Ricardo A. Pérez-Camargo

The influence of small amounts of linear polycaprolactone chains on the crystallization of cyclic analogue molecules

Cyclic poly(e-caprolactone) model chains (C-PCL) were synthesized by a ring closure click chemistry technique. Identical linear precursors (L-PCL) of equivalent molecular lengths were also prepared. The effect of adding small amounts of linear (L-PCL) to cyclic analogs (C-PCL) was studied by preparing blends (C/L) in solution of the following composition range: 95/5, 90/10 and 80/20. Two sets of blends with PCL samples of different number average molecular weights (3 and 12 kg mol−1) were studied. The blends were analyzed by polarized light optical microscopy (PLOM) and advanced Differential Scanning Calorimetry (DSC) techniques that included non-isothermal and isothermal crystallization studies and thermal fractionation by SSA (Successive Self-nucleation and Annealing). The results show that addition of small amounts of linear chains (i.e., 5 and 10 wt%) to cyclic PCLs produces synergistic decreases in crystallization and melting temperatures, crystallinity degrees and isothermal crystallization rates (for both 3 and 12 kg mol−1 samples). When the amount of linear chains reaches 20 wt%, a significant recovery of a simple mixing law behavior is obtained. Thermal fractionation demonstrated that the addition of linear chains can reduce the annealing capacity of cyclic chains. The behavior of the C/L blends can be explained by the threading of ring molecules by linear chains. This threading effect amounts to an increase in entanglement density that reduces chain diffusion and hence crystallization rate.

Crystallization of Cyclic Polymers

The effect of chain topology (ring versus linear polymer chains) on polymer crystallization is reviewed. Recent advances in ring closure and ring expansion synthetic techniques have made available a range of well-characterized samples with higher levels of purity than available decades ago. Cyclic molecules are fascinating because the structural difference between them and linear chains is relatively small, yet their behavior can be completely different from that of their linear analogs of identical chain length. The effect of having no chain ends can dramatically change the polymer coil conformation and diffusion rate, as well as the chain entanglement density in the melt. These changes are reflected in different nucleation and crystallization kinetics for cyclic and linear polymeric chains. However, the results published so far seem to be dependent on the type of polymer employed. Therefore, a careful look at the literature and evidence reported for each group of materials has been assembled and compared. The possible reasons for some of the contradictions in the evidence are also discussed.

Morphology, Nucleation, and Isothermal Crystallization Kinetics of Poly(ε-caprolactone) Mixed with a Polycarbonate/MWCNTs Masterbatch

In this study, nanocomposites were prepared by melt blending poly (ε-caprolactone) (PCL) with a (polycarbonate (PC)/multi-wall carbon nanotubes (MWCNTs)) masterbatch in a twin-screw extruder. The nanocomposites contained 0.5, 1.0, 2.0, and 4.0 wt % MWCNTs. Even though PCL and PC have been reported to be miscible, our DSC (Differential Scanning Calorimetry), SAXS (Small Angle X-ray Scattering), and WAXS (Wide Angle X-ray Scattering) results showed partial miscibility, where two phases were formed (PC-rich and PCL-rich phases). In the PC-rich phase, the small amount of PCL chains included within this phase plasticized the PC component and the PC-rich phase was therefore able to crystallize. In contrast, in the PCL-rich phase the amount of PC chains present generates changes in the glass transition temperature of the PCL phase that were much smaller than those predicted by the Fox equation. The presence of two phases was corroborated by SEM, TEM, and AFM observations where a fair number of MWCNTs diffused from the PC-rich phase to the PCL-rich phase, even though there were some MWCNTs agglomerates confined to PC-rich droplets. Standard DSC measurements demonstrated that the MWCNTs nucleation effects are saturated at a 1 wt % MWCNT concentration on the PCL-rich phase. This is consistent with the dielectric percolation threshold, which was found to be between 0.5 and 1 wt % MWCNTs. However, the nucleating efficiency was lower than literature reports for PCL/MWCNTs, due to limited phase mixing between the PC-rich and the PCL-rich phases. Isothermal crystallization experiments performed by DSC showed an increase in the overall crystallization kinetics of PCL with increases in MWCNTs as a result of their nucleating effect. Nevertheless, the crystallinity degree of the nanocomposite containing 4 wt % MWCNTs decreased by about 15% in comparison to neat PCL. This was attributed to the presence of the PC-rich phase, which was able to crystallize in view of the plasticization effect of the PCL component, since as the MWCNT content increases, the PC content in the blend also increases. The thermal conductivities (i.e., 4 wt % MWCNTs) were enhanced by 20% in comparison to the neat material. The nanocomposites prepared in this work could be employed in applications were electrical conductivity is required, as well as lightweight and tailored mechanical properties.

Morphology, Nucleation, and Isothermal Crystallization Kinetics of Poly(Butylene Succinate) Mixed with a Polycarbonate/MWCNT Masterbatch

In this study, nanocomposites were prepared by melt blending poly(butylene succinate) (PBS) with a polycarbonate (PC)/multi-wall carbon nanotubes (MWCNTs) masterbatch, in a twin-screw extruder. The nanocomposites contained 0.5, 1.0, 2.0, and 4.0 wt% MWCNTs. Differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) results indicate that the blends are partially miscible, hence they form two phases (i.e., PC-rich and PBS-rich phases). The PC-rich phase contained a small amount of PBS chains that acted as a plasticizer and enabled crystallization of the PC component. In the PBS-rich phase, the amount of the PC chains present gave rise to increases in the glass transition temperature of the PBS phase. The presence of two phases was supported by scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis, where most MWCNTs aggregated in the PC-rich phase (especially at the high MWCNTs content of 4 wt%) and a small amount of MWCNTs were able to diffuse to the PBS-rich phase. Standard DSC scans showed that the MWCNTs nucleation effects saturated at 0.5 wt% MWCNT content on the PBS-rich phase, above this content a negative nucleation effect was observed. Isothermal crystallization results indicated that with 0.5 wt% MWCNTs the crystallization rate was accelerated, but further increases in MWCNTs loading (and also in PC content) resulted in progressive decreases in crystallization rate. The results are explained by increased MWCNTs aggregation and reduced diffusion rates of PBS chains, as the masterbatch content in the blends increased.

Supernucleation and Orientation of Poly(butylene terephthalate) Crystals in Nanocomposites Containing Highly Reduced Graphene Oxide

The ring-opening polymerization of cyclic butylene terephthalate into poly(butylene terephthalate) (pCBT) in the presence of reduced graphene oxide (RGO) is an effective method for the preparation of polymer nanocomposites. The inclusion of RGO nanoflakes dramatically affects the crystallization of pCBT, shifting crystallization peak temperature to higher temperatures and, overall, increasing the crystallization rate. This was due to a supernucleating effect caused by RGO, which is maximized by highly reduced graphene oxide. Furthermore, combined analyses by differential scanning calorimetry (DSC) experiments and wide-angle X-ray diffraction (WAXS) showed the formation of a thick α-crystalline form pCBT lamellae with a melting point of ∼250 °C, close to the equilibrium melting temperature of pCBT. WAXS also demonstrated the pair orientation of pCBT crystals with RGO nanoflakes, indicating a strong interfacial interaction between the aromatic rings of pCBT and RGO planes, especially with highly reduced graphene oxide.