TY - JOUR A1 - Fischer, Daniel A1 - Hertwig, Andreas A1 - Beck, Uwe A1 - Lohse, V. A1 - Negendank, D. A1 - Kormunda, M. A1 - Esser, N. T1 - Thin SnOx films for surface plasmon resonance enhanced ellipsometric gas sensing (SPREE) N2 - Background: Gas sensors are very important in several fields like gas monitoring, safety and environmental applications. In this approach, a new gas sensing concept is investigated which combines the powerful adsorption probability of metal oxide conductive sensors (MOS) with an optical ellipsometric readout. This concept Shows promising results to solve the problems of cross sensitivity of the MOS concept. Results: Undoped tin oxide (SnOx) and iron doped tin oxide (Fe:SnOx) thin add-on films were prepared by magnetron sputtering on the top of the actual surface plasmon resonance (SPR) sensing gold layer. The films were tested for their sensitivity to several gas species in the surface plasmon resonance enhanced (SPREE) gas measurement. It was found that the undoped tin oxide (SnOx) shows higher sensitivities to propane (C3H8) then to carbon monoxide (CO). By using Fe:SnOx, this relation is inverted. This behavior was explained by a change of the amount of binding sites for CO in the layer due to this iron doping. For hydrogen (H2) no such relation was found but the sensing ability was identical for both layer materials. This observation was related to a different sensing mechanism for H2 which is driven by the Diffusion into the layer instead of adsorption on the surface. Conclusion: The gas sensing selectivity can be enhanced by tuning the properties of the thin film overcoating. A relation of the binding sites in the doped and undoped SnOx films and the gas sensing abilities for CO and C3H8 was found. This could open the path for optimized gas sensing devices with different coated SPREE sensors. KW - Doped tin oxide KW - Ellipsometry KW - Gas sensing KW - Surface plasmon KW - Resonance KW - Thin films KW - Transparent conductive oxides PY - 2017 DO - https://doi.org/10.3762/bjnano.8.56 SN - 2190-4286 VL - 8 SP - 522 EP - 529 AN - OPUS4-39391 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wessig, P. A1 - Schulze, T. A1 - Pfennig, A. A1 - Weidner, Steffen A1 - Prentzel, S. A1 - Schlaad, H. T1 - Thiol–ene polymerization of oligospiroketal rods N2 - The nucleophilic thiol–ene (thia-Michael) reaction between molecular rods bearing terminal thiols and bis-maleimides was investigated. The molecular rods have oligospiroketal (OSK) and oligospirothioketal (OSTK) backbones. Contrary to the expectations, cyclic oligomers were always obtained instead of linear rigid-rod polymers. Replacing the OS(T)K rods with a flexible chain yielded polymeric products, suggesting that the OS(T)K structure is responsible for the formation of cyclic products. The reason for the preferred formation of cyclic products is due to the presence of folded conformations, which have already been described for articulated rods. KW - Oligospiroketals KW - Polymerization KW - MALDI-TOF MS PY - 2017 DO - https://doi.org/10.1039/C7PY01569K SN - 1759-9954 SN - 1759-9962 VL - 8 IS - 44 SP - 6879 EP - 6885 PB - Royal Society of Chemistry AN - OPUS4-42685 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Otto, S. A1 - Moll, J. A1 - Förster, C. A1 - Geißler, Daniel A1 - Wang, Cui A1 - Resch-Genger, Ute A1 - Heinze, K. T1 - Three-in-One Crystal: The Coordination Diversity of Zinc Polypyridine Complexes N2 - The syntheses, structures, and photophysical properties of two new zinc(II) complexes bearing the tridentate N,N′-dimethyl-N,N′-dipyridin-2-ylpyridine-2,6-diamine (ddpd) ligand are presented. Structural investigations through single-crystal X-ray diffractometry, NMR spectroscopy, and density functional theory calculations revealed a diverse coordination behavior that depends on the counterion. Spectroscopic (UV/Vis and emission spectroscopy) and theoretical techniques (DFT and time-dependent DFT calculations) were employed to explore the photophysical properties of the complexes. KW - Zinc(II) complexes KW - X-ray diffractometry (XRD) KW - NMR spectroscopy KW - Density functional theory (DFT) KW - UV/Vis and emission spectroscopy PY - 2017 DO - https://doi.org/10.1002/ejic.201700948 SN - 1434-1948 SN - 1099-0682 VL - 43 SP - 5033 EP - 5040 PB - WILEY-VCH Verlag GmbH & Co. KGaA CY - Weinheim AN - OPUS4-43274 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dabah, Eitan