Phase Transformations In Metals Research Articles

Plasmonic Au3Cu Ordered Nanocrystals Induced Phase Transformation in 2D‐MoS2 for Efficient Hydrogen Evolution

AbstractThe synthesis of ordered gold‐copper (Au3Cu) alloy nanocrystals (≈10 nm) is reported and used in the semiconductor (2H) to metallic (1T) phase transformation of an atomically thin large‐area 2D‐MoS2 grown via CVD technique. The ordered Au3Cu nanocrystals are dispersed over 2D‐MoS2, and the phase transformation is confirmed via Raman spectroscopy followed by X‐ray photoelectron spectroscopy (XPS), while the surface properties of the Au3Cu/2D‐MoS2 is determined by the XPS valence band analysis and ultra‐violet photoemission spectroscopy (UPS). By comparing overpotential and Tafel slopes for Hydrogen Evolution Reaction (HER), a decrease is observed in overpotential by 83.2 mV and Tafel slope by ≈58.25 mV per decade for Au3Cu/MoS2 on light irradiation. This electrocatalytic enhancement of Au3Cu/MoS2 refers to the transformation of semiconducting 2D‐MoS2 to metallic phase under light illumination, thereby altering the surface electronic structures, improving carrier concentrations, lowering the valence band edge, and lowering the free energy of H* adsorption/desorption. Density functional theory (DFT) calculations, along with other surface characterizations, further illustrate that the ordered nanocrystal‐induced phase transformation in 2D‐MoS2 leads to a more durable metallic characteristic, thus, enhancing the surface electrical conductivity, reducing surface potential and Gibbs free energy, and improving the kinetics of photoelectrocatalytic performance of the hybrid structure.

Research on magnetic memory inspection signal characteristics of multi-parameter coupling pipeline welds

Magnetic memory inspection technology is an effective method for detecting early damage in ferromagnetic materials. However, the commonly used force-magnetic coupling models are insufficient for analyzing the distribution characteristics of magnetic signals in ferromagnetic material welds. This study first analyzes the influence of metal phase transformation and residual stress on the magnetic hysteresis characteristics of materials. Based on the principle of magnetic hysteresis characteristics, the magnetic charge density under the combined action of stress and phase transformation is determined, and a magnetic memory analysis model is established for multi-parameter coupling. The study quantitatively calculates the effects of phase transformation volume fraction, residual stress, the lift-off effect, and cracks on the magnetic signal features at welds. The research results show that the magnetic memory signals at welds exhibit extreme values in the tangential component and sinusoidal fluctuations with zero-crossings in the normal component. The peak-to-peak values of both the normal and tangential components of the magnetic signal increase with an increase in metal phase transformation and residual stress, while they decrease with the increase of the lift-off effect. When cracks appear in the weld, the normal component exhibits a double-peak and valley structure, with the inner side representing crack features and the outer side representing weld features. The tangential component shows a maximum value at the center of the crack. Based on the peak and valley values of the magnetic signal, a damage grade index F is determined. The damage index F can characterize the level of weld damage, decreasing approximately linearly with increasing stress.

In situ measurement of austenite grain growth and recrystallization using laser ultrasonics

The development of next generation process models and advanced high-strength steel products for thin slab casting and direct rolling requires quantification of microstructure evolution during thermomechanical processing. Laser ultrasonics is a non-contact in-situ method to record grain growth, recrystallization and phase transformations in metals and alloys. Here, we will present an improved experimental design that facilitates a continuous microstructure measurement through the various stages of simulated hot rolling from reheating to runout table cooling using a Gleeble thermomechanical simulator equipped with a laser ultrasonics for metallurgy (LUMet) system. Austenite grain growth and static recrystallization after hot deformation are quantified based on attenuation of the ultrasound waves whereas austenite decomposition can be recorded with the changes in ultrasound velocity during the phase transformation. Further, the LUMet results for a microalloyed low carbon steel are validated with conventional techniques including optical and electron microscopy as well as double-hit tests. These experimental studies demonstrate the capabilities of laser ultrasonics in the identification of both normal and abnormal grain growth, non-recrystallization temperature, recrystallization, and austenite decomposition kinetics in a single test for a given processing path, as well as its potential for accelerated optimization of process control under industrial rolling conditions.

