Search Results (503)

Stainless steel dust (SSD) is a by-product generated during the smelting process of stainless steel, which is rich in valuable metals such as Fe, Cr, Ni, and Mn. To optimize the carbothermic reduction process of SSD, this study first conducted the thermodynamic analysis of the carbothermic reduction of SSD and then employed walnut shell biochar as a reductant with non-isothermal thermogravimetric analysis with linear heating rates of 5 °C/min, 10 °C/min, 15 °C/min, and 20 °C/min. The activation energies of the carbothermic reduction reactions were calculated using the FWO method, KAS method, and Friedman method, respectively. Subsequently, the corresponding kinetic models were fitted and matched using the Málek method. The results indicate that before 600 °C, the direct reduction of SSD by carbon plays a dominant role. As the temperature increases, the indirect reduction becomes the main reduction reaction for SSD due to the generation of CO. The activation energies calculated by the Flynn–Wall–Ozawa (FWO) method, Kissinger–Akahira–Sunose (KAS) method, and Friedman method are 412.120 kJ/mol, 416.930 kJ/mol, and 411.778 kJ/mol, respectively, showing close values and a general trend of increasing activation energy as the conversion rate increased from 10% to 90%. Moreover, the reduction reaction is staged. In the conversion range of 10% to 50%, the carbothermic reduction reaction conforms to the shrinking core model within phase boundary reactions, coded as R1/4. In the conversion range of 50% to 60%, it conforms to the shrinking core model within phase boundary reactions, coded as R1/2; in the conversion range of 60% to 90%, the carbothermic reduction reaction follows the second-order chemical reaction model, coded as F2. Full article

Currently, numerous conventional airport runways suffer from cracking distresses and cannot meet their structural and functional requirements. To address the urgent demand for rapid and durable maintenance of airport runways, this study investigates the material optimization and curing behavior of cold-mix epoxy asphalt (CEA) for non-disruptive overlays. Eight commercial CEAs were examined through tensile and overlay tests to evaluate their strength, toughness, and reflective cracking resistance. Two high-performing formulations (CEA 1 and CEA 8) were selected for further curing characterization using differential scanning calorimetry (DSC) tests, and the non-isothermal curing kinetics were analyzed with different contents of Component C. The results reveal that CEA 1 and CEA 8 were selected as promising formulations with superior toughness and reflective cracking resistance across a wide temperature range. DSC-based curing kinetic analysis shows that the curing reactions follow an autocatalytic mechanism, and activation energy decreases with conversion, confirming a self-accelerating process of CEA. The addition of Component C effectively modified the curing behavior, and CEA 8 with 30% Component C reduced curing time by 60%, enabling traffic reopening within half a day. The curing times were accurately predicted for each type of CEA using curing kinetic models based on autocatalytic and iso-conversional approaches. These findings will provide theoretical and practical guidance for high-performance airport runway overlays, supporting rapid repair, extended service life, and environmental sustainability. Full article

The treatment of contaminants from road infrastructure poses significant challenges due to their variable composition and the high concentrations of chloride ions, heavy metals, and oil-derived substances. Traditional methods for protecting groundwater environments are often insufficient. A promising alternative is permeable reactive barrier (PRB) technology, which utilizes recycled materials and construction waste as reactive components within the treatment zone of the ground. This paper delves into the potential of employing a composite (MIX) consisting of modified construction aggregate (as recycled material) and activated carbon (example of reactive material) to address environmental contamination from a mixture of heavy metals and chloride. The research involved chemical modifications of the road aggregate, activated carbon, and their composite, followed by laboratory tests in glass reactors and non-flow batch tests to evaluate the kinetics and chemical equilibrium of the reactions. The adsorption process was stable and conformed to the pseudo-second-order kinetics and Langmuir, Toth, and Redlich–Peterson isotherm models. Studies using MIX from a heavy metal model solution showed that monolayer adsorption was a key mechanism for removing heavy metals, with strong fits to the Langmuir (R² > 0.80) and Freundlich models, and optimal efficiencies for Cd and Ni (R² > 0.90). The best fit, at Cd, Cu, Ni = 0.96, however, was with the Redlich–Peterson isotherm, indicating a mix of physical and chemical adsorption on heterogeneous surfaces. The Toth model was significant for all analytes, fitting Cl and Cd well and Pb and Zn moderately. The modifications made to the composite significantly enhanced its effectiveness in removing the contaminant mixture. The test results demonstrated an average reduction of chloride by 85%, along with substantial removals of heavy metals: lead (Pb) by 90%, cadmium (Cd) by 86%, nickel (Ni) by 85%, copper (Cu) by 81%, and zinc (Zn) by 79%. Further research should focus on the removal of other contaminants and the optimization of magnesium oxide (MgO) dosage. Full article

