Phase Change Behavior of Nitinol

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Shape Memory Alloys
Influence of Heat and Thermomechanical Treatments

By JosØ María Gallardo Fuentes, Paul Gümpel,* Joachim Strittmatter

Among other special characteristics Shape Memory Alloys (SMAs) have the ability to return to a
predetermined shape when heated. In fact, the phase change of an existing element can strongly be
influenced by thermal and thermo-mechanical treatments. Up to now, SMEs have been discovered in
various materials, which can generally be classified into noble-metal based, Cu-based, Fe-based, Ni-Ti-
based alloy systems and non-metallic SMAs. In this paper a general overview of the Ni-Ti system and
a detailed review over the Ni-Ti-Cu system will be given with special regard to the influence of heat
treatments upon the phase change behavior.

1. General Characteristics
Shape Memory Alloys (SMAs) are materials that have the
ability to return to a predetermined shape when heated.
Being cold or below their transformation temperatures or in
their martensitic forms (Fig. 1b), they have a very low yield
strength and can be quite easily deformed into any new shape
(Fig. 1c). However, when one alloy is heated above its trans-
formation temperature, it undergoes a change in crystal struc-
ture, reverts to austenite and recovers its previous shape
(Fig. 1a). If the SMA faces any resistance during this transfor-
mation, it can generate extremely large forces. This process is
known as one way shape memory effect (OWME).[1]
In trained SMAs two way shape memory effect (TWME)
can be observed in the sense that no mechanical deformation
is needed to complete the strain cycle, but only thermal cy-
cling. The phase transformation does not occur at a single
temperature but over a range of temperatures which varies
with each alloy system. A method of determining and nam-
ing transformation temperatures is to thermally cycle a speci-
men under load, producing a T-e-curve, as shown in Figure 2.
Most of the transformation occurs over a relatively narrow
temperature range, although the beginning and end of the
transformation during heating or cooling actually extends
over a much larger temperature range. The transformation
also exhibits hysteresis in that the transformations on heating
and on cooling do not overlap. This transformation hysteresis
(shown as T1 in Figure 2) varies with the alloy system. Differ-
Fig. 1. (a) Beta phase crystal. (b) Self-accommodating twin-related variants, A, B, C,
and D, after cooling and transformation to martensite. (c) Variant A becomes domi-
nant when stress is applied. Upon heating, the material reverts to the beta phase and
recovers its original shape [2].
ential Scanning Calorimetry (DSC) and Electrical Resistance
Testing are also used to determine transformation tempera-
tures.
Crystallography of SMAs: Thermoelastic martensites are
characterised by their low energy and glissade interfaces,
which can be driven by small temperature or stress changes.
The needle structure of martensite essentially consists of
±
[*] Prof. P. Gümpel, J. Strittmatter,
Fachhochschule Konstanz, Brauneggerstr. 55,
D-78462 Konstanz (Germany)
E-mail: guempel@fh-konstanz.de
Prof. J. M. Gallardo Fuentes, Escuela Superior de Ingenieros,
Universidad de Sevilla, Camino de los Desenbrimientos s/n
Isla de la Cartuja, E-41012 Sevilla (Spain)

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 Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys
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Fig. 2. Typical transformation versus temperature curve for a specimen under constant
load (stress) being cooled and heated. T1: transformation hysteresis; Ms: martensite
start; Mf: martensite finish; As: austenite start, Af: austenite finish [2].
twin-related, self-accommodating variants (Figure 1). The
shape change among the variants tends to cause them to elim-
inate each other. As a result, little macroscopic strain is gener-
ated. It is also possible to obtain a stress-induced martensite
below Md-temperature (Md > T > Af). In that case, or when
stressing a self-accommodating structure, the variant that can
transform and provide the greatest shape change in the direc-
tion of the applied stress is stabilised and becomes dominant
in the configuration (Figure 1c). This process creates a macro-
scopic strain, which is recoverable as the crystal structure
reverts to austenite during reverse transformation.[2]
The mechanical properties of shape memory alloys vary
greatly over the temperature range spanning their transfor-
mation. This is seen in Figure 3, where simple stress-strain
curves are shown for a nickel titanium alloy that was tested
in tension below, slightly above, and well above its trans-
formation temperature range. The martensite is easily de-
formed to several percent of strain at quite a low stress,
whereas the austenite (high temperature phase) has much
higher yield and flow stresses. The dashed line on the mar-
tensite curve in Figure 3 indicates that upon heating after
removing the stress, the sample remembered its unstrained
shape and reverted to it as the material transformed to aus-
tenite. No such shape recovery is found in the austenite
phase upon straining and heating, because no phase change
occurs. In Figure 3c, the material is tested slightly above its
transformation temperature. At this temperature, the so-
called superelastic effect occurs. This effect is also called
many times pseudoelasticity, pseudoelastic effect or supere-
lasticity.[3] It is caused by the stress-induced formation of
some martensite above its normal temperature. Because it
has been formed above its normal temperature, the marten-
site reverts immediately to undeformed austenite as soon
as the stress is removed. This process provides a very
springy, ªrubber likeº elasticity in these alloys. It then im-
mediately strains and exhibits the increasing strain at con-
stant stress behavior, seen in AB. Upon unloading, though,
the material reverts to austenite at a lower stress, as seen in
438
Fig. 3. Typical stress-strain curves at different temperatures relative to the transforma-
tion, showing (a) austenite, (b) martensite, and (c) pseudoelastic behavior [2].
line CD, and shape recovery occurs, not upon the applica-
tion of heat (even though Md > T3 > Af is maintained) but
upon a reduction of stress.
2. The Binary Ni-Ti System
2.1 Description of Ni-Ti-based Alloys
Up to now, SMEs have been discovered in various materi-
als, which can generally be classified into noble-metal based,
Cu-based, Fe-based, Ni-Ti-based alloy systems and non-me-
tallic shape memory materials. In this paper a detailed review
over the Ni-Ti- and the Ni-Ti-Cu system will be given, with
special attention devoted to the influence of heat treatments
upon the phase change behavior.[4]
SMAs based on nickel and titanium have to date provided
the best combination of material properties for most commer-
cial applications. Buehler at NOL, the Naval Ordnance Labo-
ratory, first discovered the SME in the Ni-Ti system in 1962
and thus the system is named NiTi-NOL or Nitinol, which is
commonly used when referring to Ni-Ti-based alloys. This
discovery led to a rapid growth of interest in the shape mem-
ory phenomenon. A series of extensive reports documented
the properties of Ni-Ti-based alloys, mainly in wire form, and
provided much useful information for the designer. However
since then there has been significant progress in the under-
standing of the alloy, particularly with regard to the effects of
processing and heat treatment on the mechanical and shape
memory behavior.[5]
2.1.1 Metallurgy of Binary Ni-Ti-based Alloys
Ni-Ti-based alloys are ordered intermetallic compounds
based on the equiatomic composition, of 50 at.-% or 55 wt.-%
Ni. This compound usually exists as a metastable phase
down to room temperature. Consequently, in contrast to cop-
per based alloys, no betatising and quenching are necessary
to prevent the decomposition into other phases at intermedi-
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ate temperatures. However, at low temperatures the homoge-

