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Fast and efficient (resonant) X-ray emission spectroscopy setup for the electronic structure at lower mantle conditions: high spin in laser-heated FeCO3 and a two-step spin transition in pressurized Fe2O3 with increasing valence to core intensity.

Large area manufacturing processes of thin films such as large-area vacuum roll-to-roll coating of dielectric and gas permeation barrier layers in manufacturing industry require a precise control of e.g. film thickness, homogeneity, chemical compositions, crystallinity and surface roughness. In order to determine these properties in real time, hyperspectral imaging is a novel, cost-efficient, and fast tool as in-line technology for large-area quality control. We demonstrate the application of hyperspectral imaging to characterize the thickness of thin films of the multilayer system ZTO/Ag/ITO produced by roll-to-roll magnetron sputtering on 220 mm wide PET substrate. X-ray reflectivity measurements are used to determine the thickness gradients of roll-to-roll produced foils with sub nanometer accuracy that serve as ground truth data to train a machine learning model for the interpretation of the hyperspectral imaging spectra. Based on the model, the sub-layer thicknesses on the complete substrate foil area were predicted which demonstrates the capabilities of this approach for large-scale in-line real-time quality control for industrial applications.

The determination of the electronic structure of iron-bearing compounds at high pressure and high temperature (HPHT) conditions is of crucial importance for the understanding of the Earth’s interior and planetary matter. Information on their electronic structure can be obtained by X-ray emission spectroscopy (XES) measurements, where the iron’s Kβ1,3 emission provides information about the spin state and the valence-to-core region focusses on the coordination chemistry around the iron and its electronic state. Furthermore, resonant XES (RXES) at the iron’s K-edge reveals even more detailed information about the electronic structure [1].We present a setup to investigate the electronic structure of iron-bearing compounds in situ at HPHT conditions using XES and RXES. The HPHT conditions are accomplished by diamond anvil cells (DACs) in combination with a portable double-sided Yb:YAG-laser heating setup [2]. The spectroscopy setup contains a wavelength dispersive von Hamos spectrometer in combination with a Pilatus 100K area detector [3]. This setup provides a full Kβ1,3 emission spectrum including valence-to-core emission in a single shot fashion. In combination with a dedicated sample preparation and use of highly intense synchrotron radiation of beamline P01 at PETRA III, the duration of the measurements is shortened to an extend that in situ XES, including valence-to-core, as well as in situ spin state imaging becomes feasible. The use of miniature diamonds [4] enables RXES measurements at the Fe-K edge. By using different analyzer crystals for the von Hamos spectrometer, simultaneous Kα and Kβ detection are feasible, which provides L-edge and M-edge like information.The presented sample is siderite (FeCO3), which is in focus of recent research as it is a candidate for the carbon storage in the deep Earth. Siderite exhibits a complex chemistry at pressures above 50 GPa and temperatures above 1400 K resulting in the formation of carbonates featuring tetrahedrally coordinated CO4-groups instead of the typical triangular-planar CO3-coordination. These carbonates are well understood on a structural level but information on their electronic structure is scarce [5-7]. We present information on the sample’s spin state at in situ conditions of about 75 GPa and 2000 K XES Kβ1,3 imaging as well as RXES measurements for low and high pressure siderite at ambient temperature conditions for Kα and Kβ emission.[1] M. L. Baker et al., Coordination Chemistry Reviews 345, 182 (2017)[2] G. Spiekermann et al., Journal of Synchroton Radiation, 27, 414 (2020)[3] C. Weis et al., Journal of Analytical Atomic Spectroscopy 34, 384 (2019)[4] S. Petitgirard et al., J. Synchrotron Rad. , 24, 276 (2017)[5] J. Liu et al., Scientific Reports, 5, 7640 (2015)[6] M. Merlini et al., American Mineralogist, 100, 2001, (2015)[7] V. Cerantola et al., Nature Communications 8, 15960 (2017)

The pressure stability of the first hydration shell of Y3+ ions in aqueous solution has been investigated by means of extended x-ray absorption fine-structure spectroscopy at the yttrium K-edge for...

