Equilibrium Diagram Research Articles

Calculation of critical endpoints and phase diagrams of highly asymmetric binary systems

The computation of Global Phase Equilibrium Diagrams (GPED) for binary systems, including critical and three-phase equilibrium curves, is crucial for analyzing process conditions and assessing thermodynamic models. In the past two decades, algorithmic strategies and GPEC software have become essential tools. However, numerical problems can arise with the original algorithm for highly asymmetric systems, such as gases or water with heavy compounds or polymers, hindering the completion of GPED and related diagrams.This study presents an innovative calculation methodology to address these challenges. Our approach extends existing algorithms to achieve automatic GPED generation without user intervention, focusing on nearly pure phases. We apply our methodology to systems such as methane or water with heavy alkanes, and CO2 + silicones. The proposed algorithmic strategies effectively handle asymmetric systems, different types of phase behavior, and the estimation of extremely low concentrations in nearly pure phases along the vapor-liquid-liquid equilibrium curve.

Contribution to the Study of the Chemical and Microstructural Quality of Reinforcing Bars in DR. Congo “Case of the City of Lubumbashi”

This research highlights the contribution to the study of the microstructural quality of reinforcing bars on the Lubumbashi market including bars imported from South Africa (FA), Zambia (FZ) and those produced locally ( FC) by the only steel industry, in the former province of Katanga, the iron processing company SOTRAFER, in acronym. The samples of the locally produced reinforcement bars (FC) were collected at SOTRAFER at the end of production, while the samples of the FA and FZ reinforcement bars were taken randomly on the Lushois market in a hardware store specializing in sales to avoid errors.Microstructural analysis of all bars revealed a similar microstructure consisting of a ferrite (light areas) and pearlite (dark areas) matrix and a ferrito-pearlitic structure. This microstructure, as predicted by the Fe-C equilibrium diagram, could be justified by the carbon content (lower than the eutectoid point content); the results prove that all bars are hypoeutectoid steels (%C ≤ 0.77). They can also be assimilated to the category of mild steels (0.1 ≤ %C ≤ 0.25). This also shows that all the bars have not undergone a particular heat treatment and have been cooled very slowly in order to allow the diffusion of atoms and reach equilibrium conditions. The results obtained from the variance analyses of different materials of dimensions of 10, 12 and 16 mm revealed that at the level of chemical and mechanical analyses, there was no significant difference on all the parameters studied and that all the reinforcement bars could perfectly be used in construction. Finally, the survey reveals that FA is reputed to be of better quality among consumers, for several reasons including the psychological one although its price is lower than that produced locally.

Prediction of Hydrate Formation in Supercritical CO2 Containing Impurities Long-Distance Transportation Pipelines with a Capacity of 0.36 Million t/a

Abstract Long-distance pipeline transportation is the most economical and feasible way to transport CO2. Hydrates can easily form during the transportation of supercritical CO2 containing impurities, leading to pipeline blockage. Therefore, accurate prediction of the deposition location and amount of hydrates in pipelines is crucial. This paper established a prediction model for hydrate growth in the long-distance CO2 transportation pipeline containing impurities. The phase equilibrium diagram and kinetic growth model were combined to simulate the formation behaviour of CO2 hydrate. The long-distance CO2 transportation pipeline of 0.36 million t/a in Yunlin was taken as an example. The results show that the volume of CO2 hydrate increased whereas the growth rate of CO2 hydrate gradually decreased with time. Hydrates begin to form in pipeline L11 at a distance of 35-44.3 km away from the inlet, whereas at a distance of 8.1 km away from the inlet for pipeline L12. The places with the highest amount of hydrate formation in both of the pipelines were at the end of pipelines. The area for hydrates formation in pipeline L12 was much longer than that in pipeline L11 due to the lower temperature. The cleaning cycle for pipeline L12 should be much shorter than that of pipeline L11. This paper will provide guidance for the operation of CO2 long distance pipelines.