In situ formed partially disordered phases as earth-abundant Mn-rich cathode materials

AbstractEarth-abundant cathode materials are urgently needed to enable scaling of the Li-ion industry to multiply terawatt hours of annual production, necessitating reconsideration of how good cathode materials can be obtained. Irreversible transition metal migration and phase transformations in Li-ion cathodes are typically believed to be detrimental because they may trigger voltage hysteresis, poor kinetics and capacity degradation. Here we challenge this conventional consensus by reporting an unusual phase transformation from disordered Li- and Mn-rich rock salts to a new phase (named δ), which displays partial spinel-like ordering with short coherence length and exhibits high energy density and rate capability. Unlike other Mn-based cathodes, the δ phase exhibits almost no voltage fade upon cycling. We identify the driving force and kinetics of this in situ cathode formation and establish design guidelines for Li- and Mn-rich compositions that combine high energy density, high rate capability and good cyclability, thereby enabling Mn-based energy storage.

Investigation of structural-phase transformations of weld metal and in the heat-affected zone during laser welding

The use of laser equipment is one of the promising ways to create innovative and highly efficient technologies in the production of ship structures. The main advantages of using laser technologies in the production of marine equipment are increased productivity by increasing the speed and reducing the number of welding passes, improving the quality of welded joints due to the accuracy of the assembly of structures and the level of automation, reducing the level of residual stresses, warping and leash due to significant localization of the heating and penetration zone compared with arc welding technologies, a significant reduction in the consumption of welding materials or their complete exclusion due to the smaller dimensions of the geometry of the cutting edges and the width of the assembly gaps. The mechanical properties of the welded joint are determined by the composition of the steel and its structure. The structural- phase transformations of the weld metal are determined by the temperature-time parameters that occur in the seam zone itself and in the heat-affected zone. Laser welded joints are formed under conditions in which thermal cycles differ significantly in depth and width of the weld, so the mechanical properties of the joint are determined by local changes in the structure of the seam metal and heat-affected zone. The issues of formation of the phase composition of the seam zone and heat-affected zone during laser welding are examined in the paper. On the basis of numerical modeling of thermal processes and structural- phase transformations of weld metal and heat-affected zone accompanying laser welding, a method for quantifying the volume fraction of structural- phase components of weld metal and heat-affected zone is proposed. The proposed calculation algorithm avoids solving the equation for the amount of the volume fraction of the structural- phase components of the metal at each step of the calculations.

Influence of welding method on residual stress and metallography of a mild steel welded butt-joint plate

During welding process and cooling process after welding, residual stress will be generated and the microstructure of the weld joint will be changed inevitably, which will be harmful for mechanical performance of welded structures. Hence, it is necessary to study welding-induced residual stress and metallic phase transformation, so as to provide guidance for optimization of welding process. In this paper, three butt-joint plates were fabricated by using different welding methods including shielded metal arc welding (SMAW), gas metal arc welding (GMAW), and submerged arc welding (SAW). Secondly, welding residual stress was measured through blind-hole method. Thirdly, the microstructure of the welded joint was analyzed. Fourthly, thermal elastic-plastic finite element method (FEM) was used to numerically simulate the welding process. Finally, heat cycling curves of typical gauged points were extracted, the mechanism of how welding induces residual stress and phase transformation was analyzed from the perspective of cooling rate. Experimental and numerical results show that compared with longitudinal stress, the influence of welding method on transverse stress is more significant. When SMAW is used for welding process, the distribution of transverse residual stress is more uniform than that using GMAW and SAW. Under the three welding methods, the welded joints show similar metallographic compositions. However, the content and distribution of different metallographic compositions are quite different.

