A locally adaptive peano scanning algorithm

This paper describes an algorithm which builds a ``Peano scanning,' i.e., the reciprocal mapping, from [0, 1]n to [0, 1], of the well-known ``Peano curve.' This Peano scanning is applied to a set of points in [0, 1]n and gives a one-dimensional image of it. Several applications of this technique have already been developed and are presented in this paper.     

Effect of a variety of organic additives on retention and efficiency in micellar liquid chromatography

The effect of 21 organic additives (alkanols, alkane diols, dipolar aprotic solvents, alkanes) on the chromatographic behavior (retention, elution strength, efficiency) of probe solutes of widely differing hydrophobicity, such as benzene and 2-ethylanthraquinone, have been examined using a C18 stationary phase and sodium dodecyl sulfate (SDS) micellar mobile phases. The mobile-phase elution strength parallels the octanol-water partition coefficients of the additives or their ability to bind to the SDS micellar system, due to the increased solubility in the mobile phase and reduced affinity for the additive-modified surfactant-coated stationary phase. The comparison of the elution strength of micellar mobile phases with that of a reference acetonitrile-water system indicates that the elution strength is lower for micellar systems and depends on the nature of the eluted solute. The displacement of the solute-micelle and solute-stationary phase binding equilibria is quantified for several probe solutes eluted with micellar mobile phases in the presence of 1-propanol, 1-butanol, 1-pentanol, and acetonitrile. A correlation was also observed between the number of theoretical plates and the hydrophobicity of the alcohol additives: the efficiency initially increased steeply and reached a plateau. Compared to benzene, a more hydrophobic additive was needed to attain the maximum efficiency for the more hydrophobic 2-ethylanthraquinone analyte. Dipolar aprotic solvents appear to be somewhat more effective in enhancing the efficiency than alcohols. The results are rationalized in terms of the ability of the organic additives to alter the composition, structure, dynamics, and properties of the micelles and the surfactant-coated stationary phase.     

Elution-extrusion countercurrent chromatography. Use of the liquid nature of the stationary phase to extend the hydrophobicity window

Countercurrent chromatography (CCC) is a liquid chromatography technique with a liquid stationary phase. Taking advantage of the liquid nature of the stationary phase, it is possible to perform unique operations not possible in classical liquid chromatography with a solid stationary phase. It is easy to avoid any solute-irreversible absorption in the CCC column. If the retention volumes of solutes become too high, the dual mode will be used. The roles of the phases are reversed. The stationary phase becomes the mobile phase, and the CCC column is started again. The solutes elute rapidly in what was previously the stationary phase. The theoretical basis of the dual-mode method is recalled. The dual-mode method is a discontinuous method. The separation should be stopped when the phase switch is performed. The elution-extrusion procedure is another way to avoid any irreversible adsorption of solutes in the column. The method uses the fact that the liquid volumes occupied by the solutes highly retained inside the column can be orders of magnitude lower than the mobile-phase volume that would be needed to elute them. The elution-extrusion method also has two steps: the first step is a regular CCC chromatogram. Next, the stationary phase containing the partially separated hydrophobic solutes is extruded out of the column in a continuous way using the liquid stationary phase. The theory of the process is developed and compared to the dual-mode theory. Alkylbenzene homologues are experimentally used as model compounds with the heptane/methanol/water biphasic liquid system to establish the theoretical treatment and compare the performance of two types, hydrodynamic and hydrostatic, of CCC columns. It is shown that the method can dramatically boost the separation power of the CCC technique. An apparent efficiency higher than 20 000 plates was obtained for extruded octylbenzene and a 160-mL hydrodynamic CCC column with less than 500 plates when conventionally used.     

Thermal expansion of chromium-rich iron-based or iron /nickel-based alloys reinforced by tantalum carbides

Six alloys reinforced by TaC carbides based on iron (ferritic) or both iron and nickel (austenitic) were studied in thermal expansion between 100 and 1200°C for two microstructural orientations. The heating, isothermal, and cooling parts of the dilatometry curves were characterized. The thermal expansion of the ferritic alloys is less important than the thermal expansion of the austenitic alloys. A compressive deformation of the matrix subjected to stresses applied by the carbides network was observed. The importance of this phenomenon seems to depend more on the matrix nature than on the microstructural orientation.     

