Renewable poly(lactic acid) (PLA) exhibits high strength and stiffness. PLA is fully biodegradable and has received great interest. However, the inherent brittleness of PLA largely impedes its wide applications. In this article, the recent progress in PLA toughening using various routes including plasticization, copolymerization, and melt blending with flexible polymers, was reviewed in detail. PLA toughening, particularly modification of impact toughness through melt blending, was emphasized in this review. Reactive blending was shown to be especially effective in achieving high impact strength. The relationship between composition, morphology, and mechanical properties were summarized. Toughening mechanisms were also discussed.
In this study, a poly(lactic acid) (PLA) ternary blend system consisting of PLA, an epoxycontaining elastomer, and a zinc ionomer was introduced and studied in detail. Transmission electron microscopy revealed that the "salami"-like phase structure was formed in the ternary blends. While increase in blending temperature had little effects on the tensile properties of the resulting blends, it greatly changed the impact strength. For the blends prepared at 240 °C by extrusion blending, the resulting PLA ternary blends displayed supertoughness with moderate levels of strength and modulus. It was found that the zinc ions catalyzed the cross-linking of epoxy-containing elastomer and also promoted the reactive compatibilization at the interface of PLA and the elastomer. Both blending temperature and elastomer/ionomer ratio were found to play important roles in achieving supertoughness of the blends. The significant increase in notched impact strength was attributed to the effective interfacial compatibilization at elevated blending temperatures.
Polyactide (PLA) was blended with an ethylene/n-butyl acrylate/glycidyl methacrylate (EBA-GMA) terpolymer and a zinc ionomer of ethylene/methacrylic acid (EMAA-Zn) copolymer. The phase morphology of the resulting ternary blends and its relationship with impact behaviors were studied systematically. Dynamic vulcanization of EBA-GMA in the presence of EMAA-Zn was investigated by torque rheology, and its cross-link level was evaluated by dynamic mechanical analysis. Reactive compatibilization between PLA and EBA-GMA was studied using Fourier transform infrared spectroscopy. The dispersed domains in the ternary blends displayed a “salami”-like phase structure, in which the EMAA-Zn phase evolved from occluded subinclusions into continuous phase with decrease in the EBA-GMA/EMAA-Zn ratio. An optimum range of particle sizes of the dispersed domains for high impact toughness was identified. Also, the micromechanical deformation process of these ternary blends was also investigated by observation of the impact-fractured surfaces using the electron microscope. It was suggested that the low cavitation resistance of dispersed particles in conjunction with suitable interfacial adhesion was responsible for the optimum impact toughness observed.
Colorectal cancer (CRC) is among the most common malignancies with limited treatments other than surgery. The tumor microenvironment (TME) profiling enables the discovery of potential therapeutic targets. Here, we profile 54,103 cells from tumor and adjacent tissues to characterize cellular composition and elucidate the potential origin and regulation of tumor-enriched cell types in CRC. We demonstrate that the tumor-specific FAP+ fibroblasts and SPP1+ macrophages were positively correlated in 14 independent CRC cohorts containing 2550 samples and validate their close localization by immuno-fluorescent staining and spatial transcriptomics. This interaction might be regulated by chemerin, TGF-β, and interleukin-1, which would stimulate the formation of immune-excluded desmoplasic structure and limit the T cell infiltration. Furthermore, we find patients with high FAP or SPP1 expression achieved less therapeutic benefit from an anti-PD-L1 therapy cohort. Our results provide a potential therapeutic strategy by disrupting FAP+ fibroblasts and SPP1+ macrophages interaction to improve immunotherapy.
Epoxy was modified by an incompletely condensed polyhedral oligomeric silsesquioxane
(POSS), and the phenyltrisilanol POSS [Ph7Si7O9(OH)3, POSS-triol] was incorporated into the epoxy
networks with the content of POSS up to 30 wt %. The organic−inorganic hybrid composites were prepared
via in situ polymerization of epoxy monomers in the presence of POSS-triol, which started from the
homogeneous solutions of POSS-triol and epoxy monomers. The nanocomposites of epoxy with POSS-triol can be prepared with the metal complex, aluminum triacetylacetonate ([Al]) being used as the catalyst
for the reaction between POSS-triol and diglycidyl ether of bisphenol A (DGEBA). Otherwise, the phase
separation induced by polymerization occurred, and the fine phase-separated structures were obtained,
in which the spherical POSS-triol particles (0.3−0.5 μm in diameter) were dispersed in the continuous
epoxy matrices. The hybrid composites with the different morphological structures displayed quite different
thermomechanical properties. The phase-separated composites possessed the higher glass transition
temperatures (T
g's) than the nanocomposites while the nanocomposites displayed the higher storage
modulus of glassy state in light of dynamic mechanical analysis (DMA). In terms of thermogravimetric
analysis, the nanocomposites displayed the higher initial thermal decomposition temperatures (T
d's).
The improvement in thermomechanical properties has been ascribed to the nanodispersion of POSS
moieties.
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