Shap. Mem.

Superelasticity
https://doi.org/10.1007/s40830-018-0161-4

SPECIAL ISSUE: A TRIBUTE TO PROF. JAN VAN HUMBEECK – A LIFETIME OF CONTRIBUTIONS TO UNDERSTANDING MARTENSITE, INVITED REVIEW PAPER

Frontiers of Theoretical Research on Shape Memory Alloys:

A General Overview
Piyas Chowdhury1

Ó ASM International 2018

Abstract In this concise review, general aspects of mod- Introduction

eling shape memory alloys (SMAs) are recounted. Differ-
ent approaches are discussed under four general categories, Shape memory alloys (SMA), having remarkable multi-
namely, (a) macro-phenomenological, (b) micromechani- functional capabilities, find diverse applications in a broad
cal, (c) molecular dynamics, and (d) first principles models. spectrum of technological sectors e.g., biomedical, aero-
Macro-phenomenological theories, stemming from empir- space, automotive [1–3]. The most attractive feature of
ical formulations depicting continuum elastic, plastic, and these alloys is their remarkable deformation recoverability
phase transformation, are primarily of engineering interest, achievable by simply regulating applied thermomechanical
whereby the performance of SMA-made components is or magnetic stimuli. There exists a mounting need today
investigated. Micromechanical endeavors are generally for even superior SMAs, the quest for which is also
geared towards understanding microstructural phenomena undergoing rapid expansion. In these pursuits, theoretical
within continuum mechanics such as the accommodation research has played crucial roles by providing useful pre-
of straining due to phase change as well as role of pre- dictions on: (a) actuation performance of components (as
cipitates. By contrast, molecular dynamics, being a more described by pre-defined constitutive laws) [4, 5], (b) mi-
recently emerging computational technique, concerns croscopic deformation mechanics and mechanisms (ex-
attributes of discrete lattice structures, and thus captures ploring the roles of reversible phase transformation,
SMA deformation mechanism by means of empirically precipitation, internal twinning, slipping etc. and their
reconstructing interatomic bonding forces. Finally, ab ini- mutual interactions) [6–8], and (c) discrete lattice physics
tio theories utilize quantum mechanical framework to peek (stemming from subtle quantum effects) [9, 10]. Individual
into atomistic foundation of deformation, and can pave the avenues necessitate rigorous mathematical treatments and
way for studying the role of solid-sate effects. With specific computations at multiple lengthscales ranging from con-
examples, this paper provides concise descriptions of each tinuum to sub-atomistics. Presently, there is no single
category along with their relative merits and emphases. predictive framework, which can uniformly incorporate
multiscale physical phenomena of SMA deformations due
Keywords Shape memory alloy  Molecular dynamics  to the immense complexity therein; rather, they are treated
Density functional theory  Constitutive model  through independent modeling approaches. These theoret-
Micromechanical model ical endeavors, noticeably demarcated lengthscale-wise,
are distinct in terms of governing principles, modeling
emphases and core assumptions. This paper presents an
overview on various theoretical frontiers by categorizing
& Piyas Chowdhury them as (a) macro-phenomenological, (b) micromechani-
[email protected] cal, (c) molecular dynamics, and (d) ab-intio models.
1 The extent of theoretical research on SMAs can be best
Department of Mechanical Science and Engineering,
University of Illinois at Urbana-Champaign, 1206 W. Green understood with a panoramic perspective on materials
St, Urbana, IL 61801, USA structure hierarchy as in Fig. 1(a), which also juxtaposes

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the scopes of existing experimental techniques. At the disturbance fields [16]. Predictions from such models are
largest scale, simulations of actuation capability for various typically validated with experimental characterization
SMA-made components (e.g., a cardiovascular stent) are techniques, namely, electron microscopy, electron
conducted for optimization purpose. Typically, finite ele- backscatter diffraction, X ray diffraction. Contrary to
ment analyses are performed to investigate macroscale continuum-based phenomenological and micromechanical
attributes such as stress/strain/temperature correlations, models, the evolution of phases at the nanoscale are sim-
fracture and fatigue properties [6, 11]. Phenomenological ulated using atomistic methods such as molecular dynam-
formulations of phase transformation, metal plasticity, and ics (MD) and density functional theory (DFT) [9, 10]. At
thermodynamics constitute the governing principles of the smallest spatial resolution (i.e., involving tens of
these simulations [12–15]. Alloy-specific constants needed atoms), the principal question of interest is how the elec-
for accurate modeling (e.g., transformation stress, strain, tronic structure evolves subjected to alloying, and thus
Young’s moduli, thermal expansion coefficients) are typi- regulates the lattice energetics. Discrete lattice effects are
cally obtained from empirical studies. The advantage of essentially non-trivial, in that atomic ordering/stacking,
such approaches is that they can prove very useful opti- d-orbital occupancy of constituent transition metals, etc.
mization tools from applications standpoint, and can sub- are major regulators of phase transformation propensity
stantially reduce costs associated with trial-and-errors in [17–20]. Common problems to be addressed from the
laboratory experiments. One downside, however, is the angstrom level include the stability of phases, transfor-
non-consideration of microscopic deformation phenom- mation energy pathways, elastic moduli, magnetism, defect
ena underlying macroscale responses. To that end, the energetics etc. Quantum mechanics based DFT simulation
microstructural deformation processes are modeled within tools are employed to address these ultra-small scale issues,
the framework of Eshelby’s micromechanical assumptions which are beyond the scope of any experimental charac-
[7]. The micromechanical models allow theorization of terization technique. Figure 1b presents a schematic time-
phenomena at the single grain level such as compatibility line of all these modeling aspects. It follows that since the
of transformed domains embedded in parent phase, pre- discovery of SMA in 1930s, theoretical research remained
cipitate-induced elastic disturbances, and twinning-induced meager to non-existent [21]. After the hiatus of WW II,
strain accommodations. Per the micromechanics theory, NiTi was discovered and studied with renewed interests.
the grain-level deformation phenomena (e.g., evolving The scope of the literature especially on the continuum
transformed domains, internal twins, precipitates) are frontiers has been expanding over the past half a century.
modeled as continuum defects, which generate elastic The arrival of MD models occurred in the last decade.