A modified activated carbon (AC) was developed by modifying with poly(diallyldimethylammonium) chloride (PDADMAC) to enhance its adsorption performance for water treatment applications. Different PDADMAC concentrations were explored and evaluated using methyl red as a model contaminant, with 8 w/v% PDADMAC yielding the best adsorption performance. The kinetics data were well described by the pseudo-first-order equation and homogeneous surface diffusion model. The Freundlich isotherm fit the equilibrium data well, indicating multilayer adsorption and diverse interaction types. The removal efficiency remained similar across a pH range of 5–9 and in the presence of background inorganic (NaCl)/organic compounds (sodium acetate) at different concentrations. Rapid small-scale column tests were performed to simulate continuous flow conditions, and the PDADMAC-modified AC effectively delayed the breakthrough of the contaminant compared to raw AC. Regeneration experiments showed that 0.1 M NaOH with 70% methanol effectively restored the adsorption capacity, retaining 80% of the initial efficiency after five cycles. Quantum chemical analysis revealed that non-covalent interactions, including electrostatic and Van der Waals forces, governed the adsorption mechanism. Overall, the results of this study prove that PDADMAC-AC shows great potential for enhanced organic contaminant removal in water treatment systems. Full article

Non-isothermal calorimetry is performed to study the kinetics of metal-free A₂/B₂-type azide–alkyne polyaddition between the dipropargyl ether of bisphenol A with different organic diazides. The diazide structure is varied to probe the effect of the nature of a hydrocarbon spacer between the azide groups on their reactivity. Isoconversional analysis demonstrates that the polymerization processes are characterized by the same activation energy of 84 kJ mol⁻¹ for all studied diazides. It is found that diazides with aromatic spacers demonstrate ~1.6 times higher reactivity than that of diazides with the alkyl spacer. The difference in the reactivity is explained by the difference in the electronic effects of the hydrocarbon spacers on the azide groups as well as by the difference in their steric availability. The veracity of the obtained kinetic parameters is validated by a polymerization test at the time–temperature conditions predicted from the obtained kinetic data followed by independent assessment of the monomer conversion using FTIR. Full article

In the pursuit of environmental sustainability, reduced emissions, and alignment with circular economy principles, bio-epoxy resin nanocomposites have emerged as a promising alternative to traditional petroleum-based resins. This study investigates the development of novel bio-epoxy nanocomposites incorporating iron-oxide nanoparticles (Fe₂O₃, MnP) as multifunctional fillers at loadings of 0.5 wt.% and 3.0 wt.%. MnP nanoparticles were synthesized and subsequently functionalized with citric acid (MnP-CA) to enhance their surface properties. Comprehensive characterization of MnP and MnP-CA was performed using X-ray diffraction (XRD) to determine the crystalline structure, attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), and zeta potential measurements to confirm surface functionalization. The bio-epoxy resins matrix (bio-EP), optimized for compatibility with MnP and MnP-CA, was thoroughly analyzed in terms of chemical structure, thermal stability, curing behavior, dynamic–mechanical properties, and surface characteristics. Non-isothermal differential scanning calorimetry (DSC) was employed to evaluate the curing kinetics of both the neat (bio-EP) and the MnP/MnP-CA-reinforced composites, offering insights into the influence of nanoparticle functionalization on the resin system. Surface zeta potential measurements further elucidated the effect of filler content on the surface charge and hydrophilicity. Magnetic characterization revealed superparamagnetic behavior in all MnP- and MnP-CA-reinforced (bio-EP) composites. This research provides a foundational framework for the design of green bio-epoxy nanocomposites, demonstrating their potential as environmentally friendly materials and representing an emerging class of sustainable alternatives. The results underscore the viability of bio-epoxy systems as a transformative solution for advancing sustainable resin technologies across eco-conscious industries. Full article

