Direct Simulation of a Solidification Benchmark Experiment

International audienceA solidification benchmark experiment is simulated using a three-dimensional cellular automaton-finite element solidification model. The experiment consists of a rectangular cavity containing a Sn-3 wt pct Pb alloy. The alloy is first melted and then solidified in the cavity. A dense array of thermocouples permits monitoring of temperatures in the cavity and in the heat exchangers surrounding the cavity. After solidification, the grain structure is revealed by metallography. X-ray radiography and inductively coupled plasma spectrometry are also conducted to access a distribution map of Pb, or macrosegregation map. The solidification model consists of solutions for heat, solute mass, and momentum conservations using the finite element method. It is coupled with a description of the development of grain structure using the cellular automaton method. A careful and direct comparison with experimental results is possible thanks to boundary conditions deduced from the temperature measurements, as well as a careful choice of the values of the material properties for simulation. Results show that the temperature maps and the macrosegregation map can only be approached with a three-dimensional simulation that includes the description of the grain structure

Faciès et conditions de dépôt des calcaires à archéocyathes du Cambrien inférieur de la Montagne Noire méridionale (Massif central, France)

Les calcaires de la formation de Pardailhan (Cambrien inférieur du sud de la Montagne Noire) ne contiennent des faunes d’archéocyathes que dans quelques minces couches de la séquence carbonatée-détritique, dans chaque horizon (HI, H2, H3) exposée dans plusieurs unités tectoniques superposées qui sont affectées par de sévères déformations. L’examen comparatif des assemblages d’archéocyathes associé à une investigation sédimentologique détaillée conduit à la compréhension des modes de dépôt et du style de construction des associations archéocyathes-calcimicrobes. Il permet également d’obtenir une meilleure définition des relations paléogéographiques entre les différentes unités tectoniques. H1 : archéocyathes – calcimicrobes sont concentrés dans de petits récifs “pionniers”, détritiques, avec de petits calices d’archéocyathes cylindriques (en bâtonnets), brisés et déplacés dans les dépôts interrécifaux; localement ils sont associés avec des boundstones en croûtes à Epiphyton et Girvanella. Les archéocyathes sont fréquents dans le Sud Minervois, plus irrégulièrement répartis dans le Nord Minervois, le Pardailhan nord et sud. H2 : les archéocyathes sont en bâtonnets, isolés et fréquemment déplacés comme dans H1, mais on trouve aussi des calices en place, en forme de soucoupes; des grainstones, contenant du quartz diffus à grains fins à la base des bioconstructions en croûtes à Girvanella, témoignant d’une haute énergie, sont plus developpés dans le Sud Minervois, que dans le Nord Pardailhan; un boundstone à Epiphyton et Renalcis de basse énergie est trouvé dans le Minervois et le Nord Pardailhan. H3 : les calices d’archéocyathes sont de grandes soucoupes, observées la plupart du temps sous forme de longs rubans ondulés, fragments de leur intervallum, dans un boundstone à Epiphyton et Renalcis. Dans le Nord Pardailhan, on trouve localement des faciès de tempête à la base des bioconstructions, tandis que dans le Sud Pardailhan,nodulaires, des mudstones, contenant des débris bioclastiques et quelques boundstones cryptalgaires et calcimicrobiens, sont le signe d’un environnement de basse énergie à la transition avec le bassin peu profond

Equitability revisited: why the “equitable threat score” is not equitable

In the forecasting of binary events, verification measures that are “equitable” were defined by Gandin and Murphy to satisfy two requirements: 1) they award all random forecasting systems, including those that always issue the same forecast, the same expected score (typically zero), and 2) they are expressible as the linear weighted sum of the elements of the contingency table, where the weights are independent of the entries in the table, apart from the base rate. The authors demonstrate that the widely used “equitable threat score” (ETS), as well as numerous others, satisfies neither of these requirements and only satisfies the first requirement in the limit of an infinite sample size. Such measures are referred to as “asymptotically equitable.” In the case of ETS, the expected score of a random forecasting system is always positive and only falls below 0.01 when the number of samples is greater than around 30. Two other asymptotically equitable measures are the odds ratio skill score and the symmetric extreme dependency score, which are more strongly inequitable than ETS, particularly for rare events; for example, when the base rate is 2% and the sample size is 1000, random but unbiased forecasting systems yield an expected score of around −0.5, reducing in magnitude to −0.01 or smaller only for sample sizes exceeding 25 000. This presents a problem since these nonlinear measures have other desirable properties, in particular being reliable indicators of skill for rare events (provided that the sample size is large enough). A potential way to reconcile these properties with equitability is to recognize that Gandin and Murphy’s two requirements are independent, and the second can be safely discarded without losing the key advantages of equitability that are embodied in the first. This enables inequitable and asymptotically equitable measures to be scaled to make them equitable, while retaining their nonlinearity and other properties such as being reliable indicators of skill for rare events. It also opens up the possibility of designing new equitable verification measures

