Search Results (228)

This article presents a review of several non-exclusive pathways for the sequestration of soil organic carbon, which can be classified into two large classical groups: the modification of plant and microbial macromolecules and the abiotic and microbial neoformation of humic substances. Classical studies have established a causal relationship between aromatic structures and the stability of soil humus (traditional hypotheses regarding lignin and aromatic microbial metabolites as primary precursors for soil organic matter). However, further evidence has emerged that underscores the significance of humification mechanisms based solely on aliphatics. The precursors may be carbohydrates, which may be transformed by the effects of fire or catalytic dehydration reactions in soil. Furthermore, humic-type structures may be formed through the condensation of unsaturated fatty acids or the alteration of aliphatic biomacromolecules, such as cutins, suberins, and non-hydrolysable plant polyesters. In addition to the intrinsic value of understanding the potential for carbon sequestration in diverse soil types, biogeochemical models of the carbon cycle necessitate the assessment of the total quantity, nature, provenance, and resilience of the sequestered organic matter. This emphasises the necessity of applying specific techniques to gain insights into their molecular structures. The application of appropriate analytical techniques to soil organic matter, including sequential chemolysis or thermal degradation combined with isotopic analysis and high-resolution mass spectrometry, derivative spectroscopy (visible and infrared), or ¹³C magnetic resonance after selective degradation, enables the simultaneous assessment of the concurrent biophysicochemical stabilisation mechanisms of C in soils. Full article

Searching for new and efficient transfer hydrogenation catalysts, a series of new organometallic ruthenium(II)-arene complexes of the formulae [Ru(η⁶-p-cymene)(L)Cl][PF₆] (1–8) and [Ru(η⁶-p-cymene)(L)Cl][Ru(η⁶-p-cymene)Cl₃] (9–11) were synthesized and fully characterized. These were prepared from the reaction of pyridine–quinoline and biquinoline-based ligands (L) with [Ru(η⁶-p-cymene)(μ-Cl)Cl]₂, in 1:2 and 1:1, metal (M) to ligand (L) molar ratios. Characterization includes a combination of spectroscopic methods (FT-IR, UV-Vis, multi nuclear NMR), elemental analysis and single-crystal X-ray crystallography. The pyridine–quinoline organic entities encountered, were prepared in high yield either via the thermal decarboxylation of the carboxylic acid congeners, namely 2,2′-pyridyl-quinoline-4-carboxylic acid (pqca), 8-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8-Mepqca), 6′-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (6′-Mepqca) and 8,6′-dimethyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8,6′-Me₂pqca), affording the desired ligands pq, 8-Mepq, 6′-Mepq and 8,6′-Me₂pq, or by the classical Friedländer condensation, to yield 4,6′-dimethyl-2,2′-pyridyl-quinoline (4,6′-Me₂pq) and 4-methyl-2,2′-pyridyl-quinoline (4-Mepq), respectively. The solid-state structures of complexes 1–4, 6, 8 and 9 were determined showing a distorted octahedral coordination geometry. The unit cell of 3 contains two independent molecules (Ru-3), (Ru′-3) in a 1:1 ratio, due to a slight rotation of the arene ring. All complexes catalyze the transfer hydrogenation of acetophenone, using 2-propanol as a hydrogen donor in the presence of KOiPr. Among them, complexes 1 and 5 bearing methyl groups at the 8 and 4 position of the quinoline moiety, convert acetophenone to 1-phenylethanol quantitatively, within approximately 10 min with final TOFs of 1600 h⁻¹. The catalytic performance of complexes 1–11, towards the transfer hydrogenation of p-substituted acetophenone derivatives and benzophenone, ranges from moderate to excellent. An inner-sphere mechanism has been suggested based on the detection of ruthenium(II) hydride species. Full article

