Multiphase Transformations Research Articles

Experimental Study on Water and Salt Migration and the Aggregate Insulating Effect in Coarse-Grained Saline Soil Subgrade under Freeze–Thaw Cycles

Understanding multiphase transformations and the migration of heat, water, vapor, and salt in coarse-grained saline soil under groundwater recharge and environmental freeze—thaw cycles is crucial for ensuring the stability of highway infrastructures. To clarify the water, heat, vapor, and salt migration patterns in coarse-grained saline soil, as well as the salt-insulating effect of the aggregate insulating layer, an experimental study was conducted in a soil column model under pressureless water replenishment with fluorescein-labeled liquid water under freeze—thaw cycles. The results showed that the temperature in the saline soil columns periodically changed and that hysteresis effects occurred during temperature transfer. External water replenishment and the content of liquid water inside the soil exhibited nonlinear changes with environmental temperatures. After multiple freeze—thaw cycles, two water and salt accumulation zones formed within the coarse-grained saline soil subgrade. The migration of liquid water resulted in a water and salt accumulation zone in the nonfrozen zone, whereas the migration of water vapor yielded a water and salt accumulation zone in the frozen zone. To prevent water and salt migration, a 20 cm thick gravel insulating layer could be laid at a distance of 10 cm from the bottom of the roadbed, which could provide a satisfactory salt-insulating effect. The research results provide a theoretical basis and guidance for regulating the stability of subgrades in saline soil areas.

A variational framework for Cahn–Hilliard-type diffusion coupled with Allen–Cahn-type multi-phase transformations in elastic and dissipative solids

This article presents a variational framework for coupled chemo-mechanical solids undergoing irreversible micro-structural changes at infinitesimal strains. The coupled problem is characterised by phenomena such as phase transitions, micro-structure coarsening and swelling. It is an extension of our previous work on variational inelasticity for a conserved chemo-mechanical setting to a unified conserved and non-conserved setting which include multi-phase transformations. The variational framework, again governed by continuous-time, discrete-time and discrete-space–time incremental variational principles, is outlined for coupled diffusion-phase transformation phenomena in elastic and dissipative solids. For the sake of simplicity, focus is restricted to isothermal conditions. It is shown that the governing macro- and micro-balance equations of the coupled problem appear as Euler equations of these minimisation and saddle point principles. In contrast to our previous work, extended variational principles (with the gradient of the chemical potential and phase fractions) are constructed that account for diffusion-phase transformation coupling. This is achieved by Legendre transformations. Note that the local–global solution strategy is still preserved and the resulting system of symmetric non-linear algebraic equations are solved by Newton–Raphson-type iterative methods. The applicability of the proposed framework is demonstrated by numerical simulations that qualitatively characterise lower bainitic micro-structure.

Core-Shell Tandem Catalysis Coupled with Interface Engineering For High-Performance Room-Temperature Na-S Batteries.

The sluggish redox kinetics and shuttle effect seriously impede the large application of room-temperature sodium-sulfur (RT Na-S) batteries. Designing effective catalysts into cathode material is a promising approach to overcome the above issues. However, considering the multistep and multiphase transformations of sulfur redox process, it is impractical to achieve the effective catalysis of the entire S8 →Na2 Sx →Na2 S conversion through applying a single catalyst. Herein, this work fabricates a nitrogen-doped core-shell carbon nanosphere integrated with two different catalysts (ZnS-NC@Ni-N4 ), where isolated Ni-N4 sites and ZnS nanocrystals are distributed in the shell and core, respectively. ZnS nanocrystals ensure the rapid reduction of S8 into Na2 Sx (4<x≤8), while Ni-N4 sites realize the efficient conversion of Na2 Sx into Na2 S, bridged by the diffusion of Na2 Sx from the core to shell. Besides, Ni-N4 sites on the shell can also induce an inorganic-rich cathode-electrolyte interface (CEI) on ZnS-NC@Ni-N4 to further inhibit the shuttle effect. As a result, ZnS-NC@Ni-N4 /S cathode exhibits an excellent rate-performance (650 mAh g-1 at 5 A g-1 ) and ultralong cycling stability for 2000 cycles with a low capacity-decay rate of 0.011% per cycle. This work will guide the rational design of multicatalysts for high-performance RT Na-S batteries.

