Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004     

Large melting point depression of 2–3‐nm length‐scale nanocrystals formed by the self‐assembly of an associative polymer: Telechelic,pyrene‐labeled poly(dimethylsiloxane)

Large melting point depressions for organic nanocrystals, in comparison with those of the bulk, were observed in an associative polymer: telechelic, pyrene‐labeled poly(dimethylsiloxane) (Py‐PDMS‐Py). Nanocrystals formed within nanoaggregates of pyrenyl units that were immiscible in poly(dimethylsiloxane). For 5 and 7 kg/mol Py‐PDMS‐Py, physical gels resulted, with melting points exceeding 40 °C and with small‐angle X‐ray scattering peaks indicating that the crystals were nanoconfined, were 2–3 nm long, and contained roughly 18–30 pyrenyl dye end units. In contrast, 30 kg/mol Py‐PDMS‐PY was not a gel and exhibited no scattering peak at room temperature; however, after 12 h of annealing at ?5 °C, multiple melting peaks were present at 5–30 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3470–3475, 2004     

A new luciferase reporter gene assay for the detection of androgenic and antiandrogenic effects based on a human prostate specific antigen promoter and PC3/AR human prostate cancer cells.

We developed a new mammalian cell-based luciferase reporter gene assay for androgenic and antiandrogenic activities of chemicals and environmental samples. Environmental samples usually have a complex matrix that may contain the constituents acting as androgen receptor (AR) agonists, AR antagonists or aryl hydrocarbon receptor (AhR) agonists. AhR agonists are known to elicit the antiandrogenic effect through cross-talk between AR and AhR signal transduction pathways. In this study, PC3/AR human prostate carcinoma cells were transiently transfected with a prostate-specific antigen (PSA) promoter-driven luciferase expression plasmid. The cells were treated with a test compound or an environmental sample for 24 h at 37 degrees C and then measured for luciferase activity. The luciferase activity was induced by dihydrotestosterone (DHT) in a concentration-dependent manner in a concentration range from 10 fM to 1 nM. R1881, a synthetic androgen receptor agonist, induced luciferase activity and its inductive effects was additive to that of DHT. The luciferase activity was not induced by cortisol, a glucocorticoid, progesterone, a progestin, and 17beta-estradiol, an estrogen in a concentration range of up to 1 microM. DHT-induced luciferase activity was reduced by bicalutamide and cyproterone acetate, AR antagonists, and also by benzo[a]pyrene, an aryl hydrocarbon receptor agonist, through AhR-mediated pathways. All of these findings indicate that the present assay system correctly responds to AR agonists, AR antagonists and AhR agonist and, therefore, it is a powerful tool for the sensitive and selective screening of chemicals and environmental samples for their androgenic and antiandrogenic activities. We developed the first assay system, in which the expression of luciferase was driven by the promoter of a prostate-specific antigen gene, a typical human androgen-regulated gene.     

Determination of nickel in alloys and plant leaves with salicylaldehyde 3-oxobutanoylhydrazone by spectrophotometry.

A simple and highly sensitive reagent of salicylaldehyde 3-oxobutanoylhydrazone (salicylaldehyde acetoacetic acid hydrazone, SAAH) was synthesized and studied for the spectrophotometric determination of nickel in detail. In the pH range 6, which greatly increased the selectivity, nickel reacted with SAAH to form a 1:1 yellow complex, having a sensitive absorption peak at 405 nm. Under the optimal conditions, Beer's law was obeyed over the range from 0.0117 to 0.1174 microg cm(-3). The apparent molar absorptivity was 3.025 x 10(5) dm3 mol(-1) cm(-1). The detection limit and the variation coefficient were found to be 1.752 ng cm(-3) and 1.0%, respectively. The method has been applied to the quantitative determination of nickel in different alloys and leaves.     

Dynamic surface tension measurements of surfactant solutions using the maximum bubble pressure method – limits of applicability

One of the essential differences in the design of bubble pressure tensiometers consists in the geometry of the measuring capillaries. To reach extremely short adsorption times of milliseconds and below, the so-called deadtime of the capillaries must be of the order of some 10 ms. In particular, for concentrated surfactant solutions, such as micellar solutions, short deadtimes are needed to minimize the initial surfactant load of the generated bubbles. A theoretical model is derived and confirmed by experiments performed for a wide range of experimental conditions, mainly in respect to variations in deadtime and bubble volume.     

Fingering phenomena during spreading of surfactant solutions

Fingering instabilities are observed at the contact line of drops of surfactant solutions spreading spontaneously on solid surfaces coated by a film of solvent. The occurrences of instabilities, and the characteristics of the instability pattern, are controlled by the surfactant concentration and the thickness of the film adsorbed or deposited on the substrate. This work provides experimental data as a basis for forthcoming theoretical analyses.     

Determination of the degree of cure under dynamic and isothermal curing conditions with electrical impedance spectroscopy

This article presents a new methodology for the quantitative determination of the progress of the curing reaction of a thermosetting resin, using the results of electrical impedance spectroscopy. The method is an extension of the use of the imaginary impedance maximum as a reaction progress indicator and is based on the demonstration of a close correlation between the reaction rate, as measured by conventional differential scanning calorimetry, and the rate of change of the value of the imaginary impedance spectrum maximum. Tests on a commercial aerospace epoxy resin under both isothermal and dynamic heating conditions with calorimetry and impedance spectroscopy have demonstrated the validity of the method and set the accuracy limits involved. This technique can be used as a real-time online control tool for thermoset composite manufacturing. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 146–154, 2004     

Solvent‐ and interface‐induced surface segregation in blends of isotactic polypropylene with poly(ethylene‐co‐propylene) rubber

The surface compositions and morphologies of melt‐quenched blends of isotactic polypropylene (iPP) with aspecific poly(ethylene‐co‐propylene) rubber (aEPR) were characterized by atomic force microscopy, optical microscopy, and X‐ray photoelectron spectroscopy. The surface morphologies and compositions formed in the melt are frozen‐in by crystallization of the iPP component and, depending on the processing conditions, are enriched in iPP or aEPR or contain a phase‐separated mix of iPP and aEPR. Enrichment of iPP is observed for blends melted in open air, in agreement with earlier work showing the high surface activity of atactic polypropylene at open interfaces. Surface segregation of iPP is suppressed at confined interfaces. Blends melt‐pressed between hydrophilic and hydrophobic substrates have phase‐separated iPP and aEPR domains present at the surface, which grow in size as the melt time increases. Surface enrichment of aEPR is observed after exposing melt‐pressed blends to n‐hexane vapor, which preferentially solvates aEPR and draws it to the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 421–432, 2004     

Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. III. Gel properties and irreversible modifications of poly(vinylidene fluoride) membranes under swelling in liquid electrolytes

Microporous poly(vinylidene fluoride) (PVdF) separators for lithium-ion batteries, used in liquid organic electrolytes, have been characterized with respect to the swelling phenomena on dense PVdF membranes (obtained through hot pressing). In the first and second parts of this study, we have described the swelling equilibria and swelling kinetics of dense PVdF. Here the thermal properties of PVdF gels and their irreversible modifications induced by swelling are characterized. Particular attention is paid to crystallinity modifications, polymer plasticization, and membrane degradation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2308–2317, 2004     

Statistical thermodynamics evaluation of polymer–polymer miscibility

The Simha and Somcynsky (S–S) statistical thermodynamics theory was used to compute the solubility parameters as a function of temperature and pressure [δ = δ(T, P)], for a series of polymer melts. The characteristic scaling parameters required for this task, P*, T*, and V*, were extracted from the pressure–temperature–volume (PVT) data. To determine the potential polymer–polymer miscibility, the dependence of δ versus T (at ambient pressure) was computed for 17 polymers. Close proximity of the δ versus T curves for four miscible polymer pairs: PPE/PS, PS/PVME, and PC/PMMA signaled the usefulness of this approach. It is noteworthy, that the tabulated solubility parameters (derived from the solution data under ambient conditions) propounded the immiscibility of the PVC/PVAc pair. The computed values of δ also suggested miscibility for polymer pairs of unknown miscibility, namely PPE/PVC, PPE/PVAc, and PET/PSF. In recognizing the limitations of the solubility parameter approach (the omission of several thermodynamic contributions), these preliminary results are auspicious because they indicate a new route for estimating the miscibility of any polymeric material at a given temperature and pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2909–2915, 2004