text:
Mainak Saha
email: mainaksaha1995@gmail.com

Grain boundary segregation in steels: Towards engineering the design of internal interfaces

Keywords: Grain boundaries, solute decoration, correlative microscopy, cohesive strength

Solute decoration at grain boundaries (GB) leads to a number of phenomenon such as changes in interface structure, mobility, cohesion etc. Recent experimental investigations on interfacial segregation in steels are based on microstructural characterisation using two correlative methodologies, namely, Transmission Electron Microscopy-Atom Probe Tomography (APT) and Electron Backscatter Diffraction-APT. Considering the growing interest in this avenue, the present review is aimed at addressing the common adsorption isotherms used for quantifying interfacial segregation and providing an overview of the present state of experimental research in the area of GB segregation in steels. The areas where an understanding of GB segregation may be utilised have also been highlighted with a focus on the experimental challenges associated with understanding GB segregation in steels.

Introduction

2.

Theoretical approaches towards quantifying interfacial segregation

3.

Characterising GB segregation in steels Experimental challenges with GB research from the viewpoint of solute decoration 6.

Conclusions and outlook

Introduction

In the context of polycrystalline metallic materials, grain boundaries (GBs) are planar (2D) defects which influence a wide range of properties such as tensile strength. fatigue resistance, thermal and electrical conductivity, corrosion, resistance to hydrogen (H) attack etc. [START_REF] Seah | Interface adsorption, embrittlement and fracture in metallurgy. A review[END_REF]- [START_REF] Raabe | Current Challenges and Opportunities in Microstructure-Related Properties of Advanced High-Strength Steels[END_REF].

Being a region of partial atomic disorder but with definite structure and orientation, a GB may also act as a source and sink for vacancies and dislocations [START_REF] Hondros | Grain boundary microchemistry and stress-corrosion failure of mild steel[END_REF]- [START_REF] Brandon | The structure of high-angle grain boundaries[END_REF]. In addition, they possess five macroscopic degrees of freedom (DOFs) (which include misorientation angle and axis) [START_REF] Hondros | Rule for surface enrichment in solutions[END_REF]- [START_REF] Gertsman | Grain boundary misorientation distributions in monoclinic zirconia[END_REF]. The five DOFs determine the structure of a GB [START_REF] Howe | Solid-Liquid and Solid-Solid Interfaces[END_REF]- [START_REF] Kwiatkowski Da Silva | Competition between formation of carbides and reversed austenite during tempering of a mediummanganese steel studied by thermodynamic-kinetic simulations and atom probe tomography[END_REF]. The energy of a GB (also known as GB energy) is highly sensitive to GB structure and is influenced by the local chemistry near GBs [START_REF] Weinberg | Grain boundaries in metals[END_REF], [START_REF] Mclean | Grain Boundaries in Metals[END_REF], [START_REF] Sutton | Overview no. 61 On geometric criteria for low interfacial energy[END_REF]- [START_REF] Kelly | Ductile and brittle crystals[END_REF]. The driving force for solute decoration at GBs is the minimisation of GB energy [START_REF] Geng | Influence of alloying additions on the impurity induced grain boundary embrittlement[END_REF]- [START_REF] Geng | Effect of Mo and Pd on the grainboundary cohesion of Fe[END_REF].

Special high-angle GBs (SHAGBs) with low GB energies have been reported to possess much higher resistance to corrosion, crack propagation, H diffusion, GB sliding etc. as compared to that in random HAGBs (RHAGBs) (with high GB energies) [START_REF] Birnbaum | Hydrogen-enhanced localized plasticity-a mechanism for hydrogen-related fracture[END_REF]- [START_REF] Toji | Atomic-scale analysis of carbon partitioning between martensite and austenite by atom probe tomography and correlative transmission electron microscopy[END_REF]. Such observations have led to the evolution of GB engineering (GBE) which is based on replacing RHAGBs with SHAGBs for the purpose of optimising the properties (of polycrystalline materials) [START_REF] Frolov | Thermodynamics of coherent interfaces under mechanical stresses. II. Application to atomistic simulation of grain boundaries[END_REF]- [START_REF] Mandal | Application of canonical correlation analysis to a sensitivity study of constitutive model parameter fitting[END_REF].

However, preferential segregation of different elements (with different concentration) at GBs and its associated influence needs to be considered [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Bandyopadhyay | Carbide precipitation, grain boundary segregation, and temper embrittlement in NiCrMoV rotor steels[END_REF]- [START_REF] Chen | Solute grain boundary segregation during high temperature plastic deformation in a Cr-Mo low alloy steel[END_REF]. This is highly important since most of the GB properties are influenced by segregation-induced changes which mainly include fracture toughness, electrical and thermal properties, H embrittlement, resistance to dislocation pile-up etc. [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Briant | Intergranular failure in steel: the role of grain-boundary composition[END_REF]. Such manipulation of GB structure has been referred to as GB segregation engineering (GBSE) [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. Both thermodynamic (such as co-segregation, coefficient of segregation etc.) and kinetic factors (such as deformation-induced GB phase evolution) are associated with GBSE [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Tingdong | Non-equilibrium grain-boundary segregation kinetics[END_REF]- [START_REF] Sauvage | Grain Boundary Segregation in UFG Alloys Processed by Severe Plastic Deformation[END_REF]. This implies that in addition to thermomechanical treatment, solute decoration at GBs is hugely influenced by time [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. Besides, GBSE utilises elemental segregation as a methodology for site-specific manipulation which leads to the optimisation of specific GB structure, composition and properties [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF].

Moreover, GBs may either reduce/increase the strength of polycrystalline metallic materials [START_REF] Seah | Interface adsorption, embrittlement and fracture in metallurgy. A review[END_REF]. Most metallic materials, during service, tend to fail from an intergranular fracture through void nucleation and growth owing to high stress concentration along GBs [START_REF] Seah | Segregation and the Strength of Grain Boundaries[END_REF]. Predominant GB embrittlement due to non-accommodation of plastic strains along GBs in presence of segregating solute species has been most commonly attributed to be the cause of such a failure [START_REF] Seah | Adsorption-induced interface decohesion[END_REF], [START_REF] Raabe | Metallic composites processed via extreme deformation: Toward the limits of strength in bulk materials[END_REF]. Such an embrittlement assisted failure leads to "impaired plasticity" in metallic materials [START_REF] Lejček | Effect of Variables on Equilibrium Grain Boundary Segregation[END_REF]. A very common example of such a phenomenon is the embrittlement caused by the segregation of H at different GBs in steels [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Ohmori | Effects of austenite grain size and grain boundary segregation of impurity atoms on high temperature ductility[END_REF]. On the contrary, there have also been a number of reports on the GB strengthening (in metallic materials) caused due to the accommodation of plastic strains along GBs, especially in the presence of solute segregation [START_REF] Carinci | Grain boundary segregation of boron in an austenitic stainless steel[END_REF], [START_REF] Lejček | On the thermodynamic description of grain boundary segregation in polycrystals[END_REF]- [START_REF] Song | Dependence of ductile-tobrittle transition temperature on phosphorus grain boundary segregation for a 2.25Cr1Mo steel[END_REF]. Hence, the overall aim is to design metallic materials with high overall toughness. In the context of steels, which form the backbone of the global economy, the former statement tends to be highly applicable. In other words, solute decoration at internal interfaces may be used as a design tool for developing high-performance steels [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. The present review article is aimed at addressing the common thermodynamic approaches for quantifying the extent of interfacial segregation and highlighting the present state of experimental research in the avenue of GB segregation in steels. The avenues where an understanding of GB segregation may be utilised have also been highlighted. In addition, the experimental challenges associated with GB research have been briefly discussed from the viewpoint of solute segregation.

Theoretical approaches towards quantifying interfacial segregation

Solute concentration at GB has been reported to exceed the solubility (of solutes) in the grain interior, upto several orders of magnitude [START_REF] Seah | Interface adsorption, embrittlement and fracture in metallurgy. A review[END_REF], [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Seah | Adsorption-induced interface decohesion[END_REF], [START_REF] Tschopp | Structures and energies of ∑3 asymmetric tilt grain boundaries in copper and aluminium[END_REF]- [START_REF] Chapman | Computer modelling of grain boundary segregation[END_REF]. Raabe et al. [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF] have reported that bulk solubility (solubility of a particular solute within the interior of a grain) may be used as an approximation for determining the tendency of a solute towards preferential segregation at GBs. In other words, the smaller the bulk solubility, the higher is the solute enrichment factor (𝛽 𝑖 ) of the solute at the GB which implies a higher tendency of the solute species towards GB segregation [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. Fig. 1 shows the variation of 𝛽 𝑖 as a function of the solubility limit of different solutes in α-Fe matrix.

