TG-DSC and TG-FTIR Studies of Annelated Triazinylacetic Acid Ethyl Esters-Potential Anticancer Agents.

To avoid problems associated with the storage and processing of newly developed potential medicines, there is a need to carry out thermal studies in the preclinical phase of drug development. The thermal behaviour and decomposition pathway of a whole novel class of patented potential molecular pharmaceutics, i.e., ethyl 2-[4-oxo-8-(R-phenyl)-4,6,7,8-tetrahydroimidazo[2,1-c][1,2,4]triazin-3-yl]acetates (1-6) were reported for the first time in inert and oxidative atmospheres. The experiments were conducted with the use of simultaneous thermogravimetry/differential scanning calorimetry (TG-DSC) and simultaneous thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR). The decomposition pathways of compounds 1-6 were found to be different under oxidative and inert conditions. It was proven that the investigated molecules reveal higher thermal stability under a synthetic air atmosphere than under a nitrogen atmosphere, and their decomposition is preceded by the melting process. Among all the investigated compounds, only the meta-chloro derivative (4) was found to exhibit interesting polymorphic behaviour at a low heating rate (10 °C min-1). It was proven that the oxidative decomposition process of the studied molecules proceeds in three overlapping stages accompanied by strong exothermic effects. Additionally, it was concluded that the title compounds were stable up to a temperature of 195-216 °C in an atmosphere of synthetic air, and their thermal stability decreased in the order of R at the benzene ring: 4-CH3 > 3,4-Cl2 > 4-Cl > H > 2-OCH3 > 3-Cl.

Advanced Fitting Method for the Kinetic Analysis of Thermogravimetric Data.

The article considered the solution of the inverse problem of chemical kinetics of the analysis of experimental data of a thermogravimetric experiment at a constant sample heating rate. The fitting method for identifying the parameters of a kinetic triplet using the integral method for a model of a solid-state reaction based on the modified Arrhenius equation is described. The effectiveness of the proposed approach was confirmed by solving test cases for low, medium, and high rates of material conversion. Unlike other methods, setting the parameters of the reaction mechanism is not required, as they are determined by the solution. Solutions for real data of TGA studies with high and low sample heating rates were compared with the results obtained by other authors and experimental data. A description of the full cycle of calculations used to identify kinetic parameters from thermogravimetric experimental data is given, from the derivation of calculated relationships to the implementation of a short (three to five formulas) program code for MS Excel spreadsheets. The presented code is easy to verify and reproduce and can be modified to solve various problems.

Cadmium phosphates with two types of fundamental building units and a wide ultraviolet transparency window.

Owing to diverse crystal structures and intriguing properties, metal phosphates have attracted much attention in recent studies. In this work, two cadmium phosphates, KCd6P7O24 and KCd3P3O11, were obtained by the high-temperature solution method. In the crystal structure, both the title compounds contain two types of P-O fundamental building units. Thermal and spectral analyses were carried out on the title compounds, indicating that both of them have good thermal stability and short UV cut-off edges. In addition, the relationship between the electronic structures and optical properties was studied by theoretical calculations.

Sustainable valorization of water hyacinth waste pollutant via pyrolysis for advance microbial fuel investigation.

Present study has been focused on the bio-energy potential of waste biomass (water hyacinth leaves and its stem). Pyrolysis of both biomasses were investigated at five different heating rates (5-25 °C/min) using thermogravimetric analyzer. For both biomasses, maximum thermal degradation occurred within the temperature range of 200-400 °C, which is the active pyrolytic zone. Three non-iso-conversional (degradation models) including the Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, and Starink were used to calculate the activation energy of both biomasses. The activation energy was around 92-98 kJ/mol for water hyacinth leaves and 151-153 kJ/mol for water hyacinth stems. The results suggest that these low-cost abundantly available biomasses have a good potential for the production of solid bio-fuel.

Recovery of iron from iron tailings by suspension magnetization roasting with biomass-derived pyrolytic gas.

