RESUMO
Biodegradable polymers have gained great interest as ecofriendly packaging materials. However, addition of suitable fillers to the polymer matrix enhances their barrier and mechanical properties besides gaining new features such as bactericidal activity. This work deals with investigation of mechanical, gas/water transport properties and biodegradability performance of films based on polycaprolactone (PCL) reinforced by 1wt% of reduced graphene oxide (RGO) or modified graphene (mRG). To achieve this goal, nanosheets of RGO were firstly prepared then their surfaces were modified through in situ polymerization of hyperbranched polyester (PES) to obtain mRG. Then PCL was loaded with both fillers, and the nanocomposite films were prepared by a casting technique. Studying of the thermal properties of the films showed that the addition of RGO or mRG had no influence on the crystallinity of the PCL matrix. Although the mechanical characteristics of the PCL did not change when either filler was added, there was an increase in permeability and diffusivity in the presence of the fillers regardless of their composition. Nevertheless, the nanocomposites demonstrated antimicrobial properties against S. aureus and E. coli as models for Gram-positive and Gram-negative bacteria, respectively. The biodegradability test performed on the prepared film PCL, and those containing 1% of the filler, PCL/RGO, and PCL/mRG, emphasized that the film degradation became pronounced after three months for all samples.
RESUMO
Nanocomposite films of polybutylene succinate (PBS)/graphene nanoplatelets (GnP) with a GnP content ranging from 0 to 1.35 wt.% were prepared by melt processing. The morphology of both the neat PBS and PBS/GnP nanocomposites were investigated and revealed no significant impact of GnP on the crystalline microstructure. Moisture sorption at 10 °C, 25 °C, and 40 °C were analyzed and modeled using the Guggenheim, Andersen, and De Boer (GAB) equation and Zimm-Lundberg theory, allowing for a phenomenological analysis at the molecular scale. An understanding of the transport sorption properties was proposed by the determination of the molar heat of sorption (ΔHs), and the activation energy of the diffusion (Ed) of water in the matrix since both solubility and diffusion are thermo-activable properties. Both ΔHs and Ed showed a good correlation with the water clustering theory at high water activity. Water and dioxygen permeabilities ( and ) were determined as a function of temperature and water activity. and decreased with the addition of a small amount of GnP, regardless of the studied temperature. Moreover, the evolution of as a function of water activity was driven by the solubility process, whereas at a given water activity, was driven by the diffusion process. Activation energies of the permeability (Ep) of water and dioxygen showed a dependency on the nature of the permeant molecule. Finally, from the ΔHs, Ed, and Ep obtained values, the reduction in water permeability with the addition of a low content of GnP was attributed mainly to a tortuosity effect without diffusive interfaces rather than a significant change in the transport property mechanism.
RESUMO
Polybutylene Succinate (PBS)/Graphene nanoplatelets (GnP) nanocomposites over a range of GnP from 0 to 1.35 wt.%. were prepared by a melt process. A mixture of individual graphene nanosheets and aggregates was obtained by the addition of GnP in the PBS matrix. The presence of these fillers did not significantly modify the morphology, crystalline microstructure of the matrix or its thermal stability. However, a slight reinforcement effect of PBS was reported in the presence of GnP. The water sorption isotherm modelling with Guggenheim, Andersen and De Boer (GAB) equation and Zimm-Lundberg theory allowed a phenomenological analysis at the molecular scale. The presence of GnP did not modify the water sorption capacity of the PBS matrix. From a kinetic point of view, a decrease of the diffusion coefficient with the increasing GnP content was obtained and was attributed to a tortuosity effect. The influence of water activity was discussed over a range of 0.5 to 1 and 0 to 0.9 for water and dioxygen permeability. Improvement of the barrier properties by 38% and 35% for water and dioxygen permeability respectively were obtained.
