Online monitoring of birefringence development in heat‐setting polymer films with a fast dual‐wavelength optical technique. I. Uniaxially oriented poly(ethylene naphthalate)

The purpose of this article is to study the fast structural changes that take place during the deformation and heat setting of uniaxially preoriented poly(ethylene 2,6‐naphthalate) films. For this purpose, an online birefringence measurement system coupled with a heat‐setting oven was used. In the online birefringence system, whose details were reported previously (H. Venkatesvaran and M. Cakmak, SPE ANTEC Tech Pap 1993, 39, 257; H. Venkatesvaran and M. Cakmak, Polym Eng Sci 2001, 41, 341), a green and red laser is passed through the films being annealed in a heat‐setting chamber; the resulting data are analyzed for the details of structural mechanisms that take place during this process. This technique is shown to be capable of detecting reversals in birefringence development; as a result, complex sequences of structural evolution can be tracked. The design of this system allows one to observe not only the increase or decrease in birefringence during the course of the heat‐setting process but also the rate dependencies on processing variables. In this study, we establish that the rate of structural rearrangement, as detected by birefringence, depends strongly on the state of the pre‐existing chain orientation and the level of crystallinity. Increased levels of preorientation in the films results in decreases in the rate of birefringence change during heat setting. This is primarily attributed to the increased levels of steric hindrance developed with the increase in orientation and crystallinity in the preoriented samples. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1107–1121, 2001     

Wide‐angle X‐ray scattering study of the lamellar/fibrillar transition for a semi‐crystalline polymer deformed in tension in relation with the evolution of volume strain

This work is devoted to the study of the deformation mechanisms of a high‐density polyethylene deformed in tension. Specific treatments were applied to synchrotron wide‐angle X‐ray scattering patterns obtained in situ with the aim of quantifying: (i) the evolution of the apparent crystal sizes during the deformation process, (ii) the reorientation dynamics of the fragmented crystals while aligning their chains along the drawing axis during the establishment of the fibrillar morphology, and (iii) the reorientation dynamics of the amorphous chains. In addition, the volume strain evolution was measured using 3D digital image correlation. The cavitation phenomenon was found to mainly occur during the lamellae fragmentation phase. At the end of the deformation process, when the lamellar structure is destroyed, the fragmented crystals have new degrees of freedom and become free to rotate to align their chains along the drawing axis. Crystal fragmentation is then no longer needed to allow material deformation, and there is no further volume strain increase. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1470–1480     

Enhanced third‐order nonlinear optical properties determined in thin films using the Z‐scan technique: bis(μ‐4,4′‐oxydibenzoato)bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine)cobalt(II)]

π‐Conjugated organic materials exhibit high and tunable nonlinear optical (NLO) properties, and fast response times. 4′‐Phenyl‐2,2′:6′,2′′‐terpyridine (PTP) is an important N‐heterocyclic ligand involving π‐conjugated systems, however, studies concerning the third‐order NLO properties of terpyridine transition metal complexes are limited. The title binuclear terpyridine Co^II complex, bis(μ‐4,4′‐oxydibenzoato)‐κ³O,O′:O′′;κ³O′′:O,O′‐bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine‐κ³N,N′,N′′)cobalt(II)], [Co₂(C₁₄H₈O₅)₂(C₂₁H₁₅N₃)₂], (1), has been synthesized under hydrothermal conditions. In the crystal structure, each Co^II cation is surrounded by three N atoms of a PTP ligand and three O atoms, two from a bidentate and one from a symmetry‐related monodentate 4,4′‐oxydibenzoate (ODA²⁻) ligand, completing a distorted octahedral coordination geometry. Neighbouring [Co(PTP)]²⁺ units are bridged by ODA²⁻ ligands to form a ring‐like structure. The third‐order nonlinear optical (NLO) properties of (1) and PTP were determined in thin films using the Z‐scan technique. The title compound shows a strong third‐order NLO saturable absorption (SA), while PTP exhibits a third‐order NLO reverse saturable absorption (RSA). The absorptive coefficient β of (1) is −37.3 × 10⁻⁷ m W⁻¹, which is larger than that (8.96 × 10⁻⁷ m W⁻¹) of PTP. The third‐order NLO susceptibility χ⁽³⁾ values are calculated as 6.01 × 10⁻⁸ e.s.u. for (1) and 1.44 × 10⁻⁸ e.s.u. for PTP.