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- ItemApplication of sulfonated nanoporous carbons as acid catalysts for Fischer esterification reactions(Amsterdam : Elsevier, 2015) Tamborini, L.H.; Militello, M.P.; Balach, J.; Moyano, J.M.; Barbero, C.A.; Acevedo, D.F.Heterogeneous acid catalysts were prepared by sulfonation of nanoporous carbons (NPCs). The NPCs were produced by pyrolysis of resorcinol–formaldehyde nanoporous resins (NPRs). The NPRs were synthesized as wet gels by condensation of resorcinol and formaldehyde in a sol–gel polycondensation using Na2CO3 as catalyst. A cationic polyelectrolyte (poly(diallyl dimethyl ammonium chloride)) was used as pore stabilizer, allowing to dry the gels in air without any special procedures. Five NPRs with different properties were synthesized by varying the monomer to catalyst ratio (Resorcinol/Na2CO3, R/C). The morphological and textural characterizations of the NPCs were performed by scanning electron microscopy and nitrogen adsorption–desorption isotherms. The results indicate that using a molar ratio of R/C = 200, a nanoporous carbon NPC with large surface area (695 m2/g) is obtained. This NPC was sulfonated by reaction with three different sulfonating agents: (i) concentrated sulfuric acid; (ii) fuming sulfuric acid and (iii) chlorosulfonic acid in order to obtain a novel Fischer esterification catalyst. The amount of acid groups attached to the NPC surface was determined by titration using a modified Boehm method. The catalytic activity, for Fischer esterification reaction of different sulfonated NPCs, was compared with sulfonated NPRs, sulfonated commercial porous carbons and polymeric acid catalyst (cationic ion exchange resins, sulfonated fluoropolymers). The modification of NPCs with concentrated sulfuric acid seems to render the materials with more catalytic activity. The best sulfonated material NPC (PC200-H2SO4) shows a high catalytic activity for the esterification of acetic acid (90.8%) and oleic acid (60.6%) with ethanol. The conversion and conversion rate values are better than commercial acid catalysts. The results suggest that sulfonated NPC catalysts are promising materials for the synthesis of biodiesel and related reactions.
- ItemIn-situ investigations of structural changes during cyclic loading by high resolution reciprocal space mapping(Amsterdam : Elsevier, 2017) Diederichs, Annika M.; Thiel, Felix; Lienert, Ulrich; Pantleon, WolfgangA major failure reason for structural materials is fatigue-related damage due to repeatedly changing mechanical loads. During cyclic loading dislocations self-organize into characteristic ordered structures, which play a decisive role for the materials lifetime. These heterogeneous dislocation structures can be identified using advanced electron microscopy and synchrotron techniques. A detailed characterization of the microstructure during cyclic loading by in-situ monitoring the internal structure within individual grains with high energy x-rays can help to understand and predict the materials behavior during cyclic deformation and to improve the material design. While monitoring macroscopic stress and strain during cyclic loading, reciprocal space maps of diffraction peaks from single grains are obtained with high resolution. High Resolution Reciprocal Space Mapping was applied successfully in-situ during cyclic deformation of macroscopic aluminium samples at the Advanced Photon Source to reveal the structural reorganization within single grains embedded in the bulk material during fatigue.
- ItemElectrodeposition of Sr-substituted hydroxyapatite on low modulus beta-type Ti-45Nb and effect on in vitro Sr release and cell response(Amsterdam : Elsevier, 2019) Schmidt, Romy; Gebert, Annett; Schumacher, Matthias; Hoffmann, Volker; Voss, Andrea; Pilz, Stefan; Uhlemann, Margitta; Lode, Anja; Gelinsky, MichaelBeta-type Ti-based alloys are promising new materials for bone implants owing to their excellent mechanical biofunctionality and biocompatibility. For treatment of fractures in case of systemic diseases like osteoporosis the generation of implant surfaces which actively support the problematic bone healing is a most important aspect. This work aimed at developing suitable approaches for electrodeposition of Sr-substituted hydroxyapatite (Srx-HAp) coatings onto Ti-45Nb. Potentiodynamic polarization measurements in electrolytes with 1.67 mmol/L Ca(NO3)2, which was substituted by 0, 10, 50 and 100% Sr(NO3)2, and 1 mmol/L NH4H2PO4 at 333 K revealed the basic reaction steps for OH– and PO4 3− formation needed for the chemical precipitation of Srx-HAp. Studies under potentiostatic control confirmed that partial or complete substitution of Ca2+- by Sr2+-ions in solution has a significant effect on the complex reaction process. High Sr2+-ion contents yield intermediate phases and a subsequent growth of more refined Srx-HAp coatings. Upon galvanostatic pulse-deposition higher reaction rates are controlled and in all electrolytes very fine needle-like crystalline coatings are obtained. With XRD the incorporation of Sr-species in the hexagonal HAp lattice is evidenced. Coatings formed in electrolytes with 10 and 50% Sr-nitrate were chemically analyzed with EDX mapping and GD-OES depth profiling. Only a fraction of the Sr-ions in solution is incorporated into the Srx-HAp coatings. Therein, the Sr-distribution is laterally homogeneous but non-homogeneous along the cross-section. Increasing Sr-content retards the coating thickness growth. Most promising coatings formed in the electrolyte with 10% Sr-nitrate were employed for Ca, P and Sr release analysis in Tris-Buffered Saline (150 mM NaCl, pH 7.6) at 310 K. At a sample surface: solution volume ratio of 1:200, after 24 h the amount of released Sr-ions was about 30–35% of that determined in the deposited Srx-HAp coating. In vitro studies with human bone marrow stromal cells (hBMSC) revealed that the released Sr-ions led to a significantly enhanced cell proliferation and osteogenic differentiation and that the Sr-HAp surface supported cell adhesion indicating its excellent cytocompatibility. © 2019 The Authors
