July 7, 2009 11:59 00059

Functional Materials Letters

Vol. 2, No. 2 (2009) 73–78
© World Scientific Publishing Company

THE USE OF SHAPE-MEMORY ALLOYS FOR MECHANICAL REFRIGERATION

LLUÍS MAÑOSA∗ , ANTONI PLANES and EDUARD VIVES

Departament d’Estructura i Constituents de la Materia, Facultat de Física,
Diagonal 647, 08028 Barcelona, Catalonia, Spain
ERELL BONNOT†
Departament de Física i Enginyeria Nuclear, ETSEIB, Universitat Politècnica de Catalunya, Diagonal 647,
08028 Barcelona, Catalonia, Spain
RICARDO ROMERO‡
IFIMAT, Universidad del Centro de la Provincia de Buenos Aires and CICPBA, Pinto 399, 7000 Tandil, Argentina
Funct. Mater. Lett. 2009.02:73-78. Downloaded from www.worldscientific.com

Received 2 February 2009

by UNIVERSITY OF SYDNEY on 04/30/15. For personal use only.

This letter reports on stress–strain experiments on a Cu–Zn–Al single crystal performed using a purpose-built tensile device which
enables the load applied to the specimen to be controlled while elongation is continuously monitored. From the measured isothermal
tensile curves, the stress-induced entropy changes are obtained at different temperatures. These data quantify the elastocaloric effect
associated with the martensitic transition in shape-memory alloys. The large temperature changes estimated for this effect, suggest
the possibility of using shape-memory alloys as mechanical refrigerators.

Keywords: Elastocaloric effect; martensitic transition; shape-memory alloy; magnetocaloric effect.

Shape-memory alloys are an important class of functional
materials which are being used for sensor and actuator appli-
cations. Their functionality is linked to the large reversible
deformations (up to 10%) they can experience under appro-
priate changes of temperature and stress which arise from the
martensitic transition undergone by these alloys. In the present
letter we report on a different functional application, namely
the possibility of these alloys being used as mechanical refrig-
erators. This property is based on the caloric response under
the application of an external stress (the elastocaloric effect),
which is expected to be large in the vicinity of the martensitic
transition.1
The need for environmental-friendly cooling methods
has prompted an intense search for materials exhibiting
large caloric effects at and around room temperature, which
could be an alternative to the classic compressor-based
technologies involving gases that are harmful to the envi-
ronment. Among several caloric effects, the magnetocaloric
effect has received increasing interest,2–4 although materials
∗lluis@ecm.ub.es
†erell.bonnot@upc.edu
‡rromero@exa.unicen.edu.ar
exhibiting other effects such as the electrocaloric effect5 and
the barocaloric effect6 also appear as good candidates for clean
refrigeration.
Caloric effects are inherent to any thermodynamic sys-
tem. They are expected to be particularly large in the vicinity of
first-order phase transitions where tiny variations of external
control parameters lead to significant changes in the extensive
thermodynamic quantities. For instance, in magnetic mate-
rials, the giant magnetocaloric effect is a consequence of a
first-order magnetostructural transition, which encompasses a
large entropy change, related to the latent heat of the tran-
sition.7 The martensitic transition in shape-memory alloys
meets these requirements and therefore large elastocaloric
effects take place in these materials. The similarity between
the elastocaloric effect in shape-memory alloys and the widely
reported giant magnetocaloric effect in materials undergoing
magnetostructural transitions will be presented.
In a thermodynamic system described by generalized
forces {Yi } and displacements {xi }, a differential change in
entropy is expressed as

n  
C ∂xi
dS = dT + · dYi , (1)
T ∂ T {Y j =1,...,n }
i=1

73
 July 7, 2009 11:59 00059

74 L. Mañosa et al.

where generalized Maxwell relations temperature change, induced by a change of the field from
    0 to Y :
∂S ∂xi  Y
= (2) δq
∂Yi T ,Y j =i ∂T Y j =1,...,n S(0 → Y ) ≥ (6)
0 T

have been used and C is the heat capacity at a constant value and
of the fields. Each pair of conjugated variables have the same
T irr (0 → Y ) ≥ T (0 → Y ). (7)
tensorial order.
A caloric effect associated with a differential change of For a first-order transition with a given associated hys-
a field Yi is quantified by teresis, the dissipated energy can be estimated as E diss =
   (Y − Y0 )x, where Y0 is the equilibrium transition field at
Yi ∂xi temperature T , and Y is the actual transition field at this tem-
S(0 → Yi ) = · dYi , (3)
0 ∂T {Y j =1,...,n } perature. x is the discontinuity in the generalized displace-
ment. Consideration of dissipative effects leads to a modified
when the field is applied isothermally, and Clausius–Clapeyron equation which (under the assumption of
   constant x) reads
Funct. Mater. Lett. 2009.02:73-78. Downloaded from www.worldscientific.com

Yi T ∂xi
T (0 → Yi ) = − · dYi , (4) dY S 1 d E diss
∂T =− + .
by UNIVERSITY OF SYDNEY on 04/30/15. For personal use only.

