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The application of Al or Si as antioxidants in MgO-C refractories leads to the in situ formation of new phases. Due to uncertainties regarding phase formation in some references four different test series were heat treated from 800 to 1600 °C under reducing conditions in 200 °C steps. The antioxidant systems investigated were pure Al, Al and Si in two different ratios and SiC. The addition of SiC did not lead to the formation of new phases but in case of Al and Si addition carbides, nitrides, oxycarbonitrides and oxynitrides were formed. The reaction series, its reason and its relation to equilibrium phase composition have been revealed.

Here, we aim to comprehend the mechanism of the order–order transition (OOT) from nonequilibrium, metastable phase to equilibrium phase. Polystyrene-block-polydimethylsiloxane (PS-PDMS) block copol...

Equilibrium phase diagrams serve as blueprints for rational design of nanostructured materials of block copolymers, but their construction is time-consuming and requires profound expertise. Herein, by virtue of the knowledge of self-consistent field theory (SCFT), the active-learning method is developed to autonomously construct the phase diagrams of block copolymers. Without human intervention, the SCFT-assisted active-learning method can rapidly search the undetected phases and efficiently reproduce the complicated phase diagrams of diblock copolymers and multiblock terpolymers via decreasing the number of sampling points to about 20%. It is clearly demonstrated that the combined uncertainty sampling/random selection scheme in the active-learning method shows the outperformance in spite of a small amount of initial data set. This work highlights the promising integration of theoretical modeling with machine learning and represents a crucial step toward rational design of nanostructured materials.

International audience; In this study, we analyze the effect of non-equilibrium phase change on transfer at low water content in a sandy soil by considering the contribution of film flow in the motion of liquid water. Indeed, most of the non-equilibrium study methods use for hydraulic conductivity, the van Genuchten-Mualem (VGM) capillary model which does not consider the film flow occurred at low water contents. Thus, we conduct a theoretical study by using an unidirectional non-equilibrium two phase flow model to simulate water transfers by filtration of liquid water and diffusion of water vapour coupled by liquid/gas phase change. We then compare the results of the non-equilibrium with the classical model of VGM for hydraulic conductivity function and another model considering the film flows. The numerical simulation is based on a column of sandy soil exposed to a controlled atmosphere. We observe that the shapes of the profiles of fluxes (liquid water, liquid/vapour non-equilibrium phase change) simulated using the capillary model are very different from those obtained with the model considering the film flow. In this last case, the liquid/gas nonequilibrium is not noticeable as in the case of the capillary model. It seems that the film flows occult the water vapour diffusion by delaying the phase change process, therefore a lower concentration of water vapour into the soil than in the case where the capillary flow alone has been considered.

The mechanism governing the deoxidation of vanadium metal is regarded as fundamental knowledge; however, it has not been elucidated in existing literature. In this paper, the thermodynamic data of V-H-O systems were summarized, and the Gibbs free energies of the main compounds were calculated. Consequently, the deoxidation limits of different reductants in a V-O system were evaluated, namely: Si, Al, and Mg. It was observed that Si cannot remove an O content of less than 7.27 wt% from V. However, Al was the stronger reducing agent; it could remove O contents of up to 0.01 and 0.1 wt% at 800 and 1050 ?C, respectively. Nevertheless, Mg exhibited the best reducing properties as it could remove less than 0.01 wt% of O at 1100 ?C. The addition of H2 renders the V-O solid solution unstable to a certain extent, thereby indicating that H2 facilitates deoxygenation. Furthermore, the results obtained by analyzing the equilibrium conditions were in accordance with the results of the deoxidation limit in the V-O system. In other words, this study demonstrates that the oxygen in vanadium can be effectively controlled by changing the reductant dosage and temperature.

Prefreezing is a first-order equilibrium phase transition at the melt–solid interface that results in an abrupt formation of a nanoscopic crystalline layer at the interface above the bulk melting t...

Equilibrium phase relations of synthetic minerals prepared by annealing metastable iron sulfides, followed by prolonged isothermal storage in the Earth atmosphere, have been studied by X-ray diffraction. The results demonstrate that prolonged storage of synthetic pyrrhotites annealed at different temperatures makes it possible to identify metastable and stable phases of Fe and S compounds.