Phase transformation in some hexahydrated metal(II) fluorogermanates and fluorotitanates: Optical and differential scanning calorimetry studies

• Single crystals of hydrated fluorides CoGeF 6 ∙6H 2 O, FeGeF 6 ∙6H 2 O, CoTiF 6 ∙6H 2 O, ZnTiF 6 ∙6H 2 O were grown. • Twinning, birefringence and heat capacities indicate a phase transition of the first order from trigonal to monoclinic symmetry. • Small values of the change in entropy and birefringence accompany the phase transition of CoGeF 6 ∙6H 2 O and FeGeF 6 ∙6H 2 O, and rather large values are typical for CoTiF 6 ∙6H 2 O and ZnTiF 6 ∙6H 2 O. Graphical abstract_Synopsis!!! Polarization-optical observations of (001) section of an ABF 6 ∙6H 2 0 crystals: a − optically isotropic rhombohedra phase ( T > T 0 ). Twin pattern in the studied crystals at Т < Т 0 : b − CoGeF 6 ∙6H 2 O; c − FeGeF 6 ∙6H 2 O; d − FeTiF 6 ∙6H 2 O; e − CoTiF 6 ∙6H 2 O; f − ZnTiF 6 ∙6H 2 O.

A shortcut approach for cooperative disposal of flue dust and waste acid from copper smelting: Decontamination of arsenic-bearing waste and recovery of metals

Recovering harmful elements (As, Pb) and metals (Cu, Bi, Zn) from copper smelting flue dust (CSFD) is a critical subject and task for arsenic contamination control and resource sustainability. In this work, a two-step pyrometallurgical process was developed to preferentially separate arsenic and recover metals from CSFD. During the low-temperature roasting, arsenic-bearing waste acid (AWA) from copper industry was used as an additive and effective removal of arsenic (97.8 %) was obtained at 350 °C, which follows the idea of “treating waste with waste”. Subsequently, the recovery and separation of metals were well-achieved based on the affinity between metals and sulfur in the second stage of roasting, by which 91.28 % of Pb and 95.65 % of Bi were recovered as an alloy (Pb 86.48 %, Bi 13.21 %), while 82.62 % of Cu was enriched in the matte. The migration rules of metal elements and phase transformation in the whole process were studied in-depth from theory and experiments. This process can realize the efficient removal of arsenic as well as effective recovery of metals via cooperative disposal of CSFD and AWA, and minimize the environmental impacts.

Thermal behavior and failure mechanisms of 18650 lithium ion battery induced by overcharging cycling

Overcharging is one of the most serious safety problems in large-scale application of lithium ion battery (LIB). An in-depth understanding of the failure mechanism of battery overcharge is necessary to guide the safe design of battery system. In this paper, the electrochemical performance of commercial 18650-type cylindrical battery with Li(Ni0.5Co0.2Mn0.3)O2 cathode and graphite anode as the background is evaluated with different state of charge (SOC). The dynamic thermal behavior of overcharge in adiabatic conditions is studied, and the cathode materials, separator and anode materials after long-term overcharge cycle are characterized to identify the side reactions in battery. The results show that the battery impedance increases with the increase of SOC, and thereby greatly accelerating the attenuation of battery capacity. When LIB is charged and discharged in adiabatic conditions, the battery surface temperature of 116% SOC is about 10.03 °C higher than that of 100% SOC. Therefore, the battery with higher SOC has higher heating and is easy to induce the thermal runaway reactions. During the overcharge cycle, electrolyte decomposition, transition metal dissolution and phase transformation occur at the cathode, and serious lithium plating occur at the anode, as a result, increasing battery impedance, accelerating aging and increasing heat production. These results provide feasible support for understanding the overcharge mechanism and battery management system.

Study on the mechanism of plasma jet surface hardening of rail steels by using numerical method

A multi-physics coupled numerical analysis method that fully considers the hydromechanical properties of the plasma jet was created in this paper. It was used to analyze the evolution of the metallic solid-state phase transformation, and that of the stress state, during the process of laminar plasma selective quenching (LPQ). By this method, the mechanism of LPQ was investigated. It is found that the plasma impact can significantly affect the residual stress distribution, and there is a close relationship between the residual stress distribution and the hardened layer distribution; During LPQ, the material bears tremendous alternating stress within the first 10 s, then the maximum stress begins to gradually decrease; 100 s later, the stress distribution stabilizes. This study has contributed to the understanding of the LPQ mechanism of rail steel.

