scholarly journals Critical Appraisal of Kinetic Calculation Methods Applied to Overlapping Multistep Reactions

Molecules ◽  
2019 ◽  
Vol 24 (12) ◽  
pp. 2298 ◽  
Author(s):  
Nikita V. Muravyev ◽  
Alla N. Pivkina ◽  
Nobuyoshi Koga
Keyword(s):  
Kinetic Parameters ◽  
Model Fitting ◽  
Simultaneous Occurrence ◽  
Calculation Methods ◽  
Scanning Calorimetry ◽  
Kinetic Calculation ◽  
Complex Processes ◽  
Formal Kinetic ◽  
Kinetic Deconvolution ◽  
Multistep Reactions

Thermal decomposition of solids often includes simultaneous occurrence of the overlapping processes with unequal contributions in a specific physical quantity variation during the overall reaction (e.g., the opposite effects of decomposition and evaporation on the caloric signal). Kinetic analysis for such reactions is not a straightforward, while the applicability of common kinetic calculation methods to the particular complex processes has to be justified. This study focused on the critical analysis of the available kinetic calculation methods applied to the mathematically simulated thermogravimetry (TG) and differential scanning calorimetry (DSC) data. Comparing the calculated kinetic parameters with true kinetic parameters (used to simulate the thermoanalytical curves), some caveats in the application of the Kissinger, isoconversional Friedman, Vyazovkin and Flynn–Wall–Ozawa methods, mathematical and kinetic deconvolution approaches and formal kinetic description were highlighted. The model-fitting approach using simultaneously TG and DSC data was found to be the most useful for the complex processes assumed in the study.

scholarly journals Non-Isothermal Crystallization Kinetic of Polyethylene/Carbon Nanotubes Nanocomposites Using an Isoconversional Method

2019 ◽  
Vol 3 (1) ◽  
pp. 21 ◽  
Author(s):  
Beatriz Menezes ◽  
Tiago Campos ◽  
Thais Montanheiro ◽  
Renata Ribas ◽  
Luciana Cividanes ◽  
...  
Keyword(s):  
Carbon Nanotubes ◽  
Kinetic Parameters ◽  
Isothermal Crystallization ◽  
Crystallization Kinetic ◽  
Model Fitting ◽  
Kinetic Studies ◽  
Isoconversional Method ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
Crystallite Sizes

Behavior studies of thermoplastic polymers during non-isothermal crystallization are extremely important since most of their properties are influenced by degree of crystallinity and the crystallization process. In general, an approach based on a model-fitting method is used to perform crystallization kinetic studies. Due to their inability to uniquely determine the reaction mode, many studies have used the isoconversional method, where it is not necessary to assume a crystallization model to obtain the kinetic parameters. Therefore, in this work, the influence of acid and octadecylamine functionalized carbon nanotubes (CNTs) in the crystallization kinetic of polyethylene (PE) was studied using an isoconversional method with differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The kinetic parameters and the crystallization model were determined. The incorporation of functionalized and non-functionalized CNTs into PE did not change the Johnson-Mehl-Avrami crystallization model. However, the CNTs increased the crystallization temperature and reduced the activation energy for crystallization. In addition, the Avrami coefficient values were lower for the nanocomposites when compared to pure PE. The incorporation of CNTs accelerated the crystallization of PE, reducing the crystallite sizes and modifying their morphology.

scholarly journals Applications of a simultaneous differential scanning calorimetry–thermomicroscopy system

2021 ◽  
Author(s):  
Gage P. Ashton ◽  
Edward L. Charsley ◽  
Lindsay P. Harding ◽  
Gareth M. B. Parkes
Keyword(s):  
Silver Iodide ◽  
Magnesium Nitrate ◽  
Optical Data ◽  
Nitrate Hexahydrate ◽  
Scanning Calorimetry ◽  
Rubidium Nitrate ◽  
Complex Processes ◽  
Magnesium Nitrate Hexahydrate ◽  
Intensity Measurements ◽  
Reversible Transitions