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450
nous range of the NiTi compound is very narrow and so the 400
Ni-Ti-based alloys often contain precipitates of a second 350
intermetallic phase distributed in the matrix, either Ni3Ti on 300
the Ni-rich side or Ti2Ni on the Ti-rich side. The maximum

Stress (MPa)
250
solution capacity is 57 at.-% Ni at the 1118 C Eutectic point,
200
but on the Ti-rich side of the alloy system, the capacity is only
50 at.-% Ti. The concentration range of technical interest is 150

between 49 and 52 at.-% Ni.[6] 100

The presence of oxygen is often ignored when considering
the microstructure of Ni-Ti-based alloys. Titanium is very
reactive, particularly in the molten state, and some oxygen is
invariably present in the alloy. Oxygen decreases the stoichio-
metric range of the NiTi compound and can unexpectedly
result in compositions within a three-phase field. Thus Ni3Ti
can also be present, for example in a Ti-rich alloy. Further-
more, the oxide Ti4Ni2O is isostructural with the intermetallic
Ti2Ni, which can make unique phase identification difficult.[7]
Concerning transformation temperatures related to SME the
binary Ni-Ti system is very sensitive to delicate variations of
the stoichiometric composition. A deviation of 0.1 at.-% effects
a change of transformation temperature of 10 C.[5] Thus,
depending on the desired Ms, precise composition control of
up to one tenth and one hundredth of a percent is necessary.
2.1.2 Mechanical and Shape Memory Properties of Ni-Ti-based
Alloys
Like most SMAs, Ni-Ti-based alloys show marked differ-
ences in mechanical behavior depending on whether they are
tested in the austenitic or the martensitic phases. The stress-
strain curve of the martensite can be divided into three well-
defined regions. An initial low plateau results from the stress
induced growth of one martensite orientation. This process oc-
curs by untwinning unfavourably oriented neighbours. At
higher stresses there is a second region that is usually linear,
although not purely elastic. It is believed that the deformation
mechanism in this stage is a mixture of elastic deformation of
the untwinned martensite, together with the formation of new
orientations of martensite which intersect those already pre-
sent, and which provide additional heat recoverable strain.[7]
The transition to the third region is a result of the onset of
irreversible plastic deformation, as in the case of the yielding
of all conventional metals. Thus the maximum amount of
heat recoverable or memory strain is obtained by initially
deforming to the end of stage two. If larger deformation
strains are used, then the reversible martensitic deformation
processes and the dislocations resulting from plastic flow
50
0
0 2 4 6 8
Strain (%)
Transverse
Longitudinal
Fig. 4. Martensitic stress strain curves of specimens taken longitudinally and transver-
sely from rolled sheet [7].
none exists and the stress levels are much higher. Some
further effects of thermo-mechanical treatments on the SME
behavior are described in section 2.2.
The length of the martensite plateau also determines the
strain at which the transition to the third region of the stress
strain curve occurs, and can therefore affect the amount of
memory strain. Thus although it is often stated that up to 8 %
strain is heat recoverable, the actual amount depends on the
alloy, its thermo-mechanical processing, testing direction and
deformation mode. In many cases, a conservative design
would use less than 8 % strain.
With regard to transformation temperatures, nowadays
temperatures from ±100 C to 100 C, depending on composi-
tion and thermo-mechanical treatment, are common for com-
mercial applications of Ni-Ti-based alloys, having a hysteresis
width of typically 30±50 K. The transformation temperatures
usually increase with an increasing load in a linear fashion.
This slope, as well as being of thermodynamic significance, is
also important when choosing an alloy for a particular appli-
cation. Concerning applied load/transformation temperature
relationship, the stress rate of Ni-Ti-based alloys can also
change significantly from alloy to alloy, covering a range
from 2.5 MPa/C to over 15 MPa/C.[7]
Martensitic
Phase
Change
Strain (%)

R-Phase
interact and the memory strain decreases, see the following.
Depending on the precise nature of the alloy and particu-
larly its prior thermo-mechanical history, the martensitic pla-
teau can vary from a continuous curve with an inflection
point to a clear horizontal plateau with a sharp yield point
and upturn. Figure 4 shows curves from rolled sheet, where
it can be seen that testing in the longitudinal direction results Temperature (°C)

in a well-defined plateau, whereas in the transverse direction Fig. 5. Premartensitic (R-phase) transformation in a strain-temperature diagram [5].

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 Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys

2.1.3 R-Phase Transition of the twin boundaries, while annealing rearranges these dis-
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Ni-Ti-based alloys show the phenomena of a premartensi-
tic transition, which is named R-phase in most accounts. This
can be confirmed either by Differential Scanning Calorimetry
(DSC) or electrical resistance testing, whereby a strong anom-
aly in the curve appears due to R-phase transition. Figure 5
shows that R-phase transition is also coupled to a strain
recovery, which takes place with or without small hysteresis
of 1±2 K. Although the R-phase effect is much inferior to the
normal SME (max. about 1 %), it is important for many appli-
cations such as thermal actuators, effecting a high number of
[8]
cycles without injury.
2.2 Influence of Heat Treatments and Thermo-mechanical
Processing on the Shape Memory Effect behavior of
Ni-Ti-based Alloys
Only a few years after the discovery of the SME in Ni-Ti-
based alloys, a process patent was filed, increasing the yield
strength of these alloys by cold working. Since then, the com-
bination of cold work in the martensite together with a subse-
quent anneal has been extensively explored as a way of
improving the SMA characteristics.
Cold work alone, i.e. without the annealing step, destroys
the martensitic plateau on the stress strain curve. Thus a
material cold worked 20 % in the martensite has a very high
yield strength, but its shape memory properties are poor in
that only very low recoverable strains are possible.[9] Anneal-
ing will restore the memory effect, but decrease the yield
strength. The choice of amount of cold work and the actual
annealing temperature establish the combination of those two
properties. It is concluded that cold work introduces a high
density of ªrandomº dislocations, which hinder the mobility
1200
1100
50,6 at % Ni, CW 40 %
1000
Austenitic Yield Stress (M Pa)
locations.
Figure 6 shows the effect on austenitic yield strength of
annealing temperature after 40 % cold work in the martensite
of a 50.6 at.-% Ni alloy. It can be seen that a rapid decrease is
observed in the range 350 to 450 C, followed by a more grad-
ual decrease up to 850 C. At the same time, Ms increases, and
again the increase is rapid between 350 and 450 C. Compar-
ing the two graphs in Figure 9 it is apparent that for a given
alloy, although processing can increase the yield strength, it
is done at the expense of a lower Ms.
One of the principal improvements upon the properties of
Ni-Ti-based alloys obtained by processing is cyclic behavior.
When the same binary alloy annealed at 850 C, with a strain
corresponding to an initial stress of 150 MPa being applied, is
subjected to one cycle of deformation and reheating, a large
amnesia of around 1.5 % is noticed. In other words a single
memory cycle with this stress leads to an irreversible defor-
mation of 1.5 %. Conducting the same test after cold working
40 % and annealing at 400 C results in amnesia of around
0.5 %.
The strain obtained on cooling and the amnesia on heating
are plotted in Figure 7 as a function of stress after cold work-
ing and annealing at 350 C and 450 C respectively. The
350 C anneal gives significant amnesia at all useful working
stress levels. For low temperature anneals where the amnesia
is low, the data obtained from the first cycle, as shown here,
approximates the cyclic behavior after many cycles. However
where the amnesia on the first cycle is high, the cyclic stabil-
ity is poor.[7]
When choosing a Ni-Ti-based alloy for an actuator type of
application, it must be remembered that for a given composi-
tion, a high Ms-temperature is obtained by annealing out any
effects of prior cold work. The cyclic stability is therefore
poor. Devices triggering at or above 100 C are unlikely to
have mechanical stability over tens of
thousands of cycles. However, it
90
should be remembered that this is a
mechanical instability, where the
80 strain per cycle varies at high work-
ing loads. There is no metallurgical in-

