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

Author(s):  
Martina Maria Calvino ◽  
Lorenzo Lisuzzo ◽  
Giuseppe Cavallaro ◽  
Giuseppe Lazzara ◽  
Stefana Milioto

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

Author(s):  
Milan Protic ◽  
Ana Miltojevic ◽  
Miomir Raos ◽  
Petar Đekić

In the global quest for substitution of fossil fuels, biomass is regarded as one of the most promising alternatives. Thermochemical conversion is one of the dominant biomass-to-energy processing routes with pyrolysis as one of the options that gained importance in recent years. In this paper pyrolysis experiments of cheery tree samples were performed. The objective of this research was to determine selected physical and chemical properties of cheery related to thermochemical conversion. The samples were pyrolysed in a thermogravimetric analyzer in an inert, nitrogen, atmosphere at four different heating rates 1, 2, 5 and 10 °C/min. Pyrolysis occurred, as expected, in three step: loss of moisture and light volatiles, active and passive pyrolysis. With an increase in heating rate a lateral shift of the maximum rate of weight loss for the thermal decomposition to higher temperatures was observed, as well as an increase in the amount of residual char. Moreover, kinetic studies were performed using the Kissinger method. The activation energy was calculated to be 155.26 kJ/mol, while the pre-exponential factor was 1.685×1012 min-1. Obtained results are comparable to values reported in literature. Kissinger method is straightforward and offers the possibility for fast and reliable determination of kinetic parameters.


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 ◽  
...  

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.


2018 ◽  
Vol 28 ◽  
pp. 75-89
Author(s):  
Hamid Reza Javadinejad ◽  
Sayed Ahmad Hosseini ◽  
Mohsen Saboktakin Rizi ◽  
Eiman Aghababaei ◽  
Hossein Naseri

The kinetic study for the synthesis of Fluorapatite has been done using the thermogravimetric technique under non-isothermal conditions and at four heating rates of 5, 10, 15 and 20 °C. Both model free and model-fitting methods were used to investigate kinetic parameters. Calcium oxide, phosphorus pentoxide and calcium fluoride were used as the precursor materials. The activation energy values were calculated through model-fitting and isoconversional methods and were used to predict the reaction model and pre-exponential factor. In this case several techniques were considered such as master plots and compensation effects. The results indicated that the reaction mechanism was chemically controlled with second and third order reaction models in the whole range of conversion which the activation energy varied from 25 to 43 kJ/mol.


2020 ◽  
Vol 15 (2) ◽  
Author(s):  
Aarti Tallam ◽  
Sai Rohith Bairy ◽  
Raju Kalakuntala ◽  
Naga Prapurna P.V ◽  
Srinath Suranani

AbstractThis work aims at the kinetic studies of the hydrochar produced from hydrothermal carbonization of citrulluslanatus(watermelon) peel. The hydrochar was prepared at optimized conditions regarding Carbon content, High Heating Value and Yield at experimental conditions of 210 °C and 1 h operation. The Watermelon peel hydrocharkineticswereinvestigated at heating rates of 5 °C${\text{mi}}{{\text{n}}^{ - 1}}$, 10 °C${\text{mi}}{{\text{n}}^{ - 1}}$, 15 °C${\text{mi}}{{\text{n}}^{ - 1}}$, & 20 °C${\text{mi}}{{\text{n}}^{ - 1}}$, through thermogravimetric analysis. Two iso-conversional models were applied to compute the kinetic parameters and pyrolysis behavior of hydrochar. The kinetic study using Kissinger-Akahira-Sunose (KAS) model revealed that for a conversion range of 0.1 to 0.8,the activation energy was observed to be in the range of 146 to 220 kJ/mol. Similarly, the activation energies estimated through Flynn-Wall-Ozawa (FWO) model also gave a similar range of kinetic energies from 147 to 219 kJ/mol. Moreover, higher pre-exponential factor values explained the convoluted structure of biomass. The regression coefficient (${R^{2\,}}$) for both the models is high and they have shown similar activation energies which confirms that the best reaction mechanism is predicted. This research helps in establishing an economical and efficient technology for producing clean bioenergy and useful chemicals.


2019 ◽  
Vol 33 (7) ◽  
pp. 956-966
Author(s):  
Hamidreza Azimi ◽  
Pardis Abedifard

The objective of this study was to clarify the mechanical properties and the non-isothermal degradation kinetics of Polyamide 66 (PA 66)/glass fiber (GF) composites. The non-isothermal degradation behavior of the samples was studied by thermal gravimetric analysis under nitrogen purge. The perfect compatibility of GFs with polymer matrix in composites was studied by scanning electron microscopy. It was found that with increasing content of GFs in samples due to good distribution of fibers in PA 66, the degradation temperature and calculated activation energy in composites increased in all heating rates. The activation energy was calculated by the Flynn–Wall–Ozawa method (isoconversional method). It was concluded that the model-free methods can be a reliable way to determine the kinetic parameters. Furthermore, the isokinetic relationship was used to estimate a model-independent pre-exponential factor (ln A) corresponding to a given degree of conversion.


