Poly(butylene terephthalate)/poly(ε-caprolactone) blends: Influence of PCL molecular mass on PBT melting and crystallization behavior

The isothermal crystallization kinetics and melting behavior of poly(butylene terephthalate) (PBT) in binary blends with poly(ε-caprolactone) (PCL) was investigated as a function of PCL molecular mass by differential scanning calorimetry and optical microscopy. The components are miscible in the melt when oligomeric PCL (M_w = 1250) is blended with PBT, whereas only partial miscibility was found in mixtures with higher molecular mass (M_w = 10,000 and 50,000). The equilibrium melting point of PBT in the homopolymer and in blends with PCL was determined through a non-linear extrapolation of the T_m = f(T_c) curve. The PBT spherulitic growth rate and bulk crystallization rate were found to increase with respect to plain PBT in blends with PCL1250 and PCL10000, whereas addition of PCL50000 causes a reduction of PBT solidification rate. The crystallization induction times were determined by differential scanning calorimetry for all the mixtures through a blank subtraction procedure that allows precise estimation of the crystallization kinetics of fast crystallizing polymers. The results have been discussed on the basis of the Hoffman-Lauritzen crystallization theory and considerations on both the transport of chains towards the crystalline growth front and the energy barrier for the formation of critical nuclei in miscible and partially miscible PBT/PCL mixtures are widely debated.     

Mesoscopic simulation of the aggregation behavior of fluorinated surfactant in aqueous solution

The aggregation behavior of fluorinated surfactant in aqueous solution was investigated using dissipative particle dynamics (DPD) simulation method. Simulation results show that fluorinated surfactants behave mainly as their hydrocarbon analogues, having similar sequences of phases and aggregate structures, which are capable of building micelle, hexagonal phase and lamellar phase. But fluorinated surfactants also show interesting differences from hydrocarbon analogues, which can easily form hexagonal and lamellar structures with comparative little curvature. They can also form ellipsoid or rod-like micelles even in very low concentrations instead of spheroid ones. The dynamic aggregation behavior of fluorinated surfactants, as well as the comparison with hydrogenated ones, was also investigated.     

Effects of Nonionic, Cationic, and Mixed Nonionic-Cationic Surfactants on the Acid-Base Behavior of Phenyl Salicylate

The effects of Brij 35 micelles, CTABr micelles, and mixed Brij 35–CTABr micelles on the acid–base behavior of phenyl salicylate (PST) have been studied in aqueous solution containing 2% v/v acetonitrile. The apparent pK_b (pK^app_b) of PST is decreased by 1.5 pK units with the increase in [Brij 35] from 0 to 0.02 M which is attributed to micellar medium effect. The values of pK^app_b remain almost independent of [CTABr] within its range 0.01–0.03 M. The increase in [CTABr] from 0 to 0.03 M in aqueous solution containing 0.02 M Brij 35 has not resulted in a change in pK^app_b. This shows that the characeristic structural features of nonionic Brij 35 micelles remain essentially unchanged on addition of CTABr under the present experimental conditions.     

Nucleophilic addition of bifunctional sulfimidosulfides to platinum(<Emphasis Type="SmallCaps">IV</Emphasis>)-coordinated nitriles

Reactions of the platinum(IV) nitrile complexes [PtCl₄(RCN)₂] (R = Me, CH₂Ph, Ph) with 1,2- and 1,4-PhS(=NH)C₆H₄SPh in CH₂Cl₂ afforded addition products of sulfimides and coordinated nitriles, viz., the [PtCl₄{NH=C(R)N=S(Ph)(C₆H₄SPh)}₂] complexes. The latter were isolated in 75—90% yields and characterized by elemental analysis, positive-ion FAB mass spectrometry, IR spectroscopy, and ¹H and ¹³C¹H NMR spectroscopy. The temperature dependence of the ¹H NMR spectra of the model [PtCl₄{NH=C(R)N=SPh₂}₂] complexes (R = Me, Et) in CD₂Cl₂ studied in a temperature range from +40 to -70 °C demonstrated that E—Z isomerization of the ligands is a dynamic process in a range from +40 to -10 °C. The activation free energy of this process was calculated.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1618–1622, August, 2004.     

Synthesis of molecular ferromagnetics [R3R′X]MCr(C2O4)3 (X = N,R = Bun,R′ = Prn,Et, Me; X = P,R = Ph,R′ = Bun; M = Mn,Fe, Co,Ni, Cu)

The synthesis, IR spectra, and the temperatures of the transition into a ferromagnetic state (T _c) of layered ferromagnetics [R₃RX[MCr(C₂O₄)₃ (M = Mn, Fe, Co, Cu, and Ni) with the [Ph₃BuP]⁺, [Bu₃RN]⁺ (R = Pr, Et, and Me) cations capable of subsequently changing the distances between metallooxalate layers have been considered. The temperatureT _c has been found to be independent of the size of the organic cation. It is believed that the determining factors in the transition to a ferromagnetic state are exchange interactions inside the metallooxalate layer.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2327–2330, September, 1996.     