Fig. 1 a Experimental and theoretical research on shape memory alloys across multiple lengthscales, b a timeline of theoretical research
classified into three broad categories, namely, continuum, DFT and MD (see text for discussions)

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Shap. Mem. Superelasticity

Compared to the DFT, the extent of MD literature is small which can be recovered by heating above Af. As discussed
due principally to the challenging task of developing an next, each of the four categories of the modeling approa-
accurate empirical potential. However, most recent years ches attempts to address different aspects of these behav-
are seeing a considerable emergence of new MD potentials iors of SMAs.
for SMA materials, raising the extent of scientific
publications.
Macro-phenomenological Models

A Brief Overview of General SMA Characteristics In the SMA context, the constitutive modeling based on
the macroscale phenomenology has remained a long-s-
Before describing the models, it would be instructive to tanding approach. These theories in many regards are
briefly delineate the empirically known properties of SMAs similar to classical plasticity models [22]. For instance,
and the associated microstructural evolution as in Fig. 2. they are geared primarily towards modeling the empirical
Generally, three primary thermomechanical behaviors of mechanics and thermodynamics of deformation
SMAs are noted: (a) shape memory effect, (b) superelas- [16, 23, 24] by means of seeking solutions to continuum
ticity and (c) isobaric shape memory effect. boundary-value problems. The emphasis is on developing
The shape memory effect is the complete restoration of ad hoc equations able to reproduce material-specific
inelastic mechanical strains as a result of unloading, heat- experimental stress/strain/temperature correlations. In
ing and cooling. Below Mf, the twinned martensite under doing so, both phase transformation- and plasticity-con-
stress becomes detwinned, which remains so after trolled thermomechanical constitutive responses are theo-
unloading. Heating of the stress-free detwinned martensite rized [25]. However, the physics of microscopic
above Af transforms it into an austenite, which upon deformation processes are not considered in developing
cooling recovers the original twinned martensite structure. these equations; rather, laboratory-measured uniaxial con-
This is the so-called shape memory effect. Superelasticity stitutive data remain the primary basis for model devel-
or pseudoelasticity is the complete recovery of inelastic opment. Thus, their predictive capability is contingent
strain (as induced by phase transformation under stress) by upon various empirically obtained materials constants e.g.,
merely removing the applied stress under isothermal con- Young’s (or shear) modulus, transformation stress or strain,
dition above Af. During superelastic loading/unloading, the plastic yielding stress. The objective of the macro-phe-
austenitic phase transforms into a twinned martensite, nomenological models is to provide general constitutive
which reverts back to the parent phase upon unloading. A laws, which can eventually assist in component perfor-
temperature cycling at a constant stress, where the induced mance simulations [12, 26–29]. The scope of these models
strain is recoverable, constitutes the isobaric shape memory is wide, ranging from uniaxial tension–compression
behavior. Cooling below Mf induces twinning of martensite asymmetry to multi-axial non-proportional loading
(from the original austenite) with an associated strain,

Fig. 2 Various
thermomechanical responses of
a generic shape memory alloy.
The three major attributes that
the SMAs typically demonstrate
as actuators are: shape memory
effects (SME), superelasticity
(or pseudoelasticity) and
isobaric SME. Underlying all
these behaviors are complex
microstructure changes
involving reversible martensitic
phase transformations and
twinning/detwinning processes.
See text for detailed discussions