Thermodynamic approach for designing processing routes of 4Mn quenching and partitioning steel

AbstractThe study addresses the design and optimization of chemical composition and processing routes of new quenching and partitioning medium-Mn alloy using theoretical and experimental approaches. The thermodynamic calculations using Thermo-Calc and JMatPro software were carried out to characterize the influence of Mn, Si and Al contents on cementite formation and precipitation processes. The evolution of individual phases as a function of temperature under thermodynamic equilibrium conditions was estimated. The investigations included the determination of continuous cooling transformation (CCT) and the time–temperature transformation (TTT) diagrams of a model 4Mn alloy. The calculated equilibrium diagrams were compared with the experimental diagrams determined using dilatometric tests. Microstructural observations were carried out to verify the results of dilatometric measurements. The results of thermodynamic calculations and experimental tests showed the moderate agreement. It is related to the inaccuracy of currently available models in the used software and/or non-equilibrium conditions of experimental tests.

Evaluation of Counter Current Horizontal Screw Extractor’s Performance in Determining Leaching Equilibrium of Clitoria ternatea Anthocyanins

Anthocyanin compounds as natural coloring substances contained in Clitoria ternatea flowers have higher antioxidant activity than anthocyanins from other flower extracts. Obtaining anthocyanin extract from Clitoria ternatea flower can be done using the solid-liquid extraction method. The objectives of this study include making a leaching equilibrium diagram of Clitoria ternatea flowers and determining the optimum L/S ratio and the number of equilibrium stages in the counter current horizontal screw extractor. In the maceration process, a leaching equilibrium diagram is produced, which is then used to design and determine the number of equilibrium stages. The equilibrium diagram of anthocyanins from Clitoria ternatea flowers with a gradient slope to the right is in accordance with the literature so that the equilibrium diagram can be used in the design of the extraction unit and the calculation of the theoretical stage of the multi-stage extraction unit. Based on the equilibrium diagram, the Number of Transfer Units (NTU) of 4 stages and the Height of the Transfer Unit value of this process is 0.105 m.

Molybdate and vanadate ions as corrosion inhibitors for clad aluminium alloy 2024-T3

Molybdate and vanadate ions were used as corrosion inhibitors for the clad aluminium alloy 2024-T3 in chloride solution to investigate the differences in their inhibitory effect. Electrochemical measurements in 0.1 M NaCl investigated the influence of inhibitor concentration from 0.5 mM to 250 mM, solution pH from 5 to 9 and immersion time at open circuit potential of up to 12 h. Both compounds act predominantly as anodic inhibitors; however, the effect of molybdate increases significantly at concentrations above 50 mM and leads to a broad passive range. Surface analysis of the samples exposed to inhibitor performed by X-ray photoelectron spectroscopy showed that the inhibitor layers consist of oxides of multiple valences. Scanning electron microscopy with chemical analysis was also used to characterise the inhibitor layers. Equilibrium diagrams of the aqueous species in the selected concentration range were generated to better understand the inhibition mechanism and to correlate the electrochemical data and data on surface properties.

Oxygen exchange in MIEC layered perovskite-like oxide Nd2NiO4+δ: Kinetics and equilibrium parameters

Layered Ruddlesden-Popper (RP) neodymium nickelate oxide, Nd2NiO4+δ, is considered a potential cathode material in solid oxide fuel cells. In this study, the equilibrium properties of NNO were investigated by using quasi-equilibrium oxygen release to contract the isothermal equilibrium diagram “lg pO2 – (4+δ) – T”. Furthermore, the kinetic properties of NNO were studied by oxygen partial pressure relaxation to determine the equilibrium oxygen exchange rate (R0), chemical diffusion coefficient in oxide (Dchem), and surface exchange rate constant (kchem). The Brønsted-Evans-Polanyi-type linear free energy relationship was shown to exist between the standard Gibbs energy of the reaction and the activation energy of the reaction rate constant.

In situ synchrotron X-ray diffraction study of synthesis reactions in mechanically activated Ti + Al powder mixture under linear heating conditions

In the present work, we studied the features of phase formation in mechanically activated Ti + Al powder mixture at various heating rates for the first time. The study was carried out using high-resolution diffractometry method which made it possible to study the processes of phase formation in situ at any stage of heating. It was established that ignition of the activated mixture can be initiated in the solid phase with an extremely low content of reaction products formed at the preheating stage. An increase in the heating rate leads to a decrease in the average burning rate and an increase in the ignition temperature. At high heating rates, the ignition is initiated in the presence of a liquid phase when the ignition temperatures are close to the melting temperature of aluminum. In this case, the content of reaction products formed during preheating stage is relatively high. It was found that the all main compounds presented in the equilibrium diagram of Ti-Al system are synthesized in parallel. The content of phases in the reaction products depends on the heating rate.

