Scientific publications

2016
Influence of carbon substrate on the electrochemical performance of carbon/manganese oxide hybrids in aqueous and organic electrolytes

Zeiger, Marco | Fleischmann, Simon | Kruner, Benjamin | Tolosa, Aura | Bechtel, Stephan | Baltes, Mathias | Schreiber, Anna | Moroni, Riko | Vierrath, Severin | Thiele, Simon | Presser, Volker

DOI:

Manganese oxide presents very promising electrochemical properties as an electrode material in supercapacitors, but there remain important open questions to guide further development of the complex manganese oxide/carbon/electrolyte system. Our work addresses specifically the influence of carbon ordering and the difference between outer and inner porosity of carbon particles for the application in aqueous 1 M Na2SO4 and 1 M LiClO4 in acetonitrile. Birnessite-type manganese oxide was hydrothermally hybridized on two kinds of carbon onions with only outer surface area and different electrical conductivity, and conventional activated carbon with a high inner porosity. Carbon onions with a high degree of carbon ordering, high conductivity, and high outer surface area were identified as the most promising material, yielding 179 F g-1. Pore blocking in activated carbon yields unfavorable electrochemical performances. The highest specific energy of 16.4 W h kg-1 was measured for a symmetric full-cell arrangement of manganese oxide coated high temperature carbon onions in the organic electrolyte. High stability during 10 000 cycles was achieved for asymmetric full-cells, which proved as a facile way to enhance the electrochemical performance stability.

DOI:

RSC Advances,
2016, 6 (109), 107163-107179.

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Review: Carbon onions for electrochemical energy storage

Zeiger, Marco | Jäckel, Nicolas | Mochalin, Vadym N. | Presser, Volker

DOI:

Carbon onions are a relatively new member of the carbon nanomaterials family. They consist of multiple concentric fullerene-like carbon shells which are highly defective and disordered. Due to their small size of typically below 10 nm, the moderate surface area, and high conductivity they were used for supercapacitor applications. As electrode material, carbon onions provide fast charge/discharge rates resulting in high specific power but present comparable low specific energy. They improve the performance of activated carbon electrodes as conductive additive and show suitable properties as substrate for redox-active materials. This review provides a critical discussion of the electrochemical properties of different types of carbon onions as electrode material. It also compares general advantages and disadvantages of different carbon onion synthesis methods. The structure, physical and chemical properties of carbon onions, in particular nanodiamond-derived carbon onions, are described with emphasis on those parameters especially important for electrochemical energy storage systems, including among others structure, conductivity, and porosity. Although the primary focus of current research is on electrode materials for supercapacitors, the use of carbon onions as conductive additive for activated carbon and electro-active polymers, as well as substrate for redox-active species is also discussed.

DOI:

Journal of Materials Chemistry A,
2016, 4 (9), 3172-3196.

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Plastic deformation modes of CuZr/Cu multilayers

Cui, Yan | Torrents Abad, Oscar | Wang, Fei | Huang, Ping | Lu, Tian-Jian | Xu, Ke-Wei | Wang, Jian

DOI:

We synthesized CuZr/Cu multilayers and performed nanoindentation testing to explore the dependence of plastic deformation modes on the thickness of CuZr layers. The Cu layers were 18 nm thick and the CuZr layers varied in thickness from 4 nm to 100 nm. We observed continuous plastic co-deformation in the 4 nm and 10 nm CuZr − 18 nm Cu multilayers and plastic-induced shear instability in thick CuZr layers (>20 nm). The plastic co-deformation is ascribed to the nucleation and interaction of shear transformation zones in CuZr layers at the adjacent interfaces, while the shear instability is associated with the nucleation and propagation of shear bands in CuZr layers. Shear bands are initialized in the CuZr layers due to the accumulated glide dislocations along CuZr-Cu interfaces, and propagate into adjacent Cu layers via slips on {111} plane non-parallel to the interface. Due to crystallographic constraint of the Cu layers, shear bands are approximately parallel to {111} plane in the Cu layer.

DOI:

Scientific Reports,
2016, 6, 23306.

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Effect of indentation temperature on nickel-titanium indentation-induced two-way shape-memory surfaces

Brinckmann, Stephan A. | Frensemeier, Mareike | Laursen, Christopher M. | Maier, Hans J. | Britz, Dominik | Schneider, Andreas S. | Mücklich, Frank | Frick, Carl P.

