RESEARCH PAPER

Lattice strain framework for plastic

deformation in complex concentrated
alloys including high entropy alloys
R. S. Mishra*, N. Kumar and M. Komarasamy
Alloys involving multiple solutes where the concentrations are such that it becomes difficult
to identify a ‘‘solvent’’, such as the so called ‘‘high entropy alloys’’, have the potential for
interesting combinations of properties. A key question relates to the fundamental mechanisms of
plastic deformation in these alloys. A simple lattice strain framework is proposed for complex
concentrated alloys to address the energetics and kinetics of dislocations and twins. It is argued
that the lattice strain in highly concentrated alloys raises the base energy of the crystal and
thereby reduces the additional energy required to nucleate dislocations and twins. However, the
kinetics of dislocation motion are dampened by the lattice strain and local energy variations.
This is reflected in lower values of activation volume. This framework can be used to design
non-equiatomic high entropy alloy matrixes that enhance the properties achieved thus far.
Keywords: Strengthening mechanisms, Twinning, Dislocation kinetics, Alloy design, Complex concentrated alloys, Solid solution strengthening,
Plastic deformation, Dispersion strengthening

Introduction fault energy alloy such as stainless steel is known to

undergo planar slip, which reduces the fatigue life, but
The fundamental alloying principles have attracted that is not the case for the initial results on an
metallurgists from more than a century. Structural ma- HEA alloy.7 The toughness value of v200 MPa m1/2
terials have progressively become more complex, both reported by Gludovatz et al.8 is again among the highest
compositionally and microstructurally, based on a achieved for metallic materials. With respect to high
detailed understanding of alloying principles. For temperature behaviour, HEAs show remarkable resist-
example, if one considers common structural alloy ance to elevated temperature softening9–12 and higher
families such as steels, aluminium alloys, nickel based activation energy values.13,14 What, then, are the unique
superalloys and titanium alloys, the wide range of characteristics of the deformation mechanisms that make
alloying principles can easily be appreciated. These these properties possible? Can this framework be used to
alloys will be referred to below as ‘‘conventional alloys’’. design CCAs that expand the current range of HEAs?
The focus of the present article is on the plastic defor-
mation of high entropy alloys (HEAs).1,2 However, to
provide a proper perspective, a broader approach is Brief survey of highly concentrated
taken under the nomenclature of ‘‘complex concentrated conventional alloys
alloys’’ (CCAs); a cogent case for this approach has
recently been argued by Miracle.3 A brief survey of highly concentrated conventional
Ashby’s4 materials selection criteria in the context of alloys sets the scene for the current discussion. Con-
plastic deformation based goals are strength, fatigue, sideration of solid solution strengthening in iso-
toughness and creep limiting designs. The basic mech- morphous alloy systems goes back to the early days of
anisms involved in all these deformation based approa- dislocation studies. A classic example is the Ag–Au
ches relate to dislocations and twinning. Kumar et al.5 system where maximum strength is achieved at an
have recently highlighted the excellent strength, fatigue equiatomic composition, i.e. with 50% solute. It is
limit, toughness and high temperature strength that can notable that the experimental variation of lattice par-
be achieved in the best HEAs.6–9 Hemphill et al.7 noted ameter in this system does not follow the linear average
an exceptionally high value of fatigue endurance limit. given by the lever rule. The lattice strain caused by the
Typically, the ratio of fatigue strength to ultimate tensile solute is calculated on the basis of the parent lattice
strength is in the range of 0.3–0.55, whereas the value constant (although this definition breaks down for
noted for HEAs was v0.7. A conventional low stacking equiatomic composition, i.e. 50:50). Other examples of
highly concentrated alloys span the spectrum from steels
to nickel based superalloys, which use a variety of
Center for Friction Stir Processing, Department of Materials Science and strengthening mechanisms and are usually multiphase
Engineering, University of North Texas, Denton, TX 76203, USA alloys. Representative examples are given in Table 1.
*Corresponding author, email [email protected] The Fe–Ni–Cr–Ti precipitation strengthened austenitic

Ñ 2015 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 26 March 2015; accepted 26 March 2015
DOI 10.1179/1743284715Y.0000000050 Materials Science and Technology 2015 VOL 00 NO 0 1
Mishra et al. Lattice strain framework for complex concentrated alloys