Fig. 1 Variation of 𝛽 𝑖 as a function of solubility limit of different solutes in Fe matrix, obtained from Ref. [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. The data points in this plot may be used to identify appropriate solute species with a strong tendency towards GB segregation.

In addition, the thermodynamics associated with GB segregation has a close analogy to monolayer gas adsorption at solid surfaces and may be formulated in terms of the Gibbs adsorption isotherm [START_REF] Howe | Solid-Liquid and Solid-Solid Interfaces[END_REF], [START_REF] Krakauer | Absolute atomic-scale measurements of the Gibbsian interfacial excess of solute at internal interfaces[END_REF]. Using this isotherm, the excess concentration of a given solute species at a GB (also known as GB excess) is given as: [START_REF] Howe | Solid-Liquid and Solid-Solid Interfaces[END_REF] 𝛤

𝑖 = -( 1 𝑅𝑇 ̅̅̅̅ ) ( 𝑑𝛾 𝐺𝐵 𝑑𝑥 𝑖 ) 𝑉,𝑇 (1)
where, xi are the molar concentration of the element (solute) i in the bulk (or, grain interior), 𝑑𝛾 𝐺𝐵 is the change in GB energy upon segregation at a fixed temperature T and volume V, R is the universal gas constant (~ 8.314 J/molK), and T is the absolute temperature (in K) [START_REF] Howe | Solid-Liquid and Solid-Solid Interfaces[END_REF].

Theoretically, 𝛤 𝑖 may be determined by measuring 𝑑𝛾 𝐺𝐵 as a function of 𝑑𝑥 𝑖 in logarithmic scale. In the context of GB segregation, the other form of Gibbs adsorption isotherm is commonly used which relates 𝑑𝛾 𝐺𝐵 with 𝛤 𝑖 and change in chemical potential of solute i (dμi).

It is expressed as: [START_REF] Krakauer | Absolute atomic-scale measurements of the Gibbsian interfacial excess of solute at internal interfaces[END_REF] 𝑑𝛾 𝐺𝐵 = -∑ 𝛤 𝑖 dμ 𝑖 𝑖 [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF] From a thermodynamic viewpoint, Gibbs adsorption isotherm is based on a simplistic approach towards quantifying GB segregation. However, the measurement of GB segregation as a function of bulk concentration and temperature is not possible using the aforementioned isotherm [START_REF] Hondros | Cohesion margin of copper[END_REF], [START_REF] Langmuir | The adsorption of gases on plane surfaces of glass, mica and platinum[END_REF]. In this context, the Langmuir-McLean isotherm has been widely used since it quantifies GB segregation by balancing both the adsorption and desorption rates of solute species at a GB [START_REF] Langmuir | The adsorption of gases on plane surfaces of glass, mica and platinum[END_REF]. This isotherm is given as: [START_REF] Langmuir | The adsorption of gases on plane surfaces of glass, mica and platinum[END_REF]

𝑥 𝑖 𝐺𝐵 (𝑥 𝑖 𝐺𝐵 ,0 -𝑥 𝑖 𝐺𝐵 ) = 𝑥 𝑖 𝐵 (1-𝑥 𝑖 𝐵 )
exp (-

∆𝐺 𝑖 𝐺𝐵 𝑅𝑇 ) (3)
where, 𝑥 𝑖 𝐺𝐵 is the molar concentration of solute i at GB, 𝑥 𝑖 𝐺𝐵 ,0 is the solubility limit (in terms of molar concentration) of solute i at GB, 𝑥 𝑖 𝐵 is the molar fraction of solute i at grain interior (bulk), and ∆𝐺 𝑖 𝐺𝐵 is the Gibbs molar free energy of segregation of solute i at GB [START_REF] Langmuir | The adsorption of gases on plane surfaces of glass, mica and platinum[END_REF].

Considering the system as dilute, equation (3) may be simplified as follows: [START_REF] Langmuir | The adsorption of gases on plane surfaces of glass, mica and platinum[END_REF] 𝛽 𝑖 = 𝑥 𝑖 𝐺𝐵 𝑥 𝑖 𝐵 = exp (-

∆𝐺 𝑖 𝐺𝐵 𝑅𝑇 ) (4)
∆𝐺 𝑖 𝐺𝐵 is usually an unknown quantity. Based on equations (3) and ( 4), it may be implied that GB segregation occurs when ∆𝐺 𝑖 𝐺𝐵 < 0 and with increasing temperature, there is a decrease in the tendency of segregation of solute species at GBs [START_REF] Langmuir | The adsorption of gases on plane surfaces of glass, mica and platinum[END_REF]. The major limitation of Langmuir-

McLean isotherm is that it does not consider GB energy for quantification of GB segregation unlike Gibbs adsorption isotherm [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Lejček | Why calculated energies of grain boundary segregation are unreliable when segregant solubility is low[END_REF]. Moreover, this isotherm assumes that dynamic equilibrium is established between the segregating solute species (in case of multiple decorating solutes) and that solute decoration (at GBs) is limited to only a single monolayer [START_REF] Langmuir | The adsorption of gases on plane surfaces of glass, mica and platinum[END_REF]. However, both the aforementioned isotherms treat GBs as an individual phase with properties which are different as compared to those in the grain interior and do not consider the interaction between segregating solute species at GBs [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF].

Recently, the phenomenon of entropy-dominated GB segregation has been introduced for low solute concentration at different SHAGBs and RHAGBs in α-Fe based alloys [START_REF] Lejček | Entropy-dominated grain boundary segregation[END_REF]. It has been reported that the main limitation of the Langmuir-McLean isotherm is associated with the assumption that the phenomenon of GB segregation is only controlled by enthalpy of segregation (ΔHi, for solute i) and not by the entropy of segregation (ΔSi) [START_REF] Lejček | Entropy-dominated grain boundary segregation[END_REF], [START_REF] Lejček | Entropy matters in grain boundary segregation[END_REF]. Besides, it has been theoretically shown that entropy-dominated segregation phenomenon is dominant for solutes with low solid solubility in a given matrix (solvent) especially at homologous temperatures > 0.4Tm (Tm: melting points (in K)) [START_REF] Lejček | Entropy-dominated grain boundary segregation[END_REF], [START_REF] Lejček | Entropy matters in grain boundary segregation[END_REF]. In the context of α-Fe, the two common segregating species with low solid solubility are Sb and Sn [START_REF] Lejček | Entropy-dominated grain boundary segregation[END_REF], [START_REF] Ewing | An analytical approach to interfacial entropy[END_REF]. These elements have been reported to exhibit dominant entropy-dominated GB segregation phenomenon in α-Fe at temperatures ≥ 450 °C [START_REF] Lejček | Entropy-dominated grain boundary segregation[END_REF].

Based on GB segregation maps at different temperatures, Lejček and Hoffmann [START_REF] Lejček | Thermodynamics and structural aspects of grain boundary segregation[END_REF]- [START_REF] Lejcek | Thermodynamics of grain boundary segregation and applications to anisotropy, compensation effect and prediction[END_REF] have

shown that solubility limits for different solute atoms at different GBs varies with GB character in α-Fe. Hence, it may be argued that GB segregation diagrams provide an understanding of solute segregation in dilute binary systems. However, from a practical viewpoint, it is always more useful to know about GB segregation in multicomponent alloys where mutual interactions and site competition both simultaneously play an important role, in determining the extent of solute segregation at different GBs [START_REF] Lejček | Effect of Variables on Equilibrium Grain Boundary Segregation[END_REF], [START_REF] Lejcek | Thermodynamics of grain boundary segregation and applications to anisotropy, compensation effect and prediction[END_REF]- [START_REF] Lejček | Characterization of grain boundary segregation in an Fe-Si alloy[END_REF]. In such cases, βi fails to correctly predict the amount of solute segregation at GBs [START_REF] Lejček | Thermodynamics and structural aspects of grain boundary segregation[END_REF], [START_REF] Lejček | The significance of entropy in grain boundary segregation[END_REF], [START_REF] Lejček | Solute segregation to ferrite grain boundaries in nodular cast iron: Experiment and prediction[END_REF]- [START_REF] Lejček | Grain boundary segregation diagrams of α-iron[END_REF]. According to Guttmann [START_REF] Guttmann | Interfacial Segregation in Multicomponent Systems[END_REF]- [START_REF] Guttmann | Equilibrium segregation in a ternary solution: A model for temper embrittlement[END_REF], the ΔHi for a solute i in a ternary system with matrix M and the other solute j is given by:

ΔH i = ΔH i 0 -2α Mi (𝑥 𝑖 𝐺𝐵 -𝑥 𝑖 ) + α ij (𝑥 𝑗 𝐺𝐵 -𝑥 𝑗 ) (5)
where xi GB , xj GB , and xi, xj are the GB and bulk mole fractions, respectively, of two solutes i and j. ΔHi depends on the chemical interaction between the elements, i.e., the binary interaction with the Fowler interaction coefficient αMi and the ternary interaction coefficient αij ' with the other solute species [START_REF] Guttmann | Interfacial Segregation in Multicomponent Systems[END_REF]. ΔH i 0 denotes the enthalpy of segregation for the dilute binary system M-i and is independent of temperature and composition even for a multicomponent system [START_REF] Guttmann | Equilibrium segregation in a ternary solution: A model for temper embrittlement[END_REF]. Therefore, ΔH i 0 in equation ( 5), is an independent characteristic of the segregation of solute i in matrix M [START_REF] Guttmann | Interfacial Segregation in Multicomponent Systems[END_REF]. Hence, it may be justified that the tendency of a solute to segregate at GBs is better characterized by a more fundamental thermodynamic quantity such as ΔHi as compared to βi.

