Pyrolysis of Euphorbia Rigida: A study on thermal characterizations, kinetics, thermodynamics via TG-FTIR analysis.

Euphorbia Rigida (E. Rigida), a lignocellulosic biomass with low ash content, is a suitable feedstock for pyrolysis. This work investigated the physicochemical characteristics and thermokinetic analysis of E. Rigida pyrolysis by using isoconversional and master plots methods. Ultimate and proximate analyses and oxygen bomb calorimeter were used to determine the physicochemical parameters. The activation energies were calculated using model-free methods (KAS, Friedman and Starink) and were found as 184, 178 and 185 kJ/mol, respectively. Using Fraser-Suzuki deconvolution, pseudo-components were also calculated and the active pyrolysis region was divided into three zones. The master plots showed that reaction order mechanisms (Fn) were effective in Zone I, and diffusion mechanisms (Dn) were well matched in Zone II and Zone III. The thermodynamic parameters (ΔH, ΔG and ΔS) were calculated and according to these results, E. Rigida pyrolysis was an endothermic and non-spontaneous process.

Experimental Studies on the Thermal Properties and Decomposition Course of a Novel Class of Heterocyclic Anticancer Drug Candidates.

The experimental studies on the thermal properties and decomposition course of a novel class of potential anticancer drugs (1-5) containing in their heterobicyclic structures the asymmetrical triazine template were performed with the use of differential scanning calorimetry (DSC) and simultaneous thermogravimetry/differential scanning calorimetry (TG/DTG/DSC) coupled online with Fourier transform infrared spectroscopy (FTIR) and quadrupole mass spectrometry (QMS) in inert and oxidizing conditions. All the compounds were thermally characterized in detail for the first time in this article. The DSC studies proved that the melting points of the tested compounds depended on the position and type of the substituent at the phenyl moiety, whereas they did not depend on the furnace atmosphere. All the tested polynitrogenated heterocycles proved to be molecules with high thermal stability in both atmospheres, and most of them (1, 3-5) were more stable in oxidizing conditions, which indicated the formation of a more thermally stable form of the compounds when interacting with oxygen. The simultaneous TG/FTIR/QMS analyses confirmed that their pyrolysis process occurred in one main stage resulting in the emission of volatiles such as NH3, HNCO, HCN, CO, CO2, H2O, NO2, aromatic amine derivatives, alkenes (for compounds 1-5), and HCl (for the compound 5). On the other hand, the oxidative decomposition process was more complicated and proceeded in two main stages leading to the emission of NH3, CO2, CO, HCN, HNCO, H2O, some aromatics (for compounds 1-5), HCl (for compounds 3-5) as well as the additional volatiles such as N2, NO2, NH2OH, and (CN)2. The type of the formed volatiles indicated that the decomposition process of the studied heterocycles under the influence of heating was initiated by the radical mechanism. Their decomposition was related to the symmetric cleavage of C-N and C-C bonds (inert conditions) and additional reaction of the volatiles and residues with oxygen (oxidizing conditions).

Pyrolytic kinetics, reaction mechanisms and gas emissions of waste automotive paint sludge via TG-FTIR and Py-GC/MS.

The present study experimentally quantified the pyrolysis behaviors of waste solvent-based automotive paint sludge (OAPS) and water-based automotive paint sludge (WAPS) at four different heating rates using thermogravimetric-Fourier transform infrared (TG-FTIR) spectrometry and pyrolysis-gas chromatography-mass (Py-GC/MS) spectrometry analyses. Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods combined with the master-plots method were employed to investigate the pyrolysis kinetics and reaction mechanisms of waste automotive paint sludge. Three reaction stages and three reaction peaks in stage 2 were distinguished for both OAPS and WAPS degradation. The average activation energy (Ea) estimates for OAPS (FWO: 179.09 kJ/mol; KAS: 168.28 kJ/mol) were slightly higher than WAPS (FWO: 175.90 kJ/mol; KAS: 164.80 kJ/mol) according to FWO and KAS methods. The main pyrolysis reaction mechanisms of both OAPS and WAPS closely matched with the order-based model corresponding to 3rd and 2nd order random nucleation on an individual particle. The evolved gas species of CH4, CO2, phenols, NH3, H2O, and CO from OAPS and WAPS pyrolysis were identified by TG-FTIR. According to Py-GC/MS, hydrocarbons (47.2%) and O-components (42.7%) were relatively large after OAPS and WAPS pyrolysis, respectively. Melamine was the most abundant N-component product after pyrolysis of OAPS (5.8%) and WAPS (4.8%).

