Nonequilibrium Phase Transformations Research Articles

Controlled Defective Engineering on CuIr Catalyst Promotes Nitrate Selective Reduction to Ammonia.

Electrochemical nitrate reduction reaction (NO3-RR) is a promising low-carbon and environmentally friendly approach for the production of ammonia (NH3). Herein, we develop a high-temperature quenched copper (Cu) catalyst with the aim of inducing nonequilibrium phase transformation, revealing the multiple defects (distortion, dislocations, vacancies, etc.) presented in Cu, which lead to low overpotential for NO3-RR and high efficiency for NH3 production. Further loading a low content of iridium (Ir) species on the Cu surface improves the reactivity and ammonia selectivity. The resultant CuIr electrode exhibits a Faradaic efficiency of 93% and a record yield of 6.01 mmol h-1 cm-2 at -0.22 VRHE exceeding those of state-of-the-art NO3-RR catalysts. Detailed investigations have demonstrated that the synergistic effect between multiple defects and Ir decoration effectively regulate the d-band center of copper, change the adsorption state of the catalyst surface, and promote the adsorption and reduction of intermediates and reactants. The strong H* adsorption ability of the Ir element provides more active hydrogen for the generation of ammonia, promoting the reduction of nitrate to NH3.

Effect of cladding speed on the microstructure and hardness of high-hardness B-bearing Cr17Ni2 coating

The B-bearing iron-based coating produced by laser cladding exhibits super-high hardness. However, the strengthening mechanism of B-bearing Cr17Ni2 coating and non-equilibrium phase transformation during the cooling stage require further investigation. The study focused on the B-bearing Cr17Ni2 coatings produced by laser cladding at four speeds ranging from 10 mm/s to 200 mm/s. The results show that the thickness of the single layer in the coatings gradually decrease as the increase of scanning speed. The secondary dendrite arms spacing and grain size also decrease with increasing scanning speed. The microstructure of the coating consists of a martensitic phase and a eutectic phase consisting of Cr2B compounds and austenite. Combined with G\\R diagram and finite element analysis, the microstructure refining mechanism of the coating has been concluded. The effect of fine grain strengthening, solid solution strengthening, precipitation strengthening, and dislocation strengthening on hardness is investigated. It has been observed that the coating hardness increases with increasing scanning speed. This change in the hardness of the coatings is mainly because of the grain and precipitate refining.

A continuous phase-evolution model for cold and strain-induced crystallization in semi-crystalline polymers

The dynamic crystallization during extreme thermomechanical history under producing or service strongly influences the dimensional stability of the semi-crystalline thermoplastic polymers. To produce high-precision structural components, the proper thermomechanical history needs to be carefully designed to eliminate the crystallization-induced shrinkage. On the contrary, the rapidly developed four-dimensional (4D) printing technology tries to amplify the crystallization-induced shrinkage to directly produce the complex curvatures without supporting materials. However, the crystals formed at different deformation states might have different orientations, leading to an anisotropic residual deformation. Therefore, tracing of all crystals formed with different initial configurations is the key issue to ensure the geometric accuracy of both the high-precision and the deformable components. In this study, we developed a continuous phase-evolution model for both the cold and the strain-induced crystallization in semi-crystalline thermoplastics. The irreversible cold crystallization is analogized as the raindrop falling into the pool, and the reversible strain-induced crystallization is analogized as the nonequilibrium liquid-gas phase transformation. Using the continuous phase-evolution concept, the crystal growth is described by a series of continuously formed crystal phases sequentially added into the initial amorphous medium. Each newly formed crystal phase is in a stress-free state at the formation moment, and therefore the crystallization history coupled with the whole deformation history can be memorized. By introducing the oriented growth tensor representing the stress-free state of all formed crystals, the deformation-history dependent anisotropic crystallization and the corresponding residual deformation can be traced. The developed model is validated by comparing with the experimental data of the dynamic crystallization in amorphous poly l-lactide polymers under thermomechanical loading cycles. Finally, the predictive capability of the model is illustrated by several demonstrations, to show the influences of deformation-history dependent crystallization orientations and the corresponding anisotropic residual deformation.

