Transformation Kinetics Research Articles

Effect of prior martensite on bainitic transformation of high Si hypereutectoid steel

The paper discusses the effect of prior martensite on the bainitic transformation of a high Si hypereutectoid steel. The research uses a combination of experimental techniques, high-resolution dilatometry and X-ray diffraction analysis, and theoretical calculations to investigate the impact of martensite on the transformation kinetics and microstructure evolution. The study shows that the presence of martensite, regardless of the amount, accelerates the bainitic transformation, particularly in the early and fastest stages, and at higher isothermal transformation temperatures. At lower temperatures, the preconditioning of the austenite prior to the bainitic transformation is such that its mechanical stability increases to the point where the whole transformation is inhibited. It is also suggested that the formation of cementite due to the tempering of martensite at the isothermal stage controls the final fraction of bainitic ferrite. The findings provide valuable insights into the role of prior martensite in bainitic transformation kinetics and microstructure development.

Improved uniform ductility in a high-carbon pearlitic steel via microstructural homogeneity architecture

In this work, the nucleation and growth kinetics of pearlitic transformation are quantitatively investigated to unveil the distinctive microstructural evolution behavior under a high undercooling degree. Both intra-granular and inter-granular nucleation increasingly occur with 1-2 orders of magnitude increase in nucleation rate N˙. However, a moderate increase in the growth rate GV, namely a larger N˙/GV ratio, leads to a 30%–40% size reduction in pearlitic colonies. The avalanche-type increase in nucleation events induces a more random distribution of ferrite orientation among colonies that possess a slight increase in relative misorientation but a pronounced increase in accumulative misorientation, and an arbitrary alignment of Fe3C lamellas in colony interior. Such improved microstructural homogeneity ensures more uniform and localized deformability, which allows compatible deformation between colonies or within colonies and prevents the expansion of newly-formed cracks. These results provide guidance for industrial manufacture of high-carbon pearlitic products with high safety and reliability, resulting from the improvement in localized deformability, and for low-cost wires via reducing the drawing passes, stemming from the significant increase in uniform deformability.

Description of martensitic transformation kinetics in Fe–C–X (X = Ni, Cr, Mn, Si) system by a modified model

Description of martensitic transformation kinetics in Fe–C–X (X = Ni, Cr, Mn, Si) system by a modified model

Effect of applied stress on bainite transformation, microstructure, and properties of 15CrMo steel

The effect of external stress on the isothermal bainite transformation kinetics and microstructure of 15CrMo steel was studied using dilatometer, optical microscopes (OM), electron back-scatter diffraction (EBSD), scanning electron microscopes (SEM) and X-ray diffraction (XRD). The results show that the additional mechanical driving force provided by the external stress promotes the transformation of bainite, resulting an increase volume fraction of bainite-ferrite (BF) and causing the BF laths to become slender. The application of external stress can also induce selective orientation during the bainite transformation process, and the orientation relationship between the prior austenite and the BF under stress is closer to the Kurdjumov-Sachs (K-S) relationship. There is also an incomplete transformation of bainite transformation under stress. At the same time, the Vickers hardness of 15CrMo steel would increase after applying external stress. The mechanical driving forces calculations demonstrate that when tensile stress and compressive stress are of similar magnitudes, they provide comparable mechanical driving forces. As a result, they exert similar effects on the kinetics of bainite transformation, leading to no discernible differences in the resulting bainite microstructure.

Influence of Q&P-Parameters and Al-Content on the Microstructural Evolution of Lean-Medium-Mn-Steels

Abstract This report investigates the impact of different heat treatment parameters and varying Al-contents on the microstructure of Quenching & Partitioning (Q&P) steels. Therefore, three lean-medium-Mn-steels with Al-contents between 0.3 and 0.9 wt-% underwent heat treatments according to Quenching & Partitioning regimes. For comparison, the steels were subjected to a transformation induced plasticity (TRIP) aided-bainitic-ferrite (TBF) process. In both cases, the samples were fully austenitized at 900 °C for 120 s, using dilatometry. For the Quenching & Partitioning process, the quenching temperature (TQ) ranged from 210 °C to 330 °C, while the transformation induced plasticity (TRIP) aided-bainitic-ferrite samples were cooled to 360 °C. Afterwards, the specimen were re-heated to the partitioning temperature (TP) of 400 °C and isothermally held for partitioning times (tp) of 40, 120 and 200 s. Subsequently, these steels were analyzed with regard to their phase fractions and hardness. The results indicated that in the Quenching & Partitioning process, the microstructure was primarily influenced by the partitioning temperature (TQ), while partitioning times (tp) played a minor role due to the time-independent martensitic transformation during quenching. In general, rising quenching temperature (TQ) led to an increase in retained austenite (RA) fraction. In the transformation induced plasticity (TRIP) aided-bainitic-ferrite (TBF) process, a substantial influence of partitioning times (tp) was found, which can be explained by the kinetics of the isothermal bainitic transformation. Regardless of the heat treatment concept, an increasing Al-content contributed to elevated retained austenite contents.

