Microstructure-based numerical modeling of the mechanical behavior of Mg alloys

Dentro de los materiales estructurales, el magnesio y sus aleaciones están siendo el foco de una de profunda investigación. Esta investigación está dirigida a comprender la relación existente entre la microestructura de las aleaciones de Mg y su comportamiento mecánico. El objetivo es optimizar las aleaciones actuales de magnesio a partir de su microestructura y diseñar nuevas aleaciones. Sin embargo, el efecto de los factores microestructurales (como la forma, el tamaño, la orientación de los precipitados y la morfología de los granos) en el comportamiento mecánico de estas aleaciones está todavía por descubrir. Para conocer mejor de la relación entre la microestructura y el comportamiento mecánico, es necesaria la combinación de técnicas avanzadas de caracterización experimental como de simulación numérica, a diferentes longitudes de escala. En lo que respecta a las técnicas de simulación numérica, la homogeneización policristalina es una herramienta muy útil para predecir la respuesta macroscópica a partir de la microestructura de un policristal (caracterizada por el tamaño, la forma y la distribución de orientaciones de los granos) y el comportamiento del monocristal. La descripción de la microestructura se lleva a cabo mediante modernas técnicas de caracterización (difracción de rayos X, difracción de electrones retrodispersados, así como con microscopia óptica y electrónica). Sin embargo, el comportamiento del cristal sigue siendo difícil de medir, especialmente en aleaciones de Mg, donde es muy complicado conocer el valor de los parámetros que controlan el comportamiento mecánico de los diferentes modos de deslizamiento y maclado. En la presente tesis se ha desarrollado una estrategia de homogeneización computacional para predecir el comportamiento de aleaciones de magnesio. El comportamiento de los policristales ha sido obtenido mediante la simulación por elementos finitos de un volumen representativo (RVE) de la microestructura, considerando la distribución real de formas y orientaciones de los granos. El comportamiento del cristal se ha simulado mediante un modelo de plasticidad cristalina que tiene en cuenta los diferentes mecanismos físicos de deformación, como el deslizamiento y el maclado. Finalmente, la obtención de los parámetros que controlan el comportamiento del cristal (tensiones críticas resueltas (CRSS) así como las tasas de endurecimiento para todos los modos de maclado y deslizamiento) se ha resuelto mediante la implementación de una metodología de optimización inversa, una de las principales aportaciones originales de este trabajo. La metodología inversa pretende, por medio del algoritmo de optimización de Levenberg-Marquardt, obtener el conjunto de parámetros que definen el comportamiento del monocristal y que mejor ajustan a un conjunto de ensayos macroscópicos independientes. Además de la implementación de la técnica, se han estudiado tanto la objetividad del metodología como la unicidad de la solución en función de la información experimental. La estrategia de optimización inversa se usó inicialmente para obtener el comportamiento cristalino de la aleación AZ31 de Mg, obtenida por laminado. Esta aleación tiene una marcada textura basal y una gran anisotropía plástica. El comportamiento de cada grano incluyó cuatro mecanismos de deformación diferentes: deslizamiento en los planos basal, prismático, piramidal hc+ai, junto con el maclado en tracción. La validez de los parámetros resultantes se validó mediante la capacidad del modelo policristalino para predecir ensayos macroscópicos independientes en diferentes direcciones. En segundo lugar se estudió mediante la misma estrategia, la influencia del contenido de Neodimio (Nd) en las propiedades de una aleación de Mg-Mn-Nd, obtenida por extrusión. Se encontró que la adición de Nd produce una progresiva isotropización del comportamiento macroscópico. El modelo mostró que este incremento de la isotropía macroscópica era debido tanto a la aleatoriedad de la textura inicial como al incremento de la isotropía del comportamiento del cristal, con valores similares de las CRSSs de los diferentes modos de deformación. Finalmente, el modelo se empleó para analizar el efecto de la temperatura en el comportamiento del cristal de la aleación de Mg-Mn-Nd. La introducción en el modelo de los efectos non-Schmid sobre el modo de deslizamiento piramidal hc+ai permitió capturar el comportamiento mecánico a temperaturas superiores a 150_C. Esta es la primera vez, de acuerdo con el conocimiento del autor, que los efectos non-Schmid han sido observados en una aleación de Magnesio. The study of Magnesium and its alloys is a hot research topic in structural materials. In particular, special attention is being paid in understanding the relationship between microstructure and mechanical behavior in order to optimize the current alloy microstructures and guide the design of new alloys. However, the particular effect of several microstructural factors (precipitate shape, size and orientation, grain morphology distribution, etc.) in the mechanical performance of a Mg alloy is still under study. The combination of advanced characterization techniques and modeling at several length scales is necessary to improve the understanding of the relation microstructure and mechanical behavior. Respect to the simulation techniques, polycrystalline homogenization is a very useful tool to predict the macroscopic response from polycrystalline microstructure (grain size, shape and orientation distributions) and crystal behavior. The microstructure description is fully covered with modern characterization techniques (X-ray diffraction, EBSD, optical and electronic microscopy). However, the mechanical behaviour of single crystals is not well-known, especially in Mg alloys where the correct parameterization of the mechanical behavior of the different slip/twin modes is a very difficult task. A computational homogenization framework for predicting the behavior of Magnesium alloys has been developed in this thesis. The polycrystalline behavior was obtained by means of the finite element simulation of a representative volume element (RVE) of the microstructure including the actual grain shape and orientation distributions. The crystal behavior for the grains was accounted for a crystal plasticity model which took into account the physical deformation mechanisms, e.g. slip and twinning. Finally, the problem of the parametrization of the crystal behavior (critical resolved shear stresses (CRSS) and strain hardening rates of all the slip and twinning modes) was obtained by the development of an inverse optimization methodology, one of the main original contributions of this thesis. The inverse methodology aims at finding, by means of the Levenberg-Marquardt optimization algorithm, the set of parameters defining crystal behavior that best fit a set of independent macroscopic tests. The objectivity of the method and the uniqueness of solution as function of the input information has been numerically studied. The inverse optimization strategy was first used to obtain the crystal behavior of a rolled polycrystalline AZ31 Mg alloy that showed a marked basal texture and a strong plastic anisotropy. Four different deformation mechanisms: basal, prismatic and pyramidal hc+ai slip, together with tensile twinning were included to characterize the single crystal behavior. The validity of the resulting parameters was proved by the ability of the polycrystalline model to predict independent macroscopic tests on different directions. Secondly, the influence of Neodymium (Nd) content on an extruded polycrystalline Mg-Mn-Nd alloy was studied using the same homogenization and optimization framework. The effect of Nd addition was a progressive isotropization of the macroscopic behavior. The model showed that this increase in the macroscopic isotropy was due to a randomization of the initial texture and also to an increase of the crystal behavior isotropy (similar values of the CRSSs of the different modes). Finally, the model was used to analyze the effect of temperature on the crystal behaviour of a Mg-Mn-Nd alloy. The introduction in the model of non-Schmid effects on the pyramidal hc+ai slip allowed to capture the inverse strength differential that appeared, between the tension and compression, above 150_C. This is the first time, to the author's knowledge, that non-Schmid effects have been reported for Mg alloys.

