The electroactive properties of poly(vinylidene fluoride) (PVDF) are a direct consequence of its crystalline phases. Although poorly understood, nanostructuring PVDF in confined geometries can drastically change its crystallization behavior. Therefore, we synthesized a variety of PVDF-based triblock copolymers to gain a better understanding of the melt crystallization and explore how crystallization is affected by the morphology and chemical nature of the amorphous block. Differential scanning calorimetry, small-/wide-angle X-ray scattering, and transmission electron microscopy gave us excellent insights into the morphology and the corresponding crystalline phases. We find that crystallization of PVDF inside spherical nanodomains occurs via a homogeneous nucleation mechanism leading to a large undercooling and the formation of the thermodynamically favorable ferroelectric β-phase. On the contrary, when confined crystallization occurs inside a lamellar morphology, or in the case of breakout crystallization, a heterogeneous nucleation process leads to the formation of the nonferroelectric α-phase. Furthermore, favorable melt interactions between both blocks induce crystallization into the polar γ-phase at moderate cooling rates.

In this work, we report on a novel hydrogen-bonding compound, N,N′-bis(2-hydroxyethyl)terephthalamide (BHET), and its potential as additive in poly-l-lactide (PLA). Although the hydroxyl groups of BHET can participate in transesterification with the PLA matrix, we demonstrate through gel permeation chromatography that extrusion at 200 °C does not result in a drastic decrease in molecular weight. When dissolved in the PLA matrix, BHET facilitates a plasticizing effect, indicated by a suppression in both melt viscosity and glass-transition temperature. Additionally, BHET can crystallize from the PLA melt during cooling, where the generated BHET crystals facilitate heterogeneous nucleation of the PLA matrix. In general, BHET crystallization is favored at high undercooling/superstaturation, as this yields BHET crystals with a high surface area-to-volume ratio. However, rapid cooling to temperatures below the glass-transition temperature prevents the crystallization of the BHET, effectively yielding samples where only the plasticizing effect of BHET is evident. A suppression in yield point is observed during mechanical analysis of samples with increasing BHET concentration, a characteristic feature for samples with decreasing glass-transition temperatures. In contrast, when allowed to crystallize during processing, BHET can be used to generate PLA crystals oriented along the flow direction, effectively enhancing the tensile modulus. Overall, the combined plasticizing and nucleating effect of BHET makes it a verstaile additive for controlled processing and performance of PLA.

We report on the role of temperature and shear on the melt behavior of iPP in the presence of the organic compound N1,N1′-(propane-1,3-diyl)bis(N2-hexyloxalamide) (OXA3,6). It is demonstrated that OXA3,6 facilitates a viscosity suppression when it resides in the molten state. The viscosity suppression is attributed to the interaction of iPP chains/subchains with molten OXA3,6 nanoclusters. The exact molecular mechanism has not been identified; nevertheless, a tentative explanation is proposed. The observed viscosity suppression appears similar to that encountered in polymer melts filled with solid nanoparticles, with the difference that the OXA3,6 compound reported in this study facilitates the viscosity suppression in the molten state. Upon cooling, as crystal growth of OXA3,6 progresses, the decrease in viscosity is suppressed. Retrospectively, segmental absorption of iPP chains on the surface of micrometer-sized OXA3,6 crystallites favors the formation of dangling arms, yielding OXA3,6 crystallites decorated with partially absorbed iPP chains. In other words, the resulting OXA3,6 particle morphology resembles that of a hairy particle or a starlike polymer chain. Such hairy particles effectively facilitate a viscosity enhancement, similar to branched polymer chains. This hypothesis and its implications for the shear behavior of iPP are discussed and supported using plate–plate rheometry and slit-flow experiments combined with small-angle X-ray scattering analysis.