Characterising GB segregation in steels

Common techniques for the characterisation of GB segregation

A number of characterisation techniques have been used to investigate GB segregation such as Auger Electron Spectroscopy (AES), Transmission Electron Microscopy (TEM), Scanning

Transmission Electron Microscopy (STEM), Electron Backscatter Diffraction (EBSD),

Transmission Kikuchi Diffraction (TKD), Electron Energy Loss Spectroscopy (EELS), Field

Ion Microscopy (FIM), Secondary Ion Mass Spectroscopy (SIMS) and Atom Probe Tomography (APT). All these techniques, when used individually for characterising GB segregation, have a number of limitations which primarily include a lack of crystallographic details and a lack of GB segregation information with high spatial resolution [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. Moreover, GB segregation is an atomic-scale phenomenon and hence, it is challenging to obtain GB segregation information which is precise, statistically-significant and reproducible at the same time [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. Wynblatt and Chatain [START_REF] Wynblatt | Anisotropy of segregation at grain boundaries and surfaces[END_REF] have highlighted that there recently exists a discrepancy between the present theoretical and experimental approach towards addressing GB segregation.

One of the recently evolved methodologies towards characterising GB segregation is correlative microscopy which enables a simultaneous determination of both structural and chemical information from a region near a solute-decorated GB. The two correlative characterisation methodologies employed (till date) for the determination of GB segregation in steels are based on correlative TEM-APT and EBSD-APT approach which are based on a direct lattice reconstruction from a given APT data of solute-decorated GBs [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Daly | A multi-scale correlative investigation of ductile fracture[END_REF]- [START_REF] Schwarz | Correlative transmission Kikuchi diffraction and atom probe tomography study of Cu(In,Ga)Se2 grain boundaries[END_REF]. Moreover, the GB segregation information obtained using electron microscopy techniques (such as TEM and EBSD) is influenced by a number of factors. First, the angular resolution of the electron microscopy technique used. For instance, using TEM-based nanobeam diffraction technique, it is possible to obtain an angular resolution of ~1° in contrast to that (~1-3 °) obtained using EBSD technique, depending on the instrument and analysis software used [START_REF] Herbig | Atomic-Scale Quantification of Grain Boundary Segregation in Nanocrystalline Material[END_REF]. Second, there is a huge uncertainty associated with preparing APT tips (containing GB region) using Focussed Ion Beam (FIB)-based liftout technique in a Scanning Electron Microscope (SEM) [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Li | Correlative chemical and structural investigations of accelerated phase evolution in a nanocrystalline high entropy alloy[END_REF]. Earlier, this uncertainty was addressed by conducting orientation mapping on the APT tips by using TEM and/or FIM techniques. In addition to the limited field of view, a high level of expertise is required to obtain precise orientation information (from APT tips) using these techniques. In recent times, the aforementioned uncertainty of obtaining GB probed region (using FIB technique) is eliminated by conducting orientation measurement using TKD technique and subjecting the same tips to APT analysis. In contrast to TEM and FIM techniques, TKD technique has a higher field of view [START_REF] Yao | The anatomy of grain boundaries: Their structure and atomic-level solute distribution[END_REF], [START_REF] Gault | Atom Atom probe probe crystallography[END_REF]. Besides, obtaining orientation information using TKD is much easier as compared to that using TEM and/or FIM techniques [START_REF] Gault | Specimen Preparation[END_REF]. One of the limitations of APT is the influence of projection and lens effects on the allocation of atoms to a particular GB [START_REF] Larson | Atom Probe Tomography Spatial Reconstruction : Current Status and Future Directions[END_REF]- [START_REF] Dmitrieva | Chemical gradients across phase boundaries between martensite and austenite in steel studied by atom probe tomography and simulation[END_REF]. The projection effect is based on the magnetic field surrounding the APT tip whereas the lens effect leads to errors in the positioning of field evaporated atoms and is associated with field evaporation at solute-decorated GBs [START_REF] Larson | Atom Probe Tomography Spatial Reconstruction : Current Status and Future Directions[END_REF].

Experimental investigations towards understanding GB segregation in steels

Conventional methodology

Grabke et al. [START_REF] Grabke | Effects of the alloying elements Ti, Nb, Mo and V on the grain boundary segregation of P in iron and steels[END_REF] have used FIM, APT and AES techniques to investigate the segregation of Ti, Nb, Mo and V and their carbides at RHAGBs in Fe-P based ternary and quaternary alloys (bulk composition indicated in Ref. [START_REF] Grabke | Effects of the alloying elements Ti, Nb, Mo and V on the grain boundary segregation of P in iron and steels[END_REF]). Addition of Ti and Nb was reported to prevent the segregation of P at GBs (through formation of Ti and Nb-based phosphides) in Fe-Ti-P ternary alloys [START_REF] Grabke | Effects of the alloying elements Ti, Nb, Mo and V on the grain boundary segregation of P in iron and steels[END_REF]. However, both Mo and V were reported not to influence the segregation tendency of P [START_REF] Grabke | Effects of the alloying elements Ti, Nb, Mo and V on the grain boundary segregation of P in iron and steels[END_REF]. In the context of Fe-Nb-C-P and Fe-Ti-C-P quaternary alloys, GB segregation of P was reported to increase with C concentration upto a point at which NbC precipitates form [START_REF] Grabke | Effects of the alloying elements Ti, Nb, Mo and V on the grain boundary segregation of P in iron and steels[END_REF]. Using AES, Christien et al. [START_REF] Christien | Phosphorus grain boundary segregation in steel 17-4PH[END_REF] have established a linear relationship between intergranular grooves formed during metallographic etching with the concentration of P segregated at GBs in a 17-4PH martensitic stainless steel. Takahashi et al. [START_REF] Takahashi | Quantitative analysis of grain boundaries in carbon-and nitrogen-added ferritic steels by atom probe tomography[END_REF] have investigated the segregation of C and N atoms at different GBs in Fe-0.006C-0.001N-0.04Al (C60) and Fe-0.005C-0.0054N-0.004Al (N60) (wt.%) ferritic steels using APT. Based on the observations, it was highlighted that C segregates at RHAGBs in C60 whereas N segregates at RHAGBs in N60 [START_REF] Takahashi | Quantitative analysis of grain boundaries in carbon-and nitrogen-added ferritic steels by atom probe tomography[END_REF]. However, the segregation tendency of N in N60 was determined to be lesser than that of C in C60 [START_REF] Takahashi | Quantitative analysis of grain boundaries in carbon-and nitrogen-added ferritic steels by atom probe tomography[END_REF]. In addition, the Hall-Petch coefficient of ferrite grains was reported to be influenced by the segregation of C atoms at RHAGBs (in C60) and not by the segregation of N atoms at RHAGBs (in N60) [START_REF] Takahashi | Quantitative analysis of grain boundaries in carbon-and nitrogen-added ferritic steels by atom probe tomography[END_REF].