A major industrial solid waste, iron tailings occupy a large area and pose long-term pollution risks. The pyrolysis gas of biomass was used as reducing agent to suspension magnetize and roast iron tailings to recover iron in this study. The process conditions, phase transformation and microstructure evolution of the iron tailings, pyrolysis gas production, and reaction regulations were investigated to explain the mechanism of iron recovery by suspension magnetization roasting (SMR) under the action of biomass pyrolysis gas. These studies were conducted using X-ray diffraction, scanning electron microscopy, vibrating sample magnetometer, thermo-gravimetric and differential scanning calorimetry, brunauer-emmett-teller specific surface area, and gas chromatography. The results showed that, after the grinding-magnetic separation process, the iron recovery rate was 93.32 %; the iron grade of the iron concentrate was 61.50 %. The optimal process conditions were determined as follows: fast pyrolysis temperature of 600 °C, SMR temperature of 700 °C, biomass dosage of 10 %, and SMR time of 4-5 min. The formation of Fe3O4 from the surface to the interior of the particles during the reduction process, and formation of pores and cracks led to an increase in the specific surface area. The SMR temperature not only improved the heat and mass transfer effect in the reduction process but also generated more CO and H2 through the reverse reaction of methanation, which work together to increase the saturation magnetisation of the unit sample. This method can be used to efficiently recover high quality iron from refractory iron ores.

Self-extracted corn-stalk cellulose/epoxy resin composites.

In order to make full use of crop waste stalk, corn-stalk cellulose (CSC) was extracted by acid-base method and used as modifier of epoxy resin (E51) to prepare the self-extracted corn-stalk cellulose/epoxy resin composites (CSCEC). Differential scanning calorimeter (DSC), thermogravimetry (TG) analysis, dynamic mechanical analysis (DMA), morphology analysis by scanning electron microscope (SEM), the mechanical properties by electronic universal testing machine and impact testing machine were used for characterization and analysis. The experimental results showed that when the CSC content was 20 wt%, the impact strength of the composite was 2.50 kJ/m2, which was 127.2% higher than that of pure epoxy resin. When the CSC content was 20 wt%, the Tg of epoxy resin obtained by DMA was the lowest, 167.4 °C, which decreased by 11.3 °C compared with that of pure epoxy resin. The SEM result showed that the fracture surface of the composite became obviously rough and had of obvious folds, which was a ductile fracture. These results indicated that the addition of CSC could toughen the epoxy resin.

Study the effect of drying on the oxidation thermogravimetric and functional group composition characteristics of immersed lignite.

The drying process of immersed lignite has a significant influence on the characteristics and progress of spontaneous combustion. To reveal the influence mechanism of the drying process of immersed coal on the spontaneous combustion characteristics and the change rule of the spontaneous combustion process, in this research, we measured the mass change during coal oxidation with thermogravimetry, and the change of the functional groups with Fourier transform infrared spectroscopy. The influence of the drying process on the coal was analyzed by comparing activation energy, functional group of immersed coal with different drying degrees and raw coal. The results showed that, compared with raw coal, the content of Ar-C-O- and antisymmetric stretching vibration of the carboxylate group (-COO-) as well as the stretching vibration in the quinone group (C=O) and the -OH group increased. For the content of [Formula: see text],[Formula: see text][Formula: see text], the value of Asym.CH2/Asym.CH3 decreased. The content of various functional groups changed to be favorable for oxidation and heat release. At different reaction stages, the activation energy was differently affected by the degree of drying. Average values of activation energies at different reaction stages are shown raw coal had the lowest activation energy. After soaking in water and drying, the activation energy of coal is increased to varying degrees, the reactivity is reduced, and the risk of spontaneous combustion is reduced. After soaking in water and drying, the activation energy of coal is increased to varying degrees, the reactivity is reduced, and the risk of spontaneous combustion is reduced. The activation energy of the coal samples dried for 24 h after soaking in water is the lowest among the coal samples dried for different times after soaking in water, and the moisture content is 10.5%.

Thermogravimetric Analysis and Kinetic Modeling of the AAEM-Catalyzed Pyrolysis of Woody Biomass.

