Geothermal Nano-SiO2 Waste as a Supplementary Cementitious Material for Concrete Exposed at High Critical Temperatures.

The partial replacement effect of Portland cement by geothermal nano-SiO2 waste (GNSW) for sustainable Portland-cement-based concrete was investigated to improve the properties of concrete exposed at high critical temperatures. Portland cement was partially replaced by 20 and 30 wt.% of GNSW. The partial replacement effect on Portland-cement-based concrete subjected to 350, 550, and 750 °C was evaluated by measuring the weight changes, ultrasonic pulse velocity, thermogravimetric and differential thermal analysis, X-ray diffraction, surface inspection, and scanning electron microscopy under residual conditions. The ultrasonic pulse velocity results showed that the GNSW specimens maintained suitable stability after being heated to 350 °C. The SEM analysis revealed a denser microstructure for the 20 wt.% of partial replacement of Portland cement by GNSW specimen compared to the reference concrete when exposed to temperatures up to 400 °C, maintaining stability in its microstructure. The weight losses were higher for the specimens with partial replacements of GNSW than the reference concrete at 550 °C, which can be attributed to the pozzolanic activity presented by the GNSW, which increases the amounts of CSH gel, leading to a much denser cementitious matrix, causing a higher weight loss compared to the reference concrete. GNSW is a viable supplementary cementitious material, enhancing thermal properties up to 400 °C due to its high pozzolanic activity and filler effect while offering environmental benefits by reducing industrial waste.

The effect of ZnSO4 and Fe2(SO4)3 on the pyrolysis of cocoa shells: A tg-FTIR study.

Pyrolysis stands out as one potential route for valorizing abundant agro-industrial cocoa residues. However, the products of this reaction, particularly bio-oil, do not possess the required quality for direct use in many applications. Thus, this study explores the use of iron sulfate and zinc sulfate as potential catalysts in the pyrolysis of these residues. In this investigation, the biomass, previously ground and dried, was impregnated with varying percentages of ferric sulfate and zinc sulfate. The TG-FTIR technique was employed to ascertain the effect of these salts on the pyrolysis of cocoa shell. The results were fitted with the DAEM model with three pseudo-components. It was determined that both salts induced alterations in the DTG profiles of the thermal decomposition of cocoa shell. In the evolved gases, compounds such as CO2, H2O, CH4, CO, HCN, and oxygenated compounds like HCOOH and CH3COOH were detected. Ferric sulfate significantly influenced the activation energies governing the reactions of the three pseudo-components. Conversely, the presence of zinc sulfate did not alter the activation energies associated with the decomposition of cocoa shell pseudo-components. Both catalysts induced alterations in the infrared spectra of the evolved gases, which is primarily evident in the relative intensities of bands corresponding to the stretching vibrations of constituent groups within CO2, CO, water, and oxygenated compounds.

Thermochemical behavior of agricultural and industrial sugarcane residues for bioenergy applications.

The Colombian sugarcane industry yields significant residues, categorized as agricultural and industrial. While bagasse, a widely studied industrial residue, is employed for energy recovery through combustion, agricultural residues are often left in fields. This study assesses the combustion behavior of these residues in typical collection scenarios. Additionally, it encompasses the characterization of residues from genetically modified sugarcane varieties in Colombia, potentially exhibiting distinct properties not previously documented. Non-isothermal thermogravimetrical analysis was employed to study the thermal behavior of sugarcane industrial residues (bagasse and pith) alongside agricultural residues from two different sugarcane varieties. This facilitated the determination of combustion reactivity through characteristic combustion process temperatures and technical parameters like ignition and combustion indexes. Proximate, elemental, and biochemical analyses revealed slight compositional differences. Agricultural residues demonstrated higher ash content (up to 34%) due to foreign matter adhering during harvesting, as well as soil and mud attachment during collection. Lignin content also varied, being lower for bagasse and pith, attributed to the juice extraction and milling processes that remove soluble lignin. Thermogravimetric analysis unveiled a two-stage burning process in all samples: devolatilization and char formation (~170°C), followed by char combustion (~310°C). Characteristic temperatures displayed subtle differences, with agricultural residues exhibiting lower temperatures and decomposition rates, resulting in reduced ignition and combustion indexes. This indicates heightened combustion reactivity in industrial residues, attributed to their elevated oxygen percentage, leading to more reactive functional groups and greater combustion stability compared to agricultural residues. This information is pertinent for optimizing sugarcane residues utilization in energy applications.

