 111 IS - 24 SP - 5166 EP - 5175 PB - Soc. CY - Washington, DC AN - OPUS4-15718 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Schick, C. A1 - Huth, H. A1 - Frick, B. A1 - Mayorova, M. A1 - Zorn, R. T1 - Molecular Mobility of Poly(phenyl methyl siloxane) Investigated by Thermal, Dielectric and Neutron Spectroscopy PY - 2007 SN - 0743-0515 VL - 97 SP - 948 EP - 949 PB - Division of Polymeric Materials Science and Engineering, American Chemical Society CY - Washington, DC AN - OPUS4-15736 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Schönhals, Andreas ED - Grellmann, W. ED - Seidler, S. T1 - Electrical and Dielectrical Properties KW - Polymer Testing PY - 2007 SN - 978-3-446-40900-2 IS - Kap. 6.3 SP - 335 EP - 374 PB - Carl Hanser Verlag CY - Munich AN - OPUS4-15763 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Dielectric properties of nanocomposites based on polyethylene and layered double hydroxide T2 - Frühjahrstagung der Deutschen Physikalischen Gesellschaft, Arbeitskreis Chemische Physik und Polymerphysik CY - Berlin, Germany DA - 2008-02-25 PY - 2008 AN - OPUS4-16700 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Dielectric and gas transport properties of polymeric nanocomposites based on polyhedral oligomeric silsesquioxanes T2 - Frühjahrstagung der Deutschen Physikalischen Gesellschaft, Arbeitskreis Chemische Physik, Polymerphysik CY - Berlin, Germany DA - 2008-02-25 PY - 2008 AN - OPUS4-16701 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Dynamics of n-alkyl-cyanobiphenyl and cyano-n-alkylbenzoate molecules in a surface layer adsorbed onto aerosil T2 - Frühjahrstagung der Deutschen Physikalischen Gesellschaft, Arbeitskreis Chemische Physik, Polymerphysik CY - Berlin, Germany DA - 2008-02-25 PY - 2008 AN - OPUS4-16698 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ramanujam, Maalolan A1 - Wachtendorf, Volker A1 - Mix, Renate A1 - Schönhals, Andreas A1 - Friedrich, Jörg Florian ED - Reichert, T. T1 - Influence of UV weathering and humidity on surface & bulk properties of LDPE N2 - The outdoor weathering of polymers is mainly due to UV radiation, water, Pollution, humidity, temperature etc. To understand the effects of weathering, simulated tests need to be undertaken in lab scale. Such tests must be quite efficient and similar to the effects of natural weathering. This paper mainly focuses on the effects of UV radiation along with humidity on LDPE. T2 - 5th European weathering symposium - Natural and artificial ageing of polymers CY - Lisbon, Portugal DA - 21.09.2011 KW - LDPE KW - UV weathering KW - Humidity PY - 2011 SN - 978-3-9813136-2-8 N1 - Serientitel: CEEES Publication – Series title: CEEES Publication IS - 15 SP - 211 EP - 218 PB - GUS (Gesellschaft für Umweltsimulation) CY - Pfinztal AN - OPUS4-24536 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Dielectric Spectroscopy - Basics, Effects and Examples - T2 - Graduiertenkolleg "Analyse und Simulation elektrischer Wechselwirkungen zwischen Implantaten und Biosystemen", Universität Rostock CY - Rostock, Germany DA - 2011-10-20 PY - 2011 AN - OPUS4-24638 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymer Based Nanocomposites - Interplay between Interfacial and Bulk Effects - T2 - Kolloquiumsvortrag am National Research Center Canada - Industrial Materials CY - Boucherville, Canada DA - 2011-09-30 PY - 2011 AN - OPUS4-24639 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular Dynamics in Nanometre Confinement T2 - Broadband Dielectric Spectroscopy and its Advanced Technological Applications CY - Perpignan, France DA - 2011-09-21 PY - 2011 AN - OPUS4-24640 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymer based nanocomposites as investigated by dielectric spectroscopy T2 - Kolloquiumsvortrag am Materials Physics Center, San Sebastian CY - San Sebastián, Spain DA - 2011-06-02 PY - 2011 AN - OPUS4-24641 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular relaxation processes in a MOF-5 structure - Signature of Phenylring fluctuations T2 - Frühjahrstagung der Deutschen Physikalsichen Gesellschaft, Dresden CY - Dresden, Germany DA - 2011-03-13 PY - 2011 AN - OPUS4-24642 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymer Based Nanocomposites - Interplay between Interfacial and Bulk Effects - T2 - Colloquium University Halle CY - Halle (Saale), Germany DA - 2012-02-07 PY - 2012 AN - OPUS4-25618 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Neutron Scattering on Discotic Liquid Chrystals in the Bulk and in the Nanoconfined State T2 - Frühjahrstagung der DPG CY - Berlin, Germany DA - 2012-03-26 PY - 2012 AN - OPUS4-25619 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Glass Transition of Ultrathin Films from Main Chain Polymers T2 - Symposium University Leuven CY - Leuven, Belgium DA - 2011-12-15 PY - 2011 AN - OPUS4-25620 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fahmy, A. A1 - Mix, Renate A1 - Schönhals, Andreas A1 - Friedrich, Jörg Florian T1 - Surface and bulk structure of thin spin coated and plasma-polymerized polystyrene films N2 - Polystyrene (PS) spin coated thin films were modified by O2 and Ar plasma as well as by