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 - TY - JOUR A1 - Zorn, R. A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed Aejaz A1 - Malpass-Evans, R. A1 - McKeown, N. A1 - Jalarvo, N. A1 - Tyagi, M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Microscopic molecular mobility of high-performance polymers of intrinsic microporosity revealed by neutron scattering – bend fluctuations and signature of methyl group rotation N2 - Polymers of intrinsic microporosity exhibit a combination of high gas permeability and reasonable permselectivity, which makes them attractive candidates for gas separation membrane materials. The diffusional selective gas transport properties are connected to the molecular mobility of these polymers in the condensed state. Incoherent quasielastic neutron scattering was carried out on two polymers of intrinsic microporosity, PIM-EA-TB(CH3) and its demethylated counterpart PIM-EA-TB(H2), which have high Brunauer–Emmett–Teller surface area values of 1030 m2 g-1 and 836 m2 g-1, respectively. As these two polymers only differ in the presence of two methyl groups at the ethanoanthracene unit, the effect of methyl group rotation can be investigated solely. To cover a broad dynamic range, neutron time-of-flight was combined with neutron backscattering. The demethylated PIM-EA-TB(H2) exhibits a relaxation process with a weak intensity at short times. As the backbone is rigid and stiff this process was assigned to bendand-flex fluctuations. This process was also observed for the PIM-EA-TB(CH3). A further relaxation process is found for PIM-EA-TB(CH3), which is the methyl group rotation. It was analyzed by a jump-diffusion in a three-fold potential considering also the fact that only a fraction of the present hydrogens in PIM-EATB(CH3) participate in the methyl group rotation. This analysis can quantitatively describe the q dependence of the elastic incoherent structure factor. Furthermore, a relaxation time for the methyl group rotation can be extracted. A high activation energy of 35 kJ mol-1 was deduced. This high activation energy evidences a strong hindrance of the methyl group rotation in the bridged PIM-EA-TB(CH3) structure. KW - Polymers of Intrinsic Microporosity KW - Neutron Scattering PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-604114 DO - https://doi.org/10.1039/d4sm00520a SP - 1 EP - 11 PB - RSC AN - OPUS4-60411 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zorn, R. A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed Aejaz A1 - Malpass-Evans, R. A1 - McKeown, N. A1 - Tyagi, M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Low frequency vibrations and diffusion in disordered polymers bearing an intrinsic microporosity as revealed by neutron scattering N2 - The microscopic diffusion and the low frequency density of states (VDOS) of PIM-EATB(CH3) are investigated by inelastic and quasi-elastic neutron scattering where also the demethylated counterpart of PIM-EA-TB(H2) is considered. These intrinsic microporous polymers are characterized by large BET surface area values of several hundred m2/g and pore sizes between 0.5 and 2 nm. Detailed comparison is made to the archetype of polymers of intrinsic microporosity, PIM-1, and polynorbornenes also bearing a microporosity. Due to the wavelength of neutrons, the diffusion and vibrations can be addressed on microscopic length and time scales. From the inelastic neutron scattering experiments the low frequency density of states (VDOS) is estimated which shows excess contributions to the Debye-type VDOS known as Boson peak. It was found that the maximum frequency of the Boson peak decreases with increasing microporosity characterized by the BET surface area. However, besides the BET surface area, additional factors such as the backbone stiffness govern the maximum frequency of the Boson peak. Further the mean squared displacement related to microscopic motions was estimated from elastic fixed window scans. At temperatures above 175 K, the mean squared displacement PIM-EA-TB(CH3) is higher than that for the demethylated counterpart PIM-EA-TB(H2). The additional contribution found for PIM-EATB(CH3) is ascribed to the rotation of the methyl group in this polymer because the only difference between the two structures is that PIM-EA-TB(CH3) has methyl groups where PIM-EA-TB(H2) has none. A detailed comparison of the molecular dynamics is also made to that of PIM-1 and the microporous polynorbornene PTCNSi1. The manuscript focuses on the importance of vibrations and the localized molecular mobility characterized by the microscopic diffusion on the gas Transport in polymeric separation membranes. In the frame of the random gate model localized fluctuations can open or close bottlenecks between pores to enable the diffusion of gas molecules. KW - Polymer of intrisic microporosity KW - Neutron scattering KW - Boson peak KW - Methyl group rotation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-538490 DO - https://doi.org/10.3390/cryst11121482 VL - 11 IS - 12 SP - 1 EP - 16 PB - MDPI CY - Basel AN - OPUS4-53849 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kolmangadi, Mohamed Aejaz A1 - Szymoniak, Paulina A1 - Zorn, R. A1 - Böhning, Martin A1 - Wolff, M. A1 - Zamponi, M. A1 - Schönhals, Andreas T1 - Molecular mobility in high-performance polynorbornenes:A combined broadband dielectric, advanced calorimetry,and neutron scattering investigation N2 - The molecular dynamics of two addition type polynorbornenes, exo-PNBSiand PTCNSi1, bearing microporosity has been investigated by broadbanddielectric spectroscopy, fast scanning calorimetry, and neutron scattering. Bothpolymers have the same side groups but different backbones. Due to theirfavorable transport properties, these polymers have potential applications inseparation membranes for gases. It is established in literature that molecularfluctuations are important for the diffusion of small molecules through poly-mers. For exo-PNBSi, two dielectric processes are observed, which are assignedto Maxwell/Wagner/Sillars (MWS) process due to blocking of charge carriersat internal voids or pore walls. For PTCNSi1, one MWS-polarization process isfound. This points to a bimodal pore-size distribution for exo-PNBSi. A glasstransition for exo-PNBSi and for PTCNSi1 could be evidenced for the first timeusing fast scanning calorimetry. For Tgand the corresponding apparent activa-tion energy, higher values were found for PTCNSi1 compared to exo-PNBSi.For both polymers, the neutron scattering data reveal one relaxation process.This process is mainly assigned to methyl group rotation probably overlayedby carbon–carbon torsional fluctuations. KW - Advanced calorimetry KW - Dielectric spectroscopy KW - Neutron scattering KW - Polynorbornenes PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-547086 DO - https://doi.org/10.1002/pen.25995 SN - 0032-3888 VL - 62 IS - 7 SP - 2143 EP - 2155 PB - Wiley AN - OPUS4-54708 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Schönhals, Andreas A1 - Böhning, Martin A1 - Szymoniak, Paulina ED - Schönhals, Andreas ED - Szymoniak, Paulina T1 - (Nano)Composite Materials—An Introduction N2 - The chapter gives a brief introduction to (nano)compositecomposite materials having the focus on polymer-based nanocomposites. The different dimensionalities of nanoparticles are introduced, along with their distribution in the matrix. Different application fields of polymer-based nanocomposites, like flame retardancy, filled rubbers, nanofilled thermosets and thermoplastics, separation membranes and nanodielectrics, are considered in greater detail. KW - Polymer-based nanocomposites KW - Nanoparticle KW - Distribution of nanoparticles KW - Filled rubbers KW - Filled thermosets and plastics KW - Separation membranes KW - Nanodielectrics PY - 2022 DO - https://doi.org/10.1007/978-3-030-89723-9_1 SP - 1 EP - 31 PB - Springer CY - Cham, Switzerland AN - OPUS4-54565 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Emamverdi, Farnaz A1 - Yin, Huajie A1 - Smales, Glen Jacob A1 - Harrison, W. J. A1 - Budd, P. M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Polymers of intrinsic microporosity - Molecular mobility and physical aging revisited by dielectric spectroscopy and X‑ray scattering N2 - Polymers of intrinsic