Study on the origin of inverted phase in drying solution-cast block copolymer films

In a previous study, we reported observation of the novel inverted phase (the minority blocks comprising the continuum phase) in kinetically controlled phase separating solution-cast poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer films [Zhang et al. Macromolecules 2000, 33, 9561-7]. In this study, we adopt the same approach to investigate the formation of inverted phase in a series of solution-cast poly(styrene-b-butadiene) (SB) asymmetric diblock copolymers having nearly equal polystyrene (PS) weight fraction (about 30 wt %) but different molecular weights. The microstructure of the solution-cast block copolymer films resulting from different solvent evaporation rates, R, was inspected, from which the kinetically frozen-in phase structures at qualitatively different block copolymer concentrations and correspondingly different effective interaction parameter, chieff, can be deduced. Our result shows that there is a threshold molecular weight or range of molecular weight below which the unusual inverted phase is accessible by controlling the solvent evaporation rate. In comparing the present result with that of our previous study on the SBS triblock copolymer, we find that the formation of the inverted phase has little bearing on the chain architecture. We performed numerical calculations for the free energy of block copolymer cylinders and found that the normal phase is always preferred irrespective of the interaction parameter and molecular weight, which suggests the formation of the inverted phase to have a kinetic origin.

Liquid-liquid phase behavior of toluene/polyethylene oxide/poly(ethyleneoxide-b-dimethylsiloxane) polymer-containing ternary mixtures

The experimental data of phase diagrams for both polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) binary and toluene/polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) ternary polymer-containing systems was obtained at atmosphere pressure by light scattering method. The critical points for some pre-selected compositions and the pressure effect on the phase transition behavior of ternary system were investigated by turbidity measurements. The chosen system is a mixture of ternary which is one of the very few abnormal polymer-containing systems exhibiting pressure-induced both miscibility and immiscibility. This unusual behavior is related to the toluene concentration in the mixtures. The effect of toluene on the phase transition behavior of the ternary polymer-containing mixture was traced. Such behavior can make it possible to process composite materials from incompatible polymers.

Thermodynamics of phase behavior in PEO/P(EO-b-DMS) homopolymer and block co-oligomer mixtures under pressure

The cloud-point temperatures (T-cl's) of poly(ethylene oxide) (PEO) and poly(ethylene oxide)-block-polydimethylsiloxane (P(EO-b-DMS)) homopolymer and block-oligomer mixtures were determined by turbidity measurements over a range of temperatures (105 to 130degrees), pressures (1 to 800 bar), and compositions (10-40 wt.-% PEO). The system phase separates upon cooling and T-cl was found to decrease with an increase in pressure for a constant composition. In the absence of special effects, this finding indicates negative excess volumes. Special attention was paid to the demixing temperatures as a function of the pressure for the different polymer mixtures and the plots in the T-phi plane (where phi signifies volume fractions). The cloud-point curves of the polymer mixture under pressures were observed for different compositions. The Sanchez-Lacombe (SL) lattice fluid theory was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalphy of mixing, and the volume changes of mixing. The calculated results show that modified P(EO-b-DMS) scaling parameters with the new combining rules can describe the thermodynamics of the PEO/P(EO-b-DMS) system well with the SL theory.

Three-phase extraction study in the Cyanex923-n-heptane/HNO3 system

The present paper reports a study of the extraction of HNO3 with Cyancx923 (C923)-n-heptane. A third phase appears at different aqueous HNO3 concentrations for various initial C923 concentrations. Data analysis indicates that almost all of HNO3 and H2O are extracted into the middle phase. More HNO3 and water at a fixed ratio are solubilized in the reverse micelles or microemulsion in the third phase, which leads to a sharp increase of their concentration. The effect of temperature on the phase behavior of the three-phase system has also been investigated.

Separation of scandium, yttrium and lanthanum in high-performance centrifugal partition chromatography with S-octyl phenyloxy acetic acid

Separation of scandium(III), yttrium(III) and lanthanum(III) was performed by high-performance centrifugal partition chromatography (HPCPC) employing the stationary phase of S-octyl phenyloxy acetic acid (CA-12). The liquid-liquid extraction behavior of CA-12 for Sc(III), Y(III) and La(III), the acidity of aqueous phase, and the operation conditions of HPCPC were examined. The retention volume (V-R) increased with the order of Y(III), La(III) and Sc(III) accompanied with the elution of the mobile phase in different pH, which is lowered from 4.6 to 2.1.