UV irradiation treatments. The modified PS samples were compared with plasma polymerized and commercial polystyrene. The effects of plasma (O2 and Ar) and UV irradiation treatments on the surface and the bulk properties of the polymer layers were discussed. The surface properties were evaluated by X-ray Photoelectron Spectroscopy and Contact angle measurements and the bulk properties were investigated by FTIR and dielectric relaxation spectroscopy. As a result only one second treatment time was sufficient to modify the surface. However, this study was also dedicated to understand the effect of plasma and plasma irradiation on the deposited layers of plasma polymers. The dielectric measurements showed that the plasma deposited films were not thermally stable and underwent an undesired post-plasma chemical oxidation. KW - Surface and bulk characterization KW - Plasma polymerization KW - Polystyrene KW - Surface modification KW - Thermal stability KW - Plasma polymers PY - 2012 DO - https://doi.org/10.1007/s11090-012-9372-1 SN - 0272-4324 VL - 32 IS - 4 SP - 767 EP - 780 PB - Plenum Publ. Corp. CY - New York, NY, USA AN - OPUS4-26264 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Glass Transition of Ultra-Thin Polymeric Layers Investigated by a Comination of Complementary Methods T2 - Broadband Dielectric Spectroscopy and its Applications CY - Leipzig, Germany DA - 2012-09-03 PY - 2012 AN - OPUS4-26865 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Are the termal Tg and the segmental dynamics in polymer thin films fully interdependent T2 - Broadband Dielectric Spectroscopy and its Applications CY - Leipzig, Germany DA - 2012-09-03 PY - 2012 AN - OPUS4-26866 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Neutron Scattering ti Investigate the Molecular Dynamics of Discotic Liquid Crystals in the Bulk and in the Nanoconfined State T2 - Trends and Perspectives in Neutron Scattering for Soft Matter and Biophysics CY - Tutzing, Germany DA - 2012-10-08 PY - 2012 AN - OPUS4-26867 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Structure property relationship of nanocomposites based on Polylactide and Layered Double Hydroxide T2 - Broadband Dielectric Spectroscopy and its Applications CY - Leipzig, Germany DA - 2012-09-03 PY - 2012 AN - OPUS4-26880 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polymer Based Nanocomposites - Interplay between Interfacial and Bulk Effects T2 - Kolloquiumsvortrag, Fakultät Physik, Universität Hamburg CY - Hamburg, Germany DA - 2013-05-28 PY - 2013 AN - OPUS4-28896 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Confinement Effects in Discotic Liquid Crystals in the Bulk and Embedded in Nanochannels T2 - 7th International Discussion Meeting on Relaxations in Complex Systems CY - Barcelona, Spain DA - 2013-07-21 PY - 2013 AN - OPUS4-28890 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fahmy, A. A1 - Mix, Renate A1 - Schönhals, Andreas A1 - Friedrich, Jörg Florian T1 - Structure of plasma-deposited copolymer films prepared from acrylic acid and styrene: Part II variation of the comonomer ratio N2 - Copolymers of acrylic acid and styrene (AA/S) were prepared by pulsed plasma deposition technique. Their structure–property relationships were studied in dependence on the comonomer ratio. Both, the regularity of the structure and the composition of the thin copolymer films were investigated by bulk-sensitive (dielectric spectroscopy, FTIR, and differential scanning calorimetry) as well as surface-sensitive methods such as X-ray photoelectron spectroscopy (XPS). For an unambiguous identification of the functionality of the deposited films the COOH groups were estimated by derivatization with trifluoroethanol and subsequent XPS measurement as well as by the quantitative analysis of the FTIR data. As a result, the concentration of COOH groups on the surface and in the bulk is increasing with the fraction of AA in precursor mixture in a non-monotonous way but similar to the dependence obtained by conventional free radical polymerization. KW - Acrylic acid-styrene copolymer KW - Bulk properties KW - Dielectric properties KW - Plasma polymerization KW - Surface functionalization PY - 2013 DO - https://doi.org/10.1002/ppap.201200110 SN - 1612-8850 SN - 1612-8869 VL - 10 IS - 9 SP - 750 EP - 760 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-29096 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fahmy, A. A1 - Schönhals, Andreas A1 - Friedrich, Jörg Florian T1 - Reaction of water with (radicals in) plasma polymerized allyl alcohol (and formation of OH-rich polymer layers) N2 - The pulsed plasma polymerization of allyl alcohol was employed under the aspect of maximal retention of OH groups and the formation of a regular polymer structure. It should be noted that earlier investigations on plasma polymers deposited from allyl alcohol did not show extensive postplasma addition of oxygen and water vapor from ambient air during storage, measuring the elemental O/C ratio by means of X-ray photoelectron spectroscopy (XPS).The identification of OH groups in the plasma polymerized polymer using FTIR spectroscopy was such an