The isoconversional method for determination of energy of activation at constant heating rates

1983 ◽  
Vol 27 (1) ◽  
pp. 95-102 ◽  
Author(s):  
J. H. Flynn
Keyword(s):  
Isoconversional Method ◽  
Energy Of Activation ◽  
Heating Rates ◽  
Constant Heating

Development of HPLC Method for the Purity Test by Design of Experiments and Determination of Activation Energy of Hydrolytic Degradation Reactions of Sofosbuvir

2020 ◽  
Vol 16 (7) ◽  
pp. 976-987
Author(s):  
Jakub Petřík ◽  
Jakub Heřt ◽  
Pavel Řezanka ◽  
Filip Vymyslický ◽  
Michal Douša
Keyword(s):  
Activation Energy ◽  
Design Of Experiments ◽  
Mobile Phase ◽  
Hydrolytic Degradation ◽  
Isoconversional Method ◽  
Hplc Method ◽  
Organic Modifier ◽  
Calculation Methods ◽  
Degradation Reactions

Background: The present study was focused on the development of HPLC method for purity testing of sofosbuvir by the Design of Experiments and determination of the activation energy of hydrolytic degradation reactions of sofosbuvir using HPLC based on the kinetics of sofosbuvir degradation. Methods: Following four factors for the Design of Experiments were selected, stationary phase, an organic modifier of the mobile phase, column temperature and pH of the mobile phase. These factors were examined in two or three level experimental design using Modde 11.0 (Umetrics) software. The chromatographic parameters like resolution, USP tailing and discrimination factor were calculated and analysed by partial least squares. The chromatography was performed based on Design of Experiments results with the mobile phase containing ammonium phosphate buffer pH 2.5 and methanol as an organic modifier. Separation was achieved using gradient elution on XBridge BEH C8 at 50 °C and a flow rate of 0.8 mL/min. UV detection was performed at 220 nm. The activation energy of hydrolytic degradation reactions of sofosbuvir was evaluated using two different calculation methods. The first method is based on the slope of dependence of natural logarithm of the rate constant on inverted thermodynamic temperature and the second approach is the isoconversional method. Results and Conclusion: Calculated activation energies were 77.9 ± 1.1 kJ/mol for the first method and 79.5 ± 3.2 kJ/mol for the isoconversional method. The results can be considered to be identical, therefore both calculation methods are suitable for the determination of the activation energy of degradation reactions.

scholarly journals Lifetime predictions of non-ionic and ionic biopolymers: kinetic studies by non-isothermal thermogravimetric analysis

2021 ◽  
Author(s):  
Martina Maria Calvino ◽  
Lorenzo Lisuzzo ◽  
Giuseppe Cavallaro ◽  
Giuseppe Lazzara ◽  
Stefana Milioto
Keyword(s):  
Degradation Kinetics ◽  
Kinetic Studies ◽  
Ionic Polymers ◽  
Heating Rates ◽  
Exponential Factor ◽  
Master Plot ◽  
Plot Analysis ◽  
Sustainable Polymers ◽  
Master Plot Analysis

AbstractIn this paper, films based on sustainable polymers with variable charge have been investigated by non-isothermal thermogravimetry in order to predict their lifetime, which is a key parameter for their potential use in numerous technological and biomedical applications. Specifically, chitosan has been selected as positively charged biopolymer, while alginate has been chosen as negatively charged biopolymer. Among non-ionic polymers, methylcellulose has been investigated. Thermogravimetric measurements at variable heating rates (5, 10, 15 and 20 °C min−1) have been performed for all the polymers to study their degradation kinetics by using isoconversional procedures combined with ‘Master plot’ analyses. Both integral (KAS and Starink methods) and differential (Friedman method) isoconversional procedures have shown that chitosan possesses the highest energetic barrier to decomposition. Based on the Master plot analysis, the decomposition of ionic polymers can be described by the R2 kinetic model (contracted cylindrical geometry), while the degradation of methylcellulose reflects the D2 mechanism (two-dimensional diffusion). The determination of both the decomposition mechanism and the kinetic parameters (activation energy and pre-exponential factor) has been used to determine the decay time functions of the several biopolymers. The obtained insights can be helpful for the development of durable films based on sustainable polymers with variable electrostatic characteristics. Graphical abstract

Applications of Thermal Analytical Procedures in the Study of Elastomers and Elastomer Systems

1980 ◽  
Vol 53 (3) ◽  
pp. 437-511 ◽  
Author(s):  
D. W. Brazier
Keyword(s):  
Thermal Analysis ◽  
Dynamic Properties ◽  
Evolved Gas Analysis ◽  
Gas Analysis ◽  
International Standards ◽  
New Technique ◽  
Heating Rates ◽  
Single Experiment ◽  
Rubber Compounds

