Short range ordering in rapidly quenched Fe83P17 amorphous alloys

Mössbauer spectroscopy, X-ray diffractometry and differential scanning calorimetry were used to study the effect of the preparation parameters on the short range ordering of Fe₈₃P₁₇ amorphous alloys. The samples were quenched with different quenching rates from the melt which was kept either at 1100°C or 1250°C for 20 min. The short range order of the amorphous samples was found to depend on the quenching rate due to the relaxation taking place during rapid quenching of the melt. In one case, in the sample quenched with the lowest quenching rate from the melt of 1250°C, crystalline phases identified as Fe₃P and -Fe were also found. This phase separation can be understood by taking into consideration the effect of both the melt temperature and the quenching rate. In this case, the cooling time can be long enough for separation of the phases which can be expected within the range of 1040–1250°C according to the phase diagram.     

Conversion electron Mössbauer study of short range ordering in electrochemically deposited Fe−Ni−Cr alloys

⁵⁷Fe Conversion electron Mössbauer spectroscopy, X-ray diffractometry and electron microprobe measurements were performed on Fe–Ni–Cr alloys coatings electrochemically deposited at different times (from 1 to 29 minutes). Significant differences have been found among the Mössbauer spectra of samples examined. The changes are also reflected by the hyperfine field distribution derived from the spectra. The observed changes can be associated with changes in the magnetic anisotropy and in the short range ordering in correlated to the duration of electrochemical deposition.     

Investigation of core-excited BK quantum yield spectra of amorphous and crystalline Fe40Ni40P14B6 alloys

X-ray quantum yield spectra from the BK edge in amorphous and crystalline Fe₄₀Ni₄₀P₁₄B₆ alloys are presented. ESCA core level binding energies were also measured. The quantum yield spectra are discussed together with calculated densities of states. A good coincidence between band structure calculations and experimental results is obtained. A small structure at absorption onset is interpreted as due to oxidation products at the sample surface. Crystallization effects after heating of the compound are discussed.     

19F NMR chemical shifts of CF4 in CO2 over a wide pressure range at different temperatures

¹⁹F NMR chemical shifts of CF₄ in CO₂ under extremely dilute concentrations were precisely determined at 299.8, 314.4 and 328.9 K over a wide range of pressure between 0.4 and 33 MPa. The solvent‐induced chemical shift, where the bulk magnetic susceptibility correction was made, was quantitatively expressed as a function of CO₂ density. Copyright © 2002 John Wiley & Sons, Ltd.     

Velocity sedimentation transport properties in dilute and concentrated solutions of hydroxypropyl cellulose in water at different temperatures up to phase separation

Velocity sedimentation measurements have been performed for the system hydroxypropyl cellulose in water in both dilute and concentrated solutions (0–100 kg m^?3) and at temperatures remote from as well as close to θ-conditions (25–40°). In dilute solutions, the experimentally determined concentration dependence of the sedimentation coefficient was compared with that calculated from the theory of Yamakawa; fairly good agreement was obtained. The difference between the sedimentation behaviour under good and poor solvent conditions is also discussed. Furthermore, the frictional properties are discussed and compared with those deduced from diffusion measurements.     

Acoustic and volumetric studies of uracil in aqueous urea solution at different temperatures

Volumetric, viscometric and ultrasonic studies of uracil in an aqueous urea solution in varying concentration of 2, 3 and 5?M have been carried out at 298, 308 and 318?K. The uracil concentration in the aqueous urea solution varies from 0.05% to 0.4%. Density (ρ), viscosity (η) and sound speed (u) have been measured. The experimental data are used for computing various thermodynamic and acoustic parameters, namely apparent molar volume, isentropic compressibility, apparent isentropic compressibility, relative association, intermolecular free length, acoustic impedance, viscous relaxation time, hydration number, Gibb's free energy, classical absorption coefficient of the solution and viscosity data have been further analysed in the light of Masson's equation and Jones–Dole's equations, respectively. The results have been discussed in terms of solute–solute and solute–solvent interaction and the structural changes of the solutes in solutions. The effect of variation of temperature on these interactions has also been investigated.     

Phase separation in aqueous two-phase systems containing poly(ethylene glycol) and magnesium sulphate at different temperatures

New experimental (liquid + liquid) equilibrium data have been determined for aqueous systems containing poly(ethylene glycol) of nominal molar mass 10,000 and magnesium sulphate at T = (295.15, 301.15, 305.15, and 311.15) K. The effect of temperature on the liquid compositions of coexisting phases is discussed. The experimental (liquid + liquid) equilibrium data of the systems were correlated by non-random two-liquid (NRTL) activity coefficient model. The interaction parameters of the NRTL activity coefficient model are obtained and reported. The calculated root mean square deviations (RMSD) showed that NRTL activity coefficient model can be used satisfactorily to correlate the (liquid + liquid) equilibrium data in aqueous solution of the {poly(ethylene glycol) + magnesium sulphate} system.     