Weather in collection time affects composition of sugarcane agricultural residues.Combustion of sugarcane residues occurs over similar temperature ranges.Industrial residues are more reactive to combustion than agricultural residues.Overall thermal behavior of sugarcane residues depends on their composition.

Thermal Behavior of Curaua-Aramid Hybrid Laminated Composites for Ballistic Helmet.

Hybrid composites are expanding applications in cutting-edge technology industries, which need materials capable of meeting combined properties in order to guarantee high performance and cost-effectiveness. This original article aimed for the first time to investigate the hybrid laminated composite thermal behavior, made of two types of fibers: synthetic Twaron® fabric and natural curaua non-woven mat, reinforcing epoxy matrix. The composite processing was based on the ballistic helmets methodology from the North American Personal Armor System for Ground Troops, currently used by the Brazilian Army, aiming at reduced costs, total weight, and environmental impact associated with the material without compromising ballistic performance. Thermal properties of plain epoxy, aramid fabric, and curaua mat were evaluated, as well as the other five configurations of hybrid laminated composites. These properties were compared using thermogravimetric analysis (TGA) with its derivative (DTG), differential thermal analysis (DTA), and thermomechanical analysis (TMA). The results showed that the plain epoxy begins thermal degradation at 208 °C while the curaua mat at 231 °C and the aramid fabric at 477 °C. The hybrid laminated composites curves showed two or three inflections in terms of mass loss. The only sample that underwent thermal expansion was the five-aramid and three-curaua layers composite. In the third analyzed temperature interval, related to the glass transition temperature of the composites, there was, in general, an increasing thermal stability behavior.

Pyrolysis of Chilean Southern Lignocellulosic Biomasses: Isoconversional Kinetics Analysis and Pyrolytic Products Distribution.

Biomass provides potential benefits for obtaining value-added compounds instead of straight burning; as Chile has forestry potential that supports such benefits, it is crucial to understand the biomasses' properties and their thermochemical behaviour. This research presents a kinetic analysis of thermogravimetry, and pyrolysis of representative species in the biomass of southern Chile, heating biomasses at 5 to 40 °C·min-1 rates before being subjected to thermal volatilisation. The activation energy (Ea) was calculated from conversion using model-free methods (Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Friedman (FR)), as well as the Kissinger method based on the maximum reaction rate. The average Ea varied between KAS 117 and 171 kJ·mol-1, FWO 120-170 kJ·mol-1, and FR 115-194 kJ·mol-1 for the five biomasses used. Pinus radiata (PR) was identified as the most suited wood for producing value-added goods based on the Ea profile for the conversion (α), along with Eucalyptus nitens (EN) for its high value of reaction constant (k). Each biomass demonstrated accelerated decomposition (an increase in k relative to α). The highest concentration of bio-oil containing phenolic, ketonic, and furanic compounds was produced by the forestry exploitation biomasses PR and EN, demonstrating the viability of these materials for thermoconversion processes.

Synergistic Effects and Mechanistic Insights into the Co-Hydropyrolysis of Chilean Oak and Polyethylene: Unlocking the Potential of Biomass-Plastic Valorisation.