Mango peel (MP), an abundant agro-industrial residue, was evaluated as a solid biofuel using combined physicochemical characterisation and non-isothermal thermogravimetric kinetics (TGA). Fourier transform infrared (FTIR), X-ray diffraction (XRD), and scanning electron microscopy (SEM) revealed hydroxyl-rich surfaces and porous microstructures. Thermogravimetric combustion, conducted at heating rates of 20–80 K min⁻¹, displayed three distinct stages. These stages correspond to dehydration (330–460 K), hemicellulose/cellulose oxidation (420–590 K), and cellulose/lignin oxidation (540–710 K). Kinetic analysis using six model-free methods (Friedman (FR), Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), Starink (STK), Kissinger (K), and Vyazovkin (VY)) yielded activation energies (E_a) of 52–197 kJ mol⁻¹, increasing with conversion (mean E_a ≈ 111 kJ mol⁻¹). Coats–Redfern (CR) fitting confirmed a three-dimensional diffusion mechanism (D3, R² > 0.99). Thermodynamic analysis revealed that the formation of the activated complex is endothermic, with activation enthalpy (ΔH) values of 45–285 kJ mol⁻¹. The process was found to be non-spontaneous under the studied conditions, with Gibbs free energy (ΔG) values ranging from 83 to 182 kJ mol⁻¹. With a high heating value (HHV) of 21.9 MJ kg⁻¹ and favourable combustion kinetics, MP is a promising supplementary fuel for industrial biomass boilers. However, its high potassium oxide (K₂O) content requires dedicated ash management strategies to mitigate slagging risks, a key consideration for its practical, large-scale application. Full article

Thermokinetic characterization of amorphous carbamazepine was performed utilizing non-isothermal differential scanning calorimetry (DSC) and thermogravimetry (TGA). Structural relaxation of the amorphous matrix was described in terms of the Tool–Narayanaswamy–Moynihan model with the following parameters: Δh* ≈ 200–300 kJ·mol⁻¹, β = 0.57, x = 0.44. The crystallization of the amorphous phase was modeled using complex Šesták–Berggren kinetics, which incorporates temperature-dependent activation energy and degree of autocatalysis. The activation energy of the crystal growth was determined to be >320 kJ·mol⁻¹ at the glass transition temperature (T_g). Owing to such a high value, the amorphous carbamazepine is stable at T_g, allowing for extensive processing of the amorphous phase (e.g., self-healing of the quench-induced mechanical defects or internal stress). A discussion was conducted regarding the converse relation between the activation energies of relaxation and crystal growth, which is possibly responsible for the absence of sub-T_g crystal growth modes. The high-temperature thermal decomposition of carbamazepine proceeds via multistep kinetics, identically in both an inert and an oxidizing atmosphere. A complex reaction mechanism, consisting of a series of consecutive and competing reactions, was proposed to explain the second decomposition step, which exhibited a temporary mass increase. Whereas a negligible degree of carbamazepine degradation was predicted for the temperature characteristic of the pharmaceutical hot-melt extrusion (~150 °C), the degradation risk during the pharmaceutical 3D printing was calculated to be considerably higher (1–2% mass loss at temperatures 190–200 °C). Full article