Rosa et al. [START_REF] Da Rosa | Grain-boundary segregation of boron in high-strength steel studied by nano-SIMS and atom probe tomography[END_REF] have investigated the influence of B addition to Fe-0.34C-2.45Mn-0.0100B-0.03Ti (at.%) high strength steel (with a single-phase austenitic structure) using nano-SIMS and APT techniques. Dissolution of boride (Fe2B and M23(B,C)6) precipitates at grain interior leads to segregation of B at RHAGB [START_REF] Da Rosa | Grain-boundary segregation of boron in high-strength steel studied by nano-SIMS and atom probe tomography[END_REF]. Besides, the extent of B segregation at austenite GBs was reported to increase with temperature [START_REF] Da Rosa | Grain-boundary segregation of boron in high-strength steel studied by nano-SIMS and atom probe tomography[END_REF]. Although this goes against the thermodynamically supported trend of decreasing solute segregation with increasing temperature, however, B segregation at austenite GBs was reported to follow Langmuir-

McLean adsorption isotherm [START_REF] Da Rosa | Grain-boundary segregation of boron in high-strength steel studied by nano-SIMS and atom probe tomography[END_REF]. Based on this isotherm, the ΔH i of B (at austenite GB) and the enthalpy of dissolution (ΔHdiss) of borides were calculated to be higher (by ~51% and 9.4%)

than the respective values (of ΔH i and ΔHdiss) reported in the earlier literatures [START_REF] Abdellah | The phase stability in the Fe-B binary system: Comparison between the interstitial and substitutional models[END_REF]- [START_REF] Faulkner | Radiation-induced grain boundary segregation in nuclear reactor steels[END_REF]. [START_REF] Hata | Grain-boundary phosphorus segregation in highly neutron-irradiated reactor pressure vessel steels and its effect on irradiation embrittlement[END_REF] and in neutron-irradiated AISI 304 austenitic stainless steel [START_REF] Toyama | Grain boundary segregation in neutron-irradiated 304 stainless steel studied by atom probe tomography[END_REF], [START_REF] Kenik | Radiation-induced grain boundary segregation and sensitization of a neutron-irradiated austenitic stainless steel[END_REF].

Shigesato et al. [START_REF] Shigesato | Boron segregation to austenite grain boundary in low alloy steel measured by aberration corrected STEM-EELS[END_REF] have measured non-equilibrium segregation of B at austenite RHAGBs in Fe-0.05C-0.5Mo-0.001B (wt.%) steel using aberration-corrected STEM-EELS technique.

Moreover, the influence of specimen thickness, electron beam broadening, and GB plane inclination on the GB segregation of B was also investigated in this work [START_REF] Shigesato | Boron segregation to austenite grain boundary in low alloy steel measured by aberration corrected STEM-EELS[END_REF]. Gaussian broadening model was used to determine the broadening of B concentration profile [START_REF] Shigesato | Boron segregation to austenite grain boundary in low alloy steel measured by aberration corrected STEM-EELS[END_REF]. It was reported that the extent of broadening increases with specimen thickness [START_REF] Shigesato | Boron segregation to austenite grain boundary in low alloy steel measured by aberration corrected STEM-EELS[END_REF]. However, for specimen thickness < 30 nm, the broadening of B concentration profile was obtained to be < 10% [START_REF] Shigesato | Boron segregation to austenite grain boundary in low alloy steel measured by aberration corrected STEM-EELS[END_REF]. Besides, B concentration profile was also reported to be asymmetric for GB plane inclination angle > 1.5 ° [START_REF] Shigesato | Boron segregation to austenite grain boundary in low alloy steel measured by aberration corrected STEM-EELS[END_REF]. Ma et al. [START_REF] Ma | Phase boundary segregation-induced strengthening and discontinuous yielding in ultrafine-grained duplex medium-Mn steels[END_REF] have used EBSD and APT techniques to highlight that segregation of C at ferrite/austenite interphase boundary (IB) leads to an increase in the energy barrier for dislocation emission from RHAGBs in a duplex medium Mn steel (composition: Fe-11.7Mn-2.9Al-0.064C (wt.%)) resulting in discontinuous yielding of the material at room temperature. C-decoration at the aforementioned IB coupled with dislocation nucleation and subsequent multiplication has been reported to influence the discontinuous yielding phenomenon [START_REF] Ma | Phase boundary segregation-induced strengthening and discontinuous yielding in ultrafine-grained duplex medium-Mn steels[END_REF]. Besides, it was also reported that segregation of solutes at IBs is not governed by Gibbs and Langmuir-McLean adsorption isotherms [START_REF] Ma | Phase boundary segregation-induced strengthening and discontinuous yielding in ultrafine-grained duplex medium-Mn steels[END_REF] unlike the previous reports [START_REF] Frolov | Effect of interfacial structural phase transitions on the coupled motion of grain boundaries: A molecular dynamics study[END_REF]- [START_REF] Gottstein | Grain boundary migration in metals: recent developments[END_REF].

Correlative methodology TEM-APT methodology

Herbig et al. [START_REF] Herbig | Atomic-Scale Quantification of Grain Boundary Segregation in Nanocrystalline Material[END_REF] have characterised C-decorated GBs in a nanocrystalline cold-drawn pearlitic steel (composition: Fe-4.40C-0.30Mn-0.39Si-0.21Cr (at. %)) using correlative TEM-APT methodology and reported the variation of C excess (obtained using APT) as a function of GB misorientation angle for coherent Σ5 and both coherent and incoherent Σ3 GBs (Fig. 2). Fig.

2(a)

shows the overlay of C decoration at different GBs in an APT needle. Fig. 2(b) shows the variation of C excess as a function of GB misorientation angle. For incoherent Σ3 GBs, Cexcess was found to be much higher as compared to that of coherent Σ5 and Σ3 GBs [START_REF] Herbig | Atomic-Scale Quantification of Grain Boundary Segregation in Nanocrystalline Material[END_REF].

Besides, the deviation from the ideal 60 ° misorientation (for incoherent Σ3 GBs) was attributed to the presence of misfit dislocations which, in addition, are also responsible for high C-excess at the aforementioned GB (Fig. 2(b)) [START_REF] Herbig | Atomic-Scale Quantification of Grain Boundary Segregation in Nanocrystalline Material[END_REF]. Moreover, the C excess vs GB misorientation angle plot was found to possess a good correlation with GB energy vs misorientation angle plot for the aforementioned GBs [START_REF] Herbig | Atomic-Scale Quantification of Grain Boundary Segregation in Nanocrystalline Material[END_REF]. Abramova et al. [START_REF] Abramova | Grain boundary segregation induced strengthening of an ultrafinegrained austenitic stainless steel[END_REF] have used the same methodology to highlight that segregation of Mo, Si and Cr at austenitic RHAGB leads to GB strengthening in ultra-fine grained AISI 316 austenitic stainless steel. In the context of Fe-1.62Mn-0.18Si (wt.%) ferritic steel, Han et al. [START_REF] Han | Competitive grain boundary segregation of phosphorus and carbon governs delamination crack in a ferritic steel[END_REF] have used the aforementioned methodology to report that delamination is highly influenced of competitive segregation of C and P (at RHAGBs). It was also highlighted that delamination cracks are promoted along RHAGBs with high P and low C content whereas RHAGBs with low P and high C content were observed to be resistant to delamination cracking [START_REF] Han | Competitive grain boundary segregation of phosphorus and carbon governs delamination crack in a ferritic steel[END_REF].

EBSD-APT methodology

Kuzmina et al. [START_REF] Kuzmina | Grain boundary segregation engineering and austenite reversion turn embrittlement into toughness: Example of a 9 wt.% medium Mn steel[END_REF] have used this methodology to highlight that Mn segregation leads to the embrittlement of martensite RHAGBs in Fe-9Mn-0.05C (wt.%) steel at 450 °C. In that context, addition of ~ 0.0027 wt.% of B was reported to promote GB strengthening and prevent the segregation of Mn at martensite RHAGB by promoting martensite to austenite reversion after prolonged holding (for ~ 336h) at 450 °C [START_REF] Kuzmina | Grain boundary segregation engineering and austenite reversion turn embrittlement into toughness: Example of a 9 wt.% medium Mn steel[END_REF]. A similar observation was reported in the context of Fe-12Mn-3Al-0.05C (wt.%) steel by Benzing et al. [START_REF] Benzing | Multi-scale characterization of austenite reversion and martensite recovery in a cold-rolled medium-Mn steel[END_REF]. Ravi et al. [START_REF] Ravi | Impact of austenite grain boundaries and ferrite nucleation on bainite formation in steels[END_REF] have utilised this methodology to study the influence of C segregation in Fe-0.2C-3Mn-2Si (wt.%) bainitic steel and reported that segregation of C at austenite RHAGBs promotes austenitic to bainitic transformation during isothermal holding at bainitic transformation temperature (~400 °C, in this case).

