Grain Boundary Segregation Engineering: Engineering Materials Interfaces down to the Atomic Scale


Grain boundaries are ubiquitous defects in metallic alloys governing a range of properties, such as tensile strength, fatigue resistance, fracture toughness, strain hardening, brittleness, conductivity, or corrosion.

Unlike bulk phases they are planar and require 5 parameters to be crystallographically characterized (disorientation, plane inclination). Hence, they cannot be regarded as scalar objects with homogeneous properties but as a high dimensional class of defects. For example, even for highly coherent grain boundaries such as first order twins (Σ3 CSL (coincidence site lattice)) exponential property changes can occur if the grain boundary plane is misaligned by only a few degrees from its most coherent position.

Grain boundaries can either weaken (inter-crystalline fracture, stress corrosion cracking) or strengthen (Hall-Petch effect) polycrystalline metallic materials. In either case the types of Grain boundaries involved affect the specific material response substantially as was discussed particularly in the context of highly coherent versus random grain boundaries. These observations led to the concept of grain boundary engineering which aims at designing polycrystals with specific grain boundary distributions.

The next logical step in this context lies in also considering and engineering the segregation and its effects on grain boundaries. This is an obvious thought since many if not all grain boundary properties are accessible to decoration-driven manipulation such as cohesion; energy; fracture resistance; electrical conductivity; transport coefficients; electrochemical properties; hydrogen embrittlement; mobility; and resistance to or sources of dislocations to name only a few effects that are relevant for structural alloys.

We refer to such manipulation of grain boundaries via solute decoration and even confined transformation as 'grain boundary segregation engineering' (GBSE) or just 'segregation engineering'. Applying GBSE needs to involve both, thermodynamic (segregation coefficient; co-segregation; competing bulk phases) and kinetic (diffusion) influence factors. Hence, not only the associated crystallographic degrees of freedom and all segregated elements should be considered but also time and temperature. However, as will be addressed below, GBSE can for a number of alloys even be applied when knowing the average segregation level to non-ordered or ‘random’ grain boundaries, i.e. a full 5D crystallographic description is not in all cases required.

Grain boundary segregation changes with time when the heat treatment or application temperature is high enough for diffusion. Hence, also the grain boundary properties may alter. GBSE considers solute decoration not as an undesired and inherited phenomenon but instead utilizes segregation as a tool for site-specific manipulation that allows for optimizing specific grain boundary structures, compositions and properties that enable the design of beneficial material behavior. More specific, grain boundary segregation can be used as a microstructure design method since solutes affect the structure, phase state and atomic bonds within the decorated interface. Different scenarios are conceivable: First, segregation of certain solutes might enhance grain boundary cohesion (grain boundary strengthening). Second, the reverse might apply, namely, reduction in cohesion and bonding strength (interface weakening) at grain boundaries due to segregation. Third, segregation could be strong enough, in conjunction with the available interfacial energy and local stresses, to result in a phase transformation of or at the grain boundary region. Related to the latter point is the possibility for the formation of complexions, i.e. interface stabilized phases.

An important question in that context is the accessibility of these segregation-dependent grain boundary features via an 'engineering' approach. Indeed various examples are conceivable where such misorientation- and plane-sensitive design approach can work, namely, diffusion annealing, grain growth heat treatment, and local phase transformation effects.

A typical example for an engineering heat treatment approach to tune a desired segregation level at grain boundaries lies in a combined diffusion plus grain growth heat treatment: Since the reduction and grain boundary energy may depend on both, the grain boundary plane inclination and its crystallographic misorientation, such low energy configurations can be obtained for instance by a grain growth heat treatment, where low-energy interfaces prevail owing to their comparably small capillary driving force. Another broadly applicable example of grain boundary segregation engineering lies in the reduction of the average grain size due to an overall drop in grain boundary energy caused by equilibrium segregation.

Although GBSE can be applied to such diverse systems as solar cells, superconductors, or ceramics we focus here on recent developments pertaining to metallic alloys used for structural applications.

In these materials we see particularly high relevance and opportunities of the GBSE concept for designing improved ultra fine grained and nanostructured metallic alloys where grain boundaries constitute a large fraction of the material. Particularly alloys with nanoscaled grain size suffer often from very low ductility in conjunction with inter-crystalline damage. In such materials particularly the internal interfaces are prone to void formation and damage initiation. 