Up to now, the formation mechanism of tetragonal nanoprecipitates that may dominate the large magnetostriction of Fe–Ga alloys remains unclear. Here we found that both L60- and D022-type face-centered-tetragonal nanoprecipitates are precursors of the face-centered-cubic L12 equilibrium phase, as identified in the isothermally-aged Fe73Ga27 and Fe74Ga26 alloys, respectively. The L60 phase is formed due to Ga ordering along -A2 direction and simultaneous lattice distortion. The D022 phase is formed via diffusionless lattice distortion when the D03 ordering degree is sufficient high. These findings may provide a microstructural basis for the large magnetostriction induced by soluting nonmagnetic Ga into body-centered-cubic Fe.

In order to optimize the composition and microstructure of quasicrystalline strengthened Mg-based alloy, the equilibrium phases of Mg-Zn-Y-Zr alloys with three components were studied by using thermodynamic calculation. The calculated results showed that the equilibrium phases of the three alloys were mainly Liquid phase, α-Mg matrix phase, α-Zr dispersed phase, quasicrystalline strengthening I phase, W phase and Z phase. It was observed that the specific content and temperature range of these phases were different. Among them, alloy 3 had the highest quasicrystalline content. And alloys 1 and 2 contained dispersed phase α-Zr which can lead to grain refinement.

The thermodynamic properties of ruthenium complex compound Ru(thd)3, (thd is tris(2,2,6,6-tetramethyl-3,5-heptadionate), Ru(C11H19O2)3 have been studied. Temperatures (434.8 ± 2.0, 452.2 ± 1.0, and 461.1 ± 1.0, and 487.8 ± 1 K) and thermodynamic parameters (enthalpy change ΔH = 13.3 ± 2.0, 2.1 ± 0.5, 6.0 ± 2.0, and 3.8 ± 1 kJ mol–1) of three reversible solid-phase transitions and the melting process have been determined by differential scanning calorimetry. The temperature dependence of the saturated vapor pressure in the range 392–488 K has been established by the flow method. The thermodynamic parameters of sublimation (enthalpy change ΔH = 121 ± 1, 103 ± 3, 101 ± 5, and 86 ± 2 kJ mol–1; entropy change ΔS° = 219 ± 3, 176 ± 7, 173 ± 10, 141 ± 4 J mol–1 K–1) for all four crystalline phases have been calculated. CVD diagrams have been calculated by thermodynamic modeling to determine the equilibrium phase composition of the system. The obtained results allow us to give recommendations on finding the optimal conditions for the CVD process and choosing the precursor.

Phase equilibria in the CaO–SiO2–La2O3–Nb2O5 system are important for the utilization of Nb and Rare Earth resources. In the present work, phase equilibria in the CaO–SiO2–La2O3–Nb2O5 system at 1473 K in H2 (pO2 = 10−15.47atm) were studied by the equilibrium experiment. SEM, EDS and XRD analysis were employed to identify the equilibrium phase relations. The isothermal spatial phase diagram of the CaO–SiO2–La2O3–Nb2O5 system and the isothermal section of CaO–SiO2–Nb2O5-(5%, 10%) La2O3 pseudo-ternary system were constructed. A total of eight equilibrium phase regions were determined, including Liquid + CaNb2O6+CaSiO3+LaNbO4 region, Liquid + CaNb2O6+SiO2+CaSiO3 region, Liquid + CaSiO3+CaNb2O6 region, Liquid + CaSiO3+SiO2 region, Liquid + CaNb2O6+SiO2 region, Liquid + CaSiO3 region, Liquid + SiO2 region and Liquid + CaNb2O6 region. Additionally, the influence of pO2 on equilibrium composition and temperature was also investigated considering its significant effect on phase equilibria in the slag system with variable valence elements. The results indicated that higher external pO2 can increase the equilibrium O content in a slag system, while higher equilibrium temperature corresponds to higher equilibrium pO2. Besides, the relationship between phase equilibria shown in the traditional slag system and in the related generalized alloy system was also revealed. The present experimental data can help further study on Nb-bearing and RE-bearing slag systems, and the theoretical conclusions will help the development of thermodynamic models.

The influence of the nanomorphology on phase equilibria in core-shell nanoparticles of the stratifying W – Cr solid solutions has been simulated using methods of the equilibrium chemical thermodynamics. The nanoparticle shape has been determined by the value of the fractal dimension. The dependences of the mutual solubilities on the fractal dimension of nanoparticles have been calculated and some significant changes in the thermal stability of heterogeneous states in nanoparticles of different shapes have been revealed.