Using the same approach, Herbig et al. [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF] have characterised the segregation of B, C, P, Si and Cu at an FCC RHAGB and coherent Σ3 annealing twin boundaries in Fe-28Mn-0.3C (wt.%) twinning-induced plasticity (TWIP) steel (Fig. 3). Fig. 3 C, Si, P, Mn and Cu at the two GBs highlighted (using black outlined rectangular boxes) in Fig. 3(a). The extent of Mn segregation was observed to be nearly similar for both RHAGB and at Σ3 GB (Figs. 3(b andc))). B and P were reported to segregate much strongly at RHAGB than at coherent Σ3 annealing twin boundaries (Figs. 3(b andc)) [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF]. This was attributed to the higher GB energy of RHAGB as compared to that of coherent Σ3 GB [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF]. Decoration of RHAGB by C atoms (Fig. 3(b)) was reported to increase the local SFE and subsequently, lead to high resolved shear stress for mechanical twinning (at RHAGB) [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF]. On the contrary, depletion of C (at Σ3 GB (Fig. 3(c))) was reported to lower the local SFE leading to the formation of ε-martensite (HCP) phase at austenite Σ3 boundaries [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF]. Besides, the preferential segregation of elements (B, C, P and Si) at deformation twins in a deformed Fe-22Mn-0.6C (wt.%) TWIP steel was investigated [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF]. It was reported that although crystallographically similar, deformation twins show a much lower tendency of undergoing decoration by C atoms as compared to that of annealing twins [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF]. This tendency of deformation twins may be attributed to the extremely low mobility of C atoms during the formation of deformation twins at room temperature [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF]. RHAGB in Fe-50C (ppm) ferritic steel. Based on this work, it was observed that: (i) there is a high frequency of "pop-ins" (in load-displacement curves) at RHAGB as compared to the grain interiors which suggests that dislocation nucleation and multiplication at RHAGB occurs much more easily as compared to that within grain interiors and (ii) pinning of dislocations by C atoms segregated at RHAGB leads to a high critical shear stress for emission of dislocations from RHAGB, resulting in GB strengthening [START_REF] Araki | Effect of grain boundary segregation of carbon on critical grain boundary strength of ferritic steel[END_REF]. Moreover, the critical shear stress required for dislocation emission from RHAGB, was quantified using Hertz contact theory considering elastic contact between the nanoindenter and the sample surface, before the onset of "pop-in events" in nanoindentation-based load-displacement curves [START_REF] Araki | Effect of grain boundary segregation of carbon on critical grain boundary strength of ferritic steel[END_REF]. Fe-1.62Mn-0.18Si (wt.%) C, P RHAGB [START_REF] Han | Competitive grain boundary segregation of phosphorus and carbon governs delamination crack in a ferritic steel[END_REF] EBSD-APT Fe-9Mn-0.05C (wt.%) Mn RHAGB [START_REF] Kuzmina | Grain boundary segregation engineering and austenite reversion turn embrittlement into toughness: Example of a 9 wt.% medium Mn steel[END_REF] Fe-12Mn-3Al-0.05C (wt.%) C, Mn RHAGB, IB, triple junctions [START_REF] Benzing | Multi-scale characterization of austenite reversion and martensite recovery in a cold-rolled medium-Mn steel[END_REF] Fe-0.2C-3Mn-2Si (wt.%) C RHAGB [START_REF] Ravi | Impact of austenite grain boundaries and ferrite nucleation on bainite formation in steels[END_REF] Fe-28Mn-0.3C (wt.%) B, C, P, Si coherent Σ3 [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF] Fe-22Mn-0.6C (wt.%) B, C, P, Si Σ3 deformation twins [START_REF] Herbig | Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography[END_REF] Fe-50C (ppm) C RHAGB [START_REF] Araki | Effect of grain boundary segregation of carbon on critical grain boundary strength of ferritic steel[END_REF] 4. Towards utilising GB segregation: Examples

Alloy design

In the context of steel design, one of the areas where an understanding of GB segregation may be utilised is to stabilise nano-sized grains by reducing the overall GB energy through solute decoration at GBs. For instance, discontinuous grain growth (due to high GB energy) is a common phenomenon which has been reported in a number of materials (especially steels). In that context, GB segregation helps in two possible ways. Firstly, it reduces the GB energy and subsequently, the capillary force associated with the competitive growth of two adjoining grains. Secondly, choosing adequate solutes (for decoration at GBs) leads to an enhancement in GB cohesive strength. In the context of Fe-13.6 Cr-0.44 C (wt.%) martensitic steel, Yuan et al. [START_REF] Yuan | Nanoscale austenite reversion through partitioning, segregation and kinetic freezing: Example of a ductile 2 GPa Fe-Cr-C steel[END_REF] have reported that the ultimate tensile strength and total elongation are enhanced (by ~233.33% and 53% respectively) by the segregation of C at martensite GBs. This was attributed to the reversion from martensite to austenite phase promoted by the segregation of C at martensitic GBs [START_REF] Yuan | Nanoscale austenite reversion through partitioning, segregation and kinetic freezing: Example of a ductile 2 GPa Fe-Cr-C steel[END_REF]. Li et al. [START_REF] Li | Atomic-scale mechanisms of deformation-induced cementite decomposition in pearlite[END_REF] have established a direct correlation between the extent of tensile deformation with the concentration of segregated C at ferrite RHAGBs in Fe-3.66C-0.48Mn-0.39Si-0.01P-0.01S (at.%) pearlitic steel. In addition, a similar correlation for the case of C segregated at ferrite sub-grain (or, low angle) boundaries has been reported in hypereutectoid Fe-4.40C-0.30Mn-0.39Si-0.21Cr-0.003Cu-0.01P-0.01S (at. %) pearlitic steel [START_REF] Li | Evolution of strength and microstructure during annealing of heavily cold-drawn 6.3 GPa hypereutectoid pearlitic steel wire[END_REF], [START_REF] Lia | Atom probe tomography characterization of heavily cold drawn pearlitic steel wire[END_REF].

The other area where an understanding of GB segregation may be utilized is to design steels with resistance to H embrittlement (HE). HE is one of the most common problems associated with automotive grade steels [START_REF] Chen | Direct observation of individual hydrogen atoms at trapping sites in a ferritic steel[END_REF]- [START_REF] Phaniraj | Hydrogen embrittlement in high interstitial alloyed 18Cr10Mn austenitic stainless steels[END_REF]. Being the smallest atom (with atomic radius ~0.037 nm), H easily undergoes diffusion into materials (especially steels) and leads to catastrophic and unprecedented failure of engineering components during service [START_REF] Cairney | Atoms on the move -Finding the hydrogen[END_REF]. In addition, the extremely high atomic mobility of H (due to the small atomic radius) makes it experimentally challenging to map its exact position in a material. As a result, a number of existing strategies (devised for steels such as addition of carbides) are extremely challenging to validate. Recently, Chen et al. [START_REF] Chen | Observation of hydrogen trapping at dislocations, grain boundaries, and precipitates[END_REF] have devised a deuterium charging based cryo-transfer protocol using characterisation techniques such as TEM, TKD and cryo-APT to identify the position of H atoms segregated at different GBs in Fe-0.23C-0.92Mn-0.24Si-0.049Nb (wt.%) steel. Two types of microstructures: (i) fully ferritic and (ii) fully martensitic were analysed using this approach [START_REF] Chen | Observation of hydrogen trapping at dislocations, grain boundaries, and precipitates[END_REF]. Deuterium was observed to segregate at incoherent interfaces between: (i) NbC and ferrite (in the fully ferritic microstructure) and (ii) NbC and martensite laths (in the fully martensitic microstructure) [START_REF] Chen | Observation of hydrogen trapping at dislocations, grain boundaries, and precipitates[END_REF]. This was the first experimental observation on the trapping of H atoms by a carbide. In addition, C was observed to segregate strongly at low-angle lath boundaries for the case of the fully martensitic microstructure [START_REF] Chen | Observation of hydrogen trapping at dislocations, grain boundaries, and precipitates[END_REF]. For the case of the fully ferritic microstructure, C was observed to be strongly segregated at ferrite RHAGBs [START_REF] Chen | Observation of hydrogen trapping at dislocations, grain boundaries, and precipitates[END_REF].

Besides, the GB segregation tendency for C atoms was reported to be influenced by GB misorientation angle in ferrite RHAGBs [START_REF] Chen | Observation of hydrogen trapping at dislocations, grain boundaries, and precipitates[END_REF]. In both microstructures, segregation of both C and H atoms (at different GBs) were simultaneously observed [START_REF] Chen | Observation of hydrogen trapping at dislocations, grain boundaries, and precipitates[END_REF]. However, trapping of H at GBs was reported to occur irrespective of the strong affinity of C towards H atom [START_REF] Chen | Observation of hydrogen trapping at dislocations, grain boundaries, and precipitates[END_REF].