AbstractA simultaneous DSC–thermomicroscopy system (DSC450 Linkam Scientific) was applied to the study of phase transitions in rubidium nitrate and silver iodide, the oxidation of polyethylene, the thermal degradation of polylactic acid and magnesium nitrate hexahydrate, and the reversible transitions in thermochromic inks. The results demonstrated the benefits of obtaining simultaneous optical data, both images and light intensity measurements, with DSC, particularly in the interpretation of complex processes and the detection of events with small changes in enthalpy.

scholarly journals Kinetic Parameters of Nut Shells Pyrolysis

Energies ◽  
2021 ◽  
Vol 14 (3) ◽  
pp. 682
Author(s):  
Tomasz Noszczyk ◽  
Arkadiusz Dyjakon ◽  
Jacek A. Koziel
Keyword(s):  
Kinetic Parameters ◽  
Waste Treatment ◽  
Model Fitting ◽  
Thermal Conversion ◽  
Point Of View ◽  
The European Union ◽  
Heating Rates ◽  
Isothermal Model ◽  
Biomass Residues ◽  
Conversion Point

The European Union created a European Green Deal Program (EGDP). This program aims at a sustainable economy through the transformation of the challenges related to climate and the environment. The main goal of EGDP is climate neutrality by 2050. The increase of alternative biomass residues utilization from various food processing industries and cooperation in the energy and waste management sector is required to meet these expectations. Nut shells are one of the lesser-known, yet promising, materials that can be used as an alternative fuel or a pre-treated product to further applications. However, from a thermal conversion point of view, it is important to know the energy properties and kinetic parameters of the considered biowaste. In this study, the energy and kinetic parameters of walnut, hazelnut, peanut, and pistachio shells were investigated. The results showed that raw nut shells are characterized by useful properties such as higher heating value (HHV) at 17.8–19.7 MJ∙kg−1 and moisture content of 4.32–9.56%. After the thermal treatment of nut shells (torrefaction, pyrolysis), the HHV significantly increased up to ca. 30 MJ∙kg−1. The thermogravimetric analysis (TGA) applying three different heating rates (β; 5, 10, and 20 °C∙min−1) was performed. The kinetic parameters were determined using the isothermal model-fitting method developed by Coats–Redfern. The activation energy (Ea) estimated for β = 5 °C∙min−1, was, e.g., 60.3 kJ∙mol−1∙K−1 for walnut, 59.3 kJ∙mol−1∙K−1 for hazelnut, 53.4 kJ∙mol−1∙K−1 for peanut, and 103.8 kJ∙mol−1∙K−1 for pistachio, respectively. Moreover, the increase in the Ea of nut shells was observed with increasing the β. In addition, significant differences in the kinetic parameters of the biomass residues from the same waste group were observed. Thus, characterization of specific nut shell residues is recommended for improved modeling of thermal processes and designing of bioreactors for thermal waste treatment.

Crystallization kinetics mechanism investigation of sol–gel-derived NaYF4:(Yb,Er) up-converting phosphors

CrystEngComm ◽  
2017 ◽  
Vol 19 (34) ◽  
pp. 4992-5000 ◽  
Author(s):  
C. Bartha ◽  
C. E. Secu ◽  
E. Matei ◽  
M. Secu
Keyword(s):  
Differential Scanning Calorimetry ◽  
Crystallization Kinetics ◽  
Sol Gel ◽  
Model Fitting ◽  
Crystallization Mechanism ◽  
Differential Scanning Calorimetry Analysis ◽  
Scanning Calorimetry ◽  
Model Free

The crystallization mechanism of sol–gel-derived NaYF4:(Yb,Er) up-converting phosphors has been studied by differential scanning calorimetry analysis using both model-free and model fitting approaches.

scholarly journals Thermal Properties and Non-Isothermal Crystallization Kinetics of Poly (δ-Valerolactone) and Poly (δ-Valerolactone)/Titanium Dioxide Nanocomposites

