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Fe- and steelmaking is the largest single industrial CO2 emitter, accounting for 6.5% of all CO2 emissions on the planet. This fact challenges the current technologies to achieve carbon-lean steel production and to align with the requirement of a drastic reduction of 80% in all CO2 emissions by around 2050. Thus, alternative reduction technologies have to be implemented for extracting iron from its ores. The H-based direct reduction has been explored as a sustainable route to mitigate CO2 emissions, where the reduction kinetics of the intermediate oxide product FexO wustite into Fe is the rate-limiting step of the process. The total reaction has an endothermic net energy balance. Reduction based on a H plasma may offer an attractive alternative. Here, we present a study about the reduction of hematite using H plasma. The evolution of both, chemical composition and phase transformations was investigated in several intermediate states. We found that hematite reduction kinetics depends on the balance between the initial input mass and the arc power. For an optimized input mass-arc power ratio, complete reduction was obtained within 15 min of exposure to the H plasma. The wustite reduction is also the rate-limiting step towards complete reduction. Nonetheless, the reduction reaction is exothermic, and its rates are comparable with those found in H-based direct reduction. Chemical and microstructure analysis revealed that the gangue elements partition to the remaining oxide regions, probed by energy dispersive spectroscopy and atom probe tomography. Si-enrichment was observed in the interdendritic fayalite domains, at the wustite/Fe hetero-interfaces and in the primarily solidified oxide particles inside the Fe. With proceeding reduction, however, such elements are gradually removed from the samples so that the final iron product is nearly free of gangue-related impurities.

Zircaloy-4 (Zr-1.5%Sn-0.2%Fe-0.1%Cr wt. %) was electrochemically charged with deuterium to create deuterides and subsequently analysed with atom probe tomography and scanning transmission electron microscopy to understand zirconium hydride formation and embrittlement. At the interface between the hexagonal close packed (HCP) \alpha-Zr matrix and a face centred cubic (FCC) \delta deuteride (ZrD1.5-1.65), a HCP \zeta phase deuteride (ZrD0.25-0.5) has been observed. Furthermore, Sn is rejected from the deuterides and segregates to the deuteride/\alpha-Zr reaction front.

Carbides play a central role for the strength and ductility in many materials. Simulating the impact of these precipitates on the mechanical performance requires the knowledge about their atomic configuration. In particular, the C content is often observed to substantially deviate from the ideal stoichiometric composition. In the present work, we focus on Fe-Mn-Al-C steels, for which we determined the composition of the nano-sized kappa carbides (Fe,Mn)3AlC by atom probe tomography (APT) in comparison to larger precipitates located in grain boundaries. Combining density functional theory with thermodynamic concepts, we first determine the critical temperatures for the presence of chemical and magentic disorder in these carbides. Secondly, the experimentally observed reduction of the C content is explained as a compromise between the gain in chemical energy during partitioning and the elastic strains emerging in coherent microstructures.

The effect of shear flow on mode selection and the length scale of patterns formed in a nonlinear auto-catalytic reaction-diffusion model is investigated. We predict analytically the existence of transverse and longitudinal modes. The type of the selected mode strongly depends on the difference in the flow rates of the participating species, quantified by the differential flow parameter. New spatial structures are obtained by varying the length scale of individual modes and superposing them via the differential flow parameter. Our predictions are in line with numerical results obtained from lattice Boltzmann simulations.

Glass forming liquids exhibit a rich phenomenology upon confinement. This is often related to the effects arising from wall-fluid interactions. Here we focus on the interesting limit where the separation of the confining walls becomes of the order of a few particle diameters. For a moderately polydisperse, densely packed hard-sphere fluid confined between two smooth hard walls, we show via event-driven molecular dynamics simulations the emergence of a multiple reentrant glass transition scenario upon a variation of the wall separation. Using thermodynamic relations, this reentrant phenomenon is shown to persist also under constant chemical potential. This allows straightforward experimental investigation and opens the way to a variety of applications in micro- and nanotechnology, where channel dimensions are comparable to the size of the contained particles. The results are in-line with theoretical predictions obtained by a combination of density functional theory and the mode-coupling theory of the glass transition., Comment: 11 pages and 10 figures (main paper) and 8 pages and 7 figures (Supplementary Information)

Ultrathin passive films effectively prevent the chemical attack of stainless steel grades in corrosive environments; their stability critically depends on the interplay between structure and chemistry of the constituents Fe-Cr-Mo. In particular, nanoscale inhomogeneities along the surface can have a tremendous impact on material failure, but are yet barely understood. Addressing a stainless-type glass-forming Fe50Cr15Mo14C15B6 alloy and utilizing a combination of complementary high-resolution analytical techniques, we relate near-atomistic insight into different gradual nanostructures with time- and element-resolved dissolution behavior. The progressive elemental segregation on the nanoscale is followed in its influence on the concomitant degree of passivity. A detrimental transition from Cr-controlled passivity to Mo-controlled breakdown is dissected atom-by-atom demonstrating the importance of nanoscale knowledge for understanding corrosion.