Measuring the critical resolved shear stresses in Mg alloys by instrumented nanoindentation

One of the main limiting factors in the development of new magnesium (Mg) alloys with enhanced mechanical behavior is the need to use vast experimental campaigns for microstructure and property screening. For example, the influence of new alloying additions on the critical resolved shear stresses (CRSSs) is currently evaluated by a combination of macroscopic single-crystal experiments and crystal plasticity finite-element simulations (CPFEM). This time-consuming process could be considerably simplified by the introduction of high-throughput techniques for efficient property testing. The aim of this paper is to propose a new and fast, methodology for the estimation of the CRSSs of hexagonal close-packed metals which, moreover, requires small amounts of material. The proposed method, which combines instrumented nanoindentation and CPFEM modeling, determines CRSS values by comparison of the variation of hardness (H) for different grain orientations with the outcome of CPFEM. This novel approach has been validated in a rolled and annealed pure Mg sheet, whose H variation with grain orientation has been successfully predicted using a set of CRSSs taken from recent crystal plasticity simulations of single-crystal experiments. Moreover, the proposed methodology has been utilized to infer the effect of the alloying elements of an MN11 (Mg–1% Mn–1% Nd) alloy. The results support the hypothesis that selected rare earth intermetallic precipitates help to bring the CRSS values of basal and non-basal slip systems closer together, thus contributing to the reduced plastic anisotropy observed in these alloys