Phase-field simulation for voltage profile of [formula omitted] nanoparticle during lithiation/delithiation

Tin has become one of the most promising anode materials due to its large theoretical capacity. The multi-phase transformations occurring during the (de-)lithiation process have posed a severe challenge to study their thermodynamic, kinetic and elastic properties via computational methods. In this work, a phase-field framework consisting of phase-concentration equations and Allen-Cahn equations is established. Two concepts to deliver thermodynamic and elasticity data as input quantities for the phase-field model are proposed, namely from density functional theory calculations and the thermodynamic energy of stoichiometric compounds. Using the formulated and configured phase-field model, voltage profiles, composition profiles, phases, and stress distributions of the electrode during the charging/discharging cycles are simulated. The effects of varying applied current densities and the homogeneity/inhomogeneity of the eigenstrain within the electrode on the voltage profile are discussed. According to simulation results, the establishment of stable voltage output remains a challenge under a higher C-rate due to inhomogeneous phase or stress distribution within the nanoparticle. A simulation-based derivation of linkages between electrode morphology, charging rate, stress, and capacity retention could enable an advanced design of electrode microstructures.

Desolvation Synergy of Multiple H/Li-Bonds on an Iron-Dextran-Based Catalyst Stimulates Lithium-Sulfur Cascade Catalysis.

Traditional lithium-sulfur battery catalysts are still facing substantial challenges in solving sulfur redox reactions, which involve multistep electron transfer and multiphase transformations. Here, inspired by the combination of iron dextran (INFeD) and ascorbic acid (VC) as a blood tonic for the treatment of anemia, a highly efficient VC@INFeD catalyst is developed in the sulfur cathode, accomplishing the desolvation and enrichment of high-concentration solvated lithium polysulfides at the cathode/electrolyte interface with the assistance of multiple H/Li-bonds and resolving subsequent sulfur transformations through gradient catalysis sites where the INFeD promotes long-chain lithium polysulfide conversions and VC accelerates short-chain lithium polysulfide conversions. Comprehensive characterizations reveal that the VC@INFeD can substantially reduce the energy barrier of each sulfur redox step, inhibit shuttle effects, and endow the lithium-sulfur battery with high sulfur utilization and superior cycling stability even under a high sulfur loading (5.2mg cm-2 ) and lean electrolyte (electrolyte/sulfur ratio, ≈7µL mg-1 ) condition.

Multiple 2D Phase Transformations in Monolayer Transition Metal Chalcogenides.

Phase transformation lies at the heart of materials science because it allows for the control of structural phases of solids with desired properties. It has long been a challenge to manipulate phase transformations in crystals at the nanoscale with designed interfaces and compositions. Here in situ electron microscopy is employed to fabricate novel 2D phases with different stoichiometries in monolayer MoS2 and MoSe2 . The multiphase transformations: MoS2 → Mo4 S6 and MoSe2 → Mo6 Se6 which are highly localized with atomically sharp boundaries are observed. Their atomic mechanisms are determined as chalcogen 2H ↔ 1T sliding, cation shift, and commensurate lattice reconstructions, resulting in decreasing direct bandgaps and even a semiconductor-metal transition. These results will be a paradigm for the manipulation of multiphase heterostructures with controlled compositions and sharp interfaces, which will guide the future phase engineered electronics and optoelectronics of metal chalcogenides.

Green Leaf Volatiles in the Atmosphere—Properties, Transformation, and Significance

This review thoroughly covers the research on green leaf volatiles (GLV) in the context of atmospheric chemistry. It briefly takes on the GLV sources, in-plant synthesis, and emission inventory data. The discussion of properties includes GLV solubility in aqueous systems, Henry’s constants, partition coefficients, and UV spectra. The mechanisms of gas-phase reactions of GLV with OH, NO3, and Cl radicals, and O3 are explained and accompanied by a catalog of products identified experimentally. The rate constants of gas-phase reactions are collected in tables with brief descriptions of corresponding experiments. A similar presentation covers the aqueous-phase reactions of GLV. The review of multiphase and heterogeneous transformations of GLV covers the smog-chamber experiments, products identified therein, along with their yields and the yields of secondary organic aerosols (SOA) formed, if any. The components of ambient SOA linked to GLV are briefly presented. This review recognized GLV as atmospheric trace compounds that reside primarily in the gas phase but did not exclude their transformation in atmospheric waters. GLV have a proven potential to be a source of SOA with a global burden of 0.6 to 1 Tg yr−1 (estimated jointly for (Z)-hexen-1-ol, (Z)-3-hexenal, and 2-methyl-3-buten-2-ol), 0.03 Tg yr−1 from switch grass cultivation for biofuels, and 0.05 Tg yr−1 from grass mowing.

