RESUMO
The incorporation of nanofillers such as graphene into polymers has shown significant improvements in mechanical characteristics, thermal stability, and conductivity of resulting polymeric nanocomposites. To this aim, the influence of incorporation of graphene nanosheets into ultra-high molecular weight polyethylene (UHMWPE) on the thermal behavior and degradation kinetics of UHMWPE/graphene nanocomposites was investigated. Scanning electron microscopy (SEM) analysis revealed that graphene nanosheets were uniformly spread throughout the UHMWPE's molecular chains. X-Ray Diffraction (XRD) data posited that the morphology of dispersed graphene sheets in UHMWPE was exfoliated. Non-isothermal differential scanning calorimetry (DSC) studies identified a more pronounced increase in melting temperatures and latent heat of fusions in nanocomposites compared to UHMWPE at lower concentrations of graphene. Thermogravimetric analysis (TGA) and derivative thermogravimetric (DTG) revealed that UHMWPE's thermal stability has been improved via incorporating graphene nanosheets. Further, degradation kinetics of neat polymer and nanocomposites have been modeled using equations such as Friedman, Ozawa-Flynn-Wall (OFW), Kissinger, and Augis and Bennett's. The "Model-Fitting Method" showed that the auto-catalytic nth-order mechanism provided a highly consistent and appropriate fit to describe the degradation mechanism of UHMWPE and its graphene nanocomposites. In addition, the calculated activation energy (Ea) of thermal degradation was enhanced by an increase in graphene concentration up to 2.1 wt.%, followed by a decrease in higher graphene content.
RESUMO
The UV/Cl2 process (also known as chlorine photolysis, which is the combination of chlorine and simultaneous irradiation of UV light) is conventionally applied at acidic mediums for drinking water treatment and further treatment of wastewater effluents for secondary reuse. This is because the quantum yield of HO⢠from HOCl (ÏHOâ¢, 254â¯=â¯1.4) is greater than the one from OCl- (ÏHOâ¢, 254â¯=â¯0.278) by approximately 5 times. Moreover, chlorine photolysis in acidic mediums also tends to have lower radical quenching rates than that of their alkaline counterparts by up to 1000 times. The aim of this research is to investigate the applicability of the UV/Cl2 process by assessing its efficacy on the removal of trimethoprim (TMP) at not only acidic to neutral conditions (pH 6-7), but also alkaline mediums (pH 8-9). At alkaline pH, free chlorine exists as OCl- and since OCl- has a higher molar absorption coefficient as compared to HOCl at higher wavelengths, there would be higher reactive chlorine species (RCS) formation and contribution. TMP removal followed pseudo-first order kinetics and depicted that a maximum fluence based constant (kf' = 0.275 cm2/mJ) was obtained using 42.25 µM (3 mg/L) of chlorine at pH 9, with an irradiation of 275 nm. At alkaline conditions, chlorine photolysis performance followed the trend of UV (275)/Cl2 > UV (265)/Cl2 > UV (310)/Cl2 > UV (254)/Cl2. RCS like Clâ¢, Cl2-⢠and ClO⢠contributed to the degradation of TMP. When the pH was increased from 6 to 8, contribution from hydroxyl radicals (HO⢠) was decreased whilst that of RCS was increased. Application of UV (310)/Cl2 had the highest HO⢠generation, contributing to TMP removals up to 13% to 48% as compared to 5% to 27% in UV (254, 265, 275)/Cl2 systems at pH 6-9. Artificial neural networks modelling was found to be able to verify and predict the contribution of HO⢠and RCS conventionally calculated via the general kinetic equations in the UV/Cl2 system at 254, 265, 275 and 310 nm.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Cloro , Cinética , Redes Neurais de Computação , Oxirredução , Trimetoprima , Raios UltravioletaRESUMO
To develop novel imprinted poly (methacrylic acid) nanoparticles for the controlled release of Rivastigmine Tartrate (RVS), the amalgamation of molecular imprinting techniques and polymerization of precipitates were applied in this work. By permuting different concentrations of pentaerythritol triacrylate (PETA) or trimethylolpropane triacrylate (TMPTA) as cross-linkers, ten different samples were synthesized, and their abilities assessed for RVS absorption. Among them, uniform mono-disperse nanoparticles were synthesized in an RVS/PMAA/PETA mole ratio of 1:6:12, named molecularly imprinted polymers 2 (MIP2), which showed the highest RVS absorption. Analytical procedures involving the Fourier transform infrared (FT-IR), Thermogeometric analysis (TGA), Field emission scanning electron microscopy (FE-SEM), Dynamic light scattering (DLS), and absorption/desorption porosimetry (BET) measurements were applied to characterize the morphology and physicochemical properties of the MIP2. In addition, the cytotoxicity of the MIP2 sample was measured by MTT assay on an L929 cell line. Studies pertaining to the in-vitro release of RVS from MIP2 samples showed that the prepared sample had a controlled and sustained release compared, which differed from the results obtained from the non-imprinted polymer (NIP) with the same formulization. Results obtained further reinforced the feasibility of prepared MIPs as a prime candidature for RVS drug delivery to alleviate Alzheimer's and other diseases.