Non-isothermal thermal decomposition behavior and reaction kinetics of acrylonitrile butadiene styrene (ABS).

Environmental concerns associated with the rapid rising plastic consumption have led to the search for better waste utilization and management. Pyrolysis has emerged as an ideal and promising technique for energy extraction from plastic waste. The aim of this work is to explore the waste plastic pyrolysis behavior under non-isothermal heating conditions. The decomposition characteristics, reaction mechanism, kinetics and thermodynamics of a typical widely used thermosetting plastic, acrylonitrile butadiene styrene (ABS), were studied via coupled thermogravimetry, Fourier transform infrared spectrometry and gas chromatography-mass spectrometry analysis (TG-FTIR-GC/MS). Kinetic analysis showed the average Eα values are estimated to be 187.02, 188.55, 187.04 and 185.67 kJ/mol via advanced Vyazovkin, Flynn-Wall-Ozawa (FWO), Tang and Starink model-free method, respectively. Model-fitting CR and master-plots method indicated that f(α)=(1-α)n is the most probable reaction mechanism. The equation of kinetic compensation effect was further developed as lnA = -3.1955 + 0.1736 Eα. Based on these initial inferences, a new reaction scheme coupled with Particle Swarm Optimization (PSO) was put forward for modeling ABS pyrolysis. The optimized values of E, A and n are 198.07 kJ/mol, 7.61 × 1012 s-1 and 1.56, respectively. The predicted results showed that the experimental data can be well characterized by the optimized parameters from PSO, validating the effectiveness and accuracy of the inverse modeling procedure. Moreover, it is found that the volatile products are mainly composed of aromatic compounds, ketones, amines, esters, nitrile compounds, alkenes and amines. Based on the FT-IR and GC-MS results, the possible chemical reactions for ABS pyrolysis from molecular structure were proposed. Finally, thermodynamic analysis was carried out, the calculated values of enthalpy ΔH, Gibb's free energy ΔG and entropy ΔS indicated that non-spontaneous reactions with low favorability exists during ABS decomposition, the process is complex therefore extra energy is needed to promote the reaction. The obtained results should offer as an important reference for future disposal and thermochemical management of such polymer waste.

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.

Thermal Investigations of Annelated Triazinones-Potential Analgesic and Anticancer Agents.

In this article, for the first time, TG-DSC and TG-FTIR investigations of potential pharmaceutics, i.e., analgesic and anticancer active annelated triazinones (1-9) have been presented. The thermal behaviour of these molecules was established in oxidative and inert conditions. The solid-liquid phase transition for each compound (1-9) was documented by one sharp DSC peak confirming the high purity of each sample studied. All the molecules were characterised in terms of calorimetric changes and mass changes during their heating. They revealed high thermal stability in oxidative and inert conditions. The observed tendency in thermal stability changes in relation to a substituent present at the phenyl moiety was found to be similar in air and nitrogen. It was confirmed that annelated triazinones 1-9 were stable up to a temperature range of 241-296 °C in air, and their decomposition process proceeded in two stages under oxidative conditions. In addition, it was established that their thermal stability in air decreased in the following order of R at the phenyl moiety: 4-Cl > 3,4-Cl2 > H > 3-Cl > 4-CH3 > 2-CH3 > 3-CH3 > 2-Cl > 2-OCH3. The volatile decomposition products of the investigated molecules were proposed by comparing the FTIR spectra collected during their thermogravimetric analysis in nitrogen with the spectra from the database of reference compounds. None of annelated triazinones 1-9 underwent any polymorphic transformation during thermal studies. All the compounds proved to be safe for erythrocytes. In turn, molecules 3, 6, and 9 protected red blood cells from oxidative damage, and therefore may be helpful in the prevention of free radical-mediated diseases.