This work analyzes the catalytic effects induced by alkali and alkaline earth metals (AAEMs) on pyrolysis kinetics. To this end, thermogravimetric analyses (TGA) were carried out with raw beech wood and samples impregnated with NaCl, KCl and MgCl2 at four heating rates (5, 10, 15 and 30 °C/min). Obtained results showed that AAEM compounds promote the decomposition of biomass by reducing the initial and peak pyrolysis temperatures. More specifically, the catalytic effect of the alkaline earth metal was shown to be stronger than that of alkali metals. To further interpret the obtained trends, a kinetic modeling of measured data was realized using two isoconversional methods (the Ozawa-Flynn-Wall (OFW) and Kissinger-Akahira-Sunose (KAS) models). With a view to identifying a suitable reaction model, model fitting and master plot methods were considered to be coupled with the isoconversional modeling approaches. The 3-D diffusion reaction model has been identified as being well suited to properly simulate the evolution of the conversion degree of each sample as a function of the temperature. Furthermore, the kinetic parameters derived from the present modeling work highlighted significant decreases of the activation energies when impregnating wood with AAEM chlorides, thus corroborating the existence of catalytic effects shifting the decomposition process to lower temperatures. A survey of the speculated pathways allowing to account for the impact of AAEMs on the thermal degradation of woody biomass is eventually proposed to better interpret the trends identified in this work.

A review of the main methods for composite adsorbents characterization.

Adsorption is a promising technology for removing several contaminants from aqueous matrices. In the last years, researchers worldwide have been working on developing composite adsorbents to overcome some limitations and drawbacks of conventional adsorbent materials, which depend on various factors, including the characteristics of the adsorbents. Therefore, it is essential to characterize the composite adsorbents to describe their properties and structure and elucidate the mechanisms, behavior, and phenomenons during the adsorption process. In this sense, this work aimed to review the main methods used for composite adsorbent characterization, providing valuable information on the importance of these techniques in developing new adsorbents. In this paper, we reviewed the following methods: X-Ray diffraction (XRD); spectroscopy; scanning electron microscopy (SEM); N2 adsorption/desorption isotherms (BET and BJH methods); thermogravimetry (TGA); point of zero charge (pHPZC); elemental analysis; proximate analysis; swelling and water retention capacities; desorption and reuse.

Influence of the filler distribution on PDMS-graphene based nanocomposites selected properties.

Insufficient homogeneity is one of the pressing problems in nanocomposites' production as it largely impairs the properties of materials with relatively high filler concentration. Within this work, it is demonstrated how selected mixing techniques (magnetic mixer stirring, calendaring and microfluidization) affect filler distribution in poly(dimethylsiloxane)-graphene based nanocomposites and, consequently, their properties. The differences were assessed via imaging and thermal techniques, i.a. Raman spectroscopy, differential scanning calorimetry and thermogravimetry. As microfluidization proved to provide the best homogenization, it was used to prepare nanocomposites of different filler concentration, whose structural and thermal properties were investigated. The results show that the concentration of graphene significantly affects polymer chain mobility, grain sizes, defect density and cross-linking level. Both factors considered in this work considerably influence thermal stability and other features which are crucial for application in electronics, EMI shielding, thermal interface materials etc.

Mechanical properties of toughened windmill palm fibre with different chemical compositions.

Windmill palm fibres are well-known plant fibres exhibiting the largest elongation at break. In this study, lignin or hemicellulose was removed from windmill palm fibres in a targeted manner to prepare materials with different chemical compositions. The structure and mechanical properties of the windmill palm fibres were analysed using in situ scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetry, X-ray diffraction analysis and tensile testing. The large elongation at break was attributed to the unwinding of the single fibre, the micro cracks and the small degree of orientation (<62 %). On a microscopic scale, the lumen shape of fibre cross section influences the local stress distribution. The hemicellulose-removed fibres exhibited a high breaking strength of 236 MPa with deterioration of the thermal property. The binding force between single fibres is the weakest after lignin removal. The removal of hard lignin softens the fibres and increases the elongation at break to >30 %.

Pyrolysis Kinetics and Combustion Behaviors of a High-Nitrogen Compound, 4,4'-Azobis(1,2,4-triazole).