indicator for fragmentation. The peak area of OH groups in the film which was stored was increased by about 20% compared to that measured ('in situ'). These phenomenons reflected that moisture and O2 in air played an important role in scavenging the free radicals. The addition of water and more specifically chemical bonding of OH of water in the deposited plasma polymer may serve as an indicator for monomer fragmentation, poly recombination, and the remaining radicals responsible for film formation. Moreover, the dielectric measurements show that the plasma deposited films are not thermally stable but undergo a postplasma chemical reaction during heating, where the reaction kinetics depends on pressure. PY - 2013 DO - https://doi.org/10.1021/jp406186x SN - 1520-6106 SN - 1520-5207 SN - 1089-5647 VL - 117 IS - 36 SP - 10603 EP - 10611 PB - Soc. CY - Washington, DC AN - OPUS4-29105 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(vinyl methyl ether) films N2 - Specific heat spectroscopy in the frequency range typically from 1 Hz to 1 kHz with a sensitivity of pJ/K was employed to study the glass transition behavior of ultrathin poly(vinyl methyl ether) (PVME) films with thicknesses ranging from 218 nm down to 12 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 main result no thickness dependence of the dynamic glass transition temperature was observed down to a film thickness of 12 nm within the experimental uncertainty of ±2 K. Further the width of the glass transition is independent of the film thickness which indicates that the extent of the cooperativity is essentially smaller than 12 nm. KW - Specific heat spectroscopy KW - Dynamic glass transition KW - Poly(vinyl methyl ether) PY - 2013 DO - https://doi.org/10.1016/j.polymer.2013.02.025 SN - 0032-3861 SN - 1873-2291 VL - 54 IS - 8 SP - 2067 EP - 2070 PB - Springer CY - Berlin AN - OPUS4-28011 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Füllbrandt, Marieke A1 - von Klitzing, R. A1 - Schönhals, Andreas T1 - The dielectric signature of poly(N-isopropylacrylamide) microgels at the volume phase transition: dependence on the crosslinking density N2 - Temperature sensitive poly(N-isopropylacrylamide) (pNIPAM) microgels are prepared and investigated using dielectric spectroscopy in a frequency range from 10-1 Hz to 106 Hz at temperatures from 15 °C to 50 °C. The microgels were synthesized with different crosslinker molar ratios resulting in microgels with structural differences. From the dielectric response of the pNIPAM microgels the swelling/deswelling behaviour is monitored by both the temperature (T) and the frequency (f) dependence of the conductivity spectra σ*(f, T). The volume phase transition (VPT) at the lower critical solution temperature (LCST) is deduced by a change in the T-dependence of the DC conductivity σ'DC. It can be explained by a decrease in the effective charge mobility and a reduction in the effective charge number contributing to σ'DC at T > LCST. Addressing the f-dependence of the real part of the conductivity σ', a pronounced frequency dependence at temperatures above the LCST can be observed whereas at temperatures below the LCST the conductivity spectra resemble that of the pure solvent (water) which is frequency independent. The f-dependence of σ' at T > LCST is assigned to the collapse of the microgel particles. At the interfaces of the collapsed particles charge carriers are blocked and/or entrapped giving rise to Maxwell–Wagner–Sillars (MWS) polarization effects. The dependence of the MWS effect on the crosslinker amount is studied in detail and conclusions concerning the internal structure of the microgels with respect to their crosslinking density are drawn. Moreover the dielectric data are related to dynamic light scattering data. A correlation between the MWS polarization effect and the swelling/deswelling ratio expressed by the hydrodynamic radius Rh at different temperatures is established for the first time. PY - 2013 DO - https://doi.org/10.1039/c3sm27762c SN - 1744-683X VL - 9 IS - 17 SP - 4464 EP - 4471 PB - RSC Publ. CY - Cambridge AN - OPUS4-28012 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Füllbrandt, Marieke A1 - von Klitzing, R. A1 - Schönhals, Andreas T1 - Probing the phase transition of aqueous solutions of linear low molecular weight poly(N-isopropylacrylamide) by dielectric spectroscopy N2 - Aqueous solutions of linear poly(N-isopropylacrylamide) (pNIPAM) with different polymer concentrations are investigated using dielectric spectroscopy in a frequency range of 10-1 Hz to 106 Hz at temperatures from 15 °C to 50 °C. The phase transition of pNIPAM is monitored by both the temperature (T) and the frequency (ƒ) dependence of the conductivity spectra σ*(ƒ, T). First, the T-dependence of the DC conductivity σ'DC is investigated and the phase transition ('coil-to-globule' transition) at the lower critical solution temperature (LCST) of pNIPAM is deduced by a change in the T-dependence of σ'DC. The observed hysteresis between heating and cooling runs is discussed in detail in dependence on both the polymer concentration and the rate. Second, for the first time