Cellulose acetate and polyethersulfone blend ultrafiltration membranes. Part I: Preparation and characterizations

The overall objective of this investigation is to achieve high‐performance membranes with respect to flux and rejection characteristics, with an interplay of blending polymers having desired qualities. Thus, cellulose diacetate and polyethersulfone as candidate materials, in the presence of polyethylene glycol 600 as a pore forming agent, were blended in 100/0, 95/5, 90/10, 85/15, 80,20 and 75/25% compositions using N,N′‐dimethylformamide as solvent and membranes were prepared by the phase inversion technique. Polymer blend composition, additive concentration, and casting and gelation conditions were standardized for the preparation of asymmetric membranes with various pore statistics and morphology. These blend membranes were characterized for compaction in ultrafiltration experiments at 414 kPa pressure in order to attain steady state flux and is reached within 4–5 hr. The pure water flux was measured at 345 kPa pressure and is determined largely by the composition of polyethersulfone and additive concentration. The flux was found to reach the highest values of 66.5 and 275 1/(cm² hr) at 0 and 10 wt% additive concentrations respectively, at 25% SPS content of the blend. Membrane hydraulic resistance derived by measuring water flux at various transmembrane pressure and by using an algorithm was found to be inversely proportional to pure water flux. Water content is estimated by simple drying and weighing procedures and found proportional to pure water flux for all the membranes. The molecular weight cut‐offs (MWCOs) of different membranes were determined with proteins of different molecular weights and found to vary from 20–69 kDa (globular proteins) depending on the PEG and SPS content in the casting dope. Skin surface porosity of the membranes were analyzed by scanning the frozen membrane samples using scanning electron microscopy (SEM) at different magnifications. The surface porosity is in direct correlation to the MWCO derived from solute retention experiments. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of interacting nanoparticles on the ordered morphology of block copolymer/nanoparticle mixtures

We investigated the effect of hard additives, that is, magnetic nanoparticles (NPs) and metal NPs, on the ordered morphology of block copolymers by varying the NP concentration. To characterize the structural changes of a block copolymer associated with different NP loadings, small-angle X-ray scattering and transmission electron microscopy were performed. Monodisperse maghemite (γ-Fe₂O₃) NPs (7 nm in diameter) and silver (Ag) NPs (6 nm in diameter) with surfaces modified with oleic acids were synthesized, and a cylinder-forming poly(styrene-block-isoprene) diblock copolymer was used as a structure-directing matrix for the NPs. As the NP concentration increased, domains of NP aggregates were observed for both magnetic and metal NPs. In the case of mixtures of cylinder-forming poly(styrene-block-isoprene) and Ag NPs with weak particle–particle interactions, random aggregates of Ag NPs were observed, and the ordered morphology of the block copolymer lost its long-range order with an increase in the NP concentration. However, regular, latticelike aggregates obtained with γ-Fe₂O₃ NPs, because of the strong interparticle interactions, induced an intriguing morphological transformation from hexagonal cylinders to body-centered-cubic spheres via undulated cylinders, whereas the neat block copolymer did not show such a morphological transition over a wide range of temperatures. The interplay between magnetic NPs and the block copolymer was also tested with magnetic NPs of different sizes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3571–3579, 2006     

Swelling behavior of ionically cross-linked polyampholytic hydrogels in varied salt solutions

Ionically cross-linked polyampholytic hydrogels were synthesized by redox copolymerization of acrylamide and an ionic complex of (N,N-diethylamino)ethyl methacrylate and acrylic acid (designated as PADA hydrogel). The swelling behavior of the hydrogels in water indicated that a minimal equilibrium swelling ratio is found when the molar ratio of anionic/cationic monomers was 1.55. In NaCl solution, the hydrogels exhibited the typical swelling behavior of conventional polyampholytic gels. Their equilibrium swelling ratios increased with an increase in the NaCl concentration. In solutions of multivalent ions (CaCl₂ and trisodium citrate solutions), the equilibrium swelling ratios of the hydrogels increased first and were then followed by a decrease with an increase in salt concentration. Interestingly, an unexpected abrupt swelling phenomenon was observed when the fully swollen hydrogels in salt solution were transmitted to pure water. The unique swelling behavior of PADA hydrogels depends not only on the molar ratio of the anionic/cationic monomers but also on the valency of the ions.     

Rheological Behavior for Mica-filled Polypropylene Composite Melts

The study on rheological properties of a series of mica-filled polypropylene (PP) composites was carried out. The influence of surface-treatment of mica particles on dynamic rheological behavior of the composites were dealt with. The viscosity (η) and dynamic modulus ( G‘ ) of the composite melts were higher than those of PP matrix, especially those for systems treated with silane, which was attributed to the interfacial adhesion enhancement. However, surface-treatment of mica by titanate resulted in lower η and G‘, as compared with the treatment by silane. The reason for this is believed to be the formation of the mono-molecular layer on the mica surface.     

Effect of polarization on the electrode behavior and microstructure of (La,Sr)MnO<Subscript>3</Subscript> electrodes of solid oxide fuel cells

The electrode behavior and microstructure of freshly prepared (La_0.8Sr_0.2)_0.9MnO₃ (LSM) electrodes were investigated under various polarization conditions. The original, large agglomerates in freshly prepared LSM electrodes were broken down into sphere-shaped grains when exposed to cathodic or anodic current passage of 200 mA cm^–2 at 800 °C in air for 3 h. Microstructural changes under cathodic polarization could be related to the pronounced diffusion and migration of oxygen vacancies and Mn ions on the LSM surface and lattice expansion, while lattice shrinkage under oxidation conditions most likely contributes to the structural changes under anodic polarization. Such morphological changes were irreversible and were found to be beneficial to the performance of freshly prepared LSM electrodes. Freshly prepared LSM electrodes behaved very differently with respect to the cathodic and anodic current passage treatment.