microporosity (PIMs) are promising candidates for the active layer in gas separation membranes due to their high permeability and reasonable permselectivity. These appealing properties originate from a microporous structure as a result of inefficient segment packing in the condensed state due to a combination of a ladder-like rigid backbone and sites of contortion. However, this class of polymers suffers from a significant decrease in the permeability with time due to physical aging, whereby typically, the permselectivity increases. The initial microporous structures approach a denser state via local rearrangements, leading to the reduction of the permeability. Hence, a detailed characterization of the molecular mobility in such materials can provide valuable information on physical aging. In this work, the dielectric behavior of PIM-1 films and their behavior upon heating (aging) were revisited by isothermal frequency scans during different heating/cooling cycles over a broad temperature range between 133 and 523 K (−140 to 250 °C). In addition, the obtained results were compared with data of samples that were annealed at ambient temperatures over different time scales. Multiple dielectric processes were observed: several relaxation processes due to local fluctuations and a Maxwell−Wagner−Sillars polarization effect related to the microporosity. The temperature dependence of the rates of all processes follows the Arrhenius law where the estimated activation energy depends on the nature of the process. The influence of the thermal history (aging) on the processes is discussed in detail. KW - Polymers of intrinsic microporosity PY - 2022 DO - https://doi.org/10.1021/acs.macromol.2c00934 VL - 55 SP - 7340 EP - 7350 PB - American Chemical Society CY - Washington, DC AN - OPUS4-55485 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed A. A1 - Juranyi, Fanni A1 - Böhning, Martin A1 - Zorn, Reiner A1 - Schönhals, Andreas T1 - Low-Frequency Vibrational Density of State of Janus-Polynorbornenes: The Dependence of the Boson Peak on the Nanophase-Separated Structure N2 - Inelastic incoherent neutron time-of-flight scattering was employed to investigate the low-frequency vibrational density of states (VDOSs) for a series of glassy Janus-poly(tricyclononenes), which consist of a rigid main chain and flexible alkyl side chains. Here, the length of the flexible side chains was systematically varied from propyl to octyl. Such materials have potential applications as active separation layers in gas separation membranes as a green future technology, especially for the separation of higher hydrocarbons. From the morphological point of view, the Janus polynorbornenes undergo a nanophase separation into alkyl side chain-rich nanodomains surrounded by a rigid polynorbornene matrix. Here, the influence of the nanophase-separated structure on the low-frequency VDOS is investigated from a fundamental point of view. The low-frequency VDOSs of these Janus polynorbornene show excess contributions to the Debye type VDOS known as the Boson peak (BP) for all side chain lengths. Due to the high incoherent scattering cross-section of hydrogen, most of the scattering comes from the alkyl side chain-rich domains. Compared to conventional glass-forming materials, in the considered Janus polynorbornenes, the BP has a much lower intensity and its frequency position is shifted to higher values. These experimental results are discussed in terms of the nanophase-separated structure where the alkyl chain-rich domains were constrained by the surrounding matrix dominated by the rigid backbone. With increasing alkyl chain length, the size of the alkyl chain-rich domains increases. The frequency position of the BP shifts linearly to lower frequencies with the size of these nanodomains estimated from X-ray measurements. The obtained results support the sound wave interpretation to the BP KW - Inelastic neutron scattering PY - 2023 DO - https://doi.org/10.1021/acs.macromol.3c00913 SN - 0024-9297 SP - 1 EP - 10 PB - ACS AN - OPUS4-57972 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Szymoniak, Paulina A1 - Böhning, Martin A1 - Zorn, Reiner A1 - Schönhals, Andreas T1 - Inelastic and quasielastic neutron scattering experiments on microporous membranes fro green separation processes N2 - Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. These polymers are characterized by a high permeability and reasonable permselectivity. The latter point is somehow surprising because for microporous systems a more Knudson-like diffusion is expected then a size dependent temperature activated sieving process. It was argued in the framework of a random gate model that molecular fluctuations on a time scale from ps to ns are responsible for the permselectivity. Here series of polymers of intrinsic microporosity (PIMs) as well as microporous polynorbornenes with bulky Si side groups and a rigid backbone are considered. The polymers have different microporosity characterized by high BET surface area values. First inelastic time-of-flight neutron scattering measurements were carried out to investigate the low frequency density of state (VDOS). The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. It was found that the frequency of the maximum position of the Boson peak correlates with the BET surface area value. Secondly elastic scans as well as quasielastic neutron scattering measurements by a combination of neutron time-of-flight and backscattering have been out. A low temperature relaxation process was found for both polymers. This process was assigned to the methyl group rotation. It was analysed in terms of a jump diffusion in a three-fold potential. The analysis of the dependence of the elastic incoherent structure factor on the scattering vector yields the number of methyl groups which might be immobilized. The neutron scattering experiments were accompanied by fast scanning calorimetry and broadband dielectric investigations as well as atomistic molecular dynamic simulations. T2 - Kolloquiumsvortrag an der Technischen Universität München CY - Garching, Germany DA - 20.11.2023 KW - Polymers with intrinsic microporosity PY - 2023 AN - OPUS4-59036 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Böhning, Martin A1 - Wald, Oliver A1 - Turky, Gamal A1 - Goering, Harald A1 - Brzezinka, Klaus-Werner A1 - Schartel, Bernhard A1 - Schönhals, Andreas T1 - Dielectric Relaxation and Gas Transport Properties in Polypropylene Based Nanocomposites T2 - ACS 2002 Biennial Symposium "Polymeric Nanomaterials" CY - Rohnert Park, CA, USA DA - 2002-11-17 PY - 2002 SP - 1(?) EP - 3(?) AN - OPUS4-2035 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Böhning, Martin A1 - Turky, Gamal A1 - Goering, Harald A1 - Wald, Oliver A1 - Schartel, Bernhard A1 - Schönhals, Andreas T1 - Polypropylene/Clay Nanocomposites - Dielectric Relaxation and Gas Transport Properties T2 - 2nd International Conference on Broadband Dielectric Spectroscopy and Its Applications CY - Leipzig, Germany DA - 2002-09-02 PY - 2002 AN - OPUS4-2037 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Böhning, Martin A1 - Goering, Harald A1 - Hao, Ning A1 - Mach, Reinhard A1 - Oleszak, Franz A1 - Schönhals, Andreas T1 - Molecular Mobility and Gas Transport Properties of Polycarbonate-Based Nanocomposites PY - 2003 UR - http://www.ipme.ru/e-journals/RAMS/no_3503/bohning/bohning.html SN - 1606-5131 VL - 5 SP - 155 EP - 159 PB - Advanced Study Center CY - St. Petersburg AN - OPUS4-2884 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular Mobility and Gas Transport Properties of Poly(bisphenol A carbonate) (PC) Based Nanocomposites T2 - 3th International Conference on Broadband Dielectric Spectroscopy and its Applications CY - Delft, Netherlands DA - 2004-08-23 PY - 2004 AN - OPUS4-3901 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Goering, Harald A1 - Böhning, Martin A1 - Turky, Gamal A1 - Hao, Ning A1 - Schönhals, Andreas T1 - Molecular Dynamics in Polymer Nanocomposites T2 - Workshop "Glasübergang" CY - Rostock, Germany DA - 2002-12-16 PY - 2002 AN - OPUS4-2061 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Böhning, Martin A1 - Goering, Harald A1 - Hao, Ning A1 - Schönhals, Andreas T1 - Gas Transport in Polymer based Nanocomposite Systems T2 - Workshop "Glasübergang" CY - Rostock, Germany DA - 2002-12-16 PY - 2002 AN - OPUS4-2054 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hao, Ning A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Dielectric Properties of Nanocomposites Based on Polystyrene and Polyhedral Oligomeric Phenethyl-Silsesquioxanes N2 - Nanocomposites were prepared by solution blending of polyhedral oligomeric silsesquioxane with phenethyl substituents (PhenethylPOSS) into polystyrene (PS). The prepared materials were investigated by dielectric spectroscopy, differential scanning calorimetry (DSC), and density measurements. Additional FTIR investigations were carried out. Pure polystyrene shows two relaxation processes, an intermediate β*-process at lower and the α-relaxation at higher temperatures, the latter corresponding to segmental dynamics (dynamic glass transition). The molecular assignment of the β*-process needs further investigation. PhenethylPOSS can be incorporated into PS up to about 40 wt % without any indication of phase separation. With increasing PhenethylPOSS content, the α-relaxation of the composites shifts to lower temperatures and the loss peak broadens. Thus, the main effect of the nanofiller in the polystyrene matrix is to enhance the segmental dynamics, i.e., plasticization. The incorporation of approximately 40 wt % (approximately 5 mol %) PhenethylPOSS shifts the glass transition temperature Tg by 50 K to lower temperatures. The obtained results for polystyrene are discussed together with those reported recently for polycarbonate where a phase-separated morphology is observed for higher concentrations of PhenethylPOSS. The different behavior of PhenethylPOSS in polystyrene and polycarbonate is interpreted in terms of the different interaction of the phenyl rings within the POSS substituents with the phenyl rings of the polymers. For polystyrene, the interaction is stronger than for polycarbonate which probably leads to the enhanced miscibility of PhenethylPOSS into polystyrene. A detailed analysis of the temperature dependence of the dielectric relaxation strengths points also to additional interactions in the nanocomposites when compared to pure polystyrene. The broadening of the loss peak with increasing concentration is discussed in the framework of composition fluctuations. KW - Polyhedral oligomeric silsesquioxane (POSS) KW - Polymer-based nanocomposites KW - Broadband dielectric spectroscopy KW - Polystyrene PY - 2007 DO - https://doi.org/10.1021/ma071777g SN - 0024-9297 SN - 1520-5835 VL - 40 IS - 26 SP - 9672 EP - 9679 PB - American Chemical Society CY - Washington, DC AN - OPUS4-16492 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Gas transport properties of polymeric nanocomposites based on polyhedral oligomeric silsesquioxanes T2 - Meeting America Chemical Society CY - Boston, MA, USA DA - 2007-07-19 PY - 2007 AN - OPUS4-15354 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Structure property relationship of polymeric nanocomposites based on polyhedral oligomeric silsesquioxanes T2 - Jahrestagung der Deutschen Physikalischen Gesellschaft, AK Chemische Physik/Polymerphysik CY - Regensburg, Germany DA - 2007-03-26 PY - 2007 AN - OPUS4-14591 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 dielectric spectroscopy and gas transport measurements T2 - European Polymer Congress 2007 CY - Portorož, Slovenia DA - 2007-07-02 PY - 2007 AN - OPUS4-14952 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hao, Ning A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Structure Property Relationships of Polymeric Nanocomposites based on Polyhedral Oligomeric Silsesquioxanes PY - 2007 SN - 0743-0515 VL - 97 SP - 789 EP - 790 PB - Division of Polymeric Materials Science and Engineering, American Chemical Society CY - Washington, DC AN - OPUS4-15848 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Böhning, Martin A1 - Goering, Harald A1 - Hao, Ning A1 - Mach, Reinhard A1 - Schönhals, Andreas ED - Cassidy, P. T1 - Polycarbonate/SiC nanocomposites - Influence of nanoparticle dispersion on molecular mobility and gas transport T2 - 7th International Symposium on Polymers for Advanced Technologies CY - Fort Lauderdale, FL, USA DA - 2005-09-21 KW - Nanocomposites KW - Nanoparticles KW - Polycarbonates KW - Dielectric properties KW - Gas permeation PY - 2005 VL - 16 IS - 2-3 SP - 262 EP - 268 PB - Wiley CY - Chichester AN - OPUS4-7062 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Böhning, Martin A1 - Tidjani, Adams A1 - Wald, Oliver A1 - Turky, Gamal A1 - Goering, Harald A1 - Brzezinka, Klaus-Werner A1 - Schartel, Bernhard A1 - Schönhals, Andreas T1 - Polypropylene/Clay Nanocomposites - Gas Transport Characteristics and Molecular Mobility T2 - Polydays 2002 CY - Berlin, Germany DA - 2002-09-30 PY - 2002 SP - 1(?) EP - 2(?) AN - OPUS4-2038 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polycarbonate/SiC Nanocomposites - Influence of Nanoparticle Dispersion on Molecular Mobility and Gas Transport T2 - 7th International Symposium Polymers for Advanced Technologies CY - Fort Lauderdale, FL, USA DA - 2003-09-21 PY - 2003 AN - OPUS4-4650 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Polycarbonate/SiC Nanocomposites - Influence of Nanoparticle Dispersion on Molecular mobility and Gas Transport T2 - 7th International Symposium Polymers for Advanced Technologies CY - Fort Lauderdale, FL, USA DA - 2003-09-21 PY - 2003 AN - OPUS4-4665 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Gas Transport and Dielectric Relaxation in Polymer Based Nanocomposite Systems T2 - Vortrag Universität Lyon CY - Lyon, France DA - 2003-04-04 PY - 2003 AN - OPUS4-4060 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Gas transport and dielectric relaxation in polymer based nanocomposite systems T2 - Vortrag Universität Lyon CY - Lyon, France DA - 2003-04-04 PY - 2003 AN - OPUS4-4112 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 T2 - Frühjahrstagung der Deutschen Physikalischen Ges. / AKF, Condensed Matter CY - Dresden, Germany DA - 2006-03-26 PY - 2006 AN - OPUS4-11370 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Structure-property relationsship of polymer based nanocomposites with polyhedral oligomeric silsesquioxanes as nanofillers T2 - Polydays 2006 CY - Berlin, Germany DA - 2006-10-04 PY - 2006 AN - OPUS4-13638 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Böhning, Martin A1 - Hao, Ning A1 - Schönhals, Andreas T1 - Gas transport and molecular mobility in polymer/POSS nanocomposites PY - 2006 DO - https://doi.org/10.1016/j.desal.2006.03.127 SN - 0011-9164 VL - 200 IS - 1-3 SP - 142 EP - 143 PB - Elsevier CY - Amsterdam AN - OPUS4-13707 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hao, N. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - CO2 gas transport properties of nanocomposites based on polyhedral oligomeric phenethyl-silsesquioxanes and poly(bisphenol A carbonate) N2 - Polymer-based nanocomposites were prepared by solution blending of polyhedral oligomeric silsesquioxane with phenethyl substituents (PhenethylPOSS) into poly(bisphenol A carbonate) (PBAC). First investigations focused on structure, morphology and dynamics, addressed mainly by dielectric relaxation spectroscopy are substantially extended in this study by the investigation of the CO2 gas transport behavior of these materials, i.e., permeation experiments using the time-lag technique as well as gravimetric gas sorption measurements. The nanocomposite materials were prepared with nanofiller contents ranging from 0 to about 40 wt % by solution blending and films of about 50-100 µm thickness were cast from this solution and used for the investigation of gas transport properties after drying and annealing. From the time-lag measurements the permeability and an effective diffusion coefficient for CO2 is obtained in dependence of POSS concentration and temperature. As main results, both, the permeability and the diffusivity, increase whereas the solubility decreases with increasing POSS concentration. These findings are discussed in the framework of a microphase separated morphology of the nanocomposite systems for POSS concentrations greater than a value cPOSScrit of ca. 7 wt % consisting of a polycarbonate-rich matrix and POSS-rich domains which are surrounded by an interfacial