Study of the solid-phase equilibria in the GeTe-Bi2Te3-Te system and thermodynamic properties of GeTe-rich germanium bismuth tellurides

A set of self-consistent thermodynamic parameters of the GeTe-rich germanium-bismuth tellurides were determined using an electromotive force (EMF) method with a glycerol electrolyte in a temperature range from 300 to 450 K. The solid-phase equilibrium diagram of the GeTe-Bi2Te3-Te system at 400 K was constructed using X-ray diffraction (XRD) and scanning electron miscroscope (SEM) techniques of synthesized electrode alloys, as well as available literature data. It is found that all telluride phases in GeTe-Bi2Te3 pseudo-binary section have a tie-line connection with elemental tellurium. The relative partial thermodynamic functions of GeTe in alloys were calculated using data from EMF measurements of concentration cells relative to the GeTe electrode. These findings together with the corresponding thermodynamic functions of GeTe and Bi2Te3 were used to calculate the relative partial molar functions of germanium in alloys, and also the standard thermodynamic functions of formation and standard entropies of the ternary compounds, namely Ge2Bi2Te5, Ge3Bi2Te6 and Ge4Bi2Te7.

Corrigendum to “Statistical Perspective on the Petrological Utility of Polyphase Groundmass Compositions Inferred via Defocused Beam Electron Probe Microanalysis” [Geostandards and Geoanalytical Research (2024)

Due to the incorrect speciation of iron during thermometry modelling, Coulthard et al. (2024) produced an incorrect olivine‐liquid equilibrium diagram, which failed to identify multiple potential equilibrium olivine‐melt pairs. With the new pairs identified here, the temperatures inferred from olivine‐groundmass pairs move closer in temperature space to those inferred from olivine‐glass pairs. Additionally, it is recognised that the most significant difference between these thermometry data is due to differences in inferred melt water mass fraction. If a mean value of water is used for all thermometry, the mean temperatures calculated for olivine‐glass and olivine‐groundmass pairs converge to within 10 °C of one another. This indicates that groundmass compositions inferred via the defocused beam analysis of a polyphase groundmass may reproduce enough information to confidently perform olivine‐melt thermometry despite the glass and groundmass data representing significantly different compositions in multivariate space.

Formation of Intergrowths of Platinum-Group Minerals and Gold from Magmatogenic Ores in Relation to Phase Changes in Pt-Pd-Fe-Cu-Au System

The article discusses the features of the chemical composition and the formation of intergrowths of platinum-group minerals, gold, gold-bearing phases, and other ore minerals present in placers collected from the Anabar River in the northeast part of the Siberian platform. Based on an analysis of changes in the phase compositions of these intergrowths of noble metals with other ore minerals on (Pt, Pd)-Fe-Au and Pd-Cu-Au phase equilibrium diagrams, potential trends in the crystallization of natural polymineral alloys from multicomponent low-sulfide metallic liquids are discussed. The similarity of the microstructures of natural and metallurgical alloys indicates that the formation of natural multiphase Au-PGE intergrowths occurred in a similar manner to the crystallization of multicomponent synthetic alloys. The authors suggest that magmatic Au-PGE mineralization occurs during the crystallization of a noble-metal-containing, low-sulfide, Cr-rich oxide melt separated from silicate mafic–ultramafic magma. Magmatic gold–platinum deposits are commonly associated with sulfide or oxide disseminated-schlieren ores in layered mafic–ultramafic intrusions. However, due to the high solubility of gold and platinoids in sulfide minerals, PGMs in sulfide ores occur as isomorphic impurities or as microphases and dispersed inclusions that cannot form placers. Therefore, the authors suggest that magmatic Au-PGE mineralization occurs during the crystallization of an immiscible low-sulfide, high-Cr oxide liquid separated from silicate mafic–ultramafic magma. In the northeast part of the Siberian platform, potential sources for these placers are likely alkaline, high-Ti mafic–ultramafic intrusions, as confirmed by the presence of silicate inclusions in ferroan platinum similar in composition to melteigite.