To study the thermal decomposition behavior of 4,4'-azobis(1,2,4-triazole) (ATRZ), the non-isothermal thermal decomposition kinetics of ATRZ were studied using the thermogravimetric-differential scanning calorimetry (TG-DSC) method. The TG-DSC of ATRZ was analyzed at heating rates of 5, 10, 15, and 20 K·min-1 in an argon atmosphere. The thermal decomposition kinetic parameters at peak temperature (Tp), such as apparent activation energy (Ea) and pre-exponential factor (lgA) of ATRZ, were calculated using the Kissinger, Ozawa, and Satava-Sestak methods. Ea and lgA calculated using the Kissinger, Ozawa, and Satava-Sestak methods are very close, at 780.2 kJ·mol-1/70.5 s-1, 751.1 kJ·mol-1/71.8 s-1, and 762.1 kJ·mol-1/71.8 s-1, respectively. Using a combination of three methods, the reaction mechanism function g(α) of ATRZ was obtained. The results show that the decomposition temperature of ATRZ is about 310 °C, and the decomposition is rapidly exothermic. The pyrolysis path of ATRZ was investigated through a pyrolysis-gas chromatography mass spectrometry (PY-GC/MS) experiment. ATRZ has three different decomposition paths and finally generates N2, HC-N-CH, N≡C-N, and HC=N-C≡N. The laser ignition combustion duration of ATRZ was 0.5033 s and the peak temperature was 1913 °C. The laser ignition combustion duration of ATRZ+CL-20 was 1.0277 s and the peak temperature was 2105 °C. The rapid energy release rate of ATRZ promotes the combustion energy release of CL-20.

Heterogeneous Dynamic Behavior and Synergetic Evolution Mechanism of Internal Components and Released Gases during the Pyrolysis of Aquatic Biomass.

Evolution of gaseous contaminants from biomass pyrolysis has drawn increasing attention. However, the thermal degradation, dynamics, and synergetic evolution mechanisms during real-time biomass pyrolysis remain unclear. Herein, a novel method using thermogravimetry-Fourier transform infrared spectrometry-gas chromatography/mass spectrometry (TG-FTIR-GC/MS) combined with thermal kinetics and two-dimensional correlation spectroscopy was proposed to explore the chemical properties and temperature response mechanisms of gaseous species released during Phragmites communis (PC) and Typha angustifolia (TA) pyrolysis. The thermal degradation mechanisms of PC/TA pyrolysis were mainly associated with the sigmoidal rate and random nucleation mechanisms. The formation intensities of alcohols/ethers, phenols/esters, acids, aldehydes, and ketones were higher during low-temperature TA pyrolysis and high-temperature PC pyrolysis. The average carbon oxidation state (OS¯C) of gaseous species mainly ranged from -1.5 to -0.5, and the OS¯C slope of most gaseous species was greater than -2.0, which was related to the reduction of aldehyde/ketone groups. Two-dimensional (2D)-TG-FTIR-COS analysis revealed that the sequential temperature response of gaseous species followed: acids → phenols, esters → aldehydes → hydrocarbons → alcohols, ethers → aromatics during PC/TA pyrolysis. The establishment of relationships between the sequential response of gases and degraded components provides an important basis for online monitoring/recovery of gaseous contaminants during biomass pyrolysis.

Biomass valorization of Eichhornia crassipes root using thermogravimetric analysis.

Present study focused on the thermo-chemical potential of waste biomass of Eichhornia crassipes or water hyacinth root (WHR). The pyrolysis-kinetic parameters are investigated using thermo-gravimetric analysis at the various heating rates (5, 10, 15, and 20 °C/min). Three model-free techniques, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink, were used for the thermal kinetic analysis of biomass. The average activation energy for WHR biomass was determined using KAS, FWO, and Starink, with the values of 57.87, 64.69, and 58.27 kJ/mol, respectively. From the study it is observed that the roots of water hyacinth have rich in carbon, oxygen and hydrogen composition around 24%, 70% and 4% respectively. The higher heating value of water hyacinth root was observed around 15 MJ/kg.

Mercury release behaviors of Guizhou bituminous coal during co-pyrolysis: Influence of chlorella.

