Self-nucleation (SN) is a special nucleation process triggered by selfseeds or self-nuclei that are generated in a given polymeric material by specific thermal protocols or by inducing chain orientation in the molten or partially molten state. SN increases the nucleation density of polymers by several orders of magnitude, producing significant modifications to their morphology and overall crystallization kinetics. In fact, SN can be used as a tool for investigating the overall isothermal crystallization kinetics of slow-crystallizing materials by accelerating the primary nucleation stage in a previous SN step. Additionally, SN can facilitate the formation of one particular crystalline phase in polymorphic materials. The SN behavior of a given polymer is influenced by its molecular weight, molecular topology, and chemical structure, among other intrinsic and extrinsic characteristics. This review paper focuses on the applications of DSC-based SN techniques to study the nucleation, crystallization, and morphology of different types of polymers, blends, copolymers, and nanocomposites.

The structure, morphology and thermal properties of biobased and biodegradable poly(butylene succinate-ran-butylene azelate) random copolyesters with a wide composition range were studied. These PBS-ran-PBAz copolymers can crystallize in the entire composition range despite being random, displaying a eutectic point when their melting point is plotted as a function of composition. Wide Angle Xray Scattering (WAXS) studies confirmed isodimorphic behavior where PBS-rich copolymers crystallize with PBS type unit cells with some PBAz repeating units inclusions and vice versa for PBAz-rich copolymers. Away from eutectic compositions the copolymers exhibit only one crystalline phase (PBS-rich or PBAzrich crystalline phases) while at the eutectic point both phases can crystallize. The only double crystalline copolymer amongst those prepared had a composition close to the eutectic point of 45 mol% PBS (and 55 mol% PBAz). The crystallization of the two phases occurred in the same temperature range upon cooling from the melt at 10ºC/min in a DSC (i.e., coincident crystallization). Self-nucleation (SN) studies of the PBS-rich phase were performed. After SN, the separate crystallization of each phase was clearly observed during cooling from the self-nucleation temperature (i.e., PBS and PBAz-rich phases). Small Angle X-ray Scattering (SAXS) experiments were performed for the first time for this type of isodimorphic copolymers. The results show that the lamellar long period is a strong function of composition. While limited inclusions of PBAz units within the crystal lattice only cause a slight expansion of the PBS component unit cell, the increase of comonomer content produces an unexpected synergistic increase in long periods and lamellar thickness values. In the case of the only double crystalline copolymer examined, the PBS-rich phase forms space filling spherulites (observed by Polarized Light Optical Microscopy, PLOM) at higher temperatures that template the superstructural morphology of the copolymer. These PBS-rich phase spherulites contain radial lamellar stacks whose long period was determined by SAXS. Upon further cooling, the PBAz-rich phase crystallizes in the intra-spherulitic amorphous regions with newly form lamellae that have their own distinct long period according to SAXS results. AFM observations of the PBS-rich crystalline lamellae confirmed the lamellar thickness and long spacings determined by SAXS. A schematic morphological model of the mixed spherulites produced by this double crystalline diblock copolymer is proposed based on the experimental evidences collected by SAXS, PLOM and AFM.

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In this paper, ring closure click chemistry methods have been used to produce cyclic c-PLLA and c-PDLA of a number average molecular weight close to 10 kg/mol. The effects of stereochemistry of the polymer chains and their topology on their structure, nucleation and crystallization were studied in detail employing Wide Angle X-ray Scattering (WAXS), Small Angle X-ray Scattering (SAXS), Polarized Light Optical Microscopy (PLOM) and standard and advanced Differential Scanning Calorimetry (DSC). The crystal structures of linear and cyclic PLAs are identical to each other and no differences in superstructural morphology could be detected. Cyclic PLA chains are able to nucleate much faster and to produce a higher number of nuclei in comparison to linear analogues, either upon cooling from the melt or upon heating from the glassy state. In the samples prepared in this work, a small fraction of linear or higher molecular weight cycles was detected (according to SEC analyses). The presence of such "impurities" retards spherulitic growth rates of c-PLAs making them nearly the same as those of l-PLAs. On the other hand, the overall crystallization rate determined by DSC was much larger for c-PLAs, as a consequence of the enhanced nucleation that occurs in cyclic chains. The equilibrium melting temperatures of cyclic chains were determined and found to be 5 ºC higher in comparison with values for l-PLAs. This result is a consequence of the lower entropy of cyclic chains in the melt. Self-nucleation studies demonstrated that c-PLAs have a shorter crystalline memory than linear analogues, as a result of their lower entanglement density. Successive selfnucleation and annealing (SSA) experiments reveal the remarkable ability of cyclic molecules to thicken, even to the point of crystallization with extended collapsed ring conformations. In general terms, stereochemistry had less influence on the results obtained in comparison with the dominating effect of chain topology.