Table 1 Examples of highly concentrated conventional alloys

Total alloying
Alloy Composition/wt-% additions/wt-%

316 SS Fe–17Cr–12Ni–2Mn–2.5Mo–0.75Si 34.25

Inconel 718 (Ni þ Co)–21Cr–15.2Fe–3.3Mo–5.5Nb 45.0
Hastealloy C276 Ni–16Cr–16Mo–2.5Co–4W–5Fe 43.5
Waspaloy Ni–19Cr–13Co–4Mo–3Ti–1.3Al 40.3
Stellite 6 Co–28Cr–5W–1.2C 34.2
Incoloy A 286 Fe–25Ni–14Cr–2Ti–1.3Mo–0.25V 42.55

steel (A286 steel) has almost 40% solute content and Consider the crystal structure of an HEA, which
Ni3Ti strengthening precipitates. In this case, the impacts the nature of dislocation plasticity directly.
addition of Ni stabilises the austenitic phase, but the CoCrFeMnNi HEAs form an fcc solid solution, but
lattice does represent Fe and solutes occupy substitu- only Ni has an fcc crystal structure at all temperatures;
tional sites. In addition, the stacking fault energy of Fe has an fcc structure over a certain temperature range.
such alloys is quite low, which directly influences This raises the question of whether the HEA fcc crystal
the dislocation plasticity, including planar slip. This structure ‘‘belongs’’ to any single element in this alloy, as
discussion is intended to illustrate that some conven- would be the case for a conventional fcc alloy.
tional alloys had very high alloying content before the An answer requires further research in terms of the
development of HEAs and that their microstructural relationship between the native crystal structure of the
complexity was also high. It is argued in the following alloying elements and the resultant HEA crystal struc-
section that a similar approach can be used to develop ture. Similar argument can be extended to the discussion
HEA complex alloys. of shear modulus. The shear modulus of a CoCr-
FeMnNi HEA, for example, is based on the lattice
structure and reflects the average bond strength.17
Alloying principles used to design HEAs As discussed below, this will have a direct bearing on the
and future possibilities properties of dislocations, since the line energy is directly
As highlighted in early reports, the alloying principle related to the shear modulus. Murty et al.16 have sum-
used for HEAs is distinct from that for conventional marised various possibilities for the formation of these
alloys. The conventional approach is to add alloying extended solid solutions. Even if a binary intermetallic is
elements to a host matrix (Fig. 1). Even for highly considered as the starting point to create a lattice
concentrated alloys, the host crystal structure is the basis structure that progressively turns into a concentrated
for microstructure development (see discussion below on solid solution by substitution, the final shear modulus
plastic deformation). In contrast, synthesis of the initial would be dictated by the atomic bonds in the solid sol-
HEAs was based on an equiatomic approach (Fig. 1), ution. The emerging information about atomic structure
which remains the focus of most investigations. The will shed light on whether short range preferences exist
objective is to form a solid solution with a facecentred between specific alloying elements that will affect the
cubic (fcc),1 body centred cubic1 or hexagonal close average bond strength.
packed 15 crystal structure. Murty et al.16 have produced Additionally, non-equiatomic compositions open up
a comprehensive list of such alloys in a review that the compositional and microstructural space by orders
summarises the current state of understanding. The of magnitude. While it is not possible to deal with this
nomenclature ‘‘high entropy alloy’’ derives from the broader discussion on multiphase concentrated alloys
concept of maximising the configurational entropy. here, it suffices to say that that dispersion strengthening
While this is an important aspect of these highly con- effects can be potent. The current discussion could
centrated alloys, we focus on two other aspects that provide the basis for creating matrixes for multiphase
underpin mechanical behaviour: the crystal structure complex concentrated alloys. Just a few examples of
and the modulus. non-equiatomic compositions are put forward in Fig. 2,
and it can be inferred that a vast array is possible. Types
2 and 3 are solid solutions and represent possibilities
that have been pursued, involving small additions of
elements with different properties. This concept will be
important for the discussion of lattice strain below. Type
4 is a composition purposefully designed to promote
dispersion strengthening; in an approach akin to A286
stainless steel, *2%Ti is added to an Al–Cr–Ni solid
solution matrix to form Ni3Ti precipitates. Such
approaches make the possibilities for engineering alloy
design very rich. Borrowing from aluminium alloy
metallurgy, one can adopt a 2xxx alloy approach where
the intermetallic precipitate forms with the matrix
1 Schematic illustration of conventional alloying approach element (Al with Cu) or a 7xxx alloy approach where
and HEA concept: HEA design is of interest because of its two alloying elements (Zn with Mg) form an inter-
multicomponent approach to produce stable extended metallic independent of the matrix element. In the
solid solutions microstructural design of quinary HEAs, ABCDE can

