Stoichiography for investigation of the functional materials composition,structure, and properties

Principles of the stoichiography and differential dissolution method (DD) providing deep insight into the composition of mixtures containing unknown chemical compounds are considered. Compounds can be identified using their primary feature — the stoichiometry of elemental composition; reference samples of the compounds are not needed. The DD method makes it possible to analyze mixtures of crystalline and/or amorphous phases with constant and/or variable composition in the form of dispersed powders, ceramics, crystals, thin films and nanosize objects. Various aspects of the stoichiography and DD method application to investigation of composition, structure and properties of the functional materials are discussed.     

Determination of chemical composition of solid inorganic substances and materials using the principles of stoichiography and voltammetry

The state of the art in determination of the phase composition of complex inorganic solids by chemical and electrochemical methods is discussed. The theoretical and practical essentials of stoichiography and the new stoichiographic method of differential dissolution (DD) are reported. The unique feature of this method is that reference samples of the analyzed solid phases are not necessary. The development of this stoichiographic method was strongly affected by voltammetry. The application of the DD method for determining the chemical composition of various substances and materials is presented. The complementary use of voltammetry and DD for the detection, identification, and quantitative determination of inhomogeneity of the chemical composition of high-temperature superconductors was shown to be efficient.     

Physicochemical Aspects of Development of Multicomponent Chalcogenide Phases Having the Tl<Subscript>5</Subscript>Te<Subscript>3</Subscript> Structure: A Review

The literature data on ternary structural analogues of the compound Tl₅Te₃ and multicomponent phases based on them are systematized. This class of inorganic substances is of considerable scientific and practical interest as promising functional materials having thermoelectric, optical, and magnetic properties, as well as topologically protected surface states and superconductivity. The focus of the survey is on phase equilibria in ternary and more complex systems where structural analogues of Tl₅Te₃ are formed. Crystalstructure features, thermodynamic and some physical properties of these compounds and phases of variable composition are considered.     

Extended equation for the coexistence curve of molecular liquids in the vicinity of a critical point

An extended equation of state for substances along a phase interface, based on the Van der Waals model of a gas with fluctuations of the order parameter is confirmed by experimental data along the coexistence curve of a wide class of homogeneous and inhomogeneous molecular liquids under the Earth’s field of gravity. It is shown that the parameters of the extended equation for the coexistence curve of homogeneous and spatially inhomogeneous molecular liquids are linear functions of the compressibility factor. This allows us to predict the parameters of the equations of state of molecular liquids that are difficult to investigate experimentally.     

Transformation optofluidics for large-angle light bending and tuning

Transformation optics is a new art of light bending by designing materials with spatially variable parameters for developing wave-manipulation devices. Here, we introduce a transformation optofluidic Y-branch splitter with large-angle bending and tuning based on the design of a spatially variable index. Differing from traditional splitters, the optofluidic splitter is achieved in an inhomogeneous medium by coordinate transformation. The designed bidirectional gradient index (GRIN) distribution can be achieved practically by the convection-diffusion process of liquid flowing streams. The transformation optofluidic splitter can achieve a much larger split angle with little bend loss than the traditional ones. In the experiments, a large tunable split angle up to 30° is achieved by tuning the flow rates, allowing optical signals to be freely transferred to different channels. Besides the symmetrical branch splitting, asymmetrical Y-branch splitting with approximately equal power splitting is also demonstrated by changing the composition of the liquids. The optofluidic splitter has high potential applications in biological, chemical and biomedical solution measurement and detection.     

Structural Features of Solid Phases and Topology of Phase Diagrams

The paper considers model phase diagrams of binary and ternary systems involving transformations (transitions) of phase equilibria. The relationship between the type of structural solidstate transformation and the type of phase diagram is shown. Topological series of phase diagrams of systems with continuous and limited types of solid solutions are considered, including phase diagrams with polymorphic transitions between intermediate solid phases of variable composition.     

Fusibility of Formulations Based on Phases of the System Constituted by Spinel,Mullite, and Aluminum Titanate

A set of physicochemical analytical methods was applied to study fusion and crystallization of magnesia-alumina spinel, aluminum titanate, mullite, and their binary and ternary formulations. The feasibility of elucidating phase transformations that occur when phases containing ions with variable oxidation level are fused in an inert gas medium was analyzed.     

Specific features of the dynamic mode of differential dissolution as of a method of phase analysis

The author considers the specific features of the separation properties of the stoichiographic method of differential dissolution (DD) and the role of thermodynamic and kinetic factors in the processes of the separation of solid mixtures. It is shown that the separation properties of DD should be characterized by selectivity and efficiency, as it is accepted in chromatography. The separation possibilities of DD are considered in characterizing uniformity, stoichiometry-nonstoichiometry of the elemental composition of phases, and also of their macro- and microstructures. The comparison of the principles and characteristics of DD, voltammetry, titrimetry, mass spectroscopy, and chromatography has led to the conclusion that the place of DD among the other methods is determined, primarily, by its unique property, namely, its standardless nature.     