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scenario. Let us consider several case studies (as follows) Figure 3c shows the finite element simulation of a car-
to highlight the details of such modeling approach. diovascular stent [32] using material parameters corre-
Several examples of numerical simulations of SMA- sponding to NiTi SMA. Such a device is inserted into a
made actuators based on macro-phenomenological gov- coronary artery in crimped form, and then is allowed to
erning rules are presented in Fig. 3a–d. In Fig. 3a, a finite expand. Consequently, it assists in the flow of blood. The
element simulation of a four-coil helical spring calibrated controlling constitutive laws in the simulations consider
with NiTi properties is presented (adapted from [11]). This incremental energy minimization, where the total energy
type of actuator is useful in automotive industries. In this contribution is the sum of Helmholtz free energy and the
boundary-value problem, the spring is subjected to axial deformation rate-independent dissipated energy. In the
end-forces. Based on the simulations [30], this study simulation of the stent as presented, it is crimped circum-
reports a marked non-homogeneities of stress distribution. ferentially. The distribution of martensite is then visual-
Specifically, the effective stress was found to be most ized. Notice that the maximum volume fraction of
concentrated on the inner periphery of the spring, where martensite (which is stress-induced) occurs at the bends.
damage is most likely to initiate during actual operation. The superelastic stress–strain response, the tension–com-
Similar simulations can be employed to determine the pression asymmetry as well as the materials anisotropy
optimal geometry of, for example, a bone-implant assem- effects were also captured in these simulations.
bly, whose function is to impart perfect cushioning of One important application of a SMA-made actuator is
fractured bones. For instance, Fig. 3b presents a case study the usage of chevrons in commercial jet engines for noise
[31] where two NiTi plates are implanted on the bone with reduction purpose. A chevron is a serrated aerodynamic
screws in the proximity of human humeral head (front and shape placed at the trailing end of the jet engine exhaust
back). By imposing simulated movement of the bone, the nozzle as in Fig. 3d. Based on actual test data by Boeing,
displacement and the stresses both in the bone and the Hartl, Lagoudas and co-workers [4, 5] examined (via a
plates are studied. The governing laws relating the dis- finite element model) the performance of three Ni60Ti40-
placements and the stresses are based on the theories made beams attached to a chevron. Using this 3D model,
of simple linear elasticity, phenomenological phase trans- the nature of the chevron deflection under thermome-
formation and plasticity. One can see the usefulness of such chanical loading was investigated.
simulations as critical optimization tools, which can From the representative case studies described above, it
help circumvent costs and dangers of in vivo performance seems that the combination of the finite element framework
testing. and the empirically based macro-phenomenological

Fig. 3 a Finite element

simulation of a four-coil helical
spring based on NiTi properties
[11], b the simulation of two
NiTi plates implanted on a
human bone with screws in the
proximity of humeral head
(front and back) [31], c finite
element simulation of a
cardiovascular stent [32] using
material parameters
corresponding to NiTi, and
d finite element simulation of an
aircraft engine chevron being
investigated for deformation
under operating
thermomechanical load cycling
[4, 5]. See text for detailed
discussions

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Shap. Mem. Superelasticity

models is very useful for application optimizations. The fraction), which are incorporated into the model so as to
alternative is to conduct many experimental trial-and-er- fine-tune the predictions.
rors, which would be undoubtedly more expensive and
would require rigorous resources. However, there is one Eshelby’s Inclusion and Inhomogeneity Problems
important caveat in applying these models generically.
Since the macroscale relationships are not based on the The concept of the so-called ‘‘inclusion’’ or ‘‘inhomo-
actual microscopic physics of deformation, the grain and/or geneity’’ by Eshelby [38] has remained one of the widely
sub-grain level phenomena, which can give rise to unex- researched approach of describing the microscopic defor-
pected deformation trends, remain unexplored. For mation processes in mathematical terms. To define them
instance, the embedding of precipitates in the parent simplistically, an inclusion is a ‘‘foreign’’ particle embed-
austenite would create long-range elastic straining, which ded in the matrix material, which creates a so-called eigen-
would considerably modify the local deformation behavior. strain surrounding it. On the other hand, an inhomogeneity
The macroscale properties would also be ultimately is a region of the material which has different elastic
affected. The complex interaction among various defects resistance to deformation (i.e., moduli) compared to the
e.g., localized slip, grain/twin boundaries would give rise parent phase. The presence of either type of particle would
to local weak points susceptible to cracking. Unless the create long-range elastic disturbance field as indicated
model is explicitly trained to account for these microscopic schematically in Fig. 4a. However, the intensity of the
processes, the merit of the phenomenological predictions fields is highest near the surface of these defects. Based on
could be interpreted qualitatively at best. To enhance the this simple definition, detailed mathematical formulations
capability of phenomenological continuum-based laws, the are devised to account for the stress–strain relations of the
micromechanical models are developed. material (both single and polycrystals) [7]. The objective of
the micromechanical concept is to capture the nuances of
the SMA microstructure. In particular, the martensitic
Micromechanics-Based Models phase transformation is modeled in the form of embedded
domains in a parent continuum field. The martensite forms
The purpose of micromechanics is related with determining local structures characterized by deformation twinning
the interplay of stress or strain at the lengthscale of mate- throughout the material. As these domains grow in volume,
rials microstructure [6, 13, 33–37]. The presence of mul- their mutual interaction as well as interplay with other pre-
titudes of ‘‘defects’’ (e.g., transformed martensitic domains existent defects (e.g., grain boundaries) would essentially
or precipitates embedded in the parent material, grain or control the overall hardening behavior.
twin boundaries) gives rise to a complicated network of
overlapping deformation gradient fields. The primary pur- Precipitates in SMA Microstructure
pose of micromechanical models in the SMA research
context is to connect these microscopic intricacies of Experimentally, the presence of non-transforming phase (in
deformation with the global constitutive responses. the form of precipitates) has been associated with benefi-
Although the phase transformations fundamentally stem cial effects (e.g., reduced hysteresis and transformation
from atomic rearrangements of the parent lattice, the strain) on the mechanical attributes of many SMAs
micromechanical models postulate the deformation sce- [39–42]. The presence of a precipitate in the microstructure
nario to be a continuum problem. This assumption is creates local elastic disturbance, which could overlap with
advantageous, in that the predictions of functional response other precipitates, eventually creating an intricate network
are accomplished in a computationally feasible manner. of strain fields. These fields largely influence the local
The micromechanics is primarily based upon the Hookean preference of variant formation. Since the process of twin
relation between stress and strain tensors for infinite and nucleation is essentially uni-directional in nature, the dis-
continuous material as well as boundary values for semi- turbance fields would bias the local resolved shear stress
infinite ones. The presence of each defect is postulated as a [42], thus helping nucleate a preferred variant over the
source of ‘‘disturbance’’ in an otherwise infinitely extend- other available systems. By utilizing the Eshelby’s
ing continuum field. The solutions of the associated for- micromechanical formulations, Gall, Sehitoglu and co-
mulations are typically sought either analytically (i.e., in workers [43] examined the distribution of the local
terms of closed-formed expressions) or numerically. The resolved shear stress around a single coherent precipitate
calibration of such models is strongly contingent upon (Ni4Ti3) in NiTi matrix. The results are shown in Fig. 4b.
empirically obtained various materials attributes at the From these calculations, one can see that the stress is
mesoscale (e.g., texture, grain size, precipitate volume highest in the close vicinity of the precipitate and begins to
subside away from it. High-resolution transmission