Partitioning at phase boundaries of complex steels is important for their properties. We present atom probe tomography results across martensite / austenite interfaces in a precipitation-hardened maraging TRIP steel (12.2 Mn, 1.9 Ni, 0.6 Mo, 1.2 Ti, 0.3 Al; at.%). The system reveals compositional changes at the phase boundaries: Mn and Ni are enriched while Ti, Al, Mo, and Fe are depleted. More specific, we observe up to 27 at.% Mn in a 20 nm layer at the phase boundary. This is explained by the large difference in diffusivity between martensite and austenite. The high diffusivity in martensite leads to a Mn-flux towards the retained austenite. The low diffusivity in the austenite does not allow accommodation of this flux. Consequently, the austenite grows with a Mn-composition given by local equilibrium. The interpretation is based on DICTRA and mixed-mode diffusion calculations (using a finite interface mobility).

Spatial correlations of microscopic fluctuations are investigated via real-space experiments and computer simulations of colloidal glasses under steady shear. It is shown that while the distribution of one-particle fluctuations is always isotropic regardless of the relative importance of shear as compared to thermal fluctuations, their spatial correlations show a marked sensitivity to the competition between shear-induced and thermally activated relaxation. Correlations are isotropic in the thermally dominated regime, but develop strong anisotropy as shear dominates the dynamics of microscopic fluctuations. We discuss the relevance of this observation for a better understanding of flow heterogeneity in sheared amorphous solids., Comment: 6 pages, 4 figures

The coalescence of two resting liquid droplets in a saturated vapor phase is investigated by Lattice Boltzmann simulations in two and three dimensions. We find that, in the viscous regime, the bridge radius obeys a t^{1/2}-scaling law in time with the characteristic time scale given by the viscous time. Our results differ significantly from the predictions of existing analytical theories of viscous coalescence as well as from experimental observations. While the underlying reason for these deviations is presently unknown, a simple scaling argument is given that describes our results well., Comment: 12 pages, 10 figures; as published in Phys. Fluids

Austenite reversion during tempering of a Fe-13.6Cr-0.44C (wt.%) martensite results in an ultrahigh strength ferritic stainless steel with excellent ductility. The austenite reversion mechanism is coupled to the kinetic freezing of carbon during low-temperature partitioning at the interfaces between martensite and retained austenite and to carbon segregation at martensite-martensite grain boundaries. An advantage of austenite reversion is its scalability, i.e., changing tempering time and temperature tailors the desired strength-ductility profiles (e.g. tempering at 400{\deg}C for 1 min. produces a 2 GPa ultimate tensile strength (UTS) and 14% elongation while 30 min. at 400{\deg}C results in a UTS of ~ 1.75 GPa with an elongation of 23%). The austenite reversion process, carbide precipitation, and carbon segregation have been characterized by XRD, EBSD, TEM, and atom probe tomography (APT) in order to develop the structure-property relationships that control the material's strength and ductility., Comment: in press Acta Materialia 2012

Pattern formation in reaction-diffusion systems is of great importance in surface micro-patterning [Grzybowski et al. Soft Matter. 1, 114 (2005)], self-organization of cellular micro-organisms [Schulz et al. Annu. Rev. Microbiol. 55, 105 (2001)] and in developmental biology [Barkai et al. FEBS Journal 276, 1196 (2009)]. In this work, we apply the Lattice Boltzmann method (LBM) to study pattern formation in reaction-diffusion systems. As a first methodological step, we consider the case of a single species undergoing transformation reaction and diffusion. In this case, we perform a third-order Chapman-Enskog multiscale expansion and study the dependence of the Lattice Boltzmann truncation error on the diffusion coefficient and the reaction rate. These findings are in good agreement with numerical simulations. Furthermore, taking the Gray-Scott model as a prominent example, we provide evidence for the maturity of the LBM in studying pattern formation in non-linear reaction-diffusion systems. For this purpose, we perform linear stability analysis of the Gray-Scott model and determine the relevant parameter range for pattern formation. Lattice Boltzmann simulations allow not only to test the validity of the linear stability phase diagram including Turing and Hopf instabilities, but also permit going beyond the linear stability regime, where large perturbations give rise to interesting dynamical behavior such as the so called self replicating spots. We also show that the length scale of the patterns may be tuned by rescaling all relevant diffusion coefficients in the system with the same factor while letting all the reaction constants unchanged., Comment: 32 pages