layer. The experimental solubility data suggest that the POSS-rich domains are more or less impermeable for CO2. On the basis of this assumption a quantitative model is provided to correct the solubility data for the phase separated morphology. Moreover the importance of the interfacial layer between the POSS particles or its domains for the properties of nanocomposites especially for the gas transport behavior is addressed by analyzing the sorption isotherms. Also, for the first time results from gas transport measurements and dielectric spectroscopy were quantitatively related to each other by taking the activation energies of CO2 diffusion and of the dielectric β-relaxation into consideration. The obtained clear correlation indicates that the CO2 gas transport is due to localized molecular fluctuations. As a further result, the diffusion coefficient obtained from time-lag and gas sorption measurements is in good agreement with respect to both their absolute values and in their concentration dependence. PY - 2010 DO - https://doi.org/10.1021/ma101463m SN - 0024-9297 SN - 1520-5835 VL - 43 IS - 22 SP - 9417 EP - 9425 PB - American Chemical Society CY - Washington, DC AN - OPUS4-22378 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Böhning, Martin A1 - Hao, Ning A1 - Schönhals, Andreas T1 - Correlation of activation energies of gas diffusivity and local matrix mobility in polycarbonate/POSS nanocomposites N2 - According to basic phenomenological models describing the solution-diffusion based mechanism of penetrant diffusion in dense polymers, a connection between the diffusive transport of gas molecules in a polymeric matrix and the molecular mobility of that matrix on a certain length scale is, in principle, established for a long time. However, experimental data directly showing this correlation are rare. The investigation of a series of nanocomposites based on a polyhedral oligomeric silsesquioxane (POSS) and a polycarbonate matrix allows a systematic change of the molecular mobility on a local length scale (β-relaxation) and of the corresponding activation energy EA, both determined by broadband dielectric spectroscopy. Independently, activation energies of penetrant diffusion (ED) of these nanocomposites were determined for N2, O2, CO2, and CH4 and a clear linear correlation between the two activation energies was established for the first time. KW - Broadband dielectric spectroscopy KW - Diffusion KW - Dielectric properties KW - Gas permeation KW - Molecular mobility KW - Nanocomposites KW - Polyhedral oligomeric silsesquioxane (POSS) KW - Relaxation KW - Beta-relaxation PY - 2013 UR - http://onlinelibrary.wiley.com/doi/10.1002/polb.23381/full DO - https://doi.org/10.1002/polb.23381 SN - 0887-6266 SN - 1099-0488 VL - 51 IS - 22 SP - 1593 EP - 1597 PB - Wiley CY - Hoboken, NJ AN - OPUS4-29284 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Vibrational density of states and molecular mobility in a polymer with intrinsic microporosity PIM-1 as revealed by inelastic neutron scattering N2 - Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid). The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers. Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering where the data are discussed with regard to both the q- and the temperature dependence. T2 - QENS/WINWS 2018 CY - Hong Kong, China DA - 17.07.2018 KW - Polymers with intrinic microporosity KW - Quasielastic neutron scattering PY - 2018 AN - OPUS4-45534 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Konnertz, Nora A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Dielectric investigations of nanocomposites based on matrimid and polyhedral oligomeric phenethyl-silsesquioxanes (POSS) N2 - Matrimid and Matrimid/PhenethylPOSS nanocomposites films were prepared by solution casting. They can be considered as potential membrane materials for gas separation. Theire dielectric properties were investigated using Broadband Dielectric Spectroscopy (BDS) in combination with standard techniques. Matrimid shows one relaxation process assigned as beta*-relaxation and a conductivity contribution. The relaxation process has a high activation energy of 99 kJ/mol. Thus this process is supposed to be of cooperative nature due to a π-π stacking of the phenyl rings of Matrimid. The influence of the thermal history on Matrimid was analyzed with BDS as well where an annealing effect is found. The Matrimid/PhenethylPOSS nanocomposites show up to a concentration of about 4 wt% PhenethylPOSS a miscibility on a molecular level. For higher concentrations a phase separated structure was indicated. The conductivity of both systems is explained by π-π stacking of the phenyl rings which enhances charge transport. KW - Matrimid KW - POSS KW - Nanocomposites KW - Broadband dielectric spectroscopy PY - 2016 DO - https://doi.org/10.1016/j.polymer.2016.02.060 SN - 0032-3861 VL - 90 SP - 89 EP - 101 PB - Elsevier Science AN - OPUS4-35616 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Konnertz, Nora A1 - Ding, Yi A1 - Harrison, W.J. A1 - Budd, P.M. A1 - Schönhals, Andreas A1 - Böhning, Martin T1 - Molecular mobility and gas transport properties of nanocomposites based on PIM-1 and polyhedral oligomeric phenethyl-silsesquioxanes (POSS) N2 - Polymers with intrinsic microporosity (PIMs) are of great interest in the field of gas separation membranes. Already the first synthesized PIM-1 shows extraordinary permeability and selectivity. Unfortunately, PIM-1 is susceptible to physical aging and thus gradually loses its outstanding properties. In this study a polyhedral oligomeric silsesquioxane with phenethyl substituents (PhenethylPOSS) was used as a nanofiller (0–40 wt%) in the PIM-1 matrix to potentially improve the gas transport properties and prevent physical aging. The molecular mobility of the solution-cast nanocomposite films was analyzed by Broadband Dielectric Spectroscopy (BDS). Furthermore, gas permeability was determined with the time lag method (0–20 bar upstream pressure) at 35 °C for N2, O2, CH4 and CO2. KW - Broadband Dielectric Spectroscopy KW - Gas separation KW - Gas permeation KW - Polymers of intrinsic microporosity KW - Nanocomposite KW - POSS KW - PIM-1 PY - 2017 DO - https://doi.org/10.1016/j.memsci.2017.02.007 SN - 0376-7388 SN - 1873-3123 VL - 529 SP - 274 EP - 285 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-39169 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kolmangadi, Mohamed A. A1 - Zhuoqing, L. A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard A1 - Wuckert, E. A1 - Raab, A. A1 - Laschat, S. A1 - Huber, P. A1 - Schönhals, Andreas T1 - Confinement-suppressed phase transition and dynamic self-assembly of ionic superdiscs in ordered nanochannels: Implication for nanoscale applications N2 - Ionic Liquid Crystals are ionic liquids that exhibit liquid crystalline mesomorphism together with ionic conductivity. As known confined liquid crystal mesophases can show an anomalous dynamics and phase behavior. Investigations considering the factors controlling the macroscopic properties of ILCs in confinement are scare in the literature. This study reports the molecular mobility, and the phase transition behavior of a guanidinium based columnar ILC confined in the nanopores of self-ordered anodic aluminum oxide membranes of various pore diameters (25 – 180 nm) using Broadband Dielectric Spectroscopy (BDS), calorimetry and X-ray scattering. It is aimed to reveal in which way the pore size as well as the pore surface wettability (hydrophobic or hydrophilic) alters the molecular dynamics, and phase transition behavior for this system. These properties are crucial for applications. The DSC investigations reveal: (i) the phase transition temperature for the transition from the plastic crystalline to the crystalline-liquid state has non-monotonic dependence versus the inverse pore diameter and (ii) the transition from the liquid crystalline to the isotropic phase is suppressed for all nanoconfined samples. This transition suppressed in the thermal signal was evidenced by BDS and X-ray scattering. It is discussed as a continuous phase transition taking place in the pores instead of a discontinuous first order transition as observed for the bulk. BDS investigations show different relaxation processes for the bulk and the nanoconfined ILC. Molecular origins for various relaxation processes are discussed and suggested. It is further shown that the self-assembly of this ILC is dynamic in nature which might apply for other ILCs too. The obtained results will have implications for the nanoscale applications of ionic liquid crystals. KW - Ionic Liquid Crystals PY - 2023 DO - https://doi.org/10.1021/acsanm.3c02473 VL - 6 IS - 17 SP - 15673 EP - 15684 PB - ACS AN - OPUS4-58210 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Omar, Hassan A1 - Smales, Glen Jacob A1 - Henning, S. A1 - Li, Z. A1 - Wang, D.