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Fig. 4 a Per Eshelby’s

micromechanical theory [7], the
presence of martensite in
austenite matrix creates an
eigen-strain, b the distribution
of the local resolved shear stress
around a single coherent
precipitate (Ni4Ti3) in NiTi
matrix [43], c the presence of
the multiple variants consisting
of internally twinned self-
accommodated structures as
envisioned by Huang and
Brinson [6], and d a
representative volume element
(RVE) containing a distribution
of Ni-rich precipitates in a
discrete finite element domain
[49, 50]

electron microscopy has indicated that the precipitates are Physics of Precipitation: Role of Concentration
usually rather tightly spaced [44, 45]. Thus, these stress Gradient
contours would be overlapping.
One important aspect of precipitation in the SMA
Martensite Embedded in Parent Austenite microstructure is the depletion of one element type from
the matrix as atoms diffuse to the precipitate during the
In addition to examining the effects on non-transforming aging treatment. The effects of both element concentration
precipitates, the prediction of SMA deformation behavior gradient and elastic disturbance fields in fact play a role in
can also be performed by accounting for the microme- deciding the overall alloy mechanical properties. Most
chanics of phase transformation. Early endeavors recently, Baxevanis, Lagoudas, and co-workers forwarded
[14, 46, 47] established the primary basis for modeling as a model in this regard [49, 50], which can be applicable to
the estimation of the collective interaction energies of the several SMA materials (e.g., NiTi, NiTiHf) [51]. In
embedded domains. Patoor proposed a simplified interac- Fig. 4d, the typical representative volume element (RVE)
tion energy formulation by circumventing the use of containing a distribution of oblate Ni-rich precipitates in a
Eshelby-type approach. Single- to poly-crystal transition discretized finite element domain is shown. In the right
was achieved by an averaging scheme. One similar inset, the simulation results demonstrating the Von Mises
example is provided in Fig. 4c after Huang and Brinson [6] stress distribution throughout the RVE can be seen. Notice
to illustrate the concept. The presence of the multiple a higher stress concentration in the very close vicinity of
variants (consisting of internally twinned self-accommo- the precipitates surfaces. The materials input for the pre-
dated structure) is noted in the model. In this generic multi- dictions were obtained from experiments. By accounting
variant model, principles of thermodynamics and for micromechanics and the chemical effects (e.g., Ni
micromechanics are incorporated. The microstructure is depletion from the matrix), a good agreement between the
modeled as having multiple martensite plates embedded in predictions and the experimental findings was established.
the austenite. Crystallographic input such as the habit
planes and transformation and/or twinning directions are
used to describe the local nature of deformation in a single Molecular Dynamics (MD) Models
grain under thermomechanical loads. Due to the combi-
nation of both micromechanics and thermodynamics, this Compared to the large volume of literature on other mod-
model could capture the effects of general thermome- eling avenues, molecular dynamics-based studies of SMAs
chanical stimuli. Subsequently, they extended the model to are considerably limited, centering mostly on NiTi. Some
study polycrystalline aggregates as well [48]. recent studies on Ni–Al–Co have emerged [52, 53]. This

