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Search Results (1,964)

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Keywords = reaction kinetics and mechanism

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15 pages, 3750 KB  
Article
Hydroxyl Group-Dependent Effects of Alkanolamine Additives on Rheology, Hydration, and Performance of Early-Strength Cement Slurries
by Yifei Zhao, Ya Shi, Longjiang Wang, Yan Zhuang, Yongfei Li and Gang Chen
Processes 2025, 13(9), 2681; https://doi.org/10.3390/pr13092681 - 23 Aug 2025
Viewed by 95
Abstract
Alkanolamine additives play a critical role in enhancing the early process performance of cement slurries, thereby improving construction efficiency and structural durability. This study systematically evaluates the effects of ethanolamine (EA), diethanolamine (DEA), and triethanolamine (TEA) on cement slurry properties, including the thickening [...] Read more.
Alkanolamine additives play a critical role in enhancing the early process performance of cement slurries, thereby improving construction efficiency and structural durability. This study systematically evaluates the effects of ethanolamine (EA), diethanolamine (DEA), and triethanolamine (TEA) on cement slurry properties, including the thickening time, rheology, density, shrinkage, and hydration kinetics. Clear structure–activity relationships are established based on the findings. The experimental analysis demonstrated that increasing the hydroxyl group count in the alkanolamines significantly accelerated cement hydration. At a dosage of 1.0%, the thickening time of the cement slurry was significantly shortened to 125 min (EA), 15 min (DEA), and 12 min (TEA), respectively. Concomitantly, a reduction in fluidity was observed, with flow diameters measuring 15.8 cm (EA), 14.6 cm (DEA), and 14.1 cm (TEA). The rheological analysis revealed that the alkanolamine additives significantly increased the consistency coefficient (K) and decreased the flowability index (n) of the slurry, with TEA exhibiting the most pronounced effect. The density measurements confirmed the enhanced settlement stability, as the density differences diminished to 0.1 g/cm3 at the optimal dosages (0.6% TEA and 0.8% DEA). The hydration degree analysis indicated a hydration rate acceleration of up to 32% relative to plain slurry, attributed to the hydroxyl-facilitated promotion of Ca(OH)2 formation and C3S dissolution. The XRD analysis confirmed that the alkanolamines modified the reaction kinetics without inducing phase transformation in the hydration products. Crucially, the hydroxyl group count governed the performance: a higher hydroxyl density intensified Ca2+/Al3+ complexation, thereby reducing ion mobility and accelerating setting. These findings establish a molecular design framework for alkanolamine-based additives that balances early process performance development with practical workability. The study advances sustainable cement technology by enabling targeted optimization of rheological and mechanical properties in high-demand engineering applications. Full article
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42 pages, 15245 KB  
Article
Effect of Mixing Water Temperature on the Thermal and Microstructural Evolution of Cemented Paste Backfill in Underground Mining
by Amin Safari, Cody Tennant, Aliakbar Gholampour, Jeremy Palmer and Abbas Taheri
Minerals 2025, 15(9), 887; https://doi.org/10.3390/min15090887 - 22 Aug 2025
Viewed by 103
Abstract
Cemented paste backfill (CPB) gains strength through the hydration of the binder constituent of the CPB, where mix temperature is a key influencing factor. Both rate of strength development and ultimate strength are influenced by the overarching temperature conditions in which the binder [...] Read more.