Co-pyrolysis of coal and seaweed can not only effectively decrease the carbon footprint but also improve the quality and output of coal pyrolysis products, however, the influence of seaweed on thermal releasing behaviors of mercury during co-pyrolysis process are still unclear. In this work, the chlorella and Guizhou bituminous coal were mixed and used to reveal the mercury release behavior during co-pyrolysis by the temperature programmed pyrolysis experiments, thermogravimetric and differential thermogravimetric analysis (TG-DTG) and thermogravimetry-mass spectrometry (TG-MS) methods, offering a sufficient explanation on the control technology of mercury pollutants in co-pyrolysis. The results exhibited that a large amount of reducing gases such as CO, H2 and H2O were generated in chlorella at the temperature range of 100-500°C, which was favorable for the transformation from oxidized mercury to elemental mercury, thus remarkably increased the release of elemental mercury in the raw coal sample. The mixed chlorella also significantly lowered the decomposition temperature range (from 400-600 to 300-400°C) of pyrite-bound mercury and decreased the decomposition temperatures of the pyrite-bound mercury species. Additionally, in the co-pyrolysis about 91.82% of mercury was released into the gas phase below 400°C and was 13.77% higher than that of in individual pyrolysis of coal.

Thermogravimetry combined with electrospray and atmospheric pressure chemical ionization mass spectrometry for characterization of synthetic polymers.

RATIONALE: Thermogravimetry (TG) combined with electrospray and atmospheric chemical ionization (ESI+APCI) mass spectrometry (MS) was developed to rapidly characterize thermal decomposition products of synthetic polymers and plastic products. The ESI-based TG-MS method is useful for characterizing thermally labile, nonvolatile, and polar compounds over an extensive mass range; and the APCI-based TG-MS counterpart is useful for characterizing volatile and nonpolar compounds. Both polar and nonpolar compounds can be simultaneously detected by ESI+APCI-based TG-MS. METHODS: Analytes with different volatility were produced from TG operated at different temperatures, which were delivered through a heated stainless-steel tube to the ESI+APCI source where they reacted with the primary charged species generated from electrospray and atmospheric pressure chemical ionization (ESI+APCI) of solvent and nitrogen. The analyte ions were then detected by an ion trap mass spectrometer. RESULTS: A semi-volatile PEG 600 standard was used as the sample and protonated and sodiated molecular ions together with adduct ions including [(PEG)n + 15]+ , [(PEG)n + 18]+ , and [(PEG)n + 29]+ were detected by TG-ESI+APCI-MS. The technique was further utilized to characterize thermal decomposition products of nonvolatile polypropylene glycol (PPG) and polystyrene (PS) standards, as well as a PS-made water cup and coffee cup lid. The characteristic fragments of PPG and PS with mass differences of 58 and 104 between respective ion peaks were detected at the maximum decomposition temperature (Tmax ). CONCLUSIONS: The information obtained from the TG-ESI+APCI-MS analysis is useful in rapidly distinguishing different types of polymers and their products. In addition, the signals of the additives in the polymer products, including antioxidants and plasticizers, were also detected before the TG temperature reached Tmax .

Synthesis, characterization and thermal degradation kinetics of a new pyrazole derived methacrylate polymer, poly(1,3-diphenyl-1H-pyrazol-5-yl methacrylate).

A new pyrazole derived methacrylate monomer, 1,3-diphenyl-1H-pyrazol-5-yl methacrylate, was synthesized from the reaction of 1,3-diphenyl-5-pyrazolone with methacryloyl chloride in the presence of triethylamine. After that, its homopolymerization was carried out by free radical polymerization method at 60 °C initiated with benzoyl peroxide. Spectral characterizations were achieved by 1H-NMR and FTIR spectroscopies. The kinetics of thermal degradation of the new polymer, poly(1,3-diphenyl-1H-pyrazol-5-yl methacrylate), poly(DFPMA), were investigated by thermogravimetric analysis (TGA) at different heating rates. The initial decomposition temperature of the polymer changed from 216.3 °C to 243.5 °C depending on the increasing heating rate. The thermal decomposition activation energies in a conversion range of 7-19% were 79.45 kJ/mol and 81.56 kJ/mol by the Flynn-Wall-Ozawa and Kissinger methods, respectively. Thermodegradation mechanism of the poly(DFPMA) were investigated in detail by using different kinetic methods available in the literature such as Coats-Redfern, Tang, Madhusudanan and Van Krevelen. Among all these methods, the best result was obtained for Coats-Redfern method (E =90.93 kJ/mol) at the optimum heating rate of 15 °C/min for D1 mechanism. That means the thermodegradation mechanism of poly(DFPMA) proceeds over a one-dimensional diffusion type deceleration mechanism.