2 Materials Science and Technology 2015 VOL 00 NO 0

 Mishra et al. Lattice strain framework for complex concentrated alloys

The atomic misfit strain in representative single phase

fcc HEAs alloys and conventional binary alloys is
compared in Fig. 4. To calculate the atomic misfit strain,
an average atomic radius was calculated for each alloy
considered in Fig. 4, using Vegard’s law
Xn
_r ¼ cr ð1Þ
i¼1 i i

where ci is atomic fraction, and ri is the Goldschmidt

radius of the ith element. In the theoretical description
of the fcc lattice, atoms occupying the lattice sites along
2 Non-equiatomic possibilities for complex concentrated
.110, directions touch, implying that 2r¼0.707a
alloy compositions: types 2 and 3 are solid solutions,
(where r is atomic radius and a the unit cell parameter).
and type 4 is dispersion strengthened; these are simple
Thus, a/r ¼ 2.828 in an ideal fcc crystal, making it
examples of very large number of possibilities to design
possible to calculate the theoretical lattice parameter of
non-equiatomic alloys and HEA matrixes for dispersion
a given alloy from the r value obtained from equation
strengthened alloys
(1). For the alloy Al0.1CrFeCoNi, this gives a theoretical
lattice parameter of a ¼ 0.358 nm, whereas X-ray
be treated as base and second phase can be incorporated diffraction measurements give a lattice parameter of
for dispersion strengthening. This broader approach can 0.359 nm. The negligible difference gives confidence in
be classified as CCAs, which derive the matrix crystal using equation (1) to calculate average radii for the
structure from a combination of elements and not from alloys in Fig. 4a. To calculate the lattice strain, a refer-
the conventional individual element. ence state is needed, two simple possibilities for which
are the following: (i) the atomic sites of the undistorted
Implications of lattice strain for lattice and (ii) the deviation from the calculated average
value of atomic size, based on the measured lattice
dislocations and twins: framework for parameter. Here, the average radius of an alloy has been
plastic deformation? used to calculated atomic misfit strain. Individual
Several researchers have highlighted the concept of elements in the HEAs CrFeCoNi and CrMnFeCoNi
lattice distortion in the design of HEAs, even if the show a low level of atomic misfit strain due to the
connection to mechanical behaviour is not explicitly relatively slight differences in atomic radii of the com-
framed.18–20 The creation of a framework for plastic ponents. However, the HEA containing Al shows a misfit
deformation is the focus of the present discussion strain comparable to that seen in binary aluminium alloys.
(Fig. 3) (Kumar et al., unpublished work). From the Although the magnitudes of misfit strain present in
literature, it is clear that the origin of the exceptional HEAs such as CrFeCoNi and CrMnFeCoNi are rela-
mechanical properties of HEAs, particularly the high tively small, their high concentrations would be expected
fatigue endurance limit and very high toughness, are to cause a correspondingly large distortion of the lattice.
related to the competing behaviour of dislocations and Lattice distortions for the alloy groups in Fig. 4a were
twins (see Refs. 5 and 6 for overview plots). For calculated as18
simplicity, only the fcc crystal structure is considered nXn o1=2
here, although the applicability of this framework to Lattice distortion ¼ i¼1
c i ½1 2 ðri =_rÞ 
2
ð2Þ
other crystal structures will be obvious.
The results, plotted in Fig. 4b, show a lattice distortion
in the CrFeCoNi HEA comparable to that in Al–1Mg,
whereas the distortion in CrMnFeCoNi is even higher.
This indicates the importance of adding elements that
will give higher atomic misfits, causing significant dis-
tortion of the matrix. As pointed out below, addition of
minor elements to manipulate the level of lattice strain is
a promising design approach for these alloys. The
differences in modulus among elements should also be
borne in mind in the design of solid solution strength-
ened alloys, in that a similar approach can be developed
to select alloying elements on the basis of shear modulus
values.
Consider a perfect, defect free fcc crystal with all
atoms at their saddle points; the strain energy is defined
here to be zero. With respect to this state, the core
energy of a dislocation can be estimated from the
displacement of atoms from their perfect positions.
3 a illustration of likely dislocation core energy fluctuation The difference in energy between a perfect crystal and
in highly concentrated alloys along dislocation core and b one containing dislocations is large (Fig. 5a). In this
observation of nanotwins and secondary nanotwins in conceptual argument, it is assumed that the cutoff radius
HEA (Kumar et al., unpublished work): this can be used to for dislocation energy remains the same; a typical range
develop framework involving energy and kinetics of for the cutoff radius is 50–100 times the magnitude of
dislocations and twins the Burgers vector. On the other hand, the lattice in very