In this paper, we studied fusogenic peptides of class I-III fusion proteins, which are relevant to membrane fusion for certain enveloped viruses, in contact with model lipid membranes. We resolved the vertical structure and examined the adsorption or penetration behavior of the fusogenic peptides at phospholipid Langmuir monolayers with different initial surface pressures with x-ray reflectometry. We show that the fusion loops of tick-borne encephalitis virus (TBEV) glycoprotein E and vesicular stomatitis virus (VSV) G-protein are not able to insert deeply into model lipid membranes, as they adsorbed mainly underneath the headgroups with only limited penetration depths into the lipid films. In contrast, we observed that the hemagglutinin 2 fusion peptide (HA2-FP) and the VSV-transmembrane domain (VSV-TMD) can penetrate deeply into the membranes. However, in the case of VSV-TMD, the penetration was suppressed already at low surface pressures, whereas HA2-FP was able to insert even into highly compressed films. Membrane fusion is accompanied by drastic changes of the membrane curvature. To investigate how the peptides affect the curvature of model lipid membranes, we examined the effect of the fusogenic peptides on the equilibration of cubic monoolein structures after a phase transition from a lamellar state induced by an abrupt hydrostatic pressure reduction. We monitored this process in presence and absence of the peptides with small-angle x-ray scattering and found that HA2-FP and VSV-TMD drastically accelerate the equilibration, while the fusion loops of TBEV and VSV stabilize the swollen state of the lipid structures. In this work, we show that the class I fusion peptide of HA2 penetrates deeply into the hydrophobic region of membranes and is able to promote and accelerate the formation of negative curvature. In contrast, we found that the class II and III fusion loops of TBEV and VSV tend to counteract negative membrane curvature.

Many vital processes that take place in biological cells involve remodeling of lipid membranes. These processes take place in a milieu that is packed with various solutes, ranging from ions and small organic osmolytes to proteins and other macromolecules, occupying about 30% of the available volume. In this work, we investigated how molecular crowding, simulated with the polymer polyethylene glycol (PEG), and the osmolytes urea and trimethylamine-N-oxide (TMAO) affect the equilibration of cubic monoolein structures after a phase transition from a lamellar state induced by an abrupt pressure reduction. In absence of additives, swollen cubic crystallites form after the transition, releasing excess water over several hours. This process is reflected in a decreasing lattice constant and was monitored with small angle X-ray scattering. We found that the osmotic pressure exerted by PEG and TMAO, which are displaced from narrow inter-bilayer spaces, accelerates the equilibration. When the radius of gyration of the added PEG was smaller than the radius of the water channels of the cubic phase, the effect became more pronounced with increasing molecular weight of the polymers. As the release of hydration water from the cubic structures is accompanied by an increasing membrane curvature and a reduction of the interface between lipids and aqueous phase, urea, which has a slight affinity to reside near membrane surfaces, stabilized the swollen crystallites and slowed down the equilibration dynamics. Our results support the view that cellular solutes are important contributors to dynamic membrane processes, as they can accelerate dehydration of inter-bilayer spaces and promote or counteract membrane curvature., Soft matter;18(5)

Synchrotron Radiation Instrumentation, SRI 2021, Hamburg, Germany, 28 Mar 2022 - 1 Apr 2022; Journal of physics / Conference Series 2380(1), 012128 (2022). doi:10.1088/1742-6596/2380/1/012128, The International Conference on Synchrotron Radiation Instrumentation (SRI) is a unique and significant international forum held every three years in the community of synchrotron radiation (SR) and free electron lasers (FEL). It is the prime forum for fostering connections between cutting-edge synchrotron radiation instrumentation, science, and the requirements of the user community. The SRI 2021 had originally been scheduled to take place in Hamburg in summer 2021. Due to the COVID-19 pandemic, it was postponed to 2022 and held as an online event.More than 1160 international participants from 25 countries met virtually at the SRI 2021. In nearly 290 talks and 450 posters, latest results were presented. Although it was an online-only conference, lively discussions took place in the nearly 40 parallel sessions, and the eight poster sessions were also very well attended.The main topics of the SRI conference were: new SR and FEL facilities, update plans of these facilities, and recent developments in various instrumentation areas like beamline design, X-ray optics, sample environments, detectors and spectrometers, data acquisition, and data analysis techniques or automation. These innovations contributed to new results for a wide range of experimental techniques and scientific applications such as X-ray scattering and spectroscopy, bio- and scanning imaging, structural biology crystallography, coherent techniques, or in-situ/operando methods. A dedicated session concerned industrial applications of synchrotron radiation.The field of synchrotron radiation instrumentation is currently seeing very active development due to various factors. Firstly, the number of SR sources world-wide is increasing significantly, with new sources in particular in Europe and in Asia. Secondly, a new generation of storage rings with new multi-bend achromat lattices are being implemented at a growing number of existing facilities. These facilities offer a significant increase of brilliance and coherence and thereby lead to new and improved applications of synchrotron radiation, in particular in the areas of imaging and high spatial resolution. Thirdly, the increase of soft and hard X-ray FEL sources worldwide and the maturation of their experimental techniques and scientific applications is the background for a strongly increasing number of developments for ultrafast time-resolved investigations of dynamic behaviour of materials and reactions. Most of the keynote speakers and many invited and contributed talks or posters at the conference showed new results directly related to these three major developments.Lists of International Advisory Committee (listed by facility), Scientific Programme Committee (listed by facility), Local Organising Committee (listed by facility) are available in this PDF., Published by IOP Publ., Bristol