Cemented paste backfill (CPB) gains strength through the hydration of the binder constituent of the CPB, where mix temperature is a key influencing factor. Both rate of strength development and ultimate strength are influenced by the overarching temperature conditions in which the binder hydration occurs. This study investigates the influence of mixing water temperature on the thermal behaviour, hydration kinetics, and microstructural development of CPB using a combination of thermal finite element modelling, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). Five CPB mixtures were prepared, with water temperatures ranging from 5 °C to 50 °C, and tested under controlled conditions to isolate the effects of the initial thermal input. Results show that moderate mixing water temperatures (20–35 °C) optimize hydration and mechanical strength, while excessive temperatures (≥50 °C) increase the risk of thermal cracking due to generation of excessive heat. The thermal modelling results demonstrated that the highest temperatures were observed in the bottom section of the fill mass, in contact with the surrounding rock, where the combined effects of mix-generated heat and rock conduction were most pronounced. The 50 °C mix reached a peak internal temperature of 85.6 °C with a thermal gradient of 40.5 °C, while the 5 °C mix recorded a much lower peak of 55.7 °C and a gradient of 16.8 °C. These results highlight that higher mixing water temperatures accelerate early hydration reactions and significantly influence the internal thermal profile during the first 21 days of curing. Based on these findings, the design of paste plants can be improved by incorporating a heating/cooling system for the mixing water tank—firstly, to ensure the water temperature does not exceed 50 °C and secondly, to maintain water within an optimal temperature range, potentially reducing binder consumption. Full article
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19 pages, 1939 KB  
Article
Development and Optimization of Chemical Kinetic Mechanisms for Ethanol–Gasoline Blends Using Genetic Algorithms
by Filipe Cota, Clarissa Martins, Raphael Braga and José Baeta
Energies 2025, 18(16), 4444; https://doi.org/10.3390/en18164444 - 21 Aug 2025
Viewed by 201
Abstract
Reduced chemical kinetic mechanisms are essential for enabling the use of complex fuels in 3D CFD combustion simulations. This study presents the development and optimization of a compact mechanism capable of accurately modeling ethanol–gasoline blends, including Brazilian Type-C gasoline (27% ethanol by volume) [...] Read more.
Reduced chemical kinetic mechanisms are essential for enabling the use of complex fuels in 3D CFD combustion simulations. This study presents the development and optimization of a compact mechanism capable of accurately modeling ethanol–gasoline blends, including Brazilian Type-C gasoline (27% ethanol by volume) and up to pure ethanol (E100). An initial mechanism was constructed using the Directed Relation Graph with Error Propagation (DRGEP) method applied to detailed mechanisms selected for each surrogate component. The resulting mechanism was then refined through three global iterations of a genetic algorithm targeting ignition delay time (IDT) and laminar flame speed (LFS) performance. Five candidate versions (Mec1 to Mec5), each containing 179 species and 771 reactions, were generated. Mec4 was identified as the optimal configuration based on quantitative error analysis across all tested conditions and blend ratios. The final mechanism offers a balance between predictive accuracy and computational feasibility, making it well-suited for high-fidelity simulations in complex geometries involving multi-component ethanol–gasoline fuels. Full article
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43 pages, 23033 KB  
Review
MXene-Based Electrocatalysts for Water Splitting: Material Design, Surface Modulation, and Catalytic Performance
by Mohammad R. Thalji, Farzaneh Mahmoudi, Leonidas G. Bachas and Chinho Park
Int. J. Mol. Sci. 2025, 26(16), 8019; https://doi.org/10.3390/ijms26168019 - 19 Aug 2025
Viewed by 303
Abstract
Developing efficient and sustainable hydrogen production technologies is critical for advancing the global clean energy transition. This review highlights recent progress in the design, synthesis, and electrocatalytic applications of MXene-based materials for electrochemical water splitting. It discusses the fundamental mechanisms of the hydrogen [...] Read more.
Developing efficient and sustainable hydrogen production technologies is critical for advancing the global clean energy transition. This review highlights recent progress in the design, synthesis, and electrocatalytic applications of MXene-based materials for electrochemical water splitting. It discusses the fundamental mechanisms of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), and the structure–function relationships that govern electrocatalytic behavior. Emphasis is placed on the intrinsic structural and surface properties of MXenes, such as their layered architecture and tunable surface chemistry, which render them promising candidates for electrocatalysis. Despite these advantages, several practical limitations hinder their full potential, including oxidation susceptibility, restacking, and a limited number of active sites. Several studies have addressed these challenges using diverse engineering strategies, such as heteroatom doping; surface functionalization; and constructing MXene-based composites with metal chalcogenides, oxides, phosphides, and conductive polymers. These modifications have significantly improved catalytic activity, charge transfer kinetics, and long-term operational stability under various electrochemical conditions. Finally, this review outlines key knowledge gaps and emerging research directions, including defect engineering, single-atom integration, and system-level design, to accelerate the development of MXene-based electrocatalysts for sustainable hydrogen production. Full article
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14 pages, 5789 KB  
Article
Investigation of the Influence of Pyrolysis Temperature on the Adsorption Performance of Municipal Sludge-Derived Biochar Toward Metal Ions
by Xiaomin Yang, Quanfeng Wang, Yuanling Cheng, Long Qin, Yan Zhao, Yanglu Tang and Da Sun
Water 2025, 17(16), 2459; https://doi.org/10.3390/w17162459 - 19 Aug 2025
Viewed by 218
Abstract
In response to the growing issue of iron and manganese pollution in water bodies, this study systematically investigated the adsorption performance of municipal sludge-derived biochar prepared at pyrolysis temperatures ranging from 300 to 700 °C for the removal of Fe2+ and Mn [...] Read more.
