Phasenbeziehungen und Natriumionenleitung im quasi-binären System Na2SiF6/Na3AlF6

Phase Relations and Sodium Ion Conductivity within the Quasi-binary System Na₂SiF₆/Na₂AIF₆ . The phase diagram of the Na₂SiF₆/Na₃AlF₆ system has been determined by means of x-ray powder diffraction, thermal analysis and conductivity measurements in the sub-solidus region. Na₃AlF₆ accomodates up to 73 mol.-% Na₂SiF₆ maintaining the crystal structure type. The sodium ion conductivity increases by about five orders of magnitude upon doping Na₃AlF₆ with Na₂SiF₆.     

Effects of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] on the charge distributions of low‐density polyethylene/polystyrene blends

The effect of the triblock copolymer poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) on the formation of the space charge of immiscible low‐density polyethylene (LDPE)/polystyrene (PS) blends was investigated. Blends of 70/30 (wt %) LDPE/PS were prepared through melt blending in an internal mixer at a blend temperature of 220 °C. The amount of charge that accumulated in the 70% LDPE/30% PS blends decreased when the SEBS content increased up to 10 wt %. For compatibilized and uncompatibilized blends, no significant change in the degree of crystallinity of LDPE in the blends was observed, and so the effect of crystallization on the space charge distribution could be excluded. Morphological observations showed that the addition of SEBS resulted in a domain size reduction of the dispersed PS phase and better interfacial adhesion between the LDPE and PS phases. The location of SEBS at a domain interface enabled charges to migrate from one phase to the other via the domain interface and, therefore, resulted in a significant decrease in the amount of space charge for the LDPE/PS blends with SEBS. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2813–2820, 2004     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Deformation of styrene—divinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk deformation in these processes was studied for a series of cross-linked polymers, viz., gel-type and porous styrene—divinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differences in their physical structures. An unusual effect of a sharp decrease followed by a temporary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–476, March, 2007.     

硫酰胺的快速分析（Ⅱ） 

硫酰胺生产过程中副产的大量氯化铵要干扰硫酰胺的测定，采用四苯硼钠将全部氯化铵呈沉淀析出，再用次溴酸钠把滤液中的硫酰胺分解成氮气，测其体积，计算出硫酰胺的含量。对样品进行测定的结果表明，该法重现性好、准确度高、分析周期在３５ｍｉｎ内，相对误差在±１％以内。     

Influence of heat treatment conditions on the porosity changes of sulfonated styrene/divinylbenzene copolymers

Sulfonic cation exchangers with two ion exchange group concentrations (0.5 and 2.4 mmol/g, samples A and B, respectively) were obtained by sulfonation of a porous styrene (S) and divinylbenzene (DVB) copolymer with chlorosulfonic acid. Strong thermal decomposition of the sulfonated copolymer A, accompanied by significant changes in its porous structure, starts at ca. 400°C. The char has no sulfonic groups. After heat treatment at 400°C in steam, a sorbent was obtained (yield 65%) that shows higher phenol sorption than the untreated sample when related to the bed volume. The chlorosulfonic derivatives of the initial copolymer were less thermally resistant than the sulfonic ones obtained by hydrolysis. Pyrolysis of the cation exchanger B, in its H+ and Ca²⁺ forms, was carried out at 900°C (yield of both chars close to 30%). By subsequent steam activation at 800°C to a 50% burn-off of the char, sorbents with well-developed, but distinctly different, porous structures were obtained. The activated char from the sulfonated copolymer in its hydrogen form was highly microporous and indicated an effective surface area of 1180 m²/g. However, because of a low contribution of mesopores, its ability to adsorb phenol from the liquid phase was not very high. The activated char from the calcium-doped copolymer, indicating a smaller surface area (580 m²/g) but characterized by a well-developed mesoporosity, was a better sorbent for phenol. © 1994 John Wiley & Sons, Inc.     

Difference in micellar properties of sodium dodecyl sulfonate from sodium 4-decyl naphthalene sulfonate in D2O solution studied by 1H NMR relaxation and 2D NOESY

¹H chemical shift changes of sodium 4-decyl naphthalene sulfonate (SDNS) at 313 K show that its critical micellar concentration lies between 0.82 and 0.92 mmol/dm³, which is in the same range as that of the previous study at 298 K. The spin–lattice relaxation time, spin–spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy experiments give information about the structure of the SDNS micelle and the dynamics of the molecules in the micelle. The size of the SDNS micelle remains almost unchanged in the temperature range from 298 to 313 K as deduced by analyzing the self-diffusion coefficient. Special arrangement of the naphthyl rings of SDNS in the micelles affects the packing of these hydrophobic chains. The methylene groups of the alkyl chain nearest the naphthalene groups penetrate into the aromatic region, which results in a more tightly packed hydrophobic micellar core than that of sodium dodecyl sulfonate.     

Ab initio study of sodium intercalation into metal oxides

Using the full-potential linearized augmented plane wave (FP-LAPW) method, we have studied the effect of chemistry on the average intercalation voltage (AIV) caused by the Na ions intercalating into transition metal oxides. The effect of transition metal was systematically studied by varying M=Co, Ni and Mn in NaMO₂ and fixing the α-NaFeO₂ layered structure. The effect of the guest atoms into the host material is discussed in terms of the structural and electronic properties. Comparatively to Li intercalation, a significant electron transfer towards transition metal was found. This observation suggests that the transition metal contribute to the AIV determination and confirms the common assumption that intercalated electron reduces M⁴⁺ to M³⁺.     

Oxidative Coupling of Thiols to Disulfides with Ti(IV) in the Presence of NaI under Air Atmosphere

Ti(IV) as TiCl₃(O₃SCF₃) and TiO(O₂CCF₃)₂ are used as efficient catalysts for oxidative coupling of aliphatic, aromatic and heteroaromatic thiols to their disulfides in the presence of NaI under air atmosphere.     

Sterically stabilized emulsion polymerization of styrene: Pseudo‐semicontinuous approach

The sterically stabilized emulsion polymerization of styrene initiated by a water‐soluble initiator at different temperatures has been investigated. The rate of polymerization (R_p) versus conversion curve shows the two non‐stationary‐rate intervals typical for the polymerization proceeding under non‐stationary‐state conditions. The shape of the R_p versus conversion curve results from two opposite effects—the increased number of particles and the decreased monomer concentration at reaction loci as the polymerization advances. At elevated temperatures the monomer emulsion equilibrates to a two‐phase or three‐phase system. The upper phase is transparent (monomer), and the lower one is blue colored, typical for microemulsion. After stirring such a multiphase system and initiation of polymerization, the initial coarse polymer emulsion was formed. The average size of monomer/polymer particles strongly decreased up to about 40% conversion and then leveled off. The initial large particles are assumed to be highly monomer‐swollen particles formed by the heteroagglomeration of unstable polymer particles and monomer droplets. The size of the “highly monomer” swollen particles continuously decreases with conversion, and they merge with the growing particles at about 40–50% conversion. The monomer droplets and/or large highly monomer‐swollen polymer particles also serve as a reservoir of monomer and emulsifier. The continuous release of nonionic (hydrophobic) emulsifier from the monomer phase increases the colloidal stability of primary particles and the number of polymer particles, that is, the particle nucleation is shifted to the higher conversion region. Variations of the square and cube of the mean droplet radius with aging time indicate that neither the coalescence nor the Ostwald ripening is the main driving force for the droplet instability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 804–820, 2003