María Hernando

Ordered rock-salt related nanoclusters in CaMnO2.

Oxygen engineering techniques performed under adequate controlled atmosphere show that the CaMnO(3)-CaMnO(2) topotactic reduction-oxidation process proceeds via oxygen diffusion while the cationic sublattice remains almost unaltered. Extra superlattice reflections in selected area electron diffraction patterns indicate doubling of the CaMnO(2) rock-salt cell along the cubic directions of a distorted rhombohedral cell originated by ordering of Ca(2+) and Mn(2+) ions distributed in nanoclusters into a NaCl-type matrix, as evidenced by dark field electron microscope images. The local nature of the information provided by the transmission electron microscopy techniques used to characterize the rock-salt type Ca(1-x)Mn(x)O(2) solid solution clearly hints at the existence of subtle extra ordering in other upper oxides of the Ca-Mn-O system. The combination of local characterization techniques like electron microscopy with more average ones like powder X-ray and neutron diffraction allows a very complete characterization of the system.

Magnetic Structure and Electronic Study of Complex Oxygen-Deficient Manganites

Neutron diffraction and X-ray absorption near-edge structure (XANES) studies have been performed in La0.5Ca0.5MnO2.5, La0.5Sr0.5MnO2.5 and Nd0.5Sr0.5MnO2.5 oxygen-deficient perovskite compounds obtained by topotactic reduction. They all exhibit a brownmillerite structure with G-type antiferromagnetic ordering. Mn2+, Mn3+ and Mn4+ coexist at the octahedral sites, whereas only Mn2+ is placed in the tetrahedral positions. A magnetic moment of 1.6 microB has been detected at the tetrahedral layers, which can be explained by assuming Mn2+ is in a low-spin configuration.

New stabilized phases in the Sr/Ca–Mn–Co–O system: structural–magnetic properties relationship

Polycrystalline Sr3CaMn2CoO9 and (Sr0.5Ca0.5)15Mn7Co4O33 have been synthesized and characterised by X-ray and electron diffraction, high resolution electron microscopy and magnetic measurements. These oxides constitute the α = 3, β = 1 and α = 4, β = 1 terms of the homologous series (A3B2O6)α(A3B3O9)β, respectively. Isolated rows of polyhedra sharing faces along the c-axis are made up of units of two and one face-sharing octahedra (occupied by Mn) linked by one trigonal prism (occupied by Co) in an ordered way. The chains are separated by columns of Sr/Ca atoms. Magnetic measurements suggest antiferromagnetic correlations in the two new commensurate monodimensional oxides. The influence of the size of alkaline-earth atoms on the long-range magnetic interactions is discussed.

Structure Determination of the α = 3, β = 6 Term of the (A3B2O6)α(A3B3O9)β Homologous Series (A = Ba, B = Rh) by a Combination of Powder X-ray Diffraction and Electron Microscopy

The α = 3, β = 6 term of the series (A3B2O6)α (A3B3O9)β has been synthesized in polycrystalline form. The structural characterization by powder X-ray diffraction, electron diffraction and high-resolution electron microscopy indicates that this material is isostructural with Ba9Co8O24. In the structure, seven face-sharing octahedra alternate with a trigonal prism defining chains running parallel to the c axis of a rhombohedral unit cell (Rc), with parameters a = 1.00766(4) nm and c = 4.1571(2) nm. The structural refinement shows the presence of a small percentage of Rh vacancies leading to the composition Ba9Rh7.92O24. Pauli paramagnetic behaviour is observed. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

SrMnO3 Thermochromic Behavior Governed by Size-Dependent Structural Distortions

The influence of particle size in both the structure and thermochromic behavior of 4H-SrMnO3 related perovskite is described. Microsized SrMnO3 suffers a structural transition from hexagonal (P63/mmc) to orthorhombic (C2221) symmetry at temperature close to 340 K. The orthorhombic distortion is due to the tilting of the corner-sharing Mn2O9 units building the 4H structural type. When temperature decreases, the distortion becomes sharper reaching its maximal degree at ∼125 K. These structural changes promote the modification of the electronic structure of orthorhombic SrMnO3 phase originating the observed color change. nano-SrMnO3 adopts the ideal 4H hexagonal structure at room temperature, the orthorhombic distortion being only detected at temperature below 170 K. A decrease in the orthorhombic distortion degree, compared to that observed in the microsample, may be the reason why a color change is not observed at low temperature (77 K).

