Apparent molal volumes of the solutions of CaCl2 and Ca(NO3)2 in ethanol at 298.15: experimental data and correlation by local composition models

Apparent molal volume of the solutions of CaCl₂ and Ca(NO₃)₂ in ethanol are reported and correlated using equations obtained from the various local composition (LC) models. The considered models are e-NRTL, NRF, MNRTL, and EW models. The applicability of the models has been discussed with comparing their standard deviations with those obtained from the Pitzer model and a polynomial equation. Limiting partial molal volumes of the salts have been obtained using dilute region data via the Redlich–Meyer equation.     

Thermodynamic and Dynamic Properties of Micellar Aggregates of Nonionic Surfactants with Short Hydrophobic Tails

The densities and viscosities of binary aqueous mixtures of poly(ethylenoxide)hexanols [C₆H₁₃(OCH₂CH₂)_mOH, C₆E_m] (m= 3, 4, and 5) have been studied in the micellar composition range. For the same surfactants the self-diffusion coefficients in mixtures with heavy water have been determined by the spin-echo pulsed field gradient method. The volumetric data are interpreted by means of the phase separation model, and values of the CMC, volume change, and standard free energy change of micellization are obtained. From the viscosity data the hydration numbers of the surfactant hydrophilic head in the micellar state are computed; they are in agreement with those obtained from HDO self-diffusion data. The surfactant self-diffusion data are used to calculate the apparent micelle radius and the aggregation number. The micellization parameters obtained for the different surfactants are compared and discussed.     

Massenspektrometrische-, dta- und tg-untersuchungen an eisencarbonylchalkogeniden Fe2(CO)6X2 (X  S,Se) und Fe3(CO)9X′2 (X′  S,Se, Te)

Mass spectra of Fe₃(CO)₉X₂ (X  S, Se, Te) and Fe₂(CO)₆X′₂ (X′  S, Se) are recorded and their fragmentation pattern given. The thermal decarbonylation has been studied using DTA/TG methods in the temperature range 25–600°C. The results are compared with those obtained from mass-spectroscopic studies. X-ray and magnetic measurements have been carried out on the residues obtained in the decarbonylation process.     

On the enthalpies and entropies of formation of solid nickel—zinc alloys

The enthalpies of formation of solid nickel—zinc alloys have been measured at 355 K using an isoperibol calorimeter and the technique of tin-solution calorimetry, and values have been obtained for the nickel-rich α-solid solutions and for the β₁, γ, γ₁ and δ intermediate phases. Exothermic values have been observed throughout and these have been compared with the results obtained in previous free energy studies and with those suggested by the empirical model of Miedema. The existing free energy data have been re-assessed at 900 K and the results combined with the present calorimetric enthalpies to derive entropies of formation. The possible contributions to the entropies of the phases are discussed and their Debye temperatures are estimated.     

Organosilicon polymers with bis-acetylenic units: Conductivity and ceramisation studies

The transformation poly[(silylene)diacetylene] into ceramic have been studied and SiC obtained with a quantitative yield: all the silicon atoms present in the starting material are converted into SiC. The key step is the crosslinkage of C₄ units into a carbon matrix in which the R₁SiR₂ moieties are in the vicinity one to each other allowing the quantitative transformation into SiC. The carbon content of the resulting ceramic depends on the nature of R₁ and R₂ groups. The excess of carbon has been used for the carboreduction of oxides (TiO₂, ZrO₂, HfO₂, etc…) and mixed ceramics with interpenetrating network have been obtained: SiC / TiC, SiC / ZrC, etc… Under nitrogen atmosphere, the ceramisation leads to different systems such as SiC / TiN, SiC / AlN, etc…     

Copolymerization of 2-Hydtoxypropyl Methacrylate with Alkyl Methacrylates

2-Hydroxypropyl methacrylate (2 HPMA) has been copolym-erized with ethyl methacrylate (EMA), n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (EHMA) in bulk at 60°C using benzoyl peroxide as initiator. The copolymer composition has been determined from the hydroxyl content. The reactivity ratios have been calculated by the YBR method. For copolymerization of 2-HPMA (M₁) with EMA (M₂), the reactivity ratios are: r₁=1.807 ± 0.032, r₂=0.245 ± 0.021; with BMA (M₂) they are r₁=2.378 ± 0.001, r₂=0.19 ± 0.01; and with EHMA the values are r₁=4.370 ± 0.048, r₂=0.103 ± 0.006. Since the reactivity ratios are the measure of distribution of monomer units in a copolymer chain, the values obtained are compared and discussed. This enables us to choose a suitable copolymer for synthesizing thermoset acrylic polymers, which are obtained from cross-linking of hydroxy functional groups of HPMA units, for specific end uses.     