In response to the growing issue of iron and manganese pollution in water bodies, this study systematically investigated the adsorption performance of municipal sludge-derived biochar prepared at pyrolysis temperatures ranging from 300 to 700 °C for the removal of Fe2+ and Mn2+. Among the series of adsorbents (BC300–BC700), BC600—with its well-developed pore structure and high specific surface area—exhibited the best adsorption performance for both metal ions. Kinetic and isothermal adsorption experiments, in combination with XPS characterization, collectively revealed that (1) the adsorption mechanisms of Fe and Mn differ markedly, with Fe adsorption primarily governed by physical interactions, whereas Mn adsorption is largely controlled by chemical processes; (2) Fe2+ adsorption occurs mainly via electrostatic interactions and hydrogen bonding; and (3) Mn2+ forms carbonate precipitates with C=O groups during redox reactions. Thermodynamic analysis further indicated that the adsorption process was spontaneous and endothermic. Moreover, BC600 demonstrated excellent reusability for Fe adsorption across different water matrices, maintaining efficiencies above 95% after five cycles, although the adsorption performance for Mn declined. This study provides theoretical support for the application of sludge-derived biochar as a cost-effective and efficient adsorbent for metal ion remediation. Full article
(This article belongs to the Special Issue Water Pollution Control and Ecological Restoration: 2nd Edition)
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15 pages, 4104 KB  
Article
Enhanced Degradation of Different Tetracyclines by Nonthermal Plasma and Activated Persulfate: Insights into Synergistic Effects and Degradation Mechanism
by Amina Ouzar, Bimo Tri Goutomo, Kyung-Min Lee and Il-Kyu Kim
Separations 2025, 12(8), 222; https://doi.org/10.3390/separations12080222 - 19 Aug 2025
Viewed by 174
Abstract
The increasing presence of tetracycline antibiotics (TCs) in water sources poses significant environmental and public health risks, necessitating effective treatment technologies. This study investigates the degradation of three types of TCs in water—Tetracycline (TC), Oxytetracycline (OTC), and Chlortetracycline (CTC)—using nonthermal plasma (NTP) coupled [...] Read more.
The increasing presence of tetracycline antibiotics (TCs) in water sources poses significant environmental and public health risks, necessitating effective treatment technologies. This study investigates the degradation of three types of TCs in water—Tetracycline (TC), Oxytetracycline (OTC), and Chlortetracycline (CTC)—using nonthermal plasma (NTP) coupled with the persulfate (PS) process. The combined NTP/PS system was optimized for various operational parameters, including PS concentration, pH, and reaction time, to achieve maximum degradation and mineralization efficiency. The results showed that the NTP/PS system achieved over 90% degradation of all TCs under optimal conditions, outperforming plasma alone treatment. The degradation kinetics followed a pseudo-first-order model, indicating a rapid initial breakdown of TCs. The degradation mechanism was elucidated through the identification of intermediate byproducts using liquid chromatography-mass spectrometry (LC-MS/MS). Free radicals, such as sulfate (SO4•−) and hydroxyl (OH) radicals, were identified as the primary reactive species responsible for TCs degradation. This study demonstrates the potential of the NTP/PS system as an efficient and sustainable solution for the removal of antibiotic contaminants from water. Further research on the scalability and application in real wastewater conditions is recommended. Full article
(This article belongs to the Section Environmental Separations)
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15 pages, 2317 KB  
Article
Evolution of Mechanical Properties, Mineral Crystallization, and Micro-Gel Formation in Alkali-Activated Carbide Slag Cementitious Materials
by Yonghao Huang, Guodong Huang, Zhenghu Han, Fengan Zhang, Meng Liu and Jinyu Hao
Crystals 2025, 15(8), 731; https://doi.org/10.3390/cryst15080731 - 19 Aug 2025
Viewed by 234
Abstract
For efficient utilization of carbide slag (CS) waste to high-value building materials, in this study, CS and ground granulated blast furnace slag (GBFS) were used as primary raw materials to prepare alkali-activated cementitious systems under strong alkaline excitation. Multiscale mechanisms involving macroscopic mechanical [...] Read more.