Hydrothermal Destruction and Defluorination of Trifluoroacetic Acid (TFA).

Per- and polyfluoroalkyl substances (PFAS) have received increased attention due to their environmental prevalence and threat to public health. Trifluoroacetic acid (TFA) is an ultrashort-chain PFAS and the simplest perfluorocarboxylic acid (PFCA). While the US EPA does not currently regulate TFA, its chemical similarity to other PFCAs and its simple molecular structure make it a suitable model compound for studying the transformation of PFAS. We show that hydrothermal processing in compressed liquid water transforms TFA at relatively mild conditions (T = 150-250 °C, P < 30 MPa), initially yielding gaseous products, such as CHF3 and CO2, that naturally aspirate from the solution. Alkali amendment (e.g., NaOH) promotes the mineralization of CHF3, yielding dissolved fluoride, formate, and carbonate species as final products. Fluorine and carbon balances are closed using Raman spectroscopy and fluoride ion selective electrode measurements for experiments performed at alkaline conditions, where gas yields are negligible. Qualitative FTIR gas analysis allows for establishing the transformation pathways; however, the F-balance could not be quantitatively closed for experiments without NaOH amendment. The kinetics of TFA transformation under hydrothermal conditions are measured, showing little to no dependency on NaOH concentration, indicating that the thermal decarboxylation is a rate-limiting step. A proposed TFA transformation mechanism motivates additional work to generalize the hydrothermal reaction pathways to other PFCAs.

Two-dimensional SnP3 monolayer for inhibiting the shuttle effect in lithium-sulfur batteries: A first-principles study

The problems of the shuttle effect and sluggish transformation kinetics of lithium polysulfides (LiPSs) severely inhibit the practical application of Li-S batteries. Exploring anchoring materials with catalytic properties is an effective way to overcome these obstacles. In this paper, the electrochemical performance of SnP3 monolayer as an anchoring material is explored by using first-principles calculations. SnP3 monolayer can effectively anchor soluble LiPSs under vacuum and solvent conditions, and provides abundant adsorption sites for anchoring multiple LiPSs. Importantly, the rate-limiting step has changed to the conversion of Li2S8 to Li2S6, suggesting that the monolayer can facilitate the conversion of LiPSs and inhibit their accumulation in the electrolyte. Furthermore, lower decomposition and diffusion barriers of Li2S effectively inhibit the volume expansion of Li-S batteries. Thus, SnP3 monolayer becomes a promising anchoring material with suitable catalytic properties. This work demonstrates the feasibility of SnP3 monolayer as an anchoring material and expands the membership of phosphide family for applications in the field of Li-S batteries.

ЗАСТОСУВАННЯ МАТЕМАТИЧНОГО МОДЕЛЮВАННЯ ПРИ АНАЛІЗІ ДИЛАТОГРАМ МАРТЕНСИТНОГО ПЕРЕТВОРЕННЯ У СТАЛЯХ

The paper provides practical experience of applying mathematical modeling in the analysis of the kinetics of athermal martensitic transformation in low-alloy structural steel 30HGSA (Fe-0.30С-0.86Si-1.02Mn-0.84Сr, % wt.) using the dilatogram of the real quenching process. The change in the amount of martensite formed in the studied steel as a function of temperature during continuous quenching cooling is shown. The used technique for determining the phase ratio provides in situ correlation with the microstructural mechanisms implemented in the studied material during heat treatment. The obtained results will be used to develop parameters of heat treatment based on the principle of quenching and partitioning (Q&amp;P) to improve the complex of properties of 30HGSA steel due to the creation of a multiphase structure.