Physical review / B 105(8), 085155 (2022). doi:10.1103/PhysRevB.105.085155, Iron-bearing carbonates play an important role in Earth's carbon cycle. Owing to their stability at mantle conditions, recently discovered iron carbonates with tetrahedrally coordinated carbon atoms are candidates for carbon storage in the deep Earth. The carbonates' iron oxidation and spin state at extreme pressure and temperature conditions contribute to the redox conditions and element partitioning in the deep mantle. By laser heating FeCO$_3$ at pressures of about 83 GPa, Fe$^{3+}_4$C$_3$O$_{12}$ and Fe$^{2+}_2$Fe$^{3+}_2$C$_4$O$_{13}$ were synthesized and then investigated by x-ray emission spectroscopy to elucidate their spin state, both in situ and temperature quenched. Our experimental results show both phases in a high-spin state at all pressures and over the entire temperature range investigated, i.e., up to 3000 K. The spin state is conserved after temperature quenching. A formation path is favored where Fe$^{3+}_4$C$_3$O$_{12}$ forms first and then reacts to Fe$^{2+}_2$Fe$^{3+}_2$C$_4$O$_{13}$, most likely accompanied by the formation of oxides. Density functional theory calculations of Fe$^{2+}_2$Fe$^{3+}_2$C$_4$O$_{13}$ at 80 GPa confirm the experimental findings with both ferric and ferrous iron in high-spin state with antiferromagnetic order at 80 GPa. As the intercrystalline cation partitioning between the Fe-bearing carbonates and the surrounding perovskite and ferropericlase depends on the spin state of the iron, an understanding of the redox conditions prevalent in subducted slab regions in the lower mantle has to take the latter into account. Especially, Fe$^{2+}_2$Fe$^{3+}_2$C$_4$O$_{13}$ may play a key role in subducted material in the lower mantle, potentially with a similar role as silicate perovskite., Published by Inst., Woodbury, NY

Over the last decade, great efforts have been undertaken in science and industry to provide WC-Co feedstock with nano-sized WC particles that significantly improves tribo-mechanical coating properties. For tribologically stressed surfaces, superior surface characteristics can be achieved by applying tailored surfaces, using novel technologies in the field of production engineering such as High-Feed Milling (HFM). For the first time, textured surface patterns were produced onto HVOF sprayed WC-Co coatings with nano-sized WC particles by implementing a HFM post process. In dependence to two different textures resulting from the HFM, the microstructural characteristics of the produced surfaces are analyzed. Confocal microscopy revealed the machinability of textured patterns onto a HVOF-sprayed WC-12Co hard coating, which comprise of nano-sized WC particles, by means of HFM technology. X-ray diffraction analyses confirmed the insertion of macro- and micro-scale residual stresses. The experiments showed a significant insertion of compressive residual stresses transverse to the feed direction, whereas the insertion of compresses residual stresses with its feed direction being less pronounced. It was found that the HFM post process leads to a refinement of the WC crystallite size and a distinct increase of its internal strain, which both can be attributed to plastic deformations during HFM.

We determined the intermolecular interaction potential, V(r), of dense lysozyme solutions, which governs the spatial distribution of the protein molecules and the location of its liquid–liquid phase separation (LLPS) region, in various crowding environments applying small-angle X-ray scattering in combination with liquid-state theory. We explored the effect of polyethylene glycol (PEG) on V(r) and the protein’s phase behavior over a wide range of temperatures and pressures, crossing from the dilute to the semidilute polymer regime, thereby mimicking all crowding scenarios encountered in the heterogeneous biological cell. V(r) and hence the protein–protein distances and the phase boundary of the LLPS region strongly depend on the polymer-to-protein size ratio and the polymer concentration. The strongest effect is observed for small-sized PEG molecules, leading to a marked decrease of the mean intermolecular spacing of the protein molecules with increasing crowder concentration. The effect levels off at int...

The structural properties of hafnium nitride films are mainly influenced by the deposition conditions, which are affected by the sputtering technique. A suitable use of the different sputtering modes allows to control the structural development of the films and thus to adjust the profile of the properties. NaCl-type hafnium nitride films were deposited using direct current magnetron sputtering (dcMS), mid-frequency magnetron sputtering (mfMS), and high-power impulse magnetron sputtering (HiPIMS). dcMS produces films with a columnar microstructure, whereas a fully-dense morphology is achieved by mfMS and HiPIMS. X-ray diffraction patterns show that films sputtered in dcMS mode have a (200) orientation, whereas mfMS and HiPIMS favor an orientation with the (111) plane parallel to the samples' surface. mfMS leads to films with the largest crystal sizes and lowest stresses, which is ascribed to recrystallization mechanisms during the film growth. Hafnium films with an overstoichiometric composition show the highest hardness values. In this context, the dcMS-Hf49.8N50.2, mfMS-Hf50.4N49.6, and HiPIMS-Hf49.0N51.0 have a hardness of 28.2 ± 2.1, 32.4 ± 3.4, and 30.4 ± 3.1 GPa, respectively. In summary, the sputtering technique has a crucial role on the properties of the film and can be suitable used to adjust the structure and hardness of HfN films.