Characteristics, kinetics, infrared analysis and process optimization of co-pyrolysis of waste tires and oily sludge.

The ecology was severely harmed by waste tires (WT) and oily sludge (OS). The OS and WT combinations' co-pyrolysis features, synergistic effects, and gas products were studied using thermogravimetric-infrared spectroscopy (TG-FTIR). To study kinetics and optimize pyrolysis, the Coats-Redfern and response surface methods were used. The results revealed that the OS and WT co-pyrolysis has synergistic effects. The major pyrolysis temperature range and the pyrolysis residual rate increased as the heating rate increased, and the E of the reaction increased. The strength of small-molecular-gases precipitation was modified by increasing the ratio of WT to OS, which increased OS pyrolysis. CH4, CO2, CO, and H2O are the most common gas products. The minimum estimated E and residual amount were 40.599 kJ/mol and 39.33%, respectively, when the WT mixture ratio was 58.7% and the heating rate was 10 °C/min. All the study contributes basic data to the development of the treatment of OS and WT in collaboration.

On-Line Thermally Induced Evolved Gas Analysis: An Update-Part 2: EGA-FTIR.

The on-line thermally induced evolved gas analysis (OLTI-EGA) is widely applied in many different fields. Aimed to update the applications, our group has systematically collected and published examples of EGA characterizations. Following the recently published review on EGA-MS applications, this second part reviews the latest applications of Evolved Gas Analysis performed by on-line coupling heating devices to infrared spectrometers (EGA-FTIR). The selected 2019, 2020, 2021 and early 2022 references are collected and briefly described in this review; these are useful to help researchers to easily find applications that are sometimes difficult to locate.

Comparative Thermal Research on Energetic Molecular Perovskite Structures.

Molecular perovskites are promising practicable energetic materials with easy access and outstanding performances. Herein, we reported the first comparative thermal research on energetic molecular perovskite structures of (C6H14N2)[NH4(ClO4)3], (C6H14N2)[Na(ClO4)3], and (C6H14ON2)[NH4(ClO4)3] through both calculation and experimental methods with different heating rates such as 2, 5, 10, and 20 °C/min. The peak temperature of thermal decompositions of (C6H14ON2)[NH4(ClO4)3] and (C6H14N2) [Na(ClO4)3] were 384 and 354 °C at the heating rate of 10 °C/min, which are lower than that of (C6H14N2)[NH4(ClO4)3] (401 °C). The choice of organic component with larger molecular volume, as well as the replacement of ammonium cation by alkali cation weakened the cubic cage skeletons; meanwhile, corresponding kinetic parameters were calculated with thermokinetics software. The synergistic catalysis thermal decomposition mechanisms of the molecular perovskites were also investigated based on condensed-phase thermolysis/Fourier-transform infrared spectroscopy method and DSC-TG-FTIR-MS quadruple technology at different temperatures.

Study on Thermal Decomposition Behaviors of Terpolymers of Carbon Dioxide, Propylene Oxide, and Cyclohexene Oxide.