Effects of two-step austempering processes on the wear resistance and fatigue lifetime of high-carbon nanostructured bainitic steel

The previous research on two-step austempering processes have been mainly focused on the bainitic transformation kinetics, with few details the relationships between the parameters of two-step austempering process and the wear properties and fatigue lifetime. In this paper, the effects of two-step austempering process on wear resistance and fatigue life of high carbon nano-bainite steel were investigated. The results show that the first-step bainite with high volume fraction prolongs the total bainite transformation time. The two-step austempering samples contain finer bainitic ferrite plate and higher volume fraction of retained austenite, as well as resent excellent hardnesses, tensile properties, wear resistance and fatigue lifetime. In particular, the wear resistance of the 50%-290 °C sample is better than that of the 210 °C sample, this is caused by the transformation of the high fraction of retained austenite in the two-step austempering samples into hard martensite and the microstructure refinement zone that forms on the surface of the sample during the wear process. The 50%-290 °C sample have better fatigue properties at low total strain amplitudes (0.7% and 0.8%). When the total strain amplitude is 0.7%, the fatigue life of the 50%-290 °C sample is 57.5% higher than that of the 210 °C sample, which is because of the higher yield strength and finer microstructure of the 50%-290 °C sample. These results support the later study of controlling two-step austempering process for high-carbon nanostructured steels.

Enhanced electrochemical oxidation of 5-hydroxymethylfurfural over tailored nickel nanoparticle assembly

Nickel-based materials are promising electrocatalysts for anodic oxidation of 5-hydroxymethylfurfural (HMF) to value-added 2, 5-furandicarboxylic acid (FDCA). However, their catalytic efficiency is impeded by the sluggish phase transformation of Ni(II) hydroxide to the active Ni(III) oxyhydroxide. Herein, we demonstrate for the first time that the phase transformation kinetics and the HMF oxidation activity of nickel nanoparticles can be modulated by creating self-assemblies with different particle aggregation structures: ordered nanoarrays, disordered nanoarrays, and random aggregates. Notably, the nanoparticle assembly featuring an ordered nanoarray structure exhibits the highest activity, achieving 99.8 % HMF conversion and 99.2 % FDCA yield at 1.36 V. In situ Raman spectroscopy and electrochemical analysis reveal that the ordered nanoarray effectively accelerates the transformation kinetics, attributed to the reduced dehydrogenation barrier of Ni(II) hydroxide as confirmed by density functional theory calculations. This work contributes new insights into the structure-performance relationship of Ni-based catalysts, offering valuable guidance for designing high-performing electrocatalysts.

Photochemical behaviour and toxicity evolution of phenylbenzoate liquid crystal monomers in water

Liquid crystal monomers (LCMs) are a group of emerging pollutants that pose potential environmental risks because of their ubiquitous occurrence and toxicity. Understanding their environmental transformation is essential for assessing the ecological risk. In this study, we investigated the photochemical transformation kinetics, mechanism, and photo-induced toxicity of three phenylbenzoate LCMs in water. Their apparent photolytic rate constants were within (0.023 – 0.058) min-1, and the half-lives were < 30.0 min, showing lower persistence in water. Dissolved organic matter significantly inhibited their photolysis because of light-shielding effect and quenching of excited triplet states of LCMs. Their photolysis mainly occurred through excited triplet states, and the reactive oxygen species (i.e., ⋅OH, 1O2 and ⋅O2-) contributed to their degradation. The main photolysis pathways were ester bond cleavage, ⋅OH substitution/addition, and defluorination. Experiments and computational simulation revealed that some ·OH addition/substitution products have similar toxicity with LCMs. Additionally, the ∙OH reaction rate constants (kOH) of LCMs were determined to be > 1 × 109 M-1 s-1, evidence for their high reactivity toward ⋅OH. We have further developed reliable methods to estimate kOH of other phenylbenzoate-like LCMs with quantum chemical calculations. These results are useful for understanding the transformation and fate of LCMs in aquatic environments.