International audience; The understanding of the microstructure of associated liquids promoted by hydrogen-bonding andconstrained by steric hindrance is highly relevant in chemistry physics, biology and for many aspects ofdaily life. In this study we use a combination of X-ray diffraction, dielectric spectroscopy and moleculardynamics simulations to reveal temperature induced changes in the microstructure of different octanolisomers, i.e., linear 1-octanol and branched 2-, 3- and 4-octanol. In all octanols, the hydroxyl groupsform the bases of chain-, cyclic- or loop-like bonded structures that are separated by outwardlydirected alkyl chains. This clustering is analyzed through the scattering pre-peaks observed from X-rayscattering and simulations. The charge ordering which pilots OH aggregation can be linked to thestrength of the Debye process observed in dielectric spectroscopy. Interestingly, all methods used hereconverge to the same interpretation: as one moves from 1-octanol to the branched octanols, thecluster structure evolves from loose large aggregates to a larger number of smaller, tighter aggregates.All alcohols exhibit a peculiar temperature dependence of both the pre-peak and Debye process, whichcan be understood as a change in microstructure promoted by chain association with increased chainlength possibly assisted by ring-opening effects. All these results tend to support the intuitive picture ofthe entropic constraint provided by branching through the alkyl tails and highlight its capital entropicrole in supramolecular assembly.

James Bond always takes his vodka martini shaken and never stirred. So far, he’s ordered this drink 28 times in all the movies together. And he always warns the bartender: “Shaken, not stirred!” Why is he doing this? Is there a special reason for this, or is it just some kind of trademark? Fortunately, the recipe for the original secret agent cocktail can be found in Ian Fleming’s 1953 novel Casino Royale

James Bond is celebrating an anniversary. The 25th film No Time to Die finally makes him the most successful character in film history. When Ian Fleming published the first James Bond novel entitled Casino Royale in 1953, he had no idea just what kind of a character he had created. The British secret agent James Bond, whom Ian Fleming named after an ornithologist from Philadelphia, is one of the best-known film characters ever. He has the habit of introducing himself with the words “The name is Bond, James Bond” and he enjoys a worldwide popularity that could hardly be increased. The double-O number stands for the license to kill, or as his superior M once put it, in the very first Bond movie Dr. No

Daniel Craig has now impersonated the famous secret agent five times. With him, the James Bond series was relaunched in 2006, as the film Casino Royale was intended to explain how Bond became what he is today: a cold-blooded double-O agent with the license to kill. The film also strongly oriented itself on the first Bond novel with the same title published by Ian Fleming in 1953. In contrast to all other Fleming books, this material had not yet been filmed. But since there are now more films than novels about our hero, the relationship with his creator is no longer so strong. The following three Craig Bond films therefore follow their own stories, among which Quantum of Solace stands out. With a length of 106 minutes, it is not only the shortest, but also immediately continues the story of its predecessor. In the films Skyfall and Spectre that follow, there are also repeated references to these first two Craig Bonds, so that an overarching action is created (Figure 2.1).

Every James Bond fan has noticed that our elegant secret agent wears very interesting watches and glasses. He doesn’t always put so much emphasis on style as on functionality, since the watches and glasses usually contain a technical “gimmick” that can save 007 from many a hopeless situation. But we do not want to discuss the usual equipment of a secret agent with watches and ballpoint pens containing miniature microphones and cameras. A schoolkid wearing the “ultra-modern” quartz watch with liquid crystal display, whose built-in camera is praised in the 1983 film Octopussy as a technical masterpiece, would certainly not find a girlfriend in the schoolyard today. It is also easy with today’s technical possibilities to integrate a Geiger counter into a watch, as so proudly presented by Q in the film Thunderball. Here, one simply uses semiconductor detectors in which the counter tube consists of a germanium crystal where charge separation by the incident ionizing radiation takes place. One such watch was launched on the market by a Swiss company in 2003 for 1100 US dollars. This watch should also be water-resistant at depths of up to 100 meters: “It’s waterproof, of course”, as Q remarks when presenting the watch (Figure 6.1).