Cu-based metastable microstructural template and its role in the heat flux application

The present paper focuses on developing an optimised strength-conductive alloy in Cu–Fe–Si system. We present the effect of a cost-effective rapid-casting route on modifying the microstructure. The non-equilibrium phase transformation events are tracked and the evolution sequences of metastable phases in the microstructure are elucidated. The metastable phase transformation of the precipitates from DO19- to L12-ordered structure and its role in enhancing thermal conductivity are presented. A density functional theory (DFT)-based calculation also complements the experimental evidence of the relative stability of the evolved metastable phases. One of the key findings is the evolution of L12-ordered precipitates via face centred cubic (FCC)-based interfacial matrix template.

Microstructure and mechanical properties of WRe/GH3128 alloy electron beam welded joint

This study investigates electron beam welding of WRe/GH3128 alloy, focusing on the microstructure, defects, mechanical properties, and fracture characteristics of the welded joint. Competitive grain growth within the weld, attributed to solidification rate and grain orientation, as well as the influence of electron beam keyhole oscillation on grain morphology, is analyzed. The study discusses the uneven distribution of solute concentration within the solid phase during the non-equilibrium solidification stage of the weld, along with dendritic segregation and phase transformation processes. Segregation of Cr, Re, and C elements in the interdendritic region results in abundant precipitation of σ phase and M6C. Non-equilibrium solidification phase fractions and phase transformation processes within the weld are calculated using JMartPro software. Furthermore, the potential relationship between the uneven diffusion of elements within the reaction layer and the formation of intermetallic compounds is discussed. XRD testing confirms the presence of Cr7Re3, Ni4W, Ni4Mo, and M6C within the reaction layer. The microhardness and tensile properties of the joints are evaluated, with a tensile strength of 600 MPa, representing 77% of GH3128's strength, while the elongation is only 2.5%. The increase in weld microhardness is attributed to changes in grain morphology and precipitation of M6C and σ phases, with M6C reducing joint plasticity. Cracks and defects are observed in the WRe heat-affected zone, and the role of metallurgical bonding and solid-state healing in crack repair is elucidated. Finally, an analysis is conducted on factors such as crystal microstructure defects that can lead to crack nucleation and propagation, providing separate explanations for intergranular fracture in the WRe base material and brittle fracture in the reaction layer.

Effects of rapid heating on non-equilibrium microstructure evolution and strengthening mechanisms of titanium alloy

In this paper, the effects of heating parameters, including temperature ranging from 900 °C to 1000 °C, heating rates ranging from 2 °C∙s−1 to 100 °C∙s−1, and 120 s soaking on the non-equilibrium microstructure evolution of Ti-6Al-4V alloy were studied. Microstructures after heating were characterized to reveal the mechanism of non-equilibrium phase transformation. Uniaxial tensile tests at room temperature were carried out to evaluate the effects of non-equilibrium microstructure on the mechanical properties. Results show that higher heating rate and lower temperature lead to lower β phase volume fraction and finer β grains. A transition region with element gradient forms in the αp grain near the αp/β phase boundary and transfers into β phase gradually during the heating. Rapid heating could confine the movement of the transition region, and therefore reduce the α→β transition and growth of the β phase. When the Ti-6Al-4V alloy was heated to 1000 °C at a rate of 50 °C/s and then quenched immediately, the tensile strength was improved by 19.5% and reached up to 1263.0 MPa with the elongation only decreasing from 13.6% to 9.6% compared with the initial material. The main strengthening mechanism is that the rapid heating in the single-phase region avoids the rapid growth of the β phase, which leads to fully fine martensite formation after water quenching.

Interface formation evolution of the hot-forged copper-(Cr)diamond composite and its thermal conductivity