Predicting retention in reverse‐phase liquid chromatography at different mobile phase compositions and temperatures by using the solvation parameter model

The prediction capability of the solvation parameter model in reverse‐phase liquid chromatography at different methanol‐water mobile phase compositions and temperatures was investigated. By using a carefully selected set of solutes, the training set, linear relationships were established through regression equations between the logarithm of the solute retention factor, logk, and different solute parameters. The coefficients obtained in the regressions were used to create a general retention model able to predict retention in an octadecylsilica stationary phase at any temperature and methanol‐water composition. The validity of the model was evaluated by using a different set (the test set) of 30 solutes of very diverse chemical nature. Predictions of logk values were obtained at two different combinations of temperature and mobile phase composition by using two different procedures: (i) by calculating the coefficients through a mathematical linear relationship in which the mobile phase composition and temperature are involved; (ii) by using a general equation, obtained by considering the previous results, in which only the experimental values of temperature and mobile phase composition are required. Predicted logk values were critically compared with the experimental values. Excellent results were obtained considering the diversity of the test set.     

Investigation of the phase diagram and the determination of synthesis conditions of volume amorphous alloys in the Cu-Ni-Zr system at 1123 K

The phase equilibria in the Cu-Ni-Zr system in a field enriched by zirconium at 1123 K were investigated by the methods of X-ray and electron-probe microanalysis, microdurometry, and scanning calorimetry. A fragment of the isothermal section of the given system was constructed and the borders of areas of homogeneity of double phases of the Ni-Zr and Cu-Zr systems were defined. It was established that the double compounds NiZr and NiZr₂ dissolve up to 33 and 12 at % Cu, respectively, and CuZr and CuZr₂, dissolve up to 7 at % Ni.     

Pressure-dependent Ni-O phase transitions and Ni oxide formation on Pt(111): an in situ STM study at elevated temperatures

Growth, atomic structure and O2 partial pressure dependent phase transitions of Ni-O structures and thin NiO films on Pt(111) have been studied using scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED), and Auger electron spectroscopy (AES). In situ STM experiments were performed during film growth by reactive metal deposition at elevated temperatures (400-550 K) and variable O2 pressure. Depending on the substrate temperature, one-dimensional network-like Ni-O structures and islands with (7x1) and (4x2) reconstructions are formed during the initial stages of growth. These structures transform reversibly to a (2x2) reconstruction in a narrow O2 pressure range of 1.5-2x10(-6) mbar and can be monitored by in situ STM. Upon reduction of the O2 pressure to <10(-10) mbar pseudomorphic Ni monolayers are obtained. The defect-free ordering of Ni atoms on Pt(111) in a single stacking domain indicates an O-surfactant induced growth mode. The structural properties of the O2 pressure-dependent Ni-O phases are discussed in a simple model assuming NiO(001)-like atomic arrangements in the adsorbate overlayer. At higher coverage stable (111)-oriented NiO islands grow in a three-dimensional mode.     

Dissolved carbon dioxide effect on the behavior of carbon steel in a simulated solution at different temperatures and immersion times

Dissolved carbon dioxide effect on the behavior of carbon steel (0.4%carbon), in a simulated solution at different temperatures and immersion times, has been investigated using different techniques as potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy. The observation of the steel surface was done by scanning electron microscopy. All measurements reveal that the corrosion resistance is strongly dependent on both the temperature and immersion times. The corrosion resistance of carbon steel decreases in the solution considered as the temperature increases from 20?°C to 50?°C. Potentiodynamic polarization curves showed that cathodic and anodic current densities increase with the increased temperature. Besides, the study concluded that the addition of CO₂ gas to the simulated solution affects negatively the corrosion resistance in one hand and that, on the other hand, the higher the time of immersion the higher is the resistance to corrosion.     

Thermodynamic and spectroscopic studies on cationic surfactant tetradecyltrimethylammonium bromide in aqueous solution of trisubstituted ionic liquid 1, 2-dimethyl-3-octylimidazolium chloride at different temperatures

In this work, the effects on micellar behavior of long chain cationic surfactant tetradecyltrimethylammonium bromide (TTAB) upon the addition of trisubstituted ionic liquid (IL), 1, 2-dimethyl-3-octylimidazolium chloride [odmim][Cl] at temperatures, 298.15–318.15 K has been studied. Different techniques such as conductance, surface tension, fluorescence and ¹H NMR have been employed to understand the interactional mechanisms. The values of critical micelle concentration (cmc) and various thermodynamic parameters have been calculated from conductivity measurements. The surface parameters like effectiveness of decrease in surface tension (Π_cmc), minimum surface area occupied per surfactant monomer (A_min), maximum surface excess concentration (Γ_max), and adsorption efficiency (pC₂₀) have been evaluated by surface tension measurements. Micellar aggregation number (N_agg) has been determined by quenching of pyrene. Further to understand interactions in post micellar region, ¹H NMR measurements have been performed. It has been observed that the lipophilicity of interacting ion modified the thermodynamic and aggregation properties of TTAB.     

