RESUMEN
It is generally considered that the elementary building blocks of defects in face-centred cubic (fcc) metals, e.g., interstitial dumbbells, coalesce directly into ever larger 2D dislocation loops, implying a continuous coarsening process. Here, we reveal that, prior to the formation of dislocation loops, interstitial atoms in fcc metals cluster into compact 3D inclusions of A15 Frank-Kasper phase. After reaching the critical size, A15 nano-phase inclusions act as a source of prismatic or faulted dislocation loops, dependent on the energy landscape of the host material. Using cutting-edge atomistic simulations we demonstrate this scenario in Al, Cu, and Ni. Our results explain the enigmatic 3D cluster structures observed in experiments combining diffuse X-ray scattering and resistivity recovery. Formation of compact nano-phase inclusions in fcc structure, along with previous observations in bcc structure, suggests that the fundamental mechanisms of interstitial defect formation are more complex than historically assumed and require a general revision. Interstitial-mediated formation of compact 3D precipitates can be a generic phenomenon, which should be further explored in systems with different crystallographic lattices.
RESUMEN
Some AX 2 binary compounds with the fluorite structure (space group F m 3 ¯ m ) are well-known examples of materials exhibiting transitions to ionic superconducting phases at high temperatures below their melting points. Such superionic states have been described as either highly defective crystals or part-crystal, part-liquid states where the A ions retain their crystalline order whilst the X ions undergo partial melting. However, no detailed description of the structure of these phases exists. We present here the results of our investigation of the structural changes that occur during these transitions and the structural characteristics of the resulting superionic materials. This work is based on atomic-scale molecular dynamics modelling methods as well as computational diffraction techniques. We employed a set of empirical potentials representing several compounds with the fluorite structure to investigate any potential-dependent effect. We show the importance of small-scale structure changes, with some local environments showing a hexagonal symmetry similar to what is seen in the scrutinyite structure that has been documented for example in UO2.
RESUMEN
Using molecular dynamics simulations, we study the fracture initiation of grain boundaries in NiCr2O4 and FeCr2O4 of spinel structure. These compounds are representative of corrosion layers of nickel-chromium-iron austenitic stainless alloys. Uniaxial deformation is applied to several symmetric tilt-, twist-, and random-grain boundaries until complete decohesion is reached, in order to measure the critical cleavage stresses. We find that this mechanical quantity depends on the chemical composition and the structure of the grain boundaries. A correlation between the critical stress and the misorientation angle of the grain boundaries can be established. It is also found than the twist- and the random-grain boundaries exhibit the weakest resistance. Furthermore, these simulations show a localization of the elastic response in the vicinity of the grain boundary plane. Therefore, we were able to compare our simulation results with those provided by the theoretical model based on the universal binding energy relation that relates the critical stress to the cleavage grain boundary energy. It shows that this model provides similar critical stresses than the molecular dynamics simulations if the localization distance parameter is defined as the distance related to the deformation of the grain boundary thickness during the deformation.
RESUMEN
A novel empirical potential has been developed to evaluate the thermodynamic stability of Ni(1-x)Fe(x)Cr2O4 spinels. The simulations confirm the hypothesis that the NiCr2O4-FeCr2O4 pseudo-binary has normal structure spinel up to 1000 K and stabilizes as a solid solution. However, the disordering energy (normal to inverse spinel) is found higher for FeCr2O4 than for NiCr2O4 spinel. The formation energies of tilt, twist, and random grain boundaries have been calculated in pure NiCr2O4 and FeCr2O4. The same behavior has been found for both spinels. Detail analysis of the grain boundaries structure shows that the cation coordination number is a key parameter for the stability of the grain boundaries. With this criterion, we evidenced that the structural and energetic differences are caused only by nickel and iron cations.
RESUMEN
The annealing of the B cation interstitial is shown to drive the thermokinetic of the response to irradiations of A(2)B(2)O(7) pyrochlores. Molecular dynamics simulations evidenced that the annealing of interstitials created by irradiations depends upon the nature of B. As the coordination number of B decreases, the dumbbell interstitial is stabilized at the expense of the isolated interstitial. Unlike the isolated interstitials, the recombination of the dumbbells is thermally activated and hindered at low temperatures. The occurrence of dumbbells drives the structure towards the amorphous state.
RESUMEN
Azathioprine is an immunosuppressive drug used in the treatment of inflammatory bowel disease. It is a prodrug that is hydrolysed to 6-mercaptopurine, which represents the active form. Azathioprine is also used in the treatment of leukaemia in children and in organ transplantation. Azathioprine treatment is associated with adverse effects such as leukopenia and aplasia. These adverse effects are related to a single nucleotide polymorphism, including the inability of cells to synthesize thiopurine methyltransferase (TPMT). TPMT is a detoxification enzyme that limits 6-thioguanine nucleotide production and thereby interferes with normal DNA and RNA synthesis. This review presents the different approaches used for azathioprine therapeutic monitoring in IBD treatment and discusses the discrepancies in recent clinical trials.