Third-generation synchrotron x-ray diffraction of 6-μm crystal of raite, ≈Na3Mn3Ti0.25Si8O20(OH)2⋅10H2O, opens up new chemistry and physics of low-temperature minerals

The crystal structure of raite was solved and refined from data collected at Beamline Insertion Device 13 at the European Synchrotron Radiation Facility, using a 3 × 3 × 65 μm single crystal. The refined lattice constants of the monoclinic unit cell are a = 15.1(1) Å; b = 17.6(1) Å; c = 5.290(4) Å; β = 100.5(2)°; space group C2/m. The structure, including all reflections, refined to a final R = 0.07. Raite occurs in hyperalkaline rocks from the Kola peninsula, Russia. The structure consists of alternating layers of a hexagonal chicken-wire pattern of 6-membered SiO4 rings. Tetrahedral apices of a chain of Si six-rings, parallel to the c-axis, alternate in pointing up and down. Two six-ring Si layers are connected by edge-sharing octahedral bands of Na+ and Mn3+ also parallel to c. The band consists of the alternation of finite Mn–Mn and Na–Mn–Na chains. As a consequence of the misfit between octahedral and tetrahedral elements, regions of the Si–O layers are arched and form one-dimensional channels bounded by 12 Si tetrahedra and 2 Na octahedra. The channels along the short c-axis in raite are filled by isolated Na(OH,H2O)6 octahedra. The distorted octahedrally coordinated Ti4+ also resides in the channel and provides the weak linkage of these isolated Na octahedra and the mixed octahedral tetrahedral framework. Raite is structurally related to intersilite, palygorskite, sepiolite, and amphibole.

Molecular approaches to smart materials via interface recognition and conformationally switchable cavitands

In this thesis the molecular level design of functional materials and systems is reported. In the first part, tetraphosphonate cavitand (Tiiii) recognition properties towards amino acids are studied both in the solid state, through single crystal X-ray diffraction, and in solution, via NMR and ITC experiments. The complexation ability of these supramolecular receptors is then applied to the detection of biologically remarkable N-methylated amino acids and peptides using complex dynamic emulsions-based sensing platforms. In the second part, a general supramolecular approach for surface decoration with single-molecule magnets (SMMs) is presented. The self-assembly of SMMs is achieved through the formation of a multiple hydrogen bonds architecture (UPy-NaPy complexation). Finally we explore the possibility to impart auxetic behavior to polymeric material through the introduction of conformationally switchable monomers, namely tetraquinoxaline cavitands (QxCav). Their interconversion from a closed vase conformation to an extended kite form is studied first in solution, then in polymeric matrixes via pH and tensile stimuli by UV-Vis spectroscopy.

