TY - CONF A1 - Szymoniak, Paulina A1 - Schönhals, Andreas T1 - Rigid amorphous phase in polymer nanocomposites as revealed by dielectric relaxation spectroscopy and fast scanning calorimetry N2 - For inorganic/polymer nanocomposites a so-called Rigid Amorphous Phase (RAF) is formed in the interfacial region by adsorption of polymer segments onto the nanoparticles. The segmental dynamics of RAF is expected to be altered, as compared to the pure matrix, which might percolate into the entire system, affecting the overall nanocomposite properties. A combination of two relaxation spectroscopy techniques (Broadband Dielectric Spectroscopy (BDS) and Specific Heat Spectroscopy (SHS) in a form of Temperature Modulated DSC (TMDSC)) as well as Fast Scanning Calorimetry (FSC) was employed to investigate the structure and molecular mobility of nanocomposites based on Epoxy and Layered Doubled Hydroxides with different nanoparticle content. First, BDS investigations proved the existence of a process, which is present only for nanocomposites, assigned to the dynamics of polymer segments within RAF. Second, the amount of RAF was quantified by analyzing the change of specific heat capacity step of nanocomposites, comparing to the pure material. Thirdly, the glass transition of nanocomposites was studied with FSC, applying high heating rates (500-10 000 K/s). Considering that all techniques probe essentially the same molecular process, an activation plot was constructed, delivering a complete picture of the molecular mobility and structure of the polymer nanocomposites including RAF. T2 - American Physical Society (APS) March Meeting 2019 CY - Boston, MA, USA DA - 04.03.2019 KW - Nanocomposites KW - Rigid amorphous fraction PY - 2019 AN - OPUS4-47564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Szymoniak, Paulina A1 - Schönhals, Andreas T1 - Rigid Amorphous Phase in Epoxy-based Nanocomposites as Revealed by Dielectric Spectroscopy and Fast Scanning Calorimetry N2 - For inorganic/polymer nanocomposites a so-called Rigid Amorphous Phase (RAF) is formed in the interfacial region by adsorption of polymer segments onto the nanoparticles. The segmental dynamics of RAF is expected to be altered, as compared to the pure matrix, which might percolate to the entire system, affecting the overall nanocomposite properties. A combination of two relaxation spectroscopy techniques (Broadband Dielectric Spectroscopy (BDS) and Temperature Modulated DSC (TMDSC)) as well as Fast Scanning Calorimetry (FSC) was employed to investigate the structure and molecular mobility of nanocomposites based on Epoxy and Layered Doubled Hydroxides with different nanoparticle content. First, BDS investigations proved the existence of a process, which is present only for nanocomposites, assigned to the dynamics of polymer segments within RAF. Second, the amount of RAF was quantified by analyzing the change of specific heat capacity step of nanocomposites, comparing to the pure material. Thirdly, the glass transition of nanocomposites was studied with FSC, applying high heating rates (0.5-10 kK/s). Considering that all techniques probe essentially the same molecular process, an activation plot was constructed, delivering a complete picture of the molecular mobility and structure of the polymer nanocomposites including RAF. T2 - DPG-Frühjahrstagung 2019 CY - Regensburg, Germany DA - 01.04.2019 KW - Rigid amorphous fraction KW - Nanocomposites PY - 2019 AN - OPUS4-47762 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Szymoniak, Paulina A1 - Schönhals, Andreas A1 - Madkour, Sherif T1 - Multiple Glassy Dynamics of an Asymmetric PVME/PS Blend Investigated by Broadband Dielectric and Specific Heat Spectroscopy N2 - Over the past decades research on the molecular dynamics of miscible polymer blends is of topical interest in the literature, to understand the segmental mobility of individual components, as it is affected by blending. In general, miscible polymer blends exhibit a complex dynamic behavior. For an A/B blend the relaxation times of component A and component B are affected by the spatial local compositional heterogeneity, present in binary systems on a microscopic level, regardless of the macroscopic homogeneity. Here, a combination of broadband dielectric and specific heat spectroscopy was employed to study the dynamically asymmetric PVME/PS blend with seven different compositions, focusing on samples with high PS contents. Considering that PS is dielectrically invisible, BDS is a powerful technique to study the response of PVME, as it is affected by PS segments. Here, three separate relaxation processes were found by dielectric investigations, related to confined or constrained PVME segments due to the spatial local compositional heterogeneities, which is in contrary to the previous literature findings [1]. Moreover, the dielectric data was compared with results obtained by specific heat spectroscopy, where a fourth relaxation process was found, due to the cooperative fluctuations of PVME and PS. [1] Colmenero, J., Arbe, A. Soft Matter, 2007, 3, 1474. T2 - DPG-Frühjahrstagung 2019 CY - Regensburg, Germany DA - 01.04.2019 KW - Specific heat spectroscopy KW - Polymer blends KW - Dielectric spectroscopy PY - 2019 AN - OPUS4-47764 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 - Yildirim, Arda A1 - Szymoniak, Paulina A1 - Sentker, K. A1 - Butschies, M. A1 - Bühlmeyer, A. A1 - Huber, P. A1 - Laschat, S. A1 - Schönhals, Andreas T1 - Dynamics and ionic conductivity of ionic liquid crystals forming a hexagonal columnar mesophase N2 - For the first time, the molecular mobility of two linear-shaped tetramethylated guanidinium triflate ionic liquid crystals (ILCs) having different length of alkyl chains were investigated by a combination of broadband dielectric spectroscopy (BDS) and specific heat spectroscopy (SHS). By self-assembly, these ILCs can form a hexagonal ordered mesophase besides plastic crystalline phases and the isotropic state. Three dielectric active processes were found by BDS for both samples. At low temperatures, a γ-process in the plastic crystalline state is observed which is assigned to localized fluctuations of methyl groups including nitrogen atoms in the guanidinium head. At higher temperatures but still in the plastic crystalline state, an α1-process takes place. An α2 process was detected by SHS but with a completely different temperature dependence of the relaxation times than that of the α1-relaxation. This result is discussed in detail, and different molecular assignments of the processes are suggested. At even higher temperatures, electrical conductivity is detected and an increase in the DC conductivity by four orders of magnitude at the phase transition from the plastic crystalline to the hexagonal columnar mesophase is found. This result is traced to a change in the charge transport mechanism from a delocalized electron hopping in the stacked aromatic systems (in the plastic phase) to one dominated by an ionic conduction in the quasi-1D ion channels formed along the supermolecular columns in the ILCs hexagonal mesophases. KW - Ionic liquid crystalls PY - 2018 DO - https://doi.org/10.1039/c7cp08186c SN - 1463-9084 SN - 1463-9076 VL - 20 IS - 8 SP - 5626 EP - 5635 PB - Royal Society of Chemistry AN - OPUS4-44254 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Szymoniak, Paulina A1 - Madkour, Sherif A1 - Schönhals, Andreas T1 - Unexpected behavior of thin PVME/PS blend films investigated by specific heat spectroscopy N2 - The structure and molecular dynamics of thin polymer films are of topical interest of soft matter-physics. Commonly, spatial structural heterogeneities of 1D confined thin films (surface, bulk-like and adsorbed layer), are expected to alter the glassy dynamics, compared to the bulk. Here, Specific Heat Spectroscopy (SHS) was used, to investigate the glassy dynamics of thin films of an asymmetric miscible PVME/PS 25/75 wt% blend. SHS measurements showed a non-monotonous thickness dependence of the dynamic Tg, on the contrary to the previously investigated PVME/PS 50/50 wt%. For PVME/PS 25/75 wt% thin films (> 30 nm), due to the presence of PVME-rich adsorbed and surface layers, the bulk-like layer experienced a thickness dependent increase of PS concentration. This led to a systematic increase of dynamic Tg. Further decrease of the film thickness (< 30 nm), resulted in a decrease of dynamic Tg, ascribed to the influence of the surface layer, which has a high molecular mobility. This is the first study, which shows deviations of dynamic Tg of thin films, compared to the bulk, resulting from the counterbalance of the free surface and adsorbed layer. T2 - Spring Meeting of German Physical Society CY - Berlin, Germany DA - 12.03.2018 KW - Thin polymeric films PY - 2018 AN - OPUS4-44494 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schönhals, Andreas A1 - Madkour, Sherif A1 - Szymoniak, Paulina T1 - Unraveling the dynamics of thin films of a miscible PVME/PS blend N2 - Dielectric spectroscopy (BDS) was employed to investigate the dynamics of thin films (7 – 200 nm) of a Poly (vinyl methyl ether) (PVME) / Polystyrene (PS) blend (50:50 wt%). For the BDS measurements Nano-Structured Capacitors (NSC) were employed, where films have a free surface. This method was applied for film thicknesses up to 36 nm. Thicker films were prepared between Crossed Electrodes Capacitors (CEC). The spectra of the films showed multiple processes. The first process was assigned to the -relaxation of a bulk-like layer. For films measured by NSC, its rates were higher compared to that of the bulk blend. This behavior was related to a PVME-rich free-surface layer. A second process was observed for films measured by CEC (process X) and the 36 nm film measured by NSC (process X2). This process was assigned to fluctuations of PVME constraint by PS. Its activation energy was found to be thickness dependent, due to the evidenced thickness dependency of the compositional heterogeneity. Finally, a third process with an activated temperature-dependence was observed for all films measured by NSC (process X1). It resembled the molecular fluctuations in an adsorbed layer found for films of pure PVME. T2 - Anual Meeting of the American Physical Society CY - Los Angeles, CA, USA DA - 05.03.2018 KW - Thin polymeric films PY - 2018 AN - OPUS4-44414 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Szymoniak, Paulina A1 - Madkour, Sherif A1 - Schönhals, Andreas T1 - Dynamics of nanoscopically confined PVME in thin films of an asymmetric PVME/PS blend N2 - In recent years, substantial efforts have been devoted to investigating nanoscopic confinement of polymers, and its effect on glassy dynamics. Broadband Dielectric Spectroscopy (BDS) was used to study the dynamics of ultra-thin films of PVME/PS 50/50 wt% blend, employing a novel nano-structured capacitor sample arrangement. The investigated system shows a complex dynamic behavior. First, an α-relaxation, related to a bulk-like layer was found. Second, an α’-relaxation was observed, characteristic for dynamically asymmetric blends, where the out of equilibrium dynamics is attributed to weakly-cooperative PVME segments relaxing within a frozen environment of PS segments. Thirdly, for thinnest films, an Arrhenius-like process was dominant in the dielectric spectra, indicating localized fluctuations of the segments. Relaxation rates of this process resembled that of the degenerated α-relaxation of the adsorbed layer, found for pure PVME, thus it was assigned accordingly. For thinnest films, this process undergoes a further confinement, due to the topological constraints, introduced by PS. Such multiple confinement effect has not been reported for ultra-thin films of polymer blends, before this study. T2 - Spring Meeting of German Physical Society CY - Berlin, Germany DA - 12.03.2018 KW - Thin polymeric films PY - 2018 AN - OPUS4-44502 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Szymoniak, Paulina A1 - Silbernagl, Dorothee A1 - Sturm, Heinz A1 - Ghasem Zadeh Khorasani, Media A1 - Schönhals, Andreas T1 - Competition of mobilization and immobilization effects of segmental dynamics in epoxy/Boehmite nanocomposites N2 - The polymer matrix region near a filler surface, termed as the interface, witnessed increasing interest, due to its possible influence on the macroscopic properties of the nanocomposite. The interphase is expecting to have different segmental dynamic, as compared to the pure matrix, which can percolate into the entire system. Here, the segmental dynamics of epoxy/Boehmite nanocomposite was studied by Broadband Dielectric Spectroscopy. It was found that an artificial relaxation process is present in the nanocomposite, on the contrary to the pure epoxy system. It was assigned to constrained fluctuations of polymer chains in the interfacial region, due to the nanofiller. However, the overall dynamic Tg of the system decreased with increasing filler concentration, indicating higher segmental mobility. This was in accordance with Temperature Modulated DSC investigations of specific heat capacity of the system, which was found to increase with increasing filler concentration, up to 10 wt%, indicating increasing mobility of the polymer matrix segments. Surprisingly, for the highest filler content, the heat capacity decreases, implying a formation of an immobilized rigid amorphous phase in the interfacial region. T2 - Spring Meeting of German Physical Society CY - Berlin, Germany DA - 12.03.2018 KW - Nanocomposites PY - 2018 AN - OPUS4-44503 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 - 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 - CONF A1 - Schönhals, Andreas A1 - Yin, Huajie A1 - Kolmangadi, Mohamed Aejaz A1 - Emamverdi, Farnaz A1 - Zorn, R. A1 - Szymoniak, Paulina A1 - Böhning, Martin 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 - Szymoniak, Paulina A1 - Omar, Hassan A1 - Schönhals, Andreas A1 - Qu, Xintong T1 - Spatial Inhomogeneity, Interfaces and Complex Vitrification Behavior of Epoxy-based Materials by Broadband Dielectric Spectroscopy and Calorimetry N2 - Although in the last decades epoxy-based nanocomposites have been successfully adopted by the marine, automotive and aerospace industries they are still rarely studied on a fundamental level. This work deals with an in-depth comparative investigation of the structure, molecular mobility and vitrification kinetics of three bisphenol A diglycidyl ether (DGEBA)-based materials with different nanofillers: I) taurine-modified layered double hydroxide (T-LDH), II) boehmite (BNPs) and III) halloysite nanotubes (HNTs). Moreover, the effect of different hardeners (diethylene triamine and methyl tetrahydrophtalic acid anhydride) on the unfilled epoxy matrix is addressed as well. The chosen methodology comprises I) small – and wide – angle X-ray scattering (SAXS/WAXS) II) calorimetry in the forms of a) conventional DSC and b) static fast scanning calorimetry (FSC), III) broadband dielectric spectroscopy (BDS), as well as IV) specific heat spectroscopy in the forms of a) temperature modulated DSC, and b) temperature modulated FSC. The combination of these techniques proved an intrinsic spatial heterogeneity of epoxy-based materials, evidenced by two separate segmental relaxation processes. Although, depending on the hardener the response of the systems to calorimetric and dielectric investigations was different, in a broader sense similar conclusions can be extracted on the structural heterogeneity. As expected from the two distinct α-processes, it was shown that, in parallel to the main glass transition, epoxy-based materials can exhibit an additional low temperature vitrification mechanism, which was not discussed in prior studies for an unfilled network former. Furthermore, the interfacial region (so-called rigid amorphous fraction) was qualitatively and quantitatively addressed, in dependence of the employed nanofiller structure. T2 - Webinar University of Southern Denmark CY - Online meeting DA - 20.01.2021 KW - BDS KW - Nanocomposites KW - Epoxy KW - Rigid amorphous fraction KW - TMDSC KW - Flash DSC PY - 2021 AN - OPUS4-52036 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kolmangadi, Mohamed Aejaz A1 - Schönhals, Andreas A1 - Szymoniak, Paulina A1 - Smales, Glen Jacob A1 - Böhning, Martin T1 - Molecular dynamics of Janus Polynorbornenes: Glass Transitions and Nanophase separation N2 - We report the dielectric and calorimetric investigations of an homologous series of Janus polynorbornenes with rigid main backbone and flexible -Si(OR)3 side groups, of differing length alkyl chains (R = Propyl, Butyl, Hexyl, Octyl, Decyl). Dielectric dispersion reveals two active processes at low temperatures, denoted as β- and α- relaxation. The former can be assigned to localized fluctuations, whilst the latter relates to the glassy dynamics of the flexible -Si(OR)3 side groups, that creates a nanophase separation in both the alkyl chain rich and backbone rich domains. Temperature modulated DSC measurements and X-ray scattering experiment confirm the nanophase separation. Fast Scanning Calorimetry employing both fast heating and cooling rates detects the glass transition temperatures of the backbone rich domains, which are beyond or near to their degradation temperatures in terms of conventional DSC. The cooperative length scale of glass transition and 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. T2 - IDS Online conference 2021 CY - Online meeting DA - 06.09.2021 KW - Glass transition KW - Conductivity KW - Dynamics KW - Fast Scanning Calorimetry PY - 2021 AN - OPUS4-53299 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Szymoniak, Paulina A1 - Omar, Hassan A1 - Schönhals, Andreas T1 - Spatial Inhomogeneity, Interfaces and Complex Vitrification Behavior of Epoxy-based Materials N2 - This work deals with an in-depth comparative investigation of the structure, molecular mobility and vitrification kinetics of three bisphenol A diglycidyl ether (DGEBA)-based materials with different nanofillers: taurine-modified layered double hydroxide (T-LDH) and halloysite nanotubes (HNTs). The chosen methodology comprises I) small – and wide – angle X-ray scattering (SAXS/WAXS) II) calorimetry in the forms of a) conventional DSC and b) static fast scanning calorimetry (FSC), III) broadband dielectric spectroscopy (BDS), as well as IV) specific heat spectroscopy in the forms of a) temperature modulated DSC, and b) temperature modulated FSC. T2 - Abteilungsseminar 6. - FB 6.6 CY - Online meeting DA - 06.05.2021 KW - Broadband dielectric spectroscopy KW - Epoxy nanocomposites KW - Halloysite nanotubes KW - X-ray scattering KW - Differential scanning calorimetry KW - Rigid amorphous fraction KW - Flash DSC PY - 2021 AN - OPUS4-52697 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kolmangadi, Mohamed Aejaz A1 - Szymoniak, Paulina 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 a 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, and 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, while 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 differential scanning calorimetry (TMDSC) 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 complemented with scattering experiments that show how the size of the alkyl chain-rich domains increases with the side 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. T2 - DPG Online Spring Conference 2021 CY - Online meeting DA - 22.03.2021 KW - Dynamics KW - Glass transition KW - Conductivity PY - 2021 AN - OPUS4-52335 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fortini, Renata A1 - Meyer-Plath, A. A1 - Kehren, D. A1 - Gernert, U. A1 - Agudo Jácome, Leonardo A1 - Sturm, Heinz T1 - Measurement of flexural rigidity of multi-walled carbon nanotubes by Dynamic Scanning Electron Microscopy N2 - In this work the flexural rigidity of individual large diameter multi-walled carbon nanotubes (MWCNTs) was investigated. The bending modulus were obtained by detecting the resonance frequencies of mechanically excited cantilevered carbon nanotubes using the so-called dynamic scanning electron microscopy technique, and applying the Euler–Bernoulli beam theory. For the nanotubes studied, we determined a modulus of up to 160 GPa. This agrees with values reported by other authors for MWCNTs produced by catalytic chemical vapor deposition, however, it is 6-8 times smaller than values reported for single and multi-walled carbon nanotubes produced by arc-discharge synthesis. Toxicological studies with carbon nanotubes have been showing that inhaled airborne nanofibers that reach the deep airways of the respiratory system may lead to serious, asbestos-like lung diseases. These studies suggested that their toxicity critically depends on the fiber flexural rigidity, with high rigidity causing cell lesions. To complement the correlation between observed toxicological effects and fiber rigidities, reliable and routinely applicable measurement techniques for the flexural rigidity of nanofibers are required. KW - Flexural rigidity KW - Bending modulus KW - Resonance frequency KW - Carbon nanotubes KW - Fiber toxicology PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-514190 DO - https://doi.org/10.3390/fib8050031 SN - 2079-6439 VL - 8 IS - 5 SP - 31 PB - MDPI AN - OPUS4-51419 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Ciornii, Dmitri A1 - Hodoroaba, Vasile-Dan A1 - Benismail, Nizar A1 - Altmann, Korinna T1 - Project 2: Interlaboratory Comparison on detection and quantitative assessment of microplastics by use of spectroscopic and thermo-analytical methods N2 - Validated and standardized methods in microplastic analysis are indispensable for robust monitoring and regulation. Alongside also reference materials are urgently needed. An interlaboratory comparison (ILC) offers a powerful tool to address both these challenges. The present study aimed to compare the precision and accuracy of various methods for the detection and quantification of microplastic in a water-soluble matrix. Additionally, it evaluated the suitability of the test materials (containing environmentally relevant plastic polymers) to serve as reference materials for the microplastic analysis. In this ILC several most used thermo-analytical and spectroscopic methods have been addressed: Pyrolysis-Gas Chromatography Mass Spectrometry (Py-GC/MS), Thermal Extraction-Desorption Gas Chromatography Mass Spectrometry (TED-GC/MS), micro-Fourier Transform Infrared Spectroscopy (µ-FTIR), and micro-Raman Spectroscopy and Laser Direct Infrared Spectroscopy (LDIR). Microplastic powders of polyethylene (PE) and polyethylene terephthalate (PET) were used to assess suitability of the test materials (microplastic tablets) for method validation and use in the ILCs. The participants were guided with a SOP how to dissolve the test samples and, depending on their selected method, either quantify the number of particles (by the spectroscopic methods) or determine the mass fraction of microplastic particles per sample (by the thermo-analytical methods). KW - ILC KW - Microplastic KW - FTIR KW - Raman KW - TED-GC/MS KW - Py-GC/MS PY - 2024 SP - 1 EP - 16 AN - OPUS4-60612 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Smales, Glen Jacob A1 - Pauw, Brian Richard T1 - DACHS/MOFs/AutoMOFs_2/Synthesis N2 - The DACHS (Database for Automation, Characterization and Holistic Synthesis) project aims to create completely traceable experimental data, covering syntheses, measurements, analyses, and interpretations. DACHS_MOFs focuses on the synthesis and characterisation of metal-organic frameworks, across multiple, automation-assisted experimental series (AutoMOFs), with the overall goal of producing reproducible MOF samples through tracking of the synthesis parameters. DACHS_MOFs is simultaneously used to test the DACHS principles. This upload contain synthesis data from AutoMOFs_2 in HDF5 format (.h5). Each .h5 file contains detailed information on the chemical, experimenal, and synthesis parameters used during the synthesis of a single AutoMOF sample. KW - Automation KW - Procedure KW - Synthesis KW - Traceability PY - 2024 DO - https://doi.org/10.5281/zenodo.11236074 PB - Zenodo CY - Geneva AN - OPUS4-60611 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen T1 - Low Molar Mass Cyclic Poly(L-lactide)s: Separate Transesterification Reactions of Cycles and Linear Chains in the Solid State N2 - L-Lactide (LA) was polymerized with neat tin(II) 2-ethylhexanoate (SnOct2) in toluene at 115 °C at low concentration with variation of the LA/Cat ratio. Cyclic polylactides (cPLAs) with number average molecular weights (Mn) between 7 000 and 17 000 were obtained. MALDI-TOF mass spectrometry also revealed the formation of a few percent of linear chains. Crystalline cPLAs with Mn around 9 000 and 14 000 were annealed at 140 °C in the presence of ScOct2 or dibutyl-2-stanna-1,3-dithiolane (DSTL). Simultaneously, crystallites of extended linear chains and crystallites of extended cycles were formed regardless of the catalyst, indicating that transesterification reaction proceeded different for linear chains and for cycles, governed by thermodynamic control. The formation of extended chain crystallites with low dispersity indicates the existence of symproportionation of short and long chains. A complementary experiment was carried out with a PLA ethyl ester composed mainly of linear chains with a small fraction of cycles KW - Polylactide KW - MALDI-TOF MS KW - Annealing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-606228 DO - https://doi.org/10.1039/D4SM00567H SN - 1744-6848 SP - 1 EP - 12 PB - Royal Society of Chemistry (RSC) AN - OPUS4-60622 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 - CONF A1 - Waniek, Tassilo A1 - Ghasem Zadeh Khorasani, Media A1 - Braun, Ulrike A1 - Silbernagl, Dorothee A1 - Sturm, Heinz T1 - Water as side effect of reinforcing boehmite filler Local changes in anhydride cured epoxy resin N2 - Nanocomposites offer wide opportunities for lightweight constructions and enable reduction of weight and volume. Beside macroscopic toughening nanoparticle reinforced polymers show a soft interface around boehmite (AlOOH) filler nanoparticles. A related strong interaction between boehmite and the anhydride cured resin system is widely suspected in literature but not determined by structural Analysis. Determination of the molecular structure is important to allow simulations approaching the real system and predict future reinforcing effects. DRIFT (diffuse refletance infrared fourier transformed) spectra of the boehmite reinforced anhydride cured epoxy show significant changes in the molecular structure compared to the neat polymer. Further investigations of the interactions between the single components of the resin system and the boehmite filler pointed out reactions between released water released from the boehmite filler and the anhydride hardener or amine accelerator. This leads to the discussion of competing polymerisation mechanisms that highly influence the polymer properties. Ongoing experiments and literature research approve that this impact of water is able to locally change the stoichiometrie, alter the curing mechanism or support an inhomogeneous crosslink density. T2 - Polydays 2019 CY - Erwin-Schrödinger-Zentrum, Berlin Adlershof, Germany DA - 11.09.2019 KW - Nanocomposites KW - Epoxy KW - FTIR spectroscopy KW - Boehmite alumina PY - 2019 AN - OPUS4-49010 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 - CONF A1 - Ghasem Zadeh Khorasani, Media A1 - Silbernagl, Dorothee A1 - Sturm, Heinz T1 - Mechanical and chemical alteration of polymer matrix induced by nanoparticles in epoxy-boehmite nanocomposites N2 - Inorganic nanoparticles are used to improve the performance of epoxy as the matrix phase in fiber-reinforced composites used for aerospace applications. The effectiveness of nanofillers on property enhancement of thermosetting polymers depends on many factors including the interaction between the functional groups of nanofillers and the polymer reactants. In the current work, we study the effect of boehmite nanoparticles (BNPs) on properties of anhydride-cured bisphenol-A-diglycidyl ether (DGEBA). Dynamic mechanical thermal analysis (DMTA) and a high-resolution force measurement approach called intermodulation atomic force microscopy (ImAFM) were carried out to investigate the thermomechanical and nanomechanical properties of this material, respectively. It was found that BNPs lead to decrease of glass transition temperature (Tg) and crosslink density of the polymer network meanwhile significantly enhancing the Young’s modulus. Besides formation of a soft interphase near the particles, significant changes in local stiffness of polymer matrix far from the interphase was observed with ImAFM. Thus, boehmite induces long-range chemical alteration on the matrix. This effect has a higher impact on overall composite properties compared to the formation of interphase which is only a short-range effect. The local chemical evaluations on the soft interphase using an infrared-AFM method (NanoIR) revealed the accumulation of anhydride hardener near the boehmite interface. Based on these observations the effect of boehmite on the curing of epoxy is hypothesized to be governed by the strong interaction between boehmite and the anhydride. This interaction causes changes the ratio of reactants in the epoxy mixture and hence alteration of curing pathway and the network architecture. In future studies we examine this hypothesis by measuring the thermomechanical properties of cured epoxies in which the epoxy-hardener ratio is systematically altered and further comparing to those properties of nanocomposites shown in the current study. T2 - HYMA 6th International Conference on Multifunctional, Hybrid and Nanomaterials CY - Sitges, Spain DA - 11.03.2019 KW - Nanomechanics KW - Polymer nanocomposites KW - Boehmite KW - AFM KW - Epoxy PY - 2019 AN - OPUS4-50692 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Waniek, Tassilo A1 - Ghasem Zadeh Khorasani, Media A1 - Braun, Ulrike A1 - Silbernagl, Dorothee A1 - Sturm, Heinz T1 - New Focus On Boehmite-Reinforced Nanocomposites Molecular Approach With Advanced FTIR-Techniques N2 - By FTIR-study it was possible to proof a chemical reaction between boehmite and the hardener of anhydride cured epoxy resins. Future studies can assume that the chemical environment of the resin system is changed in the surrounding of boehmite nanoparticles. This highly affects especially localized properties. T2 - 6th International Conference on Multifunctional, Hybrid and Nanomaterials CY - Sitges, Spain DA - 11.03.2019 KW - Nanocomposite KW - Boehmite KW - FTIR KW - DRIFTS KW - Epoxy PY - 2019 AN - OPUS4-47785 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Elert, Anna Maria A1 - Chen, Yong-Cin A1 - Smales, Glen J. A1 - Topolniak, Ievgeniia A1 - Sturm, Heinz A1 - Schönhals, Andreas A1 - Szymoniak, Paulina T1 - Effects of the charge density of nanopapers based on carboxymethylated cellulose nanofibrils investigated by complementary techniques N2 - Cellulose nanofibrils (CNFs) with different charge densities were prepared and investigated by a combination of different complementary techniques sensitive to the structure and molecular dynamics of the system. The morphology of the materials was investigated by scanning electron microscopy (SEM) and X-ray scattering (SAXS/WAXS). The latter measurements were quantitatively analyzed yielding to molecular parameters in dependence of the charge density like the diameter of the fibrils, the distance between the fibrils, and the dimension of bundles of nanofibrils, including pores. The influence of water on the properties and the charge density is studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and broadband dielectric spectroscopy. The TGA measurements reveal two mass loss processes. The one at lower temperatures was related to the loss of water, and the second process at higher temperatures was related to the chemical decomposition. The resulting char yield could be correlated to the distance between the microfibrils. The DSC investigation for hydrated CNFs revealed three glass transitions due to the cellulose segments surrounded by water molecules in different states. In the second heating scan, only one broad glass transition is observed. The dielectric spectra reveal two relaxation processes. At low temperatures or higher frequencies, the β-relaxation is observed, which is assigned to localized fluctuation of the glycosidic linkage. At higher temperatures and lower frequencies, the α-relaxation takes places. This relaxation is due to cooperative fluctuations in the cellulose segments. Both processes were quantitatively analyzed. The obtained parameters such as the relaxation rates were related to both the morphological data, the charge density, and the content of water for the first time. KW - Cellulose nanofibrils PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600528 DO - https://doi.org/https://doi.org/10.1021/acsomega.4c00255 SN - 2470-1343 VL - 9 SP - 20152 EP - 20166 PB - ACS AN - OPUS4-60052 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fahmy, A. A1 - Anis, B. A1 - Szymoniak, Paulina A1 - Altmann, Korinna A1 - Schönhals, Andreas T1 - Graphene Oxide/Polyvinyl Alcohol–Formaldehyde Composite Loaded by Pb Ions: Structure and Electrochemical Performance N2 - An immobilization of graphene oxide (GO) into a matrix of polyvinyl formaldehyde (PVF) foam as an eco-friendly, low cost, superior, and easily recovered sorbent of Pb ions from an aqueous solution is described. The relationships between the structure and electrochemical properties of PVF/GO composite with implanted Pb ions are discussed for the first time. The number of alcohol groups decreased by 41% and 63% for PVF/GO and the PVF/GO/Pb composite, respectively, compared to pure PVF. This means that chemical bonds are formed between the Pb ions and the PVF/GO composite based on the OH groups. This bond formation causes an increase in the Tg values attributed to the formation of a strong surface complexation between adjacent layers of PVF/GO composite. The conductivity increases by about 2.8 orders of magnitude compared to the values of the PVF/GO/Pb composite compared to the PVF. This means the presence of Pb ions is the main factor for enhancing the conductivity where the conduction mechanism is changed from ionic for PVF to electronic conduction for PVF/GO and PVF/GO/Pb. KW - Graphene oxide KW - Polyvinyl formaldehyde KW - Lead ions KW - Conductivity PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549588 DO - https://doi.org/10.3390/polym14112303 SN - 2073-4360 VL - 14 IS - 11 SP - 1 EP - 16 PB - MDPI CY - Basel AN - OPUS4-54958 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Cano Murillo, Natalia A1 - Ghasem Zadeh Khorasani, Media A1 - Silbernagl, Dorothee A1 - Emamverdi, Farnaz A1 - Cacua, K. A1 - Hodoroaba, Vasile-Dan A1 - Sturm, Heinz T1 - Carrier Fibers for the Safe Dosage of Nanoparticles in Nanocomposites: Nanomechanical and Thermomechanical Study on Polycarbonate/Boehmite Electrospun Fibers Embedded in Epoxy Resin N2 - The reinforcing effect of boehmite nanoparticles (BNP) in epoxy resins for fiber composite lightweight construction is related to the formation of a soft but bound interphase between filler and polymer. The interphase is able to dissipate crack propagation energy and consequently increases the fracture toughness of the epoxy resin. Usually, the nanoparticles are dispersed in the resin and then mixed with the hardener to form an applicable mixture to impregnate the fibers. If one wishes to locally increase the fracture toughness at particularly stressed positions of the fiber-reinforced polymer composites (FRPC), this could be done by spraying nanoparticles from a suspension. However, this would entail high costs for removing the nanoparticles from the ambient air. We propose that a fiber fleece containing bound nanoparticles be inserted at exposed locations. For the present proof-of-concept study, an electrospun polycarbonate nonwoven and taurine modified BNP are proposed. After fabrication of suitable PC/EP/BNP composites, the thermomechanical properties were tested by dynamic mechanical analysis (DMA). Comparatively, the local nanomechanical properties such as stiffness and elastic modulus were determined by atomic force microscopy (AFM). An additional investigation of the distribution of the nanoparticles in the epoxy matrix, which is a prerequisite for an effective nanocomposite, is carried out by scanning electron microscopy in transmission mode (TSEM). From the results it can be concluded that the concept of carrier fibers for nanoparticles is viable. KW - Advanced materials KW - Electrospun nanocomposite fiber KW - Nanomechanical charecteisation KW - Nanosafety KW - Epoxy nanocomposites PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-528265 DO - https://doi.org/10.3390/nano11061591 VL - 11 IS - 6 SP - 1591 PB - MDPI CY - CH - 4020 Basel, Switzerland AN - OPUS4-52826 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ghasem Zadeh Khorasani, Media A1 - Silbernagl, Dorothee A1 - Szymoniak, Paulina A1 - Hodoroaba, Vasile-Dan A1 - Sturm, Heinz T1 - The effect of boehmite nanoparticles (gamma‐AlOOH) on nanomechanical and thermomechanical properties correlated to crosslinking density of epoxy N2 - We show that complex physical and chemical interactions between boehmite nanoparticles and epoxy drastically affect matrix properties, which in the future will provide tuning of material properties for further optimization in applications from automotive to aerospace. We utilize intermodulation atomic force microscopy (ImAFM) for probing local stiffness of both particles and polymer matrix. Stiff particles are expected to increase total stiffness of nanocomposites and the stiffness of polymer should remain unchanged. However, ImAFM revealed that stiffness of matrix in epoxy/boehmite nanocomposite is significantly higher than unfilled epoxy. The stiffening effect of the boehmite on epoxy also depends on the particle concentration. To understand the mechanism behind property alteration induced by boehmite nanoparticles, network architecture is investigated using dynamic mechanical thermal analysis (DMTA). It was revealed that although with 15 wt% boehmite nanoparticles the modulus at glassy state increases, crosslinking density of epoxy for this composition is drastically low. KW - Crosslinking density KW - Epoxy KW - Intermodulation KW - Atomic force microscopy KW - Nanomechanical properties KW - Boehmite nanoparticles PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-476050 DO - https://doi.org/10.1016/j.polymer.2018.12.054 SN - 0032-3861 SN - 1873-2291 VL - 164 SP - 174 EP - 182 PB - Elsevier AN - OPUS4-47605 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Omar, Hassan A1 - Szymoniak, Paulina A1 - Hertwig, Andreas A1 - Schönhals, Andreas T1 - Growth Kinetics and Molecular Mobility of the adsorbed Layer of Poly(bisphenol-A Carbonate) (PBAC), Polysulfone (PSU), and Poly (2-Vinyl Pyridine) (P2VP) N2 - Interactions between a polymer and a substrate interface play a vital role in understanding the improvement in thin film material properties as well as serving as a model for nanocomposites. For any non-repulsive polymer-substrate interactions, polymer segments form an irreversibly adsorbed layer and show a slowdown in the glassy dynamics and thus an increase in the thermal glass transition temperature compared to the bulk-like values. The growth kinetics of the adsorbed layer obey a two-step mechanism: formation of immobilized layer with flat segmental conformations and a loosely bound layer with stretched chains pinned to the surface. Here the adsorbed layer was studied for: poly (bisphenol-A carbonate) (PBAC) and polysulfone (PSU), two bulky polymers containing a functional group (phenyl ring) in the backbone and compared to poly (2-vinyl pyridine) (P2VP), where the backbone is a vinyl-derivative and the functional group (pyridine) is in the side chain. The growth kinetics for PBAC and PSU were found to deviate from the well-known mechanism, observed for polymers such as P2VP. Atomic force microscopy and ellipsometry were used for this investigation and was additionally supported by broadband dielectric spectroscopy. T2 - Deutschen Physikalische Gesellschaft (DPG) Tagung CY - Dresden, Germany DA - 26.03.2023 KW - Thin films KW - Adsorbed Layer KW - Broadband dielectric spectroscopy KW - Atomic force microscopy KW - Growth Kinetics PY - 2023 AN - OPUS4-57282 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana A1 - Epping, Ruben T1 - View into the Depths of Copolymer Microstructure N2 - For different kinds of polymers it will be shown how it could be realized to obtain information on small, sometimes isomeric topological heterogeneities by coupling UPLC / ESI-TOF-MS and LC /MALDI-TOF-MS. T2 - DSM, Fall Meeting CY - Breda, The Netherlands DA - 07.11.2019 KW - Microstructure KW - LC-MS KW - Copolymer PY - 2019 AN - OPUS4-49587 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana A1 - Epping, Ruben T1 - Microstructure characterization of oligomers by analysis of UPLC / ESI-TOF-MS reconstructed ion chromatograms N2 - It is a well-known story that copolymers beside their molar mass distribution (MMD) can exhibit a functionality type distribution (FTD), a copolymer composition distribution (CCD), a monomer sequence distribution (MSD) and additionally different topologies within one sample. Small, often isobaric heterogeneities in topology or microstructure can usually not be simply separated chromatographically or distinguished by any common detector. Nowadays a wide range of different analytical separation techniques and multi-detection possibilities are available. The challenge consists in a clever combination of these techniques with a specific approach of data analysis. In this presentation different liquid chromatographic separation modes were combined with Electrospray Time-of-Flight mass spectrometry. The online coupling allows the analysis of reconstructed ion chromatograms (RIC) of each degree of polymerization. While a complete separation often cannot be achieved, the derived retention times and peak widths lead to information on the existence and dispersity of heterogeneities in microstructure or topology, that are otherwise inaccessible This method is suitable to detect small differences in