Preparation of large-area sources with uniform layers for the spectrometry of alpha-emitting nuclides

A procedure for the preparation of large-area sources with uniform layers for α-spectrometry for the large-area grid ionization chamber has been developed. It is based on the direct evaporation of a sample solution in the counting dish in the presence of an excess of a sublimable chemical compound like ammonium nitrate. In the course of evaporation this excess compound precipitates and thus avoids the formation of clusters during the further evaporation process. After dryness, the excess compound is removed from the source by sublimation. Samarium nitrate is added as an internal standard and the alpha-activity of the isotope¹⁴⁷Sm is chosen to measure the counting efficiency due to self-absorption. Examples are presented of the application of large-area sources for α-spectrometry for the large-area grid ionization chamber.     

Evaporation/Precipitation from a W/O Microemulsion Base

The evaporation path in a microemulsion base of water, sodium dodecylsulfate, and pentanol was extended to include the subsequent precipitation stage caused by the restriction of the surfactant solubility. The results revealed the surfactant to be the only compound to precipitate during the evaporation/precipitation stage; the relative content of the two volatile compounds in the liquid phase was adjusted to the required level by the evaporation.     

On the volatility of ruthenium

When annealing the evaporation residue formed by evaporating a solution containing ruthenium, phosphates and nitrates, ruthenium volatilizes. The amount of volatilized ruthenium (both¹⁰⁶Ru traces and milligram amuonts of Ru) depends on the solution composition before evaporation and on the temperature and time of annealing. Volatility occurs at a temperature as low as 300°C. We suppose that the volatility is due to thermal decomposition of the ruthenium compounds with phosphates. The released atoms of ruthenium are oxidized by the decomposition products of the nitrate. The formation of complex compounds of ruthenium with phosphates during the evaporation of the solution follows from the data of elemental and spectral analysis and ion exchange chromatography.     

On the nature of decrease in the particles size of nanostructured nickel oxide obtained by the sol-gel method in the presence of surfactants

A processes of formation of nanostructured powders of nickel oxide by annealing in the temperature range of 200–700°C of the nickel hydroxide obtained by the sol-gel method at 80°C from solutions of nickel nitrate by precipitation with alkali in the presence of surfactant AF-12 (polyethylene oxide alkylphenyl ether) was investigated. The formation of nanostructured powders of nickel oxide in the presence of a surfactant reduces the size of nanoparticles to 20–25 nm, which is 1.5 times smaller than the particles obtained without a surfactant. The effective influence of surfactant on the particle size begins in the temperature range of its decomposition and evaporation equal 350–400°C.     

Revisiting the Solubility Concept of Pharmaceutical Compounds

Summary.  The kinetic and thermodynamic solubilities of Roche (Ro) pharmaceutical compounds were determined by HPLC, titrimetry, and UV/Vis spectroscopy in aqueous buffers and in non-buffered systems. For kinetic solubility, a turbidimetric method that allows the rapid determination of solubilities using small amounts of compounds (5–50 mg) was used. Two types of precipitation were observed during the kinetic solubility determinations: i) a disperse precipitation where the solution became foggy with very small particles uniformly distributed in the solution, and ii) discrete precipitation characterized by formation of crystals that rapidly sediment. The thermodynamic solubility was determined by shake flask and titrimetrically using a pH-STAT. The pH-STAT titrimetric method for the pH-thermodynamic solubility profile determination eliminates the buffer species and represents a new way to approach the solubility characterization of pharmaceutical compounds. The strengths of the turbidimetric method for determining the kinetic solubility are its rapidity, minimal compound requirements, and suitability for high throughput screening. The limitations are that the maximum solubility is limited to less than 100 mg · cm⁻³, and the precipitation of trace impurities cannot be distinguished from precipitation of the analyte. The pH-STAT titrimetric approach for the thermodynamic solubility has a lower throughput and is suitable for the characterization of the lead candidate. It is not limited in its solubility range and provides a common basis for the comparison of the solubility values at different pH values in contrast to traditional buffered systems. Received August 21, 2000. Accepted (revised) February 5, 2001     