DOI:

This study investigated the effect of temperature on indentation-induced one-way and two-way shape memory properties in Ti-50.3 at% Ni alloy. Indentation temperatures ranged from below the martensite finish temperature (Mf) to above the austenite finish temperature (Af) with the explicit intent of varying the indented phase. Samples used in the study were characterized by differential scanning calorimetry and transmission electron microscopy (TEM). The topographical behavior of the shape memory effect was investigated through Vickers indentation and laser scanning 3D confocal measurements. The magnitudes of deformation recovery associated with the one-way and two-way shape-memory effect (OWSME, TWSME) decreased with increasing indentation temperatures, which is a reflection of the decreasing volume of material experiencing martensitic reorientation during indentation. Indented and subsequently planarized samples exhibited TWSME protrusions when thermally cycled. Laser scanning measurements were used to characterize the height of the protrusions as increasing depths of material were polished away, which provided insight into the overall affected volume beneath the indent. As indentation temperatures increased, both the height of the protrusions, and consequently the polish depth necessary to completely remove the effect, decreased. TEM investigations revealed that directly underneath a nanoindent the microstructure was very fine due to the high-strain deformation; this was contrasted with a much coarser grain size in the undeformed bulk material. Overall these results strongly imply that the deformation recovery associated with the OWSME and TWSME can be maximized by indenting at temperatures at Mf or below because the volume of deformed microstructure beneath the indent is maximized. This finding has important practical value for any potential application that utilizes indentation-induced phase transformation deformation recovery in NiTi.

DOI:

Materials Science and Engineering A-Structural Materials Properties Microstructure and Processing,
2016, 675, 253-261.

Generation of aspherical optical lenses via arrested spreading and pinching of a cross-linkable liquid

Roy, Abhijit Chandra | Yadav, Mridul | Arul, Edward Peter | Khanna, Anubhav | Ghatak, Animangsu

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Aspherical optical lenses with spatially varying curvature are desired for capturing high quality, aberration free images in numerous optical applications. Conventionally such lenses are prepared by multistep top-down processes which are expensive, time-consuming, and prone to high failure rate. In this context, an alternate method is presented here based on arrested spreading of a sessile drop of a transparent, cross-linkable polymeric liquid on a solid substrate heated to an elevated temperature. Whereas surface tension driven flow tends to render it spherical, rapid cross-linking arrests such flow so that nonequilibrium aspherical shapes are attained. It is possible to tune also the initial state of the drop via delayed pinching of a liquid cylinder which precedes its release on the substrate. This method has led to the generation of a wide variety of optical lenses, ranging from spherical plano convex to superspherical solid immersion to exotic lenses not achieved via conventional methods.

DOI:

Langmuir,
2016, 32 (21), 5356-5364.

Mechanical behavior of iron aluminides: A comparison of nanoindentation, compression and bending of micropillars

Zamanzade, Mohammad | Velayarce, Jorge Rafael | Torrents Abad, Oscar | Motz, Christian | Barnoush, Afrooz

DOI:

Various local testing methods, namely, nanoindentation, compression and bending tests of micropillars were used to better understand the influence of ternary Cr atoms on the extrinsic and intrinsic mechanical properties of Fe3Al intermetallics with the D03 super lattice. Using such local techniques enables us to quantify the influence of Cr on the enhancement of the Young´s modulus. Furthermore, the effect of Cr on the yield stress, strain hardening and appearance of slip traces was studied based on the stress-strain curves and secondary electron micrographs of the bended and compressed pillars.

DOI:

Materials Science and Engineering A-Structural Materials Properties Microstructure and Processing,
2016, 652, 370-376.