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scarcity is attributed to the lack of material-specific accu- subjected to modification depending on the potential. For
rate ‘‘potentials’’ that can faithfully capture multiple the case of the adapted Lai and Liu’s potential by Zhong
stable phases and their reversibility. In the MD context, a et al. [68, 69], the SME of NiTi has been associated with
potential is a pre-determined database of interatomic B2 ? B19 ? BCO ? twinned BCO transformation,
bonding energy landscape, which obviates the need for which was characterized by the formation of ‘‘macroscopic
solving computationally expensive sets of many-body twin-like’’ deformation of the nanowire.
Schrodinger’s equations [54]. Earliest endeavors on MD
simulations are initiated with Farkas et al.’s [55] proposi- Superelasticity
tion of an EAM potential i.e., embedded atom method
[56, 57]. An EAM potential theorizes the energetic Most literature on the MD-based studies on SMA supere-
expenditure for individual pair-wise interactions and for lasticity are centered on equiatomic binary NiTi
embedding atoms in an overlapping electronic cloud. They [66–70, 75, 77, 78]. Zhong et al. [68, 69] reported that the
aimed at capturing only B2 phase properties. By consid- superelastic response of NiTi nanowires at 400 K under
ering generic pair-wise interaction among metallic atoms compressive stress along the [011] direction stems from the
(in the form of Lennard-Jones potential [58]), Kastner and reversibility of the forward transformation path: B2 ?
co-workers investigated SME and the associated evolution B19 ? B190 . At lower temperature (350 K), the transfor-
of the austenite phase into martensite [59–61]. Subse- mation steps are altered to: B2 ? B19 ? BCO ?
quently, Lai and Liu developed an EAM potential [62, 63] twinned BCO at 350 K (BCO being body-centered
for predicting solid solubilities of amorphous (i.e., disor- orthorhombic). It is worth recalling that the intermediate
dered) Ni–Ti intermetallics. Lai and Liu’s potential B19 phase has not been experimentally evidenced in the
spawned several improved adaptations, most solutionized condition, rather only in aged NiTi (i.e., in the
notable among which are those by Mutter and Nielaba presence of precipitates) or when alloyed with Cu or Fe
[64, 65], and Zhong et al. [66–69]. Most recently, another [79–81]. Similarly, the likelihood of the BCO phase,
EAM potential by Ren and Sehitoglu has also been although not substantiated experimentally in NiTi, has been
reported [70]. predicted by several research groups [82–86] from first
To capture effects of covalent bonding, the EAM for- principles. Combined empirical and simulation results pose
malism can be further modified by incorporating the interesting questions about the phase stabilization pro-
directional nature of interatomic interactions for the many- cess in NiTi SMA. The occurrence of a certain phase in
body problem [71–73]. Earlier, Ishida and Hiwatari [74] atomistic simulations would be favored by its energetic
was able to employ modified EAM (MEAM) methodology state as defined in the potential. Thus, it is possible that the
to capture thermally induced and reversible B2 $ B190 transformation energy pathway in the pristine defect-free
transformations. More recently, Ko et al. [75] proposed an simulated lattice apparently may or may not contribute to
improved MEAM potential which can predict reversible the temporal and spatial stabilization of intermediate pha-
phase transformation underlying both single- and poly- ses. For instance, in the MD models by Chowdhury et al. as
crystalline deformation. well as by Ko et al. [75] B19 or BCO phases were not
observed.
Shape Memory Effect (SME) Only very recently, strain recovery properties of ternary
Co–Ni–Al SMAs are investigated by Yamakov, Mishin and
Figure 5a presents an MD case study [76] of shape memory co-workers [52, 53] as in Fig. 5b. They proposed an MD
effect (SME) of NiTi by Mutter and Nielaba who adapted model on the superelastic behavior of Co–Ni–Al-based
the original Lai and Liu’s potential by introducing smooth SMAs. The high-temperature B2 austenite structure is
cut-off behavior [64, 65]. A multi-variant B190 (indicated created via Monte Carlo equilibration. The origin of the
by light and dark brown regions) is strained up to about hysteresis is attributed to twinning followed by reversible
10% and then unloaded. In the process, one variant detwinning processes. In their simulations, pseudoelastic
undergoes progressive growth by detwinning process at the stress–strain responses under tensile and compressive loads
expense of others. The unloading followed by heating leads were found to differ significantly as two case studies on
to the reversal of the process. As a result, a twinned (i.e., [110] and [001] crystallographic directions demonstrated.
multi-variant) martensite is formed along with the full The structural changes associated with the recovery were
recovery of strain. Mutter and Nielaba attributed the traced to the reversible transformation between the parent
absence of B2 austenite phase (which is unlike the exper- B2 and the twinned L1o lattices. Interestingly, the magni-
imental findings) to a smaller energy barrier for twinning tude of the stress plateau was found to be on the order of
(during heating of the unloaded single variant) than the MPa, unlike typical MD simulations where GPa-level
B190 -to-B2 transformation. This behavior might be stresses are noted for uniaxial loading.