-Y. A1 - Schönhals, Andreas A1 - Szymoniak, Paulina T1 - Calorimetric and Dielectric Investigations of Epoxy-Based Nanocomposites with Halloysite Nanotubes as Nanofillers N2 - Epoxy nanocomposites are promising materials for industrial applications (i.e., aerospace, marine and automotive industry) due to their extraordinary mechanical and thermal properties. Here, the effect of hollow halloysite nanotubes (HNT) on an epoxy matrix (Ep) was the focus of the study. The structure and molecular mobility of the nanocomposites were investigated using a combination of X-ray scattering, calorimetry (differential (DSC) and fast scanning calorimetry (FSC)) and dielectric spectroscopy. Additionally, the effect of surface modification of HNT (polydopamine (PDA) and Fe(OH)3 nanodots) was considered. For Ep/HNT, the glass transition temperature (Tg) is was de-creased due to a nanoparticle-related decrease of the crosslinking density. For the modified system, Ep/m-HNT, the surface modification resulted in enhanced filler–matrix interactions leading to higher Tg values than the pure epoxy in some cases. For Ep/m-HNT, the amount of interface formed between the nanoparticles and the matrix ranged from 5% to 15%. Through BDS measurements, localized fluctuations were detected as a β- and γ-relaxation, related to rotational fluctuations of phenyl rings and local reorientations of unreacted components. A combination of calorimetry and BDS dielectric spectroscopy revealed a dynamic and structural heterogeneity of the matrix, as confirmed by two glassy dynamics in both systems, related to regions with different crosslinking densities. KW - Rigid amorphous fraction KW - Epoxy nanocomposites KW - Halloysite nanotubes KW - X-ray scattering KW - Differential scanning calorimetry KW - Broadband dielectric spectroscopy KW - Flash DSC PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-526668 DO - https://doi.org/10.3390/polym13101634 VL - 13 IS - 10 SP - 1634 PB - MDPI AN - OPUS4-52666 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Turky, Gamal A1 - Wolff, Dietmar A1 - Schönhals, Andreas T1 - Confinement effects on the molecular dynamics of liquid-crystalline polymethacrylates - a broadband dielectric spectroscopy study N2 - The molecular dynamics of liquid-crystalline polymethacrylates with biphenyl in the side group forming a highly ordered smectic E phase at low temperatures is investigated by dielectric spectroscopy (DS). Although no glass transition is found by DSC, DS detects a relaxation in the smectic E phase resembling to glassy dynamics. The temperature dependence of its relaxation rate is Arrhenius like at low temperatures, which changes to a VFT law at higher temperatures. Such a behavior is found to be characteristic for glassy dynamics in confining space. It is discussed, considering the structure of the polymers as nanobiphasic consisting of liquid-crystalline layers while the backbones fill the interlayer space. A comparison is made to polymethacrylates having phenyl benzoate as mesogen. KW - Dielectric properties KW - Dynamics in confining space KW - Liquid-crystalline polymers KW - Molecular dynamics PY - 2012 DO - https://doi.org/10.1002/macp.201200361 SN - 1022-1352 SN - 1521-3935 VL - 213 IS - 22 SP - 2420 EP - 2431 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-27129 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yildirim, Arda A1 - Haug, T. C. V. A1 - Fröba, M. A1 - Huber, P. A1 - Schönhals, Andreas T1 - Molecular fluctuations in mixed-metal MOF-74: influence of the metal composition N2 - A selected series of metal–organic frameworks M-MOF-74 (M = Mg, Co, Ni) and mixed metal MM-MOF-74 (Mg/Co or Mg/Ni) with different compositions of metal atoms have been prepared and further investigated by broadband dielectric spectroscopy (BDS) in a wide temperature range. The dielectric spectra show at least two relaxation processes. Process-A is observed only for the Ni-containing MOFs and is attributed to localized fluctuations of the metal oxide corners. Relaxation processes-B and -C are observed for all prepared MOFs, except that process-B is not observed for Ni-MOF-74. Large-angle fluctuations such as free rotations of the linkers can be excluded due to the structure of MOF-74, but small-angle fluctuations such as torsions are possible. According to numerical simulations carried out for MOF-74, process-B can be attributed to inward and outward fluctuations of the linkers relative to the pore center. Process-C is related to small-angle rotational fluctuations of the linker together with co-rotations of the metal nodes. The latter interpretation is supported by the dependence of the activation energy of the relaxation rate of process-C on the metal composition of the MOFs, which is discussed in terms of the bond lengths between the metal atoms and the linker which decrease in the sequence Mg, Co and Ni. KW - Metal Organic Frameworks PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639378 DO - https://doi.org/10.1039/d5ra05357a SN - 2046-2069 VL - 15 IS - 35 SP - 29109 EP - 29118 PB - Royal Society of Chemistry (RSC) AN - OPUS4-63937 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kolmangadi, Mohamed A. A1 - Raab, A. R. A1 - Szymoniak, Paulina A1 - Li, Z. A1 - Huber, P. A1 - Laschat, S. A1 - Schönhals, Andreas T1 - Molecular mobility and electrical conductivity of amino acid-based (DOPA) ionic liquid crystals in the bulk state and nanoconfinement N2 - This study explores the molecular mobility, phase behavior, and electrical conductivity of dihydroxyphenylalanine-based ionic liquid crystals (DOPAn, with alkyl side chains n = 12, 14, 16) featuring cyclic guanidiniumchloride headgroups, in both bulk and nanoconfined states. Using broadband dielectric spectroscopy, differential scanning calorimetry, and fast scanning calorimetry, the research uncovers a complex interplay between molecular structure, self-assembly, and molecular mobility. In bulk, DOPAn shows a phase sequence from plastic crystalline to hexagonal columnar and isotropic phases, driven by superdisc formation and columnar organization. Multiple relaxation processes are identified: localized side-chain dynamics (γ-relaxation), ionic headgroup or core motions (α1-relaxation), and cooperative alkyl domain fluctuations (α2-relaxation). Conductivity decreases with increasing side chain length. Under nanoconfinement in anodic aluminum oxide membranes, phase behavior changes: the Colh–Iso transition is suppressed, and a new α3-relaxation appears, linked to dynamics in an adsorbed interfacial layer. DC conductivity drops by up to four orders of magnitude due to confinement effects, altered molecular orientation, and phase transitions—especially the emergence of a nematic-like state in DOPA16. These findings highlight the importance of molecular design, pore geometry, and surface chemistry in tuning ionic liquid crystal properties for advanced applications in nanofluidics, ion transport, and responsive materials. KW - Ionic Liquid Crystals PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639657 DO - https://doi.org/10.1039/d5cp02406d SN - 1463-9084 SP - 1 EP - 17 PB - Royal Society of Chemistry (RSC) AN - OPUS4-63965 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Emamverdi, Farnaz A1 - Huang, J. A1 - Mosane Razavi, Negar A1 - Bojdys, M. J. A1 - Forster, A. B. A1 - Budd, P. M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Molecular Mobility and Gas Transport Properties of Mixed Matrix Membranes Based on PIM‑1 and a Phosphinine Containing Covalent Organic Framework N2 - Polymers with intrinsic microporosity (PIMs) are gaining attention as gas separation membranes. Nevertheless, they face limitations due to pronounced