a pronounced ƒ-dependence of the real part of conductivity σ' is observed at temperatures above the LCST whereas at temperatures below the LCST the conductivity spectra are more or less similar to that of water (frequency independent). This ƒ-dependence of σ' is assigned to the formation of a kind of soft particle ('globular structure') at the LCST which is more or less impermeable to water and ions therefore giving rise to Maxwell–Wagner–Sillars (MWS) polarization effects (blocking of charges at the soft particle). The dependence on the concentration is studied in detail. PY - 2012 DO - https://doi.org/10.1039/c2sm26826d SN - 1744-683X VL - 8 IS - 48 SP - 12116 EP - 12123 PB - RSC Publ. CY - Cambridge AN - OPUS4-27320 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Füllbrandt, Marieke A1 - Purohit, Purv A1 - Schönhals, Andreas T1 - Combined FTIR and dielectric investigation of poly(vinyl acetate) adsorbed on silica particles N2 - Samples with different amounts of poly(vinyl acetate) adsorbed on silica particles were prepared in order to study their interfacial interactions and dynamics. The interface of adsorbed polymers to a substrate plays an important role in many applications such as polymer nanocomposites, thin films, and coatings. Characterization of such interfaces is thus of high importance since they were found to differ from bulk properties. Thermogravimetric analysis (TGA) is applied to analyze the amounts of polymer adsorbed on silica particles. Broadband dielectric spectroscopy (BDS) is employed in a broad frequency (10–1–106 Hz) and temperature range (178–423 K) in order to probe the polymer/silica interface. Two relaxation processes can be identified for the composites: one corresponding to the bulklike polymer and a second one related to polymer chains close to the silica surface. For the latter the dynamic glass transition is shifted to higher temperature due to reduced mobility. This effect is investigated in dependence on the polymer content. Further investigations are done to obtain information about bound and free carbonyl fractions of poly(vinyl acetate) using Fourier transform infrared spectroscopy (FTIR) measurements. PY - 2013 DO - https://doi.org/10.1021/ma400461p SN - 0024-9297 SN - 1520-5835 VL - 46 IS - 11 SP - 4626 EP - 4632 PB - American Chemical Society CY - Washington, DC AN - OPUS4-28698 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yin, Huajie A1 - Cangialosi, D. A1 - Schönhals, Andreas T1 - Glass transition and segmental dynamics in thin supported polystyrene films: The role of molecular weight and annealing N2 - Broadband dielectric spectroscopy (BDS), specific heat spectroscopy (HCS) and capacitive scanning dilatometry (CSD) are used to study the glass transition and segmental dynamics in thin supported polystyrene (PS) films. Different molecular weights (Mw = 50 kg/mol, Mw = 260 kg/mol, Mw = 1408 kg/mol) and annealing protocols are employed in the study. The segmental dynamics is independent of the film thickness for each Mw in the temperature window of the dielectric measurement. The thermal glass transition temperature, Tg, measured by CSD depends on the film thickness and shows also a dependence on Mw. These observations are explained in terms of the formation of irreversibly adsorbed layer due to chain adsorption on the Al substrates during annealing. KW - Thin polystyrene films KW - Glass transition KW - Segmental dynamics PY - 2013 DO - https://doi.org/10.1016/j.tca.2013.05.034 SN - 0040-6031 SN - 1872-762X VL - 566 SP - 186 EP - 192 PB - Elsevier CY - Amsterdam AN - OPUS4-28736 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krause, Christina A1 - Schönhals, Andreas T1 - Phase transitions and molecular mobility of a discotic liquid crystal under nanoscale confinement N2 - The phase behavior and the molecular dynamics of a pyrene-based discotic liquid crystal when confined in nanoporous aluminum membranes with different pore sizes is studied by broadband dielectric spectroscopy and differential scanning calorimetry. In confinement the two phase transitions between plastic crystalline and hexagonal ordered phase at lower and from the latter to an isotropic state at higher temperatures are also observed, but two different phase structures close to the wall and in the pore center are evidenced by two peaks in the heat flow for the first time. While the former peak is independent of the pore size, the depression of the phase transition temperatures of the latter ones can be described by the Gibbs–Thomson equation. With decreasing pore size for both phase transitions the transition enthalpies decrease. A critical pore size for phase transformation of about 20 nm is estimated from the pore size dependence of the transition enthalpies. Like for the bulk, an a-relaxation is also observed in confinement. At the phase transition its relaxation rates show a discontinuity from which a dielectric phase transition temperature can be extracted. For temperatures above and below the phase transition the temperature of the relaxation rate can be approximated by an Arrhenius equation. The pore size dependence of the estimated