This study employed a hydrogen atmosphere in an analytical reactor to investigate the thermochemical transformation of Chilean Oak (ChO) and polyethylene. Thermogravimetric assays and compositional analyses of the evolved gaseous chemicals provided valuable insights regarding the synergistic effects during the co-hydropyrolysis of biomass and plastics. A systematic experimental design approach assessed the contributions of different variables, revealing the significant influence of the biomass/plastic ratio and hydrogen pressure. Analysis of the gas phase composition showed that co-hydropyrolysis with LDPE resulted in lower levels of alcohols, ketones, phenols, and oxygenated compounds. ChO exhibited an average oxygenated compound content of 70.13%, while LDPE and HDPE had 5.9% and 1.4%, respectively. Experimental assays under specific conditions reduced ketones and phenols to 2-3%. Including a hydrogen atmosphere during co-hydropyrolysis contributes to enhanced reaction kinetics and reduced formation of oxygenated compounds, indicating its beneficial role in improving reactions and diminishing the production of undesired by-products. Synergistic effects were observed, with reductions of up to 350% for HDPE and 200% for LDPE compared to the expected values, achieving higher synergistic coefficients with HDPE. The proposed reaction mechanism provides a comprehensive understanding of the simultaneous decomposition of biomass and polyethylene polymer chains, forming valuable bio-oil products and demonstrating the how the hydrogen atmosphere modulates and influences the reaction pathways and product distribution. For this reason, the co-hydropyrolysis of biomass-plastic blends is a technique with great potential to achieve lower levels of oxygenated compounds, which should be further explored in subsequent studies to address scalability and efficiency at pilot and industrial levels.

Physicochemical, Mechanical, and Esthetic Properties of the Composite Resin Manipulated with Glove Powder and Adhesive as a Modeling Liquid.

Composite resins with low flowability are usually handled and manipulated before insertion into the tooth preparation with gloved hands and/or using an instrument covered with a little amount of adhesive to facilitate modeling. We investigated if the modeling techniques (combined or not) affected physicochemical and esthetic properties of a composite resin. Specimens were fabricated and divided into groups according to the handling/modeling technique: Gloved-hands (composite was hand-manipulated with powdered latex gloves); Adhesive (adhesive was used in between the composite layers); Gloved-hands + Adhesive; Control (no adhesive and no touch with gloved-hands). The highest values for flexural strength (MPa), modulus of elasticity (GPa), and fracture toughness (MPa.m0.5) were obtained for Adhesive and Gloved-hands + Adhesive (p < 0.05); the lowest values were obtained for Control and Gloved-hands (p < 0.05). The Control group had the highest sorption. The Gloved-hands (p < 0.05) group had the highest solubility. Adhesive and Gloved-hands + Adhesive had a similar solubility (p > 0.05). The Control group (p < 0.05) had the lowest solubility. There was no statistical interaction between translucency vs. handling/modeling techniques and color stability vs. handling/modeling techniques. Adhesive as a modeling liquid protected the composite against sorption and solubility (if powdered gloves were used) and improved its physical/mechanical properties. Translucency and color stability were not correlated with modeling techniques.

Study of the Mandibular Bone Microstructure and Blood Minerals Bioavailability in Rainbow Trout (Oncorhynchus mykiss, Walbaum 1792) from Freshwater.

Farmed salmonids show alterations in bone structure that result in skeletal deformities during formation, repair, and regeneration processes, with loss of mineralization at the level of the axial skeleton, mainly the head and spine, affecting their quality of life and even causing death. Despite improving factors, such as farming conditions, diets, and genetics, bone alterations appear more frequently in farmed fish than in wild fish. Thus, we used SEM-EDX, and TGA-DSC to study bone mineralization in farmed and wild rainbow trouts. As expected, we found significant differences in the nutritional parameters of farmed and wild fish (p < 0.05). Microstructural analyses indicated that farmed fish have a more robust mineral structure (p < 0.05), confirming the differences in mineralization and microstructure between both groups. However, the mechanisms regulating absorption and distribution in the organism and their effect on bone mineralization remain to be known. In our study, the combined use of techniques such as SEM-EDX and TGA-DSC allows a clearer assessment and detailed characterization beneficial to understanding the relationship between diet control and bone microstructure.