Liesegang patterns: Estimation of diffusion coefficient and a plausible justification for colloid explanation

The Liesegang phenomenon is interpreted as a moving boundary problem. The existing time law, spacing law, and width law are revisited and reformulated on the basis of the new scenario. A better understanding of the basic facts associated with pattern formation is made possible with the new concept. The phenomenon is explained on the basis of colloidal kinetics. Diffusion coefficients of the outer electrolyte in the gel for various experiments in the literature are calculated. The diffusion coefficients so calculated range from 1.792-5.996᎒^-10 m² s^-1. It is suggested that such values confirm the fast colloidal dynamics during the process of periodic precipitation pattern formation.     

A model for the drying process during film formation in waterborne acrylic coatings

Establishing drying mechanisms during film formation in waterborne acrylic coatings is a technologically important problem, however complex, and still poorly understood. A model for the prediction of evaporation kinetics is proposed in this paper, where films are supposed to dry normally with respect to the film surface, and a drying front separates a top dry region from a bottom wet region. The model accounts for the competition between water evaporation and particle diffusion that determines the degree of vertical homogeneity, but also for the competition between water evaporation and particle deformation that ultimately establishes the rate-determining step in film formation processes. The model was validated by performing gravimetric water-loss experiments on latexes of acrylic polymers of various composition, various particle size and stabilizing systems, under different environmental temperatures and humidity, and various initial film thicknesses in order to evaluate the effect of the different factors that can in principle influence the film formation process.     

Prevention of evaporation of small-volume sample solutions for capillary electrophoresis using a mineral-oil overlay.

The suppression of evaporation of water from small volumes of sample solutions or reagents for capillary electrophoresis by the use of a mineral-oil overlay was investigated in affinophoresis applications, in which the affinity constant of a mutant protein of recombinant human galectin-1 to a lactose affinophore, a triply negative charged ion having a lactoside as an affinity ligand, was determined. When an injection was carried out from a minimum of 20 microL of an aqueous solution beneath the oil overlay, no oil contamination inside the capillary was observed, provided the capillary was cleanly cut so that the end was flat, and the polyimide coating had been removed for a distance of about 2 mm from the end. Affinophoresis was carried out using 20 microL of an affinophore solution covered with an oil overlay. The abnormalities in the electropherograms as the result of the evaporation of the water from the solution during storage prior to use in an automatic operation of a capillary electrophoresis instrument were suppressed, with respect to the formation of a base line gap, an increase in the detection time of a marker ion and an increase in the initial current. A solution in a vial could be used repeatedly for a longer period of time when overlaid with mineral oil than in the absence of an overlay. The use of a mineral-oil overlay is a simple but very efficient technique for solving the problem of the evaporation of water from small volumes of aqueous solutions for use in capillary electrophoresis.     

Thermal and FTIR spectral studies of various proportions of zinc magnesium ammonium sulfate

Mixed crystals of various proportions of zinc magnesium ammonium sulfate were grown by slow evaporation of aqueous solution at room temperature. The bright and transparent crystals obtained were characterized through thermal (TG–DTA) and FTIR spectral analyses. A fitting decomposition pattern for the compound was formulated on the TG curve which shows two stage mass losses between 133 and 478.75 °C. DTA curve shows exothermic peaks in this temperature range supporting the formulated decomposition pattern. The FTIR spectra show the vibration frequencies due to the formation of zinc magnesium ammonium sulfate mixed crystals. Detailed structural analysis of the compound is under progress.     

An improved model for mass transfer during the formation of polymeric membranes by the immersion-precipitation process

An analysis is presented, which describes the isothermal ternary diffusion process encountered in the formation of a cellulose acetate polymeric membrane by a direct immersion-precipitation of polymeric solutions in a nonsolvent bath. A material coordinate was employed to derive the mass transfer equations for the membrane solution and the convective mass transfer in the coagulation bath was taken into account by solving the hydrodynamic boundary layer equations. Diffusion coefficients were measured and used to deduce ternary phenomenological coefficients. The computed results are found to agree with the experimental precipitation time and membrane morphologies observed in scanning electron photomicrographs. © 1994 John Wiley & Sons, Inc.     