How magnetic field affects catalytic CO2 hydrogenation over Fe-Cu/MCM-41: In situ active metal phase—reactivity observation during activation and reaction

In this work, a systematic investigation of external magnetic field affecting metal phase transformation of Fe-Cu/MCM-41 catalysts both during activation and reaction, and their performances by means of CO2 conversion and C2 + C3 hydrocarbons selectivity were for the first time examined in-situ using time-resolved X-ray absorption spectroscopy (TRXAS) and an online quadrupole mass spectrometer. The in-situ XANES result confirmed that FeO and Fe3O4 are major active forms of the catalyst. With magnetic flux intensities of 28.91–58.59 mT, iron oxide phases, specifically Fe3O4 and FeO, within the catalysts were stabilized and maintained. The CO2 conversion was increased for 1.03 – 1.09 times, while the concentrations of C2 + C3 hydrocarbons were considerably improved by 24.03 – 35.37 times compared to those without magnetic field. The reaction steps of CO2 hydrogenation were theoretically confirmed on the isolated catalysts using M06-L with the 6-31G(d,p) + LANL2DZ mixed basis set based on the results from LCF analysis. Fe4, Fe4O4, and Fe2Cu2 clusters were used to represent the active species of pristine Fe and iron oxide (FeO) and bimetallic Fe-Cu catalyst, respectively. It was found that CO2 hydrogenation could take place via the bimolecular route in which adsorbed CO2 on the Fe center was hydrogenated by dissociative adsorption of H2 on the Cu center—promoting chain growth probability of CO2 to form C2 + C3 hydrocarbons due to the active iron oxides (Fe3O4 and FeO) were maintained by magnetic field during the reaction.

Seebeck Coefficient in a Cuprate Superconductor: Particle-Hole Asymmetry in the Strange Metal Phase and Fermi Surface Transformation in the Pseudogap Phase

We report measurements of the Seebeck effect in both the $ab$ plane ($S_{\rm a}$) and along the $c$ axis ($S_{\rm c}$) of the cuprate superconductor La$_{1.6-x}$Nd$_{0.4}$Sr$_{x}$CuO$_4$ (Nd-LSCO), performed in magnetic fields large enough to suppress superconductivity down to low temperature. We use the Seebeck coefficient as a probe of the particle-hole asymmetry of the electronic structure across the pseudogap critical doping $p^{\star} = 0.23$. Outside the pseudogap phase, at $p = 0.24 > p^{\star}$, we observe a positive and essentially isotropic Seebeck coefficient as $T \rightarrow 0$. That $S > 0$ at $p = 0.24$ is at odds with expectations given the electronic band structure of Nd-LSCO above $p^{\star}$ and its known electron-like Fermi surface. We can reconcile this observation by invoking an energy-dependent scattering rate with a particle-hole asymmetry, possibly rooted in the non-Fermi liquid nature of cuprates just above $p^{\star}$. Inside the pseudogap phase, for $ p < p^{\star}$, $S_{\rm a}$ is seen to rise at low temperature as previously reported, consistent with the drop in carrier density $n$ from $n \simeq 1 + p$ to $n \simeq p$ across $p^{\star}$ as inferred from other transport properties. In stark contrast, $S_{\rm c}$ at low temperature becomes negative below $p^{\star}$, a novel signature of the pseudogap phase. The sudden drop in $S_{\rm c}$ reveals a change in the electronic structure of Nd-LSCO upon crossing $p^{\star}$. We can exclude a profound change of the scattering across $p^{\star}$ and conclude that the change in the out-of-plane Seebeck coefficient originates from a transformation of the Fermi surface.

Evolution of the mixed-mode character of solid-state phase transformations in metals involving solute partitioning

Abstract Partitioning phase transformations in the solid state are principally subjected to two processes that take place: the redistribution, through long-range diffusion, of the partitioning element, and the lattice transformation taking place at the interface. Consequently, the usual approximation to consider one of these two processes as controlling the rate of the phase transformation is of limited accuracy. For a more accurate description, the so-called mixed-mode character of partitioning phase transformations is to be taken into account. In the present study, it is shown that the mixed-mode character can be quantified and that it has a significant effect on the kinetics. By means of examples involving either substitutional (Mo in Ti) or interstitial (C in Fe) partitioning elements, it is shown that a gradual change of the character of the transformation occurs during the phase transformation, shifting from initially interface-controlled (which implies the largest interface velocity) towards more diffusion-controlled.