Geochemistry of Apatite from rapid cooled samples

Apatite (U-Th-Sm)/He (AHe) thermochronology is increasingly used for reconstructing geodynamic processes of the upper crust and the surface. Results of AHe thermochronology, however, are often in conflict with apatite fission track (AFT) thermochronology, yielding an inverted age-relationship with AHe dates older than AFT dates of the same samples. This effect is mainly explained by radiation damage of apatite, either impeding He diffusion or causing non-thermal annealing of fission tracks. So far, systematic age inversions have only been described for old and slowly cooled terranes, whereas for young and rapidly cooled samples 'too old' AHe dates are usually explained by the presence of undetected U and/or Th-rich micro-inclusions. We report apatite (U-Th-Sm)/He results for rapidly cooled volcanogenic samples deposited in a deep ocean environment with a relatively simple post-depositional thermal history. Robust age constraints are provided independently through sample biostratigraphy. All studied apatites have low U contents (< 5 ppm on average). While AFT dates are largely in agreement with deposition ages, most AHe dates are too old. For leg 43, where deposition age of sampled sediment is 26.5-29.5 Ma, alpha-corrected average AHe dates are up to 45 Ma, indicating overestimations of AHe dates up to 50%. This is explained by He implantation from surrounding host U-Th rich sedimentary components and it is shown that AHe dates can be "corrected" by mechanically abrading the outer part of grains. We recommend that particularly for low U-Th-apatites the possibility of He implantation should be carefully checked before considering the degree to which the alpha-ejection correction should be applied.

The preparation and characterization of seven-coordinate tin(IV) complexes of the 2,6-diacetylpyridine Schiff bases of S-alkyl/aryl-dithiocarbazates and the X-ray crystal structure of the [Sn(dapsme)I-2] complex (dapsme=doubly deprotonated form of the 2,6

New tin(IV) complexes of empirical formula, Sn(SNNNS)I-2 (SNNNS = anionic form of the 2,6-diacetylpyridine Schiff bases of S-methyl- or S-benzyldithiocarbazate) have been prepared and characterized by a variety of physico-chemical techniques. The structure of Sn(dapsme)I-2 has been determined by single crystal X-ray crystallographic structural analysis. The complex has a seven-coordinate distorted pentagonal-bipyramidal geometry with the Schiff base coordinated to the tin(IV) ion as a dinegatively charged pentadentate chelating agent via the pyridine nitrogen atom, the two azomethine nitrogen atoms and the two thiolate sulfur atoms. The ligand occupies the equatorial plane and the iodo ligands are coordinated to the tin(IV) ion at axial positions. The distortion from an ideal pentagonal bipyramidal geometry is attributed to the restricted bite size of the pentadentate ligands. (C) 2004 Elsevier Ltd. All rights reserved.

Synthesis, characterization and X-ray crystal structures of dinuclear nickel(II) complexes of a novel potentially hexadentate but functionally tetradentate binucleating ligand

A binucleating potentially hexadentate chelating agent containing oxygen, nitrogen and sulfur as potential donor atoms (H2ONNO) has been synthesized by condensing alpha,alpha-xylenebis(N-methyldithiocarbazate) with 2,4-pentanedione. An X-ray crystallographic structure determination shows that the Schiff base remains in its ketoimine tautomeric form with the protons attached to the imine nitrogen atoms. The reaction of the Schiff base with nickel(II) acetate in a 1:1 stoichiometry leads to the formation of a dinuclear nickel(II) complex [Ni(ONNO)](2) (ONNO2- = dianionic form of the Schiff base) containing N,O-chelated tetradentate ligands, the sulfur donors remaining uncoordinated. A single crystal X-ray structure determination of this dimer reveals that each ligand binds two low spin nickel(II) ions, bridged by a xylyl group. The nickel(II) atoms adopt a distorted square-planar geometry in a trans-N2O2 donor environment. Reaction of the Schiff base with nickel(II) acetate in the presence of excess pyridine leads to the formation of a similar dinuclear complex, [Ni(ONNO)(py)](2), but in this case comprises five coordinate high-spin Ni(II) ions with pyridine ligands occupying the axial coordination sites as revealed by X-ray crystallographic analysis. (c) 2005 Published by Elsevier B.V.