A portable IR fiber laser-heating system, optimized for X-ray emission spectroscopy (XES) and nuclear inelastic scattering (NIS) spectroscopy with signal collection through the radial opening of diamond anvil cells near 90°with respect to the incident X-ray beam, is presented. The system offers double-sided on-axis heating by a single laser source and zero attenuation of incoming X-rays other than by the high-pressure environment. A description of the system, which has been tested for pressures above 100 GPa and temperatures up to 3000 K, is given. The XES spectra of laser-heated Mg0.67Fe0.33O demonstrate the potential to map the iron spin state in the pressure–temperature range of the Earth's lower mantle, and the NIS spectra of laser-heated FeSi give access to the sound velocity of this candidate of a phase inside the Earth's core. This portable system represents one of the few bridges across the gap between laser heating and high-resolution X-ray spectroscopies with signal collection near 90°., Journal of Synchrotron Radiation, 27 (2), ISSN:0909-0495, ISSN:1600-5775

No other James Bond adventure has achieved greater popularity among fans than the 1964 film Goldfinger. One could almost say that this film had a lasting impact on society. Some scenes made sure that myths were formed that live on to this day. There is still controversy about whether someone whose skin is covered with a wafer-thin layer of gold would really die. This is exactly what happens in one of the most famous movie scenes ever: James Bond finds Jill Masterson on her bed completely covered in gold—and dead. So what did she die of?

In the final credits of the movie The Spy Who Loved Me from 1977, it was announced that James Bond would return with the movie For Your Eyes Only. In view of the huge successes of the first Star Wars movie launched in the same year and the film Close Encounters of the Third Kind, however, these plans were changed and a space adventure was inserted. Moonraker appeared on the screen in 1979 and is the eleventh film in the James Bond series. In contrast to Goldfinger, Moonraker simply took the title of Ian Fleming’s book of the same name and devised a completely new plot for it.

An X-ray reflectivity study on the adsorption behavior of human apolipoprotein A1 (apoA1) at hydrophilic and hydrophobic interfaces is presented. It is shown that the protein interacts via electrostatic and hydrophobic interactions with the interfaces, resulting in the absorption of the protein. pH dependent measurements at the solid/liquid interface between silicon dioxide and aqueous protein solution show that in a small pH range between pH 4 and 6, adsorption is increased due to electrostatic attraction. Here, the native shape of the protein seems to be conserved. In contrast, the adsorption at the liquid/gas interface is mainly driven by hydrophobic effects, presumably by extending the hydrophobic regions of the amphipathic helices, and results in a conformational change of the protein during adsorption. However, the addition of differently charged membrane-forming lipids at the liquid/gas interface illustrates the ability of apoA1 to include lipids, resulting in a depletion of the lipids from the interface.

Investigating the correlation between structure and activity of oligomeric enzymes at high pressure is essential for understanding intermolecular interactions and reactivity of proteins in cellulo of organisms thriving at extreme environmental conditions as well as for biotechnological applications, such as high-pressure enzymology. In a combined experimental effort employing small-angle X-ray scattering, FT-IR and fluorescence spectroscopy as well as stopped-flow enzyme kinetics in concert with high-pressure techniques, we reveal the pressure-induced conformational changes of the dimeric enzyme horse liver alcohol dehydrogenase (LADH) on the quaternary, secondary and tertiary structural level. Moreover, the effects of cosolutes and crowding agents, mimicking intracellular conditions, have been addressed. Our results show that beyond an increase of enzymatic activity at low pressures, loss of enzyme activity occurs around 600-800 bar, i.e. in a pressure regime where small conformational changes take place in the coenzyme's binding pocket, only. Whereas higher-order oligomers dissociate at low pressures, subunit dissociation of dimeric LADH takes place, depending on the solution conditions, between 2000 and 4000 bar, only. Oligomerization and subunit dissociation are modulated by cosolvents such as urea or trimethylamine-N-oxide as well as by the crowding agent polyethylene glycol, based on their tendency to bind to the protein's interface or act via their excluded volume effect, respectively.

Friction minimization is an important topic which is pursued in research and industry. In addition to the use of lubricants, friction-reducing oxide phases can be utilized which occur during. These oxides are called Magneli phases and especially vanadium oxides exhibit good friction reducing properties. Thereby, the lubrication effect can be traced back to oxygen deficiencies. AlCrN thin films are being used as coatings for tools which have to withstand high temperatures. A further improvement of AlCrN thin films concerning their friction properties is possible by incorporation of vanadium. This study analyzes the temperature dependent oxidation behavior of magnetron sputtered AlCrVN thin films with different vanadium contents up to 13.5 at.-% by means of X-ray diffraction and X-ray absorption near-edge spectroscopy. Up to 400 °C the coatings show no oxidation. A higher temperature of 700 °C leads to an oxidation and formation of Magneli phases of the coatings with vanadium contents above 10.7 at.-%. Friction coefficients, measured by ball-on-disk test are correlated with the oxide formation in order to figure out the effect of vanadium oxides. At 700 °C a decrease of the friction coefficient with increasing vanadium content can be observed, due to the formation of VO 2 , V 2 O 3 and the Magneli phase V 4 O 7 .