Stress and segregation-induced phase transformation at a GB

Raabe et al. [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF] have highlighted that solute decoration (at GBs) coupled with local elastic stresses may be utilised to promote localised phase transformation at GBs. This is commonly observed in the context of martensite to austenite reversion at martensite GBs. The reversion phenomenon is influenced by the energy of martensite GBs [START_REF] Raabe | Nanoprecipitate-hardened 1.5 GPa steels with unexpected high ductility[END_REF]. Besides, the transformed region (at GBs) has been reported to facilitate further phase transformation by accommodating localised elastic stresses which leads to a localised transformation induced plasticity (TRIP) effect at the transformed austenite GBs [START_REF] Lia | Atom probe tomography characterization of heavily cold drawn pearlitic steel wire[END_REF], [START_REF] Raabe | Nanoprecipitate-hardened 1.5 GPa steels with unexpected high ductility[END_REF]. The martensite GB energy is largely dependent on the morphology of the martensite phase [START_REF] Raabe | Metallic composites processed via extreme deformation: Toward the limits of strength in bulk materials[END_REF]. For instance, a number of different martensite GBs has been reported in literature which commonly include lath, needle and packet boundaries [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Li | Evolution of strength and microstructure during annealing of heavily cold-drawn 6.3 GPa hypereutectoid pearlitic steel wire[END_REF]. Among all these boundaries, lath boundaries are associated with the minimum GB energy [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Cameron | Phase Stability Effects on Hydrogen Embrittlement Resistance in Martensite-Reverted Austenite Steels[END_REF]- [START_REF] Olson | A mechanism for the strain-induced nucleation of martensitic transformations[END_REF]. The aforementioned reversion has been reported as a highly effective methodology to prevent intergranular crack propagation along martensite GBs.

However, for the occurrence of this reversion, a number of criterion has been reported by the existing literatures [START_REF] Nakada | Variant selection of reversed austenite in lath martensite[END_REF]- [START_REF] Kehoe | The role of carbon in the strength of ferrous martensite[END_REF]. First, solute species with a high βi must be chosen [START_REF] Kehoe | The role of carbon in the strength of ferrous martensite[END_REF].

Second, the solute species must prefer to undergo preferential segregation at martensite GBs [START_REF] Raabe | Metallic composites processed via extreme deformation: Toward the limits of strength in bulk materials[END_REF]. Third, the solute species must have a higher tendency towards GB segregation as compared to that for precipitate formation (for instance, the formation of carbides by a number of transition elements such as Ti, V, Cr, Nb etc.) [START_REF] Raabe | Metallic composites processed via extreme deformation: Toward the limits of strength in bulk materials[END_REF]. Fourth, the segregated solute species must reduce the martensite to austenite transformation temperature [START_REF] Nakada | Variant selection of reversed austenite in lath martensite[END_REF], [START_REF] Hickson | The Production of Ultrafine Ferrite in Low-Carbon Steel by Strain-Induced Transformation[END_REF]. Finally, austenite nucleation at GBs must be associated with localised elastic stresses [137] and promote strengthening at GBs [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Raabe | Current Challenges and Opportunities in Microstructure-Related Properties of Advanced High-Strength Steels[END_REF].

Influence of GB segregation on GB cohesive strength

From a historical perspective, Seah [START_REF] Seah | Adsorption-induced interface decohesion[END_REF] have investigated adsorption induced interface decohesion in commercially pure α-Fe and initially considered the differences between two types of boundary separation as influenced by solute adsorption: (i) quasi-equilibrium separation with the chemical potential of solute maintained uniform throughout the system and (ii) "rapid" separation in a manner that the excess amount of solute initially residing in the boundary remains attached to the created free surfaces with no solute exchange taking place between bulk phases [START_REF] Seah | Interface adsorption, embrittlement and fracture in metallurgy. A review[END_REF]. Based on it, a model to theoretically calculate GB cohesive strength using sublimation enthalpies and atomic sizes has been presented [START_REF] Seah | The Theory of Grain Boundary Segregation in Terms of Surface Adsorption Analogues[END_REF]. Besides, it has been reported that during fracture, dislocations are emitted across the region of the crack tip and contribute to the plastic work in the fracture process [START_REF] Rajagopalan | Grain boundary segregation of interstitial and substitutional impurity atoms in alpha-iron[END_REF]. If the GB strengthening tendency is reduced, failure can occur at reduced stress levels and hence the overall plastic work involved also gets reduced [START_REF] Seah | Interface adsorption, embrittlement and fracture in metallurgy. A review[END_REF]. Before 1979, Thermochemical model was used for the theoretical study of GB cohesion which assumed that GB separates without redistribution of the solute atoms during fracture [START_REF] Seah | Interface adsorption, embrittlement and fracture in metallurgy. A review[END_REF]. However, Seah [START_REF] Seah | Adsorption-induced interface decohesion[END_REF] presented a Pair Bonding or quasi-chemical model to provide a simplified numerical evaluation of the behaviour of embrittlement in α-Fe. The Pair Bonding theory states that the actual energy required to break the bonds across the GB may be simply determined by counting the number of dangling bonds per unit area and adding their energies [START_REF] Seah | Adsorption-induced interface decohesion[END_REF], [START_REF] Wagih | Spectrum of grain boundary segregation energies in a polycrystal[END_REF]- [START_REF] Trelewicz | Grain boundary segregation and thermodynamically stable binary nanocrystalline alloys[END_REF]. The model predicted that in a Fe matrix, Bi, S, Sb, Se, Sn and Te will be highly embrittling and will lead to intergranular separation under application of mechanical stress, followed in order of reducing effect by P, As, Ge, Si and Cu [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Seah | Adsorption-induced interface decohesion[END_REF]. In increasing order of their remedial effect on embrittlement in α-Fe are N, B and C which can prevent intergranular fracture and thus, improve the overall ductility, by maintaining the GB unruptured [START_REF] Seah | Interface adsorption, embrittlement and fracture in metallurgy. A review[END_REF], [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF], [START_REF] Seah | Adsorption-induced interface decohesion[END_REF].

Gibson and Schuh [START_REF] Gibson | A survey of ab-initio calculations shows that segregationinduced grain boundary embrittlement is predicted by bond-breaking arguments[END_REF], [START_REF] Gibson | Segregation-induced changes in grain boundary cohesion and embrittlement in binary alloys[END_REF] have proposed Bond-breaking model for calculating the change in GB cohesive energy as a function of equilibrium segregation of solute species in α-Fe and developed GB segregation and associated cohesion maps for determining whether a particular combination of solute and solvent species will lead to GB embrittlement/strengthening. Based on this model, the energetic barrier to intergranular cleavage may be termed as GB cohesive energy (EGBCE) and is given as: [START_REF] Gibson | Segregation-induced changes in grain boundary cohesion and embrittlement in binary alloys[END_REF] 𝐸 𝐺𝐵𝐶𝐸 = 2𝛾 𝑠 -𝛾 𝐺𝐵 [START_REF] Hondros | Grain boundary microchemistry and stress-corrosion failure of mild steel[END_REF] where, 𝛾 𝑠 is the surface energy. Both these energies are largely influenced by the alloy composition and temperature. Hirth and Rice [START_REF] Hirth | On the thermodynamics of at interfaces as it influences decohesion[END_REF] have presented a mathematical framework for representing EGBCE as a function of 𝛤 𝑖 for solute species segregated at GBs. This thermodynamic framework is based on the assumption that there is no segregation of solute atoms at GBs during intergranular cleavage [START_REF] Hirth | On the thermodynamics of at interfaces as it influences decohesion[END_REF], [START_REF] Rice | Embrittlement of interfaces by solute segregation[END_REF]. The model is given as: [START_REF] Hirth | On the thermodynamics of at interfaces as it influences decohesion[END_REF] E GBCE (𝛤) = E GBCE (𝛤 = 0) -∫ (𝜇 𝐺𝐵 (𝛤) -𝜇 𝑆 ( 𝛤

)) 𝑑𝛤 𝛤 0 [START_REF] Spearot | Insights on slip transmission at grain boundaries from atomistic simulations[END_REF] where, 𝜇 𝐺𝐵 and 𝜇 𝑆 are the chemical potentials at GB and surface respectively [START_REF] Hirth | On the thermodynamics of at interfaces as it influences decohesion[END_REF]. The integral in equation ( 7) describes the change in E GBCE of a pure metal upon solute addition [START_REF] Hirth | On the thermodynamics of at interfaces as it influences decohesion[END_REF], [START_REF] Gibson | Segregation-induced changes in grain boundary cohesion and embrittlement in binary alloys[END_REF]- [START_REF] Hirth | Interface defects, reference spaces and the Frank-Bilby equation[END_REF]. However, there is no emphasis on the interaction between multiple solute species for multi-element segregation at GBs. Besides, there is no term to account for GB energy in equation [START_REF] Spearot | Insights on slip transmission at grain boundaries from atomistic simulations[END_REF].