A relationship between abnormal electrical properties in non-ferrous alloys and phase equilibrium diagrams

A relationship between abnormal electrical properties in non-ferrous alloys and phase equilibrium diagrams

Reservoirs and Hydrogeochemical Characterizations of the Yanggao Geothermal Field in Shanxi Province, China

Geothermal water is the product of deep circulation within the crust, and the understanding of its hydrogeochemical process can provide effective information for integrated research on its circulation pattern and formation mechanism. Based on the geothermal geological conditions of the Yanggao geothermal field, this study analyzed water samples from thermal springs and geothermal wells in the geothermal field, ascertaining their hydrochemical components, along with their hydrogen and oxygen isotopes. Using methods like piper diagrams, ionic component ratio characterization, Na–K–Mg equilibrium diagrams, and reverse path simulations, this study elucidated the recharge source of geothermal water in the study area, revealed the water–rock interactions the geothermal water experienced, and evaluated the geothermal reservoir temperatures. The results show that the geothermal water has hydrochemical types of Na–Cl–HCO3 and Na–HCO3–Cl, and is primarily recharged by the atmospheric precipitation in the northern mountainous area. The geothermal water has experienced extended water runoff and deep thermal circulation, and its hydrochemical composition primarily results from the weathering and dissolution of silicate rocks and evaporites. The major hydrogeochemical processes of the geothermal water involve the dissolution of calcite, dolomite, gypsum, and kaolinite. In addition, the canon-exchange also changes the chemical component of the geothermal water. The SiO2 Geothermometer, a multimineral equilibrium diagram, and the silica–enthalpy model reveal the presence of deep and shallow geothermal reservoirs in the study area, which exhibit temperatures of 73 °C and ranging from 125 to 150 °C, respectively. The open geothermal reservoir environment results in the mixing of geothermal water and cold water, with shallow and deep geothermal water mixing with cold water at ratios of 57% and 76%, respectively.

Solid–Liquid Phase Equilibrium: Alkane Systems for Low-Temperature Energy Storage

The thermal characterization of two binary systems of n-alkanes that can be used as Phase Change Materials (PCMs) for thermal energy storage at low temperatures is reported in this work. The construction of the solid–liquid binary phase diagrams was achieved using differential scanning calorimetry (DSC) and Raman spectroscopy. The solidus and liquidus equilibrium temperatures were determined using DSC for thirty-nine different samples, three for the pure n-alkanes and the remaining for binary mixtures at selected molar compositions and used to acquire the corresponding solid–liquid phase diagrams. The two binary systems of n-octane/n-decane (C8/C10) and n-decane/n-dodecane (C10/C12) are characterized by a eutectic behavior at low temperatures. The eutectic temperature for the system C8/C10 was found at 211.95 K and the eutectic composition appeared at the molar fraction xoctane = 0.87. For the system C10/C12, the eutectic temperature was found at 237.85 K, and the eutectic composition appeared for the molar fraction xdecane = 0.78. This work aims to fulfill the lack of available data in the existing literature, considering the potential application of these systems for low-temperature thermal energy storage. Raman spectroscopy was used to complement the DSC data for the construction of the solid–liquid phase equilibrium diagrams, enabling the identification of the solid and liquid phases of the system. Additionally, the liquidus curve of the phase diagram was successfully described using a modified freezing point depression curve as fitting equation, the absolute root mean square deviation for the data correlation of the C8/C10 and C10/C12 systems being 2.56 K and 1.22 K, respectively. Ultimately, the fitting procedure also enabled a good prediction of the eutectic point for both studied systems.