The terpolymerization of carbon dioxide (CO2), propylene oxide (PO), and cyclohexene oxide (CHO) were performed by both random polymerization and block polymerization to synthesize the random poly (propylene cyclohexene carbonate) (PPCHC), di-block polymers of poly (propylene carbonate⁻cyclohexyl carbonate) (PPC-PCHC), and tri-block polymers of poly (cyclohexyl carbonate⁻propylene carbonate⁻cyclohexyl carbonate) (PCHC-PPC-PCHC). The kinetics of the thermal degradation of the terpolymers was investigated by the multiple heating rate method (Kissinger-Akahira-Sunose (KAS) method), the single heating rate method (Coats-Redfern method), and the Isoconversional kinetic analysis method proposed by Vyazovkin with the data from thermogravimetric analysis under dynamic conditions. The values of ln k vs. T-1 for the thermal decomposition of four polymers demonstrate the thermal stability of PPC and PPC-PCHC are poorer than PPCHC and PCHC-PPC-PCHC. In addition, for PPCHC and PCHC-PPC-PCHC, there is an intersection between the two rate constant lines, which means that, for thermal stability of PPCHC, it is more stable than PCHC-PPC-PCHC at the temperature less than 309 °C and less stable when the decomposed temperature is more than 309 °C. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetric analysis/infrared spectrometry (TG/FTIR) techniques were applied to investigate the thermal degradation behavior of the polymers. The results showed that unzipping was the main degradation mechanism of all polymers so the final pyrolysates were cyclic propylene carbonate and cyclic cyclohexene carbonate. For the block copolymers, the main chain scission reaction first occurs at PC-PC linkages initiating an unzipping reaction of PPC chain and then, at CHC⁻CHC linkages, initiating an unzipping reaction of the PCHC chain. That is why the T-5% of di-block and tri-block polymers were not much higher than that of PPC while two maximum decomposition temperatures were observed for both the block copolymer and the second one were much higher than that of PPC. For PPCHC, the random arranged bulky cyclohexane groups in the polymer chain can effectively suppress the backbiting process and retard the unzipping reaction. Thus, it exhibited much higher T-5% than that of PPC and block copolymers.

Thermal Decomposition Behavior of Hydroxytyrosol (HT) in Nitrogen Atmosphere Based on TG-FTIR Methods.

The thermal decomposition behavior of olive hydroxytyrosol (HT) was first studied using thermogravimetry (TG). Cracked chemical bond and evolved gas analysis during the thermal decomposition process of HT were also investigated using thermogravimetry coupled with infrared spectroscopy (TG-FTIR). Thermogravimetry-Differential thermogravimetry (TG-DTG) curves revealed that the thermal decomposition of HT began at 262.8 °C and ended at 409.7 °C with a main mass loss. It was demonstrated that a high heating rate (over 20 K·min-1) restrained the thermal decomposition of HT, resulting in an obvious thermal hysteresis. Furthermore, a thermal decomposition kinetics investigation of HT indicated that the non-isothermal decomposition mechanism was one-dimensional diffusion (D1), integral form g(x) = x², and differential form f(x) = 1/(2x). The four combined approaches were employed to calculate the activation energy (E = 128.50 kJ·mol-1) and Arrhenius preexponential factor (ln A = 24.39 min-1). In addition, a tentative mechanism of HT thermal decomposition was further developed. The results provide a theoretical reference for the potential thermal stability of HT.

Analytical Pyrolysis of Soluble Bio-Tar from Steam Pretreatment of Bamboo by Using TG-FTIR and Py-GC/MS.

Steam pretreatment at high temperatures enables fresh bamboo to possess antifungal and antiseptic properties. The process produces a large amount of wastewater that urgently needs to be recycled. Soluble bio-tars derived from wastewater under low-temperature (LTS-tar) and high-temperature (HTS-tar) steam pretreatments of moso bamboo were studied with a thermogravimetric analyzer coupled with Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis-gas-chromatography/mass spectrometry (Py-GC/MS). Thermogravimetric analysis showed that in the three stages of the thermal decomposition process, the final residue of the bamboo and HTS-tar had two main peaks of 0.88 wt% and 6.85 wt%. The LTS-tar had much more complicated thermal decomposition behavior, with six steps and a high residue yield of 23.86 wt%. A large quantity of CH4 was observed at the maximum mass loss rates of the bamboo and bio-tars. Acids, aldehydes, ketones, esters, and phenolic compounds were found in the pyrolysis products of the bamboo and soluble bio-tars. Both bio-tars contained carbohydrates and lignin fragments, but the LTS-tar under mild steam conditions had more saccharides and was much more sensitive to temperature. The lignin in the bamboo degraded under harsh steam conditions, resulting in high aromatic and polymeric features for the HTS-tar. The significant differences between LTS-tar and HTS-tar require different techniques to achieve the resource utilization of wastewater in the bamboo industry.