During the thermal treatment of kaolinite, the main mineral phase in kaolin rock, dehydroxylation occurs, forming metakaolin through a process that has significant industrial applications. This study experimentally analyzed dehydroxylation in two kaolinite samples: a well-crystallized reference sample from the Clay Mineral Society and a locally sourced, industrial kaolin sample. The mechanism and kinetic parameters were evaluated from a series of thermogravimetric measurements. Non-isothermal kinetic analysis revealed that dehydroxylation followed a third-order (F3) reaction mechanism, with activation energies ($E_a$) ranging from 35 to 60 kcal/mol. Additionally, theoretical calculations based on Density Functional Theory were performed on four systems in which a water molecule was removed by combining OH group and H atom vacancies in the kaolinite unit cell. These models represented the onset of dehydroxylation and provided values for the reaction energy Q from first-principles calculations, which served as reference values for $E_a$. The results confirm that water molecule formation involving both OH at the kaolinite outer surface and inner surface are energetically competitive and highlight the crucial role of structural relaxations following water removal to determine Q values in the range of 30–50 kcal/mol, in very good agreement with the experiments. Full article

In this research, an emerging, non-metallic photocatalyst was prepared by the thermal polymerization method from three different precursors: urea, melamine, and three mixtures of melamine and cyanuric acid. Graphitic carbon nitride (g-C₃N₄) samples from urea and melamine were synthesized in a muffle furnace at three different temperatures: 450°, 500°, and 550 °C for 2 h, while the samples made of a mixture of melamine and cyanuric acid (with mass ratios of 1:1, 1:2, and 2:1) were synthesized at 550 °C for 2 h. All the samples were characterized in order to determine their chemical and physical properties, such as crystallite size and structure, and phase composition by the following techniques: Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS). Nitrogen adsorption/desorption isotherms were used to investigate the Brunauer, Emmett, and Teller (BET) specific surface area and Barrett–Joyner–Halenda (BJH) pore size distribution. Band gap values were determined by diffuse reflectance spectroscopy (DRS). Furthermore, adsorption and photocatalytic degradation of the local anesthetic drug procaine were monitored under UV-A, visible, and simulated solar irradiation in a batch reactor. Kinetic parameters, as well as photocatalytic mechanisms using scavengers, were determined and analyzed. The results of the photocatalysis experiments were compared to the benchmark TiO₂ Evonik Aeroxide P25. The results indicated that the g-C₃N₄ sample synthesized from urea at 500 °C for 2 h exhibited the highest degradation rate of procaine under visible light. Full article

The objective of this study was to model an adsorption column bed with biomass residues using computational software to remove Pb (II) at the industrial level and analyse the effects of parametric variation. For this purpose, several simulations of the adsorption column were performed using Aspen Adsorption software, evaluating the effects of varied height, inlet flow rate, and initial concentration on the adsorption process performance. The Langmuir II and Freundlich models are established as isotherm models, and the linear driving force (LDF) model is established as the kinetic model. The findings showed that Freundlich–LDF obtained efficiencies of up to 99.9% and Langmuir II–LDF efficiencies of up to 99.7%. The optimal simulation conditions were a column height of 4 m, an initial Pb (II) concentration of 3000 mg/L, and an inlet flow rate of 250 m³/d. This study presents a novel engineering approach to predict the potential performance of columns packed with organic waste-derived biomasses in multi-scale Pb (II) removal using computer-aided engineering tools. Full article

The use of natural materials as adsorbents and the environmentally friendly removal of pollutants and azo dyes from water are important topics today. The goal of this research work was to assess the utility of Luffa cylindrica (L. cylindrica) as a natural and non-conventional adsorbent for azo dyes in water on a large scale (2 L). An azo dye (AD) at a concentration of 0.250 g/L was removed from the solution at a rate of 63.07% using 10.0 g/L doses of L. cylindrica, and the maximum adsorption capacity of L. cylindrica was 25.25 mg/g. L. cylindrica desorbed 95.8% of the AD in 0.1 M NaOH. Thermodynamically, the adsorption occurs through pseudo-second-order kinetics and the behaviors adjust better to the Langmuir isotherm. The analysis of variance (p-value < 0.05) shows that the contact time and the concentration of AD significantly influence the adsorption capacity and removal of AD. Few studies have examined the environmentally friendly removal of azo dyes from water using a natural non-conventional adsorbent. Full article

