Rheooptical investigation of the crystallization of poly(ethylene terephthalate) under tensile strain

The crystallization of poly(ethylene terephthalate) under uniaxial tensile strain at different extension rates was investigated with optical polarimetry in a temperature range between the glass-transition temperature and the quiescent crystallization temperature. The evolution of the optical properties of the polymer, including the turbidity, birefringence, and dichroism, were monitored simultaneously with the mechanical parameters. To complete the semicrystalline microstructure characterization of the polymer under strain, an online wide-angle X-ray diffraction (WAXD) technique was used in separate experiments, which were performed under the same thermomechanical conditions. For real-time measurements, a high-energy synchrotron radiation source was used. The optical properties provided information about both the crystalline and amorphous phases, whereas the WAXD patterns essentially gave information about the crystalline phase. The two experimental techniques were then used in a complementary way to characterize the semicrystalline microstructure. Significant deviations from the stress-optical rule were found. This was attributed to both transient effects and the appearance of crystallites, which consisted of highly oriented molecular segments that could contribute to the optical anisotropy but not necessarily to the stress. The behavior of the optical dichroism was found to be qualitatively different from that of the birefringence. The latter monotonically increased with the strain, whereas the former first increased with the strain, passed through a maximum, and then decreased to a steady-state value. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1915–1927, 2004     

Li<Subscript>2</Subscript>HPO<Subscript>3</Subscript>, H<Subscript>2</Subscript>O: Crystal Structure and IR Spectrum

Abstract  

Crystal structure of Li₂HPO₃,H₂O was determined by single-crystal X-Ray diffraction analysis at 173(2) K. It crystallizes in the monoclinic system (P2_1/c) with the parameters: a = 5.0322(9) ?, b = 8.9795(17) ?, c = 17.088(4) ?, β = 92.672(16)° and Z = 8. The structure was refined to R = 0.0237 and ωR = 0.0650 for 1449 reflexions. The framework of Li₂HPO₃, H₂O can be described as layers perpendicular to the crystallographic c axis. The structure contains two types of Li-tetrahedrons. In one kind each O atom belongs to one HPO₃ group, while in the second kind one apex is an O from water. A network of hydrogen bonds interactions insures the connection between the layers.     

Crystal Structure and IR Study of (C<Subscript>6</Subscript>H<Subscript>5</Subscript>NH<Subscript>3</Subscript>)[ZnCl(HPO<Subscript>3</Subscript>)]

Abstract  

A new hybrid phosphate, (C₆H₅NH₃)[ZnCl(HPO₃)], has been synthesized and its structure characterized from single-crystal X-ray diffraction. The title compound crystallizes in the orthorhombic space group Pbca (n. 61) with the unit-cell parameters: a = 9.8635(2) ?, b = 9.4516(10) ?, c = 22.2430(4) ?, Z = 8 and V = 2,073.62(6) ?³. The final R factors were R/ωR = 0.0361/0.0924. Its framework might be described as a layered structure with two (010)-parallel cationic and anionic layers. The IR spectrum of this phase shows characteristic bands of phosphite and anilinium groups.     

Tackiness and cohesive failure of granular pastes: Mechanistic aspects

Granular pastes are dense dispersions of non-colloidal grains in a simple or a complex fluid. Typical examples are the coating, gluing or sealing mortars used in building applications. We study the rupture of a thick layer of mortar paste in a simple pulling test where the paste is confined between two flat surfaces. It is shown that, depending on the rheological properties of the paste and the plate separation velocity, two main failure modes are obtained. The first mode is the inwards shear flow of the paste with viscous fingering instabilities, similarly to what has been observed with Newtonian fluids and with non-Newtonian colloidal suspensions or polymer solutions. The second failure mode is stemming from the expansion of bubbles, similarly to what has been observed in soft adhesive polymer layers and, more recently, in highly viscous fluids. It is shown that the crossover between the two failure modes is determined by the conditions required to generate a pressure drop able to trigger the growth of pre-existing micro-bubbles smaller than the inter-granular distance.     

Flow and blockage of highly concentrated granular suspensions in non-Newtonian fluid

Studying the flow of highly concentrated granular suspensions represents a great challenge since they are characterized by a rather complex rheological behavior. In addition, macroscopic heterogeneities may be induced by the flow during rheological measurements due to the eventual relative motion between the liquid and the granular phases that may take place under certain conditions. Solid–liquid separation may ultimately lead to flow blockage. In the present investigation we consider experimentally the influence of the rheological properties of the suspending fluid on the transition between the flow and blockage of a concentrated suspension in a squeeze set-up geometry. The suspending fluid consists of an aqueous Xanthan solution for which rheological properties can be tuned by changing the polymer concentration. For each polymer concentration, it is shown that there exist flow parameters (squeeze velocity and gap thickness) for which one has a transition between homogeneous flow of the suspension and its blockage. Blockage diagrams, delimiting flowability and blockage zones, are then determined. Physical arguments are given to relate the evolution of the blockage diagrams to the flow parameters and rheological properties of suspending fluid.     

Rheological behavior of sewage sludge and strain-induced dewatering

In order to study the strain-induced water release in sewage sludge and its connection with rheological behavior, two types of rheological tests have been carried out. The rheology of sewage sludge samples stemming from a urban sewer was first characterized using a Couette cell system. In particular, the yielding behavior and the elastic modulus of the sludge has been considered under shear flow conditions. In these pure shear tests the reproducibility of the measurements was rather poor, limiting this study to low strains. Consequently, a second type of rheological tests, namely the squeeze test, which is more appropriate for these paste-like materials, has been considered. The rheological behavior along with the dewatering efficiency have been studied under the squeeze flow conditions. Surprisingly, it was found that, under certain conditions, the strain-induced water release mechanism became more effective when decreasing the squeeze speed. This was interpreted in terms of a competition between the paste flow and the water filtration through the porous media made up by the flocs.     

An organometallic tetranuclear cluster with phosphine and phosphido ligands in nonclassical bonding modes: X-ray structural characterization

The elimination of the NCMe ligand in [(C₆F₅)₂Pt(μ-PPh₂)₂M(NCCH₃)₂] (M = Pd, Pt) results in the formation of the tetranuclear clusters [Pt₂Pd₂(μ-PPh₂)₃(C₆F₅)₃(PPh₂C₆F₅)] 1 and [Pt₄(μ-PPh₂)₄(C₆F₅)₄] 2. The structure of 1 indicates that one of the palladium centres is connected to the rest of the centres through two M-M bonds and two weaker η²-C₆H₅ and η²-P-C interactions.