Due to the distinction of (111) and (100) faces on the diamond particle, the preferential formation of interface layers on the diamond particle is discovered when adding metal additives like titanium, chromium, aluminum in copper/diamond composites. The formed interface would affect the thermal conductivity of the copper/diamond composites. In this study, copper-55 vol%(Cr-coated) diamond composites were successfully produced by hot forging under 800 ℃, 900 ℃ and 1050 ℃. Heat treatment of Cr-coated diamond powders was conducted under a series of temperatures for studying the evolution of the carbide interface formation on surfaces of diamond particles. It was found that the average grain size of the Cr7C3 on diamond (111) faces was larger than that on (100) faces when the temperature is below 850 ℃, and the opposite trend was observed when the heat treatment temperature is above 850 ℃. The Cr layer was fully transformed into Cr7C3 when the temperature was above 950 ℃. Unlike the results obtained after heat treatment, the interface layers was directly transformed into Cr3C2 due to the non-equilibrium phase transformation after hot forging. The Cr3C2 interface layers were preferentially kept on (100) diamond faces, and exfoliated on (111) faces after hot forging. The grain size of the formed Cr3C2 on diamond (100) faces was increased with raising the hot forging temperature. The 1050 ℃-hot-forged sample showed the highest thermal conductivity, attributed to large grain sizes of the Cr3C2 interface layer. This study elaborates the mechanisms of the evolution of the interface layer formed under different temperatures on the diamond surfaces in copper-(Cr-coated) diamond composites, and the phenomenon of preferential formation of the interface layers is verified.

Emissivity Prediction for an IR Camera During Laser Welding of Aluminum

Laser processing is becoming increasingly important in industrial applications. The success of the process relies on two fundamental parameters: the surface temperature of the medium and the thickness of the hardened layer. One of the most important factors during a laser process is certainly the temperature, which presents high temperature gradients. The speed at which a material undergoes a phase transition, the chemical reactions that take place during processing and the properties of the material are all dependent on temperature changes. Consequently, the measure of temperature is a demanding undertaking. This study proposes to measure temperature for the duration of laser welding with the infrared camera (IR) Optris PI. To restore the real temperature based on the brightness temperature values measured by the IR camera is needed to evaluate the emissivity to be attributed to the IR camera. For this purpose, firstly, the isotherms consistent with the melting point of aluminum (785 K) were assessed and then compared with the temperature distribution gauged in the zone of irradiation of the laser. Such data were then compared with the thickness of the melted zone. The use of the melting point isotherm allowed the calculation of the value of emissivity and the restoration of the temperature. Thermography software data acquisition wrongly presupposes the emissivity value does not change. This generates incorrect thermographic data. The surface emissivity normally hinges on temperature. Therefore, the values on which the literature relies may not work for materials of interest in the conditions of the process. This is particularly the case, where welding is carried out in keyhole mode (Tmax = Tvap). However, the physical phenomena involved, including evaporation and plasma plume formation, high spatial and temporal temperature gradients, and non-equilibrium phase transformations, influence the optical conditions of the brightness of the emission of light from the molten pool, making, De Facto, the emissivity value not constant. Thus, what we propose here is a methodological procedure that allows the measurement of the effective emissivity of the surface, at the same time taking into consideration the consequence of physical phenomena and the conditions of the surface. Two procedures (Standard and Simplified) capable of providing the correct emissivity value in relation to the working parameters have been proposed. The results showed that the procedures are correct, fast, and easy to use.

Mind the miscibility gap: Cation mixing and current density driven non-equilibrium phase transformations in spinel cathode materials

Cathode materials that exhibit phase transitions with large structural rearrangements during electrochemical cycling are generally seen as disadvantageous. Large volume changes and lattice mismatches between intermediate phases tend to lead to significant kinetic barriers, as well as strain and particle cracking. In this regard, solid solution reactions are more desirable as they provide lower energy barriers and no miscibility gap between co-existing phases. The high-voltage cathode material LiNi0.5Mn1.5O4 is an interesting candidate for high power and rate capability applications, however little is known on how its phase transitions occur on the particle level. In the presented work operando X-ray diffraction was utilized together with detailed peak profile analysis to elucidate the phase transition mechanism dependency on transition metal cation order and current density. When fully disordered, the material was found to undergo a bulk single-phase solid solution reaction between the intermediate phases LiNi0.44Mn1.56O4 and Li0.5Ni0.44Mn1.56O4 followed by a first order phase transition with a coherent interphase between the intermediates Li0.5Ni0.44Mn1.56O4 and Ni0.44Mn1.6O4. When fully ordered and slightly less ordered, two separate first order phase transitions with a coherent interphase between the same intermediate phases were observed. On discharge, the fast kinetics of the transition between Li0.5Ni0.44Mn1.56O4 and LiNi0.44Mn1.56O4 resulted in less strain on the former phase. For all samples the miscibility gap between the intermediate phases narrowed with increased current density, suggesting that the solid solution domain formed at the coherent interphase can be extended when the rate of (de)lithiation exceeds the movement speed of the interphase at the phase transition. This effect was found to be larger with increasing cation disorder. The influence of transition metal ordering on the ability to form solid solutions is in good agreement with computational phase diagrams of LiNi0.5Mn1.5O4, showing that disorder is important for promoting and stabilizing solid solutions. These results indicate that the degree of transition metal ordering within the material is of importance for obtaining a material with small lattice mismatches between the involved intermediate phases and for rational design of full solid solution materials.