Tuning the thermal properties and morphology of isodimorphic poly[(butylene succinate)-ran-(ɛ-caprolactone)] copolyesters by changing composition, molecular weight and thermal history

The sequential crystallization of poly(ethylene oxide)-b-poly(e-caprolactone)-b-poly(L-lactide) (PEO-b-PCL-b-PLLA) triblock terpolymers, in which the three blocks are able to crystallize separately and sequentially from the melt, is presented. Two terpolymers with identical PEO and PCL block lengths and two different PLLA block lengths were prepared, thus the effect of increasing PLLA content on the crystallization behavior and morphology was evaluated. Wide angle X-Ray scattering (WAXS) experiments performed on cooling from the melt confirmed the triple crystalline nature of these terpolymers and revealed that they crystallize in sequence: the PLLA block crystallizes first, then the PCL block, and finally the PEO block. Differential scanning calorimetry (DSC) analysis further demonstrated that the three blocks can crystallize from the melt when a low cooling rate is employed. The crystallization process takes place from a homogenous melt as indicated by small angle X-Ray scattering (SAXS) experiments. The crystallization and melting enthalpies and temperatures of both PEO and PCL blocks decrease as PLLA content in the terpolymer increases. Polarized light optical microscopy (PLOM) demonstrated that the PLLA block templates the morphology of the terpolymer, as it forms spherulites upon cooling from the melt. The subsequent crystallization of PCL and PEO blocks occurs inside the interlamellar regions of the previously formed PLLA block spherulites. In this way, unique triple crystalline mixed spherulitic superstructures have been observed for the first time. As the PLLA content in the terpolymer is reduced the superstructural morphology changes from spherulites to a more axialitic-like structure.

In this work, we study for the first time, the isothermal crystallization behavior of isodimorphic random poly(butylene succinate)-ran-poly(ε-caprolactone) copolyesters, PBS-ran-PCL, previously synthesized by us. We perform nucleation and spherulitic growth kinetics by polarized light optical microscopy (PLOM) and overall isothermal crystallization kinetics by differential scanning calorimetry (DSC). Selected samples were also studied by real-time wide angle X-ray diffraction (WAXS). Under isothermal conditions, only the PBS-rich phase or the PCL-rich phase could crystallize as long as the composition was away from the pseudo-eutectic point. In comparison with the parent homopolymers, as comonomer content increased, both PBS-rich and PCL-rich phases nucleated much faster, but their spherulitic growth rates were much slower. Therefore, the overall crystallization kinetics was a strong function of composition and supercooling. The only copolymer with the eutectic composition exhibited a remarkable behavior. By tuning the crystallization temperature, this copolyester could form either a single crystalline phase or both phases, with remarkably different thermal properties.

ABSTRACT:The structure and thermal properties of linear lowdensity polyethylene (LLDPE)/medium soft paraffin wax blends, prepared by melt mixing, were investigated by differential scanning calorimetry (DSC) and small-and wide-angle X-ray scattering (SAXS and WAXS). The blends form a single phase in the melt as determined by SAXS. Upon cooling from the melt, two crystalline phases develop for blends with more than 10 wt % wax characterized by widely different melting points. The wax acts as an effective plasticizer for LLDPE, decreasing both its crystallization and melting temperature. The higher melting point crystalline phase is formed by less branched LLDPE fractions. On the other hand, the lower melting point crystalline phase is a wax-rich phase constituted by cocrystals of extended chain wax and short linear sequences of highly branched LLDPE chains. The presence of cocrystals was evidenced by standard DSC results, successive self-nucleation and annealing (SSA) thermal fractionation and by the detection of a new SAXS signal attributed to the lamellar long period of the cocrystals.