apparent activation energies is ascribed to the interplay between pore size and interaction effects. The cooperative nature of the underlying molecular dynamics is indicated by the occurrence of the well-known compensation law. PY - 2013 DO - https://doi.org/10.1021/jp406010d SN - 1932-7447 SN - 1089-5639 VL - 117 IS - 38 SP - 19712 EP - 19720 PB - Soc. CY - Washington, DC AN - OPUS4-29336 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Confinement effects in discotic liquid crystals in the bulk and embedded in nanochannels T2 - Workshop on Stability of Amorphos Pharmaceuticals CY - Castiglioncello, Italy DA - 2013-10-17 PY - 2013 AN - OPUS4-29331 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Behavior of Ultra-Thin Polymeric Films as Investigated by Dielectric and Thermal Spectroscopy T2 - Seminarvortrag an der Karlsuniversität Prag CY - Prague, Czech Republic DA - 2013-11-05 PY - 2013 AN - OPUS4-29505 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas T1 - Evidence for a universal crossover behaviour of the dynamic glass transition N2 - By measuring the complex dielectric function over 15 decades of frequency, the temperature dependence of the mean relaxation time and of the dielectric strength is evaluated for six low-molecular-weight glass-forming liquids and one polymeric melt. For the first time it could be shown that a universal correlation exists between both these quantities with a sharp defined crossover behaviour in the frequency range between 107 Hz and 108 Hz. So two dynamical different regions of the a-relaxation can be distinguished non-ambiguously. PY - 2001 DO - https://doi.org/10.1209/epl/i2001-00115-8 SN - 0302-072X SN - 0295-5075 SN - 1286-4854 VL - 56 IS - 6 SP - 815 EP - 821 PB - EDP Science CY - Les-Ulis AN - OPUS4-1567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Goering, Harald A1 - Schick, Ch. T1 - Segmental and chain dynamics of polymers: from the bulk to the confined state N2 - Dielectric spectroscopy and temperature modulated DSC are employed to study the molecular dynamics of oligomeric poly(propylene glycol) (PPG) melts of different molecular weights confined to nanoporous glasses (pore sizes 2.5, 5.0, 7.5 and 20 nm). Moreover the results obtained for the polymer are compared with the corresponding monomer. For large pore sizes an acceleration of the segmental dynamics compared to the bulk state is observed which is already known for low molecular-weight glass forming liquids. For smaller pore sizes the molecular dynamics is slower than in the bulk. The observed behavior is nearly independent of the molar mass of the polymer and of the treatment of internal glass surfaces. The experimental results are discussed in the frame of an interplay of confinement and adsorption effects. Moreover a length scale of about 1.6 nm is estimated as a minimal length scale for the cooperativity for the glass transition. In addition to the ?-relaxation the whole chain dynamics (normal mode relaxation) can be measured by dielectric spectroscopy because PPG has a dipole component parallel to the chain. For virgin internal surfaces the relaxation rate of the normal mode relaxation is shifted dramatically to lower relaxation rates. That can be explained by adsorption effects. For treated surfaces this effect is strongly reduced and it is concluded that also in this case the chain dynamics are influenced by geometric (confinement) effects. PY - 2002 DO - https://doi.org/10.1016/S0022-3093(02)01092-X SN - 0022-3093 VL - 305 SP - 140 EP - 149 PB - North-Holland Publ. Co. CY - Amsterdam AN - OPUS4-1568 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Kosslick, Hans-Jürgen A1 - Frunza, S. A1 - Fricke, R. A1 - Frunza, L. T1 - On the mobility of sodium ions and of confined liquid crystals in molecular sieves of faujasite type N2 - Broadband dielectric spectroscopy (10-2–109 Hz) was employed to study in a rather large temperature interval the molecular dynamics of the composite systems containing a nematic liquid crystal (LC), 4-n-pentyl-4?-cyanobiphenyl, confined to NaY, a zeolite with faujasite structure. Thermal analysis was also performed in order to get information concerning the loading of the zeolite and the possible phase transitions. No phase transitions and no relaxation processes of the LC molecules inside the pores were observed. But remarkably, in the presence of these molecules the dielectric behavior of the faujasite host changes due to modifications appeared in the mobility of Na+ ions. PY - 2002 DO - https://doi.org/10.1016/S0022-3093(02)01472-2 SN - 0022-3093 VL - 307-310 SP - 503 EP - 509 PB - North-Holland Publ. Co. CY - Amsterdam AN - OPUS4-1569 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Frunza, L. A1 - Kosslick, H. A1 - Frunza, S. T1 - Unusual relaxation behavior of water inside the sodalite cages of faujasite-type molecular sieves N2 - Broad-band dielectric spectroscopy (10-2 to 109 Hz) is applied to investigate the molecular dynamics of NaY, a zeolite of faujasite structure. A dc conductivity contribution and three relaxation processes were revealed in the dielectric spectra. The relaxation process in the high-frequency