Pyrolysis Process of Mixed Microplastics Using TG-FTIR and TED-GC-MS.

Microplastics have become a ubiquitous contaminant in the environment. The present study focuses on the identification, characterization, and quantification techniques for tracking microplastics. Due to their unique compositional structure, unambiguous identification of individual polymers in various plastic samples, usually comprised of mixtures of individual polymers, remains a challenge. Therefore, there is limited research on the pyrolysis characterization of mixed samples. In this study, two analytical methods, TG-FTIR and TED-GC-MS combined with thermogravimetric analysis were used to evaluate the thermal-degradation process of individual and mixed samples of polypropylene (PP), polyethylene terephthalate (PET), and polyvinyl chloride (PVC). The primary interaction was the volatilization of terephthalic acid bound to chlorine molecules. The reduction of vinyl-ester functional groups and aromatic hydrocarbon intermediates related to olefin branching was confirmed. Char formation was increased, due to aromatic compounds from PET and PVC. All of the polymers used in the study may be underestimated in quantity, due to combined volatilizations during pyrolysis. TG-FTIR and TED-GC-MS showed forceful advantages in identifying mixed microplastics through different discrimination mechanisms. The study provides deep insight into pyrolysis behaviors and the interactions of mixed polymers, and the obtained results can help better comprehend the complex pyrolysis process.

Eco-Friendly Coal Gangue and/or Metakaolin-Based Lightweight Geopolymer with the Addition of Waste Glass.

Massive amounts of deposited coal gangue derived from the mining industry constitute a crucial problem that must be solved. On the other hand, common knowledge about the recycling of glass products and the reuse of waste glass is still insufficient, which in turn causes economic and environmental problems. Therefore, this work investigated lightweight geopolymer foams manufactured based on coal gangue, metakaolin, and a mix of them to evaluate the influence of such waste on the geopolymer matrix. In addition, the effect of 20% (wt.) of waste glass on the foams was determined. Mineralogical and chemical composition, thermal behaviour, thermal conductivity, compressive strength, morphology, and density of foams were investigated. Furthermore, the structure of the geopolymers was examined in detail, including pore and structure thickness, homogeneity, degree of anisotropy, porosity with division for closed and open pores, as well as distribution of additives and pores using micro-computed tomography (microCT). The results show that the incorporation of waste glass increased compressive strength by approximately 54% and 9% in the case of coal-gangue-based and metakaolin-based samples, respectively. The porosity of samples ranged from 67.3% to 58.7%, in which closed pores constituted 0.3-1.8%. Samples had homogeneous distributions of pores and additions. Furthermore, the thermal conductivity ranged from 0.080 W/(m·K) to 0.117 W/(m·K), whereas the degree of anisotropy was 0.126-0.187, indicating that the structure of foams was approximate to isotropic.

The Influence of Diisocyanate Structure on Thermal Stability of Thermoplastic Polyurethane Elastomers Based on Diphenylmethane-Derivative Chain Extender with Sulfur Atoms.