Dimeric allylpalladium(II) complexes with pyrazolate bridges: Synthesis, characterization, structure and thermal behaviour

The synthesis, characterization and thermal behaviour of some new dimeric allylpalladium (II) complexes bridged by pyrazolate ligands are reported. The complexes [Pd(mu-3, 5-R'(2)pz)(eta(3)-CH2C(R)CH2)](2) [R = H; R'= CH(CH3)(2) (1a); R = H, R' = C(CH3)(3) (1b), R = H; R' = CF3 (1c); R = CH3, R' = CH(CH3)(2) (2a); R = CH3, R' = C(CH3)(3) (2b); and R = CH3, R' = CF3 (2c)] have been prepared by the room temperature reaction of [Pd(eta(3)-CH2C(R)CH2)(acac)](acac = acetylacetonate) with 3,5-disubstituted pyrazoles in acetonitrile solution. The complexes have been characterized by NMR (H-1, C-13{H-1}), FT-IR, and elemental analyses. The structure of a representative complex, viz. 2c, has been established by single-crystal X-ray diffraction. The dinuclear molecule features two formally square planar palladium centres which are bridged by two pyrazole ligands and the coordination of each metal centre is completed by allyl substituents. The molecule has non-crystallographic mirror symmetry. Thermogravimetric studies have been carried out to evaluate the thermal stability of these complexes. Most of the complexes thermally decompose in argon atmosphere to give nanocrystals of palladium, which have been characterized by XRD, SEM and TEM. However, complex 2c can be sublimed in vacuo at 2 mbar without decomposition. The equilibrium vapour pressure of 2c has been measured by the Knudsen effusion technique. The vapour pressure of the complex 2c could be expressed by the relation: In (p/Pa)(+/- 0.06) = -18047.3/T + 46.85. The enthalpy and entropy of vapourization are found to be 150.0 +/- 3 kJ mol(-1) and 389.5 +/- 8 J K-1 mol(-1), respectively. (c) 2005 Elsevier B.V. All rights reserved.

Application of edge-to-edge matching model to understand the in-plane texture of TiSi2 (C49) thin films on (001)(Si) surface

The edge-to-edge matching model, which was originally developed for predicting crystallographic features in diffusional phase transformations in solids, has been used to understand the formation of in-plane textures in TiSi2 (C49) thin films on Si single crystal (001)si surface. The model predicts all the four previously reported orientation relationships between C49 and Si substrate based on the actual atom matching across the interface and the basic crystallographic data only. The model has strong potential to be used to develop new thin film materials. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Structural studies on antifolate drugs

Single crystal X-ray structure determinations are reported for eleven compounds all of which are either biologically active or potentially biologically important. The compounds fall into two distinct classes:- 1. Substituted diaminopyrimidines 2. Substituted aminopyrimidinones The first class of compounds were all selected on the basis of their common diaminopyrimidine nucleus which has been demonstrated to be a vital requirement for antifolate activity. They may all be described as non-classical or small molecule lipophilic dihydrofolate reductase (DHFR) inhibitors, as opposed to the classical folate analogues, having the ability to cross the blood-brain barrier, enter cells via a rapid passive diffusion process, and achieve high intracellular concentrations. Thus they are an excellent choice in the search for crystallography in the solid state, providing geometrical and distance data not available from any other analytical techniques to date; supporting and enhancing data obtained in the lower resolution studies of protein crystallography. The biological importance of these compounds is discussed and an attempt is made to relate/predict their pharmacological activity to observed structural features in the crystalline environment. Special attention is focussed on hydrogen bonding, confirmational flexibility and hydrophobicity of substituents; each of which appear to make contributions to tight binding in the enzyme active site. Chapter 9 describes the use of data from the literature and the solid state modelling of an observed enzyme-substrate interaction in an attempt to define it more accurately in terms of its geometric flexibility. Of the second class, one compound (ABPP) is reported; studies in two different crystal forms. In demonstrating both antiviral and high interferon inducing activity it is possible that this compound could be useful against cancer and also viral infections.

Crystal structure and magnetic behaviour of a five-coordinate iron(III) complex of pyridoxal-4-methylthiosemicarbazone

The crystal structure and magnetic properties of a penta-coordinate iron(III) complex of pyridoxal-4-methylthiosemicarbazone, [Fe(Hmthpy)Cl](CHCHSO), are reported. The synthesised ligand and the metal complex were characterised by spectroscopic methods (H NMR, IR, and mass spectroscopy), elemental analysis, and single crystal X-ray diffraction. The complex crystallises as dark brown microcrystals. The crystal data determined at 100(1) K revealed a triclinic system, space group P over(1, ¯) (Z = 2). The ONSCl geometry around the iron(III) atom is intermediate between trigonal bipyramidal and square pyramidal (t = 0.40). The temperature dependence of the magnetic susceptibility (5-300 K) is consistent with a high spin Fe(III) ion (S = 5/2) exhibiting zero-field splitting. Interpretation of these data yielded: D = 0.34(1) cm and g = 2.078(3). © 2007 Elsevier B.V. All rights reserved.