For efficient utilization of carbide slag (CS) waste to high-value building materials, in this study, CS and ground granulated blast furnace slag (GBFS) were used as primary raw materials to prepare alkali-activated cementitious systems under strong alkaline excitation. Multiscale mechanisms involving macroscopic mechanical property development were investigated. Microstructural characterization elucidated how raw material composition affected mineral crystal formation and transformation while revealing enhancement mechanisms governing micro-gel network structure formation and evolution dynamics. The results indicate that excessive calcium components coupled with deficient Si–Al sources in CS severely inhibit the formation of C-S-H and C-A-S-H gel phases, consequently impeding mechanical performance development. Also, GBFS incorporation offsets inherent silicon–aluminum deficiencies. Active [SiO4]4− and [AlO4]5− released from GBFS drive polycondensation reactions toward advanced polymerization states. Compressive strength has a nonlinear growth kinetics characterized by rapid initial ascent, followed by asymptotic plateauing as GBFS content increases. Optimal comprehensive performance emerges at a 5:5 GBFS-to-CS mass ratio, where 28d compressive strength reaches 47.5 MPa. Full article
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12 pages, 2161 KB  
Article
Bio-Based Nanocellulose Piezocatalysts: PH-Neutral Mechanochemical Degradation of Multipollutant Dyes via Ambient Vibration Energy Conversion
by Zhaoning Yang, Zihao Yang, Xiaoxin Shu, Wenshuai Chen, Jiaolong Liu, Keqing Chen and Yanmin Jia
ChemEngineering 2025, 9(4), 90; https://doi.org/10.3390/chemengineering9040090 - 15 Aug 2025
Viewed by 245
Abstract
Piezoelectric catalytic technology has attracted much attention in the field of dye wastewater treatment, in which inorganic piezoelectric materials have been widely studied. Its core mechanism involves utilizing the piezoelectric effect to generate positive and negative charges, which react with oxygen ions and [...] Read more.
Piezoelectric catalytic technology has attracted much attention in the field of dye wastewater treatment, in which inorganic piezoelectric materials have been widely studied. Its core mechanism involves utilizing the piezoelectric effect to generate positive and negative charges, which react with oxygen ions and hydroxyl radicals, respectively, to generate reactive oxygen species to degrade organic pollutants. Currently, while organic piezoelectric catalysts theoretically offer significant advantages such as low cost and high processability, there has been a notable lack of research in this area, which presents an innovative opportunity for the exploration of new organic piezoelectric catalytic materials. In this study, new research using natural nanocellulose (FC) suspension as an efficient organic piezoelectric catalyst is reported for the first time. The experimental results showed that the catalyst exhibited excellent degradation performance for Rhodamine B (RhB), Acid Orange 7 (AO7), and Methyl Orange (MO) under ultrasonic vibration (40 kHz, 200 W): the degradation rates reached 95.4%, 72.4%, and 31.2%, respectively, for 150 min, and the corresponding first-order reaction kinetic constants were 0.0205, 0.00858, and 0.00249 min−1, respectively. It is noteworthy that the RhB solution can achieve the optimal degradation efficiency without adjustment under neutral initial pH conditions, which significantly enhances the practical application feasibility. The experimental results showed that the catalyst, with a measurable piezoelectric coefficient (d33 = 4.4 pm/V), exhibited excellent degradation performance for Rhodamine B (RhB), Acid Orange 7 (AO7), and Methyl Orange (MO) under ultrasonic vibration (40 kHz, 200 W). This organic piezoelectric catalyst, based on renewable biomass, innovatively converts mechanical vibration energy in the environment into the power to degrade pollutants. It not only expands the application boundaries of organic piezoelectric materials but also provides a new solution for sustainable water treatment technology, demonstrating extremely promising application prospects in the field of green and environmentally friendly water treatment. Full article
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20 pages, 1238 KB  
Review
Stefan Flow in Char Combustion: A Critical Review of Mass Transfer and Combustion Differences Between Air-Fuel and Oxy-Fuel Conditions
by Wenfei Bao, Zongwei Gan, Yuzhong Li and Yan Ma
Energies 2025, 18(16), 4347; https://doi.org/10.3390/en18164347 - 15 Aug 2025
Viewed by 342
Abstract
Fuel combustion is a crucial process in energy utilization. As a key bulk transport mechanism, Stefan flow significantly affects heat and mass transfer during char combustion. However, its physical nature and engineering implications have long been underestimated, and no systematic review has been [...] Read more.