The work is a continuation of the research on thermoplastic polyurethane (TPU) elastomers containing sulfur atoms which are incorporated into the polyurethane chain using aliphatic-aromatic chain extenders. These materials show some improved properties in relation to conventional ones, e.g., adhesion to metals, bacterial resistance and refractive index. The present study deals with the detailed characteristics of the process of thermal decomposition of TPU elastomers obtained from 2,2'-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 1,1'-methanediylbis(4-isocyanatobenzene) (MDI) or 1,6-diisocyanatohexane (HDI) and poly(oxytetramethylene) diol of Mn = 2000 g/mol by thermogravimetric analysis coupled on-line with Fourier transform infrared spectroscopy. The analysis was performed under inert and oxidative conditions. All TPU elastomers were found to have a relatively good thermal stability, with those based on aromatic diisocyanate being at an advantage. In helium, they are stable up to 280-282 °C (from HDI) and 299-301 °C (from MDI), whereas in synthetic air up to 252-265 °C (from HDI) and 261-272 °C (from MDI), as measured by the temperature of 1% mass loss. Depending on the content of the hard segments and the tested atmosphere, the TPU elastomers decompose from one to four stages. From the analysis of the volatile decomposition products, it follows that the decomposition of both types of hard segments was accompanied by the evolution of carbonyl sulfide, carbon dioxide, water, sulfide dioxide, alcohols and aromatic compounds. For the hard segment derived from HDI, isocyanates, amines, and unsaturated compounds were also identified, while for the MDI-derived one, aldehydes were discovered. In turn, the polyether soft segment decomposed mainly into aliphatic ethers, aldehydes, and carbon monoxide.

Reutilization of Reclaimed Asphalt Binder via Co-Pyrolysis with Rice Husk: Thermal Degradation Behaviors and Kinetic Analysis.

Realizing the utilization of reclaimed asphalt binder (RAB) and rice husk (RH) to reduce environmental pollution and expand the reutilization technique of reclaimed asphalt pavement (RAP), co-pyrolysis of RAB with RH has great potential. In this study, the co-pyrolysis behaviors, gaseous products, and kinetics were evaluated using thermogravimetric analysis and Fourier transform infrared spectroscopy (TG-FTIR). The results showed that incorporating RH into RAB improved its pyrolysis characteristics. The interactions between RAB and RH showed initial inhibition followed by subsequent promotion. The primary gaseous products formed during co-pyrolysis were aliphatic hydrocarbons, water, and carbon dioxide, along with smaller amounts of aldehydes and alcohols originating from RH pyrolysis. All average activation energy values for the blends, determined through iso-conversional methods, decreased with RH addition. The combined kinetic analysis revealed two distinct mechanisms: (1) at the lower conversion range, the pyrolysis of the blend followed a random nucleation and three-dimensional growth mechanism, while (2) at the higher conversion range, the control mechanism transitioned into three-dimensional diffusion.

Acid gas emission and ash fusion characteristics of multi-component leather solid waste incineration in bubbling fluidized bed.

The tanning sludge (TS) and other tanning solid wastes are produced in significant quantities by the leather industry. To evaluate the combustion properties, acid gaseous pollutant conversion, and ash management, co-firing of TS with various wastes was investigated in a bubbling fluidized bed. TG-FTIR test indicated that tanning solid wastes had superior combustion properties and include more gaseous pollutants than TS. The leather mixed solid waste (LMSW) formed by mixing had better fuel characteristics than TS. The conversion rates of SO2 and HCl of LMSW incineration were 67% and 40%, respectively. The co-combustion of TS and solid wastes reduces the conversion rate of acid gas. Increasing the proportion of high-inorganic chlorine raw material could further reduce the conversion rate and increase the ash fusion temperature appropriately. Because ash and slag were primarily composed of Ca and Fe elements, the addition of calcium carbonate (CaCO3) can increase ash melting point while reducing acid gas emissions. When CaCO3 was added at a calcium to sulfur (Ca/S) ratio of 2, the acid gas emission was reduced by more than 80% and the softening temperature was raised by 90 °C. When Ca/S is greater than 2, the economics of adding CaCO3 decreased.

Coupled and Simultaneous Thermal Analysis Techniques in the Study of Pharmaceuticals.