The mechanism for the upscale deposition of energy into the atmosphere from molecules and photons up to organized wind systems is examined. This analysis rests on the statistical multifractal analysis of airborne observations. The results show that the persistence of molecular velocity after collision in breaking the continuous translational symmetry of an equilibrated gas is causative. The symmetry breaking may be caused by excited photofragments with the associated persistence of molecular velocity after collision, interaction with condensed phase surfaces (solid or liquid), or, in a scaling environment, an adjacent scale having a different velocity and temperature. The relationship of these factors for the solution to the Navier–Stokes equation in an atmospheric context is considered. The scale invariant version of Gibbs free energy, carried by the most energetic molecules, enables the acceleration of organized flow (winds) from the smallest planetary scales by virtue of the nonlinearity of the mechanism, subject to dissipation by the more numerous average molecules maintaining an operational temperature via infrared radiation to the cold sink of space. The fastest moving molecules also affect the transfer of infrared radiation because their higher kinetic energy and the associated more-energetic collisions contribute more to the far wings of the spectral lines, where the collisional displacement from the central energy level gap is greatest and the lines are less self-absorbed. The relationship of events at these scales to macroscopic variables such as the thermal wind equation and its components will be considered in the Discussion section. An attempt is made to synthesize the mechanisms by which winds are generated and sustained, on all scales, by appealing to published works since 2003. This synthesis produces a view of the general circulation that includes thermodynamics and the defining role of turbulence in driving it. Full article

Despite the availability of various materials for chimney applications, ongoing research seeks alternatives with improved thermal and chemical resistance. Geopolymers are a promising solution, exhibiting exceptional resistance to high temperatures, fire, and aggressive chemicals. This study investigates fly ash-based lightweight geopolymer concretes that incorporate expanded clay aggregate (E.C.A.), perlite (P), and foamed geopolymer aggregate (F.G.A.). The composites were designed to ensure a density below 1200 kg/m³, reducing overall weight while maintaining necessary performance. Aggregate content ranged from 60 to 75 wt.%. Physical (density, thickness, water absorption), mechanical (flexural and compressive strength), and thermal (conductivity, resistance) properties were evaluated. F.G.A. 60 achieved a 76.8% reduction in thermal conductivity (0.1708 vs. 0.7366 W/(m·K)) and a 140.4% increase in thermal resistance (0.1642 vs. 0.0683). The F.G.A./E.C.A./P 60 mixture showed the highest compressive strength (18.069 MPa), reaching 52.7% of the reference concrete’s strength, with a 32.3% lower density (1173.3 vs. 1735.0 kg/m³). Water absorption ranged from 4.9% (REF.) to 7.3% (F.G.A. 60). All samples, except F.G.A. 70 and F.G.A. 75, endured heating up to 800 °C. The F.G.A./E.C.A./P 60 composite demonstrated well-balanced performance: low thermal conductivity (0.2052 W/(m·K)), thermal resistance up to 1000 °C, flexural strength of 4.386 MPa, and compressive strength of 18.069 MPa. The results confirm that well-designed geopolymer lightweight concretes are suitable for chimney and flue pipe linings operating between 500 and 1000 °C and exposed to acidic condensates and aggressive chemicals. This study marks the initial phase of a broader project on geopolymer-based prefabricated chimney systems. Full article

Earth materials in construction demonstrate significant potential attributed to their accessibility, recyclability, and low energy demands for processing. Modern techniques have enhanced their mechanical strength and durability, enabling their application in load-bearing and infill walls while preserving ecological benefits. However, existing studies on indoor heat–humidity regulation primarily emphasize material parameters and macro-level performance. Moreover, the dynamic interactions between the unique thermal storage–release mechanisms and indoor environments have not been systematically analyzed. With the Kelvin equation, capillary mechanics, adsorption theories, and microstructural analysis were integrated in this study to quantify cyclic capillary condensation and evaporation in microvoids. The results reveal that earth materials contain abundant medium-sized pores (19.85–53.83 nm) sustaining vapor exchange with their surroundings. Capillary condensation occurs 0.86–0.96 times the planar surface vapor pressure, influenced by pore size (negatively correlated) and temperature (negatively correlated). During the daytime, capillary evaporation occurs in the nanopores of the raw earth wall under the influence of the outdoor environment’s cyclical temperature and humidity. This process absorbs heat from the indoor environment and raises the ambient humidity. During the nighttime, capillary condensation occurs in the pores, releasing heat to the indoor area and absorbing moisture from the environment, contributing to the balance of the indoor thermal environment of the earth buildings. The findings lay a scientific foundation for quantitatively evaluating earth buildings’ indoor climate control performance, supporting their integration into green building systems. This research bridges knowledge gaps in micro-to-macro thermal dynamics while advancing the ecological optimization of materials for sustainable architecture. Full article