Copolymerization of 2-Hydroxypropyl Methacrylate with Alkyl Met hacrylates

2-Hydroxypropyl methacrylate (2-HPMA) has been copolym-erized with ethyl methacrylate (EMA), n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (EHMA) in bulk at 60°C using benzoyl peroxide as initiator. The copolymer composition has been determined from the hydroxyl content. The reactivity ratios have been calculated by the Yezrielev, Brokhina, and Raskin method. For copolymerization of 2-HPMA (M₁) with EMA (M₂), the reactivity ratios are r₁ = 1.807 ± 0.032 and r₂ = 0.245 ± 0.021; with BMA (M₂) they are n = 2.378 ± 0.001 and r₂ = 0.19 ± 0.01; and with EHMA the values are r₁ = 4.370 ± 0.048 and r₂ = 0.103 ± 0.006. Since reactivity ratios are the measure of distribution of monomer units in copolymer chain, the values obtained are compared and discussed. This enables us to choose a suitable copolymer for synthesizing thermoset acrylic polymers, which are obtained from cross-linking of hydroxy functional groups of HPMA units, for specific end-uses.     

PECVD of SiOxNyCzHw thin films from hexamethyldisilazane containing feed. Investigation on chemical characteristics and aging behavior

The chemical characteristics and aging behavior of thin films obtained by HMDSN/NH₃ or N₂ containing plasmas have been studied by means of FT-IR spectroscopy as a function of feed composition, substrate temperature and bias voltage. Deposits obtained with low energy ion bombardment are polyphasic and contain a consistent fraction of polysilazane. Reactive polymeric SiH₂ chains are formed when ammonia or nitrogen are added to the feed. Film aging is mainly due to the reactions of Si-H bonds and of linear polysilazane chains. Films with better stability are obtained by excluding ammonia or nitrogen from the feed and with bias superimposition.     

General Route to Synthesize Monodisperse Oxide (Hydroxide) Nanoparticles

Mono-dispersed oxide and hydroxide nanoparticles have been synthesized through the solvothermal process in alcohol-water mixtures. The products were characterized by powder x-ray diffraction (XRD) and scanning electron microscopy (SEM). Plate-like nanoparticles are obtained for Bi₂O_2.33, Fe₂O₃, and Cd(OH)₂, and spherical nanoparticles are obtained for SnO₂. The growth mechanism for the mono-dispersed nanoparticles has been preliminarily discussed.     

Silica-supported perchloric acid and potassium bisulfate as reusable green catalysts for nitration of aromatics under solvent-free microwave conditions

Silica-supported perchloric acid and bisulfate (SiO₂/HClO₄ and SiO₂/KHSO₄) have been developed as reusable green catalysts for nitration of aromatic compounds using NaNO₂ in acetonitrile medium under conventional and solvent-free microwave conditions. The reaction times under microwave irradiation are significantly shorter than conventional method even though the yields obtained in microwave-assisted reactions are comparable with those obtained under reflux conditions.     

Electrochromism of NiO-TiO2 sol gel layers

Films of NiO-TiO₂ with Ni concentration of 100, 90, 87, 83, 75, 66, 50 and 33 mol% have been obtained via the sol-gel route by dip coating technique and sintered in air between 250 and 500°C using ethanolic sols of nickel acetate tetrahydrate (Ni(CH₃COO)₂·4H₂O) and titanium n-propoxide (Ti(O-CH(CH₃)₂)₄) precursors. Xerogels obtai- ned by drying the sols have been studied up to 900°C by thermal analysis (DTA/TG) coupled to mass and IR spectroscopy. The crystalline structure and morphology of the layers in the as deposited, bleached and colored states were determined by X-ray diffractometry, scanning electron microscopy and transmission electron microscopy Their electrochromic properties have been studied in 1 M KOH aqueous electrolyte as a function of the layer composition, thickness and sintering temperature. Deep brown colour with reversible transmittance changes have been obtained using cycling voltammetry and chronoamperometry processes. The best composition to get stable sols, a high reversible transmittance change and fast switching times (<10 s) was obtained with double NiO-TiO₂ layers 160 nm thick having 75% Ni molar concentration, and sintered between 300 and 350°C. The mechanism of coloration and morphology transformation of the layer during cycling are discussed in terms of an activation and degradation period. The results are in agreement with the accepted Bode model.     

Vibrational Spectra and Quantum Calculations of Ethylbenzene

Normal vibrations of ethylbenzene in the first excited state have been studied using resonant two-photon ionization spectroscopy. The band origin of ethylbenzene of S₁←S₀ transition appeared at 37586 cm^-1. A vibrational spectrum of 2000 cm^-1 above the band origin in the first excited state has been obtained. Several chain torsions and normal vibrations are obtained in the spectrum. The energies of the first excited state are calculated by the time-dependent density function theory and configuration interaction singles (CIS) methods with various basis sets. The optimized structures and vibrational frequencies of the S₀ and S₁ states are calculated using Hartree-Fock and CIS methods with 6-311++G(2d,2p) basis set. The calculated geometric structures in the S₀ and S₁ states are gauche conformations that the symmetric plane of ethyl group is perpendicular to the ring plane. All the observed spectral bands have been successfully assigned with the help of our calculations.     