Fuel combustion is a crucial process in energy utilization. As a key bulk transport mechanism, Stefan flow significantly affects heat and mass transfer during char combustion. However, its physical nature and engineering implications have long been underestimated, and no systematic review has been conducted. This paper presents a comprehensive review of Stefan flow in char combustion, with a focus on its impact on mass transfer and combustion behavior under both air-fuel and oxy-fuel conditions. It also highlights the critical role of Stefan flow in enhancing energy conversion efficiency and optimizing carbon capture processes. The analysis reveals that Stefan flow has been widely neglected in traditional combustion models, resulting in significant errors in calculated mass transfer coefficients (up to 21% in air-fuel combustion and as high as 74% in oxy-fuel combustion). This long-overlooked deviation severely compromises the accuracy of combustion efficiency predictions and model reliability. In oxy-fuel combustion, the gasification reaction (C + CO2 = 2CO) induces a much stronger outward Stefan flow, reducing CO2 transport by up to 74%, weakening local CO2 enrichment, and substantially increasing the energy cost of carbon capture. In contrast, the oxidation reaction (2C + O2 = 2CO) results in only an 18% reduction in O2 transport. Stefan flow hinders the inward mass transfer of O2 and CO2 toward the char surface and increases heat loss during combustion, resulting in reduced reaction rates and lower particle temperatures. These effects contribute to incomplete fuel conversion and diminished thermal efficiency. Simulation studies that neglect Stefan flow produce significant errors when predicting combustion characteristics, particularly under oxy-fuel conditions. The impact of Stefan flow on energy balance is more substantial in the kinetic/diffusion-controlled regime than in the diffusion-controlled regime. This review is the first to clearly identify Stefan flow as the fundamental physical mechanism responsible for the differences in combustion behavior between air-fuel and oxy-fuel environments. It addresses a key gap in current research and offers a novel theoretical framework for improving low-carbon combustion models, providing important theoretical support for efficient combustion and clean energy conversion. Full article
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29 pages, 3331 KB  
Article
Advanced Delayed Acid System for Stimulation of Ultra-Tight Carbonate Reservoirs: A Field Study on Single-Phase, Polymer-Free Delayed Acid System Performance Under Extreme Sour and High-Temperature Conditions
by Charbel Ramy, Razvan George Ripeanu, Daniel A. Hurtado, Carlos Sirlupu, Salim Nassreddine, Maria Tănase, Elias Youssef Zouein, Alin Diniță, Constantin Cristian Muresan and Ayham Mhanna
Processes 2025, 13(8), 2547; https://doi.org/10.3390/pr13082547 - 12 Aug 2025
Viewed by 444
Abstract
This field study describes the successful implementation and evaluation of a Polymer-free Delayed Acid System, a next-generation acid retarder system that is chemically superior to traditional emulsified acid systems with an amphoteric-based surfactant. It is a polymer-free system that stimulates ultra-tight carbonate reservoirs [...] Read more.