Isobaric heat capacities of β-Si3N4 and γ-Si3N4 were measured at temperatures between 1.8 and 309.9 K with a thermal relaxation method. The measured heat capacities of γ-Si3N4 are smaller than those of β-Si3N4 in this temperature range. Using these data, we determined the standard entropies of β-Si3N4 and γ-Si3N4 to be 62.30 J·mol−1 K−1 and 51.79 J·mol−1 K−1, respectively. The equilibrium phase boundary between β-Si3N4 and γ-Si3N4 was calculated using these values and thermodynamic parameters reported in previous studies. The obtained equilibrium phase transition pressure at 2000 K is 11.4 GPa. It is lower than the experimental pressures at which γ-Si3N4 was synthesized in previous studies. The calculated Clapeyron slope at this temperature is 0.6 MPa K−1, which is consistent with those of theoretical studies.

Summary It is well established that the early malignant tumor invades surrounding extracellular matrix (ECM) in a manner that depends upon material properties of constituent cells, surrounding ECM, and their interactions. Recent studies have established the capacity of the invading tumor spheroids to evolve into coexistent solid-like, fluid-like, and gas-like phases. Using breast cancer cell lines invading into engineered ECM, here we show that the spheroid interior develops spatial and temporal heterogeneities in material phase which, depending upon cell type and matrix density, ultimately result in a variety of phase separation patterns at the invasive front. Using a computational approach, we further show that these patterns are captured by a novel jamming phase diagram. We suggest that non-equilibrium phase separation based upon jamming and unjamming transitions may provide a unifying physical picture to describe cellular migratory dynamics within, and invasion from, a tumor., Graphical abstract, Highlights • Tumor spheroids invading into a 3D matrix exhibit coexistent material phases • Invasion leads to spatiotemporal heterogeneities consistent with jamming dynamics • Phase separation patterns are captured by a model-based jamming phase diagram • Effective thermodynamic variables Teff and Pconf capture cell and matrix properties, Biophysics; Cancer; Mechanobiology

Finding safe solvents with low viscosities has been in great demand in extraction processes. Herein, R-(−)-carvone, a natural monoterpenoid rich in spearmint, was mixed with naturally occurring fatty acids and terpenes. Most eutectic mixtures presented a wide liquid window in the solid-liquid equilibrium phase diagrams. Carvone mixtures at the ideal eutectic points were characterized for physicochemical properties. Despite varying properties, all the tested solvents were immiscible with water and displayed low viscosity with reasonable biodegradability. Sigma potentials of the mixtures were applied to machine learning algorithms, suggesting carvone mixtures as substitutes for polar protic and dipolar aprotic solvents. Carvone mixtures could be successfully applied to liquid-liquid extraction of a red algae called laver, which is rich in natural hydrophobic and hydrophilic pigments of high value. This study proposes carvone as a new bio-based source of hydrophobic solvents and the eutectic mixtures as biodegradable and tunable solvents to extract hydrophobic compounds.

Funding Information: This study received financial support from Aalto University . The authors would also like to acknowledge the financial support from the China Postdoctoral Science Foundation [Grant number 2020TQ0059 , 2020M680967 ], the Fundamental Research Funds for the Central Universities [N2125010] and China Scholarship Council [Grant number 201706370096 , 201806370217 ]. Publisher Copyright: © 2021 Elsevier Ltd and Techna Group S.r.l. The combined processing of industrial wastes of titania-bearing slags with coal fly ash is an important part of the circular economy. In the present work, the effect of Al2O3 on the 1400 °C liquidus isotherms of the perovskite, rutile and tridymite primary phase fields in the CaO–SiO2–TiO2–Al2O3 system has been determined by employing a high-temperature equilibration-quenching technique, followed by X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy-Energy Dispersive X-ray Spectrometry. Titanium was confirmed to be stable as TiO2 in the present equilibria. The equilibrium solid phases of perovskite CaO·TiO2, rutile TiO2 and tridymite SiO2 were confirmed to be coexisting with the liquid oxide phase. The comparison of the addition of 0–15 wt% Al2O3 was beneficial for expanding the primary phase field of perovskite to lower TiO2 concentrations. Comparisons of the experimental 1400 °C isotherm with the predictions using FactSage and MTDATA databases confirmed some differences to the present experimental data, thus demonstrating the direction for updating the present thermodynamic titania-bearing oxide databases.