Kinetics study of heavy metal removal from the lead smelting slag by carbothermic reduction: Effect of phase transformation

As an environmentally hazardous waste, the lead smelting slag was considered as a potential secondary resource of valuable metals (Zn, Pb, and Sn) if recycled. In this study the removal mechanism and kinetics of Zn, Pb, and Sn from the lead slag by carbothermic reduction at 1423–1473 K were investigated. Microstructure evolution of the pellets and phase transformation of heavy metals was analyzed by XRD and SEM/EDS. The kinetics behaviors of heavy metal volatilization were associated to the phase transformation. The results showed that Zn, Pb and Sn removal were controlled by the three-dimensional internal diffusion. Interestingly, the volatilization of Zn presented a consistent kinetics behavior, because the volatile phases of Zn were always metallic Zn in the whole reaction process. However, the volatilization of Sn and Pb conformed to a two-staged kinetics model. It was because that the nonvolatile polymetallic sulfides (Fe-Sn-Pb-S) and Fe-Pb-Sn alloy generated with metallic iron at a higher metallization degree, which hindered the internal diffusion of Sn and Pb. On the basic of this, a staged kinetics model of heavy metal removal was established, and the apparent rate constants and activation energies were determined.

Влияние химического состава матрицы на структуру и свойства монолитных СВС-композитов

Introduction. The development of new wear-resistant materials obtained by the method of self-propagating high-temperature synthesis (SHS) is an urgent problem in materials science. The SHS method is most widely used in the field of creating new powder materials. Much less attention has been paid to the production of monolithic non-porous composites. For monolithic composites, it is very important to identify the role of the metal matrix and phase transformations in the process of secondary structure formation after the completion of the synthesis process when the obtained material is cooled. The aim of this work was to carry out a comparative analysis of the structure and properties of SHS composites of the Fe-Ti-C-B, Fe-Ni-Ti-C-B, Fe-Ni-Cr-Ti-C-B, and Cu-TiC-B systems. Materials and research methods. Composites were obtained from powder mixtures consisting of thermoreactive components Ti, C, and B, as well as matrix Fe, Fe-Ni, Fe-Ni-Cr, and Cu. The initial powders were thoroughly mixed, loaded into a steel tube container, and the powder mixture was preliminary compacted. Then, the workpieces were heated in an electric furnace to the temperature of the onset of autoignition. After completion of the SHS, the workpieces were deformed with a force of 250 MPa in a hydraulic press at a temperature not lower than 1000 ° C. Samples were cut from the obtained sandwich plates for microstructural studies, density determination, hardness measurements, transverse bending tests and abrasive wear resistance tests. Results and discussion. All investigated composites were characterized by an uneven distribution of strengthening particles TiC and TiB2 over the volume. The use of the Fe-Ni matrix led to the formation of regions with the γ-Fe + Fe2B eutectic structure in the composite and an additional strengthening phase Ni3Ti. The use of Fe-Ni-Cr metal-matrix components led to the formation of two solid solutions in the matrix - austenite and ferrite, and Cr23C6 particles were formed along the boundaries of austenite grains. The maximum transverse bending strength was shown by SHS composites of the Fe-Ti-C-B and Cu-Ti-C-B systems with a matrix of FCC solid solutions. All composites had a hardness of 66 -72 HRC and showed the same abrasion resistance.

A Review of the Boiling Curve with Reference to Steel Quenching

This review presents an analysis and discussion about heat transfer phenomena during quenching solid steel from high temperatures. It is shown a description of the boiling curve and the most used methods to characterize heat transfer when using liquid quenchants. The present work points out and criticizes important aspects that are frequently poorly attended in the technical literature about determination and use of the boiling curve and/or the respective heat transfer coefficient for modeling solid phase transformations in metals. Points to review include: effect of initial workpiece temperature on the boiling curve, fluid velocity specification to correlate with heat flux, and the importance of coupling between heat conduction in the workpiece and convection boiling to determine the wall heat flux. Finally, research opportunities in this field are suggested to improve current knowledge and extend quenching modeling accuracy to complex workpieces.