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Fig. 5 a Stress–strain response

of NiTi martensite
demonstrating evolution of
multi-variant martensite into a
single variant and the reverse
process upon heating [76],
b MD simulations of
superelastic strain recovery of
single crystals Co–Ni–Al SMA
[52, 53] undergoing reversible
transformation between B2
austenite and L1o martensite,
c the presence of a nano-sized
coherent precipitate in austenitic
NiTi matrix [87] causing
activation of different variants
while setting preference for a
certain variant, and d reversible
martensitic transformation in
nanocrystalline NiTi under
uniaxial tension at 400 K (blue
regions corresponding to
austenite while red to
martensite) [78]

Presence of Non-transforming Phase Polycrystallinity: Role of Grain Boundaries

MD studies have uncovered important mechanistic insight The aforementioned studies considered a single grain set-
into how a single nano-sized precipitate can affect the ting for modeling. In most applications, the SMAs are used
deformation properties [87, 88]. Earlier, Sato et al. [88] in their polycrystalline microstructure. The modeling of
modeled a single plate-shaped precipitate (embedded in B2 polycrystalline microstructure is of particular interest from
NiTi) to be of body-centered tetragonal (bct) symmetry. a practical engineering standpoint. In Fig. 5d, atomic
They noted the following observations: (i) a modification configuration of nanocrystalline NiTi (average grain
of the potential energy landscape at the interface, which diameter being 20 nm) under tensile loading/unloading
extends inside the precipitate lattice, and (ii) the presence cycle at 400 K is presented after Ko et al. [78]. In this
of the particle results in the reduction of applied tensile simulation, the austenite began to transform into martensite
stress. Furthermore, the interfacial mismatch was associ- in the bulk of the grains away from the grain boundaries.
ated with a preferred sited for martensite nucleation. As the loading progressed, the martensite phase was
However, experimental studies noted that the precipitates observed to expand towards the interface. By contrast,
in NiTi are of rhombohedral lattice (Ni4Ti3) and of len- during unloading, the martensite-to-austenite transforma-
ticular geometry [89–91]. Chowdhury et al. [87] studied tion began at the boundaries, which then propagated inside
the effects of a lenticular Ni4Ti3 precipitate on the phase the grain interiors.
transformation propensity as well as the associated con-
stitutive characteristics. They predicted a stress gradient
field surrounding the precipitate, which they attributed to Density Functional Theory-Based Models
the inter-lattice misfit between the rhombohedral and the
surrounding B2 matrix. The presence of the stress gradient Important discoveries made from ab initio simulations
was found to influence the variant nucleation preference. include determination of transformation energy pathway,
As in Fig. 5c, one variant (designated ‘‘variant 3’’) is elastic moduli, phase stability [82, 84, 85] etc. as a direct
preferred over the rest, a phenomenon evidenced through consequence of the electronic structure. The sub-lattice
electron microscopy earlier [92]. The MD study also im- effects are addressed by solving many-body Schrodinger’s
plied that the nano-precipitate serves to reduce transfor- equation with a view to iteratively seeking the energetic
mation stress, hysteresis, and transformation strain. ground state of the overall crystal. To reduce computa-
tional loads, Born–Oppenheimer approximations are
adopted, which dictates instantaneous and simultaneous