e. g. branching, topology, monomer sequence or tacticity and could potentially be used in production control of oligomeric products or other routinely done analyses to quickly indicate deviations from set parameters. Based on a variety of examples e.g. the topology elucidation of branched EO-PO copolymers, the possibilities and limitations of this approach were demonstrated. T2 - Analyticon 2020 CY - Online meeting DA - 05.11.2020 KW - Microstructure KW - Copolymer KW - LC-MS PY - 2020 AN - OPUS4-51540 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Cornelsen Sampaio Kling, I. A1 - Pauw, Brian Richard A1 - Agudo Jácome, Leonardo A1 - Archanjo, B. S. A1 - Simão, R. A. T1 - Development and characterization of starch film and the incorporation of silver nanoparticles N2 - Starch is one of the biopolymers being used for bioplastic synthesis. For production, starch can be combined with different plasticizers, starches from different plant sources and even with nanomaterials to improve or to add film properties. The challenge of adding these, e.g. in the form of silver nanoparticles (AgNp) is to determine the concentration so as to avoid impairing the properties of the film, agglomeration or altering the visual characteristics of the film. In this study, a starch film synthesis route and the incorporation of silver nanoparticles has been proposed in order not to alter the properties of the film while maintaining the transparency and a clear colour of the starch film. The results showed that the proposed synthesis route is promising, efficient, reproducible, fast and the film has good mechanical properties. T2 - Semana MetalMat & Painal PEMM 2020 CY - Online meeting DA - 23.11.2020 KW - Biofilm KW - Silver nanoparticle KW - Starch KW - Starch nanoparticle PY - 2020 SP - 1 EP - 2 AN - OPUS4-51940 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Miliūtė, Aistė A1 - George, Janine A1 - Mieller, Björn A1 - Stawski, Tomasz T1 - ZrV2O7 negative thermal expansion (NTE) material N2 - Zirconium vanadate (ZrV2O7) is a well-known negative thermal expansion (NTE) material that exhibits significant isotropic contraction over a broad temperature range (~150°C < T < 800°C). Therefore, it can be used to create composites with controllable expansion coefficients and prevent thermal stress, fatigue, cracking, and deformation at interfaces. We implement interdisciplinary research to analyze such material. We study the influence of the synthesis methods and their parameters on the sample's purity, crystallinity, and homogeneity. Moreover, we implement ab initio-based vibrational computations with partially treated anharmonicity in combination with experimental methods to follow temperature-induced structural changes and rationalize the negative thermal expansion in this material, including the influence of the local structure disorder. T2 - SALSA Make and Measure Conference CY - Berlin, Germany DA - 13.09.2023 KW - NTE KW - Composites KW - TEM PY - 2023 AN - OPUS4-58367 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana T1 - Biobased and biodegradable Polymers: Analytical Challenges N2 - The variability and heterogeneity in their structural composition is significant for nearly all synthetic and natural polymers. Beside molar mass also functionality type distribution, copolymer composition distribution and architectural features are responsible for changing the material properties. A wide range of analytical techniques are available to get insight into these parameters. However, in most cases it is essential to combine different sophisticated techniques to get closer to actual structures and to avoid statistical averages. Different liquid chromatographic separation modes and their coupling in a two-dimensional way (SEC, LCCC, HILIC, 2D-LC) in combination with suitable detection techniques (e.g. UV, RI, LS, IR, MALDI/ESI-MS) as well as techniques like BET, DCS, SEM/TEM were applied to make structural features visible. A few aspects are discussed for structural different polylactides from various synthesis routes and their behavior in LC-MS. T2 - 34th International Symposium on Polymer Analysis and Characterization (ISPAC) CY - Stellenbosch, South Africa DA - 24.04.2023 KW - Biobased polymers KW - Biodegradable polymers KW - Analytical techniques PY - 2023 AN - OPUS4-60002 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana T1 - A Tribute to Harald –Lignin as biobased polymer-Trends and analytical issues N2 - The presentation includes aspects of material design and characterization with a focus on lignin. Examples are the structural elucidation of lignosulfonates by means of two-dimensional chromatography, the mechanochemical degradation and functionalization of Kraft-Lignin with accompanying analytics. Future projects involving the incorporation of lignin into polymers will be presented. T2 - Farewell Symposium for Prof. Harald Pasch; Polymer Analysis: Advancements in Characterization and Quantification CY - Teltow, Germany DA - 18.03.2024 KW - Lignin KW - Biobased polymers PY - 2024 AN - OPUS4-60003 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Matthews, Lauren A1 - Sahre, Mario A1 - Hesse, R. A1 - Schusterbauer, Robert A1 - Grant, M. A1 - Agudo Jácome, Leonardo A1 - Albrecht, T. A1 - Hodoroaba, Vasile-Dan T1 - Approaches to Surface Analysis of Modified Quartz Nanopipettes N2 - Nanopipettes are a type of solid-state nanopore with needle-like geometry. Their applications range from imaging, sensing, diagnostics, and use as injectors. The response of nanopipette sensors is highly dependent on the size, geometry and chemical properties of the sensing region. As nanopipettes are increasingly tuned and modified for specific analytes, a better understanding of the surface chemistry and morphology of the inner channel is necessary. For exploring these effects, quartz nanopipettes were modified by gas phase silanization, a well-utilised technique in the field to enhance performance of nanopipettes, and further functionalised with a metal bis thiolate complex, to aid in chemical analysis. The inner channel of the sensing region was exposed with focused ion beam (FIB) milling as a dedicated sample preparation method for nanoscale surface analysis. The sample characterisation involved scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and low-energy energy dispersive x-ray spectroscopy (EDX). The results demonstrate the first steps towards full characterisation of nanopipettes at the nanoscale, notably with access to the inner channel. The methods used here can be applied to gain further understanding of the response of these sensors to complex analytes, and allow for the study of different surface functionalisation at the all-important sensing region. T2 - 2024 Spring Meeting of the European Materials Research Society (E-MRS) CY - Strasbourg, France DA - 27.05.2024 KW - Nanopipettes KW - FIB KW - Surface analysis KW - Surface modification KW - Silanisation PY - 2024 AN - OPUS4-60449 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Choi, Ching-Yi A1 - Lossada, F. A1 - Walter, K. A1 - Fleck-Kunde, T. A1 - Behrens, S. A1 - Meinelt, T. A1 - Falkenhagen, Jana A1 - Hiller, M. A1 - Oschkinat, H. A1 - Dallmann, A. A1 - Taden, A. A1 - Börner, H.G. T1 - Organic transformation of lignin into mussel-inspired glues: next-generation 2K adhesive for setting corals under saltwater N2 - The 2-methoxyphenol units (G-units) in lignin are modified by demethylation and oxidation to provide the activated lignin as one part of an advanced biobased two-component (2K) adhesive system, which exhibits promising shear strengths in dry and underwater applications. The activation of lignin is straightforward and generates quinones via demethylation and periodate oxidation. These act as Michael acceptors and react smoothly with multi-thiol-star polymers to yield thiol-catechol connectivities (TCCs). The mussel-inspired material platform acts as a very robust and versatile adhesive, combining low-cost and readily available lignin with multi-thiols to achieve outstanding adhesion strengths of up to 15 MPa in dry application. In particular, the 2K system is compatible with the marine biological environment and shows no acute toxicity to sensitive organisms such as fish eggs. Thus, one possible application of this material could be an adhesive for setting temperature-resistant corals in damaged reefs. KW - Lignin modification KW - Mussel-inspired adhesive systems PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594588 DO - https://doi.org/10.1039/d3gc03680d SN - 1463-9270 SP - 1 EP - 15 PB - RSC CY - Cambridge AN - OPUS4-59458 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Falkenhagen, Jana A1 - Kricheldorf, H. R. T1 - Polycondensations and Cyclization of Poly(L-lactide) Ethyl Esters in the Solid State N2 - The usefulness of seven different Tin catalysts, Bismuth subsalicylate and Titan tetra(ethoxide) for the polycondensation of ethyl L-lactate (ELA) was examined at 150 °C/6 d. Dibutyltin bis(phenoxides) proved to be particularly effective. Despite the low reactivity of ELA, weight average molecular masses (Mw) up to 12 500 were found along with partial crystallization. Furthermore, polylactides (PLAs) of similar molecular masses were prepared via ELA-initiated ROPs of L-lactide by means of the four most effective polycondensation catalysts. The crystalline linear PLAs were annealed at 140 or 160 °C in the presence of these catalysts. The consequences of the transesterification reactions in the solid PLAs were studied by means of matrix-assisted laser desorption/ionization (MALDI TOF) mass spectrometry, gel permeation chromatography (GPC) and small-angle X-ray scattering (SAXS). The results indicate that polycondensation and formation of cycles proceed in the solid state via formation of loops on the surface of the crystallites. In summary, five different transesterification reactions are required to explain all results. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-592934 DO - https://doi.org/10.1039/d3py01232h SN - 1759-9962 VL - 15 IS - 2 SP - 71 EP - 82 PB - RSC Publ. CY - Cambridge AN - OPUS4-59293 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sänger, Johanna C. A1 - Riechers, Birte A1 - Pauw, Brian Richard A1 - Maaß, Robert A1 - Günster, Jens T1 - Microplastic response of 2PP‐printed ceramics N2 - AbstractTwo‐photon polymerization (2PP) additive manufacturing (AM) utilizes feedstocks of ceramic nanoparticles of a few nanometers in diameter, enabling the fabrication of highly accurate technical ceramic design with structural details as small as 500 nm. The performance of these materials is expected to differ from conventional AM ceramics, as nanoparticles and three‐dimensional printing at high resolution introduce new microstructural aspects. This study applies 2PP‐AM of yttria‐stabilized zirconia to investigate the mechanical response behavior under compressive load, probing the influence of smallest structural units induced by the line packing during the printing process, design of sintered microblocks, and sintering temperature and thereby microstructure. We find a dissipative mechanical response enhanced by sintering at lower temperatures than conventional. The pursued 2PP‐AM approach yields a microstructured material with an increased number of grain boundaries that proposedly play a major role in facilitating energy dissipation within the here printed ceramic material. This microplastic response is further triggered by the filigree structures induced by hollow line packing at the order of the critical defect size of ceramics. Together, these unique aspects made accessible by the 2PP‐AM approach contribute to a heterogeneous nano‐ and microstructure, and hint toward opportunities for tailoring the mechanical response in future ceramic applications. KW - Manufacturing KW - Mechanical properties KW - Microstructure KW - Plasticity KW - Zirconia: yttria stabilized PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-605176 DO - https://doi.org/10.1111/jace.19849 SN - 1551-2916 SP - 1 EP - 10 PB - Wiley CY - Oxford AN - OPUS4-60517 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana A1 - Epping, Ruben T1 - View into the depths of copolymer microstructure by a special approach of LC-MS data evaluation N2 - It is a well-known story that copolymers beside their molar mass distribution (MMD) can exhibit a functionality type distribution (FTD), a copolymer composition distribution (CCD), a monomer sequence distribution (MSD) and additionally different topologies within one sample. This is and will remain a challenge for analysts. First a very short overview will be given concerning the common liquid separation techniques for polymers (SEC, LAC, LCCC, GELC) coupled to soft ionization mass spectrometric methods like MALDI and ESI-MS with focus on their limitations. For very broadly distributed samples or chemical very similar species the superposition of different separation mechanisms in chromatography is unavoidable or the separation efficiency cannot be optimized. Different ionization probabilities and species of the same nominal mass with completely different structures are just two problems of mass spec of complex polymer mixtures. Subsequently, different examples will be shown how these limitations in some cases could be outsmarted. First example will be the separation of statistical EO-PO copolymers of different chemical compositions by end group functionality and the quantification of end group fractions over the whole CCD. Here an UP-LCCC / ESI-TOF-MS coupling is applied. Further for different kinds of polymers it will be shown how it could be realized to obtain information on small isobaric/isomeric topological heterogeneities by coupling UP-SEC / ESI-TOF-MS. All results are based on the data processing of reconstructed ion chromatograms of single mass traces of complex ESI-MS spectra. T2 - SCM-9 CY - Amsterdam, The Netherlands DA - 29.01.2019 KW - Reconstructed ion chromatograms KW - Copolymer KW - Microstructure KW - LC x ESI-TOF-MS PY - 2019 AN - OPUS4-47836 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kling, I. C. S. A1 - Pauw, Brian Richard A1 - Agudo Jácome, Leonardo A1 - Archanjo, B. S. A1 - Simão, R. A. T1 - Development and characterization of starch film and the incorporation of silver nanoparticles N2 - Starch is one of the biopolymers being used for bioplastic synthesis. For production, starch can be combined with different plasticizers, starches from different plant sources and even with nanomaterials to improve or to add film properties. The challenge of adding these, e.g. in the form of silver nanoparticles (AgNp) is to determine the concentration so as to avoid impairing the properties of the film, agglomeration or altering the visual characteristics of the film. In this study, a starch film synthesis route and the incorporation of silver nanoparticles has been proposed in order not to alter the properties of the film while maintaining the transparency and a clear colour of the starch film. The results showed that the proposed synthesis route is promising, efficient, reproducible, fast and the film has good mechanical properties. T2 - Semana MetalMat & Painal PEMM 2020 CY - Online meeting DA - 23.11.2020 KW - Biofilm KW - Starch KW - Starch nanoparticle KW - Silver nanoparticle PY - 2020 AN - OPUS4-51828 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Goedecke, Caroline A1 - Dittmann, Daniel A1 - Eisentraut, Paul A1 - Wiesner, Yosri A1 - Schartel, Bernhard A1 - Klack, Patrick A1 - Braun, Ulrike T1 - Evaluation of thermoanalytical methods equipped with evolved gas analysis for the detection of microplastic in environmental samples N2 - Microplastic particles are currently detected in almost all environmental compartments. The results of detection vary widely, as a multitude of very different methods are used with very different requirements for analytical validity. In this work four thermoanalytical methods are compared and their advantages and limitations are discussed. One of them is thermal extraction-desorption gas chromatography mass spectrometry (TED-GC/MS), an analysis method for microplastic detection that has become established in recent years. In addition, thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS) were applied, two methods that are less common in this field but are still used in other research areas. Finally, microscale combustion calorimeter (MCC) was applied, a method not yet used for microplastic detection. The presented results are taken from a recently published interlaboratory comparison test by Becker et al. (2020). Here a reference material consisting of suspended matter and specified added polymer masses was examined, and only the results of the recoveries were presented. In the present paper, however, the results for the individual polymers are discussed in detail and individual perspectives for all instruments are shown. It was found that TED-GC/MS is the most suitable method for samples with unknown matrix and unknown, variable kinds and contents of microplastic. TGA-FTIR is a robust method for samples with known matrix and with defined kinds of microplastic. TGA-MS may offer a solution for the detection of PVC particles in the future. MCC can be used as a very fast and simple screening method for the identification of a potential microplastic load of standard polymers in unknown samples. KW - Microplastic KW - TED-GC/MS KW - TGA-MS KW - TGA-FTIR KW - MCC KW - Thermal analysis PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516687 DO - https://doi.org/10.1016/j.jaap.2020.104961 VL - 152 SP - 104961 PB - Elsevier B.V. AN - OPUS4-51668 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fink, Friedrich A1 - Emmerling, Franziska A1 - Falkenhagen, Jana T1 - Identification and Classification of Technical Lignins by means of Principle Component Analysis and k-Nearest Neighbor Algorithm N2 - The characterization of technical lignins is a key step for the efficient use and processing of this material into valuable chemicals and for quality control. In this study 31 lignin samples were prepared from different biomass sources (hardwood, softwood, straw, grass) and different pulping processes (sulfite, Kraft, organosolv). Each lignin was analysed by attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopy. Statistical analysis of the ATR-FT-IR spectra by means of principal component analysis (PCA) showed significant differences between the lignins. Hence, the samples can be separated by PCA according to the original biomass. The differences observed in the ATR-FT-IR spectra result primarily from the relative ratios of the p-hydroxyphenyl, guaiacyl and syringyl units. Only limited influence of the pulping process is reflected by the spectral data. The spectra do not differ between samples processed by Kraft or organosolv processes. Lignosulfonates are clearly distinguishable by ATR-FT-IR from the other samples. For the classification a model was created using the k-nearest neighbor (k NN) algorithm. Different data pretreatment steps were compared for k=1…20. For validation purposes, a 5-fold cross-validation was chosen and the different quality criteria Accuracy (Acc), Error Rate (Err), Sensitivity (TPR) and specificity (TNR) were introduced. The optimized model for k=4 gives values for Acc = 98.9 %, Err = 1.1 %, TPR = 99.2 % and TNR = 99.6 %. KW - Classification KW - PCA KW - K-nearest neighbor KW - FT-IR KW - Technical lignin PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-533855 DO - https://doi.org/10.1002/cmtd.202100028 VL - 1 IS - 8 SP - 350 EP - 396 PB - Wiley-VCH GmbH AN - OPUS4-53385 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Epping, Ruben A1 - Falkenhagen, Jana A1 - Panne, Ulrich A1 - Hiller, W. A1 - Gruendling, T. A1 - Staal, B. A1 - Lang, C. A1 - Lamprou, A. T1 - Simultaneous characterization of poly(acrylic acid) andpolysaccharide polymers and copolymers N2 - Copolymer products that result from grafting acrylic acid and other hydrophilicmonomers onto polysaccharides have recently gained significant interest in researchand industry. Originating from renewable sources, these biodegradable, low toxicity,and polar copolymer products exhibit potential to replace polymers from fossil sourcesin several applications and industries. The methods usually employed to character-ize these copolymers are, however, quite limited, especially for the measurement ofbulk properties. With more sophisticated applications, for example, in pharmaceu-tics requiring a more detailed analysis of the chemical structure, we describe a newapproach for this kind of complex polymers. Our approach utilizes chromatographyin combination with several detection methods to separate and characterize reactionproducts of the copolymerization of acrylic acid and chemically hydrolyzed starch.These samples consisted of a mixture of homopolymer poly (acrylic acid), homopoly-mer hydrolyzed starch, and – in a lower amount – the formed copolymers. Several chro-matographic methods exist that are capable of characterizing either poly (acrylic acid)or hydrolyzed starch. In contrast, our approach offers simultaneous characterization ofboth polymers. The combination of LC and UV/RI offered insight into the compositionand