A Simulation Study on the Effect of Residual Stress on the Multi-Layer Selective Laser Melting Processes Considering Solid-State Phase Transformation.

The selective laser melting (SLM) manufacturing process is a complex process involving moving a molten pool, rapid non-equilibrium solidification and solid phase transformation. If the thermal residual stress is too large, it may lead to warping, cracking and failure of the structures. The present work aims to establish a thermo-mechanical framework to predict temperature evolutions, molten pool configurations and residual stresses of materials in the SLM process, based on the toolpath-mesh intersection method. Moreover, the influences of the laser power, process parameters and mesh size have been discussed. The stress concentration occurred at the interface between the melt layer and substrate results in warping deformation of the materials. This work provides a novel method to reveal the resulting physical mechanism inside the molten pool in terms of residual stresses and distortions.

Diffusion-limited Nonequilibrium Phase Transformation of Nickel/Aluminum Dissimilar Materials during Laser Welding Part I: Precipitation-strengthened Polycrystalline Nickel-based Superalloy

Polycrystalline heterogeneities of grain growth, phase transformation and tensile properties are discussed by metallography, spectroscopy and fractography when choosing laser welding with butt-joint configuration to satisfactorily minimize effect of inappropriate weld pool shape on microstructure and mechanical properties of γʹʹ precipitation hardable nickel-based superalloy in aerospace industry. There is parabolic relationship between weld penetration and diffusion-limited nucleation, growth and coarseness of secondary dendrite arm spacing alongside fusion boundary through nonequilibrium solidification process, which is dendritically susceptible to grain growth variation and metallurgical discontinuities. The amount, size, morphology and distribution of nonequilibrium intermetallic phase near the dendrite boundaries are kinetically and thermodynamically rely on weld pool shape whose crystal structure is incoherent with γ solid solution austenite phase and increases preference for crack initiation and propagation of brittle intergranular and ductile dimple fracture failures to enormously contribute to losses of strength and ductility. Unsymmetrical keyhole weld is thermometallurgically inconvenient for amelioration of microstructure and mechanical properties on either side, and adversely mitigates resistance to hypereutectic-aided dendrite embrittlement. Beneficial grain refinement and suppression of detrimental nonequilibrium intermetallic phase at the same time are challenging. This problem is an integral part of inhomogeneous microstructure and mechanical properties. The finer grain size occurs, the larger grain boundary area is available for Laves/γ eutectic-type reaction and vice versa. Contributions of coarse grain kinetics and metallurgical reaction thermodynamics to weld disintegration and fracture failure mechanism of tensile properties are explained by microstructure characterization of multicomponent and multiphase weld. Finally, it is imperative to dendritically balance these important factors to minimize inevitable interface solidification products and anomalous substructure growth, and reasonably advance superior mechanical properties of reliable weld.

Effect of non-equilibrium solid state phase transformation on welding temperature field during keyhole mode laser welding of Ti6Al4V alloy

The effect of non-equilibrium solid state phase transformation on numerical simulation of welding temperature field is researched during keyhole mode laser welding of Ti6Al4V alloy. The simulation of the welding temperature field considering equilibrium phase transformation is obtained by means of the model of the heat transfer and fluid flow after the keyhole presetting. Based on the simulation considering equilibrium phase transformation, the simulation considering non-equilibrium phase transformation is modified, in terms of partitioning the regions and endowing the physical parameters considering non-equilibrium phase transformation. Compared with those considering equilibrium phase transformation in the horizontal planes, the temperature contours greater than or equal to 1300 K considering non-equilibrium phase transformation are elongated, while the temperature contours between 1100 K and 1300 K considering non-equilibrium phase transformation are shortened. The difference of the welding temperature fields considering equilibrium and non-equilibrium phase transformations basically emerges in the cooling stage. The temperature fields considering non-equilibrium phase transformation after modifying once and twice are almost the same, signifying that the simulation considering non-equilibrium phase transformation after modifying once is sufficient. The computational results considering non-equilibrium phase transformation agree well with the experimental ones in contrast with those considering equilibrium phase transformation, showing that the simulation considering non-equilibrium phase transformation after modifying once is reliable and satisfactory.