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updating of atomic nucleus and the orbiting electron cloud. noted that the existence of B33 has never been experi-
This essentially obviates the time-dependency of wave mentally substantiated. The rationale for stabilization of
functions (which represent electrons) from Schrodinger’s B190 , despite not being the global minima, is attributed to
equation. Furthermore, instead of wave functions, the the presence of an energy barrier by some researchers [100,
temporal and spatial trajectories of individual valence 101], which can be considerably enhanced due to the stress
electrons are solved in terms of ‘‘charge densities.’’ The triaxiality in the microstructure [101]. No other research
total potential energy of, say, a prototypical-simulated groups, however, discovered the presence of any energy
lattice is a function of charge distribution. Other important barrier so far; more independent research is needed for
variables directly affecting evolution of electronic cloud confirmation. Another important SMA, whose transfor-
are, namely, the quantized nature of lattice vibrations (i.e., mation paths are studied extensively, is ferromagnetic
phonons), electron spin orientation (i.e., magnetism). By Ni2MnGa. In Fig. 6b, the structural energy as a function of
accounting for these discrete lattice effects, new clarifica- tetragonality (c/a ratio) indicates a gradual decrease in the
tions on deformation propensity have emerged (discussed total energy due to martensitic transformation (from L21
next). austenite to L1o martensite). In addition, the modulated
martensite structures i.e., 10 and 14 M (also known as
Magnetic Attributes of SMAs ‘‘adaptive martensite’’) are of low energy structures with-
out substantial change in c/a ratio from the austenite phase.
Ferromagnetic SMAs such as Ni2MnGa, Ni2FeGa possess These findings are consistent with experimental observa-
unique shape-recovering capability, which is magnetically tions, where modulated phases are reported to be pre-
induced. The austenite phase is an ordered face-centered dominant in the martensitic phase [102, 103].
cubic lattice (L21) [93, 94], and the martensite can be
tetragonal or orthorhombic (with the possibility of modu- Elastic Moduli
lated structures) [95–97]. The shape recovery mechanism
involves the realignment of inherent magnetic domains, One of the significant achievements of the first-principles
which in turn generates mechanical driving force for two- models is the prediction of elastic moduli [19, 20, 85]. For
way twinning/detwinning processes. The process is instance, as shown schematically in Fig. 6c, a twinned
schematically shown in the right inset of Fig. 6a, where red martensite (single crystal) of NiTi SMA becomes fully
and yellow regions represent two different variants in the detwinned into a single variant after considerable straining.
martensitic phase [98]. In presence of an applied magnetic The elastic stretching of twinned lattice dictates the slope
field (H), the magnetic moments of individual variants of the loading curve. On the other hand, the unloading of
(indicated by arrows) would attempt to align with H, which fully detwinned martensite is controlled by the elastic
in turn would initiate detwinning of one variant at the moduli of a single-variant crystal. The two slopes (loading
expense of another. The contour map on the left inset and unloading) essentially have different magnitudes due
represents variation of energy as a function of magnetic to the differences in the twinned and detwinned lattice
moment and lattice tetragonality (i.e., c/a ratio) as pre- structures. Wagner and Windl [19] calculated the stiffness
dicted from first principles [18] for stoichiometric Ni–Mn– constants of B190 crystal, a 3D representation of which is
Ga SMA. Notice the location of absolute energy minimum shown in the inset of Fig. 6c. Sehitoglu and co-workers
at c/a = 1. It is noted that the material can reach another examined the moduli of twinned B190 lattice of NiTi from
energy minimum at larger c/a without any change in the first principles [10]. Notice that the twinned lattice
magnetic moment. These alloys are strong functions of has considerably smaller magnitude of directional moduli.
compositions. In particular, addition of Mn can substan- For example, E100 and E001 of the twinned structure are
tially modify local magnetic moment [17, 99]. one-third of the detwinned lattice. The results point to the
role of reflective symmetry of lattice (i.e., via twinning) in
Transformation Energy Pathways reducing the resistance to elastic deformation. In another
undertaking, Wagner and Windl [20] also predicted the
The significance of transformation energetics is that they moduli mismatch between a B2 NiTi and a rhombohedral
signify the relative energetic preference of all the phases Ni4Ti3 precipitate. They noted that the maximum modulus
encountered during the transformation. For instance, the difference exits along the direction perpendicular to the
energy pathway for NiTi has been studied by many inde- precipitate equatorial plane i.e., E111. Since the material
pendent groups [83–86]. It was discovered that B190 is not always seeks to minimize its strain energy, this result
the global energy ground state. A body-centered implies that the precipitate forms with a flat lenticular
orthorhombic (BCO) structure, also known as the B33 shape and a circular cross section so as to reduce the
phase, is energetically the most stable phase. It should be overall elastic strain energy.

123
 Shap. Mem. Superelasticity

Fig. 6 a Contour map

representing variation of energy
as a function of magnetic
moment and lattice tetragonality
(i.e., c/a ratio) predicted from
first principles [18] for
stoichiometric Ni–Mn–Ga
SMA. b different martensite
crystal structures (non-
modulated i.e., NM,
modulated 10 and 14 M)
([127]) and the structural energy
as a function of tetragonality (c/
a ratio) [127, 128]. c stiffness
moduli for a twinned B190
lattice [10, 19] corresponding to
slopes of elastic portions of
loading/unloading curves, and
d comparison of slip energy
barrier (cus) computed by rigid-
shear of lattice half-blocks for
five different slip systems in
NiTi austenite (B2) lattice
[9, 100]

Energetics of Plastic Deformation propensity of existing alloys, these results encourage fur-
ther potential research directed at concocting new alloys
Plastic deformation in SMAs is the reason for their per- with superior slip resistance.
formance degradation. Although nominal plastic yield
stress is much greater than the transformation stress in
SMAs, considerable slip activities can accompany phase Synergy or Unification of Multi Lengthscale
transformation processes microscopically [104–106]. Modeling Techniques
Mesoscale factors such as preferential grain orientation
(inducing maximum resolved shear stress on the slip sys- As the forgoing discussions imply, the fundamentals of
tems), interfacial incompatibility between austenite and continuum mechanics, thermodynamics, micromechanics,
martensite etc. can facilitate plastic deformation. At the statistical mechanics, quantum mechanics are quite well
atomic lengthscale, slipping is essentially a form of per- established to address SMA deformation. While it is
manent lattice shearing of the closest-pack plane, whose hypothetically possible to combine theories of multiscale
direction and magnitude are represented by the Burgers physical phenomena, the major obstacle to actual imple-
vector. By exploiting this simple yet intuitive definition, mentation thereof is the processing ability of computers.
DFT calculations have provided a unique measure of While there are many commercial softwares available for
comparing relative slipping strength of various systems. In finite element analysis, they are mostly founded on mac-
Fig. 6d, the energy barriers (unstable stacking fault energy roscale empirical laws of phase transformation and plas-
‘‘cus ’’, which is the peak on the energy-shear displacement ticity. The accuracy of these tools is as good as the
curve) to activate five different possible slip systems in the underlying constitutive formulations as programmed.
austenite phase are compared [9, 100]. The following order Today, a unification of various modeling approaches to
of energy barriers is predicted: accurately address practical engineering issues remains a
   