Reliable interpretation of the changes occurring in the samples during their heating is ensured by using more than one measurement technique. This is related to the necessity of eliminating the uncertainty resulting from the interpretation of data obtained by two or more single techniques based on the study of several samples analyzed at different times. Accordingly, the purpose of this paper is to briefly characterize thermal analysis techniques coupled to non-thermal techniques, most often spectroscopic or chromatographic. The design of coupled thermogravimetry (TG) with Fourier transform infrared spectroscopy (FTIR), TG with mass spectrometry (MS) and TG with gas chromatography/mass spectrometry (GC/MS) systems and the principles of measurement are discussed. Using medicinal substances as examples, the key importance of coupled techniques in pharmaceutical technology is pointed out. They make it possible not only to know precisely the behavior of medicinal substances during heating and to identify volatile degradation products, but also to determine the mechanism of thermal decomposition. The data obtained make it possible to predict the behavior of medicinal substances during the manufacture of pharmaceutical preparations and determine their shelf life and storage conditions. Additionally, characterized are design solutions that support the interpretation of differential scanning calorimetry (DSC) curves based on observation of the samples during heating or based on simultaneous registration of FTIR spectra and X-ray diffractograms (XRD). This is important because DSC is an inherently non-specific technique. For this reason, individual phase transitions cannot be distinguished from each other based on DSC curves, and supporting techniques are required to interpret them correctly.

Online TG-FTIR-MS analysis of the catalytic pyrolysis of polyethylene and polyvinyl chloride microplastics.

Microplastics (MPs) are frequently detected in urban waters, which would pose a threat to human health through the food chain. Thus, efficient approaches to the elimination of MPs are urgently required. Pyrolysis is a powerful technique for the potential treatment of MPs. The online thermogravimetry-Fourier transform infrared reflection-Mass spectrometry (TG-FTIR-MS) is applied for tracking the pyrolysis process of representative polyethylene (PE) and polyvinyl chloride (PVC) MPs in urban waters, together with or without the FeAlOx catalyst. TG could quantitatively determine the decomposition behavior and kinetics of MPs while FTIR and MS spectra would be capable of characterizing the pyrolysis products. The results revealed that FeAlOx is an excellent carbon support, and the deposited carbon can be gasified to CO at higher pyrolysis temperatures. Moreover, more aromatic compounds were generated from the pyrolysis of PE MPs with the catalyzation of FeAlOx. Large quantities of benzene were also produced in the PVC MPs pyrolysis with or without FeAlOx. Also, FeAlOx largely decreased the concentrations of chlorine-containing compounds in the liquid products of PVC MPs pyrolysis. This study provides a efficient technique for the online observation of the MPs' catalytic pyrolysis process, which would guide future upcycling of MPs into value-added products.

Pyrolysis Kinetic Behavior and Thermodynamic Analysis of PET Nonwoven Fabric.

This research aims to maximize polyethylene terephthalate (PET) nonwoven fabric waste and make it as a new source for benzoic acid extraction using a pyrolysis process. The treatment was performed using a thermogravimetric analyzer (TGA) and released products were characterized using FTIR spectroscopy and gas chromatography-mass spectrometry (GC-MS). The pyrolysis kinetic and thermodynamic behavior of PET fabric was also studied and simulated using different linear and nonlinear models. The results show that the PET fabric is very rich in volatile matter (80 wt.%) and can completely degrade under 490 °C with a weight loss of 84%. Meanwhile, the generated vapor was rich in the carbonylic C=O functional group (FTIR), and the GC-MS analysis concluded that benzoic acid was the major compound with an abundance of 75% that was achieved at the lowest heating rate (5 °C/min). The linear kinetic results showed that PET samples had an activation energy in the ranges of 193-256 kJ/mol (linear models) and ~161 kJ/mol (nonlinear models). The thermodynamic parameters, including enthalpy, Gibbs free energy, and entropy, were estimated in the ranges of 149-250 kJ/mol, 153-232 kJ/mol, and 256-356 J/mol K, respectively. Accordingly, pyrolysis treatment can be used to extract benzoic acid from PET fabric waste with a 134% increase in the benzoic acid abundance that can be recovered from PET bottle plastic waste.