Atom probe tomography, grain boundary, segregation engineering, Ni-alloy, martensite, interface, TEM Examples of grain boundary segregation engineering: Ni-alloy and martensite




Linear complexions: Confined chemical and structural states at dislocations
Dislocations as Linear Complexions Scien[...]
PDF-Dokument [1.5 MB]

For 5000 years, metals have been mankind’s most essential materials owing to their ductility and strength. Linear defects called dislocations carry atomic shear steps, enabling their formability. We report chemical and structural states confined at dislocations. In a body-centered cubic Fe–9 atomic percent Mn alloy, we found Mn segregation at dislocation cores during heating, followed by formation of face-centered cubic regions but no further growth. The regions are in equilibrium with the matrix and remain confined to the dislocation cores with coherent interfaces.The phenomenon resembles interface-stabilized
structural states called complexions. A cubic meter of strained alloy contains up to a light year of dislocation length, suggesting that linear complexions could provide opportunities to nanostructure alloys via segregation and confined structural states.


complexion, linear complexion,, atom probe tomography, grain boundary, segregation engineering, Ni-alloy, martensite, interface, TEM Identification of linear complexions by correlative atom probe tomography and TEM
Grain boundary segregation engineering and austenite reversion turn embrittlement into toughness: Example of a 9 wt.% medium Mn steel
Acta Materialia 86 (2015) 182-192
Acta Materialia 86 (2015) 182 Kuzmina Gr[...]
PDF-Dokument [1.8 MB]

We study grain boundary embrittlement in a quenched and tempered Fe–Mn high-purity model martensite alloy using Charpy impact tests and grain boundary characterization by atom probe tomography. We observe that solute Mn directly embrittles martensite grain boundaries while reversion of martensite to austenite at high-angle grain boundaries cleans the interfaces from solute Mn by partitioning the Mn into the newly formed austenite, hence restoring impact toughness. Microalloying with B improves the impact toughness in the quenched state and delays temper embrittlement at 450 °C. Tempering at 600 °C for 1 min significantly improves the impact toughness and further tempering at lower temperature does not cause the embrittlement to return. At higher temperatures, regular austenite nucleation and growth takes place, whereas at lower temperature, Mn directly promotes its growth.

complexion, linear complexion,, atom probe tomography, grain boundary, segregation engineering, Ni-alloy, martensite, interface, TEM Kuzmina et al. / Acta Materialia 86 (2015) 182: Grain boundary segregation engineering and austenite reversion turn embrittlement into toughness
Microstructural evolution of a Ni-based superalloy (617B) at 700 °C studied by electron microscopy and atom probe tomography
Acta Materialia 60 (2012) 1731-1740
Microstructural evolution of a Ni-based superalloy (617B) at 700 °C studied by electron microscopy and atom probe tomography
Acta Materialia 60 (2012) 1731 alloy 617[...]
PDF-Dokument [1.3 MB]
complexion, linear complexion,, atom probe tomography, grain boundary, segregation engineering, Ni-alloy, martensite, interface, TEM Acta Materialia 60 (2012) 1731-1740 Microstructural evolution of a Ni-based superalloy (617B) at 700 °C studied by electron microscopy and atom probe tomography

The demand for energy is set to double over the coming decades. In order to reduce CO2 emissions from fossil power plants there is an urgent need to improve energy conversion efficiency. To achieve this goal, the next generation
of ultra-supercritical power plants must operate at service temperatures between 700 and 720 °C and steam pressures of up to 393 bar. However, conventional ferritic steels (P92) used in current power plants cannot withstand such conditions, as they are designed for temperatures up to 600 °C and operating pressures up to 250 bar. Consequently, they are expected to be replaced
by Ni-based superalloys which show longer creep rupture life and higher corrosion resistance.

More specific, in this paper we report on the microstructural evolution of a polycrystalline Ni-based superalloy (Alloy 617B) for power plant applications at a
service temperature of 700 °C. The formation of secondary M23C6-carbides close to grain boundaries (GBs) and around primary Ti(C,N) particles is observed upon annealing at 700 °C, where gamma' is found to nucleate heterogeneously at M23C6 carbides. Using atom probe tomography, elemental partitioning to the phases and composition profiles across phase and grain boundaries are determined. Enrichments of B at gamma / M23C6 and gamma' / M23C6 interfaces as well as at grain boundaries are detected, while no B enrichment is found at gamma/gamma' interfaces. It is suggested that segregation of B in conjunction with gamma' formation stabilizes a network of secondary M23C6 precipitates near GBs and thus increases the creep rupture life of Alloy 617B. Calculations of the equilibrium phase compositions by Thermo-Calc confirm the chemical compositions measured by atom probe tomography.