physical aging. In this study a covalent organic framework containing λ5-phosphinine moieties, CPSF-EtO were incorporated as a nanofiller (concentration range 0-10 wt%) into a PIM-1 matrix forming dense films with a thickness of ca. 100 μm. The aim of the investigation was to investigate possible enhancements of gas transport properties and mitigating effects on physical aging. The incorporation of the nanofiller occurred on aggregate level with domains up to 100 nm as observed by T-SEM and confirmed by X-ray scattering. Moreover, the X-ray data show that the structure of the microporous network of the PIM-1 matrix is changed by the nanofiller. As the molecular mobility is fundamental for gas transport as well as for physical aging, the study includes dielectric investigations of pure PIM-1 and PIM-1/CPSF-EtO mixed matrix membranes to establish a correlation between the molecular mobility and the gas transport properties. Using the time-lag method the gas permeability and the permselectivity were determined for N2, O2, CH4 and CO2 for samples with variation in filler content. A significant increase in the permeability of CH4 and CO2 (50 % increase compared to pure PIM-1) was observed for a concentration of 5 wt% of the nanofiller. Furthermore, the most pronounced change in the permselectivity was found for the gas pair CO2/N2 at a filler concentration of 7 wt%. KW - Polymers of Intrinsic Microporosity KW - Nanocomposites PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595031 DO - https://doi.org/10.1021/acs.macromol.3c02419 SN - 0024-9297 VL - 57 IS - 4 SP - 1829 EP - 1845 PB - ACS Publications AN - OPUS4-59503 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Emamverdi, Farnaz A1 - Huang, J. A1 - Szymoniak, Paulina A1 - Bojdys, M. J. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Structure and molecular mobility of phosphinine-based covalent organic frameworks – glass transition of amorphous COFs N2 - Two-dimensional covalent organic frameworks (COFs) based on phosphinine and thiophene building blocks have been synthesized with two different side groups. The materials are denoted as CPSF-MeO and CPSF-EtO where CxxF correspond to the covalent framework, whereas P and S are related to heteroatoms phosphorous and sulfur. MeO and EtO indicate the substituents, i.e. methoxy and ethoxy. Their morphologies were studied by scanning electron microcopy and X-ray scattering. The absence of crystalline reflexes in the X-ray pattern reveal that both materials are amorphous and can be considered as glasses. Furthermore, N2 adsorption measurements indicate substantial Brunauer–Emmett–Teller (BET) surface area values pointing to the formation of three-dimensional pores by stacking of the aromatic 2D layer. An analysis of the porosity of both COFs showed a mean radius of the pores to be of ca. 4 nm, consistent with their chemical structure. The COFs form nanoparticles with a radius of around 100 nm. The thermal behavior of the COFs was further investigated by fast scanning calorimetry. These investigations showed that both COFs undergo a glass transition. The glass transition temperature of CPSF-EtO is found to be ca. 100 K higher than that for CPSF-MeO. This large difference in the glass transition is discussed to be due to a change in the interaction of the COF sheets induced by the longer ethoxy group. It might be assumed that for CPSF-EtO more individual COF sheets assemble to larger stacks than for CPSF-MeO. This agrees with the much larger surface area value found for CPSF-EtO compared to CPSF-MeO. To corroborate the results obtained be fast scanning calorimetry dielectric measurements were conducted which confirm the occurrence of a dynamic glass transition. The estimated temperature dependence of the relaxation rates of the dielectric relaxation and their absolute values agrees well with the data obtained by fast scanning calorimetry. Considering the fragility approach to the glass transition, it was further found that CPSF-MeO is a fragile glass former whereas CPSF-EtO behaves as a strong glass forming material. This difference in the fragility points also to distinct differences in the interaction between the 2D COF molecules in both materials. KW - Covalent Organic frameworks PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596770 DO - https://doi.org/10.1039/d3ma01123b SP - 1 EP - 10 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59677 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zorn, R. A1 - Lohstroh, W. A1 - Zamponi, M. A1 - Harrison, W. A1 - Budd, P. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Molecular mobility of a polymer of intrinsic microporosity revealed by quasielastic neutron scattering N2 - Quasielastic neutron scattering by employing a combination of time-of-flight and backscattering techniques is carried out to explore the molecular mobility of a polymer of intrinsic microporosity (PIM-1) at microscopic time scales in comparison with a high-performance polyimide. Molecular fluctuations can change the structure of the temporary network of micropores and open or close pathways for gas molecules. Therefore, the investigation might help to understand the selectivity of PIMs in gas separation processes. The performed neutron scattering experiments provide evidence for a low-temperature relaxation process, which was assigned to methyl group rotation. This methyl group rotation was analyzed in terms of jump diffusion in a three-fold potential. The analysis results in a fraction of methyl groups which are immobilized. For PIM-1 it was found that the fraction of immobilized methyl groups decreases with increasing temperature up to 350 K. At higher temperatures the number of immobilized methyl group increases gain due to an underlying relaxation process. This motional process on a somewhat larger length scale might lead to a reversible structural rearrangement which partially hinders the strongly localized methyl group rotation. In addition, it was found that the activation energy for the methyl group rotation for PIM-1 and the polyimide is significantly higher than for conventional polymers. KW - Polymer of intrinsic microporosity KW - Quasielastic neutron scattering PY - 2020 DO - https://doi.org/10.1021/acs.macromol.0c00963 SN - 0024-9297 SN - 1520-5835 VL - 53 IS - 15 SP - 6731 EP - 6739 PB - American Chemical Society CY - Washington, DC AN - OPUS4-51147 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kolmangadi, Mohamed Aejaz A1 - Szymoniak, Paulina A1 - Smales, Glen Jacob A1 - Alentiev, D. A1 - Bermeshev, M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Molecular Dynamics of Janus Polynorbornenes: Glass Transitions and Nanophase Separation N2 - For the first time, dielectric and calorimetric investigations of an homologous series of Janus polynorbornenes with rigid main backbones and flexible -Si(OR)3 side groups, of differing length alkyl chains (R = Propyl, Butyl, Hexyl, Octyl, Decyl) is reported. Generally, this class of polymers has some potential for applications in the field of gas separation membranes. Two dielectrically active processes are observed at low temperatures, denoted as β- and α- relaxation. The former can be assigned to localized fluctuations, whilst the latter is related to the glassy dynamics of the flexible -Si(OR)3 side groups, creating a nanophase separation in both the alkyl chain rich and backbone rich domains. This is confirmed through temperature modulated DSC measurements and X-ray scattering experiments. The glass transition temperatures of the backbone rich domains, which are beyond or near to their degradation temperatures in terms of conventional DSC, are determined for the first time using Fast Scanning Calorimetry employing both fast heating and cooling rates. This is complimented with scattering experiments that show how the size of the alkyl chain rich domains increases with chain length. Alongside these results, a significant conductivity contribution was observed for all poly(tricyclononenes) with -Si(OR)3 side groups, which is interpreted in terms of a percolation model. KW - Polynorbornenes KW - Broadband Dielectric Spectrscopy KW - Advanced calorimetry PY - 2020 DO - https://doi.org/10.1021/acs.macromol.0c01450 VL - 53 IS - 17 SP - 7410 EP - 7419 PB - ACS AN - OPUS4-51196 