highly coveted yet challenging task [107]. An ideal mod-
ð011Þ½011 ð001Þ½010 ð211Þ½101 ð011Þ½111
cus [ cus [ cus [ cus [ cð011Þ½001
us ; eling goal would be to incorporate all the necessary physics
of deformation across lengthscale and seek the macroscale
which establishes the (011)[001] system as the most prone
solution, which inevitably invokes massive computational
to slipping. On a physical ground, the most favorable slip
burden. Even with the arrival of exascale computing with
system corresponds to the one with smallest nearest
modern clusters, the prospect of a massive unified model-
neighbor distance. Similar energetic comparison is also
ing framework suitable for engineering purpose is not
noted for the tetragonal martensite lattice of Ni2FeGa
imminent. To address materials structural hierarchy,
SMAs. In addition to quantifying the relative slipping
research efforts have been directed towards extracting

123
Shap. Mem. Superelasticity

critical parameters from atomistics and incorporating them based models, a promising research arena that necessitates
in continuum models. For instance, the classical Peierls– combined efforts of independent research groups.
Nabarro framework has recently been revisited, whereby
DFT-based energetics are utilized to predict critical stres-
ses for slip, twinning etc. [108–110]. For phenomenologi- Concluding Remarks
cal models, these critical stresses are important parameters,
which are conventionally used on ad hoc basis. In this paper, we have highlighted the applicability and the
The importance of bridging discrete lattice effects with primary emphases of various modeling techniques under
continuum properties cannot be understated. To illustrate, the generalizations: (a) macro-phenomenological, (b) mi-
empirical data (transformation temperature, recoverable cromechanical, (c) molecular dynamics, and (d) ab-intio
strain and slip strength) for a range of SMAs is mapped, models. The modeling endeavors revolve around two broad
and compared with known atomistic data on slip resistance objectives, namely, (i) the prediction of existing materials
(in terms of normalized cus ) in Fig. 7. The desired attri- properties under various thermo-mechanical conditions,
butes in an SMA are: (i) low transformation stress so that and (ii) the understanding of microscopic mechanisms
reversible phase transformation is easily triggered, (ii) high towards designing new and novel materials. The former is
slip resistance so that plastic deformation can be avoided, more widely practiced than the latter, which nonetheless is
(iii) high recoverable strain for greater actuation capability, coming of age as a powerful tool. Now, the logical question
and (iv) low or high transformation temperature depending to ask is how one can utilize phenomena occurring at
on application. Exhaustive sets of laboratory experiments multiple physical lengthscales to address problems of more
are needed to properly map the materials property corre- immediate necessity. For instance, one of the prominent
lations such as in Fig. 7. Interestingly, the cus values real-life applicability concerns is the failure of materials
(which is an indicator of slip resistance computed from first (e.g., cracking), especially due to irreversible damage
principles based on pristine single grain configuration) induced upon substantial operating cycles. Cyclic damage
follow the same materials-specific trends observed empir- in the SMA context is generalized into [15, 111–115]:
ically. The presence of such strong correlation highlights (a) functional fatigue and (b) structural fatigue. Functional
the need for further research into the utility of micro- and fatigue is caused by the modification to superelastic
nanoscale simulations. It remains to be seen how responses over cycles, which results from persistent accu-
atomistically informed parameters can benefit continuum- mulation of slip and martensite. By contrast, structural
fatigue refers to continuous cracking (as a result of

Fig. 7 Comparison of various

shape memory alloys in terms of
their experimentally determined
transformation temperature (i.e.,
austenite finish temperature),
recoverable strain (total strain
minus elastic and plastic ones)
and slip strength (marking the
macroscale yielding of an SMA)
juxtaposed with atomistically
predicted slip resistance
(normalized by Burgers vector
magnitude, b) [9, 100]

123
 Shap. Mem. Superelasticity

localized plasticity and residual martensite) towards 13. Patoor E, Eberhardt A, Berveiller M (1996) Micromechanical
catastrophic fracture. Fatigue is of particular concern in modelling of superelasticity in shape memory alloys. Le J de
Physique IV 6(C1):C1-277
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the rising utility of SMAs in aeronautical industries, the models of pseudoelastic behaviour of shape memory alloys.
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