RESUMO
In this work, the 70/30 and 30/70 w/w polycaprolactone (PCL)/polybutylene succinate (PBS) blends and their corresponding PCL/PBS/(polycarbonate (PC)/multiwalled carbon nanotubes (MWCNTs) masterbatch) nanocomposites were prepared in a twin-screw extruder. The nanocomposites contained 1.0 and 4.0 wt% MWCNTs. The blends showed a sea-island morphology typical of immiscible blends. For the nanocomposites, three phases were formed: (i) The matrix (either PCL- or PBS-rich phase depending on the composition), (ii) dispersed polymer droplets of small size (either PCL- or PBS-rich phase depending on the composition), and (iii) dispersed aggregates of tens of micron sizes identified as PC/MWCNTs masterbatch. Atomic force microscopy (AFM) results showed that although most MWCNTs were located in the PC dispersed phase, some of them migrated to the polymer matrix. This is due to the partial miscibility and intimate contact at the interfaces between blend components. Non-isothermal differential scanning calorimetry (DSC) scans for the PCL/PBS blends showed an increase in the crystallization temperature (Tc) of the PCL-rich phase indicating a nucleation effect caused by the PBS-rich phase. For the nanocomposites, there was a decrease in Tc values. This was attributed to a competition between two effects: (1) The partial miscibility of the PC-rich and the PCL-rich and PBS-rich phases, and (2) the nucleation effect of the MWCNTs. The decrease in Tc values indicated that miscibility was the dominating effect. Isothermal crystallization results showed that the nanocomposites crystallized slower than the neat blends and the homopolymers. The introduction of the masterbatch generally increased the thermal conductivity of the blend nanocomposites and affected the mechanical properties.
RESUMO
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.
RESUMO
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.