copolymer content of the samples. Size exclusion chromatography experimentsrevealed the molar mass distribution of homopolymers and copolymers. FTIR inves-tigations confirmed the formation of copolymers while ESI-MS gave more details onthe end groups of hydrolyzed starches and poly (acrylic acids). Evidence of copolymerstructures was obtained through NMR measurements. Finally, two-dimensional chro-matography led to the separation of the copolymers from both homopolymers as wellas the additional separation of sodium clusters. The methods described in this work area powerful toolset to characterize copolymerization products of hydrolyzed starch andpoly(acrylic acid). Together, our approach successfully correlates the physicochemicalproperties of such complex mixtures with their actual composition. KW - 2D chromatography KW - LC-MS KW - SEC KW - Renewable copolymers KW - Grafting PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-508873 DO - https://doi.org/10.1002/ansa.202000044 SP - 1 EP - 12 PB - Wiley-VCH Verlag-GmbH&Co. KGaA CY - Weinheim AN - OPUS4-50887 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Geburtig, Anja A1 - Wachtendorf, Volker A1 - Falkenhagen, Jana T1 - Combined impact of UV radiation and nitric acid (HNO3) on HDPE jerrycans – comparison of outdoor and lab test N2 - A damaging action of HNO3-55% only occurs in combination with its decomposition into nitrous gases, which can be caused by UV radiation. In a laboratory test, transparent HDPE jerrycans have been exposed to both UV radiation and 55 wt-% nitric acid solution at (41 ± 2)°C, for up to 20 days. For comparison, UV radiant exposure (21 days) and nitric acid exposure (up to 6 weeks) were performed separately, at nearly equal temperatures. The respective damages are compared with FTIR spectroscopy in ATR and HT-gel permeation chromatography (GPC) on a molecular level and with hydraulic internal pressure testing as a component test. For the used jerrycans, relevant oxidation can only be found after the combined exposure. The gradual increase in oxidative damage shows the good reproducibility of the lab exposure. The decomposition of nitric acid into nitrous gases by UV radiation – as well as the jerrycan oxidation – is also observed at lower HNO3 concentration (28 wt- %). Similar results are obtained after outdoor tests. Again, the damage occurs only after combined exposure, in contrast to the exposures to UV only and to HNO3 only, which were conducted in parallel. Outdoor exposures are most readily accepted as they represent possible end-use conditions. However, the reproducibility of these exposures is poor due to the large temporal variations in weather. There are also several safety risks, which is why the number of replicates remains limited. Since the outdoor and lab exposure tests show the same qualitative results, it is appropriate to conduct systematic studies in the laboratory. After 6 days of lab exposure, the oxidation damage is rated as critical, which corresponds to about 1/10 year in Central Europe, according to the UV radiant exposure. It should be noted that this amount can also occur in two sunny weeks. T2 - 24th iapri World Packaging Conference CY - Valencia, Spain DA - 17.06.2024 KW - Ppolyethylene KW - UV exposure KW - Nitric acid KW - Oxidation PY - 2024 VL - 2 SP - 30 EP - 37 PB - ITENE AN - OPUS4-60414 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Falkenhagen, Jana A1 - Kricheldorf, H. R. T1 - SnOct2-catalyzed and alcohol-initiated ROPs of L-lactide – About the influence of initiators on chemical reactions in the melt and the solid state N2 - SnOct2 (Sn(II) 2-ethylhexanoate) catalyzed ROPs of L-lactide were performed in bulk with eight different alcohols as initiators. The time was varied between 1 h and 24 h for all initiators. For two initiators the temperature was also lowered to 115 ◦C. Even-numbered chains were predominantly formed in all polymerizations at short times, but the rate of transesterification (e.g. even/odd equilibration) and the molecular weight distribution were found to depend significantly on the nature of the initiator. Observed transesterification reactions also continued in solid poly (L-lactide), and with the most active initiator, almost total equilibration was achieved even at 130 ◦C. This means that all chains including those of the crystallites were involved in transesterification reactions proceeding across the flat surfaces of the crystallites. The more or less equilibrated crystalline polylactides were characterized by DSC and SAXS measurements with regard to their melting temperature (Tm), crystallinity and crystal thickness. KW - Polylactide KW - MALDI-TOF MS KW - Crystallization KW - Catalysts KW - SAXS PY - 2021 DO - https://doi.org/10.1016/j.eurpolymj.2021.110508 VL - 153 SP - 110508 PB - Elsevier Ltd. AN - OPUS4-52633 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Epping, Ruben A1 - Panne, Ulrich A1 - Falkenhagen, Jana T1 - Power of ultra performance liquid chromatography/electrospray ionization-MS reconstructed ion chromatograms in the characterization of small differences in polymer microstructure N2 - From simple homopolymers to functionalized, 3-dimensional structured copolymers, the complexity of polymeric materials has become more and more sophisticated. With new applications for instance in the semiconductor or pharmaceutical industry, the requirements for the characterization have risen with the complexity of the used polymers. For each additional distribution, an additional dimension in analysis is needed. Small, often isomeric heterogeneities in topology or microstructure can usually not be simply separated chromatographically or distinguished by any common detector, but affect the properties of materials significantly. For a drug delivery system for example, the degree of branching and branching distribution is crucial for the formation of micelles. Instead of a complicated, time consuming and/or expensive 2d-chromatography or ion mobility spectrometry (IMS) method, that also has its limitations, in this work a simple approach using size exclusion chromatography (SEC) coupled with electrospray ionization mass spectrometry (ESI) is proposed. The online coupling allows the analysis of reconstructed ion chromatograms (RIC) of each degree of polymerization. While a complete separation often cannot be achieved, the derived retention times and peak widths lead to information on the existence and dispersity of heterogeneities. Although some microstructural heterogeneities like short chain branching can for large polymers be characterized with methods such as light scattering, for oligomers where the heterogeneities just start to form and their influence is at the maximum, they are inaccessible with these methods. It is also shown, that with a proper calibration even quantitative information can be obtained. This method is suitable to detect small differences in e. g. branching, 3d-structure, monomer sequence or tacticity and could potentially be used in routine analysis to quickly determine deviations. KW - Polymer KW - Microstructure KW - UPLC KW - ESI-TOF-MS KW - Reconstructed ion chromatograms PY - 2018 DO - https://doi.org/10.1021/acs.analchem.7b05214 SN - 0003-2700 SN - 1520-6882 VL - 90 IS - 5 SP - 3467 EP - 3474 PB - ACS Publ. CY - Washington, DC AN - OPUS4-44423 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana T1 - Characterization of co (polyamide)s N2 - Charactrization of Co(polyamide)s Molar mass distribution; Functionalization; supression of end group effects in favor of sequence distribution analysis; Evidence of of randomization with increasing reaction time T2 - Polyamide Meeting, DSM CY - Sittard, The Netherlands DA - 20.04.2018 KW - Liquid chromatography KW - Mass spectrometry of polymers PY - 2018 AN - OPUS4-44747 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Dudziak, Mateusz A1 - Silbernagl, Dorothee A1 - Sturm, Heinz T1 - Thermal properties of polymer nanocomposites based on polycarbonate (PC) and boehmite N2 - Nanocomposites are extremely versatile due to their physicochemical properties, which differ significantly from bulk homopolymers. One of the inorganic nanomaterials which are increasingly used as a filler in polymer matrices is boehmite, typically used as an inexpensive flame retardant. Here, it is used as a nanofiller in polycarbonate and polyamide, expecting to improve their mechanical properties. For industrial use boehmite is obtained by the solvothermal method, resulting in a layered nanomaterial, whereas naturally it occurs as single crystals with the size of <100µm. In this work we are obtaining and isolating boehmite crystals by a bottom-up method, in which a reaction between aluminum nitride and sodium hydroxide. Obtaining boehmite as microcrystals is necessary for its analysis and characterization, as well as to investigate its interaction with polymer matrices at the polymer/particle interface. Here, the obtained particles in polymer matrices are characterized with differential scanning calorimetry and thermogravimetry analysis. T2 - DPG-Frühjahrstagung 2019 CY - Regensburg, Germany DA - 31.03.2019 KW - Boehmite KW - Polycarbonate PY - 2019 AN - OPUS4-47768 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Famy, A. A1 - Agudo Jácome, Leonardo A1 - Schönhals, Andreas T1 - Effect of Silver Nanoparticles on the Dielectric Properties and the Homogeneity of Plasma Poly(acrylic acid) Thin Films N2 - For the first time, structure−electrochemical relationships of thin films of a plasma-polymerized acrylic acid/carbon dioxide AA/CO2 (75/25%) copolymer modified by implanted silver nanoparticles are discussed. The pulsed plasma polymerization of AA/CO2 was utilized and adjusted to obtain a maximal amount of COOH Groups forming an almost uncross-linked polymer structure. The prepared polymer layer is rinsed by a silver nitrate solution to impregnate Ag+ ions. This step is followed by its reduction of Ag+ with NaBH4 as a chemical route in comparison to the reduction by sunlight as an ecofriendly photoreduction method. The chemical composition and morphology of the topmost surface layer of the AA/CO2 polymer thin film were investigated by X-ray photoelectron spectroscopy and atomic force microscopy. Moreover, the molecular mobility, conductivity, and thermal stability of the polymer layer were analyzed using broadband dielectric spectroscopy. The dielectric properties of the AA/ CO2 polymer thin film were studied in the presence of Ag+ ions or Ag0. It was found that a cross-linked polymer layer with a smooth surface and high conductivity was obtained in the presence of Ag+/ Ag0. KW - Nanoparticles PY - 2020 DO - https://doi.org/10.1021/acs.jpcc.0c06712 SN - 1932-7447 VL - 124 IS - 41 SP - 22817 EP - 22826 PB - ACS AN - OPUS4-51468 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Baumann, Maria A1 - Falkenhagen, Jana A1 - Weidner, Steffen A1 - Wold, C. A1 - Uliyanchenko, E. T1 - Characterization of copolymers of polycarbonate and polydimethylsiloxane by 2D chromatographic separation, MALDI-TOF mass spectrometry, and FTIR spectroscopy N2 - The structure and composition of polycarbonate polydimethylsiloxane copolymer (PC-co-PDMS) was investigated by applying various analytical approaches including chromatographic separation methods, spectrometric, and spectroscopic detection techniques. In particular, size exclusion chromatography (SEC) and liquid adsorption chromatography operating at different conditions (e.g. using gradient solvent systems) were used to achieve separations according to molar mass and functionality distribution. The coupling of both techniques resulted in fingerprint two-dimensional plots, which could be used to easily compare different copolymer batches. Matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry was applied for structural investigations. The different ionization behavior of both comonomers, however, strongly limited the applicability of this technique. In contrast to that, Fourier-transform Infrared (FTIR) spectroscopy could be used to quantify the amount of PDMS in the copolymer at different points in the chromatogram. The resulting methodology was capable of distinguishing PC-co-PDMS copolymer from PC homopolymer chains present in the material. KW - FTIR KW - Liquid chromatography KW - Mass spectrometry KW - Gradient elution KW - Polycarbonate-co-dimethylsiloxane copolymer PY - 2020 DO - https://doi.org/10.1080/1023666X.2020.1820170 VL - 25 IS - 7 SP - 1 EP - 12 PB - Taylor & Francis AN - OPUS4-51369 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana A1 - Weidner, Steffen A1 - Epping, Ruben T1 - Coupling of chromatographic and spectrometric techniques for polymer characterization N2 - Coupling of chromatographic and spectrometric techniques for polymer characterization; focus topics: LCxMALDI-TOF-MS and UPLC x ESI-TOF-MS T2 - 16. Tagung des Arbeitskreises Polymeranalytik CY - Online meeting DA - 22.03.2022 KW - Liquid chromatography KW - Mass spectrometry KW - Polymers KW - Two-dimensional chromatography (2D-LC) PY - 2022 AN - OPUS4-54567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Chatti, Saber A1 - Marestin, C. A1 - Jaffrezic, N. A1 - Falkenhagen, Jana A1 - Meyer, Klas A1 - Weidner, Steffen T1 - Chemical modification of lignin by functional polymers: towards specific green phases for the adsorption of organic pollutants in water N2 - Lignin is a highly aromatic low value biomass residue, which can be utilized for chemicals, fuels and materials production. In recent years, significant attention has focused on adsorber materials based on lignin. However, only 5% of the available lignin is exploited worldwide, thus significant opportunities for materials development still exist. Lignin has been vastly utilized as a feedstock for the synthesis of adsorbers for the removal of dyes and toxic organic molecules . To improve adsorption capacity, lignin can be chemically modified with oxygen-, nitrogen-, or sulfur-containing functional groups. Most frequently the phenolic groups of lignin were modified. In order to extend the application of lignin as adsorbers, we are especially interested in the chemical modification of this natural resource with a bio-based linear difluoro oligomers LOx (di- or monofunctional) or a heterocyclic monomer (Figure). T2 - 12. Journees maghreb-europe. Matériaux et Applications aux Dispositifs et Capteurs CY - Monastir, Tunisia DA - 08.11.2022 KW - Lignin KW - Biobased polymers KW - Modification PY - 2022 AN - OPUS4-56238 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Musl, O. A1 - Falkenhagen, Jana A1 - Sumerskii, I. A1 - Sulaeva, I. A1 - Mahler, A. K. A1 - Rosenau, T. A1 - Potthast, A. T1 - Mapping the Hydrophobic Composition of Lignosulfonates with 2D HIC-SEC aq. Liquid Chromatography N2 - 2D-LC provides in-depth information on the complex composition of lignosulfonates – information hitherto inaccessible by state-of-the-art lignin analytics. Analysis of 12 industrial lignosulfonates revealed considerable differences in their composition and functional dispersity - properties that are crucial for lignosulfonate usage T2 - Sustainable Materials Research Summit 2022, S.M.A.R.T CY - Vancouver, Canada DA - 07.08.2022 KW - Lignosulfonate KW - Lignin KW - Amphiphilicity KW - Hydrophobic interaction KW - Chromatography (HIC) KW - Size-exclusion chromatography (SEC) KW - Functionality type distribution KW - Two-dimensional liquid chromatography (2D-LC) KW - Molar mass distribution PY - 2022 AN - OPUS4-55510 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Falkenhagen, Jana T1 - Biobased and biogegradable polymers: Analytical challenges N2 - The variability and heterogeneity in their structural composition is significant for nearly all synthetic and natural polymers. Beside molar mass also functionality type distribution, copolymer composition distribution and architectural features are responsible for changing the material properties. A wide range of analytical techniques are available to get insight into these parameters. However, in most cases it is essential to combine different sophisticated techniques to get closer to actual structures and to avoid statistical averages. Different liquid chromatographic separation modes and their coupling in a two-dimensional way (SEC, LCCC, HILIC, 2D-LC) in combination with suitable detection techniques (e.g. UV, RI, LS, IR, MALDI/ESI-MS) as well as techniques like BET, DCS, SEM/TEM were applied to make structural features visible. A few aspects are discussed for structural different polylactides from various synthesis routes and their behavior in LC-MS. Moreover, some analytical results for technical lignins valorized by mechanochemical treatment or modified by functional polymers are presented. T2 - 10th Intern. Symp. on the Separation and Characterisation of Natural and Synthetic Macromolecules (SCM-10) CY - Amsterdam, Netherlands DA - 01.02.2023 KW - Poly(lactides) KW - Technical lignin PY - 2023 AN - OPUS4-57002 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Miliūtė, Aistė A1 - Bustamante, Joana A1 - Mieller, Björn A1 - Stawski, Tomasz A1 - George, Janine A1 - Knoop, F. T1 - High-quality zirconium vanadate samples for negative thermal expansion (NTE) analysis N2 - Zirconium vanadate (ZrV2O7) is a well-known negative thermal expansion (NTE) material which exhibits significant isotropic contraction over a broad temperature range (~150°C < T < 800°C). The linear thermal expansion coefficient of ZrV2O7 is −7.1×10-6 K-. Therefore, it can be used to create composites with controllable expansion coefficients and prevent destruction by thermal shock. Material characterization, leading to application, requires pure, homogenous samples of high crystallinity via a reliable synthesis route. While there is a selection of described syntheses in the literature, it still needs to be addressed which synthesis route leads to truly pure and homogenous samples. Here, we study the influence of the synthesis methods (solid-state, sol-gel, solvothermal) and their parameters on the sample's purity, crystallinity, and homogeneity. The reproducibility of results and data obtained with scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry, and thermogravimetric analysis (DSC/TGA) were analyzed extensively. The sol-gel method proves superior to the solid-state method and produces higher-quality samples over varying parameters. Sample purity also plays an important role in NTE micro and macro-scale characterizations that explain the impact of porosity versus structural changes. Moreover, we implement ab-initio-based vibrational computations with partially treated anharmonicity (quasi-harmonic approximation, temperature-dependent effective harmonic potentials) in combination with experimental methods to follow and rationalize the negative thermal expansion in this material, including the influence of the local structure disorder, microstructure, and defects. Khosrovani et al. and Korthuis et al., in a series of diffraction experiments, attributed the thermal contraction of ZrV2O7 to the transverse thermal motion of oxygen atoms in V-O-V linkages. In addition to previous explanations, we hypothesize that local disorder develops in ZrV2O7 crystals during heating. We are working on the experimental ZrV2O7 development and discuss difficulties one might face in the process as well as high-quality sample significance in further investigation. The obtained samples are currently used in the ongoing research of structure analysis and the negative thermal expansion mechanism. T2 - 16th International conference on materials chemistry (MC16) CY - Dublin, Ireland DA - 03.07.2023 KW - NTE KW - Sol-gel KW - Solid-state KW - Ab-initio KW - TDEP PY - 2023 AN - OPUS4-58134 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yesilcicek, Yasemin A1 - Haas, S. A1 - Suárez Ocano, Patricia A1 - Zaiser, E. A1 - Hesse, René A1 - Többens, D. M. A1 - Glatzel, U. A1 - Manzoni, Anna Maria T1 - Controlling Lattice Misfit and Creep Rate Through the γ' Cube Shapes in the Al10Co25Cr8Fe15Ni36Ti6 Compositionally Complex Alloy with Hf and W Additions N2 - Trace elements play an important role in the fine-tuning of complex material properties. This study focuses on the correlation of microstructure, lattice misfit and creep properties. The compositionally complex alloy Al10Co25Cr8Fe15Ni36Ti6 (in at. %) was tuned with high melting trace elements Hf and W. The microstructure consists of a γ matrix, γ' precipitates and the Heusler phase and it is accompanied by good mechanical properties for high temperature applications. The addition of 0.5 at.% Hf to the Al10Co25Cr8Fe15Ni36Ti6 alloy resulted in more sharp-edged cubic γ′ precipitates and an increase in the Heusler phase amount. The addition of 1 at.