Materials ◽  
2020 ◽  
Vol 13 (5) ◽  
pp. 1047 ◽  
Author(s):  
Mahmoud Bakr ◽  
Mohamed Omer

Thermoluminescence (TL) properties of La2O3: Dy3+, Li+, and La2O3: Eu3+, Li+, exposed to 5.12 Gy of beta radiation, and recorded at different heating rates 0.5, 1, 2, 3, 4, and 5 °C s−1 (from Molefe et al., paper 2019), were analyzed and the trap parameters were determined in this study. These parameters include the order of kinetics b, the activation energy E (eV), the frequency factor S (s−1), or the pre-exponential factor S’’ (s−1), and the initial concentration of trapped electrons no (cm−3). A new non-linear curve fitting technique, based on the general order kinetic equation and the outcomes of Hoogenstraaten’s Method, was established and applied on the TL glow peaks of La2O3: Dy3+, Li+. The fitting technique was evaluated by calculating the R-square and figure of merit (FOM) values. The results revealed that the FOM values are <1%, and the R-square values are >0.997, which demonstrates an excellent convergence between experimental and fitted curves. A modified technique based on the three-points analysis method was exploited to deconvolute complex TL glow curves of La2O3: Eu3+, Li+, and in turn to determine the trap parameters the method disclosed that each TL glow curve consists of four peaks. The trap parameters of the individual peaks were numerically determined. The fading, as a function of storage temperature and time, from the TL signals of the investigated materials was predicted and discussed based on the calculated trap parameters. The results support the value of the materials for employment in radiation dosimeter applications with a low fading fraction.


Author(s):  
K. Srinivasa Rao ◽  
Keshar N K ◽  
N Jena ◽  
M.E.B Rao ◽  
A K Patnaik

A stability-indicating LC assay method was developed for the quantitative determination of fenofibrate (FFB) in pharmaceutical dosage form in the presence of its degradation products and kinetic determinations were evaluated in acidic, alkaline and peroxide degradation conditions. Chromatographic separation was achieved by use of Zorbax C18 column (250 × 4.0 mm, 5 μm). The mobile phase was established by mixing phosphate buffer (pH adjusted 3 with phosphoric acid) and acetonitrile (30:70 v/v). FFB degraded in acidic, alkaline and hydrogen peroxide conditions, while it was more stable in thermal and photolytic conditions. The described method was linear over a range of 1.0-500 μg/ml for determination of FFB (r= 0.9999). The precision was demonstrated by relative standard deviation (RSD) of intra-day (RSD= 0.56– 0.91) and inter-day studies (RSD= 1.47). The mean recovery was found to be 100.01%. The acid and alkaline degradations of FFB in 1M HCl and 1M NaOH solutions showed an apparent zero-order kinetics with rate constants 0.0736 and 0.0698  min−1 respectively and the peroxide degradation with 5% H2O2 demonstrated an apparent first-order kinetics with rate constant k = 0.0202 per min. The t1/2, t90   values are also determined for all the kinetic studies. The developed method was found to be simple, specific, robust, linear, precise, and accurate for the determination of FFB in pharmaceutical formulations.  


1980 ◽  
Vol 53 (3) ◽  
pp. 437-511 ◽  
Author(s):  
D. W. Brazier

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.


2008 ◽  
Vol 3 ◽  
pp. ACI.S939 ◽  
Author(s):  
J. Rodríguez Flores ◽  
A.M. Contento Salcedo ◽  
L. Muñoz Fernández

Micellar electrokinetic chromatography (MEKC) was investigated for the simultaneous determination of letrozole, imipramine and their metabolites in human urine samples over a concentration range of therapeutic interest. Experimental parameters such as pH of the running electrolyte, sodium dodecylsulphate (SDS) concentration, borate concentration, voltage, etc were investigated. Under optimal conditions of 25 mM SDS, 15 mM borate buffer (pH 9.2), 15% 2-propanol, as background electrolyte; 28 kV and 40 °C, as voltage and cartridge temperature, respectively; resolution between the peaks was greater than 1.7. Before the determination, a solid phase extraction (SPE) procedure with a C18 cartridge was optimized. Good linearity, accuracy, precision, robustness and ruggedness were achieved and detection limits of 12.5 ng/mL for letrozole and its metabolite and 37.5 ng/mL, were obtained for imipramine and their metabolites. Real determinations of these analytes in two patient urines were carried out. Sensitivity achieved in this method is sufficient to perform kinetic studies in humans.


1976 ◽  
Vol 71 (2) ◽  
pp. 507-518 ◽  
Author(s):  
Michael F. Thompson ◽  
Herman S. Bachelard

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