Abstract An attempt has been made to review the development of thermoanalytical procedures as they have been applied to elastomers and elastomer systems over the past 10 years. For all rubber industry products, temperature and its effects, either alone or in conjunction with the chemical environment, play an important role from the production stage through to the final failure of the product in the field. It is thus not surprising that thermal analysis, in which temperature is the prime variable, has found such diverse applications in elastomer studies. The identification and quantitative analysis of rubber formulations have received most attention. Such formulations produce characteristic “fingerprints” when studied in DTA, DSC, TG, or TMA. In DSC, the determination of the glass transition characteristics, the observation and determination of crystallinity, the detection of cyclization reactions, and the monitoring of thermal and oxidative degradation characteristics can all be observed in a single experiment covering the temperature range from −150 to +600°C. At normal heating rates, e.g., 20°C/min, such information is available in 40 min. TG/DTG analysis can yield the elastomer or elastomers content, oil and plasticizer, carbon black (level and often type), and inorganic ash in less than 60 min. Processing and curing can also be studied. Blend compatibility can be assessed on the basis of both Tg and crystallinity measurements and the data used to determine optimum mixing times. Sulfur vulcanization and peroxide curing of elastomers is readily monitored by DSC and can be used for confirmation analysis of the presence of curatives. Limitations in such analysis exist, but as understanding and ability to interpret cure exotherms increase, valuable information about the mechanism and the nature of the cured network will be obtained. The testing of rubber compounds involves many hours of labor by current procedures. The rapidity of thermal analysis promises to offer some relief. In addition to DSC and TG, TMA, a relatively new technique, offers a rapid approach to low-temperature testing. Dynamic mechanical analysis (DMA) offers a rapid route to determining dynamic properties, but as yet, relatively little has been published on the application of this new technique to elastomers. As environmental concern increases, techniques such as evolved gas analysis (EGA) and combined techniques such as TG/gas chromatography are predicted to play an important role. As for the future, it is readily apparent that the principles of the methods have been established and, in several cases, it now remains to reduce them to a practical level. In some areas, such as vulcanization studies, much remains to be undertaken to improve our interpretive skills. Although there is some indication that certain industries have produced “in-house” standards for the analysis of rubber compounds by DSC and TG/DTG, it will only be when national and international standards organizations study and produce standard procedures, that the techniques will be generally adopted. Maurer's prediction in 1969 of increased applications of DTA and TG in elastomer studies has undoubtedly proved correct, and with the proliferation of reliable commercial instrumentation, significant developments can be anticipated in the next decade.

Theoretical Thermogravimetric Analysis at Constant Heating Rates

1980 ◽  
pp. 51-56 ◽  
Author(s):  
C. Comel ◽  
J. Veron ◽  
C. Bouster ◽  
P. Vermande
Keyword(s):  
Thermogravimetric Analysis ◽  
Heating Rates ◽  
Constant Heating

Determination of the energy of activation of kinetic elements for α-relaxation in polymers

1976 ◽  
Vol 18 (1) ◽  
pp. 32-39
Author(s):  
V.P. Petrosyan ◽  
A.V. Dzhanbaryants ◽  
Sh.T. Yegurtdzhyan
Keyword(s):  
Energy Of Activation

scholarly journals Curing Kinetic Parameters of Epoxy Composite Reinforced with Mallow Fibers

Materials ◽  
2019 ◽  
Vol 12 (23) ◽  
pp. 3939 ◽  
Author(s):  
Lucio Fabio Cassiano Nascimento ◽  
Fernanda Santos da Luz ◽  
Ulisses Oliveira Costa ◽  
Fábio de Oliveira Braga ◽  
Édio Pereira Lima Júnior ◽  
...  
Keyword(s):  
Kinetic Parameters ◽  
Industrial Process ◽  
Diglycidyl Ether ◽  
Response Surfaces ◽  
Heating Rates ◽  
Scanning Calorimetry ◽  
Exponential Factor ◽  
Curing Kinetic ◽  
Technological Tool

Knowledge about the curing behavior of a thermosetting resin and its composites includes the determination of kinetic parameters and constitutes an important scientific and technological tool for industrial process optimization. In the present work, the differential scanning calorimetry (DSC) technique was used to determine several curing parameters for pure epoxy and its composite reinforced with 20 vol % mallow fibers. Analyses were performed with heating rates of 5, 7.5, and 10 °C/min, as per the ASTM E698 standard. The kinetic related parameters, that is, activation energy (E), Avrami’s pre-exponential factor (Z), and mean time to reach 50% cure (t½), were obtained for the materials, at temperatures ranging from 25 to 100 °C. Response surfaces based on the mathematical relationship between reaction time, transformed fraction, and temperature were provided for optimization purposes. The results showed that the average curing time used for the production of diglycidyl ether of bisphenol A/triethylenetetramine (DGEBA/TETA) epoxy systems or their composites reinforced with natural mallow fibers can be considerably reduced as the temperature is increased up to a certain limit.

Sign in / Sign up

Export Citation Format

Share Document