Orientador: Fernando Antonio Cabral Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos Resumo: Neste trabalho foi estudado o fracionamento de óleo de palma bruto (Elaes guineensi) com dióxido de carbono supercrítico; mediu-se a solubilidade, a composição em ácidos graxos, carotenóides totais, tocoferóis, tocotrienóis e ácidos graxos livres. Foi determinado o equílibro de fases no intervalo de pressão de 100 a 350 bar e nas temperaturas de 40, 50 e 60°C. A quantificação dos componentes minoritários presentes nos extratos foi feita por espectrofotometria para a determinação de carotenóides totais, por cromatografia líquida de alta eficiência para a determinação dos tocoferóis e tocotrienóis e por titulação potenciométrica para os ácidos graxos livres. Realizou-se uma extração fracionada utilizando raspas de madeiras como suporte na condição de 40°C a 200 bar, onde doze amostras foram extraídas, nas quais mediu-se a solubilidade e a concentração de ácidos graxos livres e carotenóides totais. Observou-se que a composição em ácidos graxos do óleo de palma refinado e a composição dos extratos em equilíbrio com o CO2 apresentaram pequenas variações na concentração dos ácidos palmítico, oléico e linoléico. Os valores de coeficiente de distribuição, que indicam o grau de fracionamento entre as fases, foram menores que a unidade para tocoferóis e carotenóides e maiores que a unidade para ácidos graxos livres. Notou-se que o comportamento do equilíbrio de fases, transcrito em termos dos coeficientes de distribuição, concorda com os valores da literatura, exceto para os tocoferóis onde o comportamento foi diferente daqueles reportados na litertura Abstract: In this work was studied the fractionation of crude oil palm (Elaes guineensi) with supercritical carbon dioxide; it measured solubility, the free fatty acids composition, carotenoids totals, tocochromanols and free fatty acids. Was determined equilibrium phase in the interval at pressure of 100 at 350 bar and temperature of 40, 50 and 60°C. The quantification of the minor components present in extracts was made by spectrometer for the determination of carotenoids totals, liquid chromatography of high efficiency for the determination of tocochromanols and potenciometric titration for determination free fatty acids. Were fulfilled extraction fractionated using wood scraps as support in condition of 40°C at 200 bar, where twelve sample had been extracted, in which it measured the solubility and the concentration of free fatty acid and carotenoids totals. It was observed that the free fatty acid composition of refined oil palm and the composition the extracts in equilibrium with CO2 had present small variations in the palmitic acid, oleic acid and linoleic acid. The values separation factor, that indicate the degree of fractionation between the phase were smaller than unit for tocochromanols, carotenoids totals and bigger than unit for free fatty acids. It was noticed that the behavior of equilibrium phase, transcript in term of the separation factor, had agreed to the values of literature, except for the tocochromanols where the behavior was different of those reported in the literature Mestrado Mestre em Engenharia de Alimentos

The equilibrium phase behavior of main-chain liquid-crystalline polymer brushes in good solvent is investigated using self-consistent field theory. The calculation assumes semidilute brushes, where the grafting density is sufficient to cause overlap among the polymers but low enough to allow the solvent to be treated implicitly. The polymers are modeled as semiflexible wormlike chains with Maier–Saupe interactions. Previous calculations based on freely jointed chains have predicted that extended brushes collapse into folded nematic brushes, as the liquid-crystalline interaction strength is increased. For the more sophisticated model of wormlike chains, which penalizes hairpin folds, we find that extended brushes become unstable with respect to tilting prior to the onset of folding. This implies that the brushes spontaneously collapse by a symmetry-breaking transition, where the chains tilt rather than fold.

Preferential attraction of polymer chains to the substrate [i.e., poly(methyl methacrylate) (PMMA) on the hydroxyl-terminated Si substrate] typically results in the initial phase separation of spin-cast immiscible linear polymer blends [i.e., polystyrene (PS)/PMMA] with a characteristic interfacial microstructure depending on their molecular weight. A formation of the undesired microstructure in those blends is inevitable because of the thermodynamic force driving their phase separation combined with relatively rapid dynamics in solution. In contrast, the polymer ligands, which are grafted from nanoparticles, are capable of limited segmental interactions in the presence of segmental contacts of chemically distinct chains as well as hindered mobility by interpenetration (or entanglement) and thus exhibit a homogeneous but non-equilibrium phase behavior. Here, the microstructure of the blends consisting of immiscible polymer-grafted nanoparticles (PGNPs) was identified by their neutron reflectivity, in whic...

