Kinetic Analysis of the Thermal Processing of Silica and Organosilica

The incorporation of an organic group into sol–gel-derived silica causes significant changes in the structure and properties of these materials. Therefore, the thermal treatment of organosilica materials may require a different approach. In the present paper, kinetic parameters (activation energy, pre-exponential constant, and reaction models) have been determined from mass loss data for the dehydration, dehydroxylation, and decomposition reactions that take place upon heating silica and organosilica. Parameters were obtained by employing model-free isoconversional methods to data obtained under multiple heating rates as well as by multivariate analysis of the kinetics using a multistep reaction model with distributed activation energy. For silica, it can be concluded that the reaction atmosphere (i.e., inert or thermo-oxidative) has no influence on the reaction rate of the dehydration and dehydroxylation reactions that are responsible for the densification of the material. Under inert atmosphere, full dehydration can be reached without affecting the organic moiety. Achieving complete dehydroxylation of the organosilica is practically impossible as decomposition does manifest itself under commonly employed calcination temperatures. This indicates that prudence is required in designing a heat treatment program for these hybrid materials. To aid in optimizing the thermal treatment, a predictive model was developed, which can be used to forecast the extent of dehydration, dehydroxylation, and decomposition reactions under a multitude of temperature program

Pyrolysis Kinetic Analysis of Biomasses: Sugarcane Residue, Corn Cob, Napier Grass and their Mixture

The aim of this study is to investigate pyrolysis kinetic parameters of three high potential energy biomasses including sugarcane residue (tops and leaves), corn cob and Napier grass via thermogravimetry analysis (TGA). In addition, those of their mixture at 1:1:1 by mass is explored. Activation energy and pre-exponential factor were the two considered parameters calculated by following the Ozawa-Flynn-Wall method using condition of 30-900°C with heating rates of 5, 10, 20 and 40°C/min. The derivative thermogravimetric (DTG) curves indicated that there might be at least three different component structures in corn cob. The effective values of the both parameters were almost similar as 214.54, 216.60, 212.51 kJ/mol and 1.510E+19, 1.575E+19, 1.562E+19 min-1 for the sugarcane residue, the corn cob, the Napier grass, respectively. Finally, the ternary diagram suggested that the increase of Napier grass proportion would slightly affect the conversion of pyrolysis by reducing the total activation energy of the biomass mixture

Thermal Stability and Phase Transformations of Multicomponent Iron-Based Amorphous Alloys

Due to their excellent functional properties enabling their applicability in different fields of modern technology, amorphous alloys (metallic glasses) based on iron have been attracting attention of many scientists. In this chapter, the results of multidisciplinary research of five multicomponent iron-based amorphous alloys with different chemical composition, Fe81Si4B13C2, Fe79.8Ni1.5Si5.2B13C0.5, Fe75Ni2Si8B13C2, Fe73.5Cu1Nb3Si15.5B7, and Fe40Ni40P14B6, are summarized in order to study the influence of chemical composition on their physicochemical properties and functionality. The research involved thermal stability, mechanism, thermodynamics, and kinetics of microstructural transformations induced by thermal treatment and their influence on functional properties. Determination of crystallization kinetic triplets of individual phases formed in the alloys is also included. The results obtained for different alloys are compared, correlated, and discussed in terms of the alloy composition and microstructure

Thermal decomposition kinetics of the antiparkinson drug “entacapone” under isothermal and non-isothermal conditions

© 2017 Akadémiai Kiadó, Budapest, Hungary The thermal decomposition kinetics of entacapone (ENT) have been investigated via thermogravimetric analysis under non-isothermal and isothermal conditions which provide useful stability information for their processing in the pharmaceutical industry and also for predicting shelf life and suitable storage conditions. The determination of the kinetic parameters for the decomposition process under non-isothermal conditions in a nitrogen atmosphere at four heating rates (5, 10, 15, and 20 °C min −1 ) was performed. Kinetic parameters of the decomposition process for ENT were calculated through Friedman, Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose, and Li–Tang methods. This work demonstrates that the activation energies calculated from the decomposition reactions by different methods are consistent with each other. Moreover, the thermodynamic functions of the decomposition reaction were also calculated

Thermal behavior and antibacterial studies of a carbonate Mg–Al-based layered double hydroxide (LDH) for in vivo uses

