Nonlinear optical characterization of cluster dynamic in water in oil microemulsion by a pump probe laser beam technique

We present a new pump probe laser beams configuration for the nonlinear optical characterization of microemulsions. We detect the variation of the on-axis optical intensity of the probe beam as generated by the concentration profile induced in an optically thin film of microemulsion by the pump beam. A mathematical model has been introduced to describe the phenomenon. The technique allows the determination of both Kerr-like optical nonlinearity and time constants and, therefore, it gives information both on cluster dimension and their shape. We discuss its application to WAD (water/AOT/decane, where AOT denotes sodium-bis-di-ethyl-sulfosuccinate) with the application of a strong electric field of optical source. Comparison between theoretical predictions and experimental results confirms the presence of giant optical nonlinearity in the absence of turbidity divergence. Chainlike shape of clusters, of the kind already reported with the application of strong electric field, could justify this result. Received 26 October 2002 RID="a" ID="a"e-mail: vicari@na.infn.it     

Multicanonical Monte Carlo simulations on intramolecular micelle formation in copolymers

The formation of intramolecular micelles in copolymers with periodic sequence, where hydrophobic units (stickers) are periodically placed along the chain, is studied by using multicanonical Monte Carlo computer simulations for an off-lattice bead-rod model in three dimensions. With decreasing the temperature, a transition from random-coil conformations to micelles occurs and flower-type micelles are formed via the transition. The number of stickers forming a micelle core is limited by the excluded-volume effect of loop chains around micelle cores. By this effect, two intramolecular micelles are formed for long polymer chains with 60 bonds via the coil-to-micelle transition. By further decreasing the temperature, we find that another transition, i.e., a micelle-to-micelle transition, takes place. At this transition point, the two intramolecular micelles merge into one micelle. Furthermore, we extend the multicanonical MC method to study elastic properties of single polymer chains with strong attractive interactions under external force fields, and study how the intramolecular micellization affects the elastic property of single polymer chains.     

Pearling instabilities in water-dispersed copolymer cylinders with charged brushes

We investigate the structural behavior of a poly(styrene)-block-poly(acrylic acid) diblock copolymer which forms hexagonally-packed PS cylinders (C-phase) in the melt state. The water dispersion of this structure provides hairy cylinders which comprise a PAA swollen cylindrical brush with a height h tunable via its degree of ionization and the ionic strength in the solution, and a water-free, PS cylindrical core of constant radius R_C. Such system constitutes an out-of-equilibrium frustrated model system: the selective swelling of the PAA brush results in a frustration of the interface curvature, which the ratio h/R_C allows to quantify. Upon heating at a temperature higher than the glass transition temperature of the PS core, the glassiness of the core is relieved and the mechanical constraints arising from the selective swelling of the structure can be relaxed: the cylinders undergo a cylinder-to-sphere transition upon annealing at high temperature, when above a frustration threshold h/R_C 1.8. Thanks to a careful mapping of the transition diagram, an undulating cylindrical morphology (UC) is identified between unchanged cylinders ( h/R_C 1.8) and spheres ( h/R_C 2.0), which appears to result from a Rayleigh-like pearling instability of the copolymer cylinders.     

Synergistic effects in mixed wormlike micelles of dimeric and single-chain cationic surfactants at high ionic strength

The mixed micellization between the cationic gemini surfactant [ C₁₂H₂₅( CH₃)₂N⁺( C₂H₄) N⁺( CH₃)₂ C₁₂H₂₅•2Br^-] and the cationic cetyltrimethylammonium bromide (CTAB) in 150 mM KBr solutions has been investigated. The variation of the cmc of the mixtures, measured by surface tension experiments, with composition revealed synergism in micelle formation. T-Jump and light scattering experiments performed in the vicinity of the crossover volume fraction showed the existence of two micellar populations, possibly linear and toroidal micelles. Rheological and dynamic light scattering experiments allowed to fully characterize the linear viscoelasticity of the mixtures. These measurements revealed synergistic gains in viscoelastic properties with a maximum of the stress-relaxation time around the equimolar composition. These effects are ascribed to a progressive intermicellar crosslinking resulting from a continuous increase of the end-cap energy with the 12-2-12 content in the mixture. Received: 18 November 2002 / Accepted: 8 April 2003 / Published online: 27 May 2003 RID="a" ID="a"e-mail: candau@fresnel.u-strasbg.fr     

The effects of annealing on fatigue crack propagation in polyethylene

Fatigue crack propagation tests on annealed and quenched medium-density polyethylene showed the annealed specimens to have much lower resistance to crack initiation and subsequent propagation. Although the same fracture mechanism, in which the brittle crack gradually becomes more ductile, prevailed in both cases, the voided and fibrillated crack tip root craze in the annealed material was much weaker that the nonfibrillated quenched root craze. Microstructural analyses indicate that the annealed material had separate crystallite populations, whereas the quenched material had a more homogeneous morphology. The highest melting fraction of the annealed material was composed of lamellae that were about 270 Å thick, and the quenched lamellae were estimated to be 160 Å thick. The reduced fatigue crack propagation resistance of the annealed material was suggested to be a result of a lower concentration of tie molecules and its reduced damping capability, compared to the quenched material. © 1995 John Wiley & Sons, Inc.     