900
70
50,6 at % Ni, CW 40 %
stability leading to shifts in the re-
Ms at 150 MPa

800 sponse temperature as a result of

700 60 prolonged exposure to around
100 C, in contrast to Cu-based SMAs.
600
50 If superelastic behavior at ambient
500 temperature is required, then Ms
400 must be lowered, and the alloy shall
40
be nickel-riched. Another way of low-
300
ering Ms is a solution treatment fol-
30
200
300 400 500 600 700 800 900
lowed by rapid cooling and cold
300 400 500 600 700 800 900
Annealing Temperature (°C) working. But it has to be taken into
Annealing Temperature (°C)
account, that this will also provide
Fig. 6. Austenitic yield stress of 50.6 at.-% Ni alloy, cold worked 40 % and then annealed for 30 mins. at the tempera-
tures indicated (left). Transformation temperature Ms (measured at 150 Mpa) as a function of annealing temperature of
additional hardening from the pre-
the same alloy (right) [7]. cipitation of nickel-rich phases.

440 ADVANCED ENGINEERING MATERIALS 2002, 4, No. 7

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6 8

7
5 450 °C
350 °C
6

4
5

Strain (%)
Strain (%)

3 4

3
2
2

1
1

0 0
0 100 200 300 400 0 100 200 300 400

Stre s s (MPa ) S tres s (M P a)

Fig. 7. The strain obtained on cooling (upper curve) and the amnesia (lower curve) as a function of stress for a Ni-Ti
based alloy cold worked 40 % and annealed at 350 C (left) and the data after annealing at 450 C (right). [7]

2.2.1 The Influence of Thermomechanical Treatment on R-Phase Both Af and ep increased dramatically for all three materials
Transition with the Standard Superelastic faring the worst and the Cr-
doped again faring the best. The heights of the loading and
An increase in cold deformation of Ti-Ni alloy results in
unloading plateaus decreased uniformly for all three alloys
the increase in both tensile strength and R-phase transition.
with an increase in time at 400 C. Overall, exposure times at
As R-phase becomes stable, the SME will be improved and
400 C should be kept at or below 2 minutes if at all possible,
the decay of memory effect will also be controlled at fatigue
although if PTFE coating is required the decrease in the pla-
test. The increase in annealing temperature results in a de-
teau heights can be offset by selecting an alloy with higher
crease of R-phase transition range. In that case, the stability of
starting plateaus such as the Cr-doped alloy.[9]
R-phase and the SME become poor. When annealing at
600 C, the recrystallisation occurs and no R-phase is found.
Many of the previous facts were confirmed during an 2.2.2 Influences of Several Training Methods
investigation by Shape Memory Applications Inc., Santa
Especially in order to obtain the possibility of two-way
Clara, California, USA, conducted into improvements of Ni-
shape recovery, certain training methods have to be applied to
Ti-based alloys for medical applications.[9] The effect of heat
common SMAs. The training of SMAs is described as a ther-
treatment of three experimental alloys as listed in Table 1
momechanical treatment with the intent to make it possible for
were tested with regard to various coating operations, includ-
the alloy to remember both the high and the low temperature
ing polyurethane and PTFE coating.
shapes, repeatedly. Under normal circumstances, a SMA
Polyurethane coating typically exposes the material to
remembers its high temperature shape, upon heating recover-
temperatures of about 200 C for a few minutes, while PTFE
ing its austenitic shape, but immediately forgets the low
coating processes are carried out at temperatures in the
temperature (deformed) shape. However, it can be ªtrainedº
neighbourhood of 400 C. To study these heat treatment
to remember the low temperature shape as well. This is accom-
effects in general, heat treatment trials were conducted at
plished essentially by leaving some ªremindersº of the de-
200 C, 300 C, and 400 C to study the effects on critical NiTi
formed low temperature condition in the high temperature
properties. At 200 C, all three materials are relatively stable,
phase. In general, these procedures are based on repetition of a
even for times as long as 60 minutes. While the effect even of
thermomechanical cycle through the transformation region
long 300 C heat treatments on the stress plateaus was insig-
nificant, some measurable effects on Af and ep (mentioned as
amnesia above) were noted. At times as low as 15 minutes, Table 1.
both the Af and the ep of the three alloys began to increase
noticeably. In general, the effect appeared to be most dra-
Standard High Chromium
matic for the high nickel material and least dramatic for the Superelastic Nickel Doped
Cr-doped alloy. Overall, it is recommended to keep exposure
Nickel Content 55.8 wt% 56.0 wt% 55.7 wt%
times at temperatures of approximately 300 C to a maximum
of about 5 to 10 minutes. Heat treatments at 400 C had sub- Ternary Addition ± ± 0.2 wt% Cr

stantial effects on all three alloys at times as low as 2 minutes.