Hexagonal and Orthorhombic Perovskite Phases of ErMnO3 and TmMnO3 from Hydrothermal Systems

The powder crystals of RMnO 3 (R=Er, Tm) with hexagonal and orthorhombic structures were prepared under hydrothermal conditions. The different structural phases of the title compounds were controllably formed from different kinds of precursors at different reaction temperatures. All of the samples were characterized by powder X-ray diffraction, scanning electron microscopy, inductively coupled plasma analysis, and variable temperature magnetic susceptibility. Their structures were refined by Rietveld method from powder X-ray diffraction data. The measurement of magnetic behavior shows antiferromagnetic orderings at Neel temperatures around 80 and 40 K for the hexagonal and orthorhombic phases, respectively.     

Separation into Phases of Polymer Mixtures in Solution

When three different polymers are dissolved in a common solvent and the total polymer concentration is above a certain value, three liquid layers are obtained because of the limited compatibility of the polymer components with one another. Tests have been carried out at room temperature on solutions of polystyrene t polyvinyl acetate + polyvinyl chloride in tetrahydrofuran, and polystyrene t polyvinyl acetate t atactic polypropylene in benzene. Analysis of the individual layers yielded the following results: each polymer is always contained in each layer; the mixing ratios of the polymers in the three layers are generally different from one another and differ also from the mixing ratio of the starting mixture; each of the three layers is distinguished from the others by the fact that a specific polymer has been accumulated therein in preference to the other polymers. Concerning the quantitative distribution of the polymers among the layers, some laws could be found which can be explained qualitatively on the grounds of molecular-physical considerations. A solution of polystyrene t polyvinyl acetate t polyvinyl chloride t atactic polypropylene in tetrahydrofuran (equal amounts of polymers, total concentration about 10 g/100 ml) forms four layers, the composition of which was also determined by analysis.

When solutions of polymer mixtures are evaporated, separation into phases takes place because the polumers become incompatible with one another when the concentration exceeds a certain value. As a result, strongly inhomogeneous films are obtained after evaporation of the solvent. If the inhomogeneity of the films is not taken into consideration, misleading results may be obtained in the analysis of the films.

It is shown that in the system polystyrene + polyvinyl acetate, with tetrahydrofuran as solvent, surprising phenomena appear on the addition in stages of cyclohexane. The phenomena are due to the overlapping of separating and dissolving processes which have, in part, opposite actions.     

Separation of Isomers on Nematic Liquid Crystal Stationary Phases in Gas Chromatography: A Review

Understanding the composition of complex hydrocarbon mixtures is important for environmental studies in diverse fields, but many prevalent compounds cannot be confidently identified using traditional gas chromatography (GC) techniques. Increasing requirements on analyses of isomeric compounds and the problems encountered in their separation demand a study of more efficient systems which exhibit a high selectivity. Kelker and Fresenius first used nematic liquid crystals as stereospecific stationary phases in GC. Nematic liquid crystal has shown this particular selectivity and sensitivity as stationary phases for the separation of isomers having similar volatilities. Because of their unique selectivity towards rigid solute isomers, liquid crystal stationary phases were considered at one time to be a very promising class of materials that give gas chromatographic separations very different from those that can be obtained with any other stationary phase. Since then, a great deal of attention has been paid to the separation properties of this relatively wide group of substances. Liquid crystal can be used to separate a variety of compounds including isomer mixtures which cannot be separated on conventional stationary phases. This paper aims to review all specific experimental results and presents a comparative analytical study of monomeric nematic liquid crystal stationary phases used in GC. A further contribution of this review is in the field of isomeric compounds separation.     

Liquid Crystals as Stationary Phases in Chromatography

The most correct analysis of the compositions of diverse analytes mixtures is significant for analytical studies in different fields; however, many prevalent analytes cannot be identified employing traditional partition gas chromatographic methods. Thus, the increasing requirements on analytes of isomeric compounds and the problems encountered in their separation demand a study of more diverse analytical systems which are characterised by higher selectivity. Therefore, the selectivity and polarities of various liquid crystals (rod-like, banana-shape, biforked, oxygen, sulphur, nitrogen, and metal containing molecules, Schiff-base, and polymeric dendrimers) employed as liquid crystalline stationary phases (LCSPs) have been discussed from both points of views, namely, their analytical applications and thermodynamic characteristics of infinitely diluted probes with different acceptor–donor properties. Extreme particular effort has been paid to the different interdependencies between the bound up chemical structures of liquid crystal molecules with their different acceptor–donor properties and the connected resolution capabilities in the interpretation of the probe—LCSP systems, on the basis of the \( { \ln }V_{g\left( T \right)} = f\left( {\frac{1}{T}} \right) \) and \( { \ln }\left( {\frac{{a_{1} }}{{w_{1} }}} \right)^{\infty } = f\left( {\frac{1}{T}} \right) \) dependencies, with regard to the LCSP compositions, which have been controlled by the counterbalancing of the enthalpy and entropy factors. The properties of binary systems composed of liquid crystalline poly(propyleneimine) dendrimers—rod-like molecules of liquid crystals and effects of the dendrimer structure, the chemical nature, and molecular size of the non-mesogens on the ability to dissolve in the liquid crystalline phases, have been interpreted. Practical applications of metallomesogenes and chiral stationary phases for analytical separation of different organic substances have also been taken into consideration.