Dependence of the domain structure transformation kinetics on a temperature in heterophase Co/Pt/Co Films

Dependence of the domain structure transformation kinetics on a temperature in heterophase Co/Pt/Co Films

Multiwall carbon nanotube-hyperbranched polymaleimide core–shell nanowires with hierarchical porous and polar structure as sulfur host for sustainable lithium-sulfur batteries

Lithium–sulfur (Li–S) batteries have gained considerable attention as a promising alternative to current advanced batteries because of their low cost, natural abundance, high energy density, and environmental benignity of sulfur. The commercial application of Li–S batteries is being seriously impeded by the shuttle effect of lithium polysulfides (LiPSs) and the sluggish reaction kinetics of solid phase transformation. Herein, a novel composite material (PPI@MWCNT-Y) with a hierarchical porous skeleton and polar channel is prepared as a sulfur host using a convenient in-situ one-pot polymerization. PPI@MWCNT-Y is composed of conductive mesoporous multi-wall carbon nanotubes (MWCNTs) core and a microporous hyperbranched polymaleimide (PPI) shell formed by the self-polymerization of N,N′-1,4-phenylenedimaleimide (PDM). The mesoporous and conductive channels in PPI@MWCNT-Y improve the redox kinetics of the active materials by serving as a fast electron and Li-ions transportation pathway. The microporous structure and abundant adsorption sites (N and O atoms) within the PPI@MWCNT-Y served as physical and chemical barriers, preventing the loss of LiPSs, and suppressing the shuttle effect. Consequently, the S/PPI@MWCNT-38 composite exhibited a high discharge capacity of 1338 mAh g−1 at 0.2 C and a low-capacity decay rate of 0.088% for 400 cycles at 1 C.

Navigating phase diagram complexity to guide robotic inorganic materials synthesis

Efficient synthesis recipes are needed to streamline the manufacturing of complex materials and to accelerate the realization of theoretically predicted materials. Often, the solid-state synthesis of multicomponent oxides is impeded by undesired by-product phases, which can kinetically trap reactions in an incomplete non-equilibrium state. Here we report a thermodynamic strategy to navigate high-dimensional phase diagrams in search of precursors that circumvent low-energy, competing by-products, while maximizing the reaction energy to drive fast phase transformation kinetics. Using a robotic inorganic materials synthesis laboratory, we perform a large-scale experimental validation of our precursor selection principles. For a set of 35 target quaternary oxides, with chemistries representative of intercalation battery cathodes and solid-state electrolytes, our robot performs 224 reactions spanning 27 elements with 28 unique precursors, operated by 1 human experimentalist. Our predicted precursors frequently yield target materials with higher phase purity than traditional precursors. Robotic laboratories offer an exciting platform for data-driven experimental synthesis science, from which we can develop fundamental insights to guide both human and robotic chemists.

Kinetics of the plastic crystal transition in neopentyl glycol

The thermal hysteresis exhibited in plastic crystal compounds greatly reduces their cyclic efficiency, limiting their potential for replacing current environmentally harmful refrigerants. A mechanistic understanding of the origins of this hysteresis has yet to be established. Here, we systematically investigate the transformation kinetics of the model plastic crystal, neopentyl glycol (NPG), through microscopic and calorimetric techniques. We reveal an asymmetry between the forward (heating) and reverse (cooling) transitions. We also demonstrate that the forward transformation is rate-limited by the rate of growth of rotationally disordered domains. In contrast, the reverse transformation is rate-limited by the nucleation of the ordered crystal domain, demonstrated by the sharp exothermic peaks in calorimetry and rapid self-nucleation phenomena observed optically. This nucleation limitation is largely responsible for the large thermal hysteresis in NPG, which we observe to be as large as 16.7 °C for an approximately 10 mg sample cooled at 0.5 °C min−1. These findings demonstrate the underlying origin of the thermal hysteresis and introduce a direction to mitigate hysteresis in plastic crystal transformations.

Rose-like NiCo2O4 with Atomic-Scale Controllable Oxygen Vacancies for Modulating Sulfur Redox Kinetics in Lithium-Sulfur Batteries.

The long-term stability of Li-S batteries is significantly compromised by the shuttle effect and insulating nature of active substance S, constraining their commercialization. Developing efficient catalysts to mitigate the shuttle effect of lithium polysulfides (LiPSs) is still a challenge. Herein, we designed and synthesized a rose-like cobalt-nickel bimetallic oxide catalyst NiCo2O4-OV enriched with oxygen vacancies (OV) and verified the controllable synthesis of different contents of OV. Introducing the OV proved to be an efficient approach for controlling the electronic structure of the electrocatalyst and managing the absorption/desorption processes on the reactant surface, thereby addressing the challenges posed by the LiPS shuttle effect and sluggish transformation kinetics in Li-S batteries. In addition, we investigated the effect of OV in NiCo2O4 on the adsorption capacity of LiPSs using adsorption experiments and density functional theory (DFT) simulations. With the increase in the level of OV, the binding energy between the two is enhanced, and the adsorption effect is more obvious. NiCo2O4-OV contributes to the decomposition of Li2S and diffusion of Li+ in Li-S batteries, which promotes the kinetic process of the batteries.