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 Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys
and therefore are referred to as training. The widely accepted
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mechanism of the two-way memory effect (TWME) is based
on the observation that cycling the material through the
transformation region generates complex dislocation arrange-
ments. Based on this observation, the TWME has been attribut-
ed to the microscopic stress fields accompanying these disloca-
tion arrangements. The residual stress fields favour the centre
and the beginning of the growth of preferential variants. Con-
sequently, during further cooling, preferential variants grow
without any internal or external assistance, thus causing
TWME. There are several common ways to train TWME:[10]
(1) TWME Training by overdeformation while in the
martensitic condition: the alloy is cooled below Mf, and while
in the martensitic state, is severely bent to well beyond the
usual strain limit for completely recoverable shape memory.
When reheated to the austenite range, the alloy will not
completely recover the original shape, due to the excessive
deformation of the martensite. As the shape memory strain
limit is exceeded, a partial loss of memory results (amnesia).
However, if cooled again to the martensite range, the alloy
will spontaneously move part of the way back towards the
overdeformed shape.
(2) Training by shape memory cycling: this procedure con-
sists simply of repeatedly carrying out shape memory cycles
until the two-way behavior begins to be demonstrated. One
shape memory training cycle would consist of the component
being cooled to below Mf, deformed to a level below the heat-
recoverable shape memory strain limit, then heated to recover
the original high temperature shape. After perhaps 5 to 10 of
these shape memory cycles have been carried out, (the direc-
tion of the strain must be the same during each training
cycle), the component will begin to spontaneously change
shape on cooling, moving in the direction in which it has been
consistently deformed during the training cycles. The amount
of spontaneous shape change on cooling will be significantly
less than that which was being induced in the shape memory
deformation step. Typically the spontaneous shape change
will perhaps be 1/5 to 1/4 of the training strain; for example,
if the strain induced during training was 6 %, the sponta-
neous TWME strain is likely to be no more than 1 or 2 %.
(3) Training by pseudoelastic cycling (PE): it consists of
repeatedly stress-inducing martensite by loading and unload-
ing the austenite above the Af-temperature, but below Md
where pseudoelastic (or superelastic) behavior is expected.
As for the training method above, the number of training
cycles required is typically in the order of 5 to 10, and the sub-
sequent spontaneous shape change on cooling and heating is
a fraction of the training strain.
(4) TWME training by combined SME/PE cycling: a partic-
ularly effective training routine for TWME has been found
that combines some of the features of methods 2 and 3. The
component is first deformed in the austenite condition, then
cooled to below Mf while holding the induced strain in the
sample (including the elastic strain), then heated up to re-
cover the original shape. If this routine is repeated a number
of times, TWME will be obtained on subsequent cooling and
442
heating. Although effective, this method is a little more com-
plicated than the others that have been described.
(5) TWME training by constrained temperature cycling of
deformed martensite: this is a variation on the previous meth-
od, which is perhaps somewhat easier to carry out in terms of
temperature control, and is probably the most commonly
used training method at present. The sample is deformed
below Mf, thus producing a stress-corrupted martensitic
microstructure. The sample is then constrained in the
deformed condition and heated to above Af. The sample is
typically cycled from below Mf to above Af a number of
times, with the sample all the while constrained in the origi-
nal deformed shape, to complete the training routine. This
training method proves to be particularly effective and is rel-
atively straightforward to carry out.
2.3 Influence of Alloy Elements in the Ni-Ti System
The binary standard Ni-Ti-based alloys deliver quite con-
vinient properties in the transformation temperatures range
between ±30 and +80 C. They exhibit superelasticity and/or
shape memory behavior, combined with an excellent biocom-
patibility (in the case of proper treated surfaces,[11] but also
good enough in normal conditions, even if sometimes dis-
cussed controversely[12]) and are therefore successfully
applied for orthodontic devices and other medical applica-
tions.[3,12] Besides this, other applications require transforma-
tion temperatures beyond those of the binary system (e.g.
sensors), or a wider or narrower hysteresis (e.g. actuators).
This can be attained by the addition of third and fourth ele-
ments to the binary alloy system.
The addition of third or fourth elements to Ni-Ti-based
alloys provides a powerful tool for controlling the properties
and can be used to:
± control transformation temperatures
± increase the stability of Ms with respect to thermal history
± control the hysteresis width
± increase austenitic strength
± reduce or increase martensitic strength
± increase two-way effect ability
High temperature transformation was the basis of many
investigations in recent times.[13±20] Alloy systems such as Ni-
Ti-Pd, Ni-Ti-Pt, Ni-Ti-Hf, Ni-Ti-Zr, Ni-Ti-Au and Ni-Ti-Al
have been studied to explore their properties, including engi-
neering considerations like manufacturing, phase stability,
mechanical stability, and cost.
2.3.1 Nickel-Titanium-Palladium System and Nickel-Titanium-
Platinum System
These two alloy systems can be counted among the high
temperature SMAs because replacing Ni either by Pd or Pt
has similar effects on the shape memory properties. It was
observed that small additions of these elements cause a slight
decrease of Ms-temperature, and even shift it below 0 C, but
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Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys
higher additions strongly elevate the transformation tempera-
tures compared to other elements.[21] The Ms-temperature
ranges from ±26 C (for 10 at.-% Pd) to 563 C (for 50 at.-%
Pd) and from ±10 C (10 at.-% Pt) to 1040 C (for 50 at.-%
Pt),[21] see Figure 8. The Table 2 demonstrates that rising
replacement of Ni by Pd results in rising transformation tem-
peratures.[22]
For all the observed alloy systems, a OWME effect has
been achieved and also the training of TWME has been possi-
ble e.g. for the Ti-30 at.-% Ni-20 at.-%Pd alloy. Some alloys
recovered nearly 100 % from deformation and reached up to
4 % of shape memory for one±way; others recovered only a
fraction of applied strain or broke due to micro-cracks from
hot rolling.
Effect of training strain: TWME-training of Ni-Ti-Pd-based
alloys was studied in bending tests.[23] In this bending test the
specimen was (1) deformed against a cylindrical rod to a
given constant strain at room temperature, (2) unloaded, (3)
heated to Af +30C and finally, (4) quenched in water. The an-
gles after unloading, heating, and quenching, were measured
during each cycle, along with TWME, the transformation
reverse strain and the permanent strain. The variations of
recovery angles with the number of training cycles and the
training strain are shown below in Figure 9a. The angle
increases rapidly in the first few training cycles, then changes
very slowly as the number of trainings increase, finally reach-
ing a saturation value. Figure 9b shows the effect of the train-
ing strain on the TWME. It is apparent that the saturation val-
ue increases as the training strain increases. Figure 9
demonstrates that the training strain and the number of
cycles directly determine the TWME.
As stated before, the mechanism of the TWME originates
from the complex dislocation arrangements, generated by
cycling the material through the transformation region. As
the number of cycles increases, the dislocation increases and
its arrangement becomes more and more stable. Therefore,
the TWME increases as the number of cycles increased. After
1100
1000
900
800
Ms Temperature (°C)
700 Ti50 (Ni(50-x) Pt x)
600
500
400
300
200 Ti50 (Ni(50-x) Pdx)
100
0 reorientation. This is considered to be disadvantageous to the
-100
0 10 20 30 40 50
Composition (x)
Fig. 8. Plot of Ms temperatures as a function of composition for Ti-Pd-Ni and Ti-Pt-Ni
alloys [21].
ADVANCED ENGINEERING MATERIALS 2002, 4, No. 7
Table 2. DSC measured transformation temperatures of several Ni-Ti-Pd alloys [22].
REVIEWS
Sample Compound Ms/C Mf/C As/C Af/C
1 Ti50Pd50 459 427 497 533
2 TiNi10Pd40 321 587 327 366
3 TiNi20Pd30 108 80 109 153
4 TiNi22Pd28 Ð Ð 132 180
5 TiNi27Pd23 50 25 45 85
a certain cycle, the dislocations become saturated and the
two-way memory remains unchanged with a further increase
in the number of cycles. For the same reason, the increase in
the training strain also induces more dislocation arrays and
finally produces a larger TWME for the same number of
cycles.[23]
2.3.2 Nickel-Titanium-Hafnium System
Of particular interest is the Ni-Ti-Hf system because of its
low cost and high transformation temperature potential.
Transformation temperatures up to Ap=622 K (=349 C) were
recorded, exhibiting good shape memory properties.[13]
Stress-Strain behavior: the stress-strain behavior of binary
Ni-Ti-based alloys normally exhibits well-defined yielding, a
stress plateau with little work hardening and a strain of about
8%. In contrast, for an investigated Ni49Ti36Hf15 alloy,[14] the
stress plateau completely disappears and high work harden-
ing is constantly observed instead. The high work hardening
will tend to result prematurely in dislocation slip during the
martensite variant reorientation or the stress-induced marten-
sitic transformation and thereby worsen the shape memory
properties of the investigated alloy.
Tensile properties: Figure 10 shows the variation of the r0.2
stress with tensile temperature. Clearly, the r0.2 stress versus
temperature curve is approximately S-shaped, a general fea-
ture observed in SMAs. The negative temperature dependence
of the r0.2 stress is associated with the martensite variant reori-
entation in the low temperature range below about 510 K
(237 C) and with dislocation slip in the high temperature
range above about 590 K (317 C), respectively, while the posi-
tive temperature dependence of the r0.2 stress between 510±
590 K (237 C±317 C) is attributed to the stress-induced mar-
tensitic transformation. The dr0/dT of the experimental alloy
is found to be smaller than that for Ni-Ti-based alloys. Com-
pared with other SMAs, the present experimental alloy exhib-
its a relatively high critical stress for the martensite variant
shape memory properties of the Ni49Ti36Hf15 alloy.[24]
Figure 10 also shows the variation in the elongation with
tensile temperature for the Ni49Ti36Hf15 alloy. Clearly, the
elongation is strongly dependent on the tensile test tempera-
ture. Around room temperature, the elongation is about 10 %.
443