Assessing compatibility of excipients selected for a sustained release formulation of bilberry leaf extract

Abstract The study is aimed to assess the compatibility of bilberry leaf powder extract (BLPE) with six excipients selected for sustained-release (SR) tablet formulation. The BLPE was obtained with the addition of L-arginine and Myo-inositol as the carriers. Thermogravimetric (TG-DTG) analysis and Fourier-transform infrared spectroscopy (FTIR), supported by Pearson correlation analysis, were applied to detect possible interactions in the binary mixtures (1:1) of the BLPE with each excipient. The TG-DTG showed some deviations in the thermal behavior of the BLPE / excipient mixtures. However, only the thermal behavior of magnesium stearate in the mixture significantly differed from individual samples, which suggested chemical interaction for this excipient. The FTIR analysis confirmed that the BLPE is compatible with Eudragit L100, Methocel K4M, Methocel K100LV, Avicel PH-101, and Plasdone S-630. Whereas it undergoes solid-state chemical interaction in the binary mixture with magnesium stearate. According to the FTIR-spectra, it is suggested that this interaction results in the formation of stearic acid and alkalization of the medium. These findings evidence for the possibility of using TG-DTG analysis as an independent thermal technique for compatibility studies and also confirm the earlier reported interaction of basic lubricants, e.g., stearic salts, with active ingredients containing amino groups.

A Review on the Thermal Characterisation of Natural and Hybrid Fiber Composites.

The thermal stability of natural fiber composites is a relevant aspect to be considered since the processing temperature plays a critical role in the manufacturing process of composites. At higher temperatures, the natural fiber components (cellulose, hemicellulose, and lignin) start to degrade and their major properties (mechanical and thermal) change. Different methods are used in the literature to determine the thermal properties of natural fiber composites as well as to help to understand and determine their suitability for a certain applications (e.g., Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and differential mechanical thermal analysis (DMA)). Weight loss percentage, the degradation temperature, glass transition temperature (Tg), and viscoelastic properties (storage modulus, loss modulus, and the damping factor) are the most common thermal properties determined by these methods. This paper provides an overview of the recent advances made regarding the thermal properties of natural and hybrid fiber composites in thermoset and thermoplastic polymeric matrices. First, the main factors that affect the thermal properties of natural and hybrid fiber composites (fiber and matrix type, the presence of fillers, fiber content and orientation, the treatment of the fibers, and manufacturing process) are briefly presented. Further, the methods used to determine the thermal properties of natural and hybrid composites are discussed. It is concluded that thermal analysis can provide useful information for the development of new materials and the optimization of the selection process of these materials for new applications. It is crucial to ensure that the natural fibers used in the composites can withstand the heat required during the fabrication process and retain their characteristics in service.

Effect of Wholewheat Flour Particle Shape Obtained by Different Milling Processes on Physicochemical Characteristics and Quality of Bread.

