Copolymerization: A new tool to selectively induce poly(butylene naphthalate) crystal form

Poly(butylene/diethylene naphthalate) copolymers (PBN‐PDEN) were synthesized in bulk according to the polycondensation procedure and examined by NMR, GPC, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and XRD. At room temperature they appeared as semicrystalline materials; the copolymerization caused a lowering in the T_g value, a decrement of T_m and of the crystallization rate. Pure α or β′ form was obtained at low and high DEN unit content, respectively; crystalline form transition never occurred in the solid state, analogously to PBN. After cooling from the melt, the pure α form was always evidenced in PBN‐PDEN10 and PBN‐PDEN20, whereas the pure β′ crystal phase develops in the copolymer containing 40 mol % DEN units, independently on the cooling rate. In the case of PBN‐PDEN30 a pure α or β′ form was obtained at low and high cooling rate, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1356–1367, 2009     

Hypernuclei and in-medium chiral dynamics

A recently introduced relativistic nuclear energy density functional, constrained by features of low-energy QCD, is extended to describe the structure of hypernuclei. The density-dependent mean field and the spin-orbit potential of a Λ-hyperon in a nucleus, are consistently calculated using the SU(3) extension of in-medium chiral perturbation theory. The leading long-range ΛN interaction arises from kaon-exchange and 2π-exchange with a Σ-hyperon in the intermediate state. Scalar and vector mean fields, originating from in-medium changes of the quark condensates, produce a sizeable short-range spin-orbit interaction. The model, when applied to oxygen as a test case, provides a natural explanation for the smallness of the effective Λ spin-orbit potential: an almost complete cancellation between the background contributions (scalar and vector) and the long-range terms generated by two-pion exchange.     

Synthesis and Thermal Behavior of Poly(2-hydroxyethoxybenzoate) and Its Copolyesters with ε-caprolactone

Poly(2-hydroxyethoxybenzoate), poly(ε-caprolactone), and random poly(2-hydroxyethoxybenzoate/e-caprolactone) copolymers were synthesized and characterized in terms of chemical structure and molecular mass. The thermal behavior was examined by DSC. All the samples appear as semicrystalline materials; the main effect of copolymerization was lowering in the amount of crystallinity and a decrease of melting temperature with respect to homopolymers. Flory's equation described well the T _m-composition data. Amorphous samples (in the 20–100%2-hydroxyethoxybenzoate unit concentration range) obtained by quenching showed amonotonic decrease of the glass transition temperature T _g as the content of caprolactone units is increased. The Wood's equation described the T _g-composition data well. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of transesterification reactions on the crystallization behaviour and morphology of poly(butylene/diethylene succinate) block copolymers

The melting behaviour, the crystallization kinetics and the morphology of block poly(butylene/diethylene succinate) copolymers (PBSPDGS) were investigated by means of differential scanning calorimetry and hot stage optical microscopy. Multiple endotherms were evidenced in the PBSPDGS samples, due to melting and recrystallization processes, similarly to PBS. By applying the Hoffman-Weeks’ method, the of both the homopolymer and the copolymers was derived. The isothermal crystallization kinetics was analyzed according to the Avrami’s treatment. The copolymers with long PBS blocks are characterized by a very similar behaviour with respect to pure poly(butilene succinate), indicating that PBS macromolecular folding is not affected by the presence of non-crystallizable diethylene succinate blocks. On the contrary, the copolymers characterized by very short PBS block length were found to crystallize at a slower rate than the homopolymer. As a matter of fact, a higher value of the work of chain folding was also derived on the basis of Hoffman-Lauritzen nucleation theory. Anyway, in all cases the crystallization mechanism (heterogeneous nucleation and three-dimensional growth) was found to be the same.     

Miscibility of biodegradable poly(propylene succinate)/poly(propylene adipate) blends: Effect of the transesterification reactions

The miscibility of poly(propylene succinate)/poly(propylene adipate) blends was investigated by means of DSC, WAXS and NMR techniques. Poly(propylene succinate) and poly(propylene adipate) were found to be completely immiscible in as blended-state. The miscibility changes upon extended mixing at elevated temperature: for enough long mixing time, the original two phases gradually merged into a single one because of transesterification reactions. The NMR analysis showed that the transesterifications led to block copolymers whose average sequence length decreased as the mixing time is increased at a fixed temperature. Upon very long mixing time (150 min), all PPS and PPA chains are fully transformed into a random copolymer characterized by a single amorphous phase.     

Effects of a decaying cosmological fluctuation

We present the initial conditions for a decaying cosmological perturbation and study its signatures in the cosmic microwave background anisotropies and matter power spectra. An adiabatic decaying mode in the presence of components that are not described as perfect fluids (such as collisionless matter) decays slower than in a perfect-fluid dominated Universe and displays super-Hubble oscillations. Wilkinson Microwave Anisotropy Probe first year data constrain the decaying to growing ratio of scale invariant adiabatic fluctuations at the matter-radiation equality to less than 10%.     

Influence of transesterification reactions on the miscibility and thermal properties of poly(butylene/diethylene succinate) copolymers

Poly(butylene/diethylene succinate) block copolymers (PBSPDGS), prepared by reactive blending of the parent homopolymers (PBS and PDGS) in the presence of Ti(OBu)₄, were analyzed by ¹H-NMR, TGA and DSC, in order to investigate the effects of the transesterification reactions on the molecular structure and thermal properties. ¹H-NMR analysis evidenced the formation of copolymers whose degree of randomness increases with the mixing time. The thermal analysis of the melt-quenched samples showed that the melting peak, due to the crystalline phase of PBS, tends to disappear with increasing mixing time and therefore with decreasing the block length in the copolymers. As concern miscibility, a single homogeneous amorphous phase always occurred, independently on block length. Nevertheless, a phase separation, due to the tendency of the PBS blocks to crystallize, was evidenced in the copolymers with long butylene succinate sequences. The results obtained indicated that the block size had a fundamental role in determining the crystallizability and, therefore, phase behavior of the block copolymers.