Ab-initio simulation and experimental validation of beta-titanium alloys

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 desig

Industries and the bank lending effects of bank credit demand and monetary policy in Germany

This paper presents evidence on the industry effects of bank lending in Germany and identifies the industry effects of bank lending associated with changes in monetary policy and industryspecific bank credit demand. To this end, we estimate individual bank lending functions for 13 manufacturing and non-manufacturing industries and five banking groups using quarterly bank balance sheet and bank lending data for the period 1992:1-2002:4. The evidence from dynamic panel data models shows that industry-specific bank lending growth predominantly responds to changes in industry-specific bank credit demand rather than to changes in monetary policy. In fact, conclusions regarding the bank lending effects of monetary policy are very sensitive to the choice of industry. The empirical results lend strong support to the existence of industry effects of bank lending. Because industries are a prominent source of variation in the bank lending effects of bank credit demand and monetary policy, the paper concludes that the industry composition of bank credit portfolios is an important determinant of bank lending growth and monetary policy effectiveness. --Monetary policy transmission,credit channel,industry structure,dynamic panel data

Nanoscale austenite reversion through partitioning, segregation, and kinetic freezing: Example of a ductile 2 GPa Fe-Cr-C steel

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 201

Profile blunting and flow blockage in a yield stress fluid: A molecular dynamics study

The flow of a simple glass forming system (a 80:20 binary Lennard-Jones mixture) through a planar channel is studied via molecular dynamics simulations. The flow is driven by an external body force similar to gravity. Previous studies show that the model exhibits both a static [Varnik et al. J. Chem. Phys. 120, 2788 (2004)] and a dynamic [F. Varnik and O. Henrich Phys. Rev. B 73, 174209 (2006)] yield stress in the glassy phase. \blue{These observations are corroborated by the present work, where we investigate how the presence of a yield stress may affect the system behavior in a Poiseuille-type flow geometry.} In particular, we observe a blunted velocity profile across the channel: A relatively wide region in the channel center flows with a constant velocity (zero shear rate) followed by a non linear change of the shear rate as the walls are approached. The observed velocity gradients are compared to those obtained from the knowledge of the shear stress across the channel and the flow-curves (stress versus shear rate), the latter being determined in our previous simulations of homogeneous shear flow. Furthermore, using the value of the (dynamic) yield stress known from previous simulations, we estimate the threshold body force for a complete arrest of the flow. Indeed, a blockage is observed as the imposed force falls below this threshold value. Small but finite shear rates are observed at stresses above the dynamic but below the static yield stress. We discuss the possible role of the \blue{stick-slip like motion} for this observation.Comment: 22 pages, 8 figure

The gendered maths confidence gap, social influence and social integration

While there is little discernible difference between girls and boys in maths competence during secondary education, on average, girls have lower confidence in their maths skills. Over time, this difference leads to gendered choices of education and occupation. Research explaining the maths confidence gap focusses on psychological factors and socialisation into stereotypical gender roles. However, how the peer context shapes the self-perception of competence and how this self-image affects social integration and popularity of girls and boys is barely understood. We analyse friendship networks and perceptions of maths confidence in Sweden and Germany to answer these questions using the CILS4EU dataset (N = 7,472) and multi-level, longitudinal network models. We find that maths confidence of girls accurately follows their maths grades and social relations have little impact on girls’ self-evaluation. Boys tend to overestimate their ability and are more susceptible to peer processes; social comparison processes inform boys’ maths confidence. This suggests that math ability is important for boys but socially irrelevant for girls. Concerning friendship choices, we find that boys and girls with higher maths confidence are often more integrated. Thus, we do not find social pressure on girls to adhere to gendered math-stereotypes – the opposite is the case

Site-selective protein modification via disulfide rebridging for fast tetrazine/trans-cyclooctene bioconjugation

An inverse electron demand Diels–Alder reaction between tetrazine and trans-cyclooctene (TCO) holds great promise for protein modification and manipulation. Herein, we report the design and synthesis of a tetrazine-based disulfide rebridging reagent, which allows the site-selective installation of a tetrazine group into disulfide-containing peptides and proteins such as the hormone somatostatin (SST) and the antigen binding fragment (Fab) of human immunoglobulin G (IgG). The fast and efficient conjugation of the tetrazine modified proteins with three different TCO-containing substrates to form a set of bioconjugates in a site-selective manner was successfully demonstrated for the first time. Homogeneous, well-defined bioconjugates were obtained underlining the great potential of our method for fast bioconjugation in emerging protein therapeutics. The formed bioconjugates were stable against glutathione and in serum, and they maintained their secondary structure. With this work, we broaden the scope of tetrazine chemistry for site-selective protein modification to prepare well-defined SST and Fab conjugates with preserved structures and good stability under biologically relevant conditions