Platinum(IV) complexes of trans-1,2-diamino-4-cyclohexene: Prodrugs affording an oxaliplatin analogue that overcomes cancer resistance

Six platinum(IV) compounds derived from an oxaliplatin analogue containing the unsaturated cyclic diamine trans-1,2-diamino-4-cyclohexene (DACHEX), in place of the 1,2-diaminocyclohexane, and a range of axial ligands, were synthesized and characterized. The derivatives with at least one axial chlorido ligand demonstrated solvent-assisted photoreduction. The electrochemical redox behavior was investigated by cyclic voltammetry; all compounds showed reduction potentials suitable for activation in vivo. X-ray photoelectron spectroscopy (XPS) data indicated an X-ray-induced surface reduction of the Pt(IV) substrates, which correlates with the reduction potentials measured by cyclic voltammetry. The cytotoxic activity was assessed in vitro on a panel of human cancer cell lines, also including oxaliplatin-resistant cancer cells, and compared with that of the reference compounds cisplatin and oxaliplatin; all IC50 values were remarkably lower than those elicited by cisplatin and somewhat lower than those of oxaliplatin. Compared to the other Pt(IV) compounds of the series, the bis-benzoate derivative was by far (5–8 times) the most cytotoxic showing that low reduction potential and high lipophilicity are essential for good cytotoxicity. Interestingly, all the complexes proved to be more active than cisplatin and oxaliplatin even in three-dimensional spheroids of A431 human cervical cancer cells

Glucose-Coated Superparamagnetic Iron Oxide Nanoparticles Prepared by Metal Vapour Synthesis Are Electively Internalized in a Pancreatic Adenocarcinoma Cell Line Expressing GLUT1 Transporter

Iron oxide nanoparticles (IONP) can have a variety of biomedical applications due to their visualization properties through Magnetic Resonance Imaging (MRI) and heating with radio frequency or alternating magnetic fields. In the oncological field, coating IONP with organic compounds to provide specific features and to achieve the ability of binding specific molecular targets appears to be very promising. To take advantage of the high avidity of tumor cells for glucose, we report the development of very small glucose-coated IONP (glc-IONP) by employing an innovative technique, Metal Vapor Synthesis (MVS). Moreover, we tested the internalization of our gl-IONP on a tumor line, BxPC3, over-expressing GLUT 1 transporter. Both glc-IONP and polyvinylpyrrolidone-IONP (PVP-IONP), as control, were prepared with MVS and were tested on BxPC3 at various concentrations. To evaluate the role of GLUT-1 transporter, we also investigated the effect of adding a polyclonal anti-GLUT1 antibody. After proper treatment, the iron value was assessed by atomic absorption spectrometer, reported in mcg/L and expressed in mg of protein. Our IONP prepared with MVS were very small and homogeneously distributed in a narrow range (1.75-3.75 nm) with an average size of 2.7 nm and were super-paramagnetic. Glc-IONP were internalized by BxPC3 cells in a larger amount than PVP-IONP. After 6h of treatment with 50 mcg/mL of IONPs, the content of Fe was 1.5 times higher in glc-IONP-treated cells compared with PVP-IONP-treated cells. After 1h pre-treatment with anti-GLUT1, a reduction of 41% cellular accumulation of glc-IONP was observed. Conversely, the uptake of PVP-IONPs was reduced only by 14% with antibody pretreatment. In conclusion, MVS allowed us to prepare small, homogeneous, super-paramagnetic glc-IONP, which are electively internalized by a tumor line over-expressing GLUT1. Our glc-IONP appear to have many requisites for in vivo use

Relationship between solidification microstructure and hot cracking susceptibility for continuous casting of low-carbon and high-strength low-alloyed steels: A phase-field study

© The Minerals, Metals & Materials Society and ASM International 2013Hot cracking is one of the major defects in continuous casting of steels, frequently limiting the productivity. To understand the factors leading to this defect, microstructure formation is simulated for a low-carbon and two high-strength low-alloyed steels. 2D simulation of the initial stage of solidification is performed in a moving slice of the slab using proprietary multiphase-field software and taking into account all elements which are expected to have a relevant effect on the mechanical properties and structure formation during solidification. To account for the correct thermodynamic and kinetic properties of the multicomponent alloy grades, the simulation software is online coupled to commercial thermodynamic and mobility databases. A moving-frame boundary condition allows traveling through the entire solidification history starting from the slab surface, and tracking the morphology changes during growth of the shell. From the simulation results, significant microstructure differences between the steel grades are quantitatively evaluated and correlated with their hot cracking behavior according to the Rappaz-Drezet-Gremaud (RDG) hot cracking criterion. The possible role of the microalloying elements in hot cracking, in particular of traces of Ti, is analyzed. With the assumption that TiN precipitates trigger coalescence of the primary dendrites, quantitative evaluation of the critical strain rates leads to a full agreement with the observed hot cracking behavior. © 2013 The Minerals, Metals & Materials Society and ASM International

