Micromechanical modelling of coupled crystal plasticity and hydrogen diffusion

Hydrogen transport behaviour in metals is greatly influenced by the mechanical stress and the underlying microstructural features. In this work, a micromechanical model based on coupled crystal plasticity and hydrogen diffusion is developed and applied to model hydrogen diffusion and storage in a polycrystalline microstructure. Particular emphasis is laid on mechanical influences on hydrogen transport, invoked by internal stresses and by trapping of dislocations generated by plastic strains. First, a study of a precharged material is carried out where hydrogen is allowed to redistribute under the influence of mechanical loading. These simulations demonstrate to which extent hydrogen migrates from regions with compressive strains to those with tensile strains. In the next step, the influence of plastic prestraining on hydrogen diffusion is analysed. This prestraining produces internal residual stresses in the microstructure, that mimic residual stresses introduced into components during cold working. Lastly, a series of permeation simulations is performed to characterise the influence of hydrogen trapping on effective diffusivity. It is shown that the effective diffusivity decreases with stronger traps and the effect is more prominent at a larger predeformation, because the trapped hydrogen concentration increases considerably. The reduction of effective diffusivity with plastic deformation agrees very well with experimental findings and offers a way to validate and parameterise our model. With this work, it is demonstrated how micromechanical modelling can support the understanding of hydrogen transport on the microstructural level.     

Lepidium graminifolium L.: Glucosinolate Profile and Antiproliferative Potential of Volatile Isolates

Glucosinolates (GSLs) from Lepidium graminifolium L. were analyzed qualitatively and quantitatively by their desulfo-counterparts using UHPLC-DAD-MS/MS technique and by their volatile breakdown products-isothiocyanates (ITCs) using GC-MS analysis. Thirteen GSLs were identified with arylaliphatic as the major ones in the following order: 3-hydroxybenzyl GSL (glucolepigramin, 7), benzyl GSL (glucotropaeolin, 9), 3,4,5-trimethoxybenzyl GSL (11), 3-methoxybenzyl GSL (glucolimnanthin, 12), 4-hydroxy-3,5-dimethoxybenzyl GSL (3,5-dimethoxysinalbin, 8), 4-hydroxybenzyl GSL (glucosinalbin, 6), 3,4-dimethoxybenzyl GSL (10) and 2-phenylethyl GSL (gluconasturtiin, 13). GSL breakdown products obtained by hydrodistillation (HD) and CH₂Cl₂ extraction after hydrolysis by myrosinase for 24 h (EXT) as well as benzyl ITC were tested for their cytotoxic activity using MTT assay. Generally, EXT showed noticeable antiproliferative activity against human bladder cancer cell line UM-UC-3 and human glioblastoma cell line LN229, and can be considered as moderately active, while IC₅₀ of benzyl ITC was 12.3 μg/mL, which can be considered as highly active.     

Electronic Structure and Hydrogen Bonding in a Dicobalt(III) Werner Complex

The bonding of the O-O group in the dicobalt cation 1a [(NH₃)₆Co₂(μ-O₂)(μ-OH)(μ-NH₂)]³⁺ was studied by DFT methods (ADF program) and the bridging O₂ ligand was characterized as superoxide(O₂⁻). In this complex, three bridging ligands connect the two cobalt atoms, forcing a cis conformation of the Co-O-O-Co atoms. A comparison was made with [(NH₃)₁₀Co₂(μ-O₂)]⁵⁺, 2a, where a trans arrangement is observed. Superoxide binds more strongly to the dicobalt(III) fragment in 2a than in 1a, both as a result of weaker Pauli repulsion and stronger covalent interaction. It was found that in 1a the electronic structure with one unpaired electron, where cobalt is formally Co(III), d⁶, and O₂ carries one negative charge gives rise to the most stable structure, compared to possibilities with three and five unpaired electrons. The hydrogen bonds in the crystal were analyzed and the interactions between one water molecule or one nitrate ion studied in more detail.     

Homogeneous phase polymerization of vinylidene fluoride in supercritical carbon dioxide

For the first time, stabilizer‐free vinylidene fluoride (VDF) homopolymerizations were carried out in homogenous phase with supercritical CO₂ using the conventional initiator di‐tert butyl peroxide (DTBP). In‐line FT‐NIR spectroscopy showed that complete monomer conversion may be obtained. Molecular weights were determined via size‐exclusion chromatography and polymer endgroup analysis by ¹H‐NMR spectroscopy. The number average molecular weights were below 10⁴ g mol^?1 and polydispersities ranged from 3.1 to 5.7 depending on DTBP and VDF concentration. For allowing isothermal reaction, high CO₂ contents ranging from 61 to 83 wt % were used. The high‐temperature and high‐pressure conditions required for homogeneous polymerization did not alter the amount of defects in VDF chaining. Scanning electron microscopy indicated that regular stack‐type particles are obtained upon expansion of the homogeneous polymerization mixture. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5626–5635, 2007     