Towards the Standardization of Flow Chemistry Protocols for Organic Reactions

AbstractFlow chemistry studies can sometimes be difficult to reproduce. In this article we provide guidance to scientists for experimental details that should be considered as part of any organic chemistry‐based continuous flow study. A focus is placed on information that should be provided within reported studies to enable experiments to be more easily and reliably reproduced. Topics covered include flow reactor components and assembly, important parameter effects and useful performance criteria. The article covers aspects of homogeneous systems, multiphase transformations, and catalytic reactions (homogeneous and heterogeneous). A more detailed discussion of photochemistry, biocatalysis and electrochemical flow systems is outside the scope of this review.

On the performance of liquid-liquid Taylor flow electrochemistry in a microreactor – A CFD study

A comprehensive understanding of the underlying phenomena (coupled fluid flow, charge transfer, mass transfer and chemical reaction) is fundamental for a proper design, analysis and scale-out of chemical reactors when carrying out multiphase electro-organic transformations. In this study, we have explored the novel combination of organic electrochemical synthesis and computational fluid dynamics (CFD) to perform a systematic theoretical investigation concerning the effect of different operational parameters on the performance of organic-aqueous Taylor flow in electrochemical microreactors. The results indicate that operating at high concentrations of the rate-limiting species (>5 mol⋅m−3 for Di≥10-9 m2⋅s−1; 500 mol⋅m−3 for Di~10-10 m2⋅s−1) is beneficial for the reactor performance. However, excessively high concentrations (>500 mol⋅m−3) do not result in a further improvement in mass transfer and current/voltage relation. Higher diffusivities are also beneficial, but even in this scenario limiting current densities can be found when working at low concentrations. Overall, keeping an internal:external phase electrical conductivity ratio > 1 improves the reactor performance. Working at lower velocities can be beneficial in some scenarios, since higher limiting current densities can be obtained. However, the velocity impact on the reactor performance is not significant in some operating conditions (e.g., at higher concentrations and diffusivities). Finally, working with higher cell potentials is beneficial, but limiting current densities can be encountered at lower concentrations and diffusivities. Variables such as internal phase volume fraction, droplet length and interelectrode distance also have relevant impact on the reactor performance, but are subjected to the same conditioning factors previously mentioned. A comprehensive potential balance was also conducted, showing the relative importance of the activation, Ohmic and concentration overpotentials under different operating conditions. We believe the insights gained herein will be of interest to researchers in both academia and industry to develop more efficient electrochemical flow reactors for liquid–liquid transformations.

Multiphase Methods in Organic Electrosynthesis.