REVIEWS
14
a b
12
10
T W M E (d e g re e )
8 8
6 6
4 4
2 2
0 0
0 5 10 15
Number of cycles
Fig. 9. The two-way memory effect of Ti-30 at.-%Ni-20 at.-%Pd alloy as a function of the number of cycles (a), and the
variation of the saturation value due to training strain (b) [23].
With increasing tensile test temperature, the elongation grad-
ually increases and reaches a peak of about 30 % at about
510 K (237 C), slightly above Af-temperature, and then de-
creases rapidly to a minimum at about 560 K (287 C). The
maximum elongation is possibly attributed to transforma-
tion-induced plasticity.[24]
Sufficient ductility is one of the necessary conditions for
SMAs to exhibit excellent shape memory characteristics. As is
known, the memorised strain or the recoverable strain is
essentially determined by the martensite shape strain. If an
alloy is brittle, this kind of potential strain cannot be
exploited. Ni-Ti-based alloys are known to be exceptionally
ductile. However, they tend to be brittle when alloyed with
Zr, Hf, Au, Pt and Pd. Consequently, when designing high
temperature shape memory alloys in a Ni-Ti-X system a com-
promise has to be made: to obtain a Ms-temperature as high
as possible and meanwhile to keep the alloy sufficient ductile.
From this point of view, Ni-Ti-Hf-based alloys appear to be
much more attractive.
Shape memory properties: The shape recovery ratio R for
different tensile strain is listed below. The tensile deformation
temperature is 80 C. It can be seen that the magnitude of the
strain ep greatly influences the shape recovery ratio R. A com-
plete shape recovery is observed until about 3 % strain. With
further increase of the strain, the shape recovery ratio gradu-
ally decreases (see Table 3). In order to test whether the
experimental alloy exhibits pseudoelasticity the specimen
was strained slightly above Af. No pseudoelasticity was ob-
served, when the specimen was cycled.
Table 3. The shape recovery ratio R for different strains ep:
ep, % 2.01 2.93 3.51
R,% 100 100 97.8
444
Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys
14
3.8%
12
Saturation Angle Value
10
2.3%
T W M E (Degree)
1.9%
1.7%
1.3%
20 25 1 1,5 2 2,5 3 3,5 4
Training Strain %
2.3.3 Nickel-Titanium-Zirconium System
Since the high temperature SMAs of the Ni-Ti-Hf system
were produced, the development of economic high tempera-
ture SMA has attracted great interest. Studies on Ni-Ti-Zr-
based alloys have shown that the phase-transformation tem-
perature could be enhanced dramatically by adding Zr. It has
been reported that the phase transformation temperatures
(Ms, As, Ap) increase up to 240 C, as with Hf addition, with
Zr contents up to 30 at.-%. The microstructure, thermomecha-
nical behavior and shape memory properties of Ni-Ti-Zr-
based alloys are very similar to Ni-Ti-Hf-based alloys.[19]
2.3.4 Nickel-Titanium-Iron System
Contrary to the addition of Niobium, the addition of Iron
to binary Ni-Ti system, results in a dramatic decrease in
transformation temperature, and a considerable decrease of
hysteresis width. Furthermore, the addition of Fe provokes
suppression of the martensitic phase to the favour of R-phase
transition and increasing ductility results in good cycle stabil-
ity. This alloy composition thus has excellent properties for
actuator applications. It was shown that a decrease in trans-
formation temperature is achieved with rising substitution of
Ni by Fe.[22]
2.3.5 Nickel-Titanium-Niobium System
The Ni-Ti-Nb-based alloys are mainly advantageous for
pipe-joint couplings, due to its wide hysteresis. It was found
to have sufficient mechanical and fatigue strengths to be used
as a structural element at elevated temperatures in water.
A detailed study of a Ni-Ti-Nb-based alloy with a chemical
composition of 51 wt.-% Ni, 38 wt.-% Ti, and 11 wt.-% Nb
4.03 4.97 6.01
was conducted at the Mechanical Engineering Research Lab.
95.5 87.2 83.1 in Hitachi, Japan.[25] The following principle properties were
determined:
ADVANCED ENGINEERING MATERIALS 2002, 4, No. 7
Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys

REVIEWS
35 700

30 Martensite 600
Austensite
25 500
Elongation (%)

Stress (MPa)
20 400

15 300

10 200
Elongation
5 100
Stress

0 0
274 372 449 474 494 520 554 594
Fig. 10. Temperature dependence of the r0.2 stress and the
Temperature (K) elongation for the Ni49Ti36Hf15 alloy [24].

The shape-recovery finishing temperature at a pre-strain
of 12 % was around 77 C.
Young's modulus increased with the temperature, up to
400 C.
The fatigue strength at 288 C in air and in water was
slightly higher (about 1.2 times) than at 20 C in air.
The martensitic and austenitic transformation tempera-
tures (Ms, Mf, As, Af) differ, as usual for SMAs, between
before and after shape recovery. Those after shape recovery
are listed as:
N = 100 cycles to appear the R-phase transformation. Ti52-
Ni47Al alloy exhibits good shape recovery, which can reach
50 % at the Af-temperature and gradually increase to 80 % at
300 C ageing temperature. His shape recovery is much better
than that of Ti51Ni49 alloy below 130 C, but exhibits the same
behavior above 200 C. The shape recovery of this alloy in-
creases during the ageing: it can reach 90 % for the specimens
aged at more than 60 h at 400 C.