Growth and characterization of 0.1 and 0.25 zinc magnesium ammonium sulphate

Mixed crystals of 0.1 and 0.25 zinc magnesium ammonium sulphate were grown by slow evaporation of aqueous solution at room temperature. The bright and transparent crystals obtained were characterized by thermal (TG–DTA), FTIR and XRD analyses. A fitting decomposition pattern for the compound was formulated on the TG curve which shows two stage mass losses between 133 and 478.75 °C. In this temperature range, DTA curve shows exothermic peaks supporting the formulated decomposition pattern. The FTIR spectra show the vibration frequencies due to the formation of zinc magnesium ammonium sulphate mixed crystals. Detailed structural analysis of the compound is under progress.     

Preparation of Core‐Sheath Composite Nanofibers by Emulsion Electrospinning

Summary: Uniform core‐sheath nanofibers are prepared by electrospinning a water‐in‐oil emulsion in which the aqueous phase consists of a poly(ethylene oxide) (PEO) solution in water and the oily phase is a chloroform solution of an amphiphilic poly(ethylene glycol)‐poly(L ‐lactic acid) (PEG‐PLA) diblock copolymer. The obtained fibers are composed of a PEO core and a PEG‐PLA sheath with a sharp boundary in between. By adjusting the emulsion composition and the emulsification parameters, the overall fiber size and the relative diameters of the core and the sheath can be changed. A mechanism is proposed to explain the process of transformation from the emulsion to the core‐sheath fibers, i.e., the stretching and evaporation induced de‐emulsification. In principle, this process can be applied to other systems to prepare core‐sheath fibers in place of concentric electrospinning and it is especially suitable for fabricating composite nanofibers that contain water‐soluble drugs.

Schematic mechanism for the formation of core‐sheath composite fibers during emulsion electrospinning.     

Rescaling the dynamics of evaporating drops

The dynamics of evaporation of wetting droplets is investigated experimentally in an extended range of drop sizes to provide trends relevant for a theoretical analysis. A model is proposed, which generalizes Tanner's law in the presence of evaporation. A qualitative agreement is obtained, which represents a first step toward the solution of a very old, complex problem.     

Phase behaviour of binary mixtures of colloidal charged spheres

As a step towards the modelling of binary metal alloys we here report on the shape of the phase boundary of two deionized charged sphere colloidal suspensions as a function of mixing ratio and particle density. Their size ratios are r = 0.68 and r = 0.56. Both aqueous suspensions of polystyrene copolymer spheres crystallize in a body-centred cubic structure. Interesting differences in the shape of the phase boundary are observed. In the first case a peaked increase of crystal stability was observed for a mixing ratio of p = 0.2–0.3, which gives the fraction of small spheres. Also in the second case the stability of the crystalline phase is larger than expected for an ideal solid solution but over a more extended range of small p. In addition at p = 0.7–0.8 we find a pronounced suppression of crystallization and furthermore some indications of a precipitation of one species at p = 0.9. While the first phase diagram resembles that of a solid solution with possibly the onset of compound formation, the second more resembles a eutectic.     

Computer‐Aided Estimation of Diffusion Coefficients in Non‐Solvent/Polymer Systems

A novel method for estimating the mutual and self‐diffusion coefficients of a non‐solvent/polymer system is proposed in this work. The idea is to study the evaporation process from non‐solvent/solvent/polymer systems as a one‐dimensional numerical experiment and to use polymer solution weight versus time data to fit the unknown parameters of the diffusion‐coefficient correlations based on free‐volume theory. For this purpose, the evaporation process is modeled as a coupled heat‐ and mass‐transfer problem with a moving boundary, and the Galerkin finite‐element method is used to solve simultaneously the non‐linear governing equations. This method is successfully applied to the estimation of water–cellulose acetate diffusion coefficients and is valid over the whole range of temperatures and concentrations for practical applications in membrane technology. Additionally, there is a detailed discussion on if water affects the morphology of the final cellulosic membrane by studying the concentration profiles of the constituents of the casting solution.     