0 C {Y j =1,...,n } (8)
dT x x d T
when the field is applied adiabatically. In general, E diss is weakly dependent on temperature,
In a typical experiment, the control parameter is one of and thus the last term in the previous equation is small,
the components of the force tensor, say Y , while the mea- which shows that the Clausius–Clapeyron equation is still
sured quantity is the displacement component conjugated to a good approximation. Moreover, in shape-memory alloys,
this field, x. In the particular case of the elastocaloric effect, the the martensitic transformation takes place close to equilib-
field is a uniaxial tensile stress σ for which the corresponding rium conditions, and dissipative effects are small.9 Therefore,
generalized displacement is the strain ε (or relative elongation Eqs. (3) and (4) are expected to be valid in evaluating caloric
along the direction of the applied force). In the case of the effects associated with this transition.
magnetocaloric effect, the magnetization M (along the field) In the above description, we have considered the gen-
and magnetic field H are the generalized displacement and eralized displacements (and fields) to be independent of one
force, respectively. another. Coupling between different degrees of freedom is
It is worth noticing that in the vicinity of a phase tran- reflected by an explicit dependence of one coordinate on the
sition, ∂ x/∂ T is expected to be large, since x experiences remaining ones. In this case, the expressions given in this
large changes arising from discontinuities in the displace- section are still valid, but it must be taken into account that
ments at first-order phase transitions. This will lead to giant the entropy changes obtained with the above equations will
caloric effects (see Eqs. (3) and (4)). Actually, due to such contain contributions from all degrees of freedom, which are
a discontinuity, the use of Maxwell relations in computing modified when the field is changed from 0 to Y . This is partic-
the entropy change at first-order phase transitions gave rise ularly relevant in the case of giant magnetocaloric materials
to some controversy. It has been shown,4,8 however, that the for which there is strong coupling between structure and mag-
above expressions are in general valid, and they lead to the netism and the large magnetic field-induced entropy change
Clausius–Clapeyron equation in the particular case of an ideal has a significant contribution from the entropy change associ-
first-order phase transition for which Eq. (3) renders the dis- ated with the structural change.10–12
continuity in the entropy at the transition, associated with the The elastocaloric effect for a solid subjected to an applied
latent heat. uniaxial stress σ with an associated uniaxial strain ε is
So far, the thermodynamic analysis has assumed equilib- given by
 σ 
rium processes. When considering the effect of irreversibility, ∂ε
the entropy contains a reversible (d S) and irreversible (δSi ≥ S(0 → σ ) = dσ (9)
0 ∂T σ
0) contributions, so that the heat exchanged is expressed as
and
δq  σ  
= d S − δSi , T ∂ε
(5) T (0 → σ ) = − dσ. (10)
T 0 C ∂T σ