- ItemLifetime vs. rate capability: Understanding the role of FEC and VC in high-energy Li-ion batteries with nano-silicon anodes(Amsterdam : Elsevier, 2016) Jaumann, Tony; Balach, Juan; Langklotz, Ulrike; Sauchuk, Viktar; Fritsch, Marco; Michaelis, Alexander; Teltevskij, Valerij; Mikhailova, Daria; Oswald, Steffen; Klose, Markus; Stephani, Guenter; Hauser, Ralf; Eckert, Jürgen; Giebeler, LarsFluoroethylene carbonate (FEC) and vinylene carbonate (VC) are the most frequently used electrolyte components to enhance the lifetime of anode materials in Li-ion batteries, but for silicon it is still ambiguous when FEC or VC is more beneficial. Herein, a nanostructured silicon/carbon anode derived from low-cost HSiCl3 is tailored by the rational choice of the electrolyte component, to obtain an anode material outperforming current complex silicon structures. We demonstrate highly reversible areal capacities of up to 5 mA h/cm2 at 4.4 mg/cm2 mass loading, a specific capacity of 1280 mA h/gElectrode, a capacity retention of 81% after 500 deep-discharge cycles versus lithium metal and successful full-cell tests with high-voltage cathodes meeting the requirements for real application. Electrochemical impedance spectroscopy and post-mortem investigation provide new insights in tailoring the interfacial properties of silicon-based anodes for high performance anode materials based on an alloying mechanism with large volume changes. The role of fluorine in the FEC-derived interfacial layer is discussed in comparison with the VC-derived layer and possible degradation mechanisms are proposed. We believe that this study gives a valuable understanding and provides new strategies on the facile use of additives for highly reversible silicon anodes in Li-ion batteries.
- ItemComplex loading and simulation of acoustic thickness shear mode resonator(Amsterdam : Elsevier, 2010) Brünig, R.; Weihnacht, M.; Guhr, G.; Schmidt, H.During the last decades thickness shear mode resonators (TSM, QCM) have been object of comprehensive research. Many approaches were made to describe the behavior and physical effects when loaded. We present a physical model that describes the TSM in the full frequency range, including overtones for a large variety of loadings (e.g. gases, liquids or solid materials). By using an automated curve fit algorithm, absolute values for the loaded material (e.g. thickness, viscosity) can be extracted. The model has been validated with a large number of experiments including liquids with complex viscosities, biomolecule interactions, electrochemisty or vacuum deposition techniques. Additionally, the appearance of layer resonances have been predicted and verified. Layer resonances are remarkable because they appear at even-numbered overtones, which have been considered to be impossible.
- ItemElectrodeposition of Fe70Pd30 nanowires from a complexed ammonium-sulfosalicylic electrolyte with high stability(Amsterdam : Elsevier, 2010) Haehnel, V.; Fähler, S.; Schultz, L.; Schlörb, H.A highly stable plating bath for the electrodeposition of Fe-Pd nanowires into nanoporous alumina templates has been developed. Complexing of both metal ions and exchanging Fe2+ by Fe3+ avoid chemical reduction of Pd ions and, therefore, undesirable deposition. By using a pulse potential mode and appropriate adjustment of deposition potentials homogeneously filled templates without surface deposits and nanowires close to the desired composition of Fe70Pd30 have been achieved. These alloy nanowires represent a key step towards nanoactuators based on magnetic shape memory alloys. © 2010 Elsevier B.V. All rights reserved.
- ItemLarge superplastic strain in non-modulated epitaxial Ni-Mn-Ga films(Amsterdam : Elsevier, 2010) Yeduru, S.R.; Backen, A.; Fahler, S.; Schultz, L.; Kohl, M.The phase transformation and superplastic characteristics of free-standing epitaxial Ni-Mn-Ga stripes are reported. The stripes are prepared by micromachining a 1 μm thick Ni-Mn-Ga film sputter-deposited on a single crystalline MgO (100) substrate using optical lithography and a Chromium-based sacrificial layer technology. The stripes are oriented at angles of 0 and 45 degrees with respect to the Ni-Mn-Ga unit cell. Electrical resistance versus temperature characteristics reveal a reversible thermally induced phase transformation between 169°C and 191°C. Stress-strain measurements are performed with the stress applied along the [100]Ni-Mn-Ga as well as [110]Ni-Mn-Ga direction. Depending on the orientation, the twinning stress ranges between 25 and 30 MPa, respectively. For the [100] Ni-Mn-Ga and [110]Ni-Mn-Ga directions, superplastic behaviour with a strain plateau of 12 % and 4% are observed, respectively, indicating stress-induced reorientation of non-modulated martensite variants.