Measurement and correlation of phase equilibria in aqueous two-phase systems containing polyvinylpyrrolidone and di-potassium tartrate or di-potassium oxalate at different temperatures

Experimental (liquid + liquid) equilibrium (LLE) measurements and the phase diagram have been determined for aqueous two-phase systems containing polyvinylpyrrolidone (PVP) and di-potassium oxalate or di-potassium tartrate at T = (298.15, 308.15, and 318.15) K. Also, the effects of temperature on the binodal curve and tie-lines have been studied. The Merchuk equation was used to correlate the binodal curves of these systems. Furthermore, several suitable equations were used to fit the tie-line data points. The results show that at each temperature, the agreement between the correlated and the experimental values is good with all of these equations. Also, the effects of the type of salt on LLE are discussed.     

Topographical and microanalytical investigation of corrosion processes on the solid material in the system metal-metalloid glassy alloy (Fe,Cr)80(P,C,Si)20, aqueous FeCl3 solution, and air in the region of the “amorphous solid/liquid/air” phase interface

Ribbons of the metal-metalloid glassy alloy (Fe,Cr)₈₀(P,C,Si)₂₀ and Fe₇₅Cr₅P₈C₁₀Si₂, respectively, were treated with an aqueous solution of FeCl₃ (29 mass%) in an ultrasonic bath. The surface of the amorphous solid is maximally influenced at the flux line as the contact zone of glass/solution/ air. This region of the amorphous solid was studied by light microscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA) as well as the electron beam micro analysis (EBMA) after the treatment. Changes in the surface stage and the surface behaviour take place independently of the state of the initial glass surface (shiny or dull side of a ribbon). Reaction products of different morphology were formed. In the flux line of the glass an enrichment of Si and Fe could be detected. These results agree with those of electrochemical measurement. According to this, a chloride ion containing acid aqueous solution is rather corrosive to this glassy alloy.     

Influence of morphology and composition of fumed oxides on changes in their structural and adsorptive characteristics on hydrothermal treatment in steam phase at different temperatures

A series of fumed oxides such as silica, titania, alumina, silica/alumina (SA), silica/titania (ST), and alumina/silica/titania (AST), initial and hydrothermally treated (HTT) in the steam phase at T(HTT)=150, 250, and 350 degrees C was studied by adsorption, AFM, XRD, FTIR, and theoretical methods. Diminution of the size of primary particles (corresponding to increasing S(BET)) of initial silica and mixed oxides results in enhancement of their structural changes on HTT with elevating T(HTT) and increasing density of packing of primary particles in the secondary structures. Relative changes in the texture of treated fumed silicas are smaller than those of mesoporous silica gels occurring under similar HTT conditions. On HTT, aggregates of primary particles and their agglomerates become denser but their surface layers become looser because of transfer of silica fragments from one particle to another, and the smaller the initial primary particles, the greater the relative diminution of the specific surface area S(BET) for the same type of primary particle packing in aggregates. Relative changes in the pore volume V(p) (or V(BJHd)) on HTT are more complex than that of S(BET), as for many samples the V(p) value increases especially at T(HTT)=150 degrees C. Alumina and titania partially inhibit structural changes on HTT, which decrease in the series silica > SA > AST approximately ST.     

Dissolution kinetics of nanodispersed gamma-alumina in aqueous solution at different pH: unusual kinetic size effect and formation of a new phase

The dissolution of a technical, nanodispersed gamma-alumina in water was studied at 25 degrees C in the pH range 3.0 < or = pH < or = 11.0. The obtained kinetic dissolution curves showed a distinct pH dependency, whereas only for pH > or = 4.5 the typical behavior of nanodispersed materials could be observed. X-ray powder diffraction analysis and nitrogen adsorption, as well as IR and UV-Raman spectroscopy, were used to characterize the solid material collected during and at the end of each dissolution experiment. As a result the formation of a new aluminum phase-bayerite-could be proven. The analysis of the equilibrium concentration enabled us to determine the solubility constant of the corresponding phase assuming a pH-dependent species distribution. The rate constants of the dissolution process were evaluated using the model of Gibbs free energy of cluster formation, which considers the size effect, among other things. As a result, we could show that the observed maxima in the concentration profiles are due to a size effect of the starting material having a primary particle radius of 10.1 nm.     

Preconcentration and separation with Amberlite XAD-4 resin; determination of Cu, Fe, Pb, Ni, Cd and Bi at trace levels in waste water samples by flame atomic absorption spectrometry

A method for the preconcentration of Cu, Fe, Pb, Ni, Cd and Bi as their diethyldithiocarbamate chelates was proposed using a column filled with Amberlite XAD-4 resin. The retained analytes on the resin were recovered with a small volume of acetone. The metal ions in the effluent were determined by a flame atomic absorption spectrometer. Different factors including pH of sample solution, sample volume, amount of XAD-4 resin, amount of ligand, eluent volume and matrix effects for preconcentration were examined. The recoveries for the analytes under the optimum working conditions were higher than 95%. The relative standard deviations of the determinations were below 9%. The limits of detection (3 s, n=20) for analytes were found to be between 4 and 23 mug l(-1). The proposed method was applied to the analysis of some waste waters from the organized industrial region of Kayseri.