% W led to more rounded γ′ precipitates and the dissolution of the Heusler phase. The shapes of the γ' precipitates of the alloys Al9.25Co25Cr8Fe15Ni36Ti6Hf0.25W0.5 and Al9.25Co25Cr8Fe15Ni36Ti6Hf0.5W0.25, that are the alloys of interest in this paper, create a transition from the well-rounded precipitates in the alloy with 1% W containing alloy to the sharp angular particles in the alloy with 0.5% Hf. While the lattice misfit has a direct correlation to the γ' precipitates shape, the creep rate is also related to the amount of the Heusler phase. The lattice misfit increases with decreasing corner radius of the γ' precipitates. So does the creep rate, but it also increases with the amount of Heusler phase. The microstructures were investigated by SEM and TEM, the lattice misfit was calculated from the lattice parameters obtained by synchrotron radiation measurements. KW - High entropy alloy KW - Lattice misfit KW - Creep KW - Transmission electron microscopy KW - X-ray diffraction PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565655 DO - https://doi.org/10.1007/s44210-022-00009-1 SP - 1 EP - 9 PB - Springer AN - OPUS4-56565 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Matthews, Lauren A1 - Sahre, Mario A1 - Hesse, R. A1 - Schusterbauer, Robert A1 - Grant, M. A1 - Agudo Jácome, Leonardo A1 - Albrecht, T. A1 - Hodoroaba, Vasile-Dan T1 - Approaches to Surface Analysis of Modified Quartz Nanopipettes N2 - Nanopipettes are a type of solid-state nanopore with needle-like geometry. Their applications range from imaging, sensing, diagnostics, and use as injectors. The response of nanopipette sensors is highly dependent on the size, geometry and chemical properties of the sensing region. As they are increasingly tuned and modified for specific analytes, a better understanding of the surface chemistry and morphology of the inner channel is necessary. With the aim of developing a comprehensive approach for characterisation of such nanopipettes, this research focuses on combining surface-sensitive analysis methods with advanced sample preparation techniques. Quartz substrates were modified by gas phase silanization, a well-utilised technique in the field to enhance performance of nanopipettes, and further functionalised with a metal bis thiolate complex, to aid in chemical analysis. The sample characterisation involved scanning electron microscopy (SEM), low-energy dispersive x-ray spectroscopy (EDX), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and Auger electron spectroscopy (AES). Using focused ion beam (FIB) milling under gentle conditions, the inner surface of quartz nanopipettes was exposed whilst preserving the integrity of the overall structure (see figure). Owing to the challenging analysis conditions, modification and analysis of flat quartz substrates has been performed in parallel for optimisation purposes. The results demonstrate the first steps towards full characterisation of nanopipettes at the nanoscale, notably with access to the inner channel. The methods used here can be applied to gain further understanding of the response of these sensors to complex analytes and allow for the study of different surface functionalisations at the all-important sensing region. T2 - European Conference on Applications of Surface and Interface Analysis (ECASIA 2024) CY - Gothenburg, Sweden DA - 09.06.2024 KW - Quartz nanopipettes KW - Nanopipette modification KW - Silanization KW - Surface analysis KW - Focussed ion beam PY - 2024 AN - OPUS4-60447 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Musl, O. A1 - Sulaeva, I. A1 - Sumerskii, I. A1 - Mahler, A.K. A1 - Rosenau, T. A1 - Falkenhagen, Jana A1 - Potthast, A. T1 - Mapping of the Hydrophobic Composition of Lignosulfonates N2 - Lignosulfonates are industrial biorefinery products that are characterized by significant variability and heterogeneity in their structural composition. Typically, they exhibit high dispersities in molar mass (molar mass distribution-MMD) and in functionalities (functionality-type distribution - FTD), which crucially affect their material usage. In terms of FTD, state-of-the-art Lignin analytics still rely mainly on the determination of functional group contents, which are statistical averages with limited explanatory power. In contrast, our online hydrophobic interaction chromatography−size-exclusion chromatography 2D-LC approach combines the determination of both MMD and FTD in a single measurement to provide a comprehensive picture of the characteristic composition of industrial lignosulfonates information hitherto inaccessible by state-of-the-art lignin analytics. In this way, the complex inter - relationships between these two important structural parameters can be studied in an unprecedented manner. In this study, we reveal the considerable differences in terms of hydrophobic composition and its dispersity present in a range of different industrial lignosulfonates - data desperately needed in tailoring and refining of lignosulfonate composition for material usage. KW - Lignosulfonates KW - Amphiphilicity KW - Hydrophobic interaction chromatography KW - Two-dimensional chromatography (2D-LC) KW - Charge-to-size-ratio PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-538612 DO - https://doi.org/10.1021/acssuschemeng.1c06469 VL - 9 IS - 49 SP - 16786 EP - 16795 PB - ASC Publications AN - OPUS4-53861 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Battig, Alexander A1 - Müller, Patrick A1 - Bertin, Annabelle A1 - Schartel, Bernhard T1 - Hyperbranched Rigid Aromatic Phosphorus-Containing Flame Retardants for Epoxy Resins N2 - A rigid aromatic phosphorus-containing hyperbranched flame retardant structure is synthesized from 10-(2,5 dihydroxyphenyl)-10H-9-oxa- 10-phosphaphenanthrene-10-oxide (DOPO-HQ), tris(4-hydroxyphenyl)phosphine oxide (THPPO), and 1,4-terephthaloyl chloride (TPC). The resulting poly-(DOPO-HQ/THPPO-terephthalate) (PDTT) is implemented as a flame retardant into an epoxy resin (EP) at a 10 wt% loading. The effects on EP are compared with those of the monomer DOPO-HQ and triphenylphosphine oxide (OPPh3) as low molar mass flame retardants. The glass transition temperature, thermal decomposition, flammability (reaction to small flame), and burning behavior of the thermosets are investigated using differential scanning calorimetry, thermogravimetric analysis, pyrolysis combustion flow calorimetry, UL 94-burning chamber testing, and cone calorimeter measurements. Although P-contents are low at only 0.6 wt%, the study aims not at attaining V-0, but at presenting a proof of principle: Epoxy resinswith PDTT show promising fire performance, exhibiting a 25% reduction in total heat evolved (THE), a 30% reduction in peak heat release rate (PHRR) due to flame inhibition (21% reduction in effective heat of combustion (EHC)), and an increase in Tg at the same time. This study indicates that rigid aromatic hyperbranched polymeric structures offer a promising route toward multifunctional flame retardancy. KW - Hyperbranched KW - Aromatic KW - Phosphorus KW - Phosphine oxide KW - DOPO KW - Flame retardant KW - Xpoxy resin KW - Rigid PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-525910 DO - https://doi.org/10.1002/mame.202000731 SN - 1439-2054 VL - 306 IS - 4 SP - 731 PB - Wiley AN - OPUS4-52591 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dudziak, Mateusz A1 - Topolniak, Ievgeniia A1 - Silbernagl, Dorothee A1 - Altmann, Korinna A1 - Sturm, Heinz T1 - Long-time behavior of surface properties of microstructures fabricated by multiphoton lithography N2 - The multiphoton lithography (MPL) technique represents the future of 3D microprinting, enabling the production of complex microscale objects with high precision. Although the MPL fabrication parameters are widely evaluated and discussed, not much attention has been given to the microscopic properties of 3D objects with respect to their surface properties and time-dependent stability. These properties are of crucial importance when it comes to the safe and durable use of these structures in biomedical applications. In this work, we investigate the surface properties of the MPL-produced SZ2080 polymeric microstructures with regard to the physical aging processes during the post-production stage. The influence of aging on the polymeric microstructures was investigated by means of Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS). As a result, a time-dependent change in Young’s Modulus, plastic deformation, and adhesion and their correlation to the development in chemical composition of the surface of MPL-microstructures are evaluated. The results presented here are valuable for the application of MPL-fabricated 3D objects in general, but especially in medical technology as they give detailed information of the physical and chemical time-dependent dynamic behavior of MPL-printed surfaces and thus their suitability and performance in biological systems. KW - Multiphoton lithography KW - Additive manufacturing KW - Microfabrication KW - SZ2080 negative photo-resist KW - Young´s modulus KW - Aging KW - Surface properties KW - X-ray photoelectron spectroscopy KW - Atomic force microscopy KW - Force-distance-curve PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-542166 DO - https://doi.org/10.3390/nano11123285 SN - 2079-4991 VL - 11 IS - 12 SP - 1 EP - 12 PB - MDPI CY - Basel AN - OPUS4-54216 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Falkenhagen, Jana T1 - The role of transesterifications in reversible polycondensations and a reinvestigation of the Jacobson-Beckmann-Stockmayer experiments N2 - The polycondensations of adipic acid and 1,10-decanediol catalyzed by toluene sulfonic acid (TSA) were reinvestigated using MALDI TOF mass spectrometry and NMR spectroscopy. Unexpected reactions of TSA were detected along with incomplete conversion of the monomers. Furthermore, transesterification reactions of end-capped poly(1,10-decanediol adipate) and end-capped poly(ε-caprolactone) catalyzed by TSA were studied. Despite the quite different (ionic) reaction mechanisms, it was found that for polycondensations performed in bulk intermolecular transesterification is more efficient than the intramolecular “back-biting”; this scenario was not considered in the Jacobson–Stockmayer theory of reversible polycondensations. These results also confirm that the Jacobson–Stockmayer explanation of reversible polycondensations solely on the basis of ring chain equilibration is not only devoid of any experimental evidence, but also in contradiction to the results elaborated in this work. KW - Polylactide KW - MALDI-TOF MS KW - Polycondensation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543402 DO - https://doi.org/10.1039/d1py01679b SN - 1759-9962 SP - 1 EP - 9 PB - RSC Publ. CY - Cambridge AN - OPUS4-54340 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Geburtig, Anja A1 - Wachtendorf, Volker A1 - Falkenhagen, Jana T1 - Combined impact of UV radiation and nitric acid on high‐density polyethylene containers as a laboratory test N2 - In a laboratory test, transparent high‐density polyethylene (HDPE) jerrycans have been exposed to both UV radiation and 55 wt‐% nitric acid solution at (41 ± 2)°C, for up to 20 days. For comparison, UV radiant exposure (21 days) and nitric acid exposure (up to 6 weeks) were performed separately, at nearly equal temperatures. The damages are compared with FTIR spectroscopy in ATR and HT‐gel permeation chromatography(GPC) on a molecular level and with hydraulic internal pressure testing as a component test. For the used jerrycans, relevant oxidation can only be found after the combined exposure. This is caused by the decomposition of nitric acid into nitrous gases by UV radiation, which is also observed at lower concentrations (28 wt‐%). After 6 days of laboratory exposure, this is rated as critical, which corresponds to about 1/10 year in Central Europe, according to the UV radiant exposure. The gradual increase in oxidative damage shows the reproducibility of the test. KW - Molecular mass distribution KW - High-density polyethylene KW - Nitric acid KW - UV radiation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-550141 DO - https://doi.org/10.1002/pts.2673 SN - 0894-3214 SP - 1 EP - 7 PB - John Wiley & Sons Ltd AN - OPUS4-55014 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholz, Philipp A1 - Wachtendorf, Volker A1 - Elert, Anna Maria A1 - Falkenhagen, Jana A1 - Becker, Roland A1 - Hoffmann, Katrin A1 - Resch-Genger, Ute A1 - Tschiche, Harald A1 - Reinsch, Stefan A1 - Weidner, Steffen ED - Scholz, Philipp T1 - Analytical toolset to characterize polyurethanes after exposure to artificial weathering under systematically varied moisture conditions N2 - Polyether and -ester urethanes (PU) were exposed to artificial weathering at 40 °C and artificial UV radiation in a weathering chamber. In 3 parallel exposures, humidity was varied between dry, humid, and wet conditions. Material alteration was investigated by various analytical techniques like size exclusion chromatography (SEC), liquid chromatography-infrared spectroscopy (LC-FTIR), thermal-desorption gas chromatography-mass spectrometry (TD-GC-MS), fluorescence mapping and dynamic mechanical analysis (DMA). Our results show that depending on the weathering conditions, different degradation effects can be observed. By means of SEC an initial strong decrease of the molar masses and a broadening of the mass distributions was found. After a material dependent time span this was followed by a plateau where molar mass changes were less significant. A minor moisture-dependent degradation effect was only found for polyester PU. Fluorescence measurements on two materials revealed an increase in the luminescence intensity upon weathering process reaching a saturation level after about 500 h. The changes in the optical properties observed after different exposure conditions and times were very similar. The TD-GC-MS data showed the fate of the stabilizers and antioxidant in the course of weathering. LC-FTIR measurements revealed a change in peak intensities and the ratio of urethane and carbonyl bands. KW - Polyurethane KW - Artificial weathering KW - Moisture KW - Crosslinking KW - Degradation PY - 2019 UR - https://www.sciencedirect.com/science/article/pii/S0142941819303708 DO - https://doi.org/10.1016/j.polymertesting.2019.105996 SN - 0142-9418 VL - 78 SP - 105996, 1 EP - 9 PB - Elsevier CY - Amsterdam AN - OPUS4-48625 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dudziak, Mateusz A1 - Bhatia, Riya A1 - Dey, R. A1 - Falkenhagen, Jana A1 - Ullrich, M. S. A1 - Thomsen, C. A1 - Schartel, Bernhard T1 - Wastewater phosphorus enriched algae as a sustainable flame retardant in polylactide N2 - Revolutionizing our polymer industry for adaption to a sustainable carbon circular economy has become one of today’s most demanding challenges. Exploiting renewable resources to replace fossil-fuel—based plastics with biopolymers such as poly(lactic acid) (PLA) is inevitable while using waste streams as a raw material resource at least is promising. When it comes to using PLA as technical polymer, its high flammability must be addressed by flame retardants compatible with the thermoplastic processing of PLA and its compostability. This study proposes microalgae enriched with phosphorus from wastewater (P-Algae) as an elegant way towards a kind of sustainable organophosphorus flame retardant. The concept is demonstrated by investigating the processing, pyrolysis, flammability, and fire behavior of PLA/P-Algae, while varying the P-Algae content and comparing P-Algae with four alternative bio-fillers (phosphorylated lignin, biochar, thermally treated sewage sludge, and metal phytate) with different P-contents as meaningful benchmarks. KW - PLA KW - Flame Retardancy KW - Phosphorylated Algae KW - Wastewater flame retardants KW - Zink phytate KW - Phosphorylated lignin KW - Thermally treated sludge PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-604150 DO - https://doi.org/10.1016/j.polymdegradstab.2024.110885 SN - 1873-2321 SN - 0141-3910 VL - 227 SP - 1 EP - 11 PB - Elsevier Ltd. AN - OPUS4-60415 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fornacon-Wood, Christoph A1 - Stühler, Merlin R. A1 - Millanvois, Alexandre A1 - Steiner, Luca A1 - Weimann, Christiane A1 - Silbernagl, Dorothee A1 - Sturm, Heinz A1 - Paulus, Beate A1 - Plajer, Alex J. T1 - Fluoride recovery in degradable fluorinated polyesters N2 - We report a new class of degradable fluorinated polymers through the copolymerization of tetrafluorophthalic anhydride and propylene oxide or trifluoropropylene oxide which show up to 20 times quicker degradation than the non-fluorinated equivalents and allow for fluoride recovery. KW - Fluoropolymers KW - Recycling KW - PFAS KW - AFM force distance curves KW - AFM plastic deformation KW - AFM friction analysis PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-606768 DO - https://doi.org/10.1039/d4cc02513j VL - 60 SP - 7479 EP - 7482 PB - Royal Society of Chemistry AN - OPUS4-60676 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Waniek, Tassilo A1 - Omar, Hassan A1 - Szymoniak, Paulina A1 - Silbernagl, Dorothee A1 - Sturm, Heinz T1 - The influence of water released from particles in epoxy‐based nanocomposites N2 - AbstractRecent studies have hypothesized that the reinforcing effects of boehmite nanoparticles (BNPs) in polymer nanocomposites (PNCs) are partly related to the particles themselves and partly to the water released from the BNP during curing. In this work, PNCs made from dried BNP (dBNP) with concentrations up to 15 wt% are investigated to differentiate particle and water related effects. The observed trend of the storage modulus in dynamic mechanical thermal analysis measurements was found to be independent of the drying procedure. Stiffness maps from intermodulation atomic force microscopy showed that dBNP leads to a stiffening of the interphase surrounding the particles compared with the unaffected epoxy matrix, while a softer interphase was reported for PNCs with as received BNP. A slight decrease in the glass transition temperature was observed by broadband dielectric spectroscopy related to a lowered crosslink density due to the particles. A significantly higher decrease was reported for PNCs with BNP, attributed to water influencing the curing process. In conclusion, the stiffening of PNC with BNP is related to the particles themselves, while the release of water causes the formation of a soft interphase in the vicinity of the particles and a significant decrease in crosslink density. KW - AFM stiffness of interface KW - Aluminium oxide hydroxide KW - Boehmit nanoparticle KW - Glass transition temperature KW - Broadband dielectric spectroscopy KW - Crosslink density control KW - Structure–property relationship KW - Nanocomposites KW - Thermoset PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-606772 DO - https://doi.org/10.1002/app.55937 SN - 0021-8995 SP - 1 EP - 16 PB - Wiley AN - OPUS4-60677 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schütter, Jan A1 - Pietsch, Franziska A1 - Schreiber, Frank A1 - Koerdt, Andrea A1 - Özcan Sandikcioglu, Özlem T1 - Effect of surface topography and chemistry on the attachment of bacteria on solid surfaces N2 - Microbiologically induced corrosion due to bacterial biofilms causes several problems in industrial systems, technical applications and in medicine. Prior to the formation of a biofilm on a substrate, planktonic cells attach on the surface. Hence, the properties of the surface play a key role in biofilm formation and are of great importance for the development of strategies to prevent bacterial attachment and biofilm formation. This project aims at clarifying to which extent surface micro-/nanostructuring and chemical functionalization affects bacterial attachment and whether a synergistic combination of the two can be used to control bacterial adhesion. To answer these questions, model surfaces with regular patterns of 5-10 micrometers in size have been prepared, which provide distinct zones differing in terms of their chemistry or nano-roughness. This was achieved by micro contact printing of self-assembled monolayers with different functional groups and deposition of patterned ZnO nanorod arrays for studying the effect of surface chemistry and morphology, respectively. Typical contrasts studied were combinations of positively/negatively charged, hydrophobic/hydrophilic or flat/rough. The attachment behavior of bacteria on tailored surfaces were studied in a flow chamber as a function of time. The strain Pseudomonas fluorescens SBW25 was chosen as a model organism. DNA-intercalating dyes such as Syto9 have a high affinity to adsorb on ZnO nanorods. To overcome this limitation a genetic modification was performed by introducing a gene which expresses a green fluorescent protein in P. fluorescens SBW25 enabling the quantitative evaluation of the flow chamber studies by means of fluorescence microscopy. Further analysis of the attachment behavior was performed by means of scanning electron microscopy. The presentation will summarize the results of our systematic study on the role of individual parameters on bacterial attachment and highlight synergistic combinations, showing an inhibition or enhancing effect. As the investigations with model substrates enable a precise control of the surface parameters, this approach can be applied to different microorganisms and material systems to achieve a correlative description of bacterial adhesion on solid surfaces. T2 - Eurocorr2019 CY - Sevilla, Spain DA - 09.09.2019 KW - Microbial KW - Corrosion KW - MIC KW - Nanorods PY - 2019 AN - OPUS4-49730 