Melt Crystallization of Poly(butylene 2,6-naphthalate)

Poly(butylene 2,6-naphthalate) (PBN) is a crystallizable linear polyester containing a rigid naphthalene unit and flexible methylene spacer in the chemical repeat unit. Polymeric materials made of PBN exhibit excellent anti-abrasion and low friction properties, superior chemical resistance, and outstanding gas barrier characteristics. Many of the properties rely on the presence of crystals and the formation of a semicrystalline morphology. To develop specific crystal structures and morphologies during cooling the melt, precise information about the melt-crystallization process is required. This review article summarizes the current knowledge about the temperature-controlled crystal polymorphism of PBN. At rather low supercooling of the melt, with decreasing crystallization temperature, β'- and α-crystals grow directly from the melt and organize in largely different spherulitic superstructures. Formation of α-crystals at high supercooling may also proceed via intermediate formation of a transient monotropic liquid crystalline structure, then yielding a non-spherulitic semicrystalline morphology. Crystallization of PBN is rather fast since its suppression requires cooling the melt at a rate higher than 6000 K·s−1. For this reason, investigation of the two-step crystallization process at low temperatures requires application of sophisticated experimental tools. These include temperature-resolved X-ray scattering techniques using fast detectors and synchrotron-based X-rays and fast scanning chip calorimetry. Fast scanning chip calorimetry allows freezing the transient liquid-crystalline structure before its conversion into α-crystals, by fast cooling to below its glass transition temperature. Subsequent analysis using polarized-light optical microscopy reveals its texture and X-ray scattering confirms the smectic arrangement of the mesogens. The combination of a large variety of experimental techniques allows obtaining a complete picture about crystallization of PBN in the entire range of melt-supercoolings down to the glass transition, including quantitative data about the crystallization kinetics, semicrystalline morphologies at the micrometer length scale, as well as nanoscale X-ray structure information

Enthalpy relaxation, crystal nucleation and crystal growth of biobased poly(butylene isophthalate)

The crystallization behavior of fully biobased poly(butylene isophthalate) (PBI) has been investigated using calorimetric and microscopic techniques. PBI is an extremely slow crystallizing polymer that leads, after melt-crystallization, to the formation of lamellar crystals and rather large spherulites, due to the low nuclei density. Based upon quantitative analysis of the crystal-nucleation behavior at low temperatures near the glass transition, using Tammann’s two-stage nuclei development method, a nucleation pathway for an acceleration of the crystallization process and for tailoring the semicrystalline morphology is provided. Low-temperature annealing close to the glass transition temperature (Tg) leads to the formation of crystal nuclei, which grow to crystals at higher temperatures, and yield a much finer spherulitic superstructure, as obtained after direct melt-crystallization. Similarly to other slowly crystallizing polymers like poly(ethylene terephthalate) or poly(l-lactic acid), low-temperature crystal-nuclei formation at a timescale of hours/days is still too slow to allow non-spherulitic crystallization. The interplay between glass relaxation and crystal nucleation at temperatures slightly below Tg is discussed

Evidence of early stage precursors of polymer crystals by dielectric spectroscopy

Dielectric spectra of the polyester poly(propylene succinate) were measured upon crystallization. For this model aliphatic polyester the α and β relaxations appear simultaneously and are well resolved in the experimental frequency window. During isothermal crystallization, this fact allows one to use the β relaxation to characterize the crystalline structural development while the α relaxation provides information about the evolution of the amorphous phase dynamics. In this way structure development and dynamics evolution can be characterized by a single experiment during the crystallization process. The unambiguous analysis of the dielectric loss clearly supports the existence of precursors of crystallization in the induction period. © 2007 The American Physical Society.Finnancial support from the MCYT (Grant No. MAT2005-01768), Spain.Peer Reviewe

Cold-crystallization of poly(butylene 2,6-naphthalate) following Ostwald's rule of stages

Melt-crystallization of poly (butylene 2,6-naphthalate) (PBN) at temperatures lower than about 160 \ub0C follows Ostwald's rule of stages, leading first to formation of a transient smectic liquid crystalline phase (LC) which then may convert in a second step into crystals, controlled by kinetics. In the present work, the PBN melt was cooled at different rates in a fast scanning chip calorimeter to below the glass transition temperature, to obtain different structural states before analysis of the cold-crystallization behavior on heating. It was found that heating of fully amorphous PBN at 1000 K/s leads to a similar two-step crystallization process as on cooling the quiescent melt, with LC-formation occurring slightly above Tg and their transformation into crystals at their stability limit close to 200 \ub0C. In-situ polarized-light optical microscopy provided information that the transition of the LC-phase into crystals on slow heating is not connected with a change of the micrometer-scale superstructure, as the recently found Schlieren texture remains unchanged

Bio-based aliphatic/aromatic poly(trimethylene furanoate/sebacate) random copolymers:Correlation between mechanical, gas barrier performances and compostability and copolymer composition

