Application of new methodologies based on design of experiments, independent component analysis and design space for robust optimization in liquid chromatography

HPLC separations of an unknown sample mixture and a pharmaceutical formulation have been optimized using a recently developed chemometric methodology proposed by W. Dewé et al. in 2004 and improved by P. Lebrun et al. in 2008. This methodology is based on experimental designs which are used to model retention times of compounds of interest. Then, the prediction accuracy and the optimal separation robustness, including the uncertainty study, were evaluated. Finally, the design space (ICH Q8(R1) guideline) was computed as the probability for a criterion to lie in a selected range of acceptance. Furthermore, the chromatograms were automatically read. Peak detection and peak matching were carried out with a previously developed methodology using independent component analysis published by B. Debrus et al. in 2009. The present successful applications strengthen the high potential of these methodologies for the automated development of chromatographic methods.     

Nanocomposite oxide thin films grown by pulsed energy beam deposition

Highly non-stoichiometric indium tin oxide (ITO) thin films were grown by pulsed energy beam deposition (pulsed laser deposition-PLD and pulsed electron beam deposition-PED) under low oxygen pressure. The analysis of the structure and electrical transport properties showed that ITO films with a large oxygen deficiency (more than 20%) are nanocomposite films with metallic (In, Sn) clusters embedded in a stoichiometric and crystalline oxide matrix. The presence of the metallic clusters induces specific transport properties, i.e. a metallic conductivity via percolation with a superconducting transition at low temperature (about 6 K) and the melting and freezing of the In-Sn clusters in the room temperature to 450 K range evidenced by large changes in resistivity and a hysteresis cycle. By controlling the oxygen deficiency and temperature during the growth, the transport and optical properties of the nanocomposite oxide films could be tuned from metallic-like to insulating and from transparent to absorbing films.     

Crystallographic aspects related to the high pressure–high temperature phase transformation of boron nitride

Crystallographic relations between different forms of boron nitride (BN) appearing at the high pressure–high temperature structural phase transformation have been revealed by high-resolution transmission electron microscopy (HRTEM). As starting materials, crystalline hexagonal BN (hBN) with different degrees of crystallinity, or with defects intentionally introduced, were used. Cubic BN (cBN) is formed only as a minor component, the rest consisting of different forms of sp ² bonded BN: hBN, compressed, monoclinic deformed hBN, or turbostratic BN (tBN). The small cBN crystallites (300–400?nm) contain many defects such as twins, stacking faults and nanoinclusions of other BN forms: tBN, rhombohedral BN (rBN) and wurtzite BN (wBN). The cBN phase grows epitaxially on the basal plane of hBN. The nucleation sites for cBN are revealed by HRTEM. They consist of nanoarches (sp ³ hybridized, highly curved nanostructures), frequently observed at the edges of the hBN crystallites in the starting materials. Based on HRTEM observations of specimens not fully transformed, a nucleation and growth model for cBN is proposed which is consistent with existing theoretical and experimental models.     

Characterization of {111} planar defects induced in silicon by hydrogen plasma treatments

Microstructural characterization by transmission electron microscopy of the {111} planar defects induced in Si by treatment in hydrogen plasma is discussed. The {111} defects are analyzed by conventional (TEM) and high-resolution transmission electron microscopy (HRTEM). Quantitative image processing by the geometrical phase method is applied to the experimental high-resolution image of an edge-on oriented {111} defect to measure the local displacements and strain field around it. Using these data, a structural model of the defect is derived. The validity of the structural model is checked by high-resolution image simulation and comparison with experimental images.     

The ferroelectric phase transition in tridymite type BaAL2O4 studied by electron microscopy

The paraelectric-ferroelectric (PE-FE) phase transition in stuffed tridymite BaAl₂O₄ was studied in situ by transmission electron microscopy. Electron diffraction revealed that the PE and FE phases have hexagonal symmetry. The PE-FE phase transition is accompanied by a doubling of the cell dimensions in the a-b plane. The transition is reversible, takes place over a wide temperature range (400–670 K.) and the interfaces related to the transition have a fluctuating character. The crystal structure of the high temperature PE phase was determined by high resolution electron microscopy. The structures of the PE phase (space group P6₃22, a≈ 5.22 Å, c ≈ 8.8 Å) and of the FE phase (space group P6₃, a= 10.4469(1)Å, c = 8.7927(1)Å) differ mainly by the configuration of the Al-O strings oriented along the c-axis. In the PE phase all the strings are equivalent whereas straight and corrugated strings alternate in an ordered manner in the FE phase resulting in doubling of the a and b cell parameters. Translation and orientation domains due to the decrease of the translation and point symmetry were frequently observed.     