The translation method for predicting and constructing equilibrium phase diagrams of multicomponent systems is developed based on the compatibility of structural elements of partial constituent (n-component) systems and the general (n + 1)-component system with account for the requirements of the Gibbs phase rule. The invariant equilibrium states in the five-component system NaCl–KCl–MgCl2–CaCl2–H2O at 25°C are studied. This multicomponent system features the options of invariant equilibria where one and the same composition of equilibrium solid phases can be in equilibrium with saturated solutions of differing concentrations. Therefore, this invariant equilibrium is to be reflected in the diagram as a geometric (invariant) image that has a dimension (it may be conventionally referred to as a quasi-point) and not by a point. The dimension of this image is determined by the concentration bounds of components in the equilibrium saturated solution.

The solid–liquid equilibrium of the quaternary system (KBr + NaBr + MgBr2 + H2O) was accurately investigated at 298 K. The equilibrium phase diagram was obtained and consisted of seven dissolution isotherms, three co-saturated points and five solid crystallization regions under the condition of 298 K. The five solid crystallization regions contain four single salts NaBr·2H2O, NaBr, KBr, MgBr2·6H2O and one double salt KBr·MgBr2·6H2O, respectively. The largest crystallization region corresponds to KBr comprising more than half of the region of the equilibrium phase diagram. Using Pitzer’s model and mathematical calculation tools, the solubilities of the bromide minerals in this system were calculated; the calculation results are basically consistent with the experimental results. The research in this paper is of great significance in guiding the development of bromine resources of underground brines in the Western Sichuan Basin and providing fundamental thermodynamic data of bromine-containing systems.

There are many papers concerning H in Pd alloys but their corresponding para-equilibrium phase diagrams have not been given. Para-equilibrium is the most common condition under which data are obtained for Pd alloy-H systems and refers to the condition where the mobile interstitial species (H) reaches equlibrium within an immobile metal alloy framework. Based on these para-equilibrium phase diagrams, an explanation will be offered for the experimental observation that the terminal hydrogen solubilities are always greater in fcc, substitutional Pd alloys than in Pd itself where this term refers to the limiting solubility of H in the dilute phase before the hydride phase forms.

In-magnetic-field annealing (IFA) effects on Zn-modified Mn-Al and Mn-Al-C were investigated at the annealing temperature of 573 K, which was around their TC. Mn 53 Zn 2 Al 45 showed the magnetic-field-induced acceleration of the phase transformation to L10-phase (τ-phase) and the suppression of that to nonferromagnetic equilibrium phase. For Mn 55 Al 45 C 2 , IFA effects were not clearly detected. These different magnetic field effects were discussed by the difference of the mechanism in stabilization of τ-phase. It is found by a thermal analysis that the modification of Zn stabilized τ-phase against e-phase, realizing acceleration of transformation to τ-phase. The addition of carbon stabilized e-phase against τ-phase. The ineffectiveness of in-field annealing for Mn-Al-C is due to the stabilization of e-phase and the reduction of the Curie temperature. The combination of Zn modification and IFA is realized to synthesize high fraction of τ-phase for short annealing time and low annealing temperature.

This article offers a detailed analysis of the Ising model in 2D small-world networks with competing Glauber and Kawasaki dynamics. The non-equilibrium stationary state phase transitions are obtained in these networks. The phase transitions are discussed, and the phase diagrams are obtained via Monte Carlo simulations and finite-size analyzing. We find that as the addition of links increases the phase transition temperature increases and the transition competing probability of tricritical point decreases. For the competition of the two dynamics, ferromagnetic to anti-ferromagnetic phase transitions and the critical endpoints are found in the small-world networks.