     

A New Application of McReynolds Constants to the Characterization of the Chromatographic Properties of Stationary Phases

An algorithm was proposed for comparing the McReynolds constants of new gas-chromatographic stationary phases with data for not only well-known individual substances but also their binary combinations. It was found that, in most cases, sets of these parameters for the chromatographic properties of new stationary phases are inconsistent with the data for a restricted set of previously characterized phases; however, they are consistent with the properties of phase combinations. This can be interpreted in terms of the absence of specific properties. Exceptions were found only among stationary phases bearing some specific molecular fragments (such as nitro groups) and individual crown ethers.     

Plain and ion-pair thin-layer chromatography of synthetic dyes on an admixture of silica gel G and barium sulfate in an aqueous ethanol system

An easy, inexpensive, and accurate method for the analysis of synthetic dyes by means of ion-pair thin-layer chromatography (IPTLC) on mixed sorbent phases containing silica gel G and barium sulfate in an aqueous ethanol system is studied. The effect of the composition of the sorbent phases has a major effect on the hundred-fold relative migration rate, as also does the effect of the ion-pairing reagent as the impregnant. Compact and sharp spot application yields very good binary and ternary separations and enables their clear identification. IPTLC has better separations on mixed sorbent phases, which are not possible on plain mixed phases in thin-layer chromatography. The method can be applied for the trace analysis of synthetic dyes in various natural and synthetic samples.     

Investigation of W<Subscript>2</Subscript>B and β-WB high-temperature phases in coatings produced by a shaped charge explosion

Coatings containing high-temperature phases of tungsten borides W₂B and β-WB are obtained on titanium and steel targets by a shaped charge explosion. In some regions of the target, microhardness achieves ≥42 GPa. The phase composition of different regions of the coatings is examined by X-ray diffraction. The values of unit cell parameters indicate the formation of phases with variable composition. The crystal structure of β-WB is refined.     

Experimental Modeling of Formation of the Basic Mineral Phases of Calcifications

Calcium phosphate phase formation was studied under process conditions involving human blood plasma. Calcium phosphate was synthesized with variable supersaturation (S) and experimental time. It was found that a non-stoichiometric hydrated carbonated hydroxyapatite, identical in the composition to calcifications in humans, is formed under the experimental conditions. The highest amount of carbonate ions (5.54 wt %) in the solid phase corresponds to the apatite synthesized at S = 50 for 10 weeks. The dissolution rate of solid phases was determined by mathematical processing of the obtained kinetic curves; this can be used to find compounds able to stop the development of vascular calcinosis.     

Chiral Method Development Strategies for HPLC using Macrocyclic Glycopeptide-Based Stationary Phases

Chiral HPLC methods using macrocyclic glycopeptide-based chiral stationary phases have been widely used and reported; however, the development of efficient methods to separate and quantify the analytes with high resolution is a challenging task. Therefore, the knowledge regarding the optimization of chromatographic parameters regarding this type of chiral chromatography is essential. This review presents and discusses the optimization of HPLC conditions and parameters for the chiral resolution of racemic drugs on macrocyclic glycopeptide-based chiral stationary phases. Strategies for chiral method development are presented, using polar ionic, reversed phase, normal phase and polar organic modes. The effect of the most important chromatographic parameters, such as mobile phase composition, flow rate and temperature on the enantioseparation are discussed aiming the adequate screening and optimization protocol for each mode.     

Separation of Cyclodextrins Using Cyclodextrin Bonded Phases

Abstract

Two different cyclodextrin bonded phases (α and β) were used for the separation of α-, β-and γ-cyclodextrins. The β-cyclodextrin phase was found to be, in general, more effective at resolving the cyclodextrins than the α-cyclodextrin bonded phase. Acetonitrile/water mixtures were used as mobile phases. The effect of mobile phase composition on retention and resolution is examined. The elution order was found to be size dependent. The results are discussed in terms of the overall retention mechanism.     

Interaction,composition, and optical properties of the MgF<Subscript>2</Subscript>(MgO)-EuF<Subscript>3</Subscript> system

The interaction between MgO and EuF₃ resulting in the formation of magnesium fluoride and europium(III) oxyfluorides of variable composition are investigated. A substantial difference between the diffuse reflection spectra of the fluoride phase and oxyfluoride phases of europium(III) is found, specifically, an intense band peaked at 260–270 nm appears in the latter. The effect of silicon and high vacuum as reducers on the systems containing the oxide phase is investigated. For these phases, europium(II) compounds are found, which is confirmed by X-ray powder diffraction analysis and diffuse reflection and luminescence spectroscopy. The character of thermogravimetric curves for the MgF₂-EuF₃-Si and MgO-EuF₃-Si systems is fundamentally different, which allows us to propose a new method for estimating the MgO content in MgF₂.