In the present work two subclasses of the human antibody Immunoglobulin G (IgG) have been investigated by Small-Angle X-ray Scattering under high hydrostatic pressures up to 5kbar. It is shown that IgG adopts a symmetric T-shape in solution which differs significantly from available crystal structures. Moreover, high-pressure experiments verify the high stability of the IgG molecule. It is not unfolded by hydrostatic pressures of up to 5kbar but a slight increase of the radius of gyration was observed at elevated pressures.

We have gained new insight into the so-called hydrophobic gap, a molecularly thin region of decreased electron density at the interface between water and a solid hydrophobic surface, by X-ray reflectivity experiments and molecular dynamics simulations at different hydrostatic pressures. Pressure variations show that the hydrophobic gap persists up to a pressure of 5 kbar. The electron depletion in the interfacial region strongly decreases with an increase in pressure, indicating that the interfacial region is compressed more strongly than bulk water. The decrease is most significant up to 2 kbar; beyond that, the pressure response of the depletion is less pronounced.

In this work, the interaction of soy sauces with hydrophobic surfaces has been analyzed. Hydrophobic self-assembled monolayers on gold or silicon dioxide were used to harvest conditioning layers from soy sauce products with varying amounts of additives. The data was compared to adsorption of soy protein and glutamic acid as common ingredients. Spectral ellipsometry revealed that all tested sauces led to the formation of thin overlayers on hydrophobic surfaces. Products with less additives yielded adlayers in the same thickness range as pure soy protein. In contrast, sauces with more ingredients create distinctly thicker films. Using water contact angle goniometry, it is shown that all adlayers render the substrate more hydrophilic. Infrared spectroscopy provided a deeper insight into the adlayer chemistry and revealed that the adlayer composition is dominated by protein rich components. X-ray reflectivity on selected films provided further insight into the density profiles within the adlayers on the molecular scale.

The formation of thin reactive films in sliding contacts under elevated temperature provides enhanced tribological properties since the formation of Magneli phases leads to the ability of self-lubricating behavior. This phenomenon was studied for vanadium-doped coating systems which were produced using CVD and PVD technology. Vanadium-containing arc sprayed coatings were not widely examined so far. The aim of this study was to characterize Fe-V coatings deposited by the Twin Wire Arc Spraying process with respect to their oxidation behavior at elevated temperatures and to correlate the formation of oxides to the tribological properties. Dry sliding experiments were performed in the temperature range between 25 and 750 °C. The Fe-V coating possesses a reduced coefficient of friction and wear coefficient (k) at 650 and 750 °C, which were significant lower when compared to conventional Fe-based coatings. The evolution of oxide phases was identified in situ by x-ray diffraction for the investigated temperature range. Further oxidation of (pre-oxidized) arc sprayed Fe-V coatings, as verified by differential thermal analysis and thermo-gravimetric analysis, starts at about 500 °C.

Diamond impregnated metal matrix composites are the state of the art solution for the machining of mineral materials. The type of interface reactions between the metal matrix and diamond surface has an essential influence on the tool performance and durability. To improve the diamond retention, the diamonds can be coated by physical vapour deposition with metallic materials, which enforce interface reactions. Hence, this paper focuses on the investigation of the interfacial area on metal-coated monocrystalline diamonds. Hafnium and zirconium, both known as carbide forming elements, are used as coating materials. The third coating, which is used to determine its catalytic influences when applied as a physical vapour deposition (PVD)-layer, is nickel. Additionally, the coated diamond samples were heat-treated to investigate the starting point of the formation of new phases. X-ray diffraction-analyses revealed the assumed carbide formation on hafnium and zirconium coated samples. The formation temperature was identified between 800 °C and 1000 °C for hafnium and zirconium coatings.

