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Organisationseinheit der BAM
The role of cyclization in polycondensations is discussed for two different scenarios: thermodynamically-controlled polycondensation (TCPs) on the one hand and kinetically-controlled polycondensations (KCPs) on the other. The classical CarothersFlory theory of step-growth polymerization does not include cyclization reactions. However, TCPs involve the formation of cycles via back-biting degradation, and when the ringchain equilibrium is on the side of the cycles the main reaction products of the TCP will be cyclic oligomers. Two groups of examples are discussed: polycondensations of salicyclic acid derivatives (e.g. aspirin) and polycondensations of dibutyltin derivatives with long {alpha}-, {omega}-diols or dicarboxylic acids. Furthermore, various kinetically-controlled syntheses of polyesters and polyamides were studied and carefully optimized in the direction of high molecular weights. High fractions of cyclic oligomers and polymers were found by MALDI-TOF mass spectrometry, and their fractions increased with optimization of the process for molecular weight. These results disagree with the CarothersFlory theory but agree with the theoretical background of the RuggliZiegler dilution method (RZDM). When poly(ether-sulfone)s were prepared from 4,4'-difluorodiphenylsulfone and silylated bisphenol-A two different scenarios were found. With CsF as catalyst at a temperature of more than 145°C cyclic oligoethers were formed under thermodynamic control. When the polycondensation was promoted with K2CO3 in N-methylpyrolidone at ?145°C the formation of cyclic oligoethers and polyethers occurred under kinetic control. A new mathematical formula is presented correlating the average degree of polymerization with the conversion and taking into account the competition between cyclization and propagation.
New applications of ceramic multilayers, for example, in biotechnology, sensor technology, and chemical micro-reaction technique, call for cavities with complex geometries. Hot embossing offers a promising, cost-effective way to generate these structures on the surfaces of green tapes or laminates. Cavities inside low-temperature co-fired ceramic multilayer were manufactured by a combination of hot embossing, lamination by a special adhesive technique, and zero shrinkage sintering. The edge and surface quality in the green state as well as the sintered multilayers with surface structures and cavities were extensively characterized by laser surface scanning, optical and ultrasound microscopy. Sintering shrinkage of hot-embossed laminates could be reduced in the x and y directions to less than 0.5%.
The wettability of the surfaces inside the microchannels of a microfluidic device is an important property considering a liquid flows through them. Contact angle measurements usually applied to test the wettability of surfaces cannot be used for an analysis of microchannel walls within microfluidic devices. A workaround is the use of surface analytical methods, which are able to reach points of interest in microchannels and may provide information on the surface chemistry established there. In calibrating these methods by using flat polymer wafers, where the contact angle can be measured as usual, data measured in real microchannels can be evaluated in terms of wetting properties. Reference wafers of bisphenol-A polycarbonate, a polymeric material that is often used in fluidic microdevice fabrication, were treated under different oxygen plasma conditions. The modified surfaces were characterized by using XPS, time of flight (ToF)-SIMS and atomic force microscope (AFM). Surface chemistry and surface topography have been correlated with contact angle measurements. In addition, effects of ageing or rinsing after plasma treatment have also been investigated.
The complexation of a cylindrical polyelectrolyte–brush-surfactant complex (PMMPSS–C12) and an oppositely charged generation-5 PAMAM dendrimer (G5-PAMAM) in methanol (MeOH) leads to kinetically controlled formation of interpolyelectrolyte complexes. In contrast, the complexation of the same starting materials in solvents with higher dielectric constant such as dimethylformamide (DMF) or N-methylformamide (NMF) results in the formation of topologically controlled complexes of cylindrical morphology. The composition of the complexes is analyzed by static and dynamic light scattering (SLS, DLS) in solution and atomic force microscopy (AFM) after spin-casting the complexes onto mica. The analyzed complexes seem to consist of one PMMPSS–C12 molecule and, with increasing G5-PAMAM content, of an increasing number of G5-PAMAM dendrimers.
Recently, time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) instrumentation has been used to address areas of interest within micro-fluidic devices providing full access to the surface chemistry established at the bottom of micro-channels therein. After careful calibration, information on surface chemistry as obtained by ToF-SIMS or XPS can be interpreted in terms of wettability expressed as contact angles which are then characteristic for the inner walls of micro-channels. Standard contact angle measurement is not applicable in micro-channels. The approach has been demonstrated to be successful with two different micro-fluidic devices hot embossed into high-end quality poly(methyl methacrylate) (PMMA) or Polycarbonate wafers. A pre-selected surface chemistry at micro-channel walls can be established by plasma technologies but ageing and rinsing effects have to be under control. A combination of ToF-SIMS, XPS and contact angle measurement techniques has been demonstrated to provide the required information. Finally, it is shown by ToF-SIMS and XPS analysis that in the production of micro-fluidic parts during practical processing using hot embossing technologies, material originating from cover foils will reside on the polymer wafer's surface. Moreover, residues of releasing agents as silicone oil used during processing can be detected by ToF-SIMS. Both cover foil residues and silicones are issues of trouble shooting in micro-fluidics because they will change contact angles efficiently.
The certified reference material BAM-L200, a nanoscale stripe pattern for length calibration and specification of lateral resolution, is described. BAM-L200 is prepared from a cross-sectioned epitaxially grown layer stack of AlxGa1–xAs and InxGa1–xAs on a GaAs substrate. The surface of BAM-L200 provides a flat pattern with stripe widths ranging down to 1 nm. Calibration distances, grating periods and stripe widths have been certified by TEM with traceability to the length unit. The combination of gratings, isolated narrow stripes and sharp edges of wide stripes offers plenty of options for the determination of lateral resolution, sharpness and calibration of length scale at selected settings of imaging surface-analytical instruments. The feasibility of the reference material for an analysis of the lateral resolution is demonstrated in detail by evaluation of ToF-SIMS, AES and EDX images. Other applications developed in the community are summarized, too. BAM-L200 fully supports the implementation of the revised International Standard ISO 18516 (in preparation) which is based on knowledge outlined in the Technical Report ISO/TR 19319:2013.
Theophylline has been used as an active pharmaceutical ingredient (API) in the treatment of pulmonary diseases, but due to its low water solubility reveals very poor bioavailability. Based on its different hydrogen-bond donor and acceptor groups, theophylline is an ideal candidate for the formation of cocrystals. The crystal structure of the 1:1 benzamide cocrystal of theophylline, C7H8N4O2·-C7H7NO, was determined from synchrotron X-ray powder diffraction data. The compound crystallizes in the tetragonal space group P41 with four Independent molecules in the asymmetric unit. The molecules form a hunter’s fence packing.
The crystal structure was confirmed by dispersion-corrected DFT calculations.
The possibility of salt formation was excluded by the results of Raman and 1H solid-state NMR spectroscopic analyses.
In 2011, the Association of German Engineers (VDI) started working on a set of guidelines
towards increased resource efficiency. These guidelines represent a framework that defines resource efficiency and outlines considerations for the producing industry. A special guideline for SMEs is included as well as guidelines on methodologies for evaluating resource use
indicators, such as the cumulative raw material demand of products and production systems.
Resource efficiency, defined here as the relationship between a specific benefit or use and the natural resources that need to be spent or consumed to attain this benefit or use. It can be
evaluated by defining a function which expresses the specific benefit and quantifies the resource requirements through a set of indicators (use of raw materials, energy, water, land
and ecosystem services including sinks). The results from this also depend on the system boundary parameters and the allocation rules for by-products and waste treatment options. Optimising resource use is possible at all stages of a product’s or production system’s life cycle chain (raw material extraction, production and manufacturing, use and consumption, and the
end-of-life stage).
VDI guidelines are widely accepted across Germany’s industrial sector and therefore represent an important means of mainstreaming resource efficiency in this target area. As well as providing a methodological framework, the guidelines describe strategies and measures towards increasing resource efficiency, and they enable industrial producers and service providers to identify potential areas of improvement. The full article presents an overview of
the methodology and contents of these guidelines and discusses their impact in achieving absolute reductions in the industrial use of natural resources.
During R/V Meteor cruise 141/1, pore fluids of near surface sediments were investigated to find indications for hydrothermal activity in the Terceira Rift (TR), a hyperslow spreading center in the Central North Atlantic Ocean. To date, submarine hydrothermal fluid venting in the TR has only been reported for the D. João de Castro seamount, which presently seems to be inactive. Pore fluids sampled close to a volcanic cone at 2,800‐m water depth show an anomalous composition with Mg, SO4, and total alkalinity concentrations significantly higher than seawater and a nearby reference core. The most straightforward way of interpreting these deviations is the dissolution of the hydrothermally formed mineral caminite (MgSO4 0.25 Mg (OH)2 0.2H2O). This interpretation is corroborated by a thorough investigation of fluid isotope systems (δ26Mg, δ30Si, δ34S, δ44/42Ca, and 87Sr/86Sr). Caminite is known from mineral assemblages with anhydrite and forms in hydrothermal recharge zones only under specific conditions such as high fluid temperatures and in altered oceanic crust, which are conditions generally met at the TR. We hypothesize that caminite was formed during hydrothermal activity and is now dissolving during the waning state of the hydrothermal system, so that caminite mineralization is shifted out of its stability zone. Ongoing fluid circulation through the basement is transporting the geochemical signal via slow advection toward the seafloor.