Study of from the Decay of

The decay of ¹⁴⁰ ₅₇La (40.3 h) to levels in ¹⁴⁰ ₅₈Ce has been studied in the present work. The energies and relative intensities of 37 gamma-rays following the β^? decay of ¹⁴⁰ ₅₇La have been measured with high precision using Ge(Li) and HP.Ge spectrometers. log (ft) values of beta decay were determined from our gamma ray intensities using the beta branchings and a decay scheme is deduced. The sum-peak technique has been used to determine k-conversion coefficient of the transition 1596.41 keV and was found to be 6.98x10^?4 in an excellent agreement with the theoretical value 6.9×10^?4 obtained by Pauli for pure E2 transition.     

THE PREPARATION AND SURFACE CHARACTERIZATION OF AN IDEAL MODEL COLLOID

ABSTRACT

Monodisperse polystyrene latexes were prepared with and without emulsifier using persulfate initiator. The latexes were ion-exchanged with purified Dowex 50W(H⁺)-Dowex 1(0H^?) mixed resin to remove solute electrolyte and adsorbed emulsifier and to convert acidic surface groups to the H⁺ form. Conductometric titration showed that all latexes contained only strong-acid surface groups, presumably the sulfate endgroups of the polymer chains introduced by the persulfate initiator. The sulfate-stabilized latexes (H⁺ form) were hydrolyzed to the hydroxyl form after 2–8 weeks at room temperature or 48–120 hours at 363°K. The rate of the acid-catalyzed hydrolysis is enhanced by increasing the glass contact surface area, by adding Pyrex glass beads. Conductometric titration of the hydrolyzed latexes after ion exchange showed no titratable groups, indicating that the latexes were stabilized by hydroxyl groups. The latexes were oxidized to the carboxyl form by heating the hydroxyl-stabilized latex with persulfate and traces of heavy metal ions or the sulfate-stabilized latex in contact with Pyrex glass beads. For example, latex 520′ prepared without emulsifier using persulfate initiator and bicarbonate buffer contained only strong-acid surface groups after cleaning, no titratable groups after hydrolysis, and only carboxyl groups in the same number as the original sulfate groups after oxidation. Thus the three forms of the latex provide ideal model colloids, rigid monodisperse spheres stabilized with the same number of chemically bound surface groups of three types —strong-acid sulfate, weak- acid carboxyl, and uncharged hydroxyl.     

Dispersion polymerization of styrene in ethanol: Monomer partitioning behavior and locus of polymerization

A thermodynamic model has been proposed for the simulation of monomer partitioning behavior in the dispersion polymerization of styrene in ethanol. The monomer concentration in the polymer particles is very low (20 vol% at 5% conversion) and decreases further as the polymerization proceeds. It is independent of stabilizer concentration but is strongly dependent on initial monomer concentration. The partitio n coefficient ([M_p]/[M_c]) of styrene increases from 0.8 to 1.1 with incresing conversion. There are two polymerization loci in dispersion polymerization, namely the continuous and polymer phases. Competition between solution and heterogeneous polymerization has been observed in this system. The rate of dispersion polymerization is dependent on initial monomer concentration but is independent of initiator concentration at higher conversions. The molecular weight of the polymers produced by this process increases with increasing conversion and decreases with increasing initiator concentration.     

Mathematical modeling of seeded miniemulsion copolymerization for oil-soluble initiator

A mathematical model of seeded miniemulsion copolymerization of styrene-methyl methacrylate for oil-soluble initiator is presented. The mathematical model includes the mass transfer, from the miniemulsion droplets to the polymer particles, by both molecular diffusion and collision between miniemulsion droplets and the polymer particles. The mathematical model also includes the calculation of both the distribution of partices with i radicals and the average number of radicals per particle in the miniemulsion copolymerization using oil-soluble initator. Studies were carried out on the mass transfer coefficients of monomers across the interface between the miniemulsion droplet and the aqueous phase, hexadecane concentration in the miniemulsion droplets, the miniemulsion droplet sizes, and the collision between miniemulsion droplets. The results indicated that the copolymerization of styrene-methyl methacrylate was not a mass transfer controlled process. The mass transfer by collision between miniemulsion droplets and polymer particles plays an important role and was included in the model in order to predict the experimental data of seeded miniemulsion copolymerization.     

Pore structural studies of monodisperse porous polymer particles

Monodisperse polystyrene latex particles with molecular weight on the order of 10⁶ were used as inert diluents for the preparation of monodisperse porous styrene-divinylbenzene copolymer particles via seeded emulsion polymerization techniques. Mercury porosimetry and nitrogen adsorption-desorption isotherms were used to assess pore structure and pore size distribution. Pore size distribution was very sensitive to the molecular weight of the polystyrene latex particles used as inert diluent. Qualitative evidence from the techniques used indicated that the monodisperse porous polymer particles were macroporous (average pore diameter > 500 Å) in nature. As the molecular weight of the linear polymer decreased, the porous structure of the polymer particles ranged in complexity across the spectrum of macro/mesopore structures. Scanning electron microscope results indicated the existence of voids between the microspheres and their agglomerates within the porous polymer particle, and nitrogen adsorption isotherms confirmed that the pores were due to interstices between these crosslinked microspheres and agglomerates.     

Core-shell emulsion copolymerization of styrene and acrylonitrile on polystyrene seed particles

Seeded emulsion copolymerization of an azeotropic composition of styrene (St) and an acrylinitrile (AN) comonomer mixture in polystyrene (PS) seed at different polymerization temperature of 55–75°C were investigated. The kinetic data showed a transition temperature at 65°C, above which the activation energy of polymerization is low, 6.1 Kcal/mol, compared with 9.8 Kcal/mol below it. The particle-size results and thin layer chromatographic (TLC) data showed two types of particle of different composition and morphology in the final latex system: a smaller size of (St–AN) copolymer and a larger size of core-PS and (St–AN) copolymer shell, with a zone of PS grafted (St–AN) copolymer in between. Various polymerization parameters, that is emulsifier concentration, type of seed particle and its size, and monomer/polymer ratio, were studied and their effects on particle size and particle morphology were examined. The percent of grafted core-PS was 10% below a polymerization temperature of 65°C and 40% above that temperature. By adjusting the size and number of the seed particles, monomer-polymer ratio, and emulsifier concentration conditions were established in which a final copolymer latex with “perfect” core-shell morphology was achieved.     

Characterization of surface endgroups in polystrene latexes

The stability against electrolytes for all-sulfate, all-carboxyl, and all-hydroxyl, polystyrene model latexes followed the order, sulfate > carboxyl > hydroxyl when determined from an IR light scattering technique. Two types of hydroxyl endgroups were identified by ¹³C-NMR (chemical shift correlations, and model compound comparisons), for the polystyrene model latexes. One type was due to termination of growing chain with an oligomer with a single monomer unit, and the other due to termination of growing chains. The surface hydroxyl groups of an all-hydroxyl latex were derivatized with hexafluoroacetone, and quantified using ¹⁹F-NMR techniques. Good agreement with the indirect conductometric titration values were obtained.     

Emulsion polymerization of vinyl acetate using a polymerizable surfactant. II. Polymerization mechanism

The mechanism of growth of latex particles in the emulsion polymerization of vinyl acetate using a polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (TREM LF-40; Henkel) was investigated. Both the aqueous phase and the particle/water interface were found to be loci for the copolymerization of TREM LF-40 with vinyl acetate. Competitive growth experiments using TREM LF-40 and its nonpolymerizable derivative were conducted to separate the effects of aqueous phase and particle surface. Particle size analysis of the seeded and unseeded polymerizations coupled with kinetic results suggested that the reactions at the particle/water interface are more important and that the particle size of the latexes is a key parameter controlling the polymerization rate through copolymerization and chain transfer to the polymerizable surfactant at the particle surface. A decrease in particle size lead to an increase in the amount of TREM LF-40 polymerized at the particle surface and to a decrease in polymerization rate. © 1992 John Wiley & Sons, Inc.