Mechanisms of subgrain coarsening and its effect on the mechanical properties of carbon-supersaturated nanocrystalline hypereutectoid steel
Acta Materialia 84 (2015) 110-123 atom p[...]
PDF-Dokument [2.4 MB]

Carbon-supersaturated nanocrystalline hypereutectoid steels with a tensile strength of 6.35 GPa were produced from severely cold-drawn pearlite. The nanocrystalline material undergoes softening upon annealing at temperatures between 200 and 450 C. The ductility in terms of elongation to failure exhibits a non-monotonic dependence on temperature. Here, the microstructural mechanisms responsible for changes in the mechanical properties were studied using transmission electron microscopy (TEM), TEM-based automated scanning nanobeam diffraction and atom probe tomography (APT). TEM and APT investigations of the nanocrystalline hypereutectoid steel show subgrain coarsening upon annealing, which leads to strength reduction following a Hall–Petch law. APT analyzes of the Mn distribution near subgrain boundaries and in the cementite give strong evidence of capillary-driven subgrain coarsening occurring through subgrain boundary migration. The pronounced deterioration of ductility after annealing at temperatures above 350 C is attributed to the formation of cementite at subgrain boundaries. The overall segregation of carbon atoms at ferrite subgrain boundaries gives the nanocrystalline material excellent thermal stability upon annealing.


pearlite, complexion, linear complexion,, atom probe tomography, grain boundary, segregation engineering, severe plastic deformation, interface, TEM Li et al. / Acta Materialia 84 (2015) 110:Mechanisms of subgrain coarsening and its effect on the mechanical properties of carbon-supersaturated nanocrystalline hypereutectoid steel
Impact of nanodiffusion on the stacking fault energy in high-strength steels
Acta Materialia 75 (2014) 147-155
Acta Materialia 75 (2014) 147 nanodiffus[...]
PDF-Dokument [787.4 KB]

A key requirement of modern steels – the combination of high strength and high deformability – can best be achieved by enabling a local adaptation of the microstructure during deformation. A local hardening is most efficiently obtained by a modification of the stacking sequence of atomic layers, resulting in the formation of twins or martensite. Combining ab initio calculations with in situ transmission electron microscopy, we show that the ability of a material to incorporate such stacking faults depends on its overall chemical composition and, importantly, the local composition near the defect, which is controlled by nanodiffusion. Specifically, the role of carbon for the stacking fault energy in high-Mn steels is investigated. Consequences for the long-term mechanical properties and the characterisation of these materials are discussed.


Atomic-Scale Quantification of Grain Boundary Segregation in Nanocrystalline Material
Phys Rev Lett. 2014 grain boundary segre[...]
PDF-Dokument [842.8 KB]


Grain boundary segregation leads to nanoscale chemical variations that can alter a material's performance by orders ofmagnitude (e.g., embrittlement). To understand this phenomenon, a large number of grain boundaries
must be characterized in terms of both their five crystallographic interface parameters and their atomic-scale chemical composition. We demonstrate how this can be achieved using an approach that combines the accuracy of structural characterization in transmission electron microscopy with the 3D chemical sensitivity of atom probe tomography.We find a linear trend between carbon segregation and the misorientation angle ω for low-angle grain boundaries in ferrite, which indicates that ω is the most influential crystallographic parameter in this regime. However, there are significant deviations from this linear trend indicating an additional strong
influence of other crystallographic parameters (grain boundary plane, rotation axis). For high-angle grain boundaries, no general trend between carbon excess and ω is observed; i.e., the grain boundary plane and rotation axis have an even higher influence on the segregation behavior in this regime. Slight deviations from special grain boundary configurations are shown to lead to unexpectedly high levels of segregation.


Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces
Current Opinion in Solid State and Materials Science 18 (2014) 253-261
Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces
D. Raabe, M. Herbig, S. Sandlöbes, Y. Li, D. Tytko, M. Kuzmina, D. Ponge, P.-P. Choi
Current Opinion 2014 Grain Boundary Segr[...]
PDF-Dokument [1.7 MB]
Grain boundary segregation engineering, pearlite, complexion, linear complexion,, atom probe tomography, grain boundary, segregation engineering, severe plastic deformation, interface, TEM Current Opinion in Solid State and Materials Science 18 (2014) 253-261 Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces, Raabe, Herbig, Sandlöbes, Li, Tytko, Kuzmina, Ponge, Choi
Grain boundary segregation engineering; grain boundary, segregation engineering, superalloy, Boron Current Opinion in Solid State and Materials Science 18 (2014) 253-261 Grain boundary segregation engineering in metallic alloys: A pathway to the design of interfaces, Raabe, Herbig, Sandlöbes, Li, Tytko, Kuzmina, Ponge, Choi

Grain boundaries influence mechanical, functional, and kinetic properties of metallic alloys. They can be manipulated via solute decoration enabling changes in energy, mobility, structure, and cohesion or even promoting local phase transformation. In the approach which we refer here to as ‘segregation engineering’ solute decoration is not regarded as an undesired phenomenon but is instead utilized to manipulate specific grain boundary structures, compositions and properties that enable useful material behavior. The underlying thermodynamics follow the adsorption isotherm. Hence, matrix-solute combinations suited for designing interfaces in metallic alloys can be identified by considering four main aspects, namely, the segregation coefficient of the decorating element; its effects on interface cohesion, energy, structure
and mobility; its diffusion coefficient; and the free energies of competing bulk phases, precipitate phases or complexions. From a practical perspective, segregation engineering in alloys can be usually realized by a modest diffusion heat treatment, hence, making it available in large scale manufacturing.


A novel approach to measure grain boundary segregation in bulk polycrystalline materials in dependence of the boundaries’ five rotational degrees of freedom
2014 scripta Mandal GB segregation 3D EB[...]
PDF-Dokument [972.8 KB]

Here we demonstrate a simplified nondestructive 3-D electron backscatter diffraction (EBSD) methodology that enables the measurement of all five degrees of freedom of grain boundaries (GBs) combined with segregation analysis using atom probe tomography (APT). The approach is based on two 2-D EBSD measurements on orthogonal surfaces at a sharp edge of the specimen followed by site-specific GB composition analysis using APT. An example of an asymmetric R9 boundary exhibiting GB segregation emphasizes the need for complete GB characterization in this context.

Advanced Scale Bridging Microstructure Analysis of Single Crystal Ni-Base Superalloys
Adv Eng Mater 2014 Superalloy multiscale[...]
PDF-Dokument [2.8 MB]

In the present work, we show how conventional and advanced mechanical, chemical, and microstructural methods can be used to characterize cast single crystal Ni-base superalloy (SX) plates across multiple length scales. Two types of microstructural heterogeneities are important, associated with the cast microstructure (dendrites (D) and interdendritic (ID) regions – large scale heterogeneity) and with the well-known g/g0 microstructure (small scale heterogeneity). Using electron probe microanalysis (EPMA), we can show that elements such as Re, Co, and Cr partition to the dendrites while ID regions contain more Al, Ta, and Ti. Analytical transmission electron microscopy and atom probe tomography (APT) show that Al, Ta, and Ti partition to the g0 cubes while g channels show higher concentrations of Co, Cr, Re, andW.We can combine large scale (EPMA) and small-scale analytical methods (APT) to obtain reasonable estimates for g0 volume fractions in the dendrites and in the ID regions. The chemical and mechanical properties of the SX plates studied in the present work are homogeneous, when they are determined from volumes with dimensions, which are significantly larger than the dendrite spacing. For the SX plates (140mm100mm20 mm) studied in the present work this holds for the average chemical composition as well as for elastic behavior and local
creep properties. We highlight the potential of HRTEM and APT to contribute to a better understanding of the role of dislocations during coarsening of the g0 phase and the effect of cooling rates after high temperature exposure on the microstructure.