In this work, we have conducted in situ simultaneous small- and wide-angle X-ray scattering and Raman spectroscopy experiments to investigate the fundamental differences in the mechanism of the mesomorphic to α phase transition of the isotactic polypropylene homopolymer and the random ethylene–propylene copolymer. Via quantitative analysis of the results coming from the three techniques, we found that in the homopolymer, chain interlock and chain extension occur during the transition. However, these processes are not necessary for the transition to occur. Indeed, the presence of randomly distributed ethylene co-units hinders the chain interlock process in the early stages of the phase transition (T > 60 °C) and suppresses the chain elongation process at the later stages (T > 90 °C). Consequently, the mesomorphic to α-phase transition in the random copolymer occurs with inclusion of the ethylene co-units inside the crystal lattice, causing increased lateral interchain distance and larger crystalline sizes. Our results show how differences exist in the way solid phase transitions occur at the molecular scale when co-monomers are included into the macromolecular chains, leading to a better understanding of the thermal behavior of semi-crystalline polymers.

Thermoplastic composites consisting of a liquid crystalline polymer (LCP) and poly(lactide) (PLA) have the potential to combine good mechanical performance with recyclability and are therefore interesting as strong and sustainable composite materials. The viscoelastic behavior of both the LCP and the PLA is of great importance for the performance of these composites, as they determine the LCP morphology in the composite and play a crucial role in preventing the loss of mechanical performance upon recycling. Though the effect of the matrix viscosity is well-documented in literature, well-controlled systems where the LCP viscosity is tailored are not reported. Therefore, four LCPs, with the same chemical backbone but different molecular weights, are used to produce reinforced LCP-PLA composites. The differences in viscosity of the LCPs and viscosity ratio between the dispersed phase and the matrix of the blends are evident in the resultant composite morphology: in all cases fibrils are formed; however, the diameter increases considerably as the viscosity ratio increases for the higher molar mass LCPs. The fibril diameter ranges from several hundred nanometer to a few micrometer. A typical layered structure in the injection molded composites is observed, where the layer-thickness is influenced by the LCP viscosity. The LCPs are found to effectively reinforce the PLLA matrix, increasing the Young’s modulus by 60% and the maximum stress by 40% for the composite containing 30 wt % of the most viscous LCP. Remarkably, this did not result in an increase in brittleness, effectively increasing the toughness of the composite compared to pure PLLA. The feasible reprocessability of this composite is confirmed, by subjecting it to three reprocessing cycles. The relaxation of the LCPs orientation upon heating is measured via in situ WAXD. We compare the relaxation in an amorphous PLA matrix and in a semicrystalline PLLA matrix with that of the pure LCPs. The matrix viscosity is found to strongly influence the relaxation. For example, in a low viscous amorphous matrix relaxation of the LCP fibrils into droplets dominates the process, whereas a semicrystalline matrix helps in maintaining the fibril morphology and intermolecular orientation of the LCP. In the latter case, the LCPs relax via contraction and coalescence of the polydomain texture and maintains a significant degree of orientation until the PLLA crystals melt and the matrix viscosity decreases. The insights gained in this study on the role of the LCP viscosity on the morphology and performance of thermoplastic composites, as well as the relaxation of LCPs in a matrix, will aid progression toward sustainable and reprocessable LCP reinforced thermoplastic composites.

The complex physical transformations of polymers upon external thermodynamic changes are related to the molecular length of the polymer and its associated multifaceted energetic balance. The understanding of subtle transitions or multistep phase transformation requires real-time phenomenological studies using a multi-technique approach that covers several length-scales and chemical states. A combination of X-ray scattering techniques with Raman spectroscopy and Differential Scanning Calorimetry was conducted to correlate the structural changes from the conformational chain to the polymer crystal and mesoscale organization. Current research applications and the experimental combination of Raman spectroscopy with simultaneous SAXS/WAXS measurements coupled to a DSC is discussed. In particular, we show that in order to obtain the maximum benefit from simultaneously obtained high-quality data sets from different techniques, one should look beyond traditional analysis techniques and instead apply multivariate analysis. Data mining strategies can be applied to develop methods to control polymer processing in an industrial context. Crystallization studies of a PVDF blend with a fluoroelastomer, known to feature complex phase transitions, were used to validate the combined approach and further analyzed by MVA.