which leads to the following inequalities which are to be sat- The martensitic transition in shape-memory alloys is first
isfied by the isothermal entropy change and the adiabatic order, and is characterized by discontinuities in the strain ε
 July 7, 2009 11:59 00059
and entropy St (associated with the latent heat of the tran-
sition). We will restrict our analysis to non-magnetic shape-
memory alloys, for which the entropy change has a vibrational
origin,13,14 and the strain is not coupled to any other degree
of freedom. In the vicinity of the transition, the strain can be
expressed as
ε(T, σ ) = ε0 + εF [(Tt (σ ) − T )/T ], (11)
where ε0 is the strain outside the transition region, F is a
shape-function and T is a measure of the temperature range
over which the transition spreads. Tt (σ ) is the equilibrium
transition temperature for a given applied stress σ . In strict
equilibrium, T → 0 so that F approaches the Heaviside
step function.
Using expression (9) and assuming that ε0 and ε are
constant, in this equilibrium case the elastocaloric effect in
Funct. Mater. Lett. 2009.02:73-78. Downloaded from www.worldscientific.com
the vicinity of the transition is given by
by UNIVERSITY OF SYDNEY on 04/30/15. For personal use only.
 ε
− for T ∈ [Tt (0), Tt (σ )]
S(0 → σ ) = α , (12)
 In Fig. 2(a), we show the stress–strain curves correspond-
0 for T ∈/ [Tt (0), Tt (σ )]
where α ≡ d Tt /dσ is assumed to be constant. Taking into
account the Clausius–Clapeyron equation, α = −ε/St ,
where St is the transition entropy change, thus, as expected,
S(0 → σ ) = St , and T = Tσ −Tt (0) = ασ . Notice that
these results confirm the validity of using Maxwell relations
in computing the elastocaloric effect, even in the case of an
ideal first-order phase transition (involving a discontinuity in
the entropy).
A single crystal of Cu–Zn–Al, obtained by melting metals
of 99.999% purity, was grown by the Bridgman method. The
composition of the crystal was determined from EDX to be
Cu68.13 Zn15.74Al16.13. The martensitic transition temperature
under cooling without external stress is Ms = 234 K. A rectan-
gular sample with cylindrical heads was machined from the
ingot. The body of the sample has flat faces 35 mm long, 3.95
mm wide and 1.4 mm thick. The crystallographic direction of
the tensile axis is close to the [001] direction. The sample was
annealed at 1073 K for 30 min, cooled down to room temper-
ature in air and finally aged for 2 h in boiling water. This heat
treatment ensures that the sample is in the ordered state, free
from internal stresses and the vacancy concentration is close
to the equilibrium state.
Typically, stress–strain experiments are carried out by
means of tensile machines that control the sample displace-
ment while the load is continuously measured. In order to per-
form mechanical experiments that can be directly compared
to the corresponding experiments in other caloric systems
(where the field is the control parameter and the generalized
displacement is the measured quantity), we have developed a
purpose-built experimental set-up which enables external con-
trol of the load applied to the sample, while the elongation is
The Use of Shape-Memory Alloys for Mechanical Refrigeration 75
continuously monitored. The system uses special grips which
adapt to the heads of the specimen. The upper grip is attached
to a load cell hanging from the ceiling and the lower grip
holds a container that plays the role of a dead load. The load
is increased or decreased at a well-controlled rate by supply-
ing or removing water by means of a pump. A cryofurnace
enables the experiments to be conducted at different temper-
atures. Details of the device can be found in Ref. 15.
Typical stress–strain hysteresis loops at three selected
temperatures are illustrated in Fig. 1. On increasing the
stress, strain linearly increases (elastic behavior of the high-
temperature phase) until a certain stress where the martensitic
transition starts, giving rise to a large increase of strain (about
8%) at an almost constant stress. The elastic behavior of the
martensite is obtained when the stress is further increased.
Upon unloading, the strain decreases with a certain hystere-
sis (about 10 MPa) at the martensitic transition. An increase
in the transition stress with increasing temperature is clearly
observed.
ing to the loading branches measured at different temperatures.
Here the control parameter (σ ) is plotted on the horizontal
axis while the measured parameter (ε) is plotted on the ver-
tical axis. Note that with this representation, the curves are
similar to the corresponding isothermal field-magnetization
curves used to compute the magnetocaloric effect in magnetic
materials.
From the curves in Fig. 2(a) it is possible to compute the
elastocaloric effect by means of Eq. (9). In order to minimize
numerical errors, we first numerically compute the area A(T )
below the curve up to a certain stress. Results are shown in
Fig. 2(b), where the molar value V = 7.52 cm3 mol−1 has
been used to achieve the energy units. The entropy change
is then obtained from the temperature derivative of this data
set as
 σ
d dA
S = εdσ = . (13)
dT 0 dT
Fig. 1. Stress–strain hysteresis loops at different temperatures. From top to
bottom: T = 310.5 K (green), T = 305.4 K (red) and T = 296.1 K (blue). (color
online)
 July 7, 2009 11:59 00059
76 L. Mañosa et al.
(a)
Funct. Mater. Lett. 2009.02:73-78. Downloaded from www.worldscientific.com
by UNIVERSITY OF SYDNEY on 04/30/15. For personal use only.
(b)
Fig. 2. (a) Stress–strain curves at selected temperatures. From right to left,
T= 310.5, 309.4, 307.5, 306.0, 305.4, 303.1, 302.0, 299.9, 298.8, 297.9, 296.1,
295.3 and 294.6 K. (b) Area below the stress–strain curves. The color code
(and symbols) correspond to the maximum stress indicated as a vertical line
in Fig. (a). (color online)
The obtained results are plotted in Fig. 3, which shows
the stress-induced entropy change S as a function of tem-
perature, for the different levels of applied stress.
It is interesting to point out that the maximum stress-
induced entropy change remains constant within the errors
(independent of temperature and stress). This value corre-
sponds to the whole entropy change of the martensitic transi-
tion St .
As previously mentioned, the temperature and stress
dependence of the strain can be expressed by Eq. (11). In our
case, a convenient choice for the shape-function is F (z) =
tanh−1 (z), which leads to the following expression for the
stress-induced entropy change
 