With water providing a highly favored solution environment for industrial processes (and in biological processes), it is interesting to develop water-based electrolysis processes for the synthesis and conversion of organic and biomass-based molecules. Molecules with low solubility in aqueous media can be dispersed/solubilized (i) by physical dispersion tools (e.g., milling, power ultrasound, or high-shear ultraturrax processing), (ii) in some cases by pressurization/supersaturation (e.g., for gases), (iii) by adding cosolvents or "carriers" such as chremophor EL, or (iv) by adding surfactants to generate micelles, microemulsions, and/or stabilized biphasic conditions. This Account examines and compares methodologies to bring the dispersed or multiphase system into contact with an electrode. Both the microscopic process based on individual particle impact and the overall electro-organic transformation are of interest. Distinct mechanistic cases for multiphase redox processes are considered. Most traditional electro-organic transformations are performed in homogeneous solution with reagents, products, electrolyte, and possibly mediators or redox catalysts all in the same (usually organic) solution phase. This may lead to challenges in the product separation step and in the reuse of solvents and electrolytes. When aqueous electrolyte media are used, reagents and products (or even the electrolyte) may be present as microdroplets or nanoparticles. Redox transformations then occur during interfacial "collisions" under multiphase conditions or within a reaction layer when a redox mediator is present. Benefits of this approach can be (i) the use of a highly conducting aqueous electrolyte, (ii) simple separation of products and reuse of the electrolyte, (iii) phase-transfer conditions in redox catalysis, (iv) new reaction pathways, and (v) improved sustainability. In some cases, a surface phase or phase boundary processes can lead to interesting changes in reaction pathways. Controlling the reaction zone within the multiphase redox system poses a challenge, and methods based on microchannel flow reactors have been developed to provide a higher degree of control. However, detrimental effects in microchannel systems are also observed, in particular for limited current densities (which can be very low in microchannel multiphase flow) or in the development of technical solutions for scale-up of multiphase redox transformations. This Account describes physical approaches (and reactor designs) to bring multiphase redox systems into effective contact with the electrode surface as well as cases of important electro-organic multiphase transformations. Mechanistic cases considered are "impacts" by microdroplets or particles at the electrode, effects of dissolved intermediates or redox mediators, and effects of dissolved redox catalysts. These mechanistic cases are discussed for important multiphase transformations for gaseous, liquid, and solid dispersed phases. Processes based on mesoporous membranes and hydrogen-permeable palladium membranes are discussed.

Two-dimensional simulations and experiments of homogenization and Kirkendall effect in single-phase diffusion triples

A fully discrete local discontinuous Galerkin (LDG) method has been successfully adopted to simulate two-dimensional (2D) homogenization in single-phase diffusion triples controlled by diffusion process. Two Co-Ni and Co-Fe-Ni diffusion triples were prepared and analyzed to verify the simulation results at 1473 K. In areas far away from the triple conjunction of a diffusion triple, there exists composition gradient in only one direction, which can be efficiently predicted by one-dimensional (1D) sharp-interface diffusion simulations (for example, DICTRA: DIffusion-Controlled TRAnsformation simulation software). It has been extensively adopted in the study of diffusional phase transformations readily supported by multi-component multi-phase thermodynamics and full diffusion matrix establishing an integrated thermodynamics-kinetics simulation platform for engineering materials and industrial applications. However, there are composition gradients in two independent directions in the vicinity of triple conjunction (i.e. triple diffusion zone), which cannot be handled on this platform. In the present work, the LDG method combining with alloy thermodynamics and diffusion kinetics was demonstrated to tackle this 2D homogenization problem very well and the effectiveness of this method has been proved from the aspect of numerical analysis by realizing it with a standalone C++ code. In addition to the composition and flux evolutions during 2D homogenization processes, one can reasonably simulate the shift of the Kirkendall plane in the 2D single-phase diffusion zone. This standalone code serves as a solid basis to further consider 2D diffusional multi-phase transformations assuming sharp interfaces in between.

Climate background, relative rate, and runoff effect of multiphase water transformation in Qilian Mountains, the third pole region

Multiphase water transformation has great effects on alpine hydrology, but these effects remain unclear in the third pole region. Taking the Qilian Mountains as an example, the climate background and relative rates of multiphase water transformation were analyzed, and the runoff effect was evaluated based on long-term field observations. There are three climatic aspects driving multiphase water transformation, including lengthening ablation period, accelerative warming after 1990, and larger warming in the cryosphere belt than in the vegetation belt. The accelerative multiphase water transformation was quantified by three facts: the glacier area retreat rate accelerated by 50% after 1990, the percentage of snowfall in precipitation decreased by 7% after 1990, and the contribution from recycling moisture to precipitation increased by 60% from 1961–1990 to 1991–2016. Under the multiphase water transformation, the outlet runoff for three inland rivers increased by 5 × 108 m3/10 a after 1990. This runoff increase was concentrated mainly in the ablation period. For the seasonal runoff pattern, maximum runoff lagged maximum precipitation by one month under increasing glacier snow meltwater and thickening permafrost active layer. Meltwater from the cryosphere is a crucial runoff component in the Qilian Mountains. At present, these multiphase water transformations are accelerating, along with the yearly runoff increase, which will obviously have a profound impact on water resources management and flood control in the third pole region.