Ms Mf As Af
±111 C ±158 C ±76 C ±33 C
The tensile strength and r0.2 proof stress increased with
the temperature from ±60 to 20 C, they were almost constant
between 20 and 288 C, and they decreased with the increas-
ing temperature at above 288 C. Therefore three temperature
regions can be characterised for the mechanical strengths of
this Ni-Ti-Nb-based alloy: below 20 C, between 20 and
288 C, and above 288 C.
Figure 11 shows the effect of overdeformation of a Ni-Ti-
Nb-based alloy. It can be mentioned that a total strain exceed-
ing 8 % of total strain, results in a considerable loss of recov-
ered strain. Furthermore, the recovery temperature rises
nearly constantly with deformation strain up to 14 %.[26]
2.3.6 Nickel-Titanium-Aluminium System
An investigated Ti52Ni47Al1 alloy[27] has lower transforma-
tion temperatures compared to those of the binary Ti51Ni49
alloy, but higher than those of equiatomic or Ni-rich Ti-Ni
alloys. They decreased further with an increased ageing time
at 400 C. The R-phase transformation seemed to be more eas-
ily promoted by both cold rolling and thermal cycling in this
alloy. R-phase transformation appeared within the ten first
cycles, compared with Ti51Ni49 alloy, which needs more than
3 Ni-Ti-Cu System
It is possible to substitute copper for nickel in an equia-
tomic Ni-Ti-based alloy. This ternary alloy system is of partic-
ular interest. As copper is a neighbour of Ni in the periodic
table, it readily changes the properties of a Ni-Ti-Cu-based
alloy up to a concentration of 30 at.-% Cu. In contrast to addi-
tions like Co, Fe or Cr, Cu maintains the same austenitic
phase temperature, instead of depressing it to lower tempera-
tures. Beneficial modifications of Cu are in particular a nar-
rower hysteresis and lower martensitic yield strength.
3.1 Crystal Structure of Ni-Ti-Cu-based Alloys
The NiTi phase has a limited solubility for either Ni or Ti.
The Cu-Ti binary system has a phase diagram very similar to
that of the Ni-Ti system. However the austenitic phase of
NiTi has a B2 cubic structure, whereas the CuTi compound is
tetragonal. As a consequence, more than 30 at.-% Cu will
result in the presence of both tetragonal and cubic phases.
When Cu is substituted for Ni in Ni-Ti-based alloys, the over-
all Ti concentration must remain close to 50 at.-%, in order to
yield a single-phase material desirable for shape memory
applications.
In this alloy system the formation of the premartensitic
rhombic R-phase does not occur. The R-phase effect, taking

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 Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys
REVIEWS

8 80

7,5 70

R e c o v e r y Te m p e r a tu r e ( °C )
60
Recovery Strain (%)

6,5 50

6 40

5,5 30

5 20

4,5 10

4 0
4 6 8 10 12 14 16 4 6 8 10 12 14 16
Total Strain (%) Deformation Strain (%)
Fig. 11. The effects of overdeformation on the recovery strain and the recovery temperature (As) of Ni-Ti-Nb.[26]

place nearly without a hysteresis, is of interest where accu- concentrations of Cu does not change the Ms-temperature
racy and cycle stability is recommended. But the suppression significantly.[4] The addition of copper results in various
of R-phase in Ni-Ti-Cu system is considered to be advanta- alloys, all with approximately the same Ms-temperature or a
geous for electrically actuated SMA wires. While heated un- delicate increase, and reduced A-temperatures, so that
der constant load, hysteresis of Ohm-resistance of an actuator transformation hysteresis is much smaller: about 25 C at
wire is noticeably lowered by the absence of the R-phase tran- 10 at.-%Cu facing 48 C at 3 at.-% Cu[30] see Figure 12. For
sition.[5] actuator applications, amounts of about 10 wt.-%Cu substi-
Ternary alloys with copper amounts about 7 at.-% trans- tuting Ni are used. The range of possible transformation
form in a one-step and alloys containing more than 8 at.-% temperatures is placed between ±100 C and +100 C, having
Cu transform in a two-step fashion: a hysteresis of 20±25 C.[5]
below 7 at.-%Cu: B2 (cubic structure) ® B19¢ (monoclinic)
above 8 at.-%Cu: B2 (cubic structure) ® B19 (orthorhom-
bic) ® B19¢ (monoclinic)
3.3 Influence of Cu on Phase Transition Properties
The martensitic B2 ® B19 phase appears with a strong
transformation peak, which is favourable for actuator appli- Yield strength: Another property influenced by copper
cations.[5] additions is the yield strength of the martensite, i.e. the stress
level at which the twins will re-orient. The yield strengths of
binary Ni-Ti-based alloys and a Ni-Ti-10 %Cu alloy were
tested in both the martensitic and austenitic phases (see
3.2 Influence of Cu on Transformation Temperatures
Table 4).[29]
and Hysteresis
Although processed to provide similar austenite yield
As mentioned in chapter 2, the binary Ni-Ti system is very strengths, the martensitic strength of the Cu containing alloy
sensitive to delicate variations in the stoichiometric composi- is almost half that of the binary. This can be important for
tion. A deviation of 0.1 at.-% may effect a change of transfor- cyclic applications. One way of redeforming a device when it
mation temperature of 10 C. Thus, depending on the desired cools back to the martensitic phase is to provide a reset
Ms-temperature, the precise composition control of up to one spring. On heating, the SMA can do useful external work, but
tenth and one hundredth of a percent is necessary.[4] How- some of the available energy must be stored in this reset
ever the sensitivity of the transformation temperatures is no- spring. Subsequent cooling of the SMA will cause it to soften
ticeably reduced in Ni-Ti-Cu system. Compared to the binary when transforming to martensite, and if designed correctly
systems, the alloy composition is controlled less closely. It al- the reset spring will then apply sufficient force to return it to
lows for easier production of commercial quantities of materi- its original low temperature position. The softer martensite of
al having a controlled Ms±temperature for actuator use.[28,29] the ternary alloy requires a lower force, so less work is dissi-
The addition of even small concentrations of many third pated per cycle. The larger the strength differential between
elements to Ni-Ti-based alloys results in a large change in the austenite and martensite phases, the larger the work that
the Ms-temperature. In contrast, substitution of even large can be done by the SMA during recovery.