RESEARCH BACKGROUND: Wholewheat flour is a very good source of nutritional compounds and functional ingredients for human diet. However, it causes negative effect on bread quality. Different milling techniques can be used to obtain wholewheat flour, minimizing the negative effect of both bran and germ on bread quality. The aim of this work is to study the effect of particle size and shape of wholegrain flour on the interaction among the different components, water distribution, dough rheology and bread volume. EXPERIMENTAL APPROACH: Wholewheat flour of three varieties (Klein Rayo, Fuste and INTA 815) was obtained in cyclonic, hammer and roller mills. The characteristics of wholewheat flour were explored, and the water distribution and rheological properties of dough were determined by thermogravimetric analysis and Mixolab test, respectively. Finally, microscale bread was prepared. RESULTS AND CONCLUSIONS: The amount of water-soluble pentosans, damaged starch and wet gluten was affected by the milling procedure. Regarding dough rheological properties, wholewheat flour obtained in hammer mill had the lowest water absorption capacity and the highest developing time. This result could be mainly attributed to particle shape in these samples with large amount of endosperm attached to the bran, hindering protein unfolding. Thermogravimetric analysis showed that both fine and large bran particle size seem to have the same effect on water properties in wholewheat dough during heating. Bread made with Klein Rayo variety had the highest specific volume, indicating that wheat with high protein content and breadmaking quality is needed to make wholewheat bread. The results of this work showed that particle shape, rather than particle size, affected the quality of wholewheat flour for breadmaking. NOVELTY AND SCIENTIFIC CONTRIBUTION: The effect of milling type and particle shape of the wholewheat flour had a greater effect than the wheat variety. Thus, the wholegrain milling process should be carefully selected taking to account the shape of the produced particle. This may open new opportunities for developing wholewheat bread with better acceptance by consumers.

Sustained Release of Linezolid from Prepared Hydrogels with Polyvinyl Alcohol and Aliphatic Dicarboxylic Acids of Variable Chain Lengths.

A series of hydrogels with a specific release profile of linezolid was successfully synthesized. The hydrogels were synthesized by cross-linking polyvinyl alcohol (PVA) and aliphatic dicarboxylic acids, which include succinic acid (SA), glutaric acid (GA), and adipic acid (AA). The three crosslinked hydrogels were prepared by esterification and characterized by equilibrium swelling ratio, infrared spectroscopy, thermogravimetric analysis, mechanical properties, and scanning electron microscopy. The release kinetics studies of the linezolid from prepared hydrogels were investigated by cumulative drug release and quantified by chromatographic techniques. Mathematical models were carried out to understand the behavior of the linezolid release. These data revealed that the sustained release of linezolid depends on the aliphatic dicarboxylic acid chain length, their polarity, as well as the hydrogel crosslinking degree and mechanical properties. The in vitro antibacterial assay of hydrogel formulations was assessed in an Enterococcus faecium bacterial strain, showing a significant activity over time. The antibacterial results were consistent with cumulative release assays. Thus, these results demonstrated that the aliphatic dicarboxylic acids used as crosslinkers in the PVA hydrogels were a determining factor in the antibiotic release profile.

Kinetic and Thermodynamic Studies on Synthesis of Mg-Doped LiMn2O4 Nanoparticles.

In this work, a first study on kinetics and thermodynamics of thermal decomposition for synthesis of doped LiMn2O4 nanoparticles is presented. The effect of Mg doping concentration on thermal decomposition of synthesis precursors, prepared by ultrasound-assisted Pechini-type sol-gel process, and its significance on nucleation and growth of Mg-doped LiMn2O4 nanoparticles was studied through a method based on separation of multistage processes in single-stage reactions by deconvolution and transition state theory. Four zones of thermal decomposition were identified: Dehydration, polymeric matrix decomposition, carbonate decomposition and spinel formation, and spinel decomposition. Kinetic and thermodynamic analysis focused on the second zone. First-order Avrami-Erofeev equation was selected as reaction model representing the polymer matrix thermal decomposition. Kinetic and thermodynamic parameters revealed that Mg doping causes an increase in thermal inertia on conversion rate, and CO2 desorption was the limiting step for formation of thermodynamically stable spinel phases. Based on thermogravimetry experiments and the effect of Mg on thermal decomposition, an optimal two-stage heat treatment was determined for preparation of LiMgxMn2-xO4 (x = 0.00, 0.02, 0.05, 0.10) nanocrystalline powders as promising cathode materials for lithium-ion batteries. Crystalline structure, morphology, and stoichiometry of synthesized powders were characterized by XRD, FE-SEM, and AAS, respectively.

Data of preparation and evaluation of supramolecular hydrogel based on cellulose for sustained release of therapeutic substances with antimicrobial and wound healing properties.