This study investigates the impact of hydrolysis on the crystallization behavior of poly(butylene succinate-co-adipate) (PBSA), a biodegradable polyester. Hydrolysis was conducted in a controlled environment using phosphate-buffered saline at 70 °C to isolate the impact of hydrolytic degradation on the polymer’s properties. The consequent changes in molecular weight characteristics were tracked using gel permeation chromatography (GPC), revealing a decrease in both weight average molecular weight (M_w) and an increase in polydispersity index (PDI) as hydrolysis progressed. The thermal behavior of PBSA during hydrolysis was thoroughly investigated using differential scanning calorimetry (DSC), which demonstrated significant changes in melting temperature (T_m), glass transition temperature (T_g), and crystallinity (X). These changes in T_m and T_g suggest a change in copolymer composition, likely due to the greater susceptibility of the adipic acid unit to hydrolysis compared to the succinic acid unit. Furthermore, polarized optical microscopy (POM) was employed to observe the morphological evolution of PBSA, showing a transition from spherulitic structures in the early stages of hydrolysis to dendritic structures with prolonged hydrolysis time. The decrease in nucleation activity led to a reduction in the number of spherulites, which in turn allowed the remaining spherulites to grow larger. Full article

Epoxy resins (ERs) are esteemed for their mechanical robustness and adhesive qualities, particularly in steel bridge deck applications. Nonetheless, their intrinsic brittleness limits broader utility. This study addresses this limitation by modulating ER crosslink density through adjustments in curing agent concentration, incorporation of hyperbranched polymers (HBPs), and optimization of curing conditions. Employing a multi-objective optimization strategy, this research aims to enhance toughness while minimizing strength degradation. Non-isothermal curing kinetics, realized using the differential scanning calorimetry (DSC) method, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), tensile testing, and thermogravimetric analysis (TGA), were employed to investigate the effects of curing agent and HBP content on the curing reaction, mechanical properties, and thermal stability, respectively. Response surface methodology facilitated comprehensive optimization. Findings indicate that both curing agent and HBP contents significantly influence curing dynamics and mechanical performance. Curing agent content below 40% or above 50% can induce side reactions, adversely affecting properties. While a curing agent content exceeding 45% or an HBP content exceeding 5% improves the toughness of ER, these increases concurrently reduce mechanical strength and thermal stability. The study identifies an optimal formulation comprising 45.21% curing agent, a curing temperature of 60.45 °C, and 5.77% HBP content. Full article

The study of thermal developments of heavy oil feedstock, vacuum residue in particular, is a relevant factor for the development of technologies for the processing and production of petroleum products. This paper investigates the process of thermal decomposition of the vacuum residue in the manufacturing of catalyst and polymer material using thermal analysis methods, including thermogravimetric analysis (TGA) in isothermal and dynamic modes. Particular attention is paid to the measurement of kinetic parameters of thermolysis using model and non-model methods, which allows us to assess the output power and other kinetic characteristics of decomposition. The results obtained can be used for the development of new oil refining technologies for significantly increasing the efficiency and safety of processes. During the course of this study, experimental and theoretical activation energy values were obtained for the vacuum residue without a catalyst (experimentally: 91.54 kJ mol⁻¹/theoretically: 91.35 kJ mol⁻¹) and a sample with the presence of a catalyst (experimentally: 89.68 kJ mol⁻¹/theoretically: 90.87 kJ mol⁻¹). The reduction in activation energy in the presence of the catalyst confirms its catalytic activity and potential for processing heavy hydrocarbon feedstock. Full article