Nanocrystalline Fe–C alloys produced by ball milling of iron and graphite
2013-Acta-Nanocrystalline Fe–C alloys by[...]
PDF-Dokument [2.1 MB]

A series of nanocrystalline Fe–C alloys with different carbon concentrations (xtot) up to 19.4 at.% (4.90 wt.%) are prepared by ball milling. The microstructures of these alloys are characterized by transmission electron microscopy and X-ray diffraction, and partitioning of carbon between grain boundaries and grain interiors is determined by atom probe tomography. It is found that the segregation of carbon to grain boundaries of a-ferrite can significantly reduce its grain size to a few nanometers. When the grain boundaries of ferrite are saturated with carbon, a metastable thermodynamic equilibrium between the matrix and the grain boundaries is approached, inducing a decreasing grain size with increasing xtot. Eventually the size reaches a lower limit of about 6 nm in alloys with xtot > 6.19 at.%
(1.40 wt.%); a further increase in xtot leads to the precipitation of carbon as Fe3C. The observed presence of an amorphous structure in 19.4 at.% C (4.90 wt.%) alloy is ascribed to a deformation-driven amorphization of Fe3C by severe plastic deformation. By measuring the temperature dependence of the grain size for an alloy with 1.77 at.% C additional evidence is provided for a metastable equilibrium reached in the nanocrystalline alloy.


Segregation engineering enables nanoscale martensite to austenite phase transformation at grain boundaries: A pathway to ductile martensite
Raabe Acta Materialia 2013 Nanoscale-aus[...]
PDF-Dokument [6.0 MB]

In an Fe–9 at.% Mn maraging alloy annealed at 450 C reversed allotriomorphic austenite nanolayers appear on former Mn decorated lath martensite boundaries. The austenite films are 5–15 nm thick and form soft layers among the hard martensite crystals. We document the nanoscale segregation and associated martensite to austenite transformation mechanism using transmission electron microscopy and atom probe tomography. The phenomena are discussed in terms of the adsorption isotherm (interface segregation) in conjunction with classical heterogeneous nucleation theory (phase transformation) and a phase field model that predicts the kinetics
of phase transformation at segregation decorated grain boundaries. The analysis shows that strong interface segregation of austenite stabilizing elements (here Mn) and the release of elastic stresses from the host martensite can generally promote phase transformation at martensite grain boundaries. The phenomenon enables the design of ductile and tough martensite.


Grain boundary segregation in Fe–Mn–C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography
Acta Mater 2014 GB segregation twin TWIP[...]
PDF-Dokument [665.4 KB]

We report on the characterization of grain boundary (GB) segregation in an Fe–28Mn–0.3C (wt.%) twinning-induced plasticity (TWIP) steel. After recrystallization of this steel for 24 h at 700 C, 50% general grain boundaries (GBs) and 35% R3 annealing twin boundaries were observed (others were high-order R and low-angle GBs). The segregation of B, C and P and traces of Si and Cu were detected at the general GB by atom probe tomography (APT) and quantified using ladder diagrams. In the case of the R3 coherent annealing twin, it was necessary to first locate the position of the boundary by density analysis of the atom probe data, then small amounts of B, Si and P segregation and, surprisingly, depletion of C were detected. The concentration of Mn was constant across the interface for both boundary types. The depletion of C at the annealing twin is explained by a local change in the stacking sequence at the boundary, creating a local hexagonal close-packed structure with low C solubility. This finding raises the question of whether segregation/depletion also occurs at R3 deformation twin boundaries in high-Mn TWIP steels. Consequently, a previously published APT dataset of the Fe–22Mn–0.6C alloy system, containing a high density of deformation twins due to 30% tensile deformation at room temperature, was reinvestigated using the same analysis routine as for the annealing twin. Although crystallographically identical to the
annealing twin, no evidence of segregation or depletion was found at the deformation twins, owing to the lack of mobility of solutes during twin
formation at room temperature.


Chemical gradients across phase boundaries between martensite and austenite in steel studied by atom probe tomography and simulation
PDF-Dokument [2.3 MB]

Partitioning at phase boundaries of complex steels is important for their properties. We present atom probe tomography results across martensite/austenite interfaces in a precipitation-hardened maraging-TRIP steel (12.2 Mn, 1.9 Ni, 0.6 Mo, 1.2 Ti, 0.3 Al; at.%). The system
reveals compositional changes at the phase boundaries: Mn and Ni are enriched while Ti, Al, Mo and Fe are depleted. More specific,
we observe up to 27 at.% Mn in a 20 nm layer at the phase boundary. This is explained by the large difference in diffusivity between martensite and austenite. The high diffusivity in martensite leads to a Mn flux towards the retained austenite. The low diffusivity in the austenite does not allow accommodation of this flux. Consequently, the austenite grows with a Mn composition given by local equilibrium. The interpretation is based on DICTRA and mixed-mode diffusion calculations (using a finite interface mobility).