Enhanced Metakaolin Reactivity in Blended Cement with Additional Calcium Hydroxide

This study aims to increase the pozzolanic reactivity of metakaolin (MK) in Portland cement (PC) blends by adding additional calcium hydroxide (CH_add) to the initial mixture. Cement paste samples were prepared with PC, MK and water with a water-to-binder ratio of 0.6. Cement replacement ratios were chosen from 5 to 40 wt.% MK. For higher replacement ratios, i.e., 20, 30 and 40 wt.% MK, CH_add was included in the mixture. CH_add-to-MK ratios of 0.1, 0.25 and 0.5 were investigated. Thermogravimetric analysis (TGA) was carried out to study the pozzolanic reactivity after 1, 7, 28 and 56 days of hydration. A modified mass balance approach was used to normalize thermogravimetric data and to calculate the calcium hydroxide (CH) consumption of samples with CH_add. Results showed that, without CH_add, a replacement ratio of 30 wt.% or higher results in the complete consumption of CH after 28 days at the latest. In these samples, the pozzolanic reaction of MK turned out to be restricted by the amount of CH available from the cement hydration. The increased amount of CH in the samples with CH_add resulted in an enhanced pozzolanic reaction of MK as confirmed by CH consumption measurements from TGA.

Building geopolymers for CuHe part I: thermal properties of raw materials as precursors for geopolymers

This paper presents the results obtained from the thermal analysis of a set of geomaterials (clays, pyroclastic materials, and industrial recycled materials) to be used as raw materials for the synthesis of geopolymers, specifically designed for the conservation of Cultural Heritage (CH) buildings, particularly in seismic hazard zones such as Sicily. X-ray diffraction and gas volumetric analysis (calcimetry) were applied to this set of raw materials in order to characterize the materials from the chemical and structural point of view. Thermogravimetric analysis (TG), TG coupled to Fourier transform infrared spectroscopy (TG-FTIR), and differential scanning calorimetry were used to characterize their thermal behavior. The statistical treatment of the thermogravimetric data by principal component analysis and hierarchical clustering analysis highlights the direct relation between the thermal data and the material composition that will be exploited for the selection of the best materials to obtain geopolymers specifically designed for the conservation of CH buildings.

Fique as a Sustainable Material and Thermal Insulation for Buildings: Study of Its Decomposition and Thermal Conductivity

Buildings consume a large amount of energy during all stages of their life cycle. One of the most efficient ways to reduce their consumption is to use thermal insulation materials; however, these generally have negative effects on the environment and human health. Bio-insulations are presented as a good alternative solution to this problem, thus motivating the study of the properties of natural or recycled materials that could reduce energy consumption in buildings. Fique is a very important crop in Colombia. In order to contribute to our knowledge of the properties of its fibers as a thermal insulator, the measurement of its thermal conductivity is reported herein, employing equipment designed according to the ASTM C 177 standard and a kinetic study of its thermal decomposition from thermogravimetric data through the Coats–Redfern model-fitting method.

Kinetic study of the pyrolysis of polypropylene over natural clay

Clay is widely used in numerous industrial activities; however, its application as an efficient catalyst for the decomposition of plastic waste on a commercial scale is scanty. Therefore, in this study, we have made efforts to use natural clay as the catalyst for the thermal decomposition of polypropylene in a pyrolysis setup. The pyrolysis oil obtained was found rich in hydrocarbons ranging from C8–C35. Kinetics of the pyrolysis reaction was determined utilizing thermogravimetric data and the activation energy (E) and A-factor were observed as 70.33–94.80 kJ/mol and 6 × 105–2.3 × 108 min−1 using the Ozawa-Flynn-Wall method and 58.19–74.82 kJ/mol and 4.1 × 102–4.2 × 103 min−1 applying Tang Wanjun equation. The activation energy was found to increase with enhancement in conversion presenting a complex decomposition reaction. Comparing the activation energy determined in this work with previous studies confirmed that natural clay has reduced E of decomposition reaction at high fraction conversion. The pyrolysis results supported with the kinetic investigation in this work would have potential applications in disposing of plastic waste on an industrial scale and a step forward in the field of waste management.

PHYSICO-CHEMICAL PARAMETERS OF SIBERIAN LARCH (LARIX SIBIRICA) BARK EXTRACTED WITH WATER-AMINO-ALCOHOLIC EXTRACTANTS

This paper presents the results of a thermal analysis, that involved thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC), of natural bark of Siberian larch (Larix sibirica Ldb.) vs. the bark extracted with 5% water-monoethanolamine (MEA) and (vs.) 5% water-triethanolamine (TEA). Thermogravimetric data obtained in an oxidative (air) atmosphere allowed us to identify temperature ranges of thermal decomposition stages for the larch bark samples, as well as to determine the corresponding mass loss and mass loss rate at programmed heating. The Ozawa-Flynn-Wall (OFW) method was used to calculate the dependence of activation energy of the thermal decomposition of experimental samples on the conversion degree (Еа = f(a)); the symbate run of Еа = f(a) curves was established. The DSC data obtained agreed with those of TG/DTG. The integral heat of the bark thermal decomposition (9.60 kJ/g and 14.12 kJ/g for MEA and TEA, respectively) indicated the bark to be competitive with other biofuels, such as briquetted lignin, wood pellets, sunflower husk, rapeseeds, and straw.

