The glycidyl-POSS (Polyhedral Oligomeric Silsesquioxanes, Polysilsesquioxane, POSS) (Gly-POSS) and trisilanolisooctyl-POSS (HO-POSS) were applied as functional additives influencing on the viscoelastic properties of the dynamic vulcanized PLA/ENR (poly(lactic acid)/epoxidized natural rubber) blends. The plasticizing effect of HO-POSS on PLA/ENR melt, leading to the decrease of complex viscosity at 160 °C, was observed. After the incorporation of Gly-POSS into PLA/ENR blends the complex viscosity increased confirming that the epoxy groups of Gly-POSS were able to react with the functional groups of ENR and the groups present at the end of PLA chains. The incorporation of Gly-POSS into 40:60 PLA/ENR blend provided significant enhancement of the storage shear modulus G’ at 30 °C. Furthermore, the glass transition temperatures Tg of ENR phase for PLA/ENR/Gly-POSS blends were shifted to higher values of temperature as compared with blends modified by HO-POSS. Strong reduction of the elongation at break Eb for 40:60 PLA/ENR/Gly-POSS blend indicated that Gly-POSS particles acted as multifunctional cross-links reducing elasticity of the material. The modification of 40:60 PLA/ENR blend by HO-POSS molecules led to lower values of composting coefficient KC indicating stronger deterioration of the mechanical properties that resulted from more intense degradation processes occurring during disposal in soil.
The influence of intrinsic defects of 1T-TaS2 on charge density waves (CDWs) is studied using scanning tunneling microscopy and spectroscopy (STM, STS), angle-resolved photoelectron spectroscopy (ARPES), and density functional theory (DFT). We identify several types of structural defects and find that most have a local character limited to a single CDW site, with a single exception which effectively behaves as a dopant, leading to band-bending and affecting multiple neighboring sites. While only one type of defect can be observed by STM topographic imaging, all defects are easily resolved in STS mapping. Our results indicate modulation of the Mott band gap commensurate with the CDW and breaking of the three-fold symmetry of electronic states. DFT calculations (with included Coulomb interactions) are used to investigate the electronic structure, focusing on both sulfur vacancy and oxygen-sulfur substitution. The sulfur vacancy system, characterized with a metallic behavior, is identified as the origin of one of the experimentally observed defects. Additionally, the effect of oxidation of 1T-TaS2 depends on the substitution site, leading to the heterogeneity of electronic properties.
Thermo-responsive shape memory materials were developed based on recycled ethylene-propylene-diene (EPDM) rubber shred and thermoplastic elastomers (TPE). Ethylene-1-octene TPEs (Engage 8180, 8411, 8452) with varying degrees of crystallinity and Mooney viscosity were used to prepare the composite materials. To avoid the deterioration of static mechanical properties after mixing recycled EPDM rubber shred (RS) with thermoplastic elastomers, they were partially cured using dicumyl peroxide. The peroxide curing was the most effective for a rubber shred/Engage 8180 blend, where the highest cure rate index (CRI), 1.88 dNm·min−1, was observed. The curing caused an approximately 4-fold increase of tensile strength (TS) values for EPDM rubber shred/thermoplastic elastomer blend to the level acceptable for the rubber industry compared with an uncured blend. The incorporation of EPDM rubber shred changed thermoplastic elastomers' viscoelastic behavior, increasing the values of storage (G′) and loss (G″) modulus. The lowest viscosity of molten Engage 8411 during mixing led to higher compatibility of rubber shred RS/8411 blend, as confirmed by analysis of Cole-Cole plots and the blend morphology. All rubber shred RS/TPE blends showed the shape memory behavior. For the RS/Engage 8452 blend, the highest shape fixity (F) value (94%) was observed, while the shape recovery (RR) was 87%. Studies confirmed that the intelligent materials with shape memory effect could be obtained via selectively chosen thermoplastic elastomers; ethylene-1-octene as a binder for recycled EPDM. Prepared recycled TPE/rubber shred blends can be successfully reused due to their viscoelastic and mechanical properties. Therefore, such a concept can be potentially interesting for the rubber industry.
Polyhedral oligomeric silsesquioxanes (POSS) can be considered as the smallest silica particles that contain an inorganic cage-like silicon-oxygen structure surrounded by organic substituents. POSS are known to be reinforcing fillers able to enhance the fire retardancy and to increase the thermo-oxidative stability. The application of POSS with various functional groups and their effect on the properties of poly(lactic acid) (PLA) is analyzed based on the literature review. The influence of POSS with hydroxyl and glycidyl groups on the viscoelastic properties, crystallization, and thermo-oxidative degradation of PLA containing various contents of natural rubber ENR is discussed. The application of POSS with hydroxyl and glycidyl groups as an additive enhancing compatibility of PLA toughened by epoxidized rubber (ENR) is described. It is reported that POSS molecules with hydroxyl groups can enhance the thermo-oxidative stability of PLA melt.
Molybdenum trioxide shows many attractive properties, such as a wide electronic band gap and a high relative permittivity. Monolayers of this material are particularly important, as they offer new avenues in optoelectronic devices, e.g., to alter the properties of graphene electrodes. Nanoscale electrical characterization is essential for potential applications of monolayer molybdenum trioxide. We present a conductive atomic force microscopy study of an epitaxially grown 2D molybdenum oxide layer on a graphene-like substrate, such as highly oriented pyrolytic graphite (HOPG). Monolayers were also investigated using X-ray photoelectron spectroscopy, atomic force microscopy (semi-contact and contact mode), Kelvin probe force microscopy, and lateral force microscopy. We demonstrate mobility of the unpinned island under slight mechanical stress as well as shaping and detachment of the material with applied electrical stimulation. Non-stoichiometric MoO3-x monolayers show heterogeneous behavior in terms of electrical conductivity, which can be related to the crystalline domains and defects in the structure. Different regions show various I–V characteristics, which are correlated with their susceptibility to electrodegradation. In this work, we cover the existing gap regarding nanomanipulation and electrical nanocharacterization of the MoO3 monolayer.
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