Studies on the relative stabilities of Mn(II) and Mn(III) in complexes with N4O2 donor environments:crystal structures of [Mn(pybzhz)2] and [Mn(Ophsal)(imzH)2] ClO4 (pybzhz = N-(benzoyl)-N-(picolinylidene) hydrazine, Ophsal = N,N-o-phenylenebis(salicylideneimine), imzH = imidazole)

Five manganese complexes in an N 4O 2 donor environment have been prepared. Four of the compounds involve aroyl hydrazone as ligands and manganese is in a +2 oxidation state. The fifth compound was prepared using N,Nprime-o-phenylenebis(salicylideneimine) and imidazole as ligands where manganese is present in +3 oxidation state. X-ray crystal structure of one Mn +2 compound and the Mn +3 compound was determined. The relative stabilities of the Mn +2 and Mn +3 oxidation states were analyzed using the structural data and MO calculations. Manganese(II) complexes of four aroyl hydrazone ligands were prepared and characterized by different physicochemical techniques. The complexes are of the type Mn(L) 2, where L stands for the deprotonated hydrazone ligand. One of the compounds, Mn(pybzhz) 2, was also characterized by single crystal structure determination. In all these complexes, the Mn(II) is in an N 4O 2 donor environment and the Mn(II) center cannot be oxidized either chemically or electrochemically. However, when another ligand Ophsal is used to give the compound [Mn(Ophsal)(imzH) 2]ClO 4, which was also characterized by X-ray crystal structure determination, manganese can easily avail the +3 oxidation state. The relative stabilities of the +2 and +3 oxidation states of manganese were analyzed and it was concluded that the extent of distortion from the perfect octahedral geometry is the main controlling factor in these cases. © 2004 Elsevier B.V. All rights reserved.

Precipitation of chromium containing phases in aluminide coated nickel-base superalloy single crystals

The precipitation of chromium-containing phases, in both the B2 type β-phase coating matrix (nominally NiAl) and the substrate of high-activity-pack-aluminized single crystals of a nickel-base superalloy, is considered in this paper. An ‘edge-on’ transmission electron microscopy (TEM) technique is employed to examine the precipitation of M23X6, σ, α-Cr and other phases after coating and diffusion treatment and subsequent post-coating treatment at 850 and 950 °C. Initial precipitation is dominated by the formation of M23X6 in both the coating and substrate, however, in the case of single-crystal substrates the formation of this carbon-rich phase is not sustained. M23X6 precipitation is superceded by the formation of coherent precipitates of the α-Cr phase which effectively retains the basis but removes the superlattice of the β-matrix. Extensive precipitation of α-Cr has the effect of changing the balance of chromium to molybdenum in solution in the β-phase and further precipitation is dominated by Σ-phase intermetallics and other Cr-Mo-containing phases.

Crystal structure and physical properties of the new linear chain compound [Cu(1,2-bis(tetrazol-1-yl)ethane)3](ClO4)2

The synthesis and crystal structure of a novel one-dimensional Cu(II) compound [Cu(1,2-bis(tetrazol-1-yl)ethane)3](ClO4)2 are described. The single-crystal X-ray structure determination was carried out at 298 K. The molecular structure consists of a linear chain in which the Cu(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands in syn conformation. The Cu(II) ions are in a Jahn-Teller distorted octahedral environment (Cu(1)-N(11)=2.034(2) Å, Cu(1)-N(21)=2.041(2) Å and Cu(1)-N(31)=2.391(2) Å). The Cu⋯Cu separations are 7.420(3) Å.