446 ADVANCED ENGINEERING MATERIALS 2002, 4, No. 7

Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys

REVIEWS
60 80

50 75

40 70
A f -Mf (°C)

Ms (°C)
NiTi
30 65
NiTiCu

20 60

10 55

0 50
1 2 3 4 5 6 7 8 9 10 11
0 10 20 30 40
Cycle No.
At.-% Cu
Fig. 13. The Ms-temperature is less sensitive to transformation cycling for the ternary
Fig. 12. Influence of Copper on hysteresis width (Af -Mf) in Ni-Ti alloys. [30] (10 %Cu) alloy than for the binary alloy.[31]

Cycling stability and fatigue: The stability of the properties
of SMAs during cycling is a major concern. A reliable compo-
nent should exhibit a constant Ms independent of cycling.
Secondly, the amount of actually recovered shape change (or
strain) should be independent of the number of cycles. Any
inability of a shape memory component to retain these con-
stant properties can be defined as ªFatigueº.
The cyclic dependency of the Ms-temperature of annealed
binary and ternary (10 % Cu) alloys are shown in Figure 13.
As indicated, the Ms-temperature of the binary increases by
around 20 C during the first 10 thermal cycles. A further
cycling does not significantly change Ms-temperature. The
ternary alloy, however, exhibits an Ms-temperature, which is
relatively constant to cycling.[31]
A comparison of the cyclic dependence of the recoverable
strains of the binary and ternary alloys obtained during the
transformation due to an applied load is shown in Figure 14.
Data is shown for two stress levels, with the strains of the
binary alloy decreasing rapidly with the number of cycles.
However, the values for the Ni-Ti-Cu-based alloy remained
relatively constant. The reasons for these differences in
cyclic behavior are not clear. One possibility is associated
with an incomplete cycle. Heating was terminated at 100 C,
shape memory strain depends on plastic pre-strain. The
TWME (etw) in three types of alloys is plotted as a function of
plastic strain in Figure 15. In Ti-50.0 at.-%Ni, for example, the
TWME increases with increasing ep until reaching 12 % plas-
tic strain and decreases with further increasing ep. The strain
etw shows a maximum of 6 % at 10 % plastic strain in Ti-
45 at.-%Ni-5 at.-%Cu and a maximum of 5 % at 7 % plastic
strain in Ti-40 at.-%Ni-9 at.-%Cu.
Besides the fact that TWME of Ni-Ti-Cu-based alloys de-
pends on the amount of pre-strain, it has been shown that
TWME also depends on alloy composition. Figure 16 shows
the maximum TWME observed in Ti-Ni-Cu-base alloys alloys
with Cu-contents of 0 % to 10 %. The strain etw of Ti-Ni-Cu-
based alloys in this investigation is about twice as large as
that of the Ti-Ni binary alloy. This data could mean that Cu
addition is effective for increasing the two-way shape memo-
ry strain. Seen from a critical point of view, no cycle stability
has been mentioned in this investigation, which is important
for any application. Conversely, Stöckel[5] indicates that the
5
NiTi

which was below Af±temperature for the binary. Thus some NiTiCu
martensite would be retained in this case, but not in the
Transform ation Strain (% )

172,4 MPa
ternary. On the other hand, Mf±temperature for the Ni-Ti-Cu- 4 275,8 MPa
based alloy is well below Ms±temperature and cooling to
room temperature does not complete the martensite transfor-
mation for the ternary alloy. This is one reason why the initial
cycle strain is less.[29] 3

3.4 Effect of Cu Addition on Two-Way Shape Memory

Effect in Ni-Ti-based Alloys
2
The TWME is also affected by adding Cu as a third ele- 1 10 100 1000 10000
ment in Ni-Ti-based alloys. An investigation was conducted Cycle No.
at the Institute of Materials Science, University of Tsukuba, Fig. 14. The recoverable strain exhibits less fatigue due to transformation cycling for
Japan, to clarify this effect.[32] It is clear that the two-way the ternary (10 %Cu) alloy than for the binary alloy [31].

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 Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys

Table 4.
REVIEWS

6
Ni-Ti-based alloy Ni-Ti-10%Cu

Max. of Elongation tw (%)

Martensite (tested at 25C) 208 MPa 106 MPa 5

Austenite (tested at 200C) 1053 MPa 1177 MPa

4

2 TiNiCu with Cu<7,5at%

maximum reachable TWME is reduced by the addition of
copper. In the Ni-Ti-10 %Cu-alloy a TWME of less than 1 %
after 10 cycles has been measured. The substitution of Ni for
Cu in the Ni-Ti-based alloys results in minor structural
changes and numerous modifications of the shape memory
properties. However, the basic SME is observed in alloys con-
taining up to around 30 % Cu. Some advantages of adding Cu
are a narrower transformation hysteresis and a more constant
Ms-temperature, less dependent on concentration variations
and cyclic fatigue. Furthermore, the Cu-containing ternary
alloy also has a martensite phase with lower yield strength,
thereby requiring a lower reset force for some cyclic applica-
tions. Therefore, alloys with about 10 % Cu seem to establish
as a favourable standard for actuator applications.
4 NiTiCu Wires
Several experiences have been made by the authors with
NiTiCu-wires from the AMT-company (Herk-de-Stad, Bel-
gium) with the following characteristics:[33] Round wires with
0.43 mm diameter, ªtrained with the one-way-effect with
effect stability (incomplete two-way-effect)º with an Af at
approx. 75 C in the unloaded condition and a maximum
deformation of 3.4 %.
6 pression can be derived considering a linear relationship:
Ti-45Ni-5Cu
5 Ti-40Ni-9Cu
Ti-50Ni
4
Elongation tw(%)
TiNiCu with Cu>7,5at%
1
0
0 2 4 6 8 10 12
Cu-content (at%)
Fig. 16. Effect of Cu content on the maximum of the two-way shape memory strain
[32].
4.1 Influence of the Applied Load upon the Af-Temperature
In order to examine the influence of the loading on the
phase change behavior while heating, wires with a length of
290 mm were cycled in a test facility. The wires were fixed
with six screws at each end in two special grippers and had a
free length of 250 mm. One of the grippers was connected on
its other side with a steel wire. Over two rolls the steel wire
was led from a basket into a bath filled with an 80 % glycer-
ine-water-mixture, in which the NiTiCu-wire was submerged
in entirely. The other gripper was fixed in this bath. So it was
possible to charge the wire with different loadings by filling
the weights in the basket. Then the glycerine-water-liquid
was heated up very slowly to 160 C and the deformation was
measured by means of an inductive way sensor at the chang-
ing height of the basket. Af-temperature was measured ac-
cording to Figure 2. The dependence of this Af-temperatures
on preload has been plotted in Figure 17. A mathematical ex-
Af = 61.9 C + F ” 1.71 C/N (1)

where F is the applied preload in N.

3 Taking into account the wire cross section, the inverse
slope can be expressed as 4 MPa/K, which is similar to other
2 reported values for binary Ni-Ti-based alloys.[7]
It has also been possible to produce a three dimensional
1 graph considering all the measured data e, T, L (Figure 18).
With such a diagram it is possible to determine the maximum
0
percentage contraction of this wire in dependence of certain
0 10 20 30 values of the parameters load and temperature. Values of
Plastic strain (%) maximum recoverable strain are also dependent on preload.
Fig. 15. Effect of plastic strain on the maximum of two-way shape memory strain in
In the range of tested preloads (112 to 461 MPa) maximum
Ti-Ni-Cu-based alloys [32]. recoverable strain of between 3.5 to 4.5 % can be obtained.