On the role of interfacial coherency and carbon in niobium segregation at ferrite/austenite interface: An atomistic study

Co-segregation of carbon (C) and substitutional atoms at the interface can remarkably influence the kinetics of phase transformation in steels, while decoupling their contributions by experiments remains challenging. Here, we employ Molecular Statics and hybrid Molecular Dynamics/Monte Carlo simulation approaches to comparatively investigate the niobium (Nb) segregation behaviors at both the incoherent and semi-coherent ferrite/austenite interfaces in Fe-C-Nb systems. The calculations reveal that the atomic Virial stress perpendicular to the interface is crucial for the binding energy of Nb to the interface, and the C presence at the interface has both physical and chemical interactions with Nb. It is conventionally believed that C addition can promote Nb segregation due to their attractive interaction, while the current study indicates that C and Nb atoms tend to form clusters in ferrite, thereby weakening the Nb segregation. The present study provides a promising computational approach for investigating the elemental co-segregation in steels.

Effects of acicular ferrites on crystallography and incomplete transformation of low-carbon low-alloy steel

In this study, we investigated the effects of acicular ferrite (AF) on the crystallographic and incomplete transformation characteristics of low-carbon low-alloy steel. Intermediate annealing after austenitization induced a transformation yielding AFs, accelerating the isothermal transformation kinetics and regulating the microstructure. This process formed highly dense packet grain boundaries and improved the stability of untransformed austenite. AF formation increased the number of packet interfaces, increasing the crack propagation energy. The reduction and refinement of martensite/austenite (M/A) islands increased the crack nucleation energy. A displacive model was used to fit the transformation kinetics curve, indicating the significant effect of the nucleation rate on the isothermal transformation of the experimental steel at 450, 475, and 500 °C. The findings of this study indicate that nucleation regulation can accelerate transformation kinetics to strengthen and toughen bainitic structures.

Precipitation and reverted austenite formation in maraging 350 steel: Competition or cooperation?

Aged maraging steels offer unique strength and toughness via the presence of finely dispersed precipitates, allowing the material to reach values of up to 2400 MPa in yield strength in the case of 18Ni350. However, when aging heat treatments above 550 °C are conducted, simultaneous precipitation and austenite reversion can occur changing the mechanical behavior of the material. Although many studies related to the physical metallurgy of maraging steels have already been published, less attention has been given to a detailed understanding of the initial formation of austenite and its relationship with the precipitates. In this study, undeformed and cold rolled commercial 18Ni350 maraging steel samples were submitted to short aging heat treatments of 1800s at 600, 650, and 700 °C. The influence of the initial microstructure on subsequent phase evolution was studied using in-situ synchrotron X-ray diffraction and final microstructural products using transmission electron microscopy and atom probe tomography. Results show that cold rolled samples did not present faster kinetics of transformation of reverted austenite as expected, but this condition presented austenite in a different morphology than the undeformed condition. However, cold rolling changed the morphology of reverted austenite from elongated (undeformed case) to equiaxed; and induced a higher density of smaller Ni3Ti and Fe2Mo precipitates, especially after low-temperature aging. Besides, the deformation extinguished retained austenite, which influenced the reverted austenite formation, concluding that the simple increase in dislocation density is not a unique and direct factor to increase the reverted austenite kinetics.

Bainite Formation in a Carbon-Free Fe–Cr–N System

In order to promote the understanding of bainitic transformation in nitrogen alloyed steels, the microstructure, transformation kinetics, and diffusion/precipitation characteristics of an isothermally heat-treated carbon-free system Fe–5Cr–N were investigated. Quenching dilatometry was used to perform heat treatments at temperatures between 400 °C and 500 °C and simultaneously receive information about the transformation kinetics. Scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) investigations indicate a plate- to lenticular-like, fully ferritic microstructure with nanometer scale CrN. In order to analyze the diffusion and precipitation behavior of nitrogen, atom probe tomography measurements were performed. On the one hand, nitrogen segregation was found, and on the other hand, the presence of CrN precipitates and preliminary stages of CrN nitrides were validated.