Development of chromia forming Mo-W-Cr alloys: synthesis and characterization

The sintering process and microstructural characteristics of tungsten-based and molybdenum-based alloys containing chromium and group VIII metals as sintering agents have been investigated. The influences of the alloy composition, the nature of the sintering agent and the synthesis process on the microstructure and microhardness of these materials have been studied. Homogeneous alloys can be obtained with palladium or nickel as the sintering agent. The mechanisms are totally different with these two metals. In the case of nickel, diffusion of the refractory metals through a nickel layer is responsible for the densification of the alloys, whereas with palladium, a CrPd liquid phase at the grain boundaries leads to homogeneous sintering. Formation of the CrPd phase is directly dependent on the chromium content wich influences the solubility of palladium in the MoW matrix. Consequently, a low chromium content leads to a high CrPd content, and to an increase in the grain size. On the contrary, with a nickel sintering agent, ahigh Ni content leads to an increase in thickness of the interdiffusion layer and thus a decrease in the grain size. Sresses generated by uniaxial sintering and mechanical alloying are not released during the annealing sequence and contribute to increase the microhardness of the alloys. Microhardness is also a strong function of the tungsten content.     

As-cast microstructures and behavior at high temperature of chromium-rich cobalt-based alloys containing hafnium carbides

Hafnium is often used to improve the high temperature oxidation resistance of superalloys but not to form carbides for strengthen them against creep. In this work hafnium was added in cobalt-based alloys for verifying that HfC can be obtained in cobalt-based alloys and for characterizing their behavior at a very temperature. Three Co–25Cr–0.25 and 0.50C alloys containing 3.7 and 7.4 Hf to promote HfC carbides, and four Co–25Cr– 0 to 1C alloys for comparison (all contents in wt.%), were cast and exposed at 1200 °C for 50 h in synthetic air. The HfC carbides formed instead chromium carbides during solidification, in eutectic with matrix and as dispersed compact particles. During the stage at 1200 °C the HfC carbides did not significantly evolve, even near the oxidation front despite oxidation early become very fast and generalized. At the same time the chromium carbides present in the Co–Cr–C alloys totally disappeared in the same conditions. Such HfC-alloys potentially bring efficient and sustainable mechanical strengthening at high temperature, but their hot oxidation resistance must be significantly improved.     

Theory and use of the pseudophase model in gas-liquid chromatographic enantiomeric separations

The theory and use of the "three-phase" model in enantioselective gas-liquid chromatography utilizing a methylated cyclodextrin/polysiloxane stationary phase is presented for the first time. Equations are derived that account for all three partition equilibria in the system, including partitioning between the gas mobile phase and both stationary-phase components and the analyte equilibrium between the polysiloxane and cyclodextrin pseudophase. The separation of the retention contributions from the achiral and chiral parts of the stationary phase can be easily accomplished. Also, it allows the direct examination of the two contributions to enantioselctivity, i.e., that which occurs completely in the liquid stationary phase versus the direct transfer of the chiral analyte in the gas phase to the dissolved chiral selector. Six compounds were studied to verify the model: 1-phenylethanol, alpha-ionone, 3-methyl-1-indanone, o-(chloromethyl)phenyl sulfoxide, o-(bromomethyl)phenyl sulfoxide, and ethyl p-tolylsulfonate. Generally, the cyclodextrin component of the stationary phase contributes to retention more than the bulk liquid polysiloxane. This may be an important requirement for effective GC chiral stationary phases. In addition, the roles of enthalpy and entropy toward enantiorecognition by this stationary phase were examined. While enantiomeric differences in both enthalpy and entropy provide chiral discrimination, the contribution of entropy appears to be more significant in this regard. The three-phase model may be applied to any gas-liquid chromatography stationary phase involving a pseudophase.