Capillary electrophoresis with amperometric detection of curcumin in Chinese herbal medicine pretreated by solid-phase extraction

In the present study, curcumin from Chinese herbal medicine turmeric was determined by capillary electrophoresis with amperometric detection (CE-AD) pretreated by a self-designed, simple, inexpensive solid-phase extraction (SPE) cartridge based on the material of tributyl phosphate resin. An average concentration factor of 9 with the recovery of >80% was achieved when applied to the analysis of curcumin in extracts of turmeric. Under the optimized CE-AD conditions: a running buffer composed of 15 mM phosphate buffer at a pH 9.7, separation voltage at 16 W, injection for 6 s at 9 W and detection at 1.20 V, CE-AD with SPE exhibited low detection limit as 3 - 10(-8) mol/l (SIN = 3), high efficiency of 1.0(.)10(5) N, linear range of 7(.)10(-4) -3(.)10(-6) mol/l (r = 0.9986) for curcumin extracted from light petroleum. The method developed resulted in enhancement of the detection sensitivity and reduction of interference from sample matrix in complicated samples and exhibited the potential application for routine analysis, especially in food, because a relatively complete process of sample treatment and analysis was described.

Monte Carlo simulation of phase behavior of polymer blends with special interactions

Full Paper: The phase, behavior of A-B-random copolymer/C-homopolymer, blends with special interaction was studied by a. Monte, Carlo simulation in two dimensions. The interaction between I segment A and segment C was repulsive, whereas it was attractive between segment B and segment C. The simulation results showed that the blend became two large co-continuous phase domains at lower segment-B component compositions, indicating that the blend showed spinodal decomposition. With an increase of the segment-B component, the miscibility between the copolymer,and the polymer was gradually improved up to being miscible. In addition, it was found that segment B tended to move to the surface of the copolymer phase in the case of a lower component of segment B. On the other hand, if was observed that the average, end-to-end distances ((h) over bar) for both copolymer and polymer changed slowly with increasing segment-B component of the copolymer up to 40%, thereafter they increased considerably with increasing segment B component. Moreover, it was found that the (h) over bar of the copolymer was obviously shorter than that of the homopolymer for the segment-B composition, region from 0% to 80%. Finally, a, phase diagram showing I phase and - II phase regions under the condition of constant-temperature is presented.

Separation of zinc(II) from europium(III) by using hollow fiber membrane

Extraction and separation of Eu3+ and Zn2+ in sulfuric acid solution was investigated by hollow fiber membrane with cyanex 302 (bis (2,4,4-trimethylpentyl) monothiophosphinic acid) in counter-currently circulating operation. Reaction mechanism of membrane extraction and effect of extractant concentration and H+ concentration in aqueous phase on the mass transfer coefficient were discussed. It can be concluded that Zn2+ can be extracted completely from Eu3+ sulfate solution according to the kinetics competing difference. In one extractor process, extraction percentage of Zn2+ was not completely and Eu3+ was not extracted. Extraction percentage of Zn2+ reached 94.92%, but Eu3+ only reached 8.59% after 100 minutes extraction in two series connectors and that of Zn2+ and Eu3+ reached 99.9% and 6.53% respectively after 40 minutes extraction in three series connectors.

The effect of KSCN on the partition of proteins in polyethylene glycol/(NH4)(2)SO4 aqueous two-phase system

The effect of potassium thiocyanate on the partitioning of lysozyme and BSA in polyethylene glycol 2000/ammonium sulfate aqueous two-phase system has been investigated. As a result of the addition of potassium thiocyanate to the PEG/ammonium sulfate system, the PEG/mixed salts aqueous two-phase system was formed. It was found that the potassium thiocyanate could alter the pH difference between the two phases, and, thus, influence the partition coefficients of the differently charged proteins. The relationship between partition coefficient of the proteins and pH difference between two phases has been discussed. It was proposed that the pH difference between two phases could be employed as the measurement of electrostatic driving force for the partitioning of charged proteins in polyethylene glycol 2000/ammonium sulfate aqueous two-phase system.

