In this study, polypyrrole-based activated carbon was prepared by the carbonization of polypyrrole at 650 °C for 2 h in the presence of four-times the mass of KOH as a chemical activator. The structural and morphological properties of the product (polypyrrole-based activated carbon (PPyAC4)), analyzed by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and thermogravimetric analysis, support its applicability as an adsorbent. The adsorption characteristics of PPyAC4 were examined through the adsorption of lead ions from aqueous solutions. The influence of various factors, including initial ion concentration, pH, contact time, and adsorbent dose, on the adsorption of Pb2+ was investigated to identify the optimum adsorption conditions. The experimental data fit well to the pseudo-second-order kinetic model (R2 = 0.9997) and the Freundlich isotherm equation (R2 = 0.9950), suggesting a chemisorption pathway. The adsorption capacity was found to increase with increases in time and initial concentration, while it decreased with an increase in adsorbent dose. Additionally, the highest adsorption was attained at pH 5.5. The calculated maximum capacity, qm, determined from the Langmuir model was 50 mg/g.
The adsorption of methyl orange (MO) from aqueous solutions onto a KOH-activated polypyrrole-based adsorbent (PACK) was investigated using batch and fixed-bed column techniques. The structural, thermal, and morphological properties of the PACK, analyzed by various methods, support its applicability as an adsorbent. An adsorption kinetic study revealed a preferably pseudo-second-order (R2 = 0.9996) and rate-limiting step controlled by both film and intra-particle diffusions. The thermodynamic adsorption tests resulted in negative ΔG°, ΔH°, and ΔS° values, which decreased as the temperature and concentration increased, indicating the spontaneous and exothermic adsorption over 25–45 °C. The adsorption isotherms fit the experimental data in the order of Langmuir ≈ Freundlich > Temkin, with evidence of adsorption operating well via the monolayer physical adsorption process, and maximum monolayer adsorption ranging from 520.8 to 497.5 mg/g. The breakthrough curve of the fixed-bed column experiment was modeled using the Thomas, Yoon–Nelson, and Hill models, resulting in an equilibrium capacity of 57.21 mg/g. A 73% MO recovery was achieved, indicating the possibility of column regeneration. Compared to other adsorbents reported, PACK had comparable or even superior capacity toward MO. For cost-effectiveness, similar nitrogen-containing polymeric wastes could be exploited to obtain such excellent materials for various applications.
Poly(eugenyl-2-hydroxypropyl methacrylate) (PEUGMA), poly(methyl methacrylate) (PMMA) and poly(eugenyl-2-hydroxypropyl methacrylate-co-methyl methacrylate) (PEUGMA-co-MMA) were synthesized by a free radical polymerization route in the presence of azobisisobutyronitrile. EUGMA was synthesized by etherification of the eugenol phenolic hydroxyl group with glycidyl methacrylate. Polymers and copolymers were characterized using size exclusion chromatography, Fourier transform infrared, and nuclear magnetic resonance. The effects of the encumbering substituent on the thermal behavior of the polymers and copolymers were studied by differential scanning calorimetry, thermogravimetry (TG) and direct analysis, using real-time, time-of-flight mass spectroscopy (DART-ToF-MS) methods. The results obtained revealed that for PEUGMA, the average molecular weight was 1.08 × 105, and increased slowly with the decrease in the EUGMA content in the copolymer. The order of the distribution of dyads comonomer units in the copolymer chains estimated by the Igarashi method based on the reactivity ratio does reveal a random distribution with a tendency toward alternation. The glass transition temperature of PEUGMA (46 °C) increased with the MMA content in the copolymer, and those of the copolymer fit well with the Johnston’s linearized expression. The TG analysis of pure PEUGMA revealed a significantly high thermal stability compared to that of PMMA. During its degradation, the preliminary decomposition was at 340 °C, and decreased as the MMA units increased in the copolymer. The DART-ToF-MS analysis revealed that the isothermal decomposition of PEUGMA led to a regeneration of raw materials such as EUGMA, GMA and EUG, in which the maximum amount was achieved at 450 °C.
Graphene and graphene oxide based nanomaterials have attained immense significance in research because of their matchless physiochemical characteristics. Although potential biomedical applications of graphene have been extensively studied, however, dentistry related applications were rarely explored. This study aimed to investigate the effect of various percentages of surface modified reduce graphene oxide (S-rGO) in combination with SiO2 nanoparticles (bulk filler) on numerous physio-mechanical characteristics of acrylate-based (BisGMA/TEGDMA: 1:1 by wt.) composites. BisGMA/TEGDMA reinforced with 30 wt.% surface modified fumed-silica (S-A200) was considered as control group (base composite). Various concentrations (0, 0.5, 1, 2, 4 wt.%) of S-rGO were incorporated into the base composite via solution casting and high-speed mixing. The obtained composites were characterized for rheological properties before curing by using Rheometer (Anton Paar, USA) in the oscillatory mode under a frequency sweep over a range of angular frequency of 0.1–100 rad/s at 25 °C. The degree of conversion (DC) was measured by using Fourier transform infrared spectroscopy (FTIR). A Nano-indentation test was carried out to obtain nano-hardness and elastic modulus. The surface roughness was measured by optical microscope (Bruker®), 3D non-contact surface profilometer. The structural and morphological properties were studied by using Scanning Electron Microscopy (SEM). The mean and standard deviation were calculated and a simple mean comparisons test was performed for comparison using SPSS. The results revealed that the addition of a tiny proportion of S-rGO considerably increased the nano-indentation hardness, elastic modulus and DC. Conversely, a gradual reduction in viscosity was observed with increasing S-rGO concentration. The study demonstrates that a small fraction of S-rGO in combination with SiO2 could enhance physical, mechanical and rheological properties of acrylate based composites. Thus S-rGO/SiO2 combination could be used as a potential hybrid filler for dental nanocomposites.
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