Crystals ◽  
2018 ◽  
Vol 8 (12) ◽  
pp. 452 ◽  
Author(s):  
Waseem Saeed ◽  
Abdel-Basit Al-Odayni ◽  
Abdulaziz Alghamdi ◽  
Ali Alrahlah ◽  
Taieb Aouak
Keyword(s):  
Titanium Dioxide ◽  
Crystallization Kinetics ◽  
Isothermal Crystallization ◽  
Three Dimensional ◽  
Degree Of Crystallinity ◽  
Simultaneous Occurrence ◽  
Scanning Calorimetry ◽  
Isothermal Crystallization Kinetics ◽  
The Stability ◽  
Kinetics Of

New poly (δ-valerolactone)/titanium dioxide (PDVL/TiO2) nanocomposites with different TiO2 nanoparticle loadings were prepared by the solvent-casting method and characterized by Fourier transform infra-red, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy, and thermogravimetry analyses. The results obtained reveal good dispersion of TiO2 nanoparticles in the polymer matrix and non-formation of new crystalline structures indicating the stability of the crystallinity of TiO2 in the composite. A significant increase in the degree of crystallinity was observed with increasing TiO2 content. The non-isothermal crystallization kinetics of the PDVL/TiO2 system indicate that the crystallization process involves the simultaneous occurrence of two- and three-dimensional spherulitic growths. The thermal degradation analysis of this nanocomposite reveals a significant improvement in the thermal stability with increasing TiO2 loading.

scholarly journals AN INNOVATE METHOD OF THERMOGRAVIMETRIC DATA ANALYSIS

2021 ◽  
Vol 64 (3) ◽  
pp. 24-32
Author(s):  
Mihail V. Mal’ko ◽  
Sergej V. Vasilevich ◽  
Andrey V. Mitrofanov ◽  
Vadim E. Mizonov
Keyword(s):  
Experimental Data ◽  
Thermal Decomposition ◽  
Thermogravimetric Analysis ◽  
Kinetic Parameters ◽  
Calculation Method ◽  
Kinetic Calculation ◽  
Pyrolysis Mechanism ◽  
Total Mass Loss ◽  
Thermogravimetric Data ◽  
Heavy Tar

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.

scholarly journals Kinetic Analysis of the Thermal Decomposition of Polymer-Bonded Explosive Based on PETN: Model-Fitting Method and Isoconversional Method

2020 ◽  
Vol 2020 ◽  
pp. 1-12
Author(s):  
Trung Toan Nguyen ◽  
Duc Nhan Phan ◽  
Van Thom Do ◽  
Hoang Nam Nguyen
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Parameters ◽  
Model Fitting ◽  
Isoconversional Method ◽  
Isothermal Tg ◽  
Decomposition Reactions ◽  
Model Free ◽  
Negative Effect ◽  
Adverse Influence ◽  
Vacuum Stability Test

This work investigates kinetics and thermal decomposition behaviors of pentaerythritol tetranitrate (PETN) and two polymer-bonded explosive (PBX) samples created from PETN (named as PBX-PN-85 and PBX-PP-85) using the vacuum stability test (VST) and thermogravimetry (TG/DTG) techniques. Both model-free (isoconversional) and model-fitting methods were applied to determine the kinetic parameters of the thermal decomposition. It was found that kinetic parameters obtained by the modified Kissinger–Akahira–Sunose method (using non-isothermal TG/DTG data) were close to those obtained by the isoconversional and model-fitting methods that use isothermal VST data. The activation energy values of thermal decomposition reactions were 125.6–137.1, 137.3–144.9, and 143.9–152.4 kJ·mol−1 for PBX-PN-85, PETN, and PBX-PP-85, respectively. The results demonstrate the negative effect of the nitrocellulose-based binder in reducing the thermal stability of single PETN, while the polystyrene-based binder seemingly shows no adverse influence on the thermal decomposition of PETN in our presented PBX compositions.

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