Pop-In Phenomenon as a Fundamental Plasticity Probed by Nanoindentation Technique.

The attractive strain burst phenomenon, so-called “pop-in”, during indentation-induced deformation at a very small scale is discussed as a fundamental deformation behavior in various materials. The nanoindentation technique can probe a mechanical response to a very low applied load, and the behavior can be mechanically and physically analyzed. The pop-in phenomenon can be understood as incipient plasticity under an indentation load, and dislocation nucleation at a small volume is a major mechanism for the event. Experimental and computational studies of the pop-in phenomenon are reviewed in terms of pioneering discovery, experimental clarification, physical modeling in the thermally activated process, crystal plasticity, effects of pre-existing lattice defects including dislocations, in-solution alloying elements, and grain boundaries, as well as atomistic modeling in computational simulation. The related non-dislocation behaviors are also discussed in a shear transformation zone in bulk metallic glass materials and phase transformation in semiconductors and metals. A future perspective from both engineering and scientific views is finally provided for further interpretation of the mechanical behaviors of materials.

Helium-bubble-enhanced disordering of intermetallic phase under irradiation

Understanding and controlling phase transformations in metals and alloys under irradiation is vital to the design of irradiation-tolerant materials. The L12-ordered intermetallic phase in nickel-based superalloys provides superior high-temperature mechanical properties and corrosion resistance. Here, we studied the order-disorder transformation kinetics of an L12-structured gamma-prime phase in nickel-based superalloy Rene N4 under krypton ion irradiation and the effect of pre-implanted helium gas bubbles on the kinetics of phase transformation. The presence of pre-implanted helium gas bubbles significantly enhances the order-disorder transformation of L12-structured gamma-prime phase under irradiation at 300 °C. The evolution of pre-implanted helium gas bubbles under irradiation implies that helium gas bubbles could effectively trap irradiation-induced vacancies and impede the reordering process of anti-site defects in gamma-prime phase.

Physical Properties Of Rare Earth Elements

The article studies the physical properties of rare earth metals, pays special attention to their unique properties, studies the main aspects of the application of rare earth metals in industry. Also, the structure and stability of various forms of sesquioxides of rare earth elements, in particular, europium, as well as the effect of the method of oxide preparation on its structure and properties are considered. The analysis of the ongoing phase transformations of rare earth metals is made. The article emphasizes the use of correct choices to achieve a large technical and economic effect when using rare earth metals in industry. The article is intended for teachers working in the field of physics and chemistry, as well as for students of the specialty "physics and chemistry".

Spinel ferrite transformation for enhanced upgrading nickel grade in laterite ore of various types

Upgrading nickel grade in low-grade nickeliferous laterite ores before metallurgical extraction process is of utmost importance. However, most of nickel exists mainly in the form of isomorphism in serpentine or goethite, resulting in difficulty in upgrading of nickel by physical separation methods. In this paper, spinel ferrite transformation for enhanced upgrading nickel grade in laterite ore of various types was proposed. The mineral phase transformation and migration of valuable metals for various laterite ores during calcination process was investigated, as well the influences of mineral phases and chemical compositions on magnetic properties, separation efficiency, and nickel contents in separated laterite ore. The results show that spinel nickel ferrite mainly composed of nickel oxide and iron oxide could be completely formed after calcined at 800, 1000 and 900 °C for limonite, saprolite and transition laterite ore, respectively. With the increase of calcination temperature, the crystallinity and saturation magnetization Ms value of as-calcined samples become improved, leading to increased nickel recovery, while the nickel content in magnetic fraction is first increased and then slightly decreased. Under the optimum calcination conditions, the nickel recovery for limonite, saprolite and transition laterite ore could reach 68.5%, 68.9% and 67.3%, respectively, while the nickel contents in magnetic fraction are 3.01%, 3.23% and 3.15% with increasing by 1.82, 2.27 and 2.11 times, respectively. This paper could provide theoretical basis and technology support for enhanced upgrading of valuable metals from complex associated mineral resources.