Quantitative Analysis of Morphology and Surface Properties of Poly(lactic acid)/Poly(ε-caprolactone)/Hydrophilic Nano-Silica Blends.

A quantitative analysis of the morphology, as well as an analysis of the distribution of components and surface/interfacial properties in poly(lactic acid)(PLA) InegoTM 3251D, poly(ε-caprolactone) (PCL) Capa 6800 and nano-silica (SiO2) Aerosil®200 blends, was conducted in this research. The study aimed to improve the understanding of how PLA, PCL, and nano-SiO2 interact, resulting in the specific morphology and surface properties of the blends. Samples were produced by varying the concentration of all three components. They were analyzed using SEM, EDS mapping, water contact angle measurements, surface free energy calculation, adhesion parameter measurements, and FTIR-ATR spectroscopy. The results showed that the addition of SiO2 nanoparticles led to an increase in the contact angle of water, making the surface more hydrophobic. SEM images of the blends showed that increasing the PCL content reduced the size of spherical PCL elements in the blends. FTIR-ATR analysis showed that SiO2 nanoparticles influenced the structure ordering of PLA in the blend with equal portions of PLA and PCL. In the samples with a higher PCL content, the spherical elements present in the samples with a higher PLA/PCL ratio have been reduced, indicating better interactions at the interface between PLA, PCL, and SiO2. SEM-EDS mapping of the PLA/PCL 100/0 blend surfaces revealed the presence of SiO2 clusters and the silicon (Si) concentration reaching up to ten times higher than the nominal concentration of SiO2. However, with the addition of 3% SiO2 to the blend containing PCL, the structure became more granular. Specifically, Si protrusions in the sample PLA/PCL 90/10 with 3% SiO2 displayed 29.25% of Si, and the sample PLA/PCL 70/30 with 3% SiO2 displayed an average of 10.61% of Si at the protrusion locations. The results confirmed the affinity of SiO2 to be encapsulated by PCL. A better understanding of the interactions between the materials in the presented blends and the quantitative analysis of their morphology could improve the understanding of their properties and allow the optimization of their application for different purposes.

Effect of the Addition of Nano-Silica and Poly(ε-caprolactone) on the Mechanical and Thermal Properties of Poly(lactic acid) Blends and Possible Application in Embossing Process.

In this study, the mechanical and thermal properties of poly(lactic acid) (PLA) blends with an addition of poly(ε-caprolactone) (PCL) and fumed silica (SiO2) were evaluated to research the possibility of their use as relief printing plates for embossing processes. PCL and nano-silica were added to the PLA matrix at different concentrations. Morphological, thermal and mechanical analyses were performed to determine the properties and possible functional characteristics of the studied blends. SEM micrographs showed that unmodified PLA/PCL blends exhibit a morphology typical of incompatible blends with clearly visible spherical domains of dispersed PCL in PLA. In particular, the results of the hardness tests showed that the selected blends have the optimal hardness (between 65 SH D and 75 SH D) for use in the embossing process. The tensile tests showed that the addition of nano-silica to neat PLA and to the PLA/PCL blends 50/50 and 60/40 improved the mechanical properties of the blends, especially stiffness and toughness. The DMA results showed that the addition of smaller amounts of SiO2 can contribute to an increase in storage modulus, which is due to good dispersion and distribution of SiO2 in the matrix. DSC analysis showed that the addition of PCL to PLA polymer increased the thermal stability of PLA and that the addition of nano-silica increased the degree of crystallinity of PLA. The TGA results showed that the addition of nano-silica improved the thermal degradation behavior of the studied blends, especially for blends modified with 3 wt% nano-silica. The results show that it is possible to optimize the mechanical and thermal properties of the blends with the aim of using them in the embossing process.

Blends Based on Poly(ε-Caprolactone) with Addition of Poly(Lactic Acid) and Coconut Fibers: Thermal Analysis, Ageing Behavior and Application for Embossing Process.

In this research a biodegradable blend of poly(ɛ-caprolactone) (PCL) and poly(lactic acid) (PLA) is proposed as a new material for the production of a relief printing plate used for special applications on packaging materials, i.e., the embossing process. Coconut fibers (CFs) were added as a natural filler to PCL/PLA blends to improve the functional properties of the prepared blends. Thermal, mechanical and surface analyses were performed on the unaged and artificially aged blends. The results showed that CF has been proven to optimize the hardness of the blend, which is crucial for the production of relief plate for embossing applications. The lowest hardness was measured on neat PCL (53.30° Sh D) and the highest value on PCL/PLA/CF 70/30/3.0 blend (60.13° Sh D). Stronger interfacial interactions were present at the PLA/CF interface because the interfacial free energy is closer to zero and the work of adhesion and spreading coefficient are higher than for the PCL/CF interface. The results of thermal analysis of unaged and aged blends showed that ageing for 3 weeks resulted in significantly lower thermal stability, especially for neat PCL and PCL/PLA 80/20 blends. Blends with a higher content of PLA and CF showed a slightly increased ageing resistance, which is attributed to the increased crystallinity of PLA after ageing due to the addition of CF showed in the DSC diagrams.