We study scaling laws characterizing the inter-diffusive zone between two miscible fluids flowing side by side in a Y-shape laminar micromixer using the lattice Boltzmann method. The lattice Boltzmann method solves the coupled 3D hydrodynamics and mass transfer equations and incorporates intrinsic features of 3D flows related to this problem. We observe the different power law regimes occurring at the center of the channel and close to the top/bottom wall. The extent of the inter-diffusive zone scales as square root of the axial distance at the center of the channel. At the top/bottom wall, we find an exponent 1/3 at early stages of mixing as observed in the experiments of Ismagilov and coworkers [Appl. Phys. Lett. 76, 2376 (2000)]. At a larger distance from the entrance, the scaling exponent close to the walls changes to 1/2 [J.-B. Salmon et al J. Appl. Phys. 101, 074902 (2007)]. Here, we focus on the effect of finite aspect ratio on diffusive broadening. Interestingly, we find the same scaling laws regardless of the channel's aspect ratio. However,the point at which the exponent 1/3 characterizing the broadening at the top/bottom wall reverts to the normal diffusive behavior downstream strongly depends on the aspect ratio. We propose an interpretation of this observation in terms of shear rate at the side walls. A criterion for the range of aspect ratios with non-negligible effect on diffusive broadening is also provided., Comment: 19 pages, 7 figures

Chemical-Vapor-Deposition (CVD) diamond films were prepared using a variation of nitrogen addition into the gas source admixture by a direct current CVD method. The influence of nitrogen addition on the crystallographic texture and grain shape evolution in heteroepitaxial polycrystalline diamond films was investigated using high-resolution electron backscattering diffraction (HR-EBSD) and X-ray diffraction (XRD). The analysis reveals that an addition of 1.5% N2 to the CH4 gas flow leads to a strong enhancement of a {110} fiber texture. The phenomenon is discussed in terms of a competitive growth selection mechanism.

The development of the crystallinity and of the crystallographic orientation of isotactic polypropylene (iPP) during rolling deformation and subsequent heat treatment is studied. The experiments are conducted by using X-ray diffraction with an area detector. The evolution of crystallographic orientation is tracked by calculating the pole figures and by applying a quantitative 3D texture component fit method. The rolling orientation after a true strain of -1.5 mainly consists of the (010)[001], (130)[001], and [001]//RD fiber components (RD: rolling direction). The results reveal that the crystallinity drastically decreases during rolling. We suggest that decrystallization (disaggregation) is a deformation mechanism which takes place as a microscopic alternative to crystallographic intralamellar shear depending on the orientation of the lamellae relative to the imposed deformation tensor. Heat treatment after rolling leads to the recrystallization of amorphous material and to a strong enhancement of the fiber orientation component. The recrystallization orientation is explained in terms of an oriented nucleation mechanism where amorphous material aligns along existing crystalline lamellae blocks which prevailed during the preceding deformation.

The work introduces a 3D cellular automaton model for the spatial and crystallographic prediction of spherulite growth phenomena in polymers at the mesoscopic scale. The automaton is discrete in time, real space, and orientation space. The kinetics is formulated according to the Hoffman-Lauritzen secondary surface nucleation and growth theory for spherulite expansion. It is used to calculate the switching probability of each grid point as a function of its previous state and the state of the neighboring grid points. The actual switching decision is made by evaluating the local switching probability using a Monte Carlo step. The growth rule is scaled by the ratio of the local and the maximum interface energies, the local and maximum occurring Gibbs free energy of transformation, the local and maximum occurring temperature, and by the spacing of the grid points. The use of experimental input data provides a real time and space scale.

In this progress report we present a new approach to the ab-initio guided bottom up design of beta-Ti alloys for biomedical applications using a quantum mechanical simulation method in conjunction with experiments. Parameter-free density functional theory calculations are used to provide theoretical guidance in selecting and optimizing Ti-based alloys with respect to three constraints: (i) the use of non-toxic alloy elements; (ii) the stabilization of the body centered cubic beta phase at room temperature; (iii) the reduction of the elastic stiffness compared to existing Ti-based alloys. Following the theoretical predictions, the alloys of interest are cast and characterized with respect to their crystallographic structure, microstructure, texture, and elastic stiffness. Due to the complexity of the ab initio calculations, the simulations have been focused on a set of binary systems of Ti with two different high melting bcc metals, namely, Nb and Mo. Various levels of model approximations to describe mechanical and thermodynamic properties are tested and critically evaluated. The experiments are conducted both, on some of the binary alloys and on two more complex engineering alloy variants, namely, Ti-35wt.%Nb-7wt.%Zr-5wt.%Ta and a Ti-20wt.%Mo-7wt.%Zr-5wt.%Ta., Comment: 23 pages, progress report on ab initio alloy design