The goal of this work is to study the thermal behavior and the antibacterial properties of a MgAl-CO3 layered double hydroxide (LDH), which demonstrated high efficiency in removing chromium (VI) from contaminated industrial wastewater. The compound has been synthesized via co-precipitation route (direct method) followed by hydrothermal treatment, obtaining nanoscopic crystallites with a partially disordered (turbostratic) structure. After its synthesis, the compound was characterized by means of X-ray powder diffraction, field emission scanning electron microscope, inductively coupled plasma atomic emission spectroscopy and analysis and Fourier transform infrared spectroscopy. On the other hand, with the view to check the drug delivery and surgical tools usage of MgAl-CO3, antibacterial tests, performed according to the Kirby–Bauer method, revealed the inability the growth of the pathogenic bacterial strains. Thermogravimetry and differential thermal analysis revealed that evolution of water from the material occurs in two stages upon heating and a noticeable interaction takes place between water (in the vapor phase) and MgAl-CO3. Kinetic analysis of both steps provides almost constant values of activation energy, with the following average values in the range 0.1 < a < 0.9: E1 = (66 ± 9) kJ mol‒1; E2 = (106 ± 7) kJ mol‒1. Finally, prediction of reasonable reaction times extrapolated at 25 and 37 °C has been made from kinetic parameters of the first step, while almost unrealistic reaction time values were determined using the same procedure with kinetic parameters related to the second step

Processing thermogravimetric analysis data for isoconversional kinetic analysis of lignocellulosic biomass pyrolysis:Case study of corn stalk

Modeling of lignocellulosic biomass pyrolysis processes can be used to determine their key operating and design parameters. This requires significant amount of information about pyrolysis kinetic parameters, in particular the activation energy. Thermogravimetric analysis (TGA) is the most commonly used tool to obtain experimental kinetic data, and isoconversional kinetic analysis is the most effective way for processing TGA data to calculate effective activation energies for lignocellulosic biomass pyrolysis. This paper reviews the overall procedure of processing TGA data for isoconversional kinetic analysis of lignocellulosic biomass pyrolysis by using the Friedman isoconversional method. This includes the removal of “error” data points and dehydration stage from original TGA data, transformation of TGA data to conversion data, differentiation of conversion data and smoothing of derivative conversion data, interpolation of conversion and derivative conversion data, isoconversional calculations, and reconstruction of kinetic process. The detailed isoconversional kinetic analysis of TGA data obtained from the pyrolysis of corn stalk at five heating rates were presented. The results have shown that the effective activation energies of corn stalk pyrolysis vary from 148 to 473 kJ mol−1 when the conversion ranges from 0.05 to 0.85

Influence of Cellulose Characteristics on Pyrolysis Suitability

: Cellulose is the most abundant component of biomass and the one that requires the most activation energy (Ea) for pyrolysis. In this study, the dependence of Ea on the intrinsic cellulose characteristics, such as the degree of polymerization (DP), crystallinity, and crystal size, was studied in different cellulose samples, including samples from Eucalyptus globulus, Ulmus minor, Linun usitatissimum, Olea europaea, Robinia pseudoacacia, and Populus alba. Then, to describe the pyrolytic degradation of cellulose, the Ozawa–Flynn–Wall kinetic method was the most appropriate among the isoconversional models studied. An acceptable quadratic relationship of R2 > 0.9 between the Ea values of the different cellulose samples with their corresponding DP, crystallinity index, and crystal size values was found. Therefore, low crystallinity and low-to-medium crystal size values are desired to obtain lower Ea values for cellulose pyrolysis. On the other hand, DP did not present a clear effect on Ea in the studied DP rangeThis research was funded by Comunidad de Madrid and MCIU/AEI/FEDER, EU via Projects SUSTEC-CM S2018/EMT-4348 and RTI2018-096080-B-C22, respectively, and the Regional Ministry of Innovation, Science and Enterprise, Government of the Junta de Andalucía (Operational Programme FEDER Andalusia 2014-2020. Project UHU-1255540), Spain Universidad de Jaén is acknowledged for Olea europaea material. Silviculture and Forest Management Department (Forest Research Center, INIA, CSIC) is acknowledged for Robinia pseudoacacia and Populus alba materials. We thank the personnel at Puerta de Hierro Forest Breeding Centre (Ministerio para la Transición Ecológica y el Reto Demográfico) and the Spanish Elm Breeding Program for providing the Ulmus minor material. Finally, La Montañesa pulp mill (Lecta Group, Spain) and Celesa (Spain) are acknowledged for Eucalyptus globulus and Linun usitatissimum materials, respectivel