Evolution of phase,texture, microstructure and magnetic properties of Fe–Cr–Co–Mo–Ti permanent magnets

Magnetic phase evolution, crystallographic texture, microstructure and magnetic properties of Fe–28Cr–15Co–3.5Mo–1.8Ti alloy have been investigated by X-ray diffractometry, scanning transmission electron microscopy and magnetometry techniques as a function of processing conditions. Heat treatment conditions for obtaining optimum textural, microstructural and magnetic properties have been established by the experimentations. The Goss {110}〈001〉 and cube type {001}〈010〉 textures have been developed in an optimal treated Fe–28Cr–15Co–3.5Mo–1.8Ti magnets. The coercive force in Fe–28Cr–15Co–3.5Mo–1.8Ti magnets depends critically on the shape anisotropy of rod-like Fe Co Ti-rich α₁ particles and remanence on the alignment and elongation of α₁ particles parallel to applied magnetic field 〈100〉 directions. The optimum magnetic properties obtained in Fe–28Cr–15Co–3.5Mo–1.8Ti alloy are intrinsic coercive force, _iH_c, of 78.8 kA/m (990 Oe), remanence, B_r of 1.12 T (11.2 kG) and energy product, (BH)_max of 52.5 kJ/m³ (6.5 MGOe). The development of Fe–28Cr–15Co–3.5Mo–1.8Ti magnets as well as characterization of texture, microstructural and magnetic properties in the current study would be helpful in designing the new Fe–Cr–Co–Mo based magnets suitable for scientific and technological applications.     

Improving the Thermal Behavior and Flame-Retardant Properties of Poly(o-anisidine)/MMT Nanocomposites Incorporated with Poly(o-anisidine) and Clay Nanofiller

The synthesis of MMT and poly(o-anisidine) (MMT/POA) clay nanocomposites was carried out by using the chemical oxidative polymerization of POA and MMT clay with POA, respectively. By maintaining the constant concentration of POA, different percentage loads of MMT clay were used to determine the effect of MMT clay on the properties of POA. The interaction between POA and MMT clay was investigated by FTIR spectroscopy, and, to reveal the complete compactness and homogeneous distribution of MMT clay in POA, were assessed by using scanning-electron-microscope (SEM) analysis. The UV–visible spectrum was studied for the optical and absorbance properties of MMT/POA ceramic nanocomposites. Furthermore, the horizontal burning test (HBT) demonstrated that clay nanofillers inhibit POA combustion.     

Remote entanglement for quantum networks

Quantum networks are distributed many-body quantum systems with tailored topology and controlled information exchange. We present two schemes to generate remote entanglement, in atomic external degrees of freedom and between cavities. In the first scheme, we entangle two atoms with their cavities in momentum space through Bragg diffraction. Thereafter, in order to trace out the cavities, we let resonantly interact an auxiliary atom with each cavity. In the last, we perform quantum measurement on two auxiliary atoms and get remote entangled state in atomic external degrees of freedom. In the second scheme, we have a three cavities system. The other two cavities, A and B, are entangled with indistinguishable modes of cavity, C. Performing quantum measurement on third cavity, C, we disentangle it from the system and the cavities, A and B, become entangled.     

CYCLOTOMIC ELEMENTS IN K_2F,REVISITED

Basing on results of Xu and Qin [10], and Guo [12] on cyclotomic elements in K2F for local fields F, we prove that every element in K2Q is a finite or infinite product of cyclotomic elements. Next, we extend this result to finite extensions of Q satisfying some additional conditions.     

Models for a Steiner multi-ring network design problem with revenues

The Steiner multi-ring network design problem with revenues consists of designing node-disjoint multiple rings connected by a specific node (hub) and passing through all the nodes with high priority of service and some of the nodes with low priority of service. The number of nodes in each ring has an upper bound to assure a certain level of service. Besides the usual arc link costs, we also consider revenues between each pair of nodes in the same ring, even when they are not connected by a direct link. The objective is to minimize the difference between the total connection cost and total revenue. The problem is a generalization of the problem studied in Gouveia and Pires (Eur J Oper Res 133:21–31, 2001a) and it can also be seen as a combination of variants of two NP-Hard problems, the vehicle routing problem and the maximum edge-weighted clique problem. We introduce and discuss two types of integer linear programming formulations and propose some valid inequalities to strengthen the linear programming relaxation. Computational results are presented to evaluate the quality of the linear programming relaxation bounds associated with these formulations as well as efficiency of the models to obtain the optimal integer solutions.     

Successful computer guided planned synthesis of (4R)-thiazolidine carboxylic acid and its 2-substituted analogues as urease inhibitors

By using internal combinatorial library we were able to identify (4R)-thiazolidines carboxylic acid and its 2-substituted analogs as active inhibitors of urease. Molecular modeling and virtual screening were utilized to find out potential compounds. Computational techniques were employed at database of 90,000 ligands and selected the structure representing the low energy conformations, Grid and FlexX docking algorithms were used and the top binding ligands were synthesized and screened in wet-lab.