Materials Science and Technology 2015 VOL 00 NO 0 3

Mishra et al. Lattice strain framework for complex concentrated alloys

4 Comparison of a lattice misfit strain of single phase fcc HEAs and binary alloys and b lattice distortion of HEA and binary
Al–1at-%Mg alloy

concentrated alloys such as HEAs is highly distorted and higher lattice strain energy. Very low stacking fault
lattice strain is high. The nature of lattice strain caused energy values have been reported for HEAs,22 and a
by dislocations, which leads to contrast in a diffracted proportionality between the twin boundary energy and
beam, differs from the local lattice strain discussed here the stacking fault energy has been reported in some
in the context of HEAs. To differentiate between the instances.23
two, the local, atomic displacement related strain is The second aspect of dislocations in HEAs is the
termed ‘‘lattice strain’’ and strain based on systematic kinetics. The influence of solutes on dislocation mobility
lattice displacement around the dislocation core is can be measured by estimating activation volume, and the
termed ‘‘dislocation strain’’. The lattice strain can again variation of activation volume with the grain size or twin
be visualised with reference to the perfect lattice thickness is shown in Fig. 5b. As the interfacial barrier
position. In HEAs, all the atoms are likely to be dis- spacing decreases, it limits the area available for dislo-
placed from the idealised saddle point of the fcc crystal cation sweep during stress change, and consequently, the
lattice, to an extent governed by their local neighbours. activation volume goes down. A comparison of activation
These factors suggest that the energy for dislocation energy values for conventional coarse grained material
nucleation is likely to be lower in highly concentrated and a coarse grained Al0.1CoCrFeNi HEA shows a
alloys than in conventional alloys and also that stacking difference of four times. The implication is that, during a
fault energy and twin energy values will be lower. It is stress change, the area swept by a dislocation in the HEA is
well established that solid solution alloys tend to have considerably smaller. In the context of the current lattice
lower stacking fault energy.21 On a simplistic view, this strain discussion, the solutes in CCAs or HEAs can be
lowering of stacking fault energy can be attributed to the visualised as damping dislocation motion. It is like moving
a vehicle on a pebbled pathway (CCA) as opposed to a
smooth road (conventional lattice). This argument would
also apply to thickening of twins. At present, few obser-
vations of twinning have been made, but the mechanism is
worth considering. Otto et al.24 and Gludovatz et al.8
observed no twinning at ambient temperature in CoCr-
FeMnNi HEA, whereas Komarasamy et al. (unpublished
work) observed twinning in Al0.1CoCrFeNi HEA at
ambient temperature as well as at 773K during tensile
tests. As shown in Fig. 4a, the lattice strain values are
different for these alloys. The causes require further in-
vestigation, but it appears that the lattice strain framework
may explain the differences in the observation of twinning.
In conventional alloys, low stacking fault energy
5 a schematic illustration of energy difference for dislo- results in planar slip. Austenitic stainless steels are good
cation in fcc crystal of pure element and concentrated examples of this. However, the early evidence in HEAs is
alloy, in relation to role of lattice strain on dislocation that the workhardening rate is very high.25 In particular,
energy: DEconv, and DECCA are activation energy for dis- the onset of twinning in Al0.1CoCrFeNi alloy was
location nucleation in conventional alloy and in complex observed to lead to exceptional workhardening.
concentrated alloys respectively. b measured activation
volume in coarse grained HEA shows much lower
value than in conventional alloy (Komarasamy et al.,
Conclusions
unpublished work): x-axis (grain size or twin thickness) The discussion here on the use of lattice strain to design
represents interfacial barrier spacing complex concentrated alloys might be used to advantage

4 Materials Science and Technology 2015 VOL 00 NO 0

 Mishra et al. Lattice strain framework for complex concentrated alloys

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