Atomic 6p-Tl0 centers in ferroelectric Rb2ZnCl4 crystals

Abstract

Several Tl⁰ (6s²6p ¹)-type paramagnetic centers, produced by low temperature X-ray irradiation, were observed and studied by electron spin resonance (ESR) in the orthorhombic ferroelectric phase of thallium doped Rb₂ZnCl₄ crystals. The centers were formed by electron trapping at Tl⁺ ions localized substitutionally at Rb⁺ sites. The number and properties of the observed centers account for the tripling of the unit cell in the ferroelectric phase.     

Accurate determination of the spin Hamiltonian parameters for Mn2+ ions in cubic ZnS nanocrystals by multifrequency EPR spectra analysis

Accurate determination of the spin Hamiltonian (SH) parameters, describing the electron paramagnetic resonance (EPR) spectra of paramagnetic impurity ions in wide band gap semiconductor nanocrystals, is essential for determining their localization and quantum properties. Here we present a procedure, based on publicly available software, for determining with higher accuracy the SH parameters of isolated Mn(2+) impurity ions in small cubic ZnS nanocrystals. The procedure, which can be applied to other cubic II-VI semiconductor nanocrystals as well, is based on the analysis of both low and high frequency EPR spectra with line shape simulation and fitting computing programs, which include the hyperfine forbidden transitions and line broadening effects. The difficulties, limitations and errors which can affect the accuracy in determining some of the SH parameters are also discussed.     

Structural phase transformations in annealed cubic ZnS nanocrystals

The structural changes of cubic ZnS (cZnS) nanocrystals (NCs) doped with 0.2 at.% Mn²⁺ pulse annealed in vacuum and in air, up to 500 °C, were investigated by multifrequency electron paramagnetic resonance (EPR), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The samples, prepared by a surfactant (Tween20)-assisted liquid–liquid reaction at pH = 6, consist of NCs with a tight size distribution around 3 nm and high crystallinity self-assembled into a stable mesoporous structure. The EPR spectra of the as prepared samples contain only the characteristic lines of the substitutional Mn²⁺(I) centers. No spectra from Mn²⁺ ions localized in (hydro)oxidized regions of the NCs surface were observed. The absence of such a surface layer could explain the stability of the cubic (sphalerite) structure observed by XRD and TEM in the investigated cZnS:Mn NCs annealed in vacuum up to 500 °C. The observation of the cubic-hexagonal transformation for the same NCs annealed in air supports the role of such layer in promoting this structural transformation. The narrowing of the EPR spectral lines above 200 °C with the increase in the average size of the cZnS:Mn crystallites was observed. The effect was more pronounced for the sample annealed in air. EPR also revealed the formation of minute amounts of substitutional Mn²⁺-type centers in a hexagonal ZnO structure at T ~ 300 °C, corresponding to the early stages of the thermally induced oxidation of the cZnS:Mn NCs.     

Robust control volume finite element methods for numerical wave tanks using extreme adaptive anisotropic meshes

Multiphase inertia-dominated flow simulations, and free surface flow models in particular, continue to this day to present many challenges in terms of accuracy and computational cost to industry and research communities. Numerical wave tanks and their use for studying wave-structure interactions are a good example. Finite element method (FEM) with anisotropic meshes combined with dynamic mesh algorithms has already shown the potential to significantly reduce the number of elements and simulation time with no accuracy loss. However, mesh anisotropy can lead to mesh quality-related instabilities. This article presents a very robust FEM approach based on a control volume discretization of the pressure field for inertia dominated flows, which can overcome the typically encountered mesh quality limitations associated with extremely anisotropic elements. Highly compressive methods for the water-air interface are used here. The combination of these methods is validated with multiphase free surface flow benchmark cases, showing very good agreement with experiments even for extremely anisotropic meshes, reducing by up to two orders of magnitude the required number of elements to obtain accurate solutions.     

Magnetic curves in Sasakian manifolds

In this paper we classify the magnetic trajectories corresponding to contact magnetic fields in Sasakian manifolds of arbitrary dimension. Moreover, when the ambient is a Sasakian space form, we prove that the codimension of the curve may be reduced to 2. This means that the magnetic curve lies on a 3-dimensional Sasakian space form, embedded as a totally geodesic submanifold of the Sasakian space form of dimension (2n+1).