Development of a fully integrated falling film microreactor for gas–liquid–solid biotransformation with surface immobilized O2‐dependent enzyme

Microstructured flow reactors are powerful tools for the development of multiphase biocatalytic transformations. To expand their current application also to O2 -dependent enzymatic conversions, we have implemented a fully integrated falling film microreactor that provides controllable countercurrent gas-liquid phase contacting in a multi-channel microstructured reaction plate. Advanced non-invasive optical sensing is applied to measure liquid-phase oxygen concentrations in both in- and out-flow as well as directly in the microchannels (width: 600 μm; depth: 200 μm). Protein-surface interactions are designed for direct immobilization of catalyst on microchannel walls. Target enzyme (here: d-amino acid oxidase) is fused to the positively charged mini-protein Zbasic2 and the channel surface contains a negatively charged γ-Al2 O3 wash-coat layer. Non-covalent wall attachment of the chimeric Zbasic2 _oxidase resulted in fully reversible enzyme immobilization with fairly uniform surface coverage and near complete retention of biological activity. The falling film at different gas and liquid flow rates as well as reactor inclination angles was shown to be mostly wavy laminar. The calculated film thickness was in the range 0.5-1.3 × 10(-4) m. Direct O2 concentration measurements at the channel surface demonstrated that the liquid side mass transfer coefficient (KL ) for O2 governed the overall gas/liquid/solid mass transfer and that the O2 transfer rate (≥0.75 mM · s(-1) ) vastly exceeded the maximum enzymatic reaction rate in a wide range of conditions. A value of 7.5 (±0.5) s(-1) was determined for the overall mass transfer coefficient KL a, comprising a KL of about 7 × 10(-5) m · s(-1) and a specific surface area of up to 10(5) m(-1) . Biotechnol. Bioeng. 2016;113: 1862-1872. © 2016 Wiley Periodicals, Inc.

Correlation Between Crystal Structure Change and Transformation Strain for Multiphase Transformations

Transformation strains measured via dilatometry and phase fractions measured by optical metallography were used to develop a two-stage, conversional model to accurately determine phase fraction directly and continuously from measured dilation strains for multiphase transformations. The multiphase ferrite + pearlite to austenite transformation was analyzed here, but the two-stage conversional model developed may also be applied to other multiphase transformations. It was found that the lever rule provides accurate results for single-phase to single-phase transformations; the use of a conversional model is not necessary in this case.

Multi-phase transformations at large strains – Thermodynamic framework and simulation

We develop a macroscopic material model for visco-plastic material behavior accompanied by phase transformations, which are important phenomena in steel production processes. The model is formulated within a thermodynamic framework at large strains, and it will be specialized and applied to a hybrid-forming process in steel production. Moreover, thermodynamic consistency of the model will be proved, taking multi-phase transformations into account. In a prototypical situation, TRIP is caused by bainitic and martensitic transformation. The phase transformations considered are: Transformation of the ferritic-pearlitic initial state into austenite, forming of bainite and of martensite. The modelling of bainite evolution takes the incubation via nucleation into account and allows for individual evolutions of upper and lower bainite. Furthermore, the numerical implementation of the constitutive equations into a finite-element program is described. Finally, in a numerical example we investigate the material behavior of a steel shaft subjected to thermo-mechanical loading in a hybrid-forming process.

An analytical study of the static state of multi-junctions in a multi-phase field model

We investigate the properties of the multi-order parameter phase field model of Steinbach and Pezzolla [I. Steinbach, F. Pezzolla, A generalized field method for multi-phase transformations using interface fields, Physica D 134 (1999) 385–393] with respect to the behavior in triple and higher order junctions. From the structure of this model, it was speculated that “dynamical” solutions may exist in the triple junction, which could lead to a violation of Young’s law. Here we confirm analytically recent numerical simulations showing that such dynamical states do not exist, and that an equilibrium solution therefore does indeed correspond to a minimum of the free energy; this implies that Young’s law must be satisfied in the framework of the model. We show that Young’s law is a consequence of the interface kinetic equilibrium and not due to a mechanical force balance, in agreement with earlier predictions [C. Caroli, C. Misbah, On static and dynamical Young’s condition at a trijunction, J. Phys. I France 7 (1997) 1259–1265].