Strategies to stabilize new members of the (A3A'BO6)α(A3B3O9)β homologous series in the Sr-Rh-O system: Structure of the one-dimensional (α=3,β=2) [Sr10(Sr0.5Rh1.5)TP(Rh6)Oh]O24 oxide

The (α=3, β=2) member of the (A3A′BO6)α (A3B3O9)β homologous series has been stabilised in the Sr-Rh-O system for a [Sr10(Sr0.5Rh1.5)TP(Rh6)Oh]O24 composition. The structural characterisation has been performed by powder X-ray and electron diffraction measurements and high-resolution electron microscopy. In this structure, three face-sharing [RhO6] octahedra linked by one [Rh/SrO6] trigonal prism comprise the infinite one-dimensional chain that runs parallel to the c axis of a trigonal unit cell (Pc1), with parameters a=9.6411(1) and c=21.2440(4) A.

Structure–property relations in anion deficient 5H- and 3C-polytype Ba(Ti,Co)O3−δ perovskites

The polytypism and physical properties of BaTi1−yCoyO3−δ for y = 0.8 and 0.9 prepared with different δ values are reported. Samples quenched from 1293 K are strongly reduced, 3C-type perovskites (space group Pmm) with δ ∼ 0.4 and an average oxidation state of ∼Co3+ whereas slow cooled (4 °C min−1) samples are 5H-type perovskites (space group Pm1 and stacking sequence (ccchh)) with δ = 0.2 and an average oxidation state of ∼Co3.5+. An unusual feature of the 5H polymorph is the presence of ∼15 to 20% Ti(IV) on the tetrahedral (M3) sites. The 3C-polytypes are antiferromagnetic semiconductors with Neel temperatures 285 K. The reasons for the changes in polymorphism and physical properties with cation and anion content are rationalised on the basis of the different chemical nature and concentration of the Co(III), Co(IV) and Ti(IV) ions on the B-sites of these perovskites. The results are discussed in context to behaviour observed in related mixed-valent B-site perovskites to obtain a better understanding of the structure–composition–property relationships in these materials.

Atomically Resolved Short-Range Order at the Nanoscale in the Ca–Mn–O System

The elucidation of the reaction mechanisms involving redox processes in functional transition-metal oxides, which usually start in areas of very few nanometers in size, is yet a challenge to be satisfactorily achieved. Atomically resolved HAADF and EELS have provided both chemical and structural information at the nanoscale, which reveal the preservation of short-range cationic order in areas of 2-3 nm length as the driving force behind the reversibility of the Ca2Mn3O8-Ca2Mn3O5 redox process. Oxygen evolution is accommodated by cationic diffusion along the Ca and Mn layers of the cation-deficient Ca2Mn3O8 delafossite related structure, whereas Mn remains octahedrally coordinated.

Linear closed-loop control using Luenberger observer applied to insulin administration for type 1 diabetes

In this work the design of a Luenberger observer is proposed to estimate the unmeasurable state space variables from Hovorka?s model. This model is linearized and evaluated in an operation point where Luenberger observer is designed using the Ackermann methodology. The observer is employed to estimate the unmeasurable variables of virtual patients which are generated by Bergman?s model. Once the unmeasurable state variables are obtained by the Luenberger observer using only the input-output information of the Bergman?s model, a control algorithm based on eigenvalues relocation trough Ackermann methodology for linear systems is applied. In this methodology, a constant feedback gain vector is obtained in order to compute the control signal (insulin) to be applied to virtual patient and keep on normoglycemia rank. The carbohydrates ingestion is considered as the main disturbances. In order to assess the proposed methodology, two tests are designed: the first one consists of changing the reference signal in order to evaluate the control sensitivity; and the second one includes different proportions of prandial insulin used in open-loop to try the controller response under distinct operation conditions. The results are obtained via simulation using Simulink of Matlab.

Chlorine Insertion Promoting Iron Reduction in Ba–Fe Hexagonal Perovskites: Effect on the Structural and Magnetic Properties

BaFeCl0.13(2)O2.48(2) has been synthesized and studied. A proper tuning of the synthetic route has been designed to stabilize this compound as a single phase. The thermal stability and evolution, along with the magnetic and structural properties are reported here. The crystal structure has been refined from neutron powder diffraction data, and it is of the type (hhchc)2-10H. It is stable up to a temperature of 900 °C, where the composition reads BaFeCl0.13(2)O2.34(2). The study by electron microscopy shows that the crystal structure suffers no changes in the whole BaFeCl0.13(1)O3-y (2.34 ≤ 3 - y ≤ 2.48) compositional range. Refinement of the magnetic structure shows that the Fe is antiferromagneticaly ordered, with the magnetic moment parallel to the ab plane of the hexagonal structure. At higher temperature, a nonreversible phase transition into a (hchc)-4H structure type takes place with overall composition BaFeCl0.13(1)O2.26(1). Microstructural characterization shows that, in some crystals, this phase intergrows with a seemingly cubic related phase. Differences between these two crystalline phases reside in the chlorine content, which keeps constant through the phase transition for the former and disappears for the latter.