This field study describes the successful implementation and evaluation of a Polymer-free Delayed Acid System, a next-generation acid retarder system that is chemically superior to traditional emulsified acid systems with an amphoteric-based surfactant. It is a polymer-free system that stimulates ultra-tight carbonate reservoirs in extreme sour and high-temperature conditions. The candidate well, located in an onshore gulf region field, for a major oil and gas company demonstrated chronically unstable production behavior for over two years, with test volumes fluctuating unpredictably between 200 and 400 barrels of oil per day. This indicated severe near-wellbore damage, high skin, and limited matrix permeability (<0.3 mD). The well was chosen for a pilot trial of the Polymer-free Delayed Acid System technology after a thorough formation study, which included mineralogical characterization and capillary diagnostics. The innovative acid retarder formulation, designed for deep matrix penetration and controlled acid–rock reaction, uses intrinsic encapsulation kinetics to significantly increase the acid’s reactivity, allowing it to bypass damaged zones, minimize acid leak-off, and initiate dominant wormhole propagation into the tight formation. The stimulation procedure began with a custom pre-flush designed to change nanoscale wettability and interfacial tension, so increasing acid displacement and assuring effective contact with the formation rock. Real-time injectivity testing and operational data collecting were performed prior to, during, and following the acid job, with pre-stimulation injectivity peaking at 1.2 bpm, indicating poor formation conductivity. Treatment with the Polymer-free Delayed Acid System resulted in a 592% increase in post-stimulation injectivity, indicating significant increases in near-wellbore permeability and successful propagation. However, a substantial operational difficulty arose: the well remained shut down for more than two months following the acid stimulation work due to surface infrastructure delays, notably the scheduling and execution of a flowline cleanup campaign. This lengthy closure slowed immediate flowback analysis and impeded direct assessment of treatment performance because production could not be tracked in real time. Despite this, once the surface system was operational and the well was open to flow, a structured production testing program was carried out over four quarterly intervals. The well regularly produced at an average stable rate of 500 bbl/day, more than doubling pre-treatment performance and demonstrating the long-term effectiveness and mechanical durability of the acid-induced wormhole network. Despite the post-job shut-in, the Polymer-free Delayed Acid System maintained the stimulating impact even under non-ideal settings, demonstrating its robustness. The Polymer-free Delayed Acid System outperforms conventional emulsified acid systems, giving better control over acid placement and reactivity, especially under severe reservoir conditions with bottomhole temperatures reaching 200 °F. This project offers a field-proven methodology that combines advanced chemical engineering, formation-specific design, and live diagnostics, as well as a scalable blueprint for unlocking hydrocarbon potential in similarly complicated, low-permeability reservoirs. Full article
(This article belongs to the Special Issue Advanced Technology in Unconventional Resource Development)
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28 pages, 8717 KB  
Article
Thermo-Kinetic Assessment of Ammonia/Syngas Combustion: Experimental and Numerical Investigation of Laminar Burning Velocity at Elevated Pressure and Temperature
by Mehrdad Kiani, Ali Akbar Abbasian Arani, Ehsan Houshfar, Mehdi Ashjaee and Pouriya H. Niknam
Fuels 2025, 6(3), 59; https://doi.org/10.3390/fuels6030059 - 12 Aug 2025
Viewed by 398
Abstract
The utilization of ammonia as a fuel for gas turbines involves practical challenges due to its low reactivity, narrow flammability limits, and slow laminar flame propagation. One of the potential solutions to enhance the combustion reactivity of ammonia is co-firing with syngas. This [...] Read more.
The utilization of ammonia as a fuel for gas turbines involves practical challenges due to its low reactivity, narrow flammability limits, and slow laminar flame propagation. One of the potential solutions to enhance the combustion reactivity of ammonia is co-firing with syngas. This paper presents an experimental and numerical investigation of the laminar burning velocity (LBV) of ammonia/syngas/air mixtures under elevated pressures (up to 10 bar) and temperatures (up to 473 K). Experiments were conducted in a constant-volume combustion chamber with a total volume of 11 L equipped with a dual-electrode capacitive discharge ignition system. A systematic sensitivity analysis was conducted to experimentally evaluate the system performance under various syngas compositions and equivalence ratios from 0.7 to 1.6 and ultimately identify the factors with the most impact on the system. As a complement to the experiments, a detailed numerical simulation was carried out integrating available kinetic mechanisms—chemical reaction sets and their rates—to support advancements in the understanding and optimization of ammonia/syngas co-firing dynamics. The sensitivity analysis results reveal that LBV is significantly enhanced by increasing the hydrogen content (>50%). Furthermore, the LBV of the gas mixture is found to increase with the use of a rich flame, higher mole fractions of syngas, and higher initial temperatures. The results indicate that higher pressure reduces LBV by 40% but at the same time enhances the adiabatic flame temperature (by 100 K) due to an equilibrium shift. The analysis was also extended to quantify the impact of syngas mole fractions and elevated initial temperatures. The kinetics of the reactions are analyzed through the reaction pathways, and the results reveal how the preferred pathways vary under lean and rich flame conditions. These findings provide valid quantitative design data for optimizing the combustion kinetics of ammonia/syngas blends, offering valuable design data for ammonia-based combustion systems in industrial gas turbines and power generation applications, reducing NOₓ emissions by up to 30%, and guiding future research directions toward kinetic models and emission control strategies. Full article
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14 pages, 1537 KB  
Article
Impact of Demineralization on Various Types of Biomass Pyrolysis: Behavior, Kinetics, and Thermodynamics
by Shaoying Shen, Jianping Li, Yuanen Lai, Rui Zhang, Honggang Fan, Wei Zhao, Feng Shen, Yuanjia Zhang and Weiqiang Zhu
Energies 2025, 18(16), 4289; https://doi.org/10.3390/en18164289 - 12 Aug 2025
Viewed by 256
Abstract
This study systematically investigates the effects of demineralization on the pyrolysis characteristics, kinetics, and thermodynamics of three biomass types (eucalyptus, straw, and miscanthus) using thermogravimetric analysis (TGA) combined with multiple kinetic approaches. The Coats–Redfern integral model was employed to determine the reaction mechanisms. [...] Read more.