GB cohesive strength is highly influenced by the extent of solute segregation at GBs and free surfaces (FS) [START_REF] Rajagopalan | Grain boundary segregation of interstitial and substitutional impurity atoms in alpha-iron[END_REF]. The preference of a solute to segregate in either GB or FS depends on the magnitude of binding (or segregation) energy at GB and FS [START_REF] Rajagopalan | Grain boundary segregation of interstitial and substitutional impurity atoms in alpha-iron[END_REF], [START_REF] Rice | Embrittlement of interfaces by solute segregation[END_REF]. For instance, when GB segregation energy is higher than FS segregation energy, the solute atoms reduce GB cohesive strength and hence act as potential GB embrittlers [START_REF] Rajagopalan | Grain boundary segregation of interstitial and substitutional impurity atoms in alpha-iron[END_REF]. In cases where the FS segregation energy is higher than that of GB segregation energy, the solute atoms enhance the GB cohesive strength [START_REF] Rajagopalan | Grain boundary segregation of interstitial and substitutional impurity atoms in alpha-iron[END_REF]. The thermodynamic basis for such an inference is based on the Rice-Wang Model [START_REF] Olson | A mechanism for the strain-induced nucleation of martensitic transformations[END_REF]. Rajagopalan et al. [START_REF] Rajagopalan | Grain boundary segregation of interstitial and substitutional impurity atoms in alpha-iron[END_REF] have theoretically investigated the influence of substitutional elements (such as V and P) on the GB cohesive strength of symmetrical tilt Σ5(210) (θ=53.13 °) SHAGBs in α-Fe. It was shown that P reduces the GB cohesive strength of Σ5 GB whereas V increases the GB cohesive strength of the same [START_REF] Rajagopalan | Grain boundary segregation of interstitial and substitutional impurity atoms in alpha-iron[END_REF]. Table . 2 shows the proposed theoretical models (till date) for determining GB cohesive energy as a function of solute decoration at RHAGB in α-Fe.

Table 2. Theoretical models on determining GB cohesive energy as a function of solute decoration at RHAGB in α-Fe.

Proposed model Main feature (or assumption) Reference

Thermochemical GB cleavage occurs without solute redistribution. [START_REF] Seah | Segregation and the Strength of Grain Boundaries[END_REF] Pair Bonding or quasichemical Energy required to break the bonds across a GB may be determined by calculating the number of dangling bonds per unit area and adding their energies.

[48]

Hirth-Rice Constant chemical potential of the segregating species is maintained during GB cleavage.

[145]

Rice-Wang GB cleavage occurs without any local stress concentration.

[146]

Bond-breaking Solute (segregated at a GB) does not undergo diffusion during GB cleavage [START_REF] Gibson | Segregation-induced changes in grain boundary cohesion and embrittlement in binary alloys[END_REF] Silva et al. [START_REF] Kwiatkowski Da Silva | Thermodynamics of grain boundary segregation, interfacial spinodal and their relevance for nucleation during solid-solid phase transitions[END_REF] have introduced a model for correlating GB segregation with intergranular embrittlement and GB phase nucleation by coupling the thermodynamics of GB segregation in solid solutions with GB character. The proposed model was experimentally validated the model with Atom Probe Tomography (APT)-based investigations in Fe-Mn binary alloys [START_REF] Kwiatkowski Da Silva | Thermodynamics of grain boundary segregation, interfacial spinodal and their relevance for nucleation during solid-solid phase transitions[END_REF]. It was shown that an increase in solute concentration at RHAGBs (BCC RHAGBs in the context of Fe-Mn alloys) leads to an increase in ΔH i and triggers GB embrittlement at room temperature [START_REF] Kwiatkowski Da Silva | Thermodynamics of grain boundary segregation, interfacial spinodal and their relevance for nucleation during solid-solid phase transitions[END_REF]. However, once austenitic transformation occurs, there is a drastic decrease in solute decoration at RHAGBs leading to an increase in GB cohesive strength [START_REF] Kwiatkowski Da Silva | Thermodynamics of grain boundary segregation, interfacial spinodal and their relevance for nucleation during solid-solid phase transitions[END_REF]. The aforementioned model has also been extended to Fe-9Mn (wt.%) based steels [START_REF] Kwiatkowski Da Silva | Competition between formation of carbides and reversed austenite during tempering of a mediummanganese steel studied by thermodynamic-kinetic simulations and atom probe tomography[END_REF], [START_REF] Benzing | Multi-scale characterization of austenite reversion and martensite recovery in a cold-rolled medium-Mn steel[END_REF], [START_REF] Kwiatkowski Da Silva | Confined chemical and structural states at dislocations in Fe-9wt%Mn steels: A correlative TEM-atom probe study combined with multiscale modelling[END_REF], [START_REF] Kuzmina | Linear complexions: Confined chemical and structural states at dislocations[END_REF]. Yoo et al. [START_REF] Yoo | Effects of solid solution and grain-boundary segregation of Mo on hydrogen embrittlement in 32MnB5 hot-stamping steels[END_REF] have reported that addition of 0.15 at.% Mo leads to an improvement in HE resistance in a 32MnB5 hot-stamping steel. This was attributed to the reduction of H diffusivity by Mo [START_REF] Yoo | Effects of solid solution and grain-boundary segregation of Mo on hydrogen embrittlement in 32MnB5 hot-stamping steels[END_REF]. Besides, Mo was also reported to enhance GB cohesive strength and reduce strain localisation along austenite RHAGBs leading to a transition in crack propagation from intergranular to transgranular mode [START_REF] Yoo | Effects of solid solution and grain-boundary segregation of Mo on hydrogen embrittlement in 32MnB5 hot-stamping steels[END_REF]. In the context of Fe-1.62Mn-0.18Si (wt.%) ferritic steel, segregation of P (at ferrite RHAGBs) has been reported to drastically reduce GB cohesive strength [START_REF] Han | Competitive grain boundary segregation of phosphorus and carbon governs delamination crack in a ferritic steel[END_REF]. On the other hand, the presence of C (at RHAGBs) has been observed to promote strengthening at GBs [START_REF] Han | Competitive grain boundary segregation of phosphorus and carbon governs delamination crack in a ferritic steel[END_REF].

Experimental challenges with GB research from the viewpoint of solute decoration

A major challenge associated with GB research is to address all five macroscopic and three microscopic DOFs (associated with GBs). Although 3D EBSD technique (proposed in Ref. [START_REF] Rowenhorst | 3D Crystallographic and morphological analysis of coarse martensite: Combining EBSD and serial sectioning[END_REF]) addresses all five DOFs (in a GB), however, experimentally, it has still not been possible to address the three microscopic DOFs. Besides, 3D EBSD technique is highly time-consuming and requires an additional FIB setup in an SEM. Hence, unlike conventional 2D-EBSD technique, this characterisation cannot be performed in a conventional SEM. The inability of addressing the eight DOFs leads to limitations in terms of correlating the GB structure and solute decoration with their overall influence on the mechanical performance of the material.

However, when utilising GB segregation information to reduce the overall grain size, the only information required is the extent of GB segregation. In this context, information about GB plane may be neglected and hence, a full 5D GB analysis is not required [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. In addition, 3D-EBSD uses serial sectioning and hence, may be regarded as a destructive technique [START_REF] Rowenhorst | 3D Crystallographic and morphological analysis of coarse martensite: Combining EBSD and serial sectioning[END_REF], [START_REF] Calcagnotto | Orientation gradients and geometrically necessary dislocations in ultrafine grained dual-phase steels studied by 2D and 3D EBSD[END_REF]. In other words, it is not possible to devise a correlative 3D-EBSD-APT methodology for the purpose of obtaining both structural and chemical information from the same region in a microstructure as because the analysed region is already lost during 3D-EBSD mapping and hence, not available for APT analysis [START_REF] Calcagnotto | Orientation gradients and geometrically necessary dislocations in ultrafine grained dual-phase steels studied by 2D and 3D EBSD[END_REF]. Nevertheless, the understanding on how the concentration of segregating solute species and dislocation density (at pile-ups) near GBs, influences GB cohesive strength still remains limited. This may be attributed to the numerous experimental challenges associated with determining the interaction between a GB and the decorating solute species. The correlative methodology of microstructural characterisation (discussed in section 3.2.2) coupled with appropriate theoretical analyses may be used as a potential tool to address the above challenge.

Conclusions and outlook

Solute decoration at internal interfaces leads to a number of phenomenon which commonly include strain-induced phase transformation (at the internal interfaces), bulk phase formation, phase reversion and intergranular embrittlement. From a metallurgical viewpoint, interfacial decoration may be utilised for both structural and chemical manipulation of internal interfaces.

The primary aim behind the aforementioned manipulation is to enhance the overall mechanical performance of steels. Nevertheless, this is also an avenue where the methodology of correlative microscopy (coupled with appropriate theoretical analyses) may be utilised as a potential tool to design high-performance steels.

3. 1 2

 12 Common techniques for the characterisation of GB segregation 3.2 Experimental investigations towards understanding GB segregation in steels 3Stress and segregation-induced phase transformation at a GB 4.3 Influence of GB segregation on GB cohesive strength 5.

Fig. 2

 2 Fig. 2 Correlative TEM-APT analysis for Fe-4.40C-0.30Mn-0.39Si-0.21Cr (at. %) cold drawn pearlitic steel: (a) Overlay of C decoration at different GBs in an APT needle prepared using FIB-based liftout technique and (b) Variation of C excess as a function of GB misorientation angle [86].