448 ADVANCED ENGINEERING MATERIALS 2002, 4, No. 7

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After these experiences several heat treatments were car-

REVIEWS
LoadDependency of theAf Temperature
ried out on the NiTiCu-wires in order to examine the influ-
180
ence on the phase change temperatures and to explain the
160
poor results obtained with the as-supplied material. In the
A f T e m p e r a tu r e ( °C )

140
120
100
80
60
40
20
0 ± Heat treatments of 150 C/10 s and 325 C/10 s and 350 C/
0 10
Fig. 17. Load dependence of the Af-Temperature.
4.2 The Influence of Heat Treatments on the Phase Change
Behavior
In order to examine the influence of various heat treat-
ments on the phase change behavior on the above mentioned
NiTiCu-wire many tests were carried out at our own labora-
tories.
First of all, the as-supplied wires were tested in order to
assess the relationships between contraction, preload and
temperature. Loaded with different weights the pre-cooled
specimens without any prior heat-treatment were submerged
in the glycerine-water-liquid at different constant tempera-
tures. It could be seen that at constant temperature a higher
load leads to smaller contractions and that at constant load a
higher temperature leads to bigger contractions, see Fig-
ure 19. It also can be noticed, that the contraction (emax =
0.4 %) of the tested wires were far away from the expected
values (emax/unload = 3.4 %, as certified by the supplier).
first group of tests wires without any heat treatment were
examined at a constant temperature of 75 C at a constant
stress of 112 MPa. Then the wires were objected to the follow-
ing different additional treatments in a tempering furnace:
± Heat treatment of 150 C/10 s
± Heat treatments of 150 C/10 s and 325 C/10 s
20 30 40 50 60 70 10 s.
Load(N) The results showed that the heat treatments at 150 C/10 s
and 325 C/10 s lead to the best behavior concerning the con-
traction. The brief overheating of the wire considerably be-
yond the Af-temperature leads to 100 % austenitic phase.
After cooling the specimen, the phase change temperatures
are in the areas that are determined by the composition of the
alloy. (No remaining effect of this heat treatment could be ob-
served. The heat treatment with the highest temperatures did
not give as good results concerning the contraction. It may be
suggested, that damage to the lattice was already in prog-
ress).
In the second group of tests the wires were treated with
various heat treatments and then thermally cycled in the
water-bath with a constant stress of 112 MPa. So it was possi-
ble to plot the hysteresis graph with all the temperature
points of the phase changes and a comparison to the wire
without any heat treatment could be made. After every test
the specimen was taken out of the test plant and heat-treated
with the specification of the next step of the heat treatment.
The examined steps were:
± Without any heat treatment
± Heat treatment of 150 C/10 s

Force-/Temperature-Dependency of the Contraction

4,5

3,5

3
Contraction [%]

2,5

1,5 4-4,5
1 3,5-4
3-3,5
0,5
2,5-3
0 2-2,5
F=16.26[N]

154 1,5-2
144
134
F=25.30[N]

124 1-1,5
114
F=34.36[N]

104 0,5-1
94
0-0,5
F=43.39[N]

84
74
64 Temperature [˚C]
F=56.91[N]

54
Load [N] 44
F=65.94[N]

Fig. 18. Force-temperature-dependency of the contraction

translate.

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This means that e.g. by holding a piece of metal during a

REVIEWS

Contraction over the Load at Different Temperatures (Untreated)

0,45 defined period of time at a certain temperature the same

0,4
results can be obtained as by holding the same piece of metal
T=65°C
during a longer period of time at a lower temperature. This
0,35 T=70°C
T=80°C
substitution is possible in both directions.
This effect is also found in the NiTiCu-wire examined in
Contraction (%)

0,3

0,25 our tests: the relatively high temperature during the short
0,2 heat treatments in the hardening furnace was replaced by the
0,15
low temperature in the bath combined with the long holding
time, caused by the slow heating. It was therefore not very
0,1
surprising, that all the graphs plotted at constant temperature
0,05
showed exactly the same contraction value, regardless of the
0 applied heat treatment. In other words: already the first step
0 10 20 30 40 50 60 70
of heat-treatment is good enough to produce a recovery of
Load (N)
the SME in the expected range.
Fig. 19. Contraction versus load at different temperatures (as-supplied).

± Heat treatment of 200 C/10 s 5 Concluding Remarks

± Heat treatment of 250 C/10 s
± Heat treatment of 300 C/10 s
± Heat treatment of 350 C/10 s
It has to be taken into account that in each test the same
wire was used. So the wire was not only subjected to the heat
treatment of the actual step, but also to all of the previous
heat treatments. Figure 20 shows the contraction versus the
load in dependence of the temperature. The results show
clearly that a heat treatment leads to a considerably improved
maximum contraction, in this case of 4.75 %. To explain this
improvement it can be supposed, that the supplied wires,
probably stored for a long time without any thermal cycling,
have experienced an evolution in their microstructure in such
a way, that martensitic phase was estabilized. This is a well
known phenomena in material science, e.g. in the quenching
of steels. In material science it is also known that in these
fields as the treatment of ageing the factor ªtemperatureº can
be replaced by the factor ªtimeº multiplied by certain factors.
The effect of thermomechanical treatments on phase
change behavior of Nitinol alloys were reviewed. Some con-
cluding remarks are as follows:
I) Depending on the details of the alloy and its prior ther-
momechanical history the martensitic plateau resulting in a
stress-strain test can vary from a continuous curve to a clear
horizontal plateau. Also the length of the plateau, what af-
fects the heat recoverable strain, is affected.
Increasing the cold work reduces the heat recoverable
strain, but increases the yield strength.
On the other hand, a prior annealing treatment reverts the
above mentioned phenomena, increasing Ms temperature but
reducing the mechanical stability below tens of thousands
cycles.
Concerning training methods of the TWME five thermo-
mechanical training treatments are used.
II) An extensive review of different additions to Ti-Ni base
compositions was presented, stressing the main differences
observed in SME properties.

C ontraction over the Load at D ifferent T em peratures

(H eat T reated)

5
4,5
4
Contraction (%)

3,5
3
2,5
2
1,5
1
0,5
0
0 20 40 60 80 100 120 140
Load (N )

Fig. 20. Contraction versus load at different temperatures

T =65°C T =70°C T =75°C T =80°C T =85°C
(heat-treated).

450 ADVANCED ENGINEERING MATERIALS 2002, 4, No. 7

Gümpel et al./Phase Change Behavior of Nitinol Shape Memory Alloys
III) For Ni-Ti-Cu-based own experimental work showed
an increase in the applied stress of 4 MPa results in Af critical
temperature increase of 1K.
Short annealing treatments at intermediate temperatures
(from 150 C/10 s to 350 C/10 s) lead to the best value con-
cerning contraction. Nevertheless these very short treatments
showed no signifficant differences in other properties.
Received: July 06, 2001
Final version: February 23, 2002
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