The data article refers to the paper "supramolecular hydrogel based on cellulose for sustained release of therapeutic substances with antimicrobial and wound healing properties"[1]. The dataset includes the synthesis and characterization of (E)-1,3-bis(4-(allyloxy)phenyl)prop­2-en-1-one (3) (crosslinking agent). Moreover, the multiwall carbon nanotubes (MWCNTs) synthesis and functionalization (MWCNTs-COOH) are described. The formulation obtained by adding multiwalled carbon nanotubes-COOH with the crosslinked cellulose-chalcone hydrogel is abbreviated as MWCNTsCCH, and the same formulation loaded with therapeutic substances (TS) is named MWCNTsCCH-TS. The MWCNTsCCH database such as components and their amounts, swelling degree, thermogravimetric analysis, and cytotoxicity evaluation are depicted. Finally, to elucidate the mechanism of therapeutic substances release, the obtained averages of the release profiles were fitted through mathematical models.

Characterization of acerola (Malpighia emarginata) industrial waste as raw material for thermochemical processes.

Brazil stands out as one of the largest world powers in the agribusiness sector, and with the increase of production capacity, an enormous amount of waste is generated that cause serious environmental problems. Acerola is evidenced as one of the fruits of growing and important commercialization, contributing significantly to regional development through the export of concentrated powder product. Thus, in order to minimize the environmental impacts generated by the local fruit processing industry, the proximate analysis of its residue after drying in a convective oven at temperatures of 50, 75 and 100 °C was carried out in this work, aiming at the reuse of this residue for thermochemical processes. Moisture, ash, volatile matter (VM), and fixed carbon (FC) content were analyzed, as well as characterizations, such as infrared spectroscopy (FTIR), elemental analysis (CHNO), calorific value (HHV) and thermogravimetry (TG/DTG). The results showed a significant difference in the moisture contents, VM, FC and elemental carbon for the dry residue at 50 °C compared to the temperatures of 75 and 100 °C, while for the ash content there was no significant difference between the temperatures. The dry acerola residue at the three temperatures studied presented adequate properties for thermochemical application, with lignocellulosic compounds that can be converted by thermochemical route, good levels of calorific power, low moisture and ash content, associated with high amount of volatile matter.

Data on the thermochemical potential of six Cuban biomasses as bioenergy sources.

Data on the rapid, elemental and calorimetric analysis, such as ash melting behaviour and thermogravimetric profiles of six Cuban biomass feedstock are shown, in order to assess their potential for bioenergy production. The studied biomasses are Jatropha curcas husk, Moringa oleifera husk, Dichrostachys cinerea, Ulva lactuca, Chaetomorpha gracilis and Sargassum fluitants. Seed, kernels or stems and algae were characterized by weight. Sample preparation and tests were established according to referenced German standards with particle size <75 mm. In addition, thermogravimetric analyses have been performed at 10 °C/min in Argon atmosphere. Data in the paper are shown in Tables and Graphs. The data represent valuable information for simulation or further implementation of gasification or pyrolysis processes using these biomasses.

Film Dressings Based on Hydrogels: Simultaneous and Sustained-Release of Bioactive Compounds with Wound Healing Properties.

This research proposes the rational modeling, synthesis and evaluation of film dressing hydrogels based on polyvinyl alcohol crosslinked with 20 different kinds of dicarboxylic acids. These formulations would allow the sustained release of simultaneous bioactive compounds including allantoin, resveratrol, dexpanthenol and caffeic acid as a multi-target therapy in wound healing. Interaction energy calculations and molecular dynamics simulation studies allowed evaluating the intermolecular affinity of the above bioactive compounds by hydrogels crosslinked with the different dicarboxylic acids. According to the computational results, the hydrogels crosslinked with succinic, aspartic, maleic and malic acids were selected as the best candidates to be synthesized and evaluated experimentally. These four crosslinked hydrogels were prepared and characterized by FTIR, mechanical properties, SEM and equilibrium swelling ratio. The sustained release of the bioactive compounds from the film dressing was investigated in vitro and in vivo. The in vitro results indicate a good release profile for all four analyzed bioactive compounds. More importantly, in vivo experiments suggest that prepared formulations could considerably accelerate the healing rate of artificial wounds in rats. The histological studies show that these formulations help to successfully reconstruct and thicken epidermis during 14 days of wound healing. Moreover, the four film dressings developed and exhibited excellent biocompatibility. In conclusion, the novel film dressings based on hydrogels rationally designed with combinatorial and sustained release therapy could have significant promise as dressing materials for skin wound healing.