High resolution spectroscopy of small metal clusters

The optical absorption spectrum of small lithium clusters has been measured up to Li₈. In Li₃ high resolution Two Photon Ionization (TPI) spectra have been recorded allowing us to determine the geometry and potential surfaces of the ground and excited states. In larger clusters, the excited states are dissociative and the absorption spectra have been obtained by Depletion Spectroscopy. Vibronic resolution is still achieved in Li₄, but not in larger clusters. The measured spectra exhibit a rather small number of transitions to electronically excited states. In Li₇, only one intense band is observed in the blue region, while in Li₈, an intense band is also observed in the blue region and a much weaker band in the red region. All the obtained results are in very good agreement with the ab initio calculation of Bonacic-Koutecky et al. This demonstrates that molecular effects are always present in these small clusters. The semi-classical models of surface plasma resonances are also discussed.     

Determination of specific surface area of uranium oxide powders using differential thermal analysis technique

The two step oxidation of UO_2+x and reduction of U₃O₈ powders observed during Differential Thermal Analysis (DTA) has been exploited to determine their Specific Surface Areas (SSAs). The results obtained by this method have been compared with the Braunauer, Emmett and Teller (BET) method and are found to be in good agreement in the SSA range of 2–4 m²/gm in the case of UO_2+x obtained from ADU route and 4–8 m²/gm in the case of AUC route. A precision of ±0.1 m²/gm is obtained. The maximum temperature of oxidation and reduction of these oxides are dependent upon their preparative routes such as Ammonium Diuranate (ADU) and Ammonium Uranyl Carbonate (AUC).     

Extraction of uranium(VI) and thorium(IV) from nitric acid solution by N-alkylcaprolactam

Extraction of uranium(VI), thorium(IV) from nitric acid has been studied with N-octylcaprolactam and N-(2-ethyl)hexylcaprolactam. Distribution coefficients of U(VI), Th(IV) and HNO₃ as a function of aqueous NHO₃ concentration, extractant concentration and temperature have been studied. The compositions of extracted species, thermodynamic parameters of extraction have been evaluated. Third phase formation in extraction of U(VI) has been studied. Back extraction behavior of U(VI) and Th(IV) from the organic phase has also been tested. The results obtained are compared with those obtained by using TBP under the same experimental conditions.     

Multiobjective optimization of a free radical bulk polymerization reactor using genetic algorithm

A multiobjective optimization technique has been developed for free radical bulk polymerization reactors using genetic algorithm. The polymerization of methyl methacrylate in a batch reactor has been studied as an example. The two objective functions which are minimized are the total reaction time and the polydispersity index of the polymer product. Simultaneously, end‐point constraints are incorporated to attain desired values of the monomer conversion (x_m) and the number average chain length (μ_n). A nondominated sorting genetic algorithm (NSGA) has been adapted to obtain the optimal control variable (temperature) history. It has been shown that the optimal solution converges to a unique point and no Pareto set is obtained. It has been observed that the optimal solution obtained using the NSGA for multiobjective function optimization compares very well with the solution obtained using the simple genetic algorithm (SGA) for a single objective function optimization problem, in which only the total reaction time is minimized and the two end‐point constraints on x_m and μ_n are satisfied.     

Determination of the local electron number density in laser-induced plasmas by Stark-broadened profiles of spectral lines: Comparative results from Hα, Fe I and Si II lines

Measurements of the local electron density in laser-induced plasma have been carried out from the Stark-broadened profiles of three reference lines (H_α, Fe I and Si II). The plasma has been generated from a Fe–Si sample in air using a Nd:YAG laser. Compatible values of the local electron density have been obtained from the three lines. The experiment is based on the use of an imaging spectrometer, the capability for spatial resolution of a charge-coupled device and the application of a spatial deconvolution procedure to the spectra. Distributions of the emission coefficient have been obtained, showing that the three lines are emitted from different regions of the plasma. The implications in the apparent electron density values obtained in spatially-integrated measurements are discussed: similar values are obtained for the H_α and Si II lines, while the Fe I line leads to a 25% lower value.     

Ring-opening metathesis polymerization (ROMP) of fullerene-containing monomers in the presence of a first-generation Grubbs catalyst

New norbornene-type monomers containing covalently bound C60 fullerene have been obtained. In the presence of the 1st generation Grubbs catalyst [(PCy₃)₂Cl₂RuCHPh] (Cy is cyclohexyl), these monomers smoothly undergo homopolymerization and copolymerization with parent fullerene-free monomers. The homopolymers are insoluble in common organic solvents, while the copolymers obtained at different molar ratios to their fullerene-free analogues are very soluble in organic solvents and can be suitable for the preparation of thin films.     

Interface characterization of PICVD-coated polymer substrates

The binding structure in the interface region oxide film/polymer has been investigated by means of XPS and is correlated with the adhesion obtained by a Pull Test. Polycarbonate (PC) and diethyleneglycol-bisallylcarbonate (CR39) are employed as substrate and SiO_xC_yH_z-films are deposited by using a pulsed microwave plasma deposition process (PICVD). Best adhesion is obtained by pretreatment of the substrate surface with an O₂-plasma which increases the O/C ratio, in combination with a PICVD-process with low precursor content. Received: 27 July 1996 / Revised: 13 January 1997 / Accepted: 18 January 1997