Mixing enthalpy and phase behavior of PEO/PVAc blends

Phase behaviors and heats of mixing of the miscible blends of poly(ethylene oxide) (PEO) and poly(vinyl acetate) (PVAc) with different molecular weights were investigated by DSC. A method proposed by Natasohn and Ebert et al. was adopted to estimate the binodal temperatures and the enthalpies of mixing from onset temperatures and values of areas of a series of endothermic peaks (corresponding to heats of demixing), respectively, in their heating scanning thermograms obtained with different heating rates. Phase diagrams and heats of mixing of this blending system were also predicted by using Sanchez-Lacombe lattice fluid theory. A very good agreement was obtained for both. phase behaviors and heats of mixing obtained with two different methods.

Separation of Th4+ and RE3+ with hollow fiber extraction

Separation of Th4+ and RE3+ was investigated by hollow fiber membrane extraction with N1923 in countercurrent recirculating operation. The effect of Hf concentration in aqueous phase and flow rates of aqueous and organic phases on mass transfer coefficient was tested. Then the extraction of Th4+ from RE sulfate obtained from Baotou ore was carried out. The results obtained show that the mass transfer coefficient of Th4+ changes with the flow rate of aqueous phase, but does not change with the flow rate of organic phase and H+ concentration in aqueous phase, which suggests that the mass transfer rate of Th4+ is controlled bg that in the water critical layer, The mass transfer rate of RE3+ does not change with the flow rate of water phase, changes a little with the flow rate of organic phase, and changes with H+ concentration, which suggests that the mass transfer rate is controlled by their reaction rate with N1923. Th4+ could be extracted completely in 8 h from RE sulfate solution of Baotou ore with relatively less extraction of RE3+. So the separation of radioactive element under the sealed condition could be done.

Novel morphology in ring-banded spherulites from single-phase mixtures of poly(epsilon-caprolactone) with poly(styrene-co-acrylonitrile)

Novel morphology of ring-banded spherulites in the surface of poly(epsilon-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends was discovered and studied by SEM and TEM. The ring-banded spherulites separate into those exhibiting a very dark contrast, of relatively regular bundles of lamellae and others appearing with a much brighter intensity, of a coarse and irregular aggregates of lamellae. The origin of the novel morphology is not due to different crystalline structures as in the case of isotactic polypropylene because only one crystal structure exists in PCL/SAN blends. The formation may reflect whether spherulites in PCL/SAN blends are nucleated at the bottom surface or at the top (free) surface.

A study of ion kinetic energy spectrometry of o(-), m(-), and p(-) diol benzene doubly charged ions and singly charged ions in gas phase

With Mass Analyzed Ion Kinetic Energy Spectrometry (MIKES), Collisional Induced Dissociation(CID), and Electron Capture Induced Decomposition(ECID) technigues, the doubly charged ions and singly charged ions from o(-), m(-), and p(-) diol benzene in the EI source have been studied. In terms of the values of the kinetic energy releases(T) of the charge separation reactions of the doubly charged ions and the estimated intercharge distances(R) of the exploding doubly charged ions the transition structures were proposed. Some structural information about the transition states was also obtained. It is of interest that the MIKES/CID spectra of singly charged ions [C6H6O2](+) from the three isomers are of significant differences.

Rheological studies on the phase dissolution in a block copolymer

The microphase transition in a styrene-butadiene-styrene triblock copolymer was studied by rheometric mechanical spectroscopy. A high-temperature-melt rheological transition from the highly elastic, nonlinear viscous behavior typical of a multiphase structure to linear viscous behavior with insignificant elasticity typical of a single-phase structure was observed. The transition temperature is determined according to the discontinuity of the rheological properties across the transition region, which agrees well with the results obtained from the small angle X-ray scattering data and the expectation of the random phase approximation theory. Maybe for the first time, microphase dissolution was investigated theologically. The storage modulus (G') and the loss modulus (G '') increase with time during the process. An entanglement fluctuation model based on the segmental density fluctuations is presented to explain the rheological behavior in this dissolution process. (C) 1997 John Wiley & Sons.