Modeling of asymmetric membrane formation by dry-casting method

Many polymeric membranes are produced by phase inversion technique invented by Loeb and Sourirajan in 1962. The dry-casting method is one of the major phase inversion techniques in which a homogeneous polymer solution consisting of solvent(s) and nonsolvent(s) is cast on a support and then evaporation of the casting solution takes place under convective conditions. In this paper, we model membrane formation by the dry-casting method. The model takes into account film shrinkage, evaporative cooling, coupled heat, and mass transfer and incorporates practical and reliable diffusion theory as well as complex boundary conditions especially at the polymer solution/air interface. The predictions from the model provide composition paths, temperature, and thickness of the solution. By plotting the composition paths on the ternary phase diagram, we ascertain the general structural characteristics of the membranes prepared from particular casting conditions. The predictive ability of the model was evaluated by comparing the results with the experimental data obtained from gravimetric measurements for cellulose acetate (CA)–acetone–water system. In an attempt to illustrate the importance of diffusion formalism on the predictions, recently proposed multicomponent diffusion theory and its simplified forms were utilized in the model. The computational results show that the critical factor for capturing the accurate behavior of membrane formation is the diffusion formalism utilized in the model.     

Onset of Marangoni convection for evaporating sessile droplets

We have generated stability parameters using a linear stability analysis to predict the onset criteria for Marangoni convection in evaporating sessile droplets for two types of substrates, insulating and conducting. The stability problem was formulated with boundary conditions that allow for a temperature discontinuity at the liquid-vapour interface and the inclusion of an expression for the evaporation flux that considers this temperature discontinuity. We introduce no fitting coefficients; therefore, the stability parameters we generate contain only physical variables. The results indicate that spherical sessile droplets evaporating on insulating substrates are predicted to have a similar onset criteria with sessile droplets evaporating on conducting substrates. The onset prediction for sessile droplets evaporating on insulating substrates is found to be considerably different than the case of liquids evaporating from conical funnels constructed of insulating materials owing to the modification of the boundary condition from the geometrical shift and the corresponding retention of modes in the solution. A parametric analysis demonstrates how the input variables impact the stability of evaporating sessile droplets.     

Membrane formation by isothermal precipitation in polyamide-formic acid-water systems II. Precipitation dynamics

An analysis is presented, which describes the isothermal ternary diffusion process encountered in the formation of the aliphatic polyamide membranes such as Nylon-66 by direct immersion-precipitation of a polymeric solution in a nonsolvent bath. A material coordinate is employed to derive the mass transfer equations for the membrane solution. The convective mass transfer in the coagulation bath is taken into account by solving the hydrodynamic boundary layer equations. Diffusion coefficients were measured and used to deduce ternary phenomenological coefficients. The computed results are found to agree with measured precipitation times and with membrane morphologies observed by scanning electron photomicrographs. © 1995 John Wiley & Sons, Inc.     

Aggregation of primary nano and microparticles resulting in formation of hollow structures

It was demonstrated that the formation of preparations of hollow structures in oversaturated vapor or solution, varying from several micrometers to several tens millimeters in size, can be due to the following causes: (a) fast evaporation of the solvent from microdrops of the solution and crystallization of the dissolved substance in subsurface layer of a drop; (b) a chemical reaction between the substance in a drop and a substance in the environment surrounding the drop; (c) aggregation of primary nanoparticles in agitated aqueous suspension; (d) aggregation of particles produced in thermohydrolysis of the solid initial compound. Examples of hollow particle preparations matching the mechanisms indicated above are presented and their peculiarities are discussed.     

Synthesis of a magnetoactive compound by the interaction of iron(II) sulfate with potassium chromate

A study was made of the effect of synthesis conditions on the properties of a magnetoactive compound obtained by the interaction of iron(II) sulfate with potassium chromate. It was found that, in the formation of the magnetoactive compound, chromium is almost completely coprecipitates with the solid phase. To produce the magnetoactive compound with high relative magnetic susceptibility, it is necessary to precipitate it from the initial solution in no less than 10 min after its preparation at a K₂CrO₄: FeSO₄ molar ratio of 0.16–0.18.