Crystal structures and Hirshfeld surface analysis of [κ2-P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]·2CHCl3 and the product of its reaction with piperidine, [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br].

The coordination of the ligands with respect to the central atom in the complex bromido-tricarbon-yl[diphen-yl(pyridin-2-yl)phosphane-κ2 N,P]rhenium(I) chloro-form disolvate, [ReBr(C17H14NP)(CO)3]·2CHCl3 or [κ2-P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]·2CHCl3, (I·2CHCl3), is best described as a distorted octa-hedron with three carbonyls in a facial conformation, a bromide atom, and a biting P,N-di-phenyl-pyridyl-phosphine ligand. Hirshfeld surface analysis shows that C-Cl⋯H inter-actions contribute 26%, the distance of these inter-actions are between 2.895 and 3.213 Å. The reaction between I and piperidine (C5H11N) at 313 K in di-chloro-methane leads to the partial decoord-ination of the pyridyl-phosphine ligand, whose pyridyl group is replaced by a piperidine mol-ecule, and the complex bromido-tricarbon-yl[diphen-yl(pyridin-2-yl)phosphane-κP](piperidine-κN)rhenium(I), [ReBr(C5H11N)(C17H14NP)(CO)3] or [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br] (II). The mol-ecule has an intra-molecular N-H⋯N hydrogen bond between the non-coordinated pyridyl nitro-gen atom and the amine hydrogen atom from piperidine with D⋯A = 2.992 (9) Å. Thermogravimetry shows that I·2CHCl3 losses 28% of its mass in a narrow range between 318 and 333 K, which is completely consistent with two solvating chloro-form mol-ecules very weakly bonded to I. The remaining I is stable at least to 573 K. In contrast, II seems to lose solvent and piperidine (12% of mass) between 427 and 463 K, while the additional 33% loss from this last temperature to 573 K corresponds to the release of 2-pyridyl-phosphine. The contribution to the scattering from highly disordered solvent mol-ecules in II was removed with the SQUEEZE routine [Spek (2015 ▸). Acta Cryst. C71, 9-18] in PLATON. The stated crystal data for M r, µ etc. do not take this solvent into account.

Pyrolysis kinetics of biomass wastes using isoconversional methods and the distributed activation energy model.

In this work, a thermogravimetric analyser was used to assess the pyrolysis kinetics of pineapple, orange and mango peel wastes and agro-industrial by-products, rice husk and pine wood. Five isoconversional methods (KAS, FWO, Starink, Vyazovkin and Friedman) and one model-fitting method (DAEM) accurately fitted the experimental data at three heating rates (5, 10 and 20 °C/min) between 10% and 90% conversion. These methods agree with the trends shown by the activation energy (Ea) distribution calculated, with fluctuations between 150 and 550 kJ/mol. The fluctuations of Ea in the whole range of conversion, in addition to a higher number of relevant reactions obtained by DAEM for fruit peel samples compared to agro-industrial samples, are associated with a higher extractive content in the peels. Kinetic parameters fitted by DAEM were successfully verified at the highest heating rate studied.

