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Unformatted post-print version of the accepted article, There has been considerable interest in the nucleation and crystallization of polymers in the presence of nanoparticles (NPs, or nanofillers in general, NFs). Most of the extensive work in this area has focused on anisotropic, non-Brownian NFs (e.g., clay sheets, carbon nanotubes) whose spatial dispersion state in these nanocomposites is controlled by the process by which they are formed. While NF spatial dispersion is thus generally poor, or poorly characterized, in many works, thermodynamic handles that can be used to control NF dispersion state in the polymer melt include (a) favorable interactions between the polymer chains and the bare NP surfaces, or (b) the density and length of the chains, with the same chemistry as the matrix, grafted to the NP surface. These relatively large NFs merely act as immovable objects that affect the kinetics of nucleation by providing heterogeneous sites, and the crystallization rate by confining the polymer in the melt state. The dispersion state of the NFs can dramatically 2 affect the nucleation and crystallization of the matrix, but in most cases reported, the NFs increase nucleation efficiency relative to the neat polymer. At higher NF loadings, the effect of polymer confinement by the NFs dominates, leading to a decrease in crystal growth rates. In this review, we first describe the most important lessons learned from these commonly studied systems and then use this knowledge to understand the results obtained when small, mobile spherical NPs (typically smaller than 100 nm in size) are used as the nanofillers. The role of NP mobility, which provides for dynamic confinement of the polymer melt, on the kinetics of polymer crystallization (nucleation, growth, and overall crystallization) and how this behavior is mostly consistent with the case of immobile NF is a second important focus of our review. In addition to the role of NFs on crystallization kinetics, we discuss recently reported nanoparticle ordering phenomena, i.e.

The crystallization kinetics of semicrystalline polymers is often studied with isothermal experiments and analyzed by fitting the data with analytical expressions of the Avrami and Lauritzen and Hoffman (LH) theories. To correctly carry out the analysis, precautions both in experiments and data fitting should be taken. Here, we systematically discussed the factors that influence the validity of the crystallization kinetics study. The basic concepts and fundamentals of the Avrami and LH theories were introduced at first. Then, experimental protocols were discussed in detail. To clarify the impact of various experimental parameters selected common polymers, i.e., polypropylene and polylactide, were studied using various experimental techniques (i.e., differential scanning calorimetry and polarized light optical microscopy). Common mistakes were simulated under conditions when non-ideal experimental parameters were applied. Furthermore, from a practical point of view, we show how to fit the experimental data to the Avrami and the LH theories, using an Origin ® App developed by us.

Unformatted preprint version of the submitted article, Successive self-nucleation and annealing (SSA) can thermally fractionate semi-crystalline polymers, thus detecting the characteristic structural features that lead to specific melting point distributions (corresponding to the lamellar thickness distribution in the sample). SSA has been employed to investigate the structural evolution of polyamide 1012 (PA1012) when it is submitted to thermal treatments in the solid-state (below the melting point, Tm) as well as in the liquid-state (above Tm), as a function of the molecular weight of the sample. Below Tm, mainly chemical crosslinking occurred, thus provoking the decrease in the melting enthalpy of the highest temperature SSA melting fraction. The structural evolution was limited primarily by crystallization, and the high crystallinity of the low molecular weight samples led to low crosslinking rates. Above Tm, the structural evolution was correlated with the melt viscosity and the end group concentration. The concentration and diffusion ability of end groups was inversely proportional to the initial melt viscosities, therefore linear chain growing rate increased with the decrease in initial melt viscosities. Crosslinking reaction rate increased with the increase in initial melt viscosities. This work has determined the structural evolution differences of PA1012 depending on different initial states. This work can provide guidance for studies of thermal structural evolution of all AABB-type polyamides and subsequent design of high-performance materials with various structures according to their application requirements.

Unformatted post-print version of the accepted article, A series of aliphatic polyethers with different chain lengths (nCH2= 6 to 12, and 16) is studied employing differential scanning calorimetry and X-rays scattering. The calorimetric and structural behavior of samples crystallized from the melt is divided into the odd-even and saturation regions. In the odd-even region (nCH2 = 6 to 10), the odd samples (nCH2 = 7, and 9) show enhanced calorimetric properties (e.g., higher transition temperatures) and faster crystallization kinetics than the even ones (nCH2 = 6, 8 and 10). The odd samples crystallize in orthorhombic unit cells and the even ones in monoclinic unit cells. In the saturation region (nCH2 = 11 to 16), the calorimetric properties increase as nCH2 increases without alternation. However, unexpectedly, the nCH2 = 12 displayed a mixed structure (monoclinic + orthorhombic) instead of an orthorhombic one. Thus, a structural saturation effect (i.e., an orthorhombic unit cell) is not reached. This particular structural feature was investigated under varied thermal histories, induced by different cooling rates. The samples as synthesized (i.e., crystallized during precipitation from solution) exhibited a structural saturation effect since both nCH2 = 10 and 12 display an orthorhombic unit cell. But, the nCH2 = 10 exhibits a monoclinic unit cell, and the nCH2 = 12 a mixed structure when the samples crystallize from the melt at different rates. Only the nCH2 = 16 crystallizes in an orthorhombic unit cell, independently of the thermal history. Thus, the complex odd-even effects in these aliphatic polyethers are a function of the cooling rate from the melt and sample preparation procedures (solution or melt crystallization).