Highly promising fully biobased random copolyesters, poly(trimethylene 2,5-furandicarboxylate-co-trimethylene sebacate) (PTFcoPTSeb), were synthesized by using bio derived 1,3-propanediol, dimethyl ester of 2,5- furandicarboxylic acid, and sebacic acid, through eco-friendly polycondensation in the melt. Copolymers with high molecular weight containing 5, 15, 25 mol % of PTSeb were obtained, and their chemical structure confirmed by 1H NMR and FTIR spectroscopy. The thermal, tensile and gas barrier properties and composability were studied in relation to the copolymer supramolecular structure. As expected, introduction of PTSeb co-units results in lowering of glass transition temperature of copolymers and improves their flexibility. Besides, all copolymers showed outstanding gas barrier properties to O2 and CO2, with copolymer containing 15 mol % of PTSeb showing exceptional gas barrier properties, better than those of PTF and comparable to those of EVOH, currently used in multilayer packaging films. The same copolymer exhibited temperature induced shape memory behaviour. It was found that low amounts (15-25 mol %) of PTSeb in copolymer significantly modifies PTF thermal, mechanical and barrier properties and renders the final material compostable. Copolyesters containing 15 and 25 mol % of PTSeb can compete in some applications with commercially available compostable Ecoflex® polymer, but with markedly improved barrier properties.</p

Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s’ Molecular Dynamics

Abstract Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure–property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s.This research was funded by the European Union: EUSMI, H2020-INFRAIA-2016-1, PROJECT 731019, via proposals E171100043 and E171100040. The APC was funded by EUSMI. B.R.-H. and A.A. acknowledge funding from Basque Government (IT-1175-19). D.E.M.-T. acknowledges financial support via the postdoctoral fellowship “Juan de la Cierva–Incorporación” grant (IJCI-2017-31600, MCIU–Spain). G.G., M.S. and N.L. and A.M. acknowledge financial support via the framework COST Action FUR4Sustain, CA18220, supported by COST (European Cooperation in Science and Technology)

Evaluation of the Factors Affecting the Disintegration under a Composting Process of Poly(lactic acid)/Poly(3-hydroxybutyrate) (PLA/PHB) Blends

The overall migration behavior and the disintegration under composting conditions of films based on plasticized poly(lactic acid)/poly(3-hydroxybutyrate) (PLA-PHB) blends were studied, with the main aim of determining the feasibility of their application as biodegradable food packaging materials. The role of composition in the disintegration process was evaluated by monitoring the changes in physical and thermal properties that originated during the degradation process. PLA and PHB were blended in two weight ratios with 15 wt% of tributyrin, using a Haake mixer and then compression molded into ~150 µm films. We found that the migration level of all of the studied blends was below check intended meaning retained in non-polar simulants, while only plasticized blends could withstand the contact with polar solvents. The disintegration of all of the materials in compost at 58 ◦C was completed within 42 days; the plasticized PHB underwent the fastest degradation, taking only 14 days. The presence of the TB plasticizer speeded up the degradation process. Different degradation mechanisms were identified for PLA and PHB. To evaluate the annealing effect separately from bacteria degradation, the influence of temperature on materials in the absence of a compost environment was also studied. With the increasing time of degradation in compost, both melting temperature and maximum degradation temperature progressively decreased, while the crystallinity degree increased, indicating that the samples were definitely degrading and that the amorphous regions were preferentially eroded by bacteria.Fil: Iglesias Montes, Magdalena Luz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Soccio, Michelina. Università di Bologna; ItaliaFil: Luzi, Francesca. Università di Perugia; ItaliaFil: Puglia, Debora. Università di Perugia; ItaliaFil: Gazzano, Massimo. National Research Council; ItaliaFil: Lotti, Nadia. Università di Bologna; ItaliaFil: Manfredi, Liliana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Cyras, Viviana Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Laser-Induced Periodic Surface Structures on Conjugated Polymers: Poly(3-hexylthiophene)

8 pags.; 11 figs.© 2015 American Chemical Society. In this work, we report on the surface patterning of semiconducting poly(3-hexylthiophene) (P3HT) thin films by means of laser-induced periodic surface structures (LIPSS). Two different laser wavelengths, 266 and 532 nm, and a broad range of fluences and number of pulses have been used in order to optimize the LIPSS morphology. Ripples period and depth can be tuned by laser parameters. In particular, the high optical absorption of P3HT at 532 nm enables the formation of well-ordered nanostructures with periodicities around 460 nm. Near edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopy reveal a good chemical stability of P3HT thin films during LIPSS formation. Conducting atomic force microscopy (C-AFM) performed on the LIPSS reveals a higher electrical conduction in the trenches than in the ridge regions. Resonance Raman spectroscopy and grazing incidence wide-angle X-ray scattering (GIWAXS) indicate a loss of crystallinity of P3HT thin films during LIPSS formation, suggesting melting of the outer polymer surface. This effect produces ridges with molecular order lower than that of the original thin film. As a consequence of this transformation, the electrical conduction in the ridges becomes lower than that in the trenches.The authors gratefully acknowledge the financial support of the Spanish Ministry of Economy and Competitiveness (MINECO) through Projects MAT 2011-23455, MAT 2012-33517 and CTQ 2013-43086-P. A.R.-R. and E.R. are indebted to MINECO for a FPI (BES-2013-062620) and Ramon y Cajal (RYC-2011-08069) contracts, respectively. We thank the Swiss Light Source for beamtime at PolLux, where the NEXAFS experiments were performed. We also thank the ESRF for beamtime at BM26 where in situ GISAXS and GIWAXS experiments were carried out. We thank B. Watts for assistance in using beamline PolLux and G. Portale and W. Bras for beamline support at BM26. P. Müller-Buschbaum and S. Guo are thanked for seminal comments at the beginning of this workPeer Reviewe