This study systematically investigates the effects of demineralization on the pyrolysis characteristics, kinetics, and thermodynamics of three biomass types (eucalyptus, straw, and miscanthus) using thermogravimetric analysis (TGA) combined with multiple kinetic approaches. The Coats–Redfern integral model was employed to determine the reaction mechanisms. The results indicate that the primary weight-loss temperature ranges for eucalyptus, straw, and miscanthus were 222.02~500.23 °C, 205.43~500.13 °C, and 202.30~490.52 °C, respectively. Demineralization increased the initial pyrolysis temperature and significantly enhanced the reaction rates. Kinetics analysis revealed that the ash content significantly influences the activation energy of the pyrolysis reaction. The average activation energies follow the trend eucalyptus (193.48 kJ/mol) < miscanthus (245.66 kJ/mol) < straw (290.13 kJ/mol). After demineralization, the activation energies of both straw and miscanthus pyrolysis decreased, with the largest reduction observed in straw, which dropped by 77.53 kJ/mol. However, the activation energy for eucalyptus pyrolysis increased by 12.52 kJ/mol after demineralization. The Coats–Redfern model and thermodynamic analysis demonstrated that each type of biomass followed distinct reaction mechanisms at different stages, which were altered after demineralization. Additionally, demineralization leads to higher ΔH and Gibbs free energy ΔG for eucalyptus, but lower values for straw and miscanthus, which indicate that the ash content has a significant impact on the biomass pyrolysis reaction. These findings provide fundamental insights into the role of ash in biomass pyrolysis kinetics and offer theoretical support for the design of pyrolysis reactors. Full article
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19 pages, 1355 KB  
Article
Exploring the Thermal Degradation of Bakelite: Non-Isothermal Kinetic Modeling, Thermodynamic Insights, and Evolved Gas Analysis via Integrated In Situ TGA/MS and TGA/FT-IR Techniques
by Gamzenur Özsin
Polymers 2025, 17(16), 2197; https://doi.org/10.3390/polym17162197 - 12 Aug 2025
Viewed by 351
Abstract
Thermogravimetric analysis (TGA) is a key technique for evaluating the kinetics and thermodynamics of thermal degradation, providing essential data for material assessment and system design. When coupled with Fourier-transform infrared (FT-IR) spectroscopy or mass spectroscopy (MS), it enables the identification of evolved gases [...] Read more.
Thermogravimetric analysis (TGA) is a key technique for evaluating the kinetics and thermodynamics of thermal degradation, providing essential data for material assessment and system design. When coupled with Fourier-transform infrared (FT-IR) spectroscopy or mass spectroscopy (MS), it enables the identification of evolved gases and correlates mass loss with specific chemical species, offering detailed insight into decomposition mechanisms. In this study, TGA was coupled with FT-IR and MS to investigate the thermal degradation behavior of Bakelite, with the aim of evaluating its kinetic and thermodynamic parameters under non-isothermal conditions, identifying evolved volatile compounds, and elucidating the degradation process. The results showed that higher heating rates led to increased decomposition temperatures and broader dTG peaks due to thermal lag effects. The degradation proceeded in multiple stages between 220 °C and 860 °C, ultimately yielding a carbonaceous residue. The activation energy increased with conversion, particularly beyond 0.5, indicating a greater energy requirement as degradation progressed. Peak values at conversion degrees of 0.8–0.9 suggested enhanced thermal stability or changes in the dominant reaction mechanism. Detailed kinetic analysis revealed complex decomposition pathways with variable activation energies and a pronounced kinetic compensation effect. Thermodynamic analysis confirmed the endothermic nature of the process, with increasing energy demand and non-spontaneous degradation of the resulting char. TGA/FT-IR and TGA/MS analyses identified the release of several compounds, including CO2, water, formaldehyde, and phenolic derivatives, at distinct stages. This comprehensive understanding of Bakelite’s thermal behavior supports its optimization for high-temperature applications, enhances material reliability and safety, and contributes to sustainable processing and recycling strategies. Full article
(This article belongs to the Special Issue Development in Polymer Recycling)
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15 pages, 3654 KB  
Article
Kinetic Analysis of the Reaction of Silver with Elemental Sulfur in Mineral Insulating Oil
by Dejan Kolarski, Jelena Lukić, Jelena Janković and Sandra Glišić
Materials 2025, 18(16), 3771; https://doi.org/10.3390/ma18163771 - 12 Aug 2025
Viewed by 297
Abstract
Elemental sulfur (S8) reacts readily with silver, forming highly conductive silver sulfide on silver-coated components of on-load tap changers (OLTCs), forming a highly conductive silver sulfide film at the surface of an OLTC, which can lead to the failure of critical [...] Read more.