A1 - Pfretzschner, Beate A1 - Schaupp, Thomas A1 - Kardjilov, N. A1 - Manke, I. A1 - Boin, M. A1 - Woracek, R. A1 - Griesche, Axel T1 - Time-resolved Bragg-edge neutron radiography for observing martensitic phase transformation from austenitized super martensitic steel N2 - Neutron Bragg-edge imaging was applied for the visualization of a γ-Austenite to α'-martensite phase transformation. In the present study, a super martensitic stainless steel sample was heated until complete austenitization and was subsequently cooled down to room temperature. The martensitic phase Transformation started at Ms = 190 °C. Using a monochromatic neutron beam with λ = 0.390 nm, the transmitted intensity was significantly reduced during cooling below Ms, since the emerging martensitic phase has a higher attenuation coefficient than the austenitic phase at this wavelength. The phase Transformation process was visualized by filming the transmission images from a scintillator screen with a CCD camera with a temporal resolution of 30 s and a spatial resolution of 100 µm. KW - Neutron imaging KW - Bragg-edge imaging KW - Phase transformation PY - 2017 DO - https://doi.org/10.1007/s10853-016-0642-9 SN - 0022-2461 SN - 1573-4803 VL - 52 IS - 6 SP - 3490 EP - 3496 AN - OPUS4-38574 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yilmaz, M. A1 - Kilinc, Y. A1 - Nadar, G. A1 - Tasdemir, Z. A1 - Wollschläger, Nicole A1 - Österle, Werner A1 - Leblebici, Y. A1 - Alaca, B. E. T1 - Top-down technique for scaling to nano in silicon MEMS N2 - Nanoscale building blocks impart added functionalities to microelectromechanical systems (MEMS). The integration of silicon nanowires with MEMS-based sensors leading to miniaturization with improved sensitivity and higher noise immunity is one example highlighting the advantages of this multiscale approach. The accelerated pace of research in this area gives rise to an urgent need for batch-compatible solutions for scaling to nano. To address this challenge, a monolithic fabrication approach of silicon nanowires with 10-lm-thick silicon-on-insulator (SOI) MEMS is developed in this work. A two-step Si etching approach is adopted, where the first step creates a shallow surface protrusion and the second step releases it in the form of a nanowire. It is during this second deep etching step that MEMS—with at least a 2-order-of-magnitude scale difference - is formed as well. The technique provides a pathway for preserving the lithographic resolution and transforming it into a very high mechanical precision in the assembly of micro- and nanoscales with an extreme topography. Validation of the success of integration is carried out via in situ actuation of MEMS inside an electron microscope loading the nanowire up to its fracture. The technique yields nanowires on the top surface of MEMS, thereby providing ease of access for the purposes of carrying out surface processes such as doping and contact formation as well as in situ observation. As the first study demonstrating such monolithic integration in thick SOI, the work presents a pathway for scaling down to nano for future MEMS combining multiple scales. KW - Nanowires KW - Silicon KW - Top-down KW - MEMS PY - 2017 DO - https://doi.org/10.1116/1.4978047 SN - 1071-1023 VL - 35 IS - 2 SP - 022001-1 EP - 022001-7 PB - America Vacuum Society AN - OPUS4-39370 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kricheldorf, Hans R. T1 - Transesterification in the solid state of cyclic and linear poly(l-lactide)s N2 - Poly(l-lactide)s are synthesized and annealed at 120 °C and changes of the molecular weight distribution (MWD) are monitored by matrix-assited laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. For example, benzyl alcohol+SnOct2 causes equilibration of odd- and even-numbered chains and the final goal of the transesterification is the most probable distribution. The underlying intermolecular transesterification is even observed at 100 and 80 °C in the solid state. However, cyclic tin mercaptide catalysts transform the initial most probable distribution into a MWD with maxima, which display a conspicuous fine structure due to a preferential crystallization of certain ring sizes. The optimum ring sizes for the crystallization are provided by ring-ring equilibration. The gradual formation of a special morphology shifts the melting temperature to values up to 187 °C. Annealing of