  (a) shows EBSD-based image quality (IQ)+GB map. Figs. 3(b and c) show the APT-based 3D concentration profiles of B,

Fig. 3

 3 Fig. 3 Correlative EBSD-APT analysis for Fe-28Mn-0.3C (wt.%) TWIP steel: (a) EBSDbased IQ+GB map showing the two GBs: GB1 and GB2 (enclosed in black outlined rectangular boxes) analysed using APT, APT-based 3D elemental maps for different elements in (b) GB1 and (c) GB2. In part (a), LAGB abbreviates for low-angle grain boundary and general GB refers to RHAGB. To the bottom right of part (c), Density map (of Fe) shows the position of GB2 [115].

  Fedotova et al.[START_REF] Fedotova | Complex study of grain boundary segregation in long-term irradiated reactor pressure vessel steels[END_REF] have investigated irradiation-induced GB segregation of P, Mn, Ni and Si at RHAGBs in Fe-(0.04-0.07)C-(1.6-1.89)Ni-(0.006-0.01)P (wt.%) reactor pressure vessel steels using APT, AES and fractography techniques. The extent of segregation of these elements (at RHAGBs) was reported to increase with increasing bulk concentration[START_REF] Fedotova | Complex study of grain boundary segregation in long-term irradiated reactor pressure vessel steels[END_REF].

	Besides, segregation of P at RHAGB was observed to promote inter-granular fracture [101]. A
	similar tendency of P has been reported in Fe-(0.083-0.19)C-(0.26-0.38)Si-(1.22-1.41)Mn-
	(0.007-0.012)P (wt.%) reactor pressure vessel steels

Table . 1

 . summarizes the existing literatures where TEM-APT and EBSD-APT based correlative approach have been used to characterise GB segregation in steels.

Table . 1

 . A summary of reports based on correlative approach towards characterising GB segregation in steels (till date).

	Correlative	Steel composition (or grade)	Segregating	Type of GB Reference
	approach		solute species
	TEM-APT	Fe-4.40C-0.30Mn-0.39Si-	C	Coherent Σ5,	[86]
		0.21Cr (at. %)		coherent and
				incoherent Σ3
		AISI 316	Mo, Si, Cr	RHAGB	[110]

Acknowledgement

The author hereby declares that the review article is solely authored by him. No external assistance of any kind has been received for the article.


Mainak Saha
email: mainaksaha1995@gmail.com

Order within disorder

Keywords: Ordered precipitate, morphology, thermomechanical processing, strain

Over the last five years, the automotive industry has primarily focussed on utilising a number of extraordinary properties of B2-strengthened Fe-Mn steels, especially high specific strength, and high strain hardening. While reduction in density may be attributed to the addition of Al, high toughness and strain hardening may be ascribed to the precipitation of non-shearable B2 precipitates which suppresses the formation of shearable L'1 2 -κ-carbides ((Fe, Mn) 3 AlC carbides). Considering the growing interest in these steels, the present review is aimed at highlighting the present state of research and associated challenges (both fundamental and industrial) with a special emphasis on the influence of B2 precipitate distribution and morphology on the strengthening effect in these steels. In addition, the necessity of obtaining both structural and chemical information about ordered B2 precipitates using the newly emerged methodology of correlative characterisation has also been highlighted.

hardening, correlative microstructural characterisation.

Until 2015, lightweight Fe-Mn steels (also known as TRIPLEX steels) with high specific strength (density ~18% lower than that of conventional steels and strength ~1 GPa) were the main centres of attraction in the community of automotive-grade low-density steels [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF]- [START_REF] Raabe | Alloy Design, Combinatorial Synthesis, and Microstructure-Property Relations for Low-Density Fe-Mn-Al-C Austenitic Steels[END_REF].

Their microstructures comprised of α-Fe(Al, Mn) based BCC phase and finely dispersed L'1 2 -κ-carbides ((Fe,Mn) 3 AlC carbides) in FCC-austenite matrix [START_REF] Gutierrez-Urrutia | Low Density Fe-Mn-Al-C Steels: Phase Structures, Mechanisms and Properties[END_REF], [START_REF] Wang | Ultrastrong lightweight compositionally complex steels via dualnanoprecipitation[END_REF]. However, the primary limitation of these steels was the low strain hardening owing to the precipitation of shearable κ -carbides. Besides, as reported in Ref. [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF], the specific strength of these steels was not comparable to those of Al and Ti alloys. These limitations (of TRIPLEX steels) were addressed by Kim et al. [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF], wherein addition of ~5wt.% Ni to TRIPLEX steels was shown to (i) lead to the formation of non-shearable B2-(Ni, Fe)Al based precipitates and (ii) suppress the precipitation of κ-carbides [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF], [START_REF] Wang | Ultrastrong lightweight compositionally complex steels via dualnanoprecipitation[END_REF]- [START_REF] Rahnama | Multiscale micromechanical model of duplex low density steel with B2 ordered precipitates[END_REF]. This is in contrast to the conventional wisdom of FCC stabilisation by Ni [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF]. Besides, addition of C and Mn has also been reported to stabilise the FCC matrix in Ni-added TRIPLEX steels (or, Fe-Mn steels) [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF]. In the context of B2strengthened (B2s) Fe-Mn steels (B2-strengthened Fe-Mn steels will be referred to as B2s Fe-Mn steels, hereafter, in the manuscript), FCC phase provides ductility whereas B2-(Ni,Fe)Al based precipitates account for high strength [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF], [START_REF] Rahnama | Nano-mechanical properties of Fe-Mn-Al-C lightweight steels[END_REF]- [START_REF] Gao | Tensile Deformation of Ultrafine-Grained Fe-Mn-Al-Ni-C Alloy Studied by In Situ Synchrotron Radiation X-ray Diffraction[END_REF]. In other words, the high overall toughness (total elongation ~20-35% and strength ~1.6 GPa) in B2s Fe-Mn steels may be attributed to an outstanding combination of strength and ductility combination provided by the FCC matrix and B2 precipitates respectively [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF], [START_REF] Zargaran | κ-Carbide assisted nucleation of B2: A novel pathway to develop high specific strength steels[END_REF], [START_REF] Kim | Strain hardening of novel high Al low-density steel consisting of austenite matrix and B2-ordered intermetallic second phase in the perspective of non-cell forming face-centeredcubic alloy with high stacking fault energy[END_REF].

B2 precipitate morphology has been reported to influence strengthening effect in B2s Fe-Mn steels [START_REF] Park | Effect of B2 morphology on the mechanical properties of B2-strengthened lightweight steels[END_REF], [START_REF] Zargaran | κ-Carbide assisted nucleation of B2: A novel pathway to develop high specific strength steels[END_REF]. In addition, distribution of ordered B2 phase in a disordered FCC matrix hugely influences the strengthening effect in these steels [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF], [START_REF] Park | Effect of B2 morphology on the mechanical properties of B2-strengthened lightweight steels[END_REF], [START_REF] Rahnama | Nano-mechanical properties of Fe-Mn-Al-C lightweight steels[END_REF], [START_REF] Kim | Strain hardening of novel high Al low-density steel consisting of austenite matrix and B2-ordered intermetallic second phase in the perspective of non-cell forming face-centeredcubic alloy with high stacking fault energy[END_REF]. For instance, one of the most common ways of enhancing strength-ductility combination in B2s Fe-Mn steels is through an appropriate utilisation of potent nucleation sites such as FCC grain boundaries (GBs), grain edges and shear bands (formed due to plastic deformation) [START_REF] Kim | Brittle intermetallic compound makes ultrastrong lowdensity steel with large ductility[END_REF], [START_REF] Rahnama | Multiscale micromechanical model of duplex low density steel with B2 ordered precipitates[END_REF], [START_REF] Hwang | Improvement of strength -Ductility balance of B2-strengthened lightweight steel[END_REF]. At present, correlative characterisation has emerged as a powerful methodology in terms of providing both structural and chemical information from the same region in a given microstructure [START_REF] Raabe | Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces[END_REF]. However, the aforementioned methodology has not been utilised (till date) to understand the microstructure evolution of B2 precipitates in FCC matrix (in B2s Fe-Mn steels). To this end, the present review article is aimed at highlighting some of the developments (till date) and associated challenges (both fundamental and industrial) in the avenue of B2s Fe-Mn lightweight steels with a special emphasis on the influence of B2 precipitate morphology, and distribution on the deformation characteristics of these steels. In addition, the necessity of utilising correlative characterisation methodology towards understanding the microstructure evolution of ordered B2 precipitates in a disordered FCC matrix (in B2s Fe-Mn steels) has also been highlighted.