Shocking Sgr B2 (N1) with its own outflow

Aims. Because studies on complex organic molecules (COMs) in high-mass protostellar outflows are sparse, we want to investigate how a powerful outflow, such as that driven by the exciting source of the prominent hot core Sagittarius B2(N1), influences the gas molecular inventory of the surrounding medium with which it interacts. Identifying chemical differences to the hot core unaffected by the outflow and what causes them may help to better understand molecular segregation in other star-forming regions. Methods. We made use of the data taken as part of the 3 mm imaging spectral-line survey Re-exploring Molecular Complexity with ALMA (ReMoCA). We studied the morphology of the emission regions of simple and complex molecules in Sgr B2 (N1). For a selection of twelve COMs and four simpler species, spectra were modelled under the assumption of local thermodynamic equilibrium and population diagrams were derived at two positions, one in each lobe of the outflow. From this analysis, we obtained rotational temperatures and column densities. Abundances were subsequently compared to predictions of astrochemical models and to observations of L1157-B1, a position located in the well-studied outflow of the low-mass protostar L1157, and the source G+0.693-0.027 (G0.693), located in the Sgr B2 molecular cloud complex, which are other regions whose chemistry has been impacted by shocks. Results. Integrated intensity maps of SO and SiO emission reveal a bipolar structure with blue-shifted emission dominantly extending to the south-east from the centre of the hot core and red-shifted emission to the north-west. The morphology of both lobes is complex but can roughly be characterised by an emission component at a larger opening angle, containing most of the emission, and narrower features. The wider-angle component is also prominently observed in emission of S-bearing molecules and species that only contain N as a heavy element, including COMs, but also CH3OH, CH3CHO, HNCO, and NH2CHO. Rotational temperatures are found in the range of ~ 100–200 K. Abundances of N-bearing molecules with respect to CH3OH are enhanced in the outflow component compared to N1S, a position that is not impacted by the outflow. A comparison of molecular abundances with G+0.693–0.027 and L1157-B1 does not show any correlations, suggesting that a shock produced by the outflow impacts Sgr B2 (N1)’s material differently or that the initial conditions were different. Conclusions. The short distance of the analysed outflow positions to the centre of Sgr B2 (N1) lead us to propose a scenario in which a phase of hot-core chemistry (i.e. thermal desorption of ice species and high-temperature gas-phase chemistry) preceded a shock wave. The subsequent compression and further heating of the material resulted in the accelerated destruction of (mainly O-bearing) molecules. Gas-phase formation of cyanides seems to be able to compete with their destruction in the post-shock gas. The abundances of cyanopolyynes are enhanced in the outflow component pointing to (additional) gas-phase formation, possibly incorporating atomic N sourced from ammonia in the post-shock gas. To confirm such a scenario, chemical shock models need to be run that take into account the pre- and post-shock conditions of Sgr B2 (N1). In any case, the results provide new perspectives on shock chemistry and the importance of the environment in which it occurs.

Geochemical characterization and implications of soil gas and geothermal fluids in the fault zone of Xiongan new area

This study investigates the geochemical characteristics and implications of soil gas and geothermal fluids in the fault zone of Xiongan New Area (XNA). Spatial distribution analysis reveals high soil gas concentrations along the fault zone, prompting the establishment of measurement lines along specific fault segments, such as Niudong fault, with a vertical burial trend. The measured average Rn flux ranges from 71.44 to 335.35 mBq m−2s−1, while CO2 flux ranges from 25.96 to 78.23 g m−2d−1. Furthermore, the average Rn and CO2 concentration intensities range from 0.91 to 2.30 and 1.13 to 2.61, respectively, indicating significant degassing in the fault zone.Geothermal well samples are collected from the deep reservoir in XNA, displaying a predominance of Cl–Na composition. Analysis of the Na–K–Mg equilibrium diagram suggests that the chemical characteristics of deep geothermal water are a result of interactions with rocks and mixing with shallow cold water in XNA. Isotopic analysis indicates the atmospheric precipitation origin of the deep geothermal water with extensive lateral recharge from underground runoff, emphasizing strong water-rock interactions. Comparison with other tectonic units in the region reveals that the Niudong Fault Zone serves as a regional geothermal control structure, facilitating deep fluid convection.In the eastern part of XNA, the geochemical analysis reveals concentrated degassing and a relatively high proportion of mantle-derived sources near the Niudong Fault Zone. This observation suggests the fault zone serves as a primary conduit for deep gases and geothermal fluids. The findings of this research provide valuable scientific references for future urban planning, energy utilization, and geologic hazard monitoring in XNA. Continued monitoring efforts are crucial for understanding the nature of fault activity and resource distribution in the region.