commercial poly(l-lactide) with a cyclic tin catalyst also yields a distribution of mass peaks with a maximum showing the characteristic fine structure. KW - Equilibration KW - Mass spectrometry KW - Polylactides KW - Ring-opening polymerization KW - Transesterification PY - 2017 DO - https://doi.org/10.1002/macp.201700114 SN - 1521-3935 SN - 1022-1352 VL - 218 IS - 14 SP - 1700114-1 EP - 1700114-10 PB - Wiley-VCH AN - OPUS4-41732 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Agudo Jácome, Leonardo A1 - Göbenli, G. A1 - Eggeler, G. ED - Göken, M. T1 - Transmission electron microscopy study of the microstructural evolution during high-temperature and low-stress (011) [01-1] shear creep deformation of the superalloy single crystal LEK 94 N2 - The present work describes the shear creep behavior of the superalloy LEK 94 at temperatures between 980 and 1050 °C and shear stresses between 50 and 140 MPa for loading on the macroscopic crystallographic shear system (MCSS) (011)[01-1]. The strain rate versus strain curves show short primary and extended secondary creep regimes. We find an apparent activation energy for creep of Qapp = 466 kJ/mol and a Norton-law stress exponent of n = 6. With scanning transmission electron microscopy, we characterize three material states that differ in temperature, applied stress, and accumulated strain/time. Rafting develops perpendicular to the maximum principal stress direction, gamma channels fill with dislocations, superdislocations cut gamma' particles, and dislocation networks form at gamma/gamma' interfaces. Our findings are in agreement with previous results for high-temperature and low-stress [001] and [110] tensile creep testing, and for shear creep testing of the superalloys CMSX-4 and CMSX-6 on the MCSSs (111)[01-1] and (001)[100]. The parameters that characterize the evolving gamma/gamma' microstructure and the evolving dislocation substructures depend on creep temperature, stress, strain, and time. KW - Dislocations KW - Microstructure KW - Scanning transmission electron microscopy (STEM) KW - Creep KW - Shear test PY - 2017 DO - https://doi.org/10.1557/jmr.2017.336 SN - 0884-2914 SN - 2044-5326 VL - 32 IS - 24 SP - 4491 EP - 4502 PB - Cambridge University Press CY - Cambrigde AN - OPUS4-43756 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wilrich, Cordula A1 - Brandes, Elisabeth A1 - Michael-Schulz, Heike A1 - Schröder, Volkmar A1 - Schwarz, Silke A1 - Wehrstedt, Klaus-Dieter T1 - UN GHS ‒ Physical hazard classifications of chemicals: A critical review of combinations of hazard classes N2 - One of the fundamental principles of the UN-GHS (Globally Harmonized System of Classification and Labelling of Chemicals) is that all hazards of a chemical should be assigned and communicated. There is no general prioritization of hazards in the sense that certain hazard classes are not applicable if another one has been assigned. In contrast to health and environmental hazards, there are physical or chemical factors which preclude certain combinations of physical hazard classes. So far, there is no common understanding as to which combinations are relevant and which not. For example, should a pyrophoric liquid be classified as flammable liquid in addition, or is this redundant and unnecessary? In the course of the implementation of the GHS by countries or sectors and the actual application by industry all over the world, such questions become more and more important. This publication systematically discusses all combinations of the UN-GHS physical hazard classes and assesses them with regard to the relevance of possible simultaneous assignment to a chemical. For many of the combinations an unambiguous decision based on theGHS alone is not possible, thus confirming that the question which physical hazard classes might be assigned simultaneously to a chemical is not trivial. As one more milestone on the path to a globally harmonized system for the classification of hazardous chemicals, this should be discussed and ultimately solved on a global basis. It is the hope that this publication might serve as an impetus for such discussions. KW - UN-GHS KW - Globally Harmonized System of Classification and Labelling of Chemicals KW - Hazardous chemicals KW - Chemicals classification KW - Physical hazards PY - 2017 UR - https://www.sciencedirect.com/science/article/pii/S1871553217300336 DO - https://doi.org/10.1016/j.jchas.2017.03.005 