Thermo-kinetics of Forest Waste Using Model-Free Methods / Termocinética de residuos de bosque usando los métodos de modelo libre / Termocinética de resíduos de bosque usando métodos de modelo livre

Abstract Thermal behaviour of pine needles (Pinus Roxburghii) is examined through a thermogravimetry technique. The dried samples of pine needles undergo the non-isothermal decomposition at temperature range of 308-1173 K. The heating rates used for experimental purposes are: 5 ◦ C min-1, 10 ◦ C min-1 and 15 ◦ C min-1. Kinetic parameters of thermal decomposition reactions of pine needles are obtained through the model-free schemes. The estimated values of activation energy and frequency factor derived from Kissinger method are 132.77 kJ mol-1 and 13.15 x 107 min-1, respectively. Furthermore, the averaged values of the same kinetics parameters retrieved from the isoconversional methods are 82.38 kJ mol-1 and 74.833 kJ mol-1, 25.42 x 1013 min-1 and 13.449 x 1010 min-1, respectively. Instead of the Flynn-Wall- Ozawa (FWO) and Kissinger- Akahira- Sunrose (KAS) schemes, the kinetic parameters derived from the Kissinger method are relatively promising for the thermal decomposition process, since the kinetic parameters are highly affected by intermediate stages and overlapping of the concurrent reaction occurred during pyrolysis.

Resumen Se examina el comportamiento térmico de las agujas de pino (Pinus roxburghii) a través de la técnica de termogravimetría. Las muestras secas de las agujas de pino se someten a una descomposición no isotérmica en un rango de temperatura de 308-1173 K. Las tasas de calentamiento usadas para los propósitos experimentales son: 5 °C min-1, 10 °C min-1 y 15 °C min-1. Los parámetros cinéticos de las reacciones de descomposición térmica de las agujas de pino se obtuvieron a través de esquemas de modelo libre. Los valores estimados de la energía de activación y el factor de frecuencia derivado del método Kissinger son: 132.77 kJ mol-1 y 13.15 x 107 min-1, respectivamente. Por otra parte, los valores promediados de los mismos parámetros cinéticos recuperados por los métodos isoconversionales son 82.38 kJ mol-1 y 74.833 kJ mol-1, 25.42 x 1013 min-1 y 13.449 x 1010 min-1, respectivamente. A diferencia de los esquemas Flynn-Wall-Ozawa (FWO) y Kissinger-Akahira-Sunrose (KAS), los parámetros cinéticos derivados del método Kissinger son relativamente promisorios para los procesos de descomposición térmica, ya que estos parámetros se afectan grandemente por los estados intermedios y la superposición de la reacción concurrente que ocurre durante la pirólisis.

Resumo O comportamento térmico de agulhas de pinheiro (Pinus roxburghii) foi examinado por meio da técnica de gravimetria. As amostras secas das agulhas de pinheiro se submeteram a uma decomposição não-isotérmica em uma faixa de temperatura de 308-1173 K. As taxas de aquecimento usadas para propósitos experimentais foram: 5 °C min-1, 10 °C min-1 e 15 °C min-1. Os parâmetros cinéticos das reações de decomposição térmica das agulhas de pinheiro se obtiveram por meio de esquemas de modelo livre. Os valores estimados da energia de ativação e o fator de frequência derivado do método Kissinger são: 132.77 kJ mol-1 e 13.15 x 107 min-1, respectivamente. Adicionalmente, os valores médios dos mesmos parâmetros cinéticos recuperados pelos métodos isoconversionais são 82.38 kJ mol-1 e 74.833 kJ mol-1, 25.42 x 1013 min-1 y 13.449 x 1010 min-1, respectivamente. Diferentemente dos esquemas Flynn-Wall-Ozawa (FWO) e Kissinger-Akahira-Sunrose (KAS), os parâmetros cine'ticos derivados do método Kissinger são relativamente promissórios para os processos de decomposição térmica, já que estes parâmetros são altamente afetados pelos estados intermediários e sobreposição da reação concorrente que ocorre durante a pirólise.