X-ray emission and X-ray Raman scattering spectroscopy are powerful tools to investigate the local electronic and atomic structure of high and low Z elements in situ. Notably, these methods can be applied for in situ spectroscopy at high pressure and high temperature using resistively or laser-heated diamond anvil cells in order to achieve thermodynamic conditions which appear in the Earth's interior. We present a setup for combined X-ray emission and X-ray Raman scattering studies at beamline P01 of PETRA III using a portable wavelength-dispersive von Hamos spectrometer together with the permanently installed multiple-analyzer Johann-type spectrometer. The capabilities of this setup are exemplified by investigating the iron spin crossover of siderite FeCO 3 up to 49.3 GPa by measuring the Fe M 2,3 -edge and the Fe Kβ 1,3 emission line simultaneously. With this setup, the Fe valence-to-core emission can be detected together with the Kβ 1,3 emission line providing complementary information on the sample's electronic structure. By implementing a laser-heating device, we demonstrate the strength of using a von Hamos type spectrometer for spin state mapping at extreme conditions. Finally, we give different examples of low Z elements' absorption edges relevant for application in geoscience that are accessible with the Johann-type XRS spectrometer. With this setup new insights into the spin transition and compression mechanisms of Earth's mantle materials can be obtained of importance for comprehension of the macroscopic physical and chemical properties of the Earth's interior.

In the field of surface engineering, the use of self-lubricous coatings with the incorporation of vanadium represent a promising approach to reduce friction, thus contributing to the wear behavior. For vanadium containing hard coatings produced by means of thin film technology, the reduction in friction at elevated temperatures was repeatedly attributed to temperature-induced and tribo-oxidatively formed oxides which act as solid lubricant. Only very few studies focused on the tribological characteristics of vanadium containing arc sprayed coatings. In this study, the tribological characteristics of a vanadium containing iron-based arc sprayed deposit were investigated in dry sliding experiments under ambient conditions and different temperatures. Types of wear at the worn surfaces and counterparts were examined by means of electron microscopy and energy dispersive X-ray (EDX) spectroscopy. The speciation of vanadium in the superficial layer was determined using X-ray absorption near edge structure (XANES) spectroscopy. It was found that the vanadium-containing coating exhibited a distinctly reduction of the coefficient of friction above 450 °C which further decreased with increasing temperature. XANES spectroscopy indicated an increased oxidation state for the V component on the coating surface, suggesting the prevalence of specific vanadium oxides which promote a self-lubricating ability of the coating., Coatings;Jg. 9, Heft: 1. S. 18-1-18-15

In recent years, great effort has been taken in science and industry to find novel material-related solutions, which provide improved properties for future technological applications. One of these approaches is the use of fine structured and nanostructured materials. Within the field of wear protection, the use of fine or nanostructured WC-Co powder feedstock in the thermal spray process enables the application of highly wear resistant, thin near net-shape coatings on parts with complex geometries. In this study, the processing of WC-12Co powders by means of High Velocity Oxy-Fuel (HVOF) flame spraying is fundamentally investigated and the results are compared to those obtained with conventional powders. The influence of process parameter and scaling effects on the spray process and the thermo-kinetic particle behavior in the flame, the heating of the substrate as well as on the coating properties, the microstructure, the behavior of elements and phases and the residual stress is discussed comprehensively. The investigations of this work have shown that HVOF spraying of fine and nanostructured WC-12Co powders instead of conventional ones leads to a significant alteration of the thermo-kinetic spray conditions. Under optimized spray conditions, achieved by the use of special spray equipment and statistical design of experiments (DoE), improvements in terms of the economy of the spray process (higher deposition efficiencies) and the mechanical properties (higher microhardness and fracture toughness, lower porosity and roughness) can be achieved.

A study on the interaction between butane and lipid membranes is presented. Monomolecular films of stearic acid were prepared on a water surface and were exposed to dense gas phases of n -butane and isobutane. From X-ray reflectivity measurements and grazing incidence X-ray diffraction, the accumulation of gas molecules at the liquid–gas interface was analyzed. We show that the gas molecules penetrate into the lipid membrane and accumulate between the head group and tail group of the lipids. This process goes in hand with an increase of the long-range lateral crystallographic order within the lipid film. This and the formation of multilayer islands points to an expulsion of lipids by the gas molecules. At higher pressures close to the condensation pressure of the studied gases, the vertical and lateral order is lost, indicating an adsorbed liquid film in which the lipids are dissolved.

The effect of hydrostatic pressure on the structure of a bicontinuous microemulsion in the presence of a solid interface has been studied by X-ray reflectometry and compared to the bulk behavior determined by small-angle X-ray scattering. Surface-induced lamellar ordering is observed close to the hydrophilic interface, which persists upon compression. The lamellar domains are compressed, but the correlation length of lamellar order does not change with pressure. SAXS measurements on the bulk microemulsion revealed an increased order upon pressurization. Although pressure can cause the formation of highly ordered lamellar phases from ordered bicontinuous cubic phases, such a scenario is not observed for the disordered analogue studied here. High pressure increases the stiffness of the interfacial surfactant layer, but this is not sufficient to overcome the loss in conformational entropy that would result from a transition to an ordered lamellar phase. Possible technological and biological implications of our results are briefly discussed.