Correlation between melting behavior and ringed spherulites in poly(trimethylene terephthalate)

The lamellar types as revealed by the multiple melting peaks and possible mechanisms of ringed spherulites in poly(trimethylene terephthalate) (PTT) were analyzed with differential scanning calorimetry (DSC), optical microscopy, and scanning electron microscopy. Several interesting correlations were found. If PTT is melt‐crystallized in a certain temperature range, it shows multiple melting peaks and rings in PTT. Once rings are formed in the original melt‐crystallized PTT, they do not disappear but persist and become even more apparent upon postcrystallization annealing at higher temperatures. Furthermore, for PTT that is capable of exhibiting ringed spherulites, a temperature range exists where rings do not form. This behavior can be interpreted in relation with the demonstrated thermal behavior in PTT. Reorganization took place upon postcrystallization scanning or annealing to or at higher temperatures. A postulation was proposed and rigorously tested with evidence to correlate the ringed spherulites and melting behavior. Rings in PTT may be related to multiple lamellae in the spherulites. Consequently, if a temperature of crystallization is selected so that there is only one type of lamella in the spherulites, then there should be no rings. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 80–93, 2002     

MORPHOLOGY EVOLUTION IN PTFE AS A FUNCTION OF MELT TIME AND TEMPERATURE Ⅱ. LOW MOLECULAR WEIGHT FOLDED CHAIN SINGLE CRYSTALS AND BAND STRUCTURES

The effect of sintering dispersed and bulk, low molecular weight (Mn = 50,000 Da), nano-emulsion polytetrafluoroethylene (PTFE) particles near their melting point is described. With the nascent particles consisting of ca.75 nm diameter, hexagonal, single crystals, sintering at, e.g., 350℃, results, initially, in merger of neighboring particles,followed by individual molecular motion on the substrate and the formation of folded chain, lamellar single crystals and spherulites, and on-edge ribbons. It is suggested these structures develop, with time, in the mesomorphic "melt". Sintering of the bulk resin yields extended chain, band structures, as well as folded chain lamellae; end-surface to end-surface merger,possibly by end-to-end polymerization, occurs with increasing time.     

Theory of myelin coiling

A new model is proposed to explain coiling of myelins composed of fluid bilayers. This model allows the constituent bilayer cylinders of a myelin to be non-coaxial and the bilayer lateral tension to vary from bilayer to bilayer. The calculations show that a myelin would bend or coil to lower its free energy when the bilayer lateral tension is sufficiently large. From a mechanical point of view, the proposed coiling mechanism is analogous to the classical Euler buckling of a thin elastic rod under axial compression. The analysis of a simple two-bilayer case suggests that a bilayer lateral tension of about 1 dyne/cm can easily induce coiling of myelins of typical lipid bilayers. This model signifies the importance of bilayer lateral tension in determining the morphology of myelinic structures.     

硬弹性聚丙烯的排状堆积片晶

用广角X射线衍射、小角X光散射等手段对硬弹性聚丙烯中排状堆积片晶的形成及结构进行了研究。结果表明,应力场下聚丙烯熔体结晶,得到的硬弹性聚丙烯具有垂直于挤出方向而又平行堆积的片晶结构(即排状堆积片晶)。熔融温度越高,排状堆积片晶所需的熔体拉伸比越高。而随着熔体所受拉伸比的增加,片晶厚度有所增加。随着熔融温度升高,片晶厚度下降。热处理温度在110-120℃之间,片晶厚度随热处理温度升高明显增加。     

The effect of molecular weight and crystallite structure on yielding in ethylene copolymers

Nominal stress-strain curves of a series of random ethylene-hexene copolymers having narrow composition and most probable molecular weight distributions were investigated. A series of such molecular weight copolymers with a constant concentration of branches were crystallized under a variety of conditions. In each molecular weight series the level of crystallinity was approximately constant. Particular attention was focused on the yield region and the nature of the yielding process. It was found, quite surprisingly, that the yield stress was not solely dependent on the crystallinity level. Moreover, the shape of the force-elongation curve in the yield region was very dependent on the molecular weight and the crystallization mode. These changes in yielding correlated quite well with the overall crystallite structure that was characterized by thin section transmission electron microscopy. The orthorhombic unit cell of polyethylene was maintained in all the samples despite the changes that occurred in the overall crystallite structure. © 1997 John Wiley & Sons, Inc.