Search Results (6)

The radical statistical copolymerization of N–vinyl pyrrolidone (NVP) and 2–chloroethyl vinyl ether (CEVE) was conducted using the Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization technique, employing [(O–ethylxanthyl)methyl]benzene (CTA-1) and O–ethyl S–(phthalimidylmethyl) xanthate (CTA-2) as the Chain Transfer Agents (CTAs), leading to P(NVP–stat–CEVE) products. After optimizing copolymerization conditions, monomer reactivity ratios were estimated using various linear graphical methods, as well as the COPOINT program, which was applied in the framework of the terminal model. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the monomers’ mean sequence lengths. Thermal properties of the copolymers were studied by Differential Scanning Calorimetry (DSC) and kinetics of their thermal degradation by Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG), applying the isoconversional methodologies of Ozawa–Flynn–Wall (OFW) and Kissinger–Akahira–Sunose (KAS). Full article

The development of instrumentation has allowed thermal analysis to become a widely used method not only in calorimetry but also in the field of non-isothermal kinetics that, however, provides a simplified philosophy of measurements. From the beginning, a methodology is used describing the course of reaction in a simplified temperature regime measured in an inert sample. In a most common case of DTA, the degree of reaction is subtracted from the partial areas of the as-cast peak in the unified mode of the peak linear background. Usually, the effect of thermal inertia, resulting from the reality of heat transfer and changing the peak background to a non-linear s-shaped form, is not incorporated. Therefore, the question of whether or not to include this effect of thermal inertia has become a current underlying problem of thermo-analytical kinetics. The analysis of the rectangular input heat pulses and their DTA responding fundamentally point to the need to include it thus becoming essential and not negligible. In the case of parallel evaluations, the effect of inertia can be partially compensated for each other such as in the Kissinger evaluation method. The study presents a broad overview of the thermo-analytical methodology used and points to the often-neglected literature. However, standard mainstream kinetics procedures need be fixed, and an improved solution found to account for the effect of heat transfer and dissipation, which is becoming the focus of thermal analysis methods of future and also the intention of this review. Full article

Torrefaction has been investigated to improve the desirable properties of biomass as solid biofuel, usually used in natura as firewood in several countries. This paper has the main objective to present a broad characterization of the biomass Prosopis juliflora (P. juliflora), investigating its potential as a solid biofuel after its torrefaction process. The methodology was based on different procedures. The experimental runs were carried out at 230, 270, and 310 °C for 30 min, using a bench-scale torrefaction apparatus, with an inert atmosphere. In order to investigate the effect of temperature in constant time, torrefaction parameters were calculated, such as mass yield, energy yield, calorific value, base-to-acid ratio (B/A), and the alkaline index (AI). The physicochemical properties of the torrefied samples were determined and thermogravimetric analysis was used to determine the kinetic parameters at four different heating rates of 5, 10, 20, and 30 °C/min. Pyrolysis kinetics was investigated using the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) isoconversional methods. Highly thermally stable biofuels were obtained due to the great degradation of hemicellulose and cellulose during torrefaction at higher temperatures. The highest heating value (HHV) of the samples varied between 18.3 and 23.1 MJ/kg, and the energy yield between 81.1 and 96.2%. The results indicate that P. juliflora torrefied becomes a more attractive and competitive solid biofuel alternative in the generation of heat and energy in northeast Brazil. Full article

Recent environmental restrictions constrained car manufacturers to promote cast aluminum alloys working at high temperatures (180 °C–300 °C). The development of new alloys permits the fabrication of higher-strength components in engine downsizing. Those technologies increase internal loadings and specific power and stretch current materials to their limits. Transition metals in aluminum alloys are good candidates to improve physical, mechanical, and thermodynamic properties with the aim of increasing service life of parts. This study is focused on the modified AlSi7Cu3.5Mg0.15 alloy where Mn, Zr, and V have been added as alloying elements for high-temperature applications. The characterization of the cast alloy in this study helps to evaluate and understand its performance according to their physical state: As-cast, as-quenched, or artificially aged. The precipitation kinetics of the AlSi7Cu3.5Mg0.15 (Mn, Zr, V) alloy has been characterized by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) observations, and micro-hardness testing. The Kissinger analysis was applied to extract activation energies from non-isothermal DSC runs conducted at different stationary heating rates. Finally, first-order evaluations of the interfacial mobility of precipitates were obtained. Full article

Branched polymers are a valuable class of polymeric materials. In the present study, anionic polymerization techniques were employed for the synthesis of low molecular weight poly(ethylene oxide) (PEO) macromonomers bearing norbornenyl end groups. The macromonomers were characterized by SEC, MALDI-TOF and NMR spectroscopy. Subsequent ring opening metathesis polymerization (ROMP) of the macromonomers using ruthenium catalysts (Grubbs catalysts of the 1st, 2nd and 3rd generations) afforded the corresponding polymacromonomers. The effects of the macromonomer molecular weight, the type of the catalyst, the nature of the solvent, the monomer concentration and the polymerization temperature on the molecular characteristics of the branched polymers were examined in detail. The crystallization behavior of the macromonomers and the corresponding polymacromonomers were studied by Differential Scanning Calorimetry (DSC). The thermal stability and the kinetics of the thermal decomposition of the samples were also studied by Thermogravimetric Analysis (TGA). The activation energies of the thermal decomposition were analyzed using the Ozawa–Flynn–Wall and Kissinger methodologies. Full article

Statistical copolymers of norbornene (NBE) with cyclopentene (CP) were prepared by ring-opening metathesis polymerization, employing the 1st-generation Grubbs’ catalyst, in the presence or absence of triphenylphosphine, PPh₃. The reactivity ratios were estimated using the Finemann-Ross, inverted Finemann-Ross, and Kelen-Tüdos graphical methods, along with the computer program COPOINT, which evaluates the parameters of binary copolymerizations from comonomer/copolymer composition data by integrating a given copolymerization equation in its differential form. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies. Finally, the effect of triphenylphosphine on the kinetics of copolymerization, the reactivity ratios, and the kinetics of thermal decomposition were examined. Full article