SN - 1871-5532 VL - 24 IS - 6 SP - 15 EP - 28 PB - Elsevier Inc. AN - OPUS4-42704 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Madkour, Sherif A1 - Szymoniak, Paulina A1 - Schick, Ch. A1 - Schönhals, Andreas T1 - Unexpected behavior of ultra-thin films of blends of polystyrene/poly(vinyl methyl ether) studied by specific heat spectroscopy N2 - Specific heat spectroscopy (SHS) employing AC nanochip calorimetry was used to investigate the glassy dynamics of ultra-thin films (thicknesses: 10 nm–340 nm) of a polymer blend, which is miscible in the bulk. In detail, a Poly(vinyl methyl ether) (PVME)/Polystyrene (PS) blend with the composition of 25/75 wt. % was studied. The film thickness was controlled by ellipsometry while the film topography was checked by atomic force microscopy. The results are discussed in the framework of the balance between an adsorbed and a free surface layer on the glassy dynamics. By a self-assembling process, a layer with a reduced mobility is irreversibly adsorbed at the polymer/substrate interface. This layer is discussed employing two different scenarios. In the first approach, it is assumed that a PS-rich layer is adsorbed at the substrate. Whereas in the second approach, a PVME-rich layer is suggested to be formed at the SiO2 substrate. Further, due to the lower surface tension of PVME, with respect to air, a nanometer thick PVME-rich surface layer, with higher molecular mobility, is formed at the polymer/air interface. By measuring the glassy dynamics of the thin films of PVME/PS in dependence on the film thickness, it was shown that down to 30 nm thicknesses, the dynamic Tg of the whole film was strongly influenced by the adsorbed layer yielding a systematic increase in the dynamic Tg with decreasing the film thickness. However, at a thickness of ca. 30 nm, the influence of the mobile surface layer becomes more pronounced. This results in a systematic decrease in Tg with the further decrease of the film thickness, below 30 nm. These results were discussed with respect to thin films of PVME/PS blend with a composition of 50/50 wt.%as well as literature results. KW - Ultra thin polymer films PY - 2017 DO - https://doi.org/10.1063/1.4978505 SN - 0021-9606 SN - 1089-7690 VL - 146 IS - 20 SP - 203321-1 EP - 203321-9 PB - AIP Publishing AN - OPUS4-39558 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Madkour, Sherif A1 - Szymoniak, Paulina A1 - Radnik, Jörg A1 - Schönhals, Andreas T1 - Unraveling the Dynamics of Nanoscopically Confined PVME in Thin Films of a Miscible PVME/PS Blend N2 - Broadband dielectric spectroscopy (BDS) was employed to investigate the glassy dynamics of thin films (7−200 nm) of a poly(vinyl methyl ether) (PVME)/polystyrene (PS) blend (50:50 wt %). For BDS measurements, nanostructured capacitors (NSCs) were employed, where films are allowed a free surface. This method was applied for film thicknesses up to 36 nm. For thicker films, samples were prepared between crossed electrode capacitors (CECs). The relaxation spectra of the films showed multiple processes. The first process was assigned to the α-relaxation of a bulklike layer. For films measured by NSCs, the rates of α-relaxation were higher compared to those of the bulk blend. This behavior was related to the PVME-rich free surface layer at the polymer/air interface. The second process was observed for all films measured by CECs (process X) and the 36 nm film measured by NSCs (process X2). This process was assigned to fluctuations of constraint PVME segments by PS. Its activation energy was found to be thickness-dependent because of the evidenced thickness dependency of the compositional heterogeneity. Finally, a third process with an activated temperature dependence was observed for all films measured by NSCs (process X1). It resembled the molecular fluctuations in an adsorbed layer found for thin films of pure PVME, and thus, it is assigned accordingly. This process undergoes an extra confinement because of frozen adsorbed PS segments at the polymer/substrate interface. To our knowledge, this is the first example where confinement-induced changes were observed by BDS for blend thin films KW - Thin Films KW - Broadband Dielectric Spectroscopy PY - 2017 DO - https://doi.org/10.1021/acsami.7b10572 SN - 1944-8244 VL - 9 IS - 42 SP - 37289 EP - 37299 PB - ACS Publications AN - OPUS4-42652 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -