Hydrolytic aging of polypropylene studied by X‐ray photoelectron spectroscopy

X‐ray photoelectron spectroscopy (XPS) was used to study the hydrolytic aging of polypropylene according to the pHs of degrading buffer solutions and the time of aging. The study was concentrated over periods of 3, 6, and 9 months for values of pH close to the real environments of use of the material (pH of 6, 7, and 8). The polypropylene underwent an oxidation of its polymeric matrix, independently of the range of pH values, by the production of C? OH, C?O, and O?C? O groups. These chemical functions were observed in high resolution XPS spectra around C1s and O1s peaks. Beginning with these results and from mechanisms of (photochemical, thermal, and others) aging proposed in the literature, it was then possible to propose mechanisms of hydrolytic ageing of polypropylene. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3830–3838, 2004     

A New Method for Identifying Osmotically Limited and Gel Layer Controlled Pressure Independent Flux in Ultrafiltration

An unequivocal determination of whether pressure independent flux regime is osmotically controlled or gel layer dominated, is still open for discussion in the membrane literature. The present work reports a method that could be used to address this issue. It is shown that analysis of post steady state transient filtration data leads to clear demarcation of osmotically limited and gel layer controlled filtration. The method proposed in this work can also be used to estimate the additional filtration resistance offered by the polarization layer to the permeate flow in macromolecular ultrafiltration and has been verified experimentally. It has also been shown that the polarization layer thickness is not sensitive to the feed pressure but varies as a function of the bulk solute concentration; higher the bulk concentration, thicker is the polarization layer.     

Study of Tire Particle Mixing in a Moving and Stirred Bed Vacuum Pyrolysis Reactor

The paper studies the motion of scrap tire shreds in a moving and stirred bed vacuum pyrolysis reactor. The reactor configuration is a novel concept. The pattern and the residence time distribution (RTD) of the particle motion in the reactor were investigated using tracers, for different feed rates and blade speeds. It was shown that the particle motion in the reactor is plug flow nature with intermediate dispersion (σ² = 0.02—0.055). The mean residence time is in the range of 7—23 min, depending on the speed of the blades and the feed rate. The ratio of mean particle speed and the speed of blades v_m/v_b varied between 0.03 and 0.07.     

Sequence analysis and fiber properties of a blend of poly(ethylene terephthalate) and poly(ethylene terephthalate‐co‐4,4′‐bibenzoate)

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐4,4′‐ bibenzoate) (PETBB) are prepared by coextrusion. Analysis by ¹³C‐NMR spectroscopy shows that little transesterification occurs during the blending process. Additional heat treatment of the blend leads to more transesterification and a corresponding increase in the degree of randomness, R. Analysis by differential scanning calorimetry shows that the as‐extruded blend is semicrystalline, unlike PETBB15, a random copolymer with the same composition as the non‐ random blend. Additional heat treatment of the blend leads to a decrease in the melting point, T_m, and an increase in glass transition temperature, T_g. The T_m and T_g of the blend reach minimum and maximum values, respectively, after 15 min at 270°C, at which point the blend has not been fully randomized. The blend has a lower crystallization rate than PET and PETBB55 (a copolymer containing 55 mol % bibenzoate). The PET/PETBB55 (70/30 w/w) blend shows a secondary endothermic peak at 15°C above an isothermal crystallization temperature. The secondary peak was confirmed to be the melting of small and/or imperfect crystals resulting from secondary crystallization. The blend exhibits the crystal structure of PET. Tensile properties of the fibers prepared from the blend are comparable to those of PET fiber, whereas PETBB55 fibers display higher performance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1793–1803, 2004     

Recovery of deuterium from hydrogen–deuterium mixture using palladium

The applicability of palladium for the separation of hydrogen isotopes (hydrogen and deuterium) is evaluated systematically by generating isotherm data and conducting column experiments in a laboratory set-up. Effect of various parameters such as concentration of the isotopic mixture, particle size, eluent flow rate, etc. is studied experimentally. A fixed-bed chromatographic model is developed and validated using the experimental data. The model is further used to predict the performance of a multi-column configuration for large-scale separation. Chromatographic separation is thus found to be a promising technique to achieve the required purity and hence it may be clubbed with the existing systems (e.g. cryogenic distillation) to obtain enhanced performance.     

Electrochemical treatment of cotton textile-based dyeing effluent

The electrochemical treatment (ECT) of textile wastewater was carried out in a 1.5 dm³ electrolyte batch reactor using iron electrodes. With the four plate configurations, a current density (CD) of 89.2 A/m² and a pH value of 8.5 were found to be optimal, at which maximum reduction in chemical oxygen demand (COD) and colour achieved were 86% and 79%, respectively. Loss of 0.0666 kg/m³ iron electrode and 18.44 kWh/m³ power consumption was observed during ECT with a maximum COD reduction of 79%. The settling characteristics of electrochemically treated effluents as well as the characteristics of foam and residue were also analysed.     

Current Understanding of Structure–Processing–Property Relationships in BaTiO3–Bi(M)O3 Dielectrics

As part of a continued push for high permittivity dielectrics suitable for use at elevated operating temperatures and/or large electric fields, modifications of BaTiO₃ with Bi(M)O₃, where M represents a net‐trivalent B‐site occupied by one or more species, have received a great deal of recent attention. Materials in this composition family exhibit weakly coupled relaxor behavior that is not only remarkably stable at high temperatures and under large electric fields, but is also quite similar across various identities of M. Moderate levels of Bi content (as much as 50 mol%) appear to be crucial to the stability of the dielectric response. In addition, the presence of significant Bi reduces the processing temperatures required for densification and increases the required oxygen content in processing atmospheres relative to traditional X7R‐type BaTiO₃‐based dielectrics. Although detailed understanding of the structure–processing–property relationships in this class of materials is still in its infancy, this article reviews the current state of understanding of the mechanisms underlying the high and stable values of both relative permittivity and resistivity that are characteristic of BaTiO₃‐Bi(M)O₃ dielectrics as well as the processing challenges and opportunities associated with these materials.     

Phase separation and crystallization in double crystalline symmetric binary polymer blends

Blending of two or more pure polymers is an effective way to produce composites with tunable properties. In this paper, we report dynamic Monte Carlo simulation results on the crystallization of crystalline/crystalline (A/B) symmetric binary polymer blend, wherein the melting temperature of A-polymer is higher than B-polymer. We study the effect of segregation strength (arises from the immiscibility between A- and B-polymers) on crystallization and morphological development. Crystallization of A-polymer precedes the crystallization of B-polymer upon cooling from a homogeneous melt. Simulation results reveal that the morphological development is controlled by the interplay between crystallization driving force (viz., attractive interaction) and de-mixing energy (viz., repulsive interaction between two polymers). With increasing segregation strength, the interface becomes more rigid and restricts the development of crystalline structures. Mean square radius of gyration shows a decreasing trend with increasing segregation strength, reflecting the increased repulsive interaction between A- and B-polymers. As a consequence, a large number of smaller size crystals form with lesser crystallinity. Isothermal crystallization reveals that the transition pathways strongly depend on segregation strength. We also observe a path-dependent crystallization behavior in isothermal crystallization: two-step (sequential) isothermal crystallization yields superior crystalline structure in both A- and B-polymers than one-step (coincident) crystallization.     

Tuning of Cloud Point by the Nature of Surfactant Headgroup: Influence of Counterion and Additives

Work was performed to distinguish the role of sulfonate (–SO₃ ^?) and sulfate (–OSO₃ ^?) with respect to the micellization and clouding phenomenon in ionic surfactant solutions. The clouding phenomenon is a recent addition to the conventional one observed with nonionic surfactants. Three ionic surfactants [sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and sodium dodecylsulfonate (SDSo)] are chosen and the effects of added tetra-n-pentylammonium bromide (TPeAB) and benzyl tributylammonium bromide (BTAC) have been studied on micellization and clouding behaviors in aqueous solution. Based on critical micelle concentration (CMC) and cloud point (CP) measurements, the following order has been observed: SDBS < SDS < SDSo. Though both SDBS and SDSo contain sulfonate groups, they are found at the two ends of the ordering. Therefore, the role of the phenyl ring is also having importance in clouding phenomena. For a typical surfactant, TPeAB was found to be more effective than BTAC. Based on the CP studies, two compositions of SDSo + TPeAB/BTAC were chosen and the effects of different additives (carbohydrate, amino acid, and l-ascorbic acid) on the CP were investigated. Additive may either decrease or increase CP, depending on the structure of the counterion or additive. The present work shows a few novelties: (1) headgroup/counterion dependence of CP and (2) hydrophobicity of counterion/surfactant has an important bearing on the phenomenon. The data can be utilised in improving cloud point extraction methodologies (CPEMs).