Insight in the crystallization kinetics of AlPO4-11 molecular sieve using di-isopropylamine as template

The hydrothermal synthesis of aluminophosphate molecular sieve type AlPO4-11 was processed from chemicals containing psueudobohemite, 85% phosphoric acid, water, and di-isopropylamine as templating agent. The crystallization of the samples was studied by taking samples in times from 2 to 74 hours. The obtained white powder products have been characterized by XRD patterns, FT-IR spectra, thermogravimetric data, scanning electron microscopy and pH measurement of the mother liquor. The pore volume, as determined from TG and DTG curves, was ca. 0.17 cm3g-1. The crystallization process of the aluminophosphate exhibited in its initial phase a behavior of first order reaction with a specific velocity constant of ca. 0.25 h-1, as determined from XRD and FT-IR data.

A Logistic Approach for Kinetics of Isothermal Pyrolysis of Cellulose

A kinetic model is proposed to fit isothermal thermogravimetric data obtained from cellulose in an inert atmosphere at different temperatures. The method used here to evaluate the model involves two steps: (1) fitting of single time-derivative thermogravimetric curves (DTG) obtained at different temperatures versus time, and (2) fitting of the rate parameter values obtained at different temperatures versus temperature. The first step makes use of derivative of logistic functions. For the second step, the dependence of the rate factor on temperature is evaluated. That separation of the curve fitting from the analysis of the rate factor resulted to be very flexible since it proved to work for previous crystallization studies and now for thermal degradation of cellulose.

AN INNOVATE METHOD OF THERMOGRAVIMETRIC DATA ANALYSIS

The objective of the study is to examine the Coats-Redfern approximation and to propose an innovative kinetic calculation method for the complex process of the heavy tar thermal decomposition under non-isothermal process. The thermal decomposition process was examined using the thermogravimetric analysis. There are several kinetic models proposed to analyze pyrolysis mechanism in terms of the formal reaction. In this manner, the kinetic parameters of the pyrolysis process can be evaluated based on total mass loss (thermogravimetric analysis –TGA). The TGA procedures can be conducted with isothermal or non-isothermal conditions, but the experimental data obtained according to this procedure have to be transformed into appropriate correlation. The obtained results have shown that the reaction takes place within temperature range of 540 K to 700 K and the inductive period of the process is about 224 min. Kinetic parameters were estimated with using of the conventional Coats-Redfern method. A new kinetic calculation method has been designed to provide a less laboriousness of identifications procedures compared with Coats-Redfern approximation and to take into account an induction time of the process. As the outcome of this study, it was shown that the kinetic parameters estimated with using of the proposed model-fitted method gives the more appropriate correlation in comparison with the conventional Coats-Redfern method. The proposed method uses the Coats-Redfern algorithm for evaluation of the reaction mechanism, but the value of the constant rate is defined directly from experimental data on the conversion rate.

CINÉTICA DE PIRÓLISE PARA O SORGO LIGNOCELULÓSICO: ANÁLISE DE DADOS TERMOGRAVIMÉTRICOS PARA APLICAÇÃO DO MODELO DE FRIEDMAN

PYROLYSIS KINETICS FOR LIGNOCELLULOSIC SORGHUM: THERMOGRAVIMETRIC DATA ANALYSIS FOR FRIEDMAN MODEL APPLICATION. Renewable resources are alternatives to fossil fuels and pyrolysis is identified as a process for the generation of biofuel products. The lignocellulosic sorghum is a cereal produced in brazil and it presents several applications, such as the production of second-generation ethanol. The present work aimed to study the slow pyrolysis of lignocellulosic sorghum, the biomass was characterized by means of proximate, ultimate, composition and carbohydrate analyzes. Thermogravimetric analyzes were performed with heating rates between 5 and 25 K min-1 and with N2 atmosphere. The Friedman model allows obtaining the kinetic parameters of biomass decomposition and is widely used due to its simplicity and precision; however, since it is sensitive to experimental noise, an algorithm was developed for the calculation of kinetic parameters for the slow pyrolysis of this biomass, enabling an accurate analysis of the experimental data. The activation energy found by the proposed methodology was 122.65 ± 19.24 kJ mol-1, with determination coefficients above 0.97. The comparison between experimental and theoretical data presented deviation values of 0.934%, 3.408% and 1.101% for heating rates of 5, 10 and 15 K min-1, respectively, showing the accuracy for the determined kinetic parameters.