HP8-to-cP4 structural transition in Ni3In compounds at high temperature and pressure: Theoretical assessment of compression and phase stability information

According to Webb et al. (1986) by heating the Ni3In (hP8) compound at 800–1200 °C under a pressure (P) of 6.5 GPa, a cP4 phase was formed, which reverted to hP8 when annealed at low pressure. A striking X-ray result is that the atomic volume (V) of cP4 was higher than that of hP8. Webb et al. determined the V versus P relations in samples quenched to room temperature and reported that the compressibility of the cP4 phase was significantly larger than that of the hP8 phase. These various findings have been theoretically analyzed in the current work by using ab initio density-functional-theory (DFT) calculations, including an account of the vibrational and electronic contributions to the thermodynamic properties. Calculations of the V versus P relations are used to reassess the compressibility relation between the cP4 and hP8 phases, and Gibbs energy calculations to characterize the relative stability of these structures. In particular, detailed comparisons are reported with the only information available on the thermal properties of the hP8 phase, viz., the Gibbs energy estimates obtained in CALPHAD-type phenomenological modeling of the Ni–In equilibrium diagram. The key qualitative result of the current work is that cP4 should be considered as a high-temperature phase, which might be stabilized by heating to the temperature chosen to anneal the hP8 material under pressure. On this basis it is suggested that the seemingly anomalous relative stability relations discussed by Webb et al. might be a consequence of considering only the effect of pressure on the cP4/hP8 relative phase stability.

Modeling of temperature-concentration ranges of phase stability and liquidus surface in the ternary Fe–P–C system and phase composition experimental study

This paper reports thermodynamic properties and phase equilibria in the iron-phosphorus-carbon system for developing a technology for smelting ferrophosphorus as well as for utilizing them in the processes of phosphorus-alloying of metals. According to the results of thermodynamic calculations, we plotted a ternary Fe–P–C phase equilibrium diagram (liquidus surface) in the form of graphical dependences, which indicate the concentration fields of phase coexistence. The results of simulation allowed finding out five nonvariant points, three of which are new: E1 eutectic (teutectic=12170С), U1 peritectic (tperitectic=10950С), and Е3 eutectic (teutectic=3380С). The experimental studies of the phase composition of ferrophosphorus showed that the phosphorus microstructure is represented by Fe3P phosphide, Fe3C carbide, and carbophosphide eutectic. We carried out the thermodynamic calculation of the temperature-concentration ranges of phase stability in the Fe–P–C system that are at equilibrium with the smelts of both the carbon solid solutions and phosphorus ones in - and -iron, FeP, Fe2P, Fe3P phosphides, and graphite. In this study, three previously unknown nonvariant equilibria have been determined: a eutectic equilibrium at 1216.580C; a peritectic one with a transformation point at 1095.190C; and a eutectic one at a temperature of 337.510C. In experiments, we obtained an equilibrium concentration of carbon which decreases in the Fe–P–C system when the content of phosphorus increases. The research findings largely reveal special features of preparation of ferrophosphorus by carbon reduction of phosphorites.

Phase equilibrium diagrams for the nature of non-metallic inclusions in low-carbon steels modified with calcium and cerium

Phase equilibrium diagrams for the nature of non-metallic inclusions in low-carbon steels modified with calcium and cerium

Vacuum free self-fusion solidification bonding of aluminum by 60/40 brass insert metal

The self-fusion solidification bonding process occurs the isothermal fusion and the isothermal solidification by the reaction diffusion between the base metal and the dissimilar insert metal. The bonding process is carried out below the melting points of the base metal. 60/40 brass was used as the insert metal for the self fusion solidification bonding of aluminum in this study. The periodic motion under the load control was applied to the bonding interface at the bonding temperature. The joint by 60/40 brass insert metal was obtained at the bonding temperature of 893 K. The phases by the isothermal fusion and solidification in the bond were evaluated by the chemical composition of the phase and the ternary phase equilibrium diagram.