A new multi-zone model for porosity distribution in Al–Si alloy castings

A new multi-zone model is proposed that explains how porosity forms in various regions of a casting under different conditions and leads to distinct zonal differences in pore shape, size and distribution. This model was developed by considering the effect of cooling rate on solidification and distribution of porosity in Al–Si alloys cast as plates in moulds made with silica, ilmenite or zirconia sand cores or steel chills facing the major plate faces. The alloys cast were Al–7 wt.% Si and Al–12.5 wt.% Si in unmodified and modified forms, the latter with either Na or Sr addition. It is found that, regardless of cooling condition, Si content and modification treatment, the microstructure can be divided into three zones of varying size (across the casting thickness) that are determined by the local cooling conditions and the nucleation and growth mode of the Al–Si eutectic. The zones are: (1) an outer shell-like zone where directional columnar dendritic grains and a fine-celled, coherent eutectic form a low-porosity shell at the casting surface; (2) a transitional zone where equiaxed, eutectic cells grow between columnar dendritic grains and irregular pores become trapped in the mush; and finally (3) a central zone where the thermal gradient is low and equiaxed dendritic grains and eutectic cells grow at the centre of the casting and larger, rounded pores tend to form. The paper discusses how Si content, modification type and cooling conditions influence the location and size (i.e. depth) of each of these zones and how the distribution of porosity is thus affected

Columnar and Equiaxed Solidification of Al-7 wt.% Si Alloys in Reduced Gravity in the Framework of the CETSOL Project

International audienceDuring casting, often a dendritic microstructure is formed, resulting in a columnar or an equiaxed grain structure, or leading to a transition from columnar to equiaxed growth (CET). The detailed knowledge of the critical parameters for the CET is important because the microstructure affects materials properties. To provide unique data for testing of fundamental theories of grain and microstructure formation, solidification experiments in microgravity environment were performed within the European Space Agency Microgravity Application Promotion (ESA MAP) project Columnar-to-Equiaxed Transition in SOLidification Processing (CETSOL). Reduced gravity allows for purely diffusive solidification conditions, i.e., suppressing melt flow and sedimentation and floatation effects. On-board the International Space Station, Al-7 wt.% Si alloys with and without grain refiners were solidified in different temperature gradients and with different cooling conditions. Detailed analysis of the microstructure and the grain structure showed purely columnar growth for nonrefined alloys. The CET was detected only for refined alloys, either as a sharp CET in the case of a sudden increase in the solidification velocity or as a progressive CET in the case of a continuous decrease of the temperature gradient. The present experimental data were used for numerical modeling of the CET with three different approaches: (1) a front tracking model using an equiaxed growth model, (2) a three-dimensional (3D) cellular automaton–finite element model, and (3) a 3D dendrite needle network method. Each model allows for predicting the columnar dendrite tip undercooling and the growth rate with respect to time. Furthermore, the positions of CET and the spatial extent of the CET, being sharp or progressive, are in reasonably good quantitative agreement with experimental measurements

Synthesis, characterization and biological activity of novel Cu(II) complexes of 6-methyl-2-oxo-1,2-dihydroquinoline-3-carbaldehy de-4N-substituted thiosemicarbazones

Three new 6-methyl-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-thiosemicarbazones-N-4-substituted pro-ligands and their Cu(II) complexes (1, -NH2; 2, -NHMe; 3, -NHEt) have been prepared and characterized. In both the X-ray structures of 1 and 3, two crystallographically independent complex molecules were found that differ either in the nature of weakly metal-binding species (water in 1a and nitrate in 1b) or in the co-ligand (water in 3a and methanol in 3b). Electron Paramagnetic Resonance (EPR) measurements carried out on complexes 1 and 3 confirmed the presence of such different species in the solution. The electrochemical behavior of the pro-ligands and of the complexes was investigated, as well as their biological activity. Complexes 2 and 3 exhibited a high cytotoxicity against human tumor cells and 3D spheroids derived from solid tumors, related to the high cellular uptake. Complexes 2 and 3 also showed a high selectivity towards cancerous cell lines with respect to non-cancerous cell lines and were able to circumvent cisplatin resistance. Via the Transmission Electron Microscopy (TEM) imaging technique, preliminary insights into the biological activity of copper complexes were obtained