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schönhals, Andreas A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed Aejaz A1 - Böhning, Martin A1 - Zamponi, M. A1 - Frick, B. A1 - Appel, M. A1 - Günther, G. A1 - Russina, M. A1 - Alentiev, D. A1 - Bermeshev, M. A1 - Zorn, R. T1 - Microscopic dynamics of highly permeable super glassy polynorbornenes revealed by quasielastic neutron scattering N2 - The molecular dynamics of addition-type poly(tricyclononenes) with Si-substituted bulky side groups has been investigated by a combination of neutron time-of-flight and neutron backscattering spectroscopy methods on a time scale from 0.1 ps to ca. 3 ns. The investigated poly(tricyclononenes) PTCNSi1 and PTCNSi2g both bear a high microporosity which makes them promising candidates for active separation layers for gas separation membranes. At least for larger gas molecules it is assumed that the pathways for diffusion require an enlargement of pre-existing micropores in terms of an activated zone. A low temperature relaxation process was found for both polymers by the performed neutron scattering experiments. This process was assigned to the methyl group rotation. It was analysed in terms of a jump diffusion in a three-fold potential. The analysis of the dependence of the elastic incoherent structure factor on the scattering vector yields the number of methyl groups which might be immobilized. For PTCNSi1 (3 methyl groups in the monomeric unit) it was found that all methyl groups take part in the methyl group rotation whereas for PTCNSi2g (6 methyl groups in monomeric unit) a considerable number of methyl groups are blocked in their rotation. This immobilization of methyl groups is due to the sterically demanding arrangement of the methyl groups in PTCNSi2g. This conclusion is further supported by the result that the activation energy for the methyl group rotation is three times higher for PTCNSi2g than that of PTCNSi1. KW - Highly permeably polynorbornenes KW - Polymers of intrinsic microporosity KW - Gas separation membranes KW - Quasielastic neutron scattering PY - 2021 DO - https://doi.org/10.1016/j.memsci.2021.119972 SN - 0376-7388 VL - 642 PB - Elesevier B.V. AN - OPUS4-53508 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kolmangadi, Mohamed Aejaz A1 - Szymoniak, Paulina A1 - Smales, Glen Jacob A1 - Bermeshev, M. A1 - Schönhals, Andreas A1 - Böhning, Martin T1 - Molecular mobility of polynorbornenes with trimethylsiloxysilyl side groups: Influence of the polymerization mechanism N2 - We report dielectric and calorimetric studies on metathesis and addition-type polytricyclononenes, both based on the same monomer bearing three pendant OSiMe3 groups. For the addition-type polymer, dielectric spectroscopy reveals a β*-process related to the microporosity, whereas for its metathesis counterpart, the segmental dynamics manifests as an α-process related to a glass transition. Besides active dielectric processes, a significant conductivity contribution is detected for both samples which for the microporous additiontype polymer is three orders of magnitude greater than for the metathesis polymer. The broadband dielectric spectroscopy is complemented by detailed calorimetric investigations, comprising DSC, FSC, and TMDSC. The calorimetric methods detected the glass transition for the metathesis polymer in agreement with the observed dielectric α-process. Furthermore, the already reported gas transport properties for both polymers are compared, setting them in correlation with the observed molecular mobility and conductivity behavior. The discussed results reflect significant differences in molecular mobility of the two polymers affecting the appearance of microporosity which strongly determines the gas transport properties. KW - Microporous polymers KW - Molecular mobility KW - Electrical conductivity KW - Membrane polymers KW - Gas separation PY - 2022 DO - https://doi.org/10.22079/JMSR.2021.538060.1495 SN - 2476-5406 VL - 8 IS - 3 SP - 1 EP - 9 PB - Membrane Processes Research Laboratory (MPRL) CY - Tehran AN - OPUS4-54303 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zorn, R. A1 - Szymoniak, Paulina A1 - Kolmangadi, Mohamed Aejaz A1 - Wolf, M. A1 - Alentiev, D. A1 - Bermeshev, M. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Low frequency vibrational density of state of highly permeable super glassy polynorbornenes – The Boson peak N2 - Inelastic incoherent neutron time-of flight scattering was employed to measure the low frequency density of states for a series of addition polynorbornenes with bulky side groups. The rigid main chain in combination with the bulky side groups give rise to a microporosity of these polymers in the solid state. The microporosity characterized by the BET surfaces area varies systematically in the considered series. Such materials have some possible application as active separation layer in gas separation membranes. All investigated materials show excess contributions to the Debye type density of states characteristic for glasses known as Boson peak. The maximum position of the Boson peak shifts to lower frequency values with increasing microporosity. Data for PIM-1 and Matrimid included for comparison are in good agreement to this dependency. This result supports the sound wave interpretation of the Boson peak. KW - Polynorbornes KW - Neutron Scattering PY - 2020 DO - https://doi.org/10.1039/d0cp03360j SN - 1463-9076 VL - 22 IS - 33 SP - 18381 EP - 18387 PB - Royal Chemical Society AN - OPUS4-51165 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Physical investigations on Super glassy Polymers having possible applications in gas Separation Membranes N2 - The properties of polymers of intrinsic microporosity were investigated by fast scanning calorimetry, dielectric spectroscopy and neutron scattering T2 - University of Pennsylvania CY - Online meeting DA - 25.01.2021 KW - Polymer of intrisic microporosity PY - 2021 AN - OPUS4-52065 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Inelastic neutron scattering as a tool to investigate  polymers of intrinsic microporosity for green membrane processes and electronic applications N2 - Polymers with intrinsic microporosity are promising candidates for the active separation layer in green gas separation membranes and as active materials for electronic applicatons. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid). The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers. Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analysed in detail by quasielastic neutron scattering combining Time-of-Flight and backscattering where the data are discussed with regard to both the q- and the temperature dependence. T2 - Symposium on Large Scale Facilities CY - Berlin, Germany DA - 09.03.2020 KW - Polymer membranen PY - 2020 AN - OPUS4-50546 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Böhning, Martin A1 - Goering, Harald A1 - Hao, Ning A1 - Schönhals, Andreas T1 - Polymer-based Nanocomposites - Particle Dispersion and Physical Properties T2 - Nanofair 2005 CY - Dresden, Germany DA - 2005-11-29 KW - Polymerbasierte Nanokomposite PY - 2005 SN - 3-18-091920-5 N1 - Serientitel: VDI-Berichte – Series title: VDI-Berichte IS - 1920 SP - 263 EP - 267 PB - VDI-Verl. CY - Düsseldorf AN - OPUS4-11589 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kamoun, E. A1 - Afifi, K. A1 - Szymoniak, Paulina A1 - Schönhals, Andreas A1 - Fahmy, Alaa T1 - Structure-property relationship of cross-linked chitosan-ethyl cellulose membranes N2 - Intensive research is focused on creating cost-effective, high-performance polyelectrolyte membranes (PEMs) for electrochemical devices designed to generate and/or store electrical energy. On the other hand, biopolymer materials have been utilized in a wide range of applications across medical and engineering fields, as well as in the textile and energy sectors. Therefore, in this study, chemically cross-linked chito-san/ethyl cellulose-citric acid (CS-EC-CA) membranes were prepared by a casting technique. The structure-property relationship of CS-EC/CA has been discussed based on the molar ratio of CS. The structural properties of the resultant membrane were characterized using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy, thermal stability was assessed using