The polycondensation of silica from soluble silicic acid is at the basis of several chemical processes. The usual industrial route requires harsh pH conditions and high concentrations of the precursor molecules, not to mention a thermal treatment for obtaining condensed structures. On the other hand, biological organisms can promote the precipitation of silica under physiological conditions, including temperature and pH, and low concentrations of precursors. The key to this process is the use of polycationic molecules. Despite the relevance of these processes in modern industrial inorganic chemistry, this fascinating process is still not completely understood. Recent studies converge in pointing out that the role of the polycation is to create supersaturation of silicic acid in its immediate proximity, which would explain the impact of the polycation on the reaction rates. However, it remains unclear whether these polycations also directly influence the reaction mechanism at a molecular level. In this manuscript, we address this question by analyzing the reaction pathway of silicic acid dimerization in the presence of guanidinium as a mimic of the arginine side chain, through DFT calculations. We found that the impact on the reaction pathway is minimal, which strengthens the hypothesis of the local supersaturation driven by the polycationic molecules. Full article

This study explores how production technology influences spray-applied rigid polyurethane (PUR) foam insulation’s cryogenic performance. In cryogenic applications such as liquid gas storage, insulation must minimise heat transfer and resist moisture ingress under severe thermal gradients. Experimental aluminium vessels were insulated with PUR foam of varying thicknesses and surface conditions—rough, machined smooth, and with a urea-based protective coating—and then tested using dynamic boil-off of liquid nitrogen (LN₂). Foam properties, including adhesion, mechanical strength, thermal expansion, thermal conductivity, and closed-cell content, were evaluated. The results revealed that thicker insulation reduced both effective thermal conductivity and moisture uptake. Although the urea-coated vessel showed minimal water absorption, the coating increased overall thermal conductivity due to its heat conduction and condensation behaviour. Moisture was primarily absorbed near the foam surface, and no cumulative effects were observed during repeated tests. The effective thermal conductivity was determined by interpolating boil-off data, confirming that insulation performance strongly depends on thickness, surface condition, and environmental humidity. These findings provide valuable guidance for the design and application of PUR foam insulation in cryogenic environments. Full article

With the rapid advancement of electronic devices toward higher frequencies, faster speeds, increased integration, and miniaturization, the resulting elevated operating temperatures pose significant challenges to the performance and longevity of electronic components. These developments have intensified the demand for high-performance thermal interface materials (TIMs). Conventional silicone rubber-based TIMs often suffer from silicone oil-bleeding and the volatilization of low-molecular-weight siloxanes under elevated temperatures and mechanical stress. The release of these volatile organic compounds can lead to their deposition on circuit boards and electronic components, causing signal interference or distortion in optical and electronic systems, ultimately compromising device functionality. Additionally, the intrinsic thermal conductivity of traditional TIMs is insufficient to meet the escalating demands for efficient heat dissipation. To overcome these limitations, this study introduces a novel, non-silicone TIM based on a calcium ion-crosslinked sodium alginate matrix, prepared via ion-exchange curing. This bio-derived polymer matrix serves as an environmentally benign alternative to silicone rubber. Furthermore, a brush-coating technique is employed to induce the oriented alignment of boron nitride (BN) fillers within the alginate matrix. Experimental characterization reveals that this aligned microstructure markedly enhances the thermal conductivity of the composite, achieving a value of 7.87 W·m⁻¹·K⁻¹. The resulting material also exhibits outstanding thermal and mechanical stability, with no observable leakage or condensate formation under high-temperature and high-pressure conditions. This work offers a new design paradigm for environmentally friendly, high-performance TIMs with considerable potential for advanced electronic and optoelectronic applications. Full article

Heat pipes are highly efficient heat transfer devices relying on phase-change mechanisms, with performance heavily influenced by working fluids and operational dynamics. This review article comprehensively examines hydrodynamics and heat transfer in heat pipes, contrasting conventional working fluids with nanofluid-enhanced systems. In the present work we discuss mathematical models governing fluid flow and heat transfer, emphasizing continuum and porous media approaches for wick structures. Functional dependencies of thermophysical properties (e.g., viscosity, surface tension, thermal conductivity) are reviewed, highlighting temperature-driven correlations and nanofluid modifications. Transport mechanisms within wicks are analyzed, addressing capillary-driven flow, permeability, and challenges posed by nanoparticle integration. Fourth, interfacial phase-change conditions—evaporation and condensation—are modeled, focusing on kinetic theory and empirical correlations. Also, numerical and experimental results are synthesized to quantify performance enhancements from nanofluids, including thermal resistance reduction and capillary limit extension, while addressing inconsistencies in stability and pressure drop trade-offs. Finally, applications spanning electronics cooling, aero-space, and renewable energy systems are evaluated, underscoring nanofluids’ potential to expand heat pipe usability in extreme environments. The review identifies critical gaps, such as long-term nanoparticle stability and scalability of lab-scale models, while advocating for unified frameworks to optimize nanofluid selection and wick design. This work serves as a foundational reference for researchers and engineers aiming to advance heat pipe technology through nanofluid integration, balancing theoretical rigor with practical feasibility. Full article

Thermotropic polyesters are a subject of keen interest due to their exceptional heat resistance, thermal stability, and high strength. However, these thermal characteristics pose significant constraints on standard manufacturing processes, as the melting temperatures of these polymers can exceed 300 °C. This study explored the feasibility of manufacturing final items molded from prepolymers through a solid-state polymerization process. A copolymer composed of 4-acetoxybenzoic acid (4ABA), 3-acetoxybenzoic acid (3ABA), and 4′-acetoxybiphenyl-4-carboxylic acid (ABCA) was synthesized using melt polycondensation. To comprehensively evaluate the performance of the resulting material, several sets of samples were prepared, including those containing TiO₂. Experimental samples from the pre-polymers were obtained through injection molding followed by high-temperature solid-state post-polymerization. The final products underwent a range of tests, including rheological and mechanical analyses, as well as thermal evaluations. The products demonstrated sufficient strength and stability. The proposed method of solid-state post-condensation offers significant potential advantages for the practical application of manufacturing high-performance engineering materials. Full article

Condensate oil, due to its inherent physical and chemical properties, can accelerate the spontaneous combustion of corrosion products in storage tanks during transportation or storage, posing significant risks to the safety and sustainability of energy infrastructure. While prior research has primarily examined crude oil or reactive sulfur effects on tank corrosion, the mechanistic role of condensate oil in promoting corrosion product ignition remains unclear. To address this knowledge gap, this study investigates the impact of condensate oil on simulated tank corrosion product compounds (STCPCs) through a combination of microstructural analysis (XRD and SEM) and thermal behavior characterization (TG-DSC). The results reveal that condensate oil treatment markedly increases STCPC surface roughness, inducing crack formation and pore proliferation. These structural changes may enhance the adsorption of O₂ and condensate oil, thereby amplifying STCPC reactivity. Notably, condensate oil reduces the thermal stability of STCPC, increasing its spontaneous combustion propensity. DSC analysis further demonstrates that condensate oil introduces additional exothermic peaks during oxidative heating, releasing heat that accelerates STCPC ignition. Moreover, condensate oil lowers the apparent activation energy of STCPC by 1.44 kJ/mol and alters the dominant reaction mechanism. These insights advance the understanding of corrosion-induced spontaneous combustion and highlight critical sustainability challenges in petrochemical storage and transportation. By elucidating the hazards associated with condensate oil, this study provides actionable theoretical guidance for improving the safety and environmental sustainability of energy logistics. Future work should explore mitigation strategies, such as corrosion-resistant materials or optimized storage conditions, to align industrial practices with sustainable development goals. Full article

This study explores sustainable foamed polyester materials derived from natural or bio-based building blocks, including succinic, glutaric, and adipic acids, combined with trimethylolpropane and pentaerythritol. By precisely tuning the ratio of functional groups, the resulting polymers contain minimal free functionalities, leading to lower hygroscopicity and enhanced stability. The reaction is monitored by tracking the mass loss associated with water formation, the primary condensation by-product, which reveals a first-order kinetic behaviour. Infrared spectroscopy indicates that foaming occurs in a narrow time window, while esterification begins earlier and continues afterwards. Thermogravimetric analysis confirms thermal stability up to ~400 °C, with complete decomposition at 500 °C and no residue. Scanning electron microscopy images of test specimens with varying densities reveal dense, microporosity-free cell walls in both materials, indicating a homogeneous polymer matrix that contributes to the overall stabilisation of the foam structure. In flammability tests, the foams resist ignition during two 10 s methane flame exposures and, under prolonged flame, burn 40 times more slowly than conventional foams. These results demonstrate a modular system for creating bio-based foams with tunable properties—from soft and elastic to rigid—suitable for diverse applications. The materials offer a sustainable alternative to petrochemical foams while retaining excellent mechanical and thermal properties. Full article

The Paleozoic strata in the Kongxi slope zone of the Dagang oilfield, Huanghua depression, exhibit significant hydrocarbon exploration potential. Although bitumen is widely present in the Paleozoic reservoirs, its formation process and genetic mechanism remain poorly understood. This study systematically investigates the occurrence, maturity, origin, and evolutionary processes of Paleozoic reservoir bitumen in the Kongxi zone through core observations, microscopic analyses, geochemical testing, and thermal simulation experiments. The results reveal that reservoir bitumen in the Kongxi slope zone is characteristically black with medium to medium-high maturity. In core samples, bitumen occurs as bands, veins, lines, and dispersions within partially filled fractures and breccia pores. Petrographic analysis shows bitumen partially occupying intergranular pores and intergranular pores of Lower Paleozoic carbonate rocks and Upper Paleozoic sandstones, either as complete or partial pore fills. Additional bitumen occurrences include strip-like deposits along microfractures and as bitumen inclusions. Dark brown bitumen fractions were also identified in crude oil separates. The formation and evolution of Paleozoic reservoir bitumen in the Kongxi slope zone occurred in two main stages. The first-stage bitumen originated from Ordovician marine hydrocarbon source rocks, subsequently undergoing oxidative water washing and biodegradation during tectonic uplift stage. This bitumen retains compositional affinity with crude oils from Lower Paleozoic carbonate rocks. Second-stage bitumen formed through the thermal evolution of Carboniferous crude oil during deeper burial, showing compositional similarities with Carboniferous source rocks and their oil. This two-stage bitumen evolution indicates charging events in the Paleozoic reservoirs. While early uplift and exposure destroyed some paleo-reservoirs, unexposed areas within the Dagang oilfield may still contain preserved primary accumulations. Furthermore, second-stage hydrocarbon, dominated condensates derived from Carboniferous coal-bearing sequences since the Eocene, experienced limited thermal evolution to form some bitumen. These condensate accumulations remain the primary exploration target in the Paleozoic Formations. Full article

The Second Law of Thermodynamics states that entropy S increases in a spontaneous process in an ideal isothermal and isolated system. Real systems are influenced by external forces and fields, including the temperature field. In this case, only entropy is not enough, and we suggest using a new function, $L_s$, which is analogous to the Lagrangian in classical mechanics. It includes total potential energy but instead of mechanical kinetic energy, $L_s$ includes the product ST, and the system always evolves towards increasing this modified Lagrangian. It reaches an equilibrium when total potential force is balanced by both entropic and thermal forces. All forces have the same units, Newton/mol, and may be added or subtracted. For condensed systems with friction forces, it is a molecular transport velocity, and not acceleration, which is proportional to the acting force. Our approach has several advantages compared to Onsager’s non-equilibrium thermodynamics with its thermodynamic forces, which may have different units, including 1/T for energy transport. For isolated systems, the description is reduced to Second Law and Clausius inequality. It easily explains diffusion, Dufour effect, and Soret thermodiffusion. The combination of electric, thermal, and entropic forces explains thermoelectric phenomena, including Peltier–Seebeck and Thomson (Lord Kelvin) effects. Gravitational and entropic forces together inside a black hole may lead to a steady state or the black hole evaporation. They are also involved in and influenced by solar atmospheric processes. Full article

As a bio-based polymer, polybutylene succinate (PBS) has extensive applications in plastic products and film manufacturing. However, its low melt strength results in poor spinnability, and during the forming process, it tends to form large-sized spherulites and exhibit filament adhesion phenomena. These limitations have hindered its development in the field of fiber spinning. To enhance fiber strength, this work systematically investigated the effects of spinning temperature and spinning speed on the properties and structure of PBS pre-oriented yarns (PBS-POY). The results indicated that appropriately lowering the spinning temperature and increasing the spinning speed could improve the mechanical properties of the fibers. When the spinning temperature was 195 °C and the spinning speed reached 2500 m/min, the tensile strength of pre-oriented yarns achieved 2.09 cN/dtex. Furthermore, the evolution of properties and structures of pre-oriented yarns under maximum drawing conditions across different spinning speed systems was examined. By synchronously analyzing the correlations among mechanical properties, thermal behavior and condensed state structures, the structural performance regulation mechanism under the synergistic effect of spinning–drawing processes was revealed. The results demonstrated that fibers produced at higher spinning speeds contained more numerous and smaller spherulites. After maximum drawing, these smaller spherulites split into lamellae with higher uniformity, resulting in final fibers with smaller crystal sizes, higher crystallinity and improved orientation. As the spinning speed increased, the average crystal size of the final fibers decreased; the long period of the final fibers extended from 8.55 nm to 9.99 nm, and the mechanical strength improved to 2.72 cN/dtex. Full article