In this work, the structure of solid-supported lipid multilayers exposed to increased hydrostatic pressure was studied in situ by X-ray reflectometry at the solid-liquid interface between silicon and an aqueous buffer solution. The layers' vertical structure was analyzed up to a maximum pressure of 4500 bar. The multilayers showed phase transitions from the fluid into different gel phases. With increasing pressure, a gradual filling of the sublayers between the hydrophilic head groups with water was observed. This process was inverted when the pressure was decreased, yielding finally smaller water layers than those in the initial state. As is commonly known, water has an abrasive effect on lipid multilayers by the formation of vesicles. We show that increasing pressure can reverse this process so that a controlled switching between multi- and bilayers is possible.

The influence of natural cosolvent mixtures on the pressure-dependent structure and protein-protein interaction potential of dense protein solutions is studied and analyzed using small-angle X-ray scattering in combination with a liquid-state theoretical approach. The deep-sea osmolyte trimethylamine-N-oxide is shown to play a crucial and singular role in its ability to not only guarantee sustainability of the native protein's folded state under harsh environmental conditions, but it also controls water-mediated intermolecular interactions at high pressure, thereby preventing contact formation and hence aggregation of proteins.

Supramolecular relaxations of the Debye or near-Debye type are featured by monohydroxy alcohols, water, and several other liquids. Mainly focusing on results from broadband dielectric spectroscopy, shear rheology, X-ray diffraction, and near-infrared absorption, scaling properties of chain-forming and ring-forming monohydroxy alcohols are examined. Deviations from ideal-mixing behavior in binary solutions involving these liquids in their supercooled state are given particular attention. The present survey is selective rather than comprehensive with a focus on exciting recent developments in this scientific area. Although most of the research summarized in this chapter is based on experiments and analyses carried out under linear-response and ambient-pressure conditions, phenomena emerging beyond these regimes are briefly touched upon as well. Finally, aiming at a faithful representation of the molecular dynamics taking place in these liquids at the microscopic level, overarching aspects arising from the complementary application of experimental techniques as well as perspectives for future developments are discussed.

The monohydroxy alcohol 2-ethyl-1-hexanol mixed with the halogen-substituted alkyl halides 2-ethyl-1-hexyl chloride and 2-ethyl-1-hexyl bromide was studied using synchrotron-based x-ray scattering. In the diffraction patterns, an oxygen-related prepeak appears. The concentration dependence of its intensity, shape, and position indicates that the formation of the hydrogen-bonded associates of monohydroxy alcohols is largely hindered by the halogen alkane admixture. Using dielectric spectroscopy and high-resolution rheology on the same liquid mixtures, it is shown that these structural features are correlated with the relaxation mechanisms giving rise to supramolecular low-frequency dynamics.

The behavior of magnetically responsive aqueous Fe(III) surfactant solutions at liquid interfaces is analyzed. Such surfactants attracted much attention, because of the ability to manipulate interfaces by magnetic fields without any use of magnetic nanoparticles. A detailed analysis of the surface properties proves that the mixing of paramagnetic electrolyte solution with anionic, cationic and nonionic surfactants yields the similar magnetic response and no effect of the surfactant charge can be observed. We conclude that the observed magnetic shiftability of interfaces is caused by a combination of the paramagnetic behavior of the bulk liquid and a reduction of the surface tension. Thus, this work gives an alternative interpretation of the properties of "magnetic surfactants" compared to the ones claimed in the literature.

Structural and mechanical properties of molecularly thick polysiloxane membranes were studied on different liquid subphases to investigate the impact of the subphase's pH value on the cross-linking process. The lateral structure of these films was studied in-situ by grazing incidence diffraction while torsions pendulum experiments reveal the response of the system to mechanical stress. The results show a hindered cross-linking on acidic subphases. At alkaline and neutral pH conditions the cross-linking process was not effected. The data revealed that the degree of polymerization can be tuned by regulating the subphase's pH value, which opens the opportunity to build complex polysiloxane membranes in a controlled manner.

“It's what happens on the pitch that matters,” said Adi Preissler and Otto Rehhagel, former German footballers and coaches, in some oft-quoted words of football wisdom. Statistically, the German national side managed by Jogi Low is 6.5 times more likely than an “average” team to finally bring home the title again. Here is a scientific approach to a World Cup forecast that uses a few mathematical tricks and computer simulations.

„Entscheidend is auf'm Platz”, wussten schon Adi Preisler und Otto Rehagel. Zumindest im Zahlenspiel der Fusballstatistik aber hat Jogi Lows Team eine 6,5 Mal hohere Wahrscheinlichkeit als ein „Durchschnittsteam”, endlich einmal wieder den Titel zu holen. Eine WM-Prognose der wissenschaftlichen Art mit mathematischen Kniffen und Computersimulationen.