St Tt (σ ) − T
S(0 → σ ) = 1 + tanh . (14)
2 T
This expression has been fitted to the stress-induced
entropy change data given in Fig. 2(a), and the results for
each value of the applied stress are shown as continuous lines.
By averaging over the whole set of curves, we obtain the value
St = −1.21 ± 0.15 J mol−1 K−1 .
It is interesting to compare the value obtained for the
whole entropy change (St ) to the value given by the
Fig. 3. Stress-induced entropy change at selected values of the stress ranging
from 105 to 143 MPa. The color code (and symbols) correspond to the stress
value indicated in Fig. 2(a) by a vertical line. The continuous lines are fits
based on the Eq. 14. (color online)
Fig. 4. Transition stress as a function of temperature. The line corresponds
to a linear fit.
Clausius–Clapeyron equation. Figure 4 shows the transition
stress as a function of temperature, where σt has been taken as
the inflection point of each isothermal stress–strain curve. A
linear rise in σt with increasing temperature is observed, with a
slope dσt /d T = 2.01 MPa/K. By taking an average value for
the discontinuity of strain ε = 0.075 ± 0.005 (see Fig. 5(a)),
we obtain St = −1.15 ± 0.05 J/mol K. The good agreement
of this value with that obtained from the elastocaloric effect,
suggests that irreversible effects are negligible for the marten-
sitic transition under study. To support this assertion, we have
computed the area of the hysteresis loops obtained at differ-
ent temperatures, which quantify the dissipated energy in a
f
full cycle E diss (to within a good approximation it is twice the
energy dissipated in each branch, E diss). Results are shown
in Fig. 5(b). It is evident that there is no significant depen-
dence of the dissipated energy on temperature, which leads to
a vanishing second term in Eq. (8), thus confirming that the
Clausius–Clapeyron equation is valid to obtain the entropy
change at the martensitic transition for this class of materials.
In order to explore the possibilities of the elastocaloric
effect for mechanical refrigeration, it is important to estimate
the temperature change associated with the application of a
 July 7, 2009 11:59 00059
(a)
Fig. 5. (a) Strain discontinuity at different values of temperature and (b) dissipated energy computed from the area of hysteresis loops, as a function of
temperature.
Funct. Mater. Lett. 2009.02:73-78. Downloaded from www.worldscientific.com
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given stress, which under the assumption of constant C, can
be obtained as
T in the magnetic case) above which the first-order transition no
T ≈ − S. (15)
C longer occurs. Actually, the upper bound for the applied stress
In the temperature range of interest here, for Cu–Zn–Al,
C  25 J K−1 mol−1 ,16 so for an adiabatic drop in stress σ
(involving the whole transition) of about 30 MPa, the maxi-
mum expected temperature change is 15 K. Notice that this
value is several orders of magnitude larger than the typical
values given by the conventional elastic behavior in solids
far from any phase transition. It is worth mentioning that the
expected temperature change for mechanical refrigeration is
even larger than the values reported for the magnetocaloric
materials for magnetic fields up to 2 T (achievable by perma-
nent magnets). Hence, the 15 K value estimated is competi-
tive with the values reported for pure Gd (6 K) and Gd–Si–Ge
(7 K).17
Another figure of merit to be considered is the refrigerant
capacity, which is defined as2

R= S(T )d T  ST, (16)
T
which in the case of elastocaloric effect is equal to R =
−εσ , where σ is the change of stress necessary to
change the transition temperature by T (S and ε are
assumed to be constants). For the investigated alloy, we obtain
R = 2.5 J cm−3 for σ = 30 MPa. The interest in mechanical
refrigeration is that σ can be chosen in a broad range of val-
ues (see Fig. 3). In contrast, this is not the case for giant mag-
netocaloric materials for which large entropy changes are only
obtained in a relatively narrow temperature interval. The main
difference is due to the fact that while tensile experiments can
be performed at temperatures well above the transition tem-
perature at zero stress, in magnetic experiments, the field is
always applied close to the transition temperature at zero field.
Such a different experimental procedure is made possible by
The Use of Shape-Memory Alloys for Mechanical Refrigeration 77
(b)
the strong dependence of transition temperature on stress (see
Fig. 4), and also by the lack of a critical point (as occurring
is imposed by the elastic limit of the cubic phase.
In summary by means of stress–strain experiments, it has
been shown that shape-memory alloys exhibit a large elas-
tocaloric effect. The estimated temperature changes associ-
ated with this effect are larger than those reported for giant
magnetocaloric materials for fields achievable by permanent
magnets. In addition, the energy losses associated with the
first-order character of the transition have been found to be
weak. Present results suggest that shape-memory alloys have a
potential use for close-to-room temperature mechanical refrig-
eration. This new functional property adds to the well-known
shape-memory properties in this class of alloys, and opens-up
the possibility of designing multi-functional devices based on
shape-memory alloys.
Acknowledgments
We acknowledge financial support from CICyT (Spain) under
project MAT2007-62100 and from DURSI (Generalitat de
Catalunya) through project 2005SGR00969.
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