thermogravimetric analysis. Moreover, the ion exchange capacity (IEC) and water uptake of the membrane were studied. FTIR analysis revealed a significant broadening of absorption peaks in the range of 3200–3500 cm-1 , corresponding to -OH groups, presence of CA. A new peak at 1725 cm-1 confirmed the formation of chemical linkages between CA and CS-EC. The results of the thermal analysis revealed that a thermally stable membrane was obtained when it was chemically cross-linked compared to non-cross-linked membranes. The IEC values of the modified membranes were enhanced significantly, increasing from 0.08 mmol/g for pure CS to 0.5 mmol/g for CS (50%) and 0.8 mmol/g for CS (50%) cross-linked withCA. Furthermore, the cross-linked membranes demonstrated the lowest water and ethanol uptake values, emphasizing their suitability for fuel cell applications. KW - Polyelectrolyte membranes PY - 2025 DO - https://doi.org/10.1063/5.0279022 SN - 1089-7666 VL - 37 IS - 8 SP - 1 EP - 11 PB - AIP Publishing AN - OPUS4-63890 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Böhning, Martin A1 - Tidjani, Adams A1 - Wald, Oliver A1 - Brzezinka, Klaus-Werner A1 - Turky, Gamal A1 - Goering, Harald A1 - Schartel, Bernhard A1 - Schönhals, Andreas T1 - Dielectric and gas transport properties of polypropylene-clay 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 5.4 SP - 425 CY - Bad Honnef AN - OPUS4-2036 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular Mobility and Gas Transport of Polymer Based Nanocomposites T2 - International Seminar on Nanomaterials -Experiments and Simulations - Festseminar anläßlich des 80. Geburtstages von Prof. M. Kryszewski, ehemaliges Mitglied des Präsidium der Polnischen Akademie der Wissenschaften. Eingeladener Vortrag CY - Lodz, Poland DA - 2005-04-15 PY - 2005 AN - OPUS4-7311 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Conductivity and Gas Sorption Properties of Carbon Nanotube / Polycarbonate Nanocomposites T2 - Frühjahrstagung der Deutschen Physikalischen Gesellschaft (DPG) CY - Berlin, Germany DA - 2005-03-04 PY - 2005 AN - OPUS4-7129 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Konnertz, Nora A1 - Ding, Yi A1 - Harrison, W.J. A1 - Budd, P.M. A1 - Schönhals, Andreas A1 - Böhning, Martin T1 - Molecular mobility of the high performance membrane polymer PIM-1 as investigated by dielectric spectroscopy N2 - The increasing demand for energy efficient separation processes fosters the development of new high performance polymers as selective separation layers for membranes. PIM-1 is the archetypal representative of the class of polymers of intrinsic microporosity (PIM) which are considered most promising in this sector, especially for gas separations. Since their introduction, PIMs stimulated a vast amount of research in this field and meanwhile evolved to the state of the art in membrane technology for gas separation. The major obstacle for extending the practical membrane application is their strong tendency to physical aging. For the first time, investigations by broadband dielectric spectroscopy (BDS) addressing molecular dynamics and conductivity in PIM 1 are presented. As chain packing during film formation from the casting solution and physical aging are key factors determining the separation performance of PIMs as membrane materials, characterization of the molecular mobility in such materials as revealed by BDS will provide valuable information for further development and optimization. KW - PIM-1 KW - BDS broadband dielectric spectroscopy KW - Relaxation KW - Membrane PY - 2016 DO - https://doi.org/10.1021/acsmacrolett.6b00209 SN - 2161-1653 VL - 5 IS - 4 SP - 528 EP - 532 PB - ACS American Chemical Society CY - Washington, DC, USA AN - OPUS4-35798 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Konnertz, Nora A1 - Böhning, Martin A1 - Schönhals, Andreas A1 - Ding, Yi T1 - Molecular mobility and gas transport properties of PIM-1 and nano composites based on PIM-1 and phenethylPOSS N2 - Polymers with intrinsic microporosity are of highly interest in the field of gas separation membranes. Especially the first synthesized PIM-1 shows extraordinary permeabilities and selectivities. Unfortunately, PIM-1 tends to physical aging and loses its good properties. Physical aging is related to the molecular mobility of PIM-1 which was here investigated by broadband dielectric spectroscopy (BDS). Besides the studies on pure PIM-1 a polyhedral oligomeric silsesquioxane with phenethyl substituents (PhenethylPOSS) was used as nanofiller (0 - 40 wt-%) in the PIM-1 matrix to improve the gas transport properties and prevent physical aging. The molecular mobility of the solution casted nano composite films was analyzed by BDS as well. Furthermore, gas transport properties were determined with the time lag method (0 - 20 bar) in a temperature range of 35°C to 65°C with N2, O2, CH4 and CO2. T2 - 80. Jahrestagung der DPG und DPG-Frühjahrstagung CY - Regensburg, Germany DA - 06.03.2016 KW - PIM-1 PY - 2016 AN - OPUS4-35541 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zorn, R. A1 - Yin, Huajie A1 - Lohstroh, W. A1 - Harrison, W. A1 - Budd, P.M. A1 - Pauw, Brian Richard A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - Anomalies in the low frequency vibrational density of states for a polymer with intrinsic microporosity - the Boson peak of PIM-1 N2 - Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, the vibrational density of states (VDOS) for PIM-1, the prototypical polymer with intrinsic microporosity, is investigated by means of inelastic neutron scattering. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid). The measured data show the characteristic low frequency excess contribution to VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers. For an annealed PIM-1 sample, the Boson peak shifts to higher frequencies in comparison to the un-annealed sample. These changes in the VDOS of the annealed PIM-1 sample are related to changes in the microporous structure as confirmed by X-ray scattering. KW - Polymers KW - Boson peak KW - Neutron scattering KW - Physical aging KW - Polymer of intrinsic microporosity PY - 2018 DO - https://doi.org/10.1039/C7CP07141H SN - 1463-9076 SN - 1463-9084 VL - 20 IS - 3 SP - 1355 EP - 1363 PB - The Royal Society of Chemistry AN - OPUS4-43808 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yin, Huajie A1 - Chua, Y. Z. A1 - Yang, B. A1 - Schick, C. A1 - Harrison, W. A1 - Budd, P. A1 - Böhning, Martin A1 - Schönhals, Andreas T1 - First clear cut experimental evidence for a glass transition in a polymer with intrinsic microporosity: PIM-1 N2 - Polymers with intrinsic microporosity (PIMs) represent a novel, innovative class of materials with great potential in various applications from high-performance gas separation membranes to electronic devices. Here for the first time, for PIM-1, as the archetypal PIM, fast scanning calorimetry provides definitive evidence for a glass transition (Tg=715 K, heating rate 3·10^4 K/s) by decoupling the time-scales responsible for glass transition and decomposition. As the rigid molecular structure of PIM-1 prevents any conformational changes, small-scale bend and flex fluctuations must be considered the origin of its glass transition. This result has strong implications for the fundamental understanding of the glass transition and for the physical aging of PIMs and other complex polymers, both topical problems of materials science. KW - Polymers with intrinsic microporosity KW - Fast Scanning Calorimetry PY - 2018 DO - https://doi.org/10.1021/acs.jpclett.8b00422 SN - 1948-7185 VL - 9 IS - 8 SP - 2003 EP - 2008 PB - ACS AN - OPUS4-44683 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas T1 - Molecular mobility and physical aging of polymers with intrinsic microporosity as revealed by dielectric spectroscopy N2 - The dielectric properties of different polymers with intrinsic microporosity are investigated by braodband dielectric spectroscopy. The results are discussed with regard to the structure T2 - Spring Meeting of German Physical Society CY - Berlin, Germany DA - 12.03.2018 KW - Polymers with intrinsic microporosity KW - Gas separation membranes KW - Dielectric spectroscopy PY - 2018 AN - OPUS4-44490 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -