Thermodynamic Model Research Articles

Performance improvement of glass-based lightweight aggregates through thermodynamic modelling design and lightweight mortar validation

To reduce environmental impact of sintered lightweight aggregates (LWAs), in this study, novel glass-based LWAs were produced from municipal solid wastes at 900 °C. The mix was designed by thermodynamic modelling to optimize the phase composition, liquid phase properties, and microstructure of the LWAs. Results demonstrated that the inclusion of incinerated sewage sludge ash (ISSA) increased the viscosity of the liquid phase, resulting in a refined pore structure characterized by smaller, more isolated pores, and thicker pore walls. Additionally, ISSA facilitated the formation of various crystalline phases (e.g. wollastonite) to stabilize the pore structure, thereby enhancing densification and matrix strength. Leaching behaviour tests confirmed the suitability of glass-based LWAs for environmentally safe lightweight products. Lightweight mortars incorporating developed LWAs exhibited a high 28-day compressive strength (up to 57.9 MPa) with a low density of 1688 kg/m3 and a low thermal conductivity of 1.0 W/(m·K). The energy simulation revealed substantial reductions in energy consumption when the lightweight mortars were utilized in the building compared with the reference building using normal-weight C30 concrete, underscoring its promising role in conserving energy and reducing carbon emissions.

Modelling and simulation of growth driven by mechanical and non-mechanical stimuli

Living tissues can remarkably adapt to their mechanical and biochemical environments through growth and remodelling mechanisms. Over the years, extensive research has been dedicated to understanding and modelling the complexities of growth. However, the majority of growth laws are based on phenomenological, ad hoc, proposed evolution equations. This work aims to describe a general bulk growth model that developed in the framework of generalised continuum mechanics. This new model of growth is based on a continuum description of the growth process and is an extension of the work of DiCarlo and Quiligotti of the early 2000s. This model builds on the virtual power principle, and the constitutive theory is thermodynamically consistent. The proposed framework allows the inclusion of different constitutive theories linking the elastic strain and stresses, together with accommodating different non-mechanical mechanisms. Moreover, the framework supports anisotropy of both the material and growth, allowing the exploration of complex growth processes further. The descriptive capabilities of the model are demonstrated through numerical benchmarks and simulations describing real-life scenarios, such as the growth of the spine and an artery. The simulation results indicate that the developed thermodynamic consistent growth model is versatile and holds the potential to capture the complexities of living tissue growth, offering valuable insights into biological phenomena and pathologies.

Development of a DFT-driven thermodynamic framework for ferrous alloy electrochemistry in acidic media

The electrochemical behavior of different phases (ferrite, austenite, martensite, cementite) and effect of alloying addition in ferrous alloys was examined in acidic media. A comprehensive thermodynamic model, incorporating first-principles calculations, was constructed to predict cathodic and anodic behavior in acidic environments. Cementite emerged as the most corrosion resistant phase, followed by austenite, while ferrite displayed the least resistance. Interestingly, carbon additions improved corrosion resistance in ferrite and austenite. Alloying with Cr, Mn, and Cu was observed to hinder anodic dissolution, reducing electrochemical activity. Finally, the thermodynamic framework provides a reliable and efficient screening tool that can accelerate the development of alloys and coatings.

Thermodynamic modeling and process evaluation of advanced ionic liquid-based solvents for CO2/CH4 separation

Carbon capture technology is a prospective strategy to address the increasing concentration of CO2 in the atmosphere, with the core challenge of developing new cost-effective processes. In this work, the energy analysis and economic evaluation were conducted based on rigorous thermodynamic models and the process simulation results of a novel chemical absorption-dominated hybrid solvent which consists of functional ionic liquid of choline triazole ([Cho][Triz]) and sulfolane (TMS) to separate CO2 from shale gas. The solubility of CO2 and CH4 in different solvents were calculated using phase equilibrium model including the NRTL activity coefficient equation, the RK equation of state, chemical reaction equilibrium equations, and the mass balance equation. The physical properties of the ionic liquid-based solvent systems were calculated with empirical equations which was corrected using experimental data. The results obtained from the thermodynamic models exhibited good agreement with experimental data. Subsequently, the established models and the parameters obtained were embedded into Aspen Plus for further analysis. The total CO2 capture energy consumption of 1.65 GJ·t−1 CO2 and the cost of 48.07 $·t−1 CO2 were achieved using the new solvent when the mass fraction of IL was 60 wt%. Compared with the commercial 30 wt% MDEA carbon capture process, it reduced the energy consumption and economic cost of 64.16 % and 45.59 %, respectively.

Improving the Estimation of Lake Ice Thickness with High-Resolution Radar Altimetry Data

Lake ice thickness (LIT) is a sensitive indicator of climate change, identified as a thematic variable of Lakes as an Essential Climate Variable (ECV) by the Global Climate Observing System (GCOS). Here, we present a novel and efficient analytically based retracking approach for estimating LIT from high-resolution Ku-band (13.6 GHz) synthetic-aperture radar (SAR) altimetry data. The retracker method is based on the analytical modeling of the SAR radar echoes over ice-covered lakes that show a characteristic double-peak feature attributed to the reflection of the Ku-band radar waves at the snow–ice and ice–water interfaces. The method is applied to Sentinel-6 Unfocused SAR (UFSAR) and Fully Focused SAR (FFSAR) data, with their corresponding tailored waveform model, referred to as the SAR_LIT and FFSAR_LIT retracker, respectively. We found that LIT retrievals from Sentinel-6 high-resolution SAR data at different posting rates are fully consistent with the LIT estimations obtained from thermodynamic lake ice model simulations and from low-resolution mode (LRM) Sentinel-6 and Jason-3 data over two ice seasons during the tandem phase of the two satellites, demonstrating the continuity between LRM and SAR LIT retrievals. By comparing the Sentinel-6 SAR LIT estimates to optical/radar images, we found that the Sentinel-6 LIT measurements are fully consistent with the evolution of the lake surface conditions, accurately capturing the seasonal transitions of ice formation and melt. The uncertainty in the LIT estimates obtained with Sentinel-6 UFSAR data at 20 Hz is in the order of 5 cm, meeting the GCOS requirements for LIT measurements. This uncertainty is significantly smaller, by a factor of 2 to 3 times, than the uncertainty obtained with LRM data. The FFSAR processing at 140 Hz provides even better LIT estimates, with 20% smaller uncertainties. The LIT retracker analysis performed on data at the higher posting rate (140 Hz) shows increased performance in comparison to the 20 Hz data, especially during the melt transition period, due to the increased statistics. The LIT analysis has been performed over two representative lakes, Great Slave Lake and Baker Lake (Canada), demonstrating that the results are robust and hold for lake targets that differ in terms of size, bathymetry, snow/ice properties, and seasonal evolution of LIT. The SAR LIT retrackers presented are promising tools for monitoring the inter-annual variability and trends in LIT from current and future SAR altimetry missions.

Hydrogen storage solutions for residential heating: A thermodynamic and economic analysis with scale-up potential

The study presents a thermodynamic and economic assessment of different hydrogen storage solutions for heating purposes, powered by PV panels, of a 10-apartment residential building in Milan, and it focuses on compressed hydrogen, liquid hydrogen, and metal hydride. The technical assessment involves using Python to code thermodynamic models to address technical and thermodynamic performances. The economic analysis evaluates the CAPEX, the ROI, and the cost per unit of stored hydrogen and energy. The study aims to provide an accurate assessment of the thermodynamic and economic indicators of three of the storage methods introduced in the literature review, pointing out the one with the best techno-economic performance for further development and research. The performed analysis shows that compressed hydrogen represents the best alternative but its cost is still too high for small residential applications. Applying the technology to a big system case would enable the solution making it economically feasible.

Thermodynamic modeling of silicon carbide formation during the Acheson process in non-stoichiometric mixtures

A brief review and critical evaluation of the literature related to the mechanism of carbothermic reduction of silicon oxide is presented. To resolve the contradictions in the literature data about the number of chemical reactions and key intermediate substances during the Acheson process, thermodynamic modeling of products of carbothermic reduction of silicon (IV) oxide at 1 bar total pressure was carried out. It was determined that CO2 and Si were absent among the intermediates at temperatures close to the silicon carbide formation temperature (from 1520 to ~2500 °С). Out of several dozen possible reactions, the two dominant reactions that result in the formation of silicon carbide in the Acheson process were identified. The effect of reagents temperature from 1000 to 3000 °С, bulk and local deviation from stoichiometry of the initial mixture on the composition of the reaction products was discovered. Obtained new data explains some empirical observations and greatly simplifies the physicochemical modeling of the Acheson process.

Study on the carbon migration from fossil fuel to liquid methanol by integrating solar energy into the advanced power system

Coupling advanced systems with carbon dioxide (CO2) capture and CO2-to-methanol technologies is a possible solution for both greenhouse gas emissions and low-carbon use of fossil energy. In view of this, this study further develops an advanced molten carbonate fuel cell (MCFC)/steam turbine (ST) hybrid system. The existing single pressurized liquefaction for storing CO2 is expanded to co-exist with liquid methanol synthesis for storing CO2. In detail, the valid thermodynamic models are presented, and the evaluation criteria for energy conversion are described. The case study shows that the energy efficiency of the referenced MCFC/ST system reaches about 62.60 %, without cutting down this performance, the photovoltaic methanol efficiency is in the range of about 54 %–63 %, which is at a current leading level. This study also investigates the effect of oxygen purity in cryogenic air separation unit (ASU), hydrogen production pressure of proton membrane electrolytic cells (PEMEC), and incident irradiation on CO2-to-methanol conversion. The results indicate that O2 purity of 0.97 in ASU, H2 production pressure of 13.6 bar in PEMEC and a dual-axis tracking method is recommended. These findings provide theoretical guidance for improving the CO2-to-methanol performance and providing a possible solution to the storage of intermittent renewable electricity.

Separation of 2-ethoxyethanol from wastewater by four esters: Correlation of LLE thermodynamic modeling, influence of molecular structure, and investigation of component interactions

To prevent the wastewater containing 2-ethoxyethanol (2EE) from causing environmental pollution and economic waste, liquid–liquid extraction was used to recover 2-ethoxyethanol from wastewater in this study. The liquid–liquid equilibrium behavior of water + 2-ethoxyethanol + four solvents (propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate) was investigated at 303.2 K and atmospheric pressure. The distribution coefficient (D) and separation factor (S) were used to compare and discuss the extraction efficiency of each system. The results indicated that all esters could effectively separate 2-ethoxyethanol from water. Among them, isobutyl acetate exhibited the highest values for D and S, demonstrating its superior separation capability. The experimental data were correlated with the thermodynamic model and interaction parameters were obtained. These parameters were verified using the GUI-MATLAB tool, and all four systems passed validation, confirming the reliability of the obtained binary interaction parameters. Furthermore, the root mean square deviation (RMSD) was used to assess the deviation between the experimental and regression values. The RMSD values for the NRTL and UNIQUAC models were 0.008 and 0.007, respectively. The interactions between 2-ethoxyethanol and water or esters were explored using σ-Profile, and it was found that esters with a branched chain structure provided better extraction. To explain the properties of the extractants microscopically, the interaction energies between 2-ethoxyethanol molecules and water or ester molecules, as well as the non-bonding energies of 2-ethoxyethanol in different media, were calculated.

Crystal structure and crystal chemistry of the τ-Mg32(Al,Zn)49 solid solution using first-principles calculations and thermodynamic modelling

This paper presents a study of the crystal structure and crystal chemistry of the τ-Mg32(Al,Zn)49 phase. We first performed DFT calculations to resolve conflicting data concerning the occupancy of site 2a of the solid solution crystal structure. Subsequently, 16 ordered configurations derived from the mixing of Al/Zn on sites 24g1, 24g2 and 48h of the solid solution structure, as well as the mixing of Mg/Zn on site 12e1 were generated. We then used DFT calculations to derive the formation enthalpies of all the end-members of the solid solution, their elastic constants by imposing 51 finite deformations for each end-member, and their energies as a function of volume. These calculations were used in a Debye-Wang model (in Slater form) to calculate the heat capacities of the 16 end-members and to obtain in fine their Gibbs energies. At last, these calculations were used to support a thermodynamic model based on the Bragg-Williams approximation, enabling all mixed sites occupancies to be calculated at any temperature and chemical composition. For instance, the predictions we carried out at 633 K and 800 K are in very good agreement with the available measurements. On the basis of these new results, we have determined the chemical ordering of the solid solution over a very wide range of chemical composition and temperature, which has enabled us to propose a new sublattice model for the τ-Mg32(Al,Zn)49 solid solution. This sublattice model is both simpler and more accurate than all the other models used in the literature since it agrees with the crystal structure and the crystal chemistry of the τ-Mg32(Al,Zn)49 phase in a large range of temperature and chemical composition.

Evaluating the impact of control measures on sulfate-nitrate-ammonium aerosol variations and their formation mechanism in northern China during 2022 Winter Olympic Games

Sulfate, nitrate, and ammonium (SNA) significantly contribute to fine particulate matter (PM2.5). To ensure good air quality during 2022 Winter Olympic Games (WOG), stringent control measures were implemented in northern China. In this study, comprehensive atmospheric observations were conducted from 2022 January to March in four representative cities to investigate the changes in SNA and their formation mechanism in response to these control measures. The SNA concentrations obviously decreased (29.45%–42.83%) during the control periods in the four cities, but their proportion of PM2.5 remained relatively stable (>50%). SNA was the key factor driving the decrease and increase in the PM2.5 concentration during WOG, with nitrate making the most prominent contribution. The formation of SNA was largely dominated by aqueous heterogeneous chemistry instead of gas-phase oxidation. However, the aerosol liquid water content (ALWC) decreased while odd oxygen (OX) increased during the control periods. Such a variation influenced the role of aqueous heterogeneous and gas-phase reactions in SNA formation, with the former's dominant role being replaced by the latter. After the control periods, the aqueous heterogeneous reactions were enhanced again due to the increased ALWC. Among the cities in the study region, SNA formation became more intense from north to south with increased air temperature and relative humidity (RH). Moreover, ISORROPIA-II thermodynamic modelling revealed notable impacts of sulfate, ammonium, and nonvolatile cations (NVCs) on variations in particle acidity throughout WOG. These results provide a more comprehensive understanding of SNA responses to pollution control on a regional scale and insight into future conventional control.

Construction of coal fly ash-based spherical grain adsorbents and their adsorption characteristics on phenolic compounds

Addressing the significant emissions and severe pollution hazards posed by coal fly ash waste in the coal chemical industry, as well as the challenges in recovering phenolic substances from coal chemical wastewater, this study utilized coal fly ash as a raw material to construct two types of spherical grain adsorbents: coal fly ash and coal gangue spherical grain (CFAGsg) and coal fly ash and pyrite spherical grain (CFAPsg). The adsorption performance of CFAGsg and CFAPsg towards phenolic substances in coal chemical wastewater was investigated. The research results demonstrated that CFAGsg and CFAPsg exhibited adsorption capacities of 20.31 mg/L and 30.42 mg/L for phenol, respectively, and maintained stable adsorption performance even after multiple regeneration cycles. Further analysis using kinetic, isotherm, and thermodynamic models, along with various characterization techniques, revealed that the adsorption of phenol onto CFAGsg and CFAPsg was primarily governed by physical and chemical adsorption, involving an endothermic reaction. Moreover, the study on the adsorption mechanism of phenol revealed that the adsorption behavior of CFAGsg and CFAPsg was mainly driven by pore filling, π-π stacking, and hydrogen bonding. Additionally, hydrophobic interactions were involved in the adsorption of phenol onto CFAGsg, while surface complexation forces played a role in the adsorption of phenol onto CFAPsg. Overall, the research findings provide vital theoretical support and practical application prospects for the high-value utilization of coal fly ash and the clean production of the coal chemical industry.

Molecular interactions and thermodynamic modelling of N,N-dimethyl benzyl amine-alkoxy ethanol mixtures: an FT-IR spectroscopy and Jouyban–Acree model approach

ABSTRACT This study examines intermolecular interactions in binary mixtures of N,N-dimethyl benzyl amine (DMBA) with short-chain alkoxy ethanols (2-methoxy ethanol (ME), 2-ethoxy ethanol (EE) and 2-butoxy ethanol (BE)). Densities (ρ), speeds of sound (u) and viscosities (η) were measured from 303.15 K to 313.15 K at atmospheric pressure for all compositions. These data were used to determine excess thermodynamic and transport properties: excess molar volume (V E ), excess isentropic compressibility (κs E ), viscosity deviation (Δη) and excess Gibbs free energy of activation (ΔG *E ). Partial and infinite dilution molar partial properties were also calculated. Results focus on complex formation driven by chemical forces. The Jouyban–Acree model predicted these properties, with accuracy assessed using mean relative deviations (MRDs) and individual relative deviations (IRDs). FTIR spectroscopy provided additional insights into intermolecular interactions.

Entropy of Liquid Water as Predicted by the Two-Phase Thermodynamic Model and Data-Driven Many-Body Potentials.

We investigate the entropy of liquid water at ambient conditions using the two-phase thermodynamic (2PT) model, applied to both common pairwise-additive water models and the MB-pol and MB-pol(2023) data-driven many-body potentials. Our simulations demonstrate that the 2PT model yields entropy values in semiquantitative agreement with experimental data when using MB-pol and MB-pol(2023). Additionally, our analyses indicate that the entropy values predicted by pairwise-additive water models may benefit from error compensation between the inherent approximations of the 2PT model and the known limitations of these water models in describing many-body interactions. Despite its approximate nature, the simplicity of the 2PT model makes it a valuable tool for estimating relative entropy changes of liquid water across various environments, especially when combined with water models that provide a consistently robust representation of the structural, thermodynamic, and dynamical properties of liquid water.

Bending shape memory properties and multi-scale viscoelastic behaviors of knitted-fabric reinforced polymer composites

Knitted fabrics with easily deformable loop structure have the potential in the development of shape memory polymeric composites with large recovery deformations. The knitted fabric reinforced shape memory epoxy polymer composites (SMPC) were prepared in this work. The effects of loop densities, orientations and bending radii on shape memory properties of SMPC were investigated. The shape fixity ratio and shape recovery ratio of SMPC subjected to U-shaped bending radius of 5 mm are above 98 %. The shape recovery force of SMPC can reach up to 5.9 N. The thermodynamic properties of SMP were also characterized to obtain mechanical parameters and a user-defined material subroutine (UMAT) of shape memory epoxy polymer (SMEP) was written. Based on viscoelastic theory and the multi-scale geometrical structures, the macroscopic homogeneous thermodynamic model and mesoscopic thermodynamic model of knitted fabric reinforced SMPC were established to study the macro-scale stress distribution and meso-scale deformation evolution during shape memory process, respectively. The neutral surface position of SMPC during bending deformation is offset inner. The unique anisotropic loop structure of knitted fabric determines the shape memory behavior of the SMPC. Finally, micro-CT characterizations of knitted fabric reinforced SMPC were conducted to further understand the loop deformation mechanism during shape memory process. This study will provide important theoretical and technical support for large deformation structure design and deformation prediction of smart composites.

Thermodynamic description of U(IV) solubility and hydrolysis in chloride systems: Pitzer activity model for the system U4+–Na+–Mg2+–Ca2+–H+–Cl––OH––H2O(l)

This study presents updated chemical, thermodynamic, and activity models for the system U4+–Na+–Mg2+–Ca2+–H+–Cl––OH––H2O(l) derived using the Pitzer formalism and a strict ion interaction approach. The models build on comprehensive solubility datasets in dilute to concentrated NaCl, MgCl2, and CaCl2 solutions. The Nuclear Energy Agency-Thermochemical Database (NEA-TDB) selection of solubility and hydrolysis constants in the reference state were taken as anchoring point, and were extended further with the solid nanocrystalline phase UO2∙H2O(ncr) and the ternary complex Ca4[U(OH)8]4+. The former was identified in long-term solubility experiments at ambient conditions, whereas the latter has been selected in analogy to Th(IV), Np(IV), and Pu(IV) considering experimental evidences available for these An(IV) in alkaline, concentrated CaCl2 solutions. These models represent an improved tool for the calculation of U(IV) solubility and aqueous speciation in a variety of geochemical conditions including concentrated brine systems relevant in salt-based repositories for nuclear waste disposal.

Solubility Behavior, Hansen Solubility Parameters, and Thermodynamic Modeling of 9-Phenylcarbazole in 12 Monosolvents from 283.15 to 323.15 K

Solubility Behavior, Hansen Solubility Parameters, and Thermodynamic Modeling of 9-Phenylcarbazole in 12 Monosolvents from 283.15 to 323.15 K

Performance of a high-temperature transcritical pumped thermal energy storage system based on CO2 binary mixtures

Pumped thermal energy storage is a novel energy storage technology with features of high efficiency, geographical independence and suitable for bulk capacity energy storage. As a subset of pump thermal energy storage system, the transcritical CO2 arrangements have received widespread attention due to their excellent thermodynamic performance. However, the high cost and low efficiency of heat exchange progress caused by CO2 phase transition hinder the transformation of this system from scientific theory to practical application. CO2 binary mixtures is innovatively employed as working fluid in proposed system. The temperature of mixture is variable rather than remaining constant during the evaporation and condensation progresses. R134a, R290, R600 and R601 are selected respectively to mix with CO2 to form the new working fluids. Advanced thermodynamic and economic models are established to investigate the performance of novel systems. Results indicate that the system driven by CO2/R134a with a refrigerant mass fraction of 0.15 exhibits the optimal overall performance. At the optimal point of the 10 MW/8h system, the round trip efficiency and levelized cost of storage are 66.18 % and 0.146 $/kWh, respectively. Moreover, the investigation of system performance with various energy storage capacities is put forward. It is shown that when the energy system capacity reaches 300 MW, the levelized cost of storage can be reduced to 0.122 $/kWh. To adapt to different peak and valley periods in different regions, systems with different charge and discharge times are investigated and it is found that the charge duration should better be equal to the discharge duration.

The Thermodynamic Responses of FG Conical/Cylindrical/Annular Panels with Circumferentially Variable Dimensions

This paper is the first to develop a meshless thermodynamic model with circumferentially variable dimensions to analyze the thermal-vibration mechanisms of typical functionally graded (FG) panel-type structures, mainly including conical, cylindrical, and annular panels. The longitudinal variation of the panel-type structure’s circumferential dimensions is taken into account according to specific rules. The Thin Plate Inverse Mapping (TPIM) meshless shape functions are introduced to characterize the displacement components associated with each substructure. Thermodynamic equations are formulated based on FSDT thermo-elastic theory as well as Hamilton’s principle. Rectangular and exponential pulse loads are taken into consideration for forced vibration analysis in this formulation. Numerical convergence and comparative cases are provided. Solutions from the literature and finite element simulation results are utilized for comparison, revealing that the percentage differences observed are all less than 0.025%. This confirms the reliability and accuracy of the developed analysis model. In conclusion, a detailed investigation is conducted on the influences of geometrical dimensions, boundary conditions, as well as thermal and external loads on the thermodynamic behaviors of FG panel-type structures with circumferentially variable dimensions.

Thermodynamic modeling of Bi2Te3 in the defect energy formalism

Bi2Te3 is a promising thermoelectric material that is often touted as one of the best-performing low-temperature thermoelectric materials. As a result, it has been widely used commercially, both for clean energy generation and in cooling devices. Like many other thermoelectric materials, defects play a key role in the performance of Bi2Te3. As a result, numerous studies have attempted to experimentally and computationally map out the dominant defects in the phase, these include efforts to determine the dominant defect, estimate defect energies, and predict their concentration. The computer coupling of phase diagrams and thermochemistry (CALPHAD) is one of many tools under the auspices of the materials genome initiative (MGI) that enables the rapid design of new functional materials with improved properties. The Defect energy formalism (DEF) with a charged sublattice, an offshoot of the Compound energy formalism (CEF), provides a way to directly include first-principle defect energy calculations into CALPHAD descriptions of solid phases. The introduction of the charge sublattice enables the estimation of the free carrier concentrations in the phase. Here we apply the DEF to the Bi2Te3 system, emphasizing the robustness of the DEF in describing meaningful endmembers and the elimination of fitting parameters. Unlike previous assessments using the Wagner–Schottky defect model, we include the description of the charged defects in our assessment. The DEF with a charged sublattice provides a good prediction of the non-stoichiometry of the phase when compared with experimental data and also predicts a thermodynamic defect concentration at low temperature that is physically reasonable.