In-situ observation of the phase evolution during an electromagnetic-assisted sintering experiment of an intermetallic γ-TiAl based alloy

Electromagnetic-assisted sintering offers the possibility for a time-efficient densification of intermetallic γ-TiAl based powders. Since the microstructure of the densified material and, thus, its mechanical properties can be controlled by the imposed temperature profile, the kinetics and transformations of the occurring phases are of particular interest. The present study describes a diffraction setup for the in-situ observation of the phase evolution by high-energy X-ray diffraction during an electromagnetic-assisted sintering process using induction heating. Starting from Ti-46.3Al-2.2W-0.2B powder (in at.%), this experiment grants time-resolved insights into the non-equilibrium and equilibrium phase transformations during this powder consolidation process for the first time. The microstructural accordance of the electromagnetic-assisted sintered specimen with spark plasma sintered material densified at the same dwell temperature highlights the transferability of both techniques and allows an allocation of the determined phase transformation data to the spark plasma sintering technology.

Observation of microstructure evolution during inertia friction welding using in-situ synchrotron X-ray diffraction.

The widespread use and development of inertia friction welding is currently restricted by an incomplete understanding of the deformation mechanisms and microstructure evolution during the process. Understanding phase transformations and lattice strains during inertia friction welding is essential for the development of robust numerical models capable of determining optimized process parameters and reducing the requirement for costly experimental trials. A unique compact rig has been designed and used in-situ with a high-speed synchrotron X-ray diffraction instrument to investigate the microstructure evolution during inertia friction welding of a high-carbon steel (BS1407). At the contact interface, the transformation from ferrite to austenite was captured in great detail, allowing for analysis of the phase fractions during the process. Measurement of the thermal response of the weld reveals that the transformation to austenite occurs 230 °C below the equilibrium start temperature of 725 °C. It is concluded that the localization of large strains around the contact interface produced as the specimens deform assists this non-equilibrium phase transformation.

Nonequilibrium phase transformations in alloys under severe plastic deformation

Experimental results and theoretical concepts of anomalous phase transformations in alloys under severe plastic deformation (SPD) are reviewed. The unconventional phase and structural state of alloys that emerges as a result of SPD determines the unique combination of physical and chemical properties that is of interest for various applications in technology. The driving forces and possible mechanisms that implement the anomalous transformations as a function of SPD intensity, alloy composition, and temperature are discussed. We distinguish among these mechanisms two fundamental and qualitatively different ones that are due to: (i) direct ‘mixing’ of atoms in slip bands or (ii) accelerated diffusion on defects under locally alternating thermodynamic conditions and subsequent ‘freezing’ of the nonequilibrium state that is reached. Summarizing the experimental data and theoretical concepts regarding the change in microscopic transformation mechanisms as a function of temperature and/or intensity of treatment, we suggest a diagram of nonequilibrium stationary states attainable during the development of phase and structural instability under SPD. The proposed approach enables the prediction of the structural state of alloys and compounds by controlling thermodynamic and kinetic parameters of the system.

The emergence of dissipative structures under non-equilibrium crystallization

This research is devoted to studying the structure forming phenomena in the systems with eutectic transformations under nonequilibrium conditions. It has been demonstrated that the dissipate structures form in the liquid and solid state under nonequilibrium phase transformation. This work also considers the matter of driving forces for crystallization processes under nonequilibrium conditions of cooling alloys of eutectic systems. Having analyzed heat processes, the author has proposed a structural model for a thin layer of smelt on the crystal-liquid boundary; and according to this model, convective processes result in occurrence of cellular liquid structures shaped as even hexahedrons. Excessive temperature cooling, which occurs in such cases in the cell centers and on their boundaries, is the driving force for crystallization. These cellulars are liquid dissipate structures under nonequilibrium conditions of phase transformations. Such model have been developed for two-phase crystallization. While considering the conditions of coupled crystal growth in different phases it has been demonstrated that quasieutectics are solid dissipate structures which formed in the non-eutectic alloy compositions and which had clear section boundary with main structure. The critical overcooling must be achieved for the formation of both types of structures. It has been shown that concurrent growth of phases and formation of colonial structures are feasible at average cooling rates, only provided at least one of the phases has an atomic-rough surface.