The Influence of the Material Heat Treatment and Phase Transformations in Forming Processes

The majority of metals undergo thermomechanical treatments at least during some part of their processing history. The aim of these treatments is to achieve material properties that could not be obtained otherwise. However, in heat treatment processes, such as quenching, complex residual stresses fields develop during the cooling process of the material. The influence of heat treatments in the forming process of steels is studied in this work. A thermo-mechanical model that considers generalised multi-phase transformations is applied to predict the material properties and characteristics during the combined heat treatment and plastic deformation, which may or may not occur simultaneously. The plastic transformation of each constituent phase is introduced considering a previous material cooling from austenite at high temperature. The JMAK equation and the Koistinen-Marburger model are used to characterize the non-isothermal transformation kinetics and the diffusionless transformation, respectively. The total strain is the addition of the elastic, plastic and volumetric strain induced from the phase transformation parts. An isotropic yield surface is used for the different phases. Numerical tests were performed to validate the previous models implementation considering continuous cooling. The influence of the heat treatment performed by the cooling conditions is also studied carrying out subsequent forming processes. It is shown that the heat treatment and the resulting material phases have a considerable influence on the forming stage.

ChemInform Abstract: Multiphase Transformations Controlled by Ostwald′s Rule in Nanostructured Ce0.5Zr0.5O2 Powders Prepared by a Modified Pechini Route.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Multiphase Transformations Controlled by Ostwald’s Rule in Nanostructured Ce0.5Zr0.5O2 Powders Prepared by a Modified Pechini Route

The thermal stability of nanostructured Ce(0.5)Zr(0.5)O(2) powders prepared by the Pechini method was studied on the nanometric scale by X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), transmission electron microscopy (TEM), nuclear magnetic resonance (NMR), and Raman techniques. Obtained results demonstrate that amorphous powders coming from the thermal decomposition of the precursor transform into the stable crystalline state through one highly disordered and metastable intermediate. This is a new example of successive reactions controlled by Ostwald's rule in inorganic systems. At low calcination temperatures, the combination of Raman spectroscopy, high-resolution electron microscopy, and EDS nanoanalysis showed the formation from the precursor powder of a disordered pseudocubic phase. At 900 degrees C, metastable T' and stable T and C phases were detected in XRD patterns. As increasing temperature, crystallites growth and proportions of stable T and C phases increased at the expense of the T' phase, which completely disappeared at 1300 degrees C. In analyzed samples, the Raman technique and (crystal by crystal) EDS nanoanalyses were used to detect local phase inhomogeneity. Compositions and relative percentages of phases were investigated by XRD Rietveld analysis and discussed in terms of phase diagrams previously reported.

Temperature, stress and microstructure in 10Ni5CrMoV steel plate during air–arc cutting process

Although the air–arc cutting process has been widely used in the material processing engineering, little information about temperature, stress and microstructure in the plate air–arc cut is known. A three-dimensional finite element model including the material removal and the thermal effect of the arc is developed to study the temperature and stress fields of 10Ni5CrMoV steel plate during air–arc cutting process in this paper. The microstructures and micro-mechanical properties of the parts near the groove especially in heat affected zone (HAZ) are studied by experimental methods, and they also can be used as a method to verify the numerical results. Effects of stresses induced by air–arc cutting process on the initial residual stress fields of base materials are also researched. The results show that the cooling velocity in HAZ is higher than the one of the welding process for the same base material, and the zone with high temperature is very narrow, which means that the temperature gradients near the groove are very steep during the air–arc cutting process; this special temperature field depresses multiphase transformations and coarse microstructures. The evolution of the stress during the air–arc cutting is described, and the numerical results indicate that the characteristics of the evolution of stresses and the residual stresses distribution in the plate in air–arc cutting process seem to be similar to the ones of the butt welding for flat plates. The influences of air–arc cutting process on initial stress fields present two aspects: thermal effect and material removal effect, and the former plays a primary role. Both numerical temperature and stress fields are compared with the experimental ones. It is very important for researchers to clarify the temperatures, stresses and microstructures in the plate during air–arc cutting process, and understand fully the mechanism of influences of air–arc cutting on the plate; it is also very valuable for engineering application of the air–arc cutting process.