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Li, M. A1 - Schlaich, C. A1 - Zhang, J. A1 - Donskyi, Ievgen A1 - Schwibbert, Karin A1 - Schreiber, Frank A1 - Xia, Y. A1 - Radnik, Jörg A1 - Schwerdtle, T. A1 - Haag, R. T1 - Mussel-inspired multifunctional coating for bacterial infection prevention and osteogenic induction N2 - Bacterial infection and osteogenic integration are the two main problems that cause severe complications after surgeries. In this study, the antibacterial and osteogenic properties were simultaneously introduced in biomaterials, where copper nanoparticles (CuNPs) were generated by in situ reductions of Cu ions into a mussel-inspired hyperbranched polyglycerol (MI-hPG) coating via a simple dip-coating method. This hyperbranched polyglycerol with 10 % catechol groups’ modification presents excellent antifouling property, which could effectively reduce bacteria adhesion on the surface. In this work, polycaprolactone (PCL) electrospun fiber membrane was selected as the substrate, which is commonly used in biomedical implants in bone regeneration and cardiovascular stents because of its good biocompatibility and easy post-modification. The as-fabricated CuNPs-incorporated PCL membrane [PCL-(MI-hPG)-CuNPs] was confirmed with effective antibacterial performance via in vitro antibacterial tests against Staphylococcus aureus (S. aureus), Escherichia coli (E. coli), and multi-resistant E. coli. In addition, the in vitro results demonstrated that osteogenic property of PCL-(MI-hPG)-CuNPs was realized by upregulating the osteoblast-related gene expressions and protein activity. This study shows that antibacterial and osteogenic properties can be balanced in a surface coating by introducing CuNPs. KW - Mussel-inspired coating KW - CuNPs KW - Multi-resistant bacteria KW - Antibacterial KW - Antifouling KW - Osteogenesis PY - 2021 DO - https://doi.org/10.1016/j.jmst.2020.08.011 SN - 1005-0302 VL - 68 SP - 160 EP - 171 PB - Elsevier Ltd. AN - OPUS4-51519 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sachse, René A1 - Pfüger, Mika A1 - Velasco-Vélez, Juan-Jesús A1 - Sahre, Mario A1 - Radnik, Jörg A1 - Bernicke, Michael A1 - Bernsmeier, Denis A1 - Hodoroaba, Vasile-Dan A1 - Krumrey, Michael A1 - Strasser, Peter A1 - Kraehnert, Ralph A1 - Hertwig, Andreas T1 - Assessing optical and electrical properties of highly active IrOx catalysts for the electrochemical oxygen evolution reaction via spectroscopic ellipsometry N2 - Efficient water electrolysis requires highly active electrodes. The activity of corresponding catalytic coatings strongly depends on material properties such as film thickness, crystallinity, electrical conductivity, and chemical surface speciation. Measuring these properties with high accuracy in vacuum-free and nondestructive methods facilitates the elucidation of structure−activity relationships in realistic environments. Here, we report a novel approach to analyze the optical and electrical properties of highly active oxygen evolution reaction (OER) catalysts via spectroscopic ellipsometry (SE). Using a series of differently calcined, mesoporous, templated iridium oxide films as an example, we assess the film thickness, porosity, electrical resistivity, electron concentration, electron mobility, and interband and intraband transition energies by modeling of the optical spectra. Independently performed analyses using scanning electron microscopy, energy-dispersive X-ray spectroscopy, ellipsometric porosimetry, X-ray reflectometry, and absorption spectroscopy indicate a high accuracy of the deduced material properties. A comparison of the derived analytical data from SE, resonant photoemission spectroscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy with activity measurements of the OER suggests that the intrinsic activity of iridium oxides scales with a shift of the Ir 5d t2g sub-level and an increase of p−d interband transition energies caused by a transition of μ1-OH to μ3-O species. KW - Spectroscopic ellipsometry KW - Electrocatalysis KW - Oxygen evolution reaction KW - Mesoporous iridium oxide films KW - Non-destructive ambient analysis KW - Intrinsic OER activity KW - Complementary methodology and metrology PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516288 DO - https://doi.org/10.1021/acscatal.0c03800 SN - 2155-5435 VL - 10 IS - 23 SP - 14210 EP - 14223 PB - American Chemical Society AN - OPUS4-51628 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Richter, Anja A1 - Buchberger, G. A1 - Stifter, D. A1 - Duchoslav, J. A1 - Hertwig, Andreas A1 - Bonse, Jörn A1 - Heitz, J. A1 - Schwibbert, Karin T1 - Spatial Period of Laser-Induced Surface Nanoripples on PET Determines Escherichia coli Repellence N2 - Bacterial adhesion and biofilm formation on surfaces are associated with persistent microbial contamination, biofouling, and the emergence of resistance, thus, calling for new strategies to impede bacterial surface colonization. Using ns-UV laser treatment (wavelength 248 nm and a pulse duration of 20 ns), laser-induced periodic surface structures (LIPSS) featuring different submicrometric periods ranging from ~210 to ~610 nm were processed on commercial poly(ethylene terephthalate) (PET) foils. Bacterial adhesion tests revealed that these nanorippled surfaces exhibit a repellence for E. coli that decisively depends on the spatial periods of the LIPSS with the strongest reduction (~91%) in cell adhesion observed for LIPSS periods of 214 nm. Although chemical and structural analyses indicated a moderate laser-induced surface oxidation, a significant influence on the bacterial adhesion was ruled out. Scanning electron microscopy and additional biofilm studies using a pili-deficient E. coli TG1 strain revealed the role of extracellular appendages in the bacterial repellence observed here. KW - Laser-induced periodic surface structures (LIPSS) KW - Laser processing KW - Polyethylene terephthalate KW - Biofilm formation KW - Cell appendages KW - Biomimetic KW - F pili PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537431 DO - https://doi.org/10.3390/nano11113000 VL - 11 IS - 11 SP - 3000 PB - MDPI AN - OPUS4-53743 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Florian, Camilo A1 - Fischer, Daniel A1 - Freiberg, K. A1 - Duwe, M. A1 - Sahre, Mario A1 - Schneider, S. A1 - Hertwig, Andreas A1 - Krüger, Jörg A1 - Rettenmayr, M. A1 - Beck, Uwe A1 - Undisz, A. A1 - Bonse, Jörn T1 - Single Femtosecond Laser-Pulse-Induced Superficial Amorphization and Re-Crystallization of Silicon N2 - Superficial amorphization and re-crystallization of silicon in <111> and <100> orientation after irradiation by femtosecond laser pulses (790 nm, 30 fs) are studied using optical imaging and transmission electron microscopy. Spectroscopic imaging ellipsometry (SIE) allows fast data acquisition at multiple wavelengths and provides experimental data for calculating nanometric amorphous layer thickness profiles with micrometric lateral resolution based on a thin-film layer model. For a radially Gaussian laser beam and at moderate peak fluences above the melting and below the ablation thresholds, laterally parabolic amorphous layer profiles with maximum thicknesses of several tens of nanometers were quantitatively attained. The accuracy of the calculations is verified experimentally by high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (STEM-EDX). Along with topographic information obtained by atomic force microscopy (AFM), a comprehensive picture of the superficial re-solidification of silicon after local melting by femtosecond laser pulses is drawn. KW - Femtosecond laser KW - Silicon KW - Amorphization KW - Crystallization KW - Spectroscopic imaging ellipsometry PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523687 UR - https://www.mdpi.com/1996-1944/14/7/1651 DO - https://doi.org/10.3390/ma14071651 SN - 1996-1944 VL - 14 IS - 7 SP - 1651-1 EP - 1651-21 PB - MDPI AG CY - Basel, Switzerland AN - OPUS4-52368 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weigert, Florian A1 - Müller, A. A1 - Häusler, I. A1 - Geißler, Daniel A1 - Skroblin, D. A1 - Unger, Wolfgang A1 - Radnik, Jörg A1 - Resch-Genger, Ute T1 - Combining HR‑TEM and XPS to elucidate the core–shell structure of ultrabright CdSe/CdS semiconductor quantum dots N2 - Controlling thickness and tightness of surface passivation shells is crucial for many applications of core–shell nanoparticles (NP). Usually, to determine shell thickness, core and core/shell particle are measured individually requiring the availability of both nanoobjects. This is often not fulfilled for functional nanomaterials such as many photoluminescent semiconductor quantum dots (QD) used for bioimaging, solid state lighting, and display technologies as the core does not show the applicationrelevant functionality like a high photoluminescence (PL) quantum yield, calling for a whole nanoobject approach. By combining high-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS), a novel whole nanoobject approach is developed representatively for an ultrabright oleic acid-stabilized, thick shell CdSe/CdS QD with a PL quantum yield close to unity. The size of this spectroscopically assessed QD, is in the range of the information depth of usual laboratory XPS. Information on particle size and monodispersity were validated with dynamic light scattering (DLS) and small angle X-ray scattering (SAXS) and compared to data derived from optical measurements. In addition to demonstrating the potential of this novel whole nanoobject approach for determining architectures of small nanoparticles, the presented results also highlight challenges faced by different sizing and structural analysis methods and method-inherent uncertainties. KW - Photoluminescence KW - Single particle KW - Microscopy KW - Particle architecture KW - Thickness KW - SAXS KW - Shell KW - XPS KW - TEM KW - Semiconductor KW - Quantum dot KW - Photophysics KW - Quantum yield PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517911 DO - https://doi.org/10.1038/s41598-020-77530-z VL - 10 IS - 1 SP - 20712 PB - Springer Nature AN - OPUS4-51791 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schutter, Jan David A1 - Eberhardt, Karl A1 - Elert, Anna Maria A1 - Radnik, Jörg A1 - Geißler, Daniel A1 - Özcan Sandikcioglu, Özlem T1 - Synthesis and characterization of lipopolysaccharide (LPS) anchored polystyrene microparticles as a synthetic model system for attachment studies N2 - Outer membrane lipopolysaccharides (LPS) play a crucial role in determining attachment behavior and pathogenicity of bacteria. The aim of this study was to develop a simple procedure for anchoring bacterial lipopolysaccharides to polystyrene (PS) microparticles as a model system for in situ attachment studies. By using a swellcapture methodology, commercially available LPS of Pseudomonas aeruginosa (strain ATCC 27316 serotype 10.22) was anchored onto PS microparticles in a proof-of-concept study. A detailed chemical and morphological characterization has proven the success of LPS incorporation. It was shown that the coverage and structure of the LPS film was concentration dependent. The procedure can easily be adapted to LPS of other bacterial strains to generate a synthetic model toolkit for attachment studies. KW - Bacterial lipopolysaccharides KW - Pseudomonas aeruginosa KW - Polystyrene microparticles KW - Swell-capture KW - Biomimicry PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-579818 DO - https://doi.org/10.1016/j.colsurfb.2023.113301 SN - 0927-7765 VL - 226 SP - 1 EP - 7 PB - Elsevier B.V. AN - OPUS4-57981 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Omar, Hassan A1 - Hiid, Gundula A1 - Szymoniak, Paulina A1 - Hertwig, Andreas A1 - Schönhals, Andreas T1 - Growth kinetics of the adsorbed layer of poly(bisphenol A carbonate) and its effect on the glass transition behavior in thin films N2 - The glass transition behavior of thin films of poly(bisphenol A carbonate) (PBAC) was studied employing ellipsometry. The glass transition temperature increases with the reduction of the film thickness. This result is attributed to the formation of an adsorbed layer with a reduced mobility compared to bulk PBAC. Therefore, for the first time, the growth kinetics of the adsorbed layer of PBAC was investigated, prepared by leaching samples from a 200 nm thin film which were annealed for several times at three different temperatures. The thickness of each prepared adsorbed layer was measured by multiple scans using atomic force microscopy (AFM). Additionally, an unannealed sample was measured. Comparison of the measurements of the unannealed and the annealed samples provides proof of a pre-growth regime for all annealing temperatures which was not observed for other polymers. For the lowest annealing temperature after the pre-growth stage only a growth regime with a linear time dependence is observed. For higher annealing temperatures the growth kinetics changes from a linear to a logarithmic growth regime at a critical time. At the longest annealing times the films showed signs of dewetting where segments of the adsorbed film were removed from the substrate (dewetting by desorption). The dependence of the surface roughness of the PBAC surface on annealing time also confirmed that the films annealed at highest temperatures for the longest times desorbed from the substrate. KW - Ultra thin polymer films PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-574531 DO - https://doi.org/10.1039/D3RA02020G SN - 2046-2069 VL - 13 IS - 21 SP - 14473 EP - 14483 PB - RSC Publishing CY - London AN - OPUS4-57453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sachse, René A1 - Bernsmeier, D. A1 - Schmack, R. A1 - Häusler, I. A1 - Hertwig, Andreas A1 - Kraffert, K. A1 - Nissen, J. A1 - Kraehnert, R. T1 - Colloidal bimetallic platinum–ruthenium nanoparticles in ordered mesoporous carbon films as highly active electrocatalysts for the hydrogen evolution reaction N2 - Hydrogen features a very high specific energy density and is therefore a promising candidate for clean fuel from renewable resources. Water electrolysis can convert electrical energy into storable and transportable hydrogen gas. Under acidic conditions, platinum is the most active and stable monometallic catalyst for the hydrogen evolution reaction (HER). Yet, platinum is rare and needs to be used efficiently. Here, we report a synthesis concept for colloidal bimetallic platinum–ruthenium and rhodium–ruthenium nanoparticles (PtRuNP, RhRuNP) and their incorporation into ordered mesoporous carbon (OMC) films. The films exhibit high surface area, good electrical conductivity and well-dispersed nanoparticles inside the mesopores. The nanoparticles retain their size, crystallinity and composition during carbonization. In the hydrogen evolution reaction (HER), PtRuNP/OMC catalyst films show up to five times higher activity per Pt than Pt/C/Nafion® and PtRu/C/Nafion® reference catalysts. KW - Ordered mesoporous carbon KW - Bimetallic noble metal nanoparticles KW - Platinum-ruthenium colloid KW - Electrolysis KW - Hydrogen evolution reaction PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-506868 DO - https://doi.org/10.1039/C9CY02285F SN - 2044-4753 VL - 10 IS - 7 SP - 2057 EP - 2068 PB - Royal Society of Chemistry AN - OPUS4-50686 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mezera, Marek A1 - Alamri, S. A1 - Hendriks, W. A. P. M. A1 - Hertwig, Andreas A1 - Elert, Anna Maria A1 - Bonse, Jörn A1 - Kunze, T. A1 - Lasagni, A. F. A1 - Römer, G. R. B. E. T1 - Hierarchical micro-/nano-structures on polycarbonate via UV pulsed laser processing N2 - Hierarchical micro/-nanostructures were produced on polycarbonate polymer surfaces by employing a two-step UV-laser processing strategy based on the combination of Direct Laser Interference Patterning (DLIP) of gratings and pillars on the microscale (3 ns, 266 nm, 2 kHz) and subsequently superimposing Laser-induced Periodic Surface Structures (LIPSS; 7–10 ps, 350 nm, 100 kHz) which adds nanoscale surface features. Particular emphasis was laid on the influence of the direction of the laser beam polarization on the morphology of resulting hierarchical surfaces. Scanning electron and atomic force microscopy methods were used for the characterization of the hybrid surface structures. Finite-difference time-domain (FDTD) calculations of the laser intensity distribution on the DLIP structures allowed to address the specific polarization dependence of the LIPSS formation observed in the second processing step. Complementary chemical analyzes by micro-Raman spectroscopy and attenuated total reflection Fourier-transform infrared spectroscopy provided in-depth information on the chemical and structural material modifications and material degradation imposed by the laser processing. It was found that when the linear laser polarization was set perpendicular to the DLIP ridges, LIPSS could be formed on top of various DLIP structures. FDTD calculations showed enhanced optical intensity at the topographic maxima, which can explain the dependency of the morphology of LIPSS on the polarization with respect to the orientation of the DLIP structures. It was also found that the degradation of the polymer was enhanced for increasing accumulated fluence levels. KW - Direct laser interference patterning KW - Laser-induced periodic surface structures (LIPSS) KW - Polycarbonate KW - Hierarchical structures KW - Surface functionalization PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509101 DO - https://doi.org/10.3390/nano10061184 SN - 2079-4991 VL - 10(6) IS - Special issue "Laser-generated periodic nanostructures" SP - 1184-1 EP - 1184-19 PB - MDPI CY - Basel AN - OPUS4-50910 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kirner, Sabrina V. A1 - Slachciak, Nadine A1 - Elert, Anna Maria A1 - Griepentrog, Michael A1 - Fischer, Daniel A1 - Hertwig, Andreas A1 - Sahre, Mario A1 - Dörfel, Ilona A1 - Sturm, Heinz A1 - Pentzien, Simone A1 - Koter, Robert A1 - Spaltmann, Dirk A1 - Krüger, Jörg A1 - Bonse, Jörn T1 - Tribological performance of titanium samples oxidized by fs-laser radiation, thermal heating, or electrochemical anodization N2 - Commercial grade-1 titanium samples (Ti, 99.6%) were treated using three alternative methods, (i) femtosecond laser processing, (ii) thermal heat treatment, and (iii) electrochemical anodization, respectively, resulting in the formation of differently conditioned superficial titanium oxide layers. The laser processing (i) was carried out by a Ti:sapphire laser (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz) in a regime of generating laser-induced periodic surface structures (LIPSS). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning setup for the processing of several square-millimeters large surface areas covered homogeneously by these nanostructures. The differently oxidized titanium surfaces were characterized by optical microscopy, micro Raman spectroscopy, variable angle spectroscopic ellipsometry, and instrumented indentation testing. The tribological performance was characterized in the regime of mixed friction by reciprocating sliding tests against a sphere of hardened steel in fully formulated engine oil as lubricant. The specific tribological performance of the differently treated surfaces is discussed with respect to possible physical and chemical mechanisms. KW - Femtosecond laser KW - Titanium KW - Oxidation KW - Friction PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-445609 DO - https://doi.org/10.1007/s00339-018-1745-8 SN - 0947-8396 SN - 1432-0630 VL - 124 IS - 4 SP - 326, 1 EP - 10 PB - Springer-Verlag AN - OPUS4-44560 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Almalla, A. A1 - Hertwig, Andreas A1 - Fischer, Daniel A1 - Özcan Sandikcioglu, Özlem A1 - Witt, Julia T1 - Development of layer-by-layer assembled thin coatings on aluminium alloy AA2024-T3 for high resolution studies of local corrosion processes N2 - The aim of this study is to develop nanometer-thin epoxy-based films on aluminium alloy AA2024-T3 as a model coating system for high resolution corrosion studies. Spin coating was used for the layer-by-layer (LbL) deposition of poly-(ethylenimine) (PEI) and poly([o-cresyl glycidyl ether]-co-formaldehyde) (CNER) bilayers. The film chemistry and the cross-linking process were characterized by means of Fourier-transform infrared spectroscopy (FTIR). Ellipsometric data confirmed the linear increase of film thickness. The potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) results indicate the improvement of the film barrier properties with increasing film thickness. Mapping of the topography and the volta potential was performed by means of scanning Kelvin probe force microscopy (SKPFM). The results indicate the presence of a homogeneous film structure, while the intermetallic phases can still be identified below the coating. The SKPFM Analysis confirmed that the model films are suitable for investigation of corrosion processes at the coating/metal interface. KW - Spectroscopy KW - Coatings KW - Electrochemistry KW - Microscopy KW - Resins PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-514627 DO - https://doi.org/10.1002/app.49826 SN - 0021-8995 VL - 137 IS - 48 SP - e49826-1 EP - e49826-9 PB - Wiley CY - New York, NY AN - OPUS4-51462 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Minenkov, Alexey A1 - Hollweger, Sophia A1 - Duchoslav, Jiri A1 - Erdene-Ochir, Otgonbayar A1 - Weise, Matthias A1 - Ermilova, Elena A1 - Hertwig, Andreas A1 - Schiek, Manuela T1 - Monitoring the Electrochemical Failure of Indium Tin Oxide Electrodes via Operando Ellipsometry Complemented by Electron Microscopy and Spectroscopy N2 - Transparent conductive oxides such as indium tin oxide (ITO) are standards for thin film electrodes, providing a synergy of high optical transparency and electrical conductivity. In an electrolytic environment, the determination of an inert electrochemical potential window is crucial to maintain a stable material performance during device operation. We introduce operando ellipsometry, combining cyclic voltammetry (CV) with spectroscopic ellipsometry, as a versatile tool to monitor the evolution of both complete optical (i.e., complex refractive index) and electrical properties under wet electrochemical operational conditions. In particular, we trace the degradation of ITO electrodes caused by electrochemical reduction in a pH-neutral, water-based electrolyte environment during electrochemical cycling. With the onset of hydrogen evolution at negative bias voltages, indium and tin are irreversibly reduced to the metallic state, causing an advancing darkening, i.e., a gradual loss of transparency, with every CV cycle, while the conductivity is mostly conserved over multiple CV cycles. Post-operando analysis reveals the reductive (loss of oxygen) formation of metallic nanodroplets on the surface. The reductive disruption of the ITO electrode happens at the solid–liquid interface and proceeds gradually from the surface to the bottom of the layer, which is evidenced by cross-sectional transmission electron microscopy imaging and complemented by energy-dispersive X-ray spectroscopy mapping. As long as a continuous part of the ITO layer remains at the bottom, the conductivity is largely retained, allowing repeated CV cycling. We consider operando ellipsometry a sensitive and nondestructive tool to monitor early stage material and property changes, either by tracing failure points, controlling intentional processes, or for sensing purposes, making it suitable for various research fields involving solid–liquid interfaces and electrochemical activity. KW - General Materials Science PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597625 DO - https://doi.org/10.1021/acsami.3c17923 SN - 1944-8252 VL - 16 IS - 7 SP - 9517 EP - 9531 PB - American Chemical Society (ACS) AN - OPUS4-59762 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Grundmann, Jana A1 - Bodermann, Bernd A1 - Ermilova, Elena A1 - Weise, Matthias A1 - Hertwig, Andreas A1 - Klapetek, Petr A1 - Rafighdoost, Jila A1 - Pereira, Silvania F. T1 - Optical and tactile measurements on SiC sample defects N2 - Abstract. In power electronics, compound semiconductors with large bandgaps, like silicon carbide (SiC), are increasingly being used as material instead of silicon. They have a lot of advantages over silicon but are also intolerant of nanoscale material defects, so that a defect inspection with high accuracy is needed. The different defect types on SiC samples are measured with various measurement methods, including optical and tactile methods. The defect types investigated include carrots, particles, polytype inclusions and threading dislocations, and they are analysed with imaging ellipsometry, coherent Fourier scatterometry (CFS), white light interference microscopy (WLIM) and atomic force microscopy (AFM). These different measurement methods are used to investigate which method is most sensitive for which type of defect to be able to use the measurement methods more effectively. It is important to be able to identify the defects to classify them as critical or non-critical for the functionality of the end product. Once these investigations have been completed, the measurement systems can be optimally distributed to the relevant defects in further work to realize a hybrid analysis of the defects. In addition to the identification and classification of defects, such a future hybrid analysis could also include characterizations, e.g. further evaluation of ellipsometric data by using numerical simulations. KW - Compound semiconductors KW - Hybrid metrology KW - Material defects KW - Spectroscopic Ellipsometry KW - Scanning Probe Microscopy KW - White-light Interference Microscopy PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601220 DO - https://doi.org/10.5194/jsss-13-109-2024 SN - 2194-878X VL - 13 IS - 1 SP - 109 EP - 121 PB - Copernicus GmbH AN - OPUS4-60122 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Müller, Kai A1 - Mirabella, Francesca A1 - Knigge, Xenia A1 - Mezera, Marek A1 - Weise, Matthias A1 - Sahre, Mario A1 - Wasmuth, Karsten A1 - Voss, Heike A1 - Hertwig, Andreas A1 - Krüger, Jörg A1 - Radnik, Jörg A1 - Hodoroaba, Vasile-Dan A1 - Bonse, Jörn T1 - Chemical and topographical changes upon sub-100-nm laser-induced periodic surface structure formation on titanium alloy: the influence of laser pulse repetition rate and number of over-scans N2 - Titanium and its alloys are known to allow the straightforward laser-based manufacturing of ordered surface nanostructures, so-called high spatial frequency laser-induced periodic surface structures (HSFL). These structures exhibit sub-100 nm spatial periods – far below the optical diffraction limit. The resulting surface functionalities are usually enabled by both, topographic and chemical alterations of the nanostructured surfaces. For exploring these effects, multi-method characterizations were performed here for HSFL processed on Ti–6Al–4V alloy upon irradiation with near-infrared ps-laser pulses (1030 nm, ≈1 ps pulse duration, 1–400 kHz) under different laser scan processing conditions, i.e., by systematically varying the pulse repetition frequency and the number of laser irradiation passes. The sample characterization involved morphological and topographical investigations by scanning electron microscopy (SEM), atomic force microscopy (AFM), tactile stylus profilometry, as well as near-surface chemical analyses hard X-ray photoelectron spectroscopy (HAXPES) and depth-profiling time-of-flight secondary ion mass spectrometry (ToF-SIMS). This provides a quantification of the laser ablation depth, the geometrical HSFL characteristics and enables new insights into the depth extent and the nature of the non-ablative laser-induced near-surface oxidation accompanying these nanostructures. This allows to answer the questions how the processing of HSFL can be industrially scaled up, and whether the latter is limited by heat-accumulation effects. T2 - 2023 E-MRS Spring Meeting, Symposium L "Making light matter: lasers in material sciences and photonics" CY - Strasbourg, France DA - 29.05.2023 KW - Laser-induced periodic surface structures (LIPSS) KW - Ultrashort laser pulses KW - Laser processing KW - Hard X-ray photoelectron spectroscopy (HAXPES) KW - Time-of-flight secondary ion mass spectrometry (ToF-SIMS) PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-589902 UR - https://onlinelibrary.wiley.com/doi/full/10.1002/pssa.202300719 DO - https://doi.org/10.1002/pssa.202300719 SN - 1862-6319 VL - 220 SP - 1 EP - 12 PB - Wiley-VCH GmbH CY - Weinheim AN - OPUS4-58990 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Voss, Heike A1 - Knigge, Xenia A1 - Knapic, D. A1 - Weise, Matthias A1 - Sahre, Mario A1 - Hertwig, Andreas A1 - Sacco, A. A1 - Rossi, A. M. A1 - Radnik, Jörg A1 - Müller, Kai A1 - Wasmuth, Karsten A1 - Krüger, Jörg A1 - Hassel, A. W. A1 - Hodoroaba, Vasile-Dan A1 - Bonse, Jörn T1 - Picosecond laser processing of hierarchical micro–nanostructures on titanium alloy upon pre- and postanodization: morphological, structural, and chemical effects N2 - Recent publications indicate that the order of electrochemical anodization (before or after the laser processing step) plays an important role for the response of bone-forming osteoblasts—an effect that can be utilized for improving permanent dental or removable bone implants. For exploring these different surface functionalities, multimethod morphological, structural, and chemical characterizations are performed in combination with electrochemical pre- and postanodization for two different characteristic microspikes covered by nanometric laser-induced periodic surface structures on Ti–6Al–4V upon irradiation with near-infrared ps-laser pulses (1030 nm wavelength, ≈1 ps pulse duration, 67 and 80 kHz pulse repetition frequency) at two distinct sets of laser fluence and beam scanning parameters. This work involves morphological and topographical investigations by scanning electron microscopy and white light interference microscopy, structural material examinations via X-ray diffraction, and micro-Raman spectroscopy, as well as near-surface chemical analyses by X-ray photoelectron spectroscopy and hard X-ray photoelectron spectroscopy. The results allow to qualify the mean laser ablation depth, assess the spike geometry and surface roughness parameters, and provide new detailed insights into the near-surface oxidation that may affect the different cell growth behavior for pre- or postanodized medical implants. T2 - 2023 E-MRS Spring Meeting, Symposium L "Making light matter: lasers in material sciences and photonics" CY - Strasbourg, France DA - 29.05.2023 KW - Hierarchical micro-nanostructures KW - Laser-induced periodic surface structures (LIPSS) KW - Ultrashort laser pulses KW - Ti-6Al-4V alloy KW - X-ray photoelectron spectroscopy PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601962 DO - https://doi.org/10.1002/pssa.202300920 SN - 1862-6319 SP - 1 EP - 11 PB - Wiley-VCH GmbH CY - Weinheim AN - OPUS4-60196 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hertwig, Andreas T1 - New analytic ways to characterise mesoporous thin layers used in electrocatalytic water splitting N2 - Mesoporous materials are needed in many applications where a high specific surface area and adsorptive behaviour is needed. Important examples are separation techniques and barrier layers and catalysts. Electrochemical water splitting is the key technology for producing green hydrogen and there is no foreseeable alternative to this process for producing elementary hydrogen from green electrical power. Water electrolysis can be divided into the anodic Oxygen Evolution Reaction (OER) and the cathodic Hydrogen Evolution Reaction (HER). Both processes have to be heavily optimised to a large extent to avoid energy losses caused by overvoltage. The development of electrodes for these processes is especially difficult due to the many boundary conditions. Water splitting is a catalytic as well as electrochemical process. The contact area between the electrolyte and the electrode must be maximised maintaining the stability of the surface. Side reactions must be suppressed, and effective gas transport must be ensured. The whole process has to be tolerant with respect to temperature, harsh chemical conditions from the electrolyte as well as high current densities. We present a hybrid analytical method combining several analytical techniques for determining the properties of thin layers of mixed oxides of the general composition Ir:TiOx. These materials are promising candidates for electrocatalytical top coatings of OER electrodes. To lower the costs of the electrolysers, the main goal is to lower the Ir content retaining the system efficiency. The main properties which are hard to determine are the porous volume fraction and the Ir:Ti element ratio. By a combination of electron microscopy, spectroscopic operando ellipsometry, ellipsometric porosimetry, and other techniques, we can determine key features of mesoporous thin layer materials. We aim to develop operando capable techniques used in process monitoring as well as measurement techniques optimised for accuracy. By developing reference materials, we support long term uptake of our methodology. This work can directly be used for optimising electrocatalytic layers and is a good example for the power of hybrid metrology for improving materials design. T2 - International Conference on Resource Chemistry CY - Alzenau, Germany DA - 11.03.2024 KW - Ellipsometry KW - Electrocatalytic Water Splitting KW - Mesoporous Materials KW - Electron Probe Microanalysis KW - Hydrogen Generation PY - 2024 AN - OPUS4-59764 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hertwig, Andreas A1 - Piquemal, François A1 - Hoffmann, Johannes A1 - Kaya, Khaled A1 - Gaultier, Brice A1 - Fabricius, Norbert A1 - Sachse, René T1 - ELENA: a European project for electrical nanoscale metrology in industry N2 - A competitive advantage in the semiconductors industry is gained through the exploitation of new materials and processes, translating into improved components’ performances. This requires a metrological infrastructure allowing reliable nanoscale characterisation of new materials and devices, particularly in terms of their electrical parameters and properties. Traceability and reliability of nanoscale measurements stand as a major challenge for electrical properties (i.e. resistance, impedance) using conductive atomic force microscopy (C-AFM) and scanning microwave microscopy (SMM) techniques. The non-destructive analysis nature of these two methods is of paramount importance for the characterization of devices and components. However, the state of the art still lacks established measurement protocols, easy to use reference standards, well-defined best practice guides and easy to use 3D models to assess environmental and external stimulation effects. Moreover, costly instrumentation, particularly for high-frequency measurements, still hinders efficient advancements in these directions. ELENA is a 3-years European project that aims at bringing solutions to the aforementioned difficulties. To achieve this goal, the project uses a combination of nanoscale electrodynamic scanning probe methods in combination with optical tools such as spectroscopic ellipsometry on several lateral length scales to determine the electrical properties of layers and small structures. T2 - ICSE-9: The 9th International Conference on Spectroscopic Ellipsometry CY - Beijing, China DA - 2022-05-21 KW - Imaging Ellipsometry KW - Electrical thin layers KW - Scanning Probe methods KW - Hybrid metrology PY - 2022 AN - OPUS4-55464 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Omar, Hassan A1 - Szymoniak, Paulina A1 - Hertwig, Andreas A1 - Schönhals, Andreas T1 - Probing Nanoscale Relaxation Behavior in Thin Polymer Films N2 - The investigations into the complicated effects of film thickness on bulk properties of thin polymer films has yielded conflicting results. The reduction in molecular mobility, and with it an increase in the glass transition temperature, for thin films of poly (bisphenol A carbonate) (PBAC) was assigned to the formation of an adsorbed layer. The adsorbed layer was obtained by washing away the loosely bounded chains using a good solvent. Next, using atomic force microscopy (AFM), the thickness of each sample was measured after annealing for various times at three different annealing temperatures. The growth of this adsorbed layer was shown to deviate from the previously reported 2-step mechanism seen for other polymers. For PBAC, after very long annealing times at high temperatures the thin films were dewetted, where segments of the adsorbed layer were removed from the substrate. T2 - Royal Society of Chemistry (RSC) Poster CY - Online meeting DA - 28.02.2023 KW - Thin films KW - Adsorbed Layer KW - Broadband dielectric spectroscopy KW - Atomic force microscopy KW - Growth Kinetics PY - 2023 AN - OPUS4-57196 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wolff, M. A1 - Wonneberger, R. A1 - Freiberg, K.E. A1 - Hertwig, Andreas A1 - Bonse, Jörn A1 - Giebeler, L. A1 - Koitzsch, A. A1 - Kunz, C. A1 - Weber, H. A1 - Hufenbach, J.K. A1 - Müller, F.A. A1 - Gräf, S. T1 - Formation of laser-induced periodic surface structures on Zr-based bulk metallic glasses with different chemical composition N2 - Bulk metallic glasses (BMG) are amorphous metal alloys known for their unique physical and mechanical properties. In the present study, the formation of femtosecond (fs) laser-induced periodic surface structures (LIPSS) on the Zr-based BMGs Zr46Cu46Al8, Zr61Cu25Al12Ti2, Zr52.5Cu17.9Al10Ni14.6Ti5 (Vit105) and Zr57Cu15.4Al10Ni12.6Nb5 (Vit106) was investigated as a function of their different chemical composition. For this purpose, LIPSS were generated on the sample surfaces in an air environment by fs-laser irradiation (λ = 1025 nm, τ = 300 fs, frep = 100 kHz). The surface topography was characterized by scanning electron microscopy and atomic force microscopy. Moreover, the impact of LIPSS formation on the structure and chemical surface composition was analyzed before and after fs-laser irradiation by X-ray diffraction and X-ray photoelectron spectroscopy as well as by transmission electron microscopy in combination with energy dispersive X-ray spectroscopy. Despite the different chemical composition of the investigated BMGs, the fs-laser irradiation resulted in almost similar properties of the generated LIPSS patterns. In the case of Zr61Cu25Al12Ti2, Vit105 and Vit106, the surface analysis revealed the preservation of the amorphous state of the materials during fs-laser irradiation. The study demonstrated the presence of a native oxide layer on all pristine BMGs. In addition, fs-laser irradiation results in the formation of laser-induced oxide layers of larger thickness consisting of an amorphous ZrAlCu-oxide. The precise laser-structuring of BMG surfaces on the nanoscale provides a versatile alternative to thermoplastic forming of BMG surfaces and is of particular interest for the engineering of functional material surfaces. KW - Bulk metallic glasses KW - Femtosecond laser KW - Laser-induced periodic surface structures (LIPSS) KW - Chemical analysis KW - Oxidation PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-581799 DO - https://doi.org/10.1016/j.surfin.2023.103305 SN - 2468-0230 VL - 42 SP - 1 EP - 11 PB - Elsevier B.V. AN - OPUS4-58179 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Bresch, Harald A1 - Rühle, Bastian A1 - Hodoroaba, Vasile-Dan A1 - Seeger, Stefan A1 - Resch-Genger, Ute A1 - Braun, Ulrike A1 - Jann, Oliver A1 - Wilke, Olaf A1 - Geißler, Daniel A1 - Schmidt, Alexandra A1 - Unger, Wolfgang A1 - Sturm, Heinz T1 - Stand der Aktivitäten zur gemeinsamen Forschungsstrategie N2 - Die gemeinsame Forschungsstrategie der Bundesoberbehörden zur Nanotechnologie wurde 2016 veröffentlicht. Die darin enthaltenen Aufgaben wurden von den Bundesoberbehörden vielfältig bearbeitet. Diese Präsentation gibt einen Überblick über die Projekte, die von der BAM bis 2019 bearbeitet wurden/werden und sich in den Rahmen der Forschungsstrategie einordnen. T2 - Workshop zur gemeinsamen Forschungsstrategie der Bundesoberbehörden „Nanomaterialien und andere innovative Werkstoffe: anwendungssicher und umweltverträglich“ CY - Berlin, Germany DA - 02.09.2019 KW - Nano KW - Bundesoberbehörden KW - Forschungsstrategie KW - Nanomaterialien KW - Nanotechnologie PY - 2019 AN - OPUS4-49586 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Omar, Hassan A1 - Szymoniak, Paulina A1 - Hertwig, Andreas A1 - Schönhals, Andreas T1 - Growth Kinetics and Molecular Mobility of the Adsorbed Layer of Poly(bisphenol-A Carbonate) (PBAC), Polysulfone (PSU), and Poly (2-Vinyl Pyridine) (P2VP) N2 - Interactions between a polymer and a substrate interface play a vital role in understanding the improvement in thin film material properties as well as serving as a model for nanocomposites. For any non-repulsive polymer-substrate interactions, polymer segments form an irreversibly adsorbed layer and show a slowdown in the glassy dynamics and thus an increase in the thermal glass transition temperature compared to the bulk-like values. The growth kinetics of the adsorbed layer showed a deviation for both poly (bisphenol-A carbonate) (PBAC) and polysulfone (PSU), two bulky polymers containing a functional group (phenyl ring) in the backbone, compared to conventional polymers previously studied like poly-2-vinyl pyridine (P2VP). This deviation was attributed to the bulkiness of the phenyl rings. . Further investigations into the influence of the adsorbed layer on glassy dynamics were conducted. The molecular mobility and glass transition for thin films of PBAC and PSU were compared to bulk samples of each polymer. Broadband dielectric spectroscopy, atomic force microscopy, and ellipsometry were primarily used and additionally supported by sum frequency generation spectroscopy. T2 - Deutsche Physikalische Gesellschaft (DPG) Tagung CY - Berlin, Germany DA - 17.03.2024 KW - Thin films KW - Adsorbed Layer KW - Atomic Force Microscopy KW - Ellipsometry KW - Dielectric Spectroscopy PY - 2024 AN - OPUS4-59821 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schusterbauer, Robert A1 - Sahre, Mario A1 - Mrkwitschka, Paul A1 - John, Elisabeth A1 - Lange, Thorid A1 - Zurutuza, A. A1 - Jones, E. A1 - Donskyi, I. A1 - Radnik, Jörg A1 - Hodoroaba, Vasile-Dan T1 - Correlative chemical imaging to reveal the nature of different commercial graphene materials N2 - Since the original report in 2004 by Novoselov and Geim, Graphene gained incredible attention due to its fascinating properties. In the past 20 years, the synthesis and functionalization of graphene has evolved significantly[3]. Different synthesis techniques were developed which led to other graphenerelated materials such as graphene oxide (GO) or elemental-doped graphene. Further chemical functionalization can enhance but also alter or reduce specific properties of the graphene. To reveal the nature of these materials a proper physico‑chemical characterization with different analytical techniques is crucial. Single-layer GO flakes kindly provided by Graphenea (Spain) were prepared for systematic image analysis. These flakes were disposed on an alignment-marked SiO2 substrate and correlatively imaged by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and Raman spectroscopy. The high lateral resolution and/ or extreme surface sensitivity of the mentioned techniques is necessary to explore monolayers. The ToF-SIMS images match well with the SEM and AFM images and provide information about the chemistry. With 2D Raman spectroscopy it is possible to differentiate between the number of stacked single-layer flakes. This is visualized in a 3D image (Figure b). Well-defined GO flakes could be used as a reference material for imaging of graphene-like structures but also of other types of 2D materials. In addition to these monolayer GO flakes, commercial graphene-containing inks (Haydale) with a more complex morphology were also correlatively imaged. ToF-SIMS and SEM images were merged to identify the origin of different chemical fragments. The findings correlate closely with the expectation that the specific functionalizations (with fluorine and nitrogen as marker elements) are present only on the graphene flakes as presumed from the SEM images. Energy-dispersive X-ray spectroscopy (EDX) supports these results, yet with a much lower sensitivity compared to ToF-SIMS. T2 - MaterialsWeek 2024 CY - Limassol, Cyprus DA - 17.06.2024 KW - Graphene oxide flakes KW - ToF-SIMS KW - SEM KW - Raman KW - Correlative imaging PY - 2024 AN - OPUS4-60681 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schusterbauer, Robert A1 - Sahre, Mario A1 - Mrkwitschka, Paul A1 - John, Elisabeth A1 - Lange, Thorid A1 - Zurutuza, A. A1 - Jones, E. A1 - Donskyi, I. A1 - Radnik, Jörg A1 - Hodoroaba, Vasile-Dan T1 - Correlative chemical imaging to reveal the nature of different commercial graphene materials N2 - Since the original report in 2004 by Novoselov and Geim, Graphene gained incredible attention due to its fascinating properties. In the past 20 years, the synthesis and functionalization of graphene has evolved significantly[3]. Different synthesis techniques were developed which led to other graphenerelated materials such as graphene oxide (GO) or elemental-doped graphene. Further chemical functionalization can enhance but also alter or reduce specific properties of the graphene. To reveal the nature of these materials a proper physico‑chemical characterization with different analytical techniques is crucial. Single-layer GO flakes kindly provided by Graphenea (Spain) were prepared for systematic image analysis. These flakes were disposed on an alignment-marked SiO2 substrate and correlatively imaged by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and Raman spectroscopy. The high lateral resolution and/ or extreme surface sensitivity of the mentioned techniques is necessary to explore monolayers. The ToF-SIMS images match well with the SEM and AFM images and provide information about the chemistry. With 2D Raman spectroscopy it is possible to differentiate between the number of stacked single-layer flakes. This is visualized in a 3D image (Figure b). Well-defined GO flakes could be used as a reference material for imaging of graphene-like structures but also of other types of 2D materials. In addition to these monolayer GO flakes, commercial graphene-containing inks (Haydale) with a more complex morphology were also correlatively imaged. ToF-SIMS and SEM images were merged to identify the origin of different chemical fragments. The findings correlate closely with the expectation that the specific functionalizations (with fluorine and nitrogen as marker elements) are present only on the graphene flakes as presumed from the SEM images. Energy-dispersive X-ray spectroscopy (EDX) supports these results, yet with a much lower sensitivity compared to ToF-SIMS. T2 - ECASIA 2024 CY - Gothenburg, Sweden DA - 09.06.2024 KW - Correlative imaging KW - ToF-SIMS KW - SEM KW - Graphene oxide flakes KW - Raman PY - 2024 AN - OPUS4-60680 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholtz, Lena A1 - Tavernaro, Isabella A1 - Eckert, J. G. A1 - Lutowski, Marc A1 - Geißler, Daniel A1 - Hertwig, Andreas A1 - Hidde, Gundula A1 - Bigall, N. C. A1 - Resch-Genger, Ute T1 - Influence of nanoparticle encapsulation and encoding on the surface chemistry of polymer carrier beads N2 - Surface-functionalized polymer beads encoded with molecular luminophores and nanocrystalline emitters such as semiconductor nanocrystals, often referred to as quantum dots (QDs), or magnetic nanoparticles are broadly used in the life sciences as reporters and carrier beads. Many of these applications require a profound knowledge of the chemical nature and total number of their surface functional groups (FGs), that control bead charge, colloidal stability, hydrophobicity, and the interaction with the environment and biological systems. For bioanalytical applications, also the number of groups accessible for the subsequent functionalization with, e.g., biomolecules or targeting ligands is relevant. In this study, we explore the influence of QD encoding on the amount of carboxylic acid (COOH) surface FGs of 2 μm polystyrene microparticles (PSMPs). This is done for frequently employed oleic acid and oleylamine stabilized, luminescent core/shell CdSe QDs and two commonly used encoding procedures. This included QD addition during bead formation by a thermally induced polymerization reaction and a post synthetic swelling procedure. The accessible number of COOH groups on the surface of QD-encoded and pristine beads was quantified by two colorimetric assays, utilizing differently sized reporters and electrostatic and covalent interactions. The results were compared to the total number of FGs obtained by a conductometric titration and Fourier transform infrared spectroscopy (FTIR). In addition, a comparison of the impact of QD and dye encoding on the bead surface chemistry was performed. Our results demonstrate the influence of QD encoding and the QD-encoding strategy on the number of surface FG that is ascribed to an interaction of the QDs with the carboxylic acid groups on the bead surface. These findings are of considerable relevance for applications of nanoparticle-encoded beads and safe-by-design concepts for nanomaterials. KW - Optical spectroscopy KW - Particle KW - Optical assay KW - IR spectroscopy KW - Fluorescence KW - Quantum yield KW - Quality assurance KW - Nano KW - Synthesis KW - Surface chemistry KW - Quantification KW - Method KW - Conductometry PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-581502 DO - https://doi.org/10.1038/s41598-023-38518-7 SN - 2045-2322 VL - 13 IS - 1 SP - 1 EP - 15 PB - Springer Nature CY - London AN - OPUS4-58150 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sachse, René A1 - Hodoroaba, Vasile-Dan A1 - Kraehnert, R. A1 - Hertwig, Andreas T1 - Multilevel effective material approximation for modeling ellipsometric measurements on complex porous thin films N2 - Catalysts are important components in chemical processes because they lower the activation energy and thus determine the rate, efficiency and selectivity of a chemical reaction. This property plays an important role in many of today’s processes, including the electrochemical splitting of water. Due to the continuous development of catalyst materials, they are becoming more complex, which makes a reliable evaluation of physicochemical properties challenging even for modern analytical measurement techniques and industrial manufacturing. We present a fast, vacuum-free and non-destructive analytical approach using multi-sample spectroscopic ellipsometry to determine relevant material parameters such as film thickness, porosity and composition of mesoporous IrOx–TiOy films. Mesoporous IrOx–TiOy films were deposited on Si wafers by sol–gel synthesis, varying the composition of the mixed oxide films between 0 and 100 wt%Ir. The ellipsometric modeling is based on an anisotropic Bruggeman effective medium approximation (a-BEMA) to determine the film thickness and volume fraction of the material and pores. The volume fraction of the material was again modeled using a Bruggeman EMA to determine the chemical composition of the materials. The ellipsometric fitting results were compared with complementary methods, such as scanning electron microscopy (SEM), electron probe microanalysis (EPMA) as well as environmental ellipsometric porosimetry (EEP). KW - Electrochemical catalysts KW - Mixed metal oxide KW - Multi-sample analysis KW - Spectroscopic ellipsometry KW - Thin mesoporous films PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-551026 DO - https://doi.org/10.1515/aot-2022-0007 SN - 2192-8584 SN - 2192-8576 VL - 11 IS - 3-4 (Topical issue: Ellipsometry) SP - 137 EP - 147 PB - De Gruyter CY - Berlin AN - OPUS4-55102 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Völzke, Jule L. A1 - Hodjat Shamami, Parya A1 - Gawlitza, Kornelia A1 - Feldmann, Ines A1 - Zimathies, Annett A1 - Meyer, Klas A1 - Weller, Michael G. T1 - High-purity corundum as support for affinity extractions from complex samples N2 - Nonporous corundum powder, known as an abrasive material in the industry, was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices. The materials based on corundum were characterized by TEM, ESEM, BET, DLS, EDS, and zeta potential measurements. The strong Al-O-P bonds between the corundum surface and amino phosphonic acids were used to introduce functional groups for further conjugations. The common crosslinker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter was oxidized with periodate to generate aldehyde groups that can covalently react with the amines of the surface and the amino groups from the protein via a reductive amination process. The amount of bound protein was quantified via aromatic amino acid analysis (AAAA). This work shows that oxidized polyglycerol can be used as an alternative to glutaraldehyde. With polyglycerol, more of the model protein bovine serum albumin (BSA) could be attached to the surface under the same conditions, and lower non-specific binding (NSB) was observed. As a proof of concept, IgG was extracted with protein A from crude human plasma. The purity of the product was examined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). A binding capacity of 1.8 mg IgG per gram of corundum powder was achieved. The advantages of corundum include the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, convenient handling, and flexible application. KW - Corundum KW - Sapphire KW - Affinity chromatography KW - Antibodies KW - Self-assembled monolayers (SAM) KW - Polyglycerol KW - Dendrimer KW - Nonspecific binding (NSB) KW - Purification KW - Solid-phase extraction (SPE) PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-559342 DO - https://doi.org/10.3390/separations9090252 VL - 9 IS - 9 SP - 1 EP - 13 PB - MDPI CY - Basel AN - OPUS4-55934 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - INPR A1 - Völzke, Jule L. A1 - Hodjat Shamami, Parya A1 - Gawlitza, Kornelia A1 - Feldmann, Ines A1 - Zimathies, Annett A1 - Weller, Michael G. T1 - High-purity corundum as support for affinity extractions from complex samples N2 - Nonporous corundum powder, known as an abrasive material in the industry, was functionalized covalently with protein binders to isolate and enrich specific proteins from complex matrices. The materials based on corundum were characterized by TEM, ESEM, BET, DLS, and zeta potential measurements. The strong Al-O-P bonds between the corundum surface and amino phosphonic acids are used to introduce functional groups for further conjugations. The common cross-linker glutaraldehyde was compared with a hyperbranched polyglycerol (PG) of around 10 kDa. The latter is oxidized with periodate to generate aldehyde groups that can covalently react with the amines of the surface and the amino groups from the protein via a reductive amination process. The amount of bound protein was quantified via aromatic amino acid analysis (AAAA). This work shows that oxidized polyglycerol can be used as an alternative to glutaraldehyde. With polyglycerol, more of the model protein bovine serum albumin (BSA) could be attached to the surface under the same conditions, and lower nonspecific binding (NSB) was observed. As a proof of concept, IgG was extracted with protein A from crude human plasma. The purity of the product was examined by SDS-PAGE. A binding capacity of 1.8 mg IgG per g of corundum powder was achieved. The advantages of corundum are the very low price, extremely high physical and chemical stability, pressure resistance, favorable binding kinetics, and flexible application. KW - Protein KW - Bioseparation KW - Purification KW - Immunoprecipitation KW - Affinity chromatography KW - Polyglycerol KW - Glutaraldehyde KW - Linker KW - Bioconjugation KW - Self-assembled monolayer (SAM) KW - Periodate oxidation KW - Reductive amination KW - Antibodies KW - Igg KW - Immunoglobulins KW - Carrier KW - Solid phase KW - Hyperbranched polymer KW - Aromatic amino acid analysis aaaa PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-555142 DO - https://doi.org/10.20944/preprints202208.0004.v1 SN - 2310-287X SP - 1 EP - 13 PB - MDPI CY - Basel AN - OPUS4-55514 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ponader, Marco A1 - Röder, Bettina A1 - Paul, Martin A1 - Weller, Michael G. T1 - Sintered glass monoliths as supports for affinity columns N2 - A novel stationary phase for affinity separations is presented. This material is based on sintered borosilicate glass readily available as semi-finished filter plates with defined porosity and surface area. The material shows fast binding kinetics and excellent long-term stability under real application conditions due to lacking macropores and high mechanical rigidity. The glass surface can be easily modified with standard organosilane chemistry to immobilize selective binders or other molecules used for biointeraction. In this paper, the manufacturing of the columns and their respective column holders by 3D printing is shown in detail. The model system protein A/IgG was chosen as an example to examine the properties of such monolithic columns under realistic application conditions. Several specifications, such as (dynamic) IgG capacity, pressure stability, long-term performance, productivity, non-specific binding, and peak shape, are presented. It could be shown that due to the very high separation speed, 250 mg antibody per hour and column can be collected, which surpasses the productivity of most standard columns of the same size. The total IgG capacity of the shown columns is around 4 mg (5.5 mg/mL), which is sufficient for most tasks in research laboratories. The cycle time of an IgG separation can be less than 1 min. Due to the glass material’s excellent pressure resistance, these columns are compatible with standard HPLC systems. This is usually not the case with standard affinity columns, limited to manual use or application in low-pressure systems. The use of a standard HPLC system also improves the ability for automation, which enables the purification of hundreds of cell supernatants in one day. The sharp peak shape of the elution leads to an enrichment effect, which might increase the concentration of IgG by a factor of 3. The final concentration of IgG can be around 7.5 mg/mL without the need for an additional nano-filtration step. The purity of the IgG was > 95% in one step and nearly 99% with a second polishing run. KW - Affinity Chromatography KW - Affinity Extraction KW - Affinity Separation KW - Protein Purification KW - Down Stream Processing KW - Antibody Purification KW - Diagnostic Antibodies KW - Therapeutic Antibodies KW - Automated Purification KW - HPLC KW - FPLC KW - IgG determination KW - Concentration step KW - Monoclonal Antibodies KW - Polyclonal Antibodies KW - Human Plasma KW - Glass Support KW - Borosilicate Glass KW - Monolith KW - Sintered Material KW - Additive Manufacturing KW - Column holder KW - Construction KW - Open Science KW - Citizen Science KW - Protein A KW - Regeneration KW - High-Speed Separations KW - Robustness PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-527581 DO - https://doi.org/10.3390/separations8050056 SN - 2297-8739 N1 - Geburtsname von Ponader, Marco: Wilke, M. - Birth name of Ponader, Marco: Wilke, M. VL - 8 IS - 5 SP - 1 EP - 16 PB - MDPI CY - Basel AN - OPUS4-52758 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hertwig, Andreas A1 - Radnik, Jörg A1 - Ermilova, Elena A1 - Hodoroaba, Vasile-Dan T1 - Accuracy on all scales: Hybrid metrology for micro- and nanomanufacturing N2 - In this presentation, we discuss hybrid metrology and correlative imaging. These techniques are used to improve the design and quality monitoring of nanomaterials used in energy technology and for referencing the properties of nanoparticles. T2 - EMN for Advanced Manufacturing workshop CY - Berlin, Germany DA - 22.05.2024 KW - Nanotechnology KW - Nanoanalytics KW - Correlative Spectroscopy KW - Correlative Imaging PY - 2024 AN - OPUS4-60240 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Hertwig, Andreas A1 - Ermilova, Elena T1 - Optical constants of a single AlN layer on Si N2 - Spectroscopic ellipsometry was used to determine the thickness and dielectric function of a Aluminium Nitride (AlN) layer on a Si wafer. The layer was determined to be 170 nm thick. The layer was provided by AIXTRON and manufactured by means of MOVPE. The data was created using a M2000DI spectroscopic ellipsometer from Woollam Co. Inc. Analysis was done using the CompleteEASE software. The model used is a multi-peak oscillator model for the AlN layer. The data resembles common database values for the material AlN. KW - Aluminium nitride KW - Thin solid layers KW - Spectroscopic ellipsometry KW - Compund semiconductors KW - MOVPE PY - 2024 UR - https://zenodo.org/records/12743500 DO - https://doi.org/10.5281/zenodo.12743499 PB - Zenodo CY - Geneva AN - OPUS4-60661 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sachse, René A1 - Pflüger, Mika A1 - Velasco Vélez, Juan Jesús A1 - Sahre, Mario A1 - Radnik, Jörg A1 - Bernicke, Michael A1 - Bernsmeier, Denis A1 - Hodoroaba, Vasile-Dan A1 - Krumrey, Michael A1 - Strasser, Peter A1 - Kraehnert, Ralph A1 - Hertwig, Andreas T1 - Operando electrochemical spectroscopic ellipsometry: Material properties of highly active mesoporous IrO IrOxfilms revealed under realistic OER conditions N2 - In the face of rising energy demand and the impending climate change the development of a sustainable, fossil-free fuel and chemical production is of global importance. One possible goal is the development of electrochemical conversion processes using catalysts. Porous materials play an important role in such energy applications. The activity and stability of each catalyst is highly dependent on the properties of the coating, i.e., phase composition, crystallinity, accessible surface area, and many other factors. The key to the development of improved catalysts is a better understanding of the relations between their performance, stability and physico-chemical properties. However, the complex morphology of such catalysts constitutes a challenge even for modern analytical techniques. Spectroscopic ellipsometry (SE) is a versatile method for studying material properties by using appropriate models (e.g., film thickness, optical and electronic properties). Ellipsometric models need to be validated in order to produce accurate results. In a first step, the model for the ellipsometric fit studies of a calcination series of mesoporous iridium oxide films (300 – 600 °C) was investigated and validated with respect to their material properties.[4] The information on electronic structure of the catalysts shows a direct correlation with electrochemical activities. The development of an environmental electrochemical cell offers the possibility of investigations under operando conditions. Thus, changes in optical and electronic properties can be induced and monitored during the electrocatalytic oxygen evolution reaction. T2 - 9th International Conference on Spectroscopic Ellipsometry CY - Beijing, China DA - 22.05.2022 KW - Mesoporous iridium oxide films KW - Non-destructive operando analysis KW - Oxygen evolution reaction KW - Spectroscopic ellipsometry PY - 2022 AN - OPUS4-54915 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -