Search

The effect of the addition of n-hexanol as co-surfactant on the structure of cetyltrimethylammonium bromide (CTAB) micelles has been studied using small-angle X-ray and neutron scattering (SAXS, SANS). Contrast variation neutron scattering experiments were performed to determine the structure of both pure CTAB and n-hexanol modified CTAB micelles. The incorporation of n-hexanol leads to an elongation of the ellipsoidal CTAB micelles. The scattering length density of the micellar shell linearly depends on the degree of deuteration of the dispersion medium water and revealed the existence of substantial amounts of water in the micellar shell. The water content in the shell increased from 20 vol-% observed for pure CTAB micelles to 44 vol-% found for n-hexanol modified CTAB micelles. The amount of n-hexanol in the micellar shell was determined by varying the amount of fully deuterated and protonated n-hexanol. These experiments revealed a volume fraction of 26 vol-% of n-hexanol molecules in the micellar core which equals a molar fraction of 50 % n-hexanol within the CTAB micelles. The total composition of micellar core and shell was estimated. The packing density of headgroups, water molecules and bromide ions turned out to drastically increase in n-hexanol modified CTAB micelles. These findings contribute to a fundamental understanding of the stabilization mechanism of micelles by alcoholic co-surfactants and the resulting alteration of the morphology and interface composition. These results will facilitate the optimization of processes where CTAB and other comparable surfactants are used as phase transfer catalysts, structure directing agents or stabilizers in colloidal dispersions or emulsions.

The analysis of lithium-ion battery aging relies on correct differentiation between irreversible and reversible capacity changes. Anode overhang regions have been observed to influence Coulombic Efficiency (CE) measurements through lithium diffusion into and out of these areas, complicating precise capacity determination. This work presents an analysis of the extent of graphite anode overhang lithiation after calendar storage by means of local X-ray diffraction (XRD), CE measurements, and color change analysis. We found LiC12 lithiation of the anode overhang area after 20 month storage at 40 °C at high state of charge (SoC) and partial lithiation (LiC18) at medium SoC storage at 40 °C and 25 °C. Graphite color changes in the overhang areas are observed and consistent with the state of lithiation measured by XRD. Coulombic efficiencies greater than unity and increasing capacity during 1200 h of cycling are detected for high SoC storage cells. The capacity difference between high and low storage SoC batteries decreases by up to 40 mAh (3.6% of nominal capacity) after cycling compared to tests directly after storage. Consequently, the size of the anode overhang areas as well as the battery storage temperature and duration need to be considered in CE analysis and state of health assessment.

ZnO nanoparticles (NPs) are highly relevant for various industrial applications, however, after synthesis of the NPs residual chemicals need to be removed from the colloidal raw product by washing, as they may influence the performance of the final device. In the present study we focus on the effect of washing by antisolvent flocculation with subsequent redispersion of the NPs on the stabilizing acetate shell. Purification of the ZnO nanoparticles is reported to be optimal with respect to zeta potential that has a maximum after one washing cycle. In this work, we will shed light on this observation using small angle X-ray and neutron scattering (SAXS, SANS) by demonstrating that after the first washing cycle the content of acetate in the ligand shell around the ZnO NPs increases. In detail, it was observed that the diffuse acetate shell shrinks to the size of a monolayer upon washing but the acetate content of this monolayer is higher than within the diffuse shell of the particles of the native dispersion. A second washing cycle reduces the acetate concentration within the stabilizing shell and the stability of the dispersion drops accordingly. After another (third) washing cycle strong agglomeration was observed for all investigated samples.

Co-Re alloys are being developed to supplement Ni-base superalloys in future gas turbines for ultra-high temperature applications. The finely distributed mono-carbide phase of TaC is an important strengthening phase in this alloy, and interacts with dislocations during high temperature creep deformation. This study aims to determine and to understand the volume fraction and size distribution of TaC precipitates in dependence of C/Ta stoichiometry and heat treatment by means of in-situ small-angle neutron scattering. At measuring temperatures of 1173 K, 1373 K and 1473 K, a stable population of fine TaC

Immobilization of proteins on a solid electrode is to date done by chemical cross-linking or by addition of an adjustable intermediate. In this paper we introduce a concept where a solid with variable surface properties is optimized to mediate binding of the electron-transfer protein Cytochrome c (Cyt c) by mimicking the natural binding environment. It is shown that, as a carbon-based material, boron-doped diamond can be adjusted by simple electrochemical surface treatments to the specific biochemical requirements of Cyt c. The structure and functionality of passively adsorbed Cyt c on variously terminated diamond surfaces were characterized in detail using a combination of electrochemical techniques and atomic force microscopy with single-molecule resolution. Partially oxidized diamond allowed stable immobilization of Cyt c together with high electron transfer activity, driven by a combination of electrostatic and hydrophobic interactions. This surface mimics the natural binding partner, where coarse orientation is governed by electrostatic interaction of the protein's dipole and hydrophobic interactions assist in formation of the electron transfer complex. The optimized surface mediated electron transfer kinetics around 100 times faster than those reported for other solids and even faster kinetics than on self-assembled monolayers of alkanethiols.

The mechanism behind the self-assembly of diamond nanoparticles onto silicon dioxide surfaces is explained by simple electrostatic attraction. This electrostatic attraction can be controlled by the surface functional groups of the particles and the pH of the solution. By these simple techniques the nucleation density of diamond nanoparticles on SiO2 surfaces can be controlled up to 1012 cm−2, ideal for the seeding of high performance nanocrystalline diamond. Very low nucleation densities of discrete diamond nanoparticles are also obtainable, which is of use for single photon sources.

Various nano-pores in nano-crystalline diamond (NCD) thin films have been fabricated and characterized. Therefore in this work two aspects of NCD thin films synthesized by microwave assisted chemical-vapour-deposition (MWCVD) have been investigated. Firstly, the influence of CVD-growth conditions on the film morphology and chemical grain boundary composition and their impact on the mechanical properties. Second, the formation of nano-pores by selective etching of the non-diamond phase. Freestanding NCD membranes were fabricated and bulged to calculate the Young’s modulus which can reach surprisingly high values (1100 GPa) close to single crystal diamond. The presence of nano-pores was verified by electrochemical experiments where ions have been used to detect the porosity.

Nanotextured diamond surfaces with geometrical properties close to protein dimensions were used for the realization of direct electron transfer of cytochrome c (cyt c) without any covalent bonding. The peroxidase activity of native and denatured cyt c was also investigated. Cyclic voltammograms of native cyt c show quasi-reversible electron transfer reactions, while no heme redox activity is detected for denatured cyt c. Unfolding (denaturation) of cyt c can be achieved in the presence of hydrogen peroxide. Partially or fully denatured cyt c showed higher peroxidase activity than native cyt c. This is because denatured cyt c loses its tertiary structure and hydrogen peroxide is easier to access the heme redox center. The apparent Michaelis–Menten constant Km for native and denatured cyt c has been determined to be 0.23 mM and 0.08 mM. Keywords: Cytochrome c, Peroxidase activity, Nano-structures, Diamond electrochemistry

Nanocrystalline diamond films thinner than 140 nm are demonstrated to exhibit Young’s moduli as high as single crystal and microcrystalline bulk diamond when grown under appropriate conditions. The Young’s modulus of nanocrystalline diamond is shown to be a function of the methane concentration and the microwave power density when grown by microwave plasma enhanced chemical vapour deposition. The variation of Young’s modulus can be correlated with the sp2 content and crystallite size of the films as characterised by Raman spectroscopy and Scanning Electron Microscopy.

We report on a general method to fabricate transition metal related defects in diamond. Controlled incorporation of Mo and W in synthetic CVD diamond was achieved by adding volatile metal precursors to the diamond chemical vapor deposition (CVD) growth process. Effects of deposition temperature, grain structure and precursor exposure on the incorporation efficiency were systematically studied, and doping levels of up to 0.25 at.% have been achieved. The metal atoms are uniformly distributed throughout the diamond grains without any indication of inclusion formation. These results are discussed in context of the kinetically controlled growth process of CVD diamond.

The investigation of orientation dependent crystal growth and etch processes can provide deep insights into the underlying mechanisms and thus helps to validate theoretical models. Here, we report on homoepitaxial diamond growth and oxygen etch experiments on polished, polycrystalline CVD diamond wafers by use of electron backscatter diffraction (EBSD) and white-light interferometry (WLI). Atomic force microscopy (AFM) was applied to provide additional atomic scale surface morphology information. The main advantage of using polycrystalline diamond substrates with almost random grain orientation is that it allows determining the orientation dependent growth (etch) rate for different orientations within one experiment. Specifically, we studied the effect of methane concentration on the diamond growth rate, using a microwave plasma CVD process. At 1% methane concentration a maximum of the growth rate near and a minimum near is detected. Increasing the methane concentration up to 5% shifts the maximum towards while the minimum stays at . Etch rate measurements in a microwave powered oxygen plasma reveal a pronounced maximum at . We also made a first attempt to interpret our experimental data in terms of local micro-faceting of high-indexed planes.

Magnetotransport parallel to quantum wires in Si/SiGe heterostructures was conducted in the quasi-ballistic regime. We observed magnetoresistance oscillations due to the depopulation of quasi-one dimensional sub-bands, and at low magnetic fields a well pronounced peak arising from diffuse scattering at the wire boundaries emerges. The analysis of these features yields a maximum sub-band spacing of 1 meV at a corresponding wire width of 70 nm. Electron transport perpendicular to shallow etched wires was investigated in lateral superlattices with a period of 350 nm. At magnetic fields below 0.7 T magnetotransport measurements show commensurability oscillations corresponding up to three periods of the wire grating. However, the modulated lateral potential is not purely sinusoidal, resulting in a splitting of the commensurability oscillations.