The interplay between thermodynamics and kinetics in the solid-state synthesis of layered oxides.

In the synthesis of inorganic materials, reactions often yield non-equilibrium kinetic byproducts instead of the thermodynamic equilibrium phase. Understanding the competition between thermodynamics and kinetics is a fundamental step towards the rational synthesis of target materials. Here, we use in situ synchrotron X-ray diffraction to investigate the multistage crystallization pathways of the important two-layer (P2) sodium oxides Na0.67MO2 (M = Co, Mn). We observe a series of fast non-equilibrium phase transformations through metastable three-layer O3, O3' and P3 phases before formation of the equilibrium two-layer P2 polymorph. We present a theoretical framework to rationalize the observed phase progression, demonstrating that even though P2 is the equilibrium phase, compositionally unconstrained reactions between powder precursors favour the formation of non-equilibrium three-layered intermediates. These insights can guide the choice of precursors and parameters employed in the solid-state synthesis of ceramic materials, and constitutes a step forward in unravelling the complex interplay between thermodynamics and kinetics during materials synthesis.

On the distribution of the trace elements V and Cr in an Al–Zn–Si alloy coating on a steel substrate

The Zn–55Al–1.6Si alloy is widely used in hot-dip galvanizing to coat steel and displays a multilayered microstructure (steel substrate/intermetallic compound (IMC) layer/coating overlay) that offers protection from corrosion. Trace level V and Cr are hypothesized to influence the corrosion performance of the coated steel via localized segregation. In this paper, the distribution of trace V and Cr is studied by using synchrotron X-ray fluorescence microscopy (XFM) and scanning transmission electron microscopy (STEM). It is revealed that V and Cr are both primarily segregated into the IMC layer and the top surface layer of the coating and are distributed continuously. The average concentrations for V and Cr are measured by XFM to be 7.7 ppm and 15.2 ppm in the IMC layer, and 4.6 ppm and 19.4 ppm on the top surface, respectively. STEM shows that the V distribution in the IMC layer is localized on the side adjacent to the coating overlayer. It is proposed that the IMC layer forms in two ways. One is the equilibrium phase transformation at 600 °C in the liquid Zn–55Al–1.6Si bath. The other way is the nonequilibrium phase transformation at the IMC/overlayer interface after V and Cr are rejected during solidification of the overlayer.

Processing of X65MoCrWV3‐2 Cold Work Tool Steel by Laser Powder Bed Fusion

Laser powder bed fusion (L‐PBF) of forming tools has become of major interest in the tooling industry because of the high geometrical flexibility of this process. During L‐PBF, a metallic powder bed is melted selectively by a laser beam, enabling the layer‐wise manufacturing of parts from 3D computer‐aided design data. The process is characterized by a locally and temporally unsteady heat flow in the solidified part and in the melt pool, causing nonequilibrium solidification and phase transformations. In addition, rapid heating and cooling occur, promoting the formation of microstructural defects, cold cracks, and distortion. Because of the high tendency to form cold cracks, processing of martensitic tool steels is still a challenging task. Tool steel X65MoCrWV3‐2 is processed by L‐PBF and the resulting microstructure and the associated local properties are investigated by microhardness measurements, nanoindentation, and scanning electron microscopy. It is gathered from the investigations that regions of different microstructures and mechanical properties on both micro‐ and macroscale are present in the L‐PBF‐densified steel. The different microstructures and properties are the result of the alternating heat insert at different temperature regimes, forming heat‐affected zones in which the tempering processes are triggered and strongly varying properties are generated.

Неравновесные фазовые превращения в сплавах при интенсивной пластической деформации

Неравновесные фазовые превращения в сплавах при интенсивной пластической деформации