The role of organic solvents in governing the crystallization and morphology of semi-crystalline poly-l-lactide (PLLA) sheets was systematically investigated. Three different organic solvents; ethyl acetate (EA), o-dichlorobenzene (ODCB), and nitrobenzene (NB), with a solubility parameter analogous to PLLA and with a high capability of swelling, were chosen. It has been witnessed that the degree of crystallization and crystal morphology depends highly on the degree of swelling and evaporation rate of the solvent. Besides, the temperature and time of treatment played a significant role in the crystallization of polymers. The effect of different solvents and curing times are reflected by the measured X-ray diffraction (XRD) peaks and the differences are best shown by the unit cell size. The largest variation is observed along the c-axis, indicating shorter bonds, thus, showing better conformation after NB and ODCB treatment. The percentage of crystallinity calculated using the classical relative crystallinity index of XRD shows closer values to those calculated with differential scanning calorimetry (DSC) data, but a huge variation is observed while using the LeBail deconvolution method. The strong birefringence of polarised optical micrograph (POM) and the crystal morphology of scanning electron micrograph (SEM) also evidenced the orientation of polymer crystallites and increased crystallinity after solvent-supported heat treatment.
Glassy carbon foam (GCF) catalyst supports were synthesized from waste polyurethane elastomers by impregnating them in sucrose solution followed by pyrolysis and activation (AC) using N2 and CO2 gas. The palladium nanoparticles were formed from Pd(NO3)2. The formed palladium nanoparticles are highly dispersive because the mean diameters are 8.0 ± 4.3 (Pd/GCF), 7.6 ± 4.2 (Pd/GCF-AC1) and 4.4 ± 1.6 nm (Pd/GCF-AC2). Oxidative post-treatment by CO2 of the supports resulted in the formation of hydroxyl groups on the GCF surfaces, leading to a decrease in zeta potential. The decreased zeta potential increased the wettability of the GCF supports. This, and the interactions between –OH groups and Pd ions, decreased the particle size of palladium. The catalysts were tested in the hydrogenation of nitrobenzene. The non-treated, glassy-carbon-supported catalyst (Pd/GCF) resulted in a 99.2% aniline yield at 293 K and 50 bar hydrogen pressure, but the reaction was slightly slower than other catalysts. The catalysts on the post-treated (activated) supports showed higher catalytic activity and the rate of hydrogenation was higher. The maximum attained aniline selectivities were 99.0% (Pd/GCF-AC1) at 293 K and 98.0% (Pd/GCF-AC2) at 323 K.
The suitability of a new type of polyurethane-based composite carbon foam for several possible usages is evaluated and reported. A comparison of the properties of the as-prepared carbon foams was performed with widely available commercial biomass-derived activated carbon. Carbon foams were synthesized from polyurethane foams with different graphite contents through one-step activation using CO2. In this work, a carbon catalyst was synthesized with a moderately active surface (SBET = 554 m2/g), a thermal conductivity of 0.09 W/mK, and a minimum metal ion content of 0.2 wt%, which can be recommended for phosgene production. The composite carbon foams exhibited better thermal stability, as there is a very little weight loss at temperatures below 500 °C, and weight loss is slower at temperatures above 500 °C (phosgene synthesis: 550–700 °C). Owing to the good surface and thermal properties and the negligible metallic impurities, composite carbon foam produced from polyurethane foams are the best alternative to the conventional coconut-based activated carbon catalyst used in phosgene gas production.
3 May 2023 in Journal of Photochemistry and Photobiology A: Chemistry