Elemental sulfur (S8) reacts readily with silver, forming highly conductive silver sulfide on silver-coated components of on-load tap changers (OLTCs), forming a highly conductive silver sulfide film at the surface of an OLTC, which can lead to the failure of critical components in power transformers. This study investigates the reaction between metallic silver and elemental sulfur dissolved in mineral insulating oil across temperatures from 60 °C to 180 °C. The process involves three stages: the diffusion of sulfur through oil, surface reaction, and product diffusion. For low-viscosity oil, diffusion is not the limiting factor, and sulfur does not react immediately on the silver’s surface, suggesting possible adsorption or intermediate formation. A kinetic analysis revealed that the reaction follows first-order kinetics, with a change in mechanism above 150 °C. The reaction follows the Arrhenius equation in two separate regions: 60–150 °C and 150–180 °C. Activation energy was calculated as 23.67 kJ mol−1, and it can be concluded that the reaction is controlled by the diffusion of sulfur through mineral oil, and at higher temperatures (150 °C to 180 °C), the calculated activation energy is 160.69 kJ mol−1, which leads to the conclusion that the combined chemisorption and diffusion through a silver sulfide–oil interface becomes the new limiting factor. Full article
(This article belongs to the Section Corrosion)
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27 pages, 7417 KB  
Article
Simulation of Corrosion Cracking in Reinforced Concrete Based on Multi-Phase Multi-Species Electrochemical Phase Field Modeling
by Tianhao Yao, Houmin Li, Keyang Wu, Jie Chen, Zhengpeng Zhou and Yunlong Wu
Materials 2025, 18(16), 3742; https://doi.org/10.3390/ma18163742 - 10 Aug 2025
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Abstract
Non-uniform corrosion cracking in reinforced concrete buildings constitutes a fundamental difficulty resulting in durability failure. This work develops a microscopic-scale multi-species electrochemical phase field model to tackle this issue. The model comprehensively examines the spatiotemporal coupling mechanisms of the full “corrosion-rust swelling-cracking” process [...] Read more.
Non-uniform corrosion cracking in reinforced concrete buildings constitutes a fundamental difficulty resulting in durability failure. This work develops a microscopic-scale multi-species electrochemical phase field model to tackle this issue. The model comprehensively examines the spatiotemporal coupling mechanisms of the full “corrosion-rust swelling-cracking” process by integrating electrochemical reaction kinetics, multi-ion transport processes, and a unified phase field fracture theory. The model uses local corrosion current density as the primary variable to accurately measure the dynamic interactions among electrochemical processes, ion transport, and rust product precipitation. It incorporates phase field method simulations of fracture initiation and propagation in concrete, establishing a bidirectional link between rust swelling stress and crack development. Experimental validation confirms that the model’s predictions about cracking duration, crack shape, and ion concentration distribution align well with empirical data, substantiating the efficacy of local corrosion current density as an indicator of electrochemical reaction rate. Parametric studies were performed to examine the effects of interface transition zone strength, oxygen diffusion coefficient, protective layer thickness, reinforcing bar diameter, and reinforcing bar configuration on cracking patterns. This model’s multi-physics field coupling framework, influenced by dynamic corrosion current density, facilitates cross-field interactions, offering sophisticated theoretical tools and technical support for the quantitative analysis, durability evaluation, and protective design of corrosion-induced cracking in reinforced concrete structures. Full article
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