Investigation and modelling of the pyrolysis kinetics of industrial biomass wastes.

Pyrolysis of the waste organic fraction is expected to be a central element to meet the primary energy demand in future: it increases the impact of renewable energy sources on the power generation sector and allows the amount of waste to be reduced, putting an end to landfills. In the present study, kinetic studies on the pyrolysis of biomass wastes are carried out. Two kinds of industrial organic waste are investigated: brewery spent grain (BSG) and medium-density fiberboard (MDF). The main target of this work is to provide a global equation for the one-step pyrolysis reaction of the investigated materials in an argon atmosphere using isoconversional methods. The conducted analysis allowed to estimate the activation energy as 225.4-253.6 kJ/mol for BSG and 197.9-216.7 kJ/mol for MDF. For both materials nth order reaction was proposed with reaction order of 7.69-8.70 for BSG and 6.32-6.55 for MDF. The developed equation allowed to simulate the theoretical curves of thermal conversion. These curves indicated the highest conversion at the temperature of the degradation of dominant component, which was experimentally verified. By this method, a one-step kinetic model is derived, which can be applied for the reaction kinetics in the CFD modelling of, e.g., pyrolysis and gasification processes.

Pyrolysis properties and kinetics of photocured waste from photopolymerization-based 3D printing: A TG-FTIR/GC-MS study.

The emerging photopolymerization-based 3D printing industry has led to a growing concern for the disposal of photocured waste (PCW), which is inevitably generated during the life cycle of photopolymerization-based 3D printing. In order to shed light on suitable thermochemical treatment and utilization approaches of PCW, this work comprehensively investigated the properties and kinetics during PCW pyrolysis via TG-FTIR/GC-MS analysis. The results demonstrated that the main decomposition of PCW sample happened in the range 320-550 °C with a total weight loss of 93.34 wt%. According to the result of four kinetic models, the activation energy of PCW sample was approximately 228.58-245.05 kJ/mol. Finally, the FTIR and GC-MS results manifested that the main components of volatiles released at different heating rates were the same. The volatiles mainly include (S)-(+)-2-hydroxy-2-phenylprop, benzaldehyde, benzophenone (photo-initiator), benzoic acid, benzoylformic acid etc., which have a multitude of potential applications. However, these volatiles produced by PCW pyrolysis have a certain toxicity and potential hazard. This study demonstrates insightful fundamentals for thermochemical disposal of PCW, which appears to be potentially valuable with the rapid development of the photopolymerization-based 3D printing industry.

Management of university solid waste in China through gasification technology: An analysis of waste composition and energy potential.

This study explored the composition and energy potential of university solid waste (USW) in China. Five combustible components, namely hard plastics (HP), paper (PP), soft plastics (SP), biomass (BM), and rubber (RB), were screened with the compositions 51%, 29%, 9%, 4%, and 3%, respectively. Each USW sample was gasified using a thermogravimetric analyzer (TGA) coupled with mass spectrometry (MS) at the heating rates of 5, 10, and 15 ℃/min and a final process temperature of 900 ℃. Thermal weight loss (TG) curves exposed the degradation in the order HP > SP > RB > BM > PP. Derivative thermogravimetric (DTG) peaks revealed that HP, PP, BM, and SP were degraded in three temperature-oriented phases in the range 172-731 ℃. The RB took an additional phase in the range 584-660 ℃. Major released gases, H2, CH4, CO, and CO2, were detected using MS via mass-to-charge (m/z) ratios. Higher H2 and total gas yield produced in the case of the HP dominated other materials at the lower heating rate of 5 ℃/min. Validation of data was assessed by equating experimental and calculated curves; therefore, the regression coefficient (R2) ranged between 0.884 and 0.997. The kinetics of the process were estimated by applying the Flynn-Wall-Ozawa (FWO) model at the conversion rates (α) of 0.2, 0.5, and 0.8, which presented reasonable results. Overall, the lower heating rates supported higher thermal conversion and a high quantity of gaseous products for all the components.