[EN]In the present work, crystallization of a soluble nucleator N, N′, N″-tricyclohexyl-1,3,5-benzenetricarboxylamide (TMC-328) in a poly(l-lactic acid) (PLLA) matrix has been studied at different temperatures. Based on the change in solubility with temperature, different levels of supersaturation of TMC-328 in a PLLA matrix can be obtained. This nucleator presents a fibrous structure produced via self-assembling and develops into an interconnected network when the temperature is lowered. The TMC-328 crystal nuclei density is quantified via optical microscopy, using the average distance of the adjacent fibrillar structure, which shows a steady decrease with the decrease in temperature. The crystallization rates of TMC-328 were assessed through rheological measurements of network formation. Both fibrils’ density and crystallization kinetics display a power law dependence on supersaturation. For the first time, the solid–melt interfacial energy, the size of the critical nucleus, and the number of molecules making up the critical nucleus of the nucleator TMC-328 in the PLLA matrix have been determined by adopting the classical nucleation theory. The subsequent crystallization of PLLA induced by this nucleator was investigated as a function of the fibrils’ spatial density. The crystallization rate of PLLA is enhanced with the increase in the TMC-328 fibrils’ density because of the availability of a larger nucleating surface. The self-assembled fibril of TMC-328 can serve as shish to form a hybrid shish-kebab structure after the crystallization of PLLA, regardless of the number of nucleation sites.

Unformatted preprint version of the submitted article, In this work, we studied the composition-dependent miscibility of polyamide 6 and biobased polyamide 4,10 (PA6/PA410) blends, as triggered by crystallization driven phase segregation. The blends were prepared by extrusion melt blending in a wide composition range and studied by Differential Scanning Calorimetry (DSC), X-ray diffraction (both in-situ and ex-situ SAXS/WAXS), and Polarized Light Optical Microscopy (PLOM) during non-isothermal crystallization. The blends were found to be miscible in the amorphous state, as demonstrated by a single Tg that follows the Fox equation as a function of composition. The blends were also considered to be miscible in the melt, as no evidence of phase segregation was found by SAXS or phase contrast microscopy in the melt. The miscibility of the blends in the crystalline state is a strong function of composition. When only 10 or 20% PA6 is present in the blends, co-crystallization was evidenced by DSC and WAXS and the blends exhibited a single PA410 rich crystalline phase. On the other hand, as 30% or more PA6 is added to PA410, crystallization driven phase segregation occurs and progressively increased with PA6 content in the blends. Hence double crystalline blends are formed with both PA6 rich and PA410 rich crystalline phases. Clear evidence of either one or two crystalline phases was demonstrated by temperature-dependent measurements employing DSC, PLOM, WAXS and SAXS. Both the single and double crystalline PA6/PA410 blends exhibited good mechanical properties in view of the excellent compatibility displayed by the blends. The mechanical properties are in line with those exhibited by miscible blends following a simple rule of mixtures.

Unformatted preprint version of the submitted article, The crystallization of heterogeneously nucleated bulk polymers typically occurs in a single exothermic process, within a narrow temperature range, i.e., a single exothermic peak is detected by Differential Scanning Calorimetry when the material is cooled from the melt. However, when a bulk semicrystalline polymer is subdivided or dispersed into a multitude of totally (or partially) isolated microdomains (e.g., droplets or cylinders), in number comparable to that of commonly available nucleating heterogeneities, several separated crystallization events are typically observed, i.e., fractionated crystallization. This situation is often found for the minor crystallizable component in immiscible blends. When the bulk polymer is dispersed into a number of microdomains that is several orders of magnitude higher than the available number of heterogeneities within it, most microdomains will be heterogeneity-free. In these clean microdomains the nucleation can occur by contact with the interfaces (i.e., surface nucleation) or by homogeneous nucleation inside the microdomain volume. These cases can be easily encountered in cylinders or spheres within strongly segregated block copolymers, or in infiltrated polymers within nanopores of alumina templates. In this work, a comprehensive review of the known cases of fractionated crystallization is provided. The changes upon decreasing microdomain sizes from a dominant single heterogeneous nucleation, through fractionated crystallization, to surface or homogeneous nucleation are critically reviewed. Emphasis is placed on the common features of the phenomenon across the different systems, and thus on the general conclusions that can be drawn from the analysis of representative semicrystalline polymers. The origin of the fractionated crystallization effects and their dramatic consequences on the nucleation and crystallization kinetics of semicrystalline polymers are also discussed.