A process of heating-cooling combined mold horizontal continuous casting→cold rolling→solid-solution treatment was used to produce Cu-1.7 wt% Be alloy sheet, and the precipitation behavior, microstructure and properties of the Cu-1.7 wt% Be alloy sheet during aging were investigated. The results showed that the phase transformation sequence of the alloy during aging at 325 °C was GP zone→γ″→γ′→γ equilibrium phase. The reasonable aging parameters were aging temperature of 325 °C and aging time of 3 h, and the hardness, tensile strength and yield strength of the aged alloy reached the peak values of 375 HV, 1042 MPa and 778 MPa, which were 172%, 116%, and 255% higher than those of the solid-solution alloy, respectively, and the electrical conductivity was 22.4% IACS. The formation of a large number of dispersed nano-sized γ′ phase was mainly responsible for the high strength of the alloy. A dynamic model of aging precipitation was established and the yield strength of the peak-aged alloy was calculated by the strengthening model. The deviation of the calculated value (797 MPa) and the measured value (778 MPa) was 2.4%, and the strengthening mechanism of the peak-aged alloy was determined as the Orowan bypass mechanism.

Orientador: Charlles Rubber de Almeida Abreu Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química Resumo: O estudo a nível microscópico do Equilíbrio Sólido-Líquido (ESL) só se desenvolveu a partir do século XX e ainda existem aspectos de tal fenômeno que não são bem compreendidos, mesmo para os sistemas mais simples. Por esse motivo, é necessário que métodos eficientes para simular diretamente o ESL sejam formulados. O principal objetivo deste trabalho foi desenvolver e implementar Métodos Monte Carlo Multicanônicos para simular o ESL de sistemas de Lennard-Jones e, então, avaliar a aplicabilidade de tais métodos com base na sua eficiência. Primeiramente, buscou-se melhorar os resultados do método desenvolvido por Muguruma e Okamoto (2008), que visava amostrar a energia do sistema uniformemente e o volume com probabilidade de Boltzmann, enquanto mantinha-se fixo o número de partículas da caixa de simulação cúbica. Em seguida, uma nova abordagem foi proposta, cuja principal característica é não restringir o formato da caixa, embora a amostragem fosse realizada da mesma forma. Em ambos os métodos, a densidade de estados do sistema foi estimada usando a técnica da matriz de transições e uma abordagem de paralelização das simulações foi empregada a fim de se obter uma amostragem mais efetiva. Os resultados obtidos com o primeiro método mostraram que uma simulação como essa depende significativamente do número de partículas. Além disso, a amostragem dos estados de energia ficou presa na fase sólida. Já os resultados obtidos com a nova metodologia foram ligeiramente melhores que os obtidos com o método anterior. A amostragem para o sistema com o menor número de partículas foi equivalente para as duas fases em questão. No entanto, as simulações com sistemas maiores apresentaram o mesmo problema apontado no método anterior. A princípio, sugeriu-se a existência de uma transição polimórfica. No entanto, simulações na fase sólida com a nova metodologia apontam o contrário. Apesar dos resultados insatisfatórios, este trabalho se constitui em um passo importante no estudo de um tema complexo, que é a previsão de Equilíbrio Sólido-Líquido utilizando métodos de simulação direta Abstract: The study at the microscopic level of Solid-Liquid Equilibrium (SLE) was only developed in the 20th century and still exist some aspects of this phenomenon that are not well understood, even for the simplest systems. Therefore, it is necessary the development of efficient methods to directly simulate the SLE. The main objective of this work was to develop and implement Multicanonical Monte Carlo methods to simulate the SLE of the Lennard-Jones system and then evaluate their applicability based on efficiency. First, we sought to improve the performance of a method used by Muguruma and Okamoto (2008), which aimed to sample the system energy uniformly and the volume with the Boltzmann probability, while keeping fixed the number of particles in a cubic simulation box. Then a new approach was proposed, whose main feature was let the shape of the box free, although the sampling was performed in the same way. In both methods, the density of states of the system was estimated using the transition matrix technique and an approach for parallelization of the simulations was employed to obtain a more effective sampling. The results obtained with the first method showed that such a simulation depends on the number of particles present in the system. Moreover, the sampling of energy states got stuck in the solid phase. The results obtained with the new method were slightly better than those obtained with the previous method. The sampling for the system with the lowest number of particles was equivalent for the two phases concerned. However, simulations with larger systems presented the same problem of the previous method. At first, it was suggested the existence of a polymorphic transition. However, simulations in the solid phase with the new methodology show the opposite. Despite the unsatisfactory results, this work constitutes na important step in studying a complex subject, which is the prediction of Solid-Liquid Equilibrium using direct simulation methods Mestrado Engenharia de Processos Mestre em Engenharia Química

We studythe effect of shear deformation on graphitic g-C3N4 under pressures of up to 80 GPa at room temperature. g-C3N4 samples are transformed from initial amorphous flakes into onion-like structures, in which the nitrogen content in the quenched samples decreases with increasing pressure (from 42% in the initial conditions to 1% at 80 GPa). The concentration of the sp2 bonds also decreases from 1 (the initial sample) to 0.62 with increasing pressure to 80 GPa. This transformation of the sample is due to the fact that in the pressure range of 55–115 GPa, the equilibrium phase is not a diamond, but instead, carbon onions cross-linked by sp3 bonds, which are denser than diamonds. The results of our study show that the presence of nitrogen in sp3-bonded structures at pressures of higher than 55 GPa reduces the density and, accordingly, carbon structures without nitrogen become thermodynamically favorable.

Singularities of dynamical large-deviation functions are often interpreted as the signal of a dynamical phase transition and the coexistence of distinct dynamical phases, by analogy with the correspondence between singularities of free energies and equilibrium phase behavior. Here we study models of driven random walkers on a lattice. These models display large-deviation singularities in the limit of large lattice size, but the extent to which each model's phenomenology resembles a phase transition depends on the details of the driving. We also compare the behavior of ergodic and non-ergodic models that present large-deviation singularities. We argue that dynamical large-deviation singularities indicate the divergence of a model timescale, but not necessarily one associated with cooperative behavior or the existence of distinct phases.

Extensive research and clinical trials have improved our understanding of tumor immunology but despite considerable clinical benefits, current immunotherapies only provide durable responses in a minority of patients. The challenge is to identify key biological parameters preventing immune escape and maintaining an equilibrium state characterized by a stable subclinical tumor mass. Based on a space and size structured partial differential equation model, we developed numerical methods to predict the parameters of the equilibrium without running simulations of the evolution problem. By using global sensitivity analysis methods, we identified the elimination rate of tumor cells by immune cells as the leading parameter influencing the equilibrium size of the tumor and combined therapies that sustain and strengthen the anti-tumor immune response as most effective. Applied to the biological parameters that define a cancer type, such numerical investigation can provide hints for the design and optimization of cancer treatments. Significance: Based on a space and size structured PDE model, the analyses of the equilibrium phase in immune surveillance of cancer provide numerical methods to evaluate the influence of immune response and tumor growth parameters and hints for the design and optimization of cancer treatments.

Abstract Biomolecular condensates in cells are often rich in catalytically active enzymes. This is particularly true in the case of the large enzymatic complexes known as metabolons, which contain different enzymes that participate in the same catalytic pathway. One possible explanation for this self-organization is the combination of the catalytic activity of the enzymes and a chemotactic response to gradients of their substrate, which leads to a substrate-mediated effective interaction between enzymes. These interactions constitute a purely non-equilibrium effect and show exotic features such as non-reciprocity. Here, we analytically study a model describing the phase separation of a mixture of such catalytically active particles. We show that a Michaelis–Menten-like dependence of the particles’ activities manifests itself as a screening of the interactions, and that a mixture of two differently sized active species can exhibit phase separation with transient oscillations. We also derive a rich stability phase diagram for a mixture of two species with both concentration-dependent activity and size dispersity. This work highlights the variety of possible phase separation behaviours in mixtures of chemically active particles, which provides an alternative pathway to the passive interactions more commonly associated with phase separation in cells. Our results highlight non-equilibrium organizing principles that can be important for biologically relevant liquid-liquid phase separation. Graphic abstract

This research study is about the design and evaluation of interactive learning media using Augmented Reality (AR) application for learning the Equilibrium Phase Diagram. Augmented reality gives better approaches for users to rapidly getting information which comes “alive” instantly to help and attract the students to learn equilibrium phase diagram effectively. Augmented Reality also was found helpful in reducing the problems of visualization in the topic of Equilibrium Phase Diagram. In order to ensure the learning process is successful, the instructional design model: ADDIE Hybrid Model, has been used in the development of the interactive learning media using augmented reality to learn the equilibrium phase diagram. There were five phases involved to make sure that the process of before, during and after using the interactive learning media with augmented reality applications has achieved the objectives.