The springtail cuticle as a blueprint for omniphobic surfaces

Hensel, René | Neinhuis, Christoph | Werner, Carsten

DOI:

Omniphobic surfaces found in nature have great potential for enabling novel and emerging products and technologies to facilitate the daily life of human societies. One example is the water and even oil-repellent cuticle of springtails (Collembola). The wingless arthropods evolved a highly textured, hierarchically arranged surface pattern that affords mechanical robustness and wetting resistance even at elevated hydrostatic pressures. Springtail cuticle-derived surfaces therefore promise to overcome limitations of lotus-inspired surfaces (low durability, insufficient repellence of low surface tension liquids). In this review, we report on the liquid-repellent natural surfaces of arthropods living in aqueous or temporarily flooded habitats including water-walking insects or water spiders. In particular, we focus on springtails presenting an overview on the cuticular morphology and chemistry and their biological relevance. Based on the obtained liquid repellence of a variety of liquids with remarkable efficiency, the review provides general design criteria for robust omniphobic surfaces. In particular, the resistance against complete wetting and the mechanical stability strongly both depend on the topographical features of the nano- and micropatterned surface. The current understanding of the underlying principles and approaches to their technological implementation are summarized and discussed.

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Chemical Society Reviews,
2016, 45 (2), 323-341.

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Temperature-dependent size effects on the strength of Ta and W micropillars

Torrents Abad, Oscar | Wheeler, Jeffrey M. | Michler, Johann | Schneider, Andreas S. | Arzt, Eduard

DOI:

The strength of metals increases with decreasing sample size, a trend known as the size effect. In particular, focused ion beam-milled body-centered cubic (BCC) micropillars exhibit a size effect known to scale with the ratio of the test temperature to the critical temperature (Tc) of the BCC metal, a measure of how much the yield stress is governed by the lattice resistance. In this paper, this effect is systematically studied by performing high-temperature compression tests on focused ion beam-manufactured Ta and W single crystal pillars ranging in diameter from 500 nm to 5 μm at temperatures up to 400 °C, and discussed in the context of bulk strength and size dependent stresses. Both metals show larger size effects at higher temperatures, reaching values that are in the range of FCC metals at temperatures near Tc. However, it is demonstrated that size effects can be considerably affected by material parameters such as dislocation density and lattice friction, as well as by the yield criterion used. Furthermore, for W, a change from uniform wavy deformation to localized deformation is observed with increasing temperature and pillar size, further indicating that the temperature ratio strongly influences the relative motion of screw and edge dislocations.

DOI:

Acta Materialia,
2016, 103, 483-494.

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On the process of co-deformation and phase dissolution in a hard-soft immiscible CuCo alloy system during high-pressure torsion deformation

Bachmaier, Andrea | Schmauch, Jörg | Aboulfadl, Hisham | Verch, Andreas | Motz, Christian

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In this study, dual phase CuCo composites with a total immiscibility in the solid state and a very different initial phase strength are deformed by severe plastic deformation. Nanocrystalline supersaturated solid solutions are reached in all CuCo composites independent of the initial composition. The deformation and mechanical mixing process is studied thoroughly by combining scanning electron microscopy, transmission electron microscopy, three-dimensional atom probe tomography and nanoindentation. The indentation hardness of the Cu and Co phase and its evolution as a function of the applied strain is linked to deformation and mechanical mixing process to gain a better understanding how the phase strength mismatch of the Cu and Co phase effects the amount of co-deformation and deformation-induced mixing. Our results show that co-deformation is not a necessary requirement to achieve mechanical mixing.

DOI:

Acta Materialia,
2016, 115, 333-346.

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Feature adaptive sampling for scanning electron microscopy

Dahmen, Tim | Engstler, Michael | Pauly, Christoph | Trampert, Patrick | de Jonge, Niels | Mücklich, Frank | Slusallek, Philipp

DOI:

A new method for the image acquisition in scanning electron microscopy (SEM) was introduced. The method used adaptively increased pixel-dwell times to improve the signal-to-noise ratio (SNR) in areas of high detail. In areas of low detail, the electron dose was reduced on a per pixel basis, and a-posteriori image processing techniques were applied to remove the resulting noise. The technique was realized by scanning the sample twice. The first, quick scan used small pixel-dwell times to generate a first, noisy image using a low electron dose. This image was analyzed automatically, and a software algorithm generated a sparse pattern of regions of the image that require additional sampling. A second scan generated a sparse image of only these regions, but using a highly increased electron dose. By applying a selective low-pass filter and combining both datasets, a single image was generated. The resulting image exhibited a factor of ~ ‰3 better SNR than an image acquired with uniform sampling on a Cartesian grid and the same total acquisition time. This result implies that the required electron dose (or acquisition time) for the adaptive scanning method is a factor of ten lower than for uniform scanning.

DOI:

Scientific Reports,
2016, 6, 25350.

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