range ascribed to orientational fluctuations of water molecules inside the sodalite cages is studied in detail. As a main result it is found that its mean relaxation time has an unusual saddle-like temperature dependence, which obeys neither an Arrhenius nor a Vogel-Fulcher-Tammann law. A quantitative description was given on the basis of a model recently developed by Feldman et al. (J. Phys. Chem. B 2001, 105, 1845) to analyze the dynamics of water confined in nanoporous glasses. Reasonable values for the activation energies of orientational fluctuations and of defect formation as well as for the defect concentration were obtained. PY - 2002 DO - https://doi.org/10.1021/jp021281v SN - 1520-6106 SN - 1520-5207 SN - 1089-5647 VL - 106 IS - 36 SP - 9191 EP - 9194 PB - Soc. CY - Washington, DC AN - OPUS4-1571 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Goering, Harald A1 - Brzezinka, Klaus-Werner A1 - Schick, C. T1 - Behaviour of polymers confined to nanoporous glasses studied by dielectric, thermal and vibrational spectroscopy - Cut - off length scale for glass transition? T2 - Frühjahrstagung des Arbeitskreises Festkörperphysik bei der DPG CY - Regensburg, Germany DA - 2002-03-11 PY - 2002 SN - 0420-0195 SN - 0372-5448 SN - 0343-9216 IS - CPP 7.2 SP - 428 CY - Bad Honnef AN - OPUS4-2029 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Goering, Harald A1 - Schick, C. ED - Schick, C. T1 - Molecular dynamics and thermodynamics of polymers confined to nanoporous glasses T2 - 7th Lähnwitzseminar on Calorimetry ; 17th IUPAC Conference on Chemical Thermodynamics CY - Rostock, Germany DA - 2002-07-28 PY - 2002 VL - 403 IS - 1 PB - Elsevier CY - Amsterdam AN - OPUS4-2030 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Szymoniak, Paulina A1 - Schönhals, Andreas ED - Schönhals, Andreas ED - Szymoniak, Paulina T1 - Epoxy-Based Nanocomposites—What Can Be Learned from Dielectric and Calorimetric Investigations? N2 - Epoxy-based nanocomposites are promisingmaterials for industrial applications (i.e., aerospace, marine, and automotive industries) due to their extraordinary mechanical and thermal properties. Regardless of the broad field of applications, there is still a considerable need to identify their structure–property relationships. Here, a detailed dielectric and calorimetric (DSC and fast scanning calorimetry) study on different epoxy-based nanocomposites was performed. Bisphenol A diglycidyl ether (DGEBA) cured with diethylenetriamine (DETA) was employed as the polymeric matrix, which was reinforced with three diverse nanofillers that exhibit different interaction strengths with the epoxy matrix (halloysite nanotubes, surface modified halloysite nanotubes, and taurine-modified layered double hydroxide). The structure, molecular mobility, and vitrification behavior are discussed in detail, focusing on the intrinsic structural and dynamic heterogeneity, as well as interfacial properties. KW - Nanocomposites KW - Epoxi nanocomposites KW - Dynamics KW - Interphase KW - Ridis amorphous fraction KW - Dielectric spectroscopy KW - Flash DSC KW - Temparatur modulated Flash DSC KW - Temperature modulated DSC PY - 2022 DO - https://doi.org/10.1007/978-3-030-89723-9_11 SP - 335 EP - 367 PB - Springer CY - Cham, Switzerland AN - OPUS4-54566 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Madkour, Sherif A. A1 - Gawek, Marcel A1 - Penner, P. A1 - Paneff, F. A1 - Zhang, X. A1 - Gölzhäuser, A. A1 - Schönhals, Andreas T1 - Can Polymers be Irreversibly Adsorbed on Carbon Nanomembranes? A Combined XPS, AFM, and Broadband Dielectric Spectroscopy Study N2 - Carbon nanomembranes are synthetic two-dimensional sheets with nanometer thickness, macroscopic lateral dimensions, and high structural homogeneity. They have great application potential in various branches of nanotechnology. Because of their full carbon structure, it is not clear whether macromolecules like poly(methyl methacrylate) (PMMA) can be irreversibly adsorbed on their surface. Here, irreversible adsorption means that the polymer chains cannot be removed by a leaching process, which is assumed in technological transfer processes. However, if polar defects are present on the carbon nanomembranes (CNMs), it may occur that polymers can be irreversibly adsorbed. To address this question, PMMA was spin-coated on top of CNMs, annealed for a specific time at different temperatures, and then tried to be removed by a acetone treatment in a leaching approach. The samples were investigated in detail by atomic force microscopy, X-ray photoelectron spectroscopy, and broadband dielectric spectroscopy, where the latter method has been applied to CNMs for the first time. Unambiguously, it was shown that PMMA can be adsorbed on the surface of CNMs after annealing the sample above the glasstransition temperature of PMMA. The general occurrence of polar defects on the surface of CNMs and the adsorption of polymers open opportunities for advanced innovative hybrid materials combining the properties of the CNM with those of the polymer. KW - Carbon Nanomembranes KW - Irreversible adsorption KW - Broadband dielectric spectroscopy KW - XPS spctroscopy KW - Atomic force microscopy PY - 2022 DO - https://doi.org/10.1021/acsapm.2c01320 SN - 2637-6105 VL - 4 IS - 11 SP - 8377 EP - 8385 PB - ACS AN - OPUS4-56067 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pleskunov, P. A1 - Nikitin, D. A1 - Tafiichuk, R. A1 - Shlemin, A. A1 - Hanus, J. A1 - Kousal, J. A1 - Krtous, Z. A1 - Khalakhan, I. A1 - Kus, P. A1 - Nasu, T. A1 - Nagahama, T. A1 - Funaki, C. A1 - Sato, H. A1 - Gawek, Marcel A1 - Schönhals, Andreas A1 - Choukourov, A. T1 - Plasma polymerization of acrylic acid for the tunable synthesis of glassy abd carboxylated nanoparticle N2 - Polymer nanoparticles (NPs) can be highly attractive in numerous applications including biomedicine where the use of inorganic matter may be detrimental for living tissues. In conventional wet chemistry, polymerization and functionalization of NPs with specific chemical groups involves complex and often numerous reactions. Here, we report on a solvent-free, single-step, low temperature plasma-based synthesis of carboxylated NPs produced by polymerization of acrylic acid under the conditions of a glow discharge. In a monomer-deficient regime, strong fragmentation of the monomer molecules by electron impact results in the formation of 15 nm-sized NPs with <1% retention of the carboxyl groups. In an energy-deficient regime, larger 90 nm-sized NPs are formed with better retention of the carboxyls that reaches 16 %. All types of the NPs exhibit the glass transition above the room temperature which makes them highly stable under aqueous environment with no dissolution or swelling. They are also found to degrade thermally when heated above 150 °C with a decrease of the mean NP size, yet with the retention of the chemical composition. Thus, plasma polymerization proves to be a versatile approach for the production of polymer NPs with tuneable size distribution, chemical composition and physical properties. KW - Nanoparticles PY - 2020 DO - https://doi.org/10.1021/acs.jpcb.9b08960 VL - 124 SP - 668 EP - 678 PB - ACS AN - OPUS4-50351 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed A. A1 - Schönhals, Andreas T1 - Application of Fast Scanning Calorimetry in Soft Matter Research – Two Examples: 1. Polymers for Gas separation membranes 2. Ionic Liquid Crystals N2 - The application of fast scanning calorimetry (FSC) with heating rates in the range from 10 K/s to 10,000 K/s in soft matter research is discussed through two examples. In the first part, FSC is applied to polymers of intrinsic microporosity (PIMs). No glass transition could be measured for these polymers by conventional calorimetry before their degradation. By decoupling the time scales of chemical degradation and the glass transition, it could be shown for the first time that PIMs undergo a glass transition. In the second part, FSC is applied to ionic liquid crystals to investigate their molecular mobility. In order to cover a broad dynamical range, FSC is combined with temperature-modulated differential scanning calorimetry, and temperature-modulated FSC. T2 - Colloqium at the physics department of the Charles university Prague CY - Prague, Czech Republic DA - 12.11.2024 KW - Fast Scanning Calorimetry PY - 2024 AN - OPUS4-61670 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Szymoniak, Paulina A1 - Juranyi, F. A1 - Kruteva, M. A1 - Zorn, R. A1 - Schönhals, Andreas T1 - Low-Frequency Vibrational Density of States of Nanophase- Separated Poly(n‑alkyl methacrylate)s: Confined Phonons and Relationship to Specific Heat N2 - This study investigates the low-frequency vibrational Density of states of nanophase-separated poly(n-alkyl methacrylate)s (PnMAs) and its relationship to specific heat. This system undergoes a nanophase separation for n > 1 in alkyl side chain-rich domains and a backbone-rich matrix. Using inelastic neutron scattering, the low-frequency vibrational density of states (Boson peak, BP) of PnMAs with varying alkyl side chain lengths (methyl, butyl, hexyl, and octyl) is measured. The results reveal that the BP shifts to higher frequencies with increasing side chain length reaching a maximum. This result indicates a counterbalance of confinement effects and the scattering of the matrix. The behavior of the Boson peak of the PnMAs is compared to other nanophase-separated systems, such as Janus-polynorbornenes and hexakis(n-alkyloxy)triphenylene discotic liquid crystals. The study also explores the connection between the BP and specific heat capacity, showing a linear relationship between the maximum frequency of the BP and the maximum temperature of the specific heat capacity anomaly. Moreover, from the measured vibrational density of states, the specific heat capacity is calculated and compared to experimental results. The comparison reveals qualitative agreement between the calculated and experimental data. These findings provide evidence for the sound wave interpretation of the Boson peak. KW - Inelastic Neutron Scattering PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-636928 DO - https://doi.org/10.1021/acs.macromol.5c00898 SN - 1520-5835 SP - 1 EP - 12 PB - ACS Publications AN - OPUS4-63692 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed A. A1 - Böhning, Martin A1 - Frick, B. A1 - Apple, M. A1 - Mole, R. A. A1 - De Souza, N. R. A1 - Zorn, R. A1 - Schönhals, Andreas T1 - Confined Segmental Diffusion in Nanophase Separated Janus Polynorbornenes as Investigated by Quasielastic Neutron Scattering N2 - A combination of neutron time-of-flight and neutron backscattering spectroscopy was used to investigate the molecular dynamics of Janus polynorbornenes (Janus poly(tricyclononenes)) on a microscopic level. These Janus polynorbornenes, denoted as PTCNSiOR, have a semirigid backbone with −Si(OR)3 side groups attached to it. R represents the length of the alkyl side chain. Here side chain lengths of R = 3 (propyl) and R = 8 (octyl) were considered. It is worth mentioning that these polymers have some potential as active layers in gas separation membranes, especially for the separation of higher hydrocarbons. The combination of time-of-flight and backscattering will ensure a reasonably broad time window for analysis where the incoherent intermediate scattering function SInc(q,t) is considered. Previously, it was shown by X-ray investigations that the system undergoes a nanophase separation into alkyl side chain-rich domains surrounded by a backbone-rich matrix. For PTCNSiOPr (R = 3), the alkyl side-chain-rich domains are truly isolated in the backbone-rich matrix, whereas for PTCNSiOOc (R = 8) these domains percolate through the matrix. Further, it was also previously shown that the alkyl side-chain-rich domains undergo a glass transition. The advantage of neutron scattering experiments discussed here is that besides temporal also spatial information is obtained which will allow conclusions to be drawn about the type of molecular fluctuations. At the lowest measured temperature, the decay in Sinc(q,t) is due to the methyl group rotation. The methyl group dynamics is analyzed in terms of a modified jump-diffusion in a 3-fold potential and yields to a reasonable fraction of hydrogens which contribute to the methyl group rotation. At higher temperatures, the decay in SInc(q,t) is due to both the methyl group rotation and the segmental dynamics in the alkyl side-chain-rich domains. The segmental diffusion is modeled by a sublinear diffusion. For the analysis of the scattering function SInc(q,t) of PTCNSiOPr an elastic scattering due to the immobilized backbone-rich matrix must be taken into account. The analysis reveals that the segmental dynamics is confined by the finite size of alkyl chain-rich domains and that it is intrinsically heterogeneous in nature. Both effects are more pronounced for PTCNSiOPr in comparison to those of PTCNSiOOc. KW - Polynorbornene KW - Quasielastic Neutron Scattering PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608712 DO - https://doi.org/10.1021/acs.macromol.4c01045 SP - 1 EP - 14 PB - ACS Publications AN - OPUS4-60871 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed A. A1 - Böhning, Martin A1 - De Souza, N. R. A1 - Juranyi, F. A1 - Zorn, R. A1 - Schönhals, Andreas T1 - Inelastic and Quasielastic Neutron Scattering on Polynorbornenes with Bulky Carbocyclic Side groups N2 - This study investigates the molecular mobility and vibrational properties of polynorbornenes with bulky carbocyclic side groups using inelastic and quasielastic neutron scattering techniques. The polymers, synthesized via metathesis and addition polymerization, exhibit varying degrees of microporosity, which ignificantly influences their gas separation performance. By inelastic neutron scattering experiments, it could be shown that all considered polymers have excess contributions to the low frequency vibrational density of states known as the Boson peak. The maximum frequency of the Boson peak correlates to the microporosity of the polymers. This correlation supports the sound wave interpretation of the Boson peak, suggesting that the microporous structure enhances the compressibility of the material at a microscopic length scale. The molecular mobility, particularly the methyl group rotation, was characterized using elastic scans and quasielastic neutron scattering. The study revealed a temperature dependent relaxation process, with the onset of molecular fluctuations observed around 200 K for the polymer containing methyl groups. For the polymer having no methyl groups only elastic scattering is observed. The methyl group rotation was analyzed in terms of a jump diffusion in a threefold potential with three equivalent energy minima. This leads to an almost correct description of the q dependence of the elastic incoherent scattering function when the number of hydrogen nuclei undergoing the methyl group rotation is considered. It was further evidenced that the fraction of methyl undergoing the methyl group rotation increases with increasing temperature. KW - Polymers of Intrinsic Microporosity KW - Neutron scattering PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630297 DO - https://doi.org/10.1016/j.polymer.2025.128358 SN - 1873-2291 VL - 328 SP - 241 PB - Elsevier Ltd. AN - OPUS4-63029 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -