Materials Science and Engineering A 481–482 (2008) 395–403

On the influence of austenitization on the morphology of ␣-phase in

tempered Cu–Zn–Al shape memory alloys
Leandru-Gheorghe Bujoreanu ∗
Faculty of Materials Science & Engineering, The “Gh.Asachi” Technical University from Iasi, Bd.D.Mangeron 63, 700050 Iasi, Romania
Received 17 May 2006; received in revised form 13 December 2006; accepted 22 December 2006

Abstract
The paper reports some austenitization effects on the ␣-phase morphology in a tempered martensitic Cu–21.57 Zn–7 Al (wt.%) shape memory
alloy (SMA). By means of differential scanning calorimetry, X-ray diffraction and optical and electron microscopy, it has been shown that the
effects of the stress-state induced in austenite persist even after martensitic transformation and tempering at 773 K. The two analyzed austenitization
states, hot-pressed and homogenized, respectively, aimed to reproduce two steps of an industrial technologic flow for SMA manufacturing.
Basically, austenitic hot-working diminished the size of disoriented ␣-phase precipitates while austenitic homogenization enabled the formation
of a Widmanstätten structure with oriented long ␣-phase needles, among which those corresponding to ␣(1 1 1) intersect at about 70◦ and those
corresponding to ␣(2 0 0) at 90◦ .
© 2007 Elsevier B.V. All rights reserved.

Keywords: Constrained recovery; Training-cycling tests in bending; Bainite formation; Stabilized phases; ␣-Phase preferred formation

1. Introduction is ␤ which is thermally or stress-induced from ordered ␤2 (B2)

Cu–Zn–Al-type shape memory alloys (SMAs), with
critical temperatures Ms = 73–373 K, typically contain
Cu–(19–30)Zn–(4–8)Al (wt.%) and small additions of some
grain-refining elements, such as B, Zr, Mn, Ti, Co, etc. [1,2].
Within the above compositional range, up to three equilibrium
phases, namely ␣, ␤ and ␥ [3–6], as well as up to three
martensitic phases, designated as ␣ , ␤ and ␥ [7], are normally
expected to occur. The equilibrium phases ␣ and ␥ are generally
avoided basically because they do not transform martensitically
and impede martensitic transformation being too soft and too
hard, respectively. Therefore the only phase useful for the SM
behavior is ␤ (bcc) with electron concentration ne /na = 1.48
[8] and stability range near the eutectoid composition in the
ternary system [9]. Since it undergoes either a thermally
or a stress-induced martensitic transformation it is termed
“austenite” [10]. During cooling, prior to martensitic transfor-
mation, austenite may experience up to two ordering reactions
A2 → B2 → L21 , providing no high cooling rates are applied
[11]. Among the above three martensites the most common one
∗ Tel.: +40 727 486406; fax: +40 232 225986.
E-mail address: lgbujor@tuiasi.ro.
or ␤3 (L21 ) austenites, as ␤2 (9R) or as ␤3 (18R), respectively
[12].
The optimal functioning of the applications made from
ordinary Cu–Zn–Al-type SMAs should comprise only the
fully reversible martensitic transformations ␤2 (B2) ↔ ␤2 (9R) or
␤3 (L21 ) ↔ ␤3 (18R). However various previous works reported
that, owing to some diffusion-controlled phenomena, either
intermediate or equilibrium phases can precipitate during
martensite ageing. For instance, ␣-phase was observed with a
textured shape in commercial Cu–Zn–Al-type springs before
training [13] and with a specific orientation [14] and morphol-
ogy [15] in tempered martensitic alloys. On the other hand, at
higher Zn contents, the precipitation of ␥-phase was observed
in stabilized martensite [16] especially after prolonged ageing
[17] being favored by the formation of vacancies clusters [18] or
by the formation of stabilized stress-induced martensite [19]. In
alloys with less than 7 wt.% Al, during martensite ageing above
473 K lath martensite with higher Al content was formed that
eventually decomposed by eutectoid reaction into ␣ + ␥ [20].
If the Al content was up to 5 wt.%, during isothermal ageing
of martensitic alloys in the range 453–573 K, the formation
of transitory ␣1 bainite (9R) was reported that became disor-
dered (3R) and finally transformed into equilibrium ␣-phase
[21].

0921-5093/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.12.223
396 L.-G. Bujoreanu / Materials Science and Engineering A 481–482 (2008) 395–403
Being considered as a product of competitive mechanism
of eutectoid decomposition that nucleates after an incubation
time and requires diffusion for its growth [22], ␣1 bainite was
observed after isothermal transformation, firstly in Cu–Zn alloys
[23] and subsequently in Cu–Zn–Al [24]. For Cu–Zn–Al alloys,
the mechanism [25] and morphology [26] of bainite transfor-
mation during isothermal ageing were studied both in free-state
and under applied stress [27]. Since it has a diffusionless nucle-
ation and a diffusion-controlled growth, even if its formation is
accompanied by a geometry change designated as reverse shape
memory effect [28], bainitic transformation is irreversible, in
contrast to martensitic transformation.
Besides high temperature decomposition, martensite can be
subjected to low temperature stabilization [29] accompanied by
the change of long range atomic order [30] which prevents the
reverse martensitic transformation thus causing the degradation
of the shape memory effect [31].
The present paper aims to report the shape memory behav-
ior of a martensitic Cu–Zn–Al SMA with 7 wt.% Al and to
reveal the role of tempering in the properties adjustment by
means of structural changes. Special emphasis is laid on the
influence of austenitization on the morphology of ␣-phase
precipitated during tempering in the martensitic alloy under
study. Two austenitic conditions that reproduce two consecu-
tive steps of an industrial technologic flow are considered and
the interaction between ␤2 austenite (B2, a = 0.294 nm) [32],
␤2 martensite (M9R, a = 0.441 nm; b = 0.268 nm, c = 1.92 nm
and β = 88.4◦ ) [33], ␣1 bainite (9R, a = 0.452 nm; b = 0.264 nm
and c = 1.918 nm) [21] and ␣-phase (fcc, a = 0.375 nm)
[32] during tempering and subsequent water cooling is
analyzed.
2. Experimental details
A Cu–21.57 Zn–7 Al (wt.%) SMA was cast, hot pressed
(40% thickness reduction) and heat treated according to Fig. 1.
Thus, lamellar specimens for constrained recovery [34] tensile
tests and for training-cycling tests in bending [15] as well as
square specimens for X-ray diffraction studies were cut under
adequate cooling to the final dimensions 1.5 mm × 2.2 mm
with active length 80 mm, 0.5 mm × 4 mm × 50 mm and
2 mm × 20 mm × 20 mm, respectively. X-ray diffraction (XRD)
specimens were ground, polished and etched in the same way as
Fig. 1. Schematic thermogram illustrating the heat treatments applied to the
experimental alloy.
metallographic specimens. Etching was performed during 1 min
with a solution (20 g-K2 S2 O5 , 5.5 ml-Na2 S2 O3 , 50 ml-distilled
water) which was neutralized with water, acetone and ethanol.
Thin foils for transmission electron microscopy (TEM) were
prepared by twin-jet electropolishing in an electrolyte solution
consisting of 75 vol.% methyl alcohol and 25 vol.% nitric acid.
Constrained recovery tensile tests were performed on a
Heckert FPZ 100/1 tensile testing machine by electrical resis-
tive heating of elongated specimens, according to a previously
described procedure [35].
Training-cycling tests in bending were carried out on an
experimental device called deflectometer [36] the functioning
principle of which was previously detailed [37]. Essentially the
specimens in martensitic state were bent by three different loads
of 0.24, 0.44, 2.94 N. With the loads fastened at their free end,
the specimens were subjected to heating–cooling cycles during
which they lifted the loads by shape memory effect (SME) and
lowered them due to the softening induced by direct martensitic
transformation. The device is equipped with limit stops that auto-
matically commute between the heating and cooling modes and
with sensors that enable recording the variation of the displace-
ment of specimen’s free end as a function of temperature with a
precision of 0.5 mm and 1 K, respectively.
XRD experiments were performed on a Dron 2,0 diffractome-
ter with Cobalt anode, with particular care in order to avoid
texturing effects. The Miller indices of the diffraction max-
ima were ascribed with a precision of ±0.1◦ , by simulating
Fig. 2. Stress variations with time during four constrained recovery tensile tests
performed on a specimen A0 initially loaded up to 250 MPa which developed
the same maximum stress during heating at four decreasing strains maintained
constant.
 L.-G. Bujoreanu / Materials Science and Engineering A 481–482 (2008) 395–403 397

the corresponding diffractograms for the phases mentioned in
the previous section, by means of the POWDER CELL pro-
gram [38]. The error for determining the relative intensity on
the recorded diffractograms has been 1.5%.
Differential scanning calorimetry (DSC) measurements were
conducted on a 2920 Modulated DSC TA INSTRUMENTS unit,
with a temperature variation rate of 10 K/min and isothermal
maintaining for 3 min at the end of each ramp.
Metallographic observations were performed on a LEICA
optical line comprising Aristomet light microscope and
Orthomat E exponometer.
TEM observations were made with a JEM 2000FX transmis-
sion electron microscope operating at 200 kV, using a double tilt
sample holder.
3. Results
strain of 1.54% where a total stress of 250 MPa was developed,
as well, on heating.
When analyzing the variation of the stress developed by con-
strained recovery SME, on the portions bi ci , as a function of the
constant strain where the tests were performed, it appears that
recovery stress decreased with the applied strain, according to a
third order polynomial relationship.
3.2. Training-cycling tests in bending
Three specimens A0 were trained in bending under three loads
applied at their respective free ends. After five heating–cooling
cycles, the variation of free end displacement as a function of
temperature became cyclic, closed loops being obtained in all
three cases. The corresponding displacement–temperature vari-

3.1. Constrained recovery tensile tests

Constrained recovery SME involves the development of

rather elevate recovery forces due to the external constrains that
prevent the SM element to restore its hot shape. Fig. 2 summa-
rizes the results of an experiment comprising several constrained
recovery tensile tests, performed on a specimen A0 loaded to
250 MPa that reached the same maximum stress of 250 MPa
during heating at different strains maintained constant. The spec-
imen was initially loaded up to 250 MPa that corresponds to a
strain of 2.38%. While this strain was maintained constant, the
specimen was heated. At the beginning of the resistive heat-
ing, a1 b1 , thermal expansion occurred that lowered the stress
but constrained recovery SME subsequently was produced that
raised stress back to its initial level, b1 c1 . Heating stopped at
250 MPa and the specimen was cooled in air to room tempera-
ture (RT), c1 d1 . Then strain was reduced to 2.13%, d1 b2 , which
also decreased stress correspondingly and a new heating was
applied during which stress increased back to 250 MPa. After
three gradual unloadings, stress reached 0 MPa at a permanent

Fig. 3. Variation of the free end displacement as a function of temperature for Fig. 4. Simplified X-ray diffractograms of the heat treated specimens according
specimens A0 subjected to training in bending under three different loads, from to Fig.1, emphasizing tempering effects: (a) hot forged specimens A0 , A13–15 ;
the beginning (1st cycle) to the end (5th cycle) of training. (b) homogenized specimens B0 , B13–15 .
398 L.-G. Bujoreanu / Materials Science and Engineering A 481–482 (2008) 395–403

Fig. 5. DSC charts recorded during heating up to 873 K, indicating three known
phase-transitions, designated with A, B and C, respectively and possibly bainite
formation above 600 K: (a) specimen A0 ; (b) specimen B0 .
ations for the applied loads of 0.24, 0.44 and 2.94 N in the first
and the fifth training cycles were summarized in Fig. 3 with solid
and dashed line, respectively.
By means of the so-called “tangent method” the critical tem-
perature As was determined as in the example shown in Fig. 3.
The evolution of the displacement–temperature curves, from the
first to the fifth cycle and their dependence on the applied load,
showed that with increasing the number of cycles the permanent
deformation increased less and less until becoming stabilized in
the fifth cycle, critical temperature As decreased and transforma-
Fig. 6. DSC charts recorded during a cooling-heating cycle between 423 and
193 K indicating a reversible martensitic transformation: (a) specimen A0 ; (b)
specimen B0 .
tion hysteresis (proportional to the surface area between heating
and cooling curves) decreased as well. At the specimen trained
in bending under an applied load of 2.94 N, the displacement of
its free end reached 4.73 mm, which represents the largest value
of the three above cases.
After removing the load, this trained specimen was further
subjected to heating–cooling cycles during which it developed
two-way shape memory effect (TWSME). Since it was no longer
constrained by the load, the specimen’s free end increased its
stroke but the two limit stops confined the displacement to 5 mm.
During TWSME cycling, the same decreasing tendencies of both
As critical temperature and transformation hysteresis were gen-

Table 1
Analytical and experimental data used for indexing the diffraction maxima from Fig. 4
Phase Calculated parameters for Co K␣ radiation Specimen (measured values of 2θ (◦ ))

h k l d (nm) 2θ (◦ ) A0 A13 A14 A15 B0 B13 B14 B15

␤2 −1 −1 1 0.2278 46.41 46.6 46.8 – – – – – –

0 −1 −5 0.2197 48.04 48 – – – – – – –
␣1 −1 −1 3 0.2146 49.26 – – – – – 49.3 – –
␣ 1 1 1 0.2125 49.79 50 49.58 50.27 50.17 – – 49.98 49.7
␤2 1 1 4 0.2078 50.98 – – – – – 50.56 – –
␤2 1 1 0 0.2056 51.57 51.43 51.18 – 51.37 – – – 50.99
␤2 0 −1 −6 0.2054 51.62 52 52.06 51.64 – 51.99 – 51.69 –
−1 −1 5 0.1954 54.48 54.1 54.64 – – 54.32 54.23 – –
−2 0 −5 0.1935 55.07 – – – – – 54.7 – –
−1 −1 6 0.1849 57.85 – – – – – 57.37 – –
␣ 2 0 0 0.184 58.18 58.2 58.04 58.18 58.33 – – 58.09 58.39
 L.-G. Bujoreanu / Materials Science and Engineering A 481–482 (2008) 395–403
erally noticed from the 100th to the 1000th TWSME cycle. Thus,
As decreased from 410 to 405 K while transformation hysteresis
decreased with 43%.
3.3. XRD observations
The X-ray simplified diffractograms of the eight specimens
defined in Fig. 1 are illustrated in Fig. 4 in such a way as to reveal
both homogenization and tempering effects. The calculated val-
ues of Miller indices, interplanar spacings and 2θ angles, as well
as measured values of 2θ, in the significant region 40–60◦ , are
summarized in Table 1, for the recorded maxima.
The two austenitization states, hot pressed air cooled A0 and
homogenized water quenched B0 have different structures due
to both ␣-phase and ␤2 austenite expected to occur in speci-
men A0 which has a multivariant martensitic structure. In hot
pressed specimens ␣-phase persists, even after tempering and
air-cooling, with crystallites that contain the close packed planes
(1 1 1) and (2 0 0) oriented parallel to the specimen’s surface. The
ratio between the relative intensities, corresponding to the two
orientations, ␣(2 0 0)/␣(1 1 1) increased with tempering temper-
ature up to a maximum value of 0.41 [14], value which remained
unchanged after water cooling [15].
Fig. 7. DSC charts recorded during a cooling-heating cycle between 423 and
193 K of the specimens tempered at 573 K: (a) reversible martensitic transfor-
mation in specimen A13 ; (b) absence of transformation in specimen B13 .
399
3.4. Tempering effects
Fig. 5 shows the DSC charts recorded for specimens A0 and
B0 during heating up to 873 K. In both charts three transfor-
mations occurred which in this case, according to literature,
have been ascribed to: A—endothermic reverse martensitic
transformation; B—exothermic precipitation of ␣-phase and
C—endothermic order–disorder transition of austenite [39]. In
spite of the different treatments applied to A0 and B0 which
have different structure, the three transformations occurred at
approximately the same temperatures. In addition to the three
transitions, a fourth flat endothermic peak located above 600 K
has been illustrated in Fig. 5. It is presumed that this peak, which
was previously observed on the DTA thermograms as well [40],
could correspond to bainite formation.
In order to reveal tempering effects on the martensitic
transformation, each of the eight specimens were heated at a tem-
perature where, according to Fig. 5, martensite reversion should
be complete and then subjected to a cooling–heating cycle.
The reverse martensitic transformation (designated as A in
Fig. 5) has been ascertained by means of the DSC charts shown
in Fig. 6, recorded during a cooling–heating cycle between 423
and 193 K.
A much more significant difference between hot pressed and
homogenized specimens is noticeable in Fig. 7 that shows the
Fig. 8. Optical micrographs of the specimens tempered at 573 K: (a) specimen
A13 ; (b) specimen B13 .
400 L.-G. Bujoreanu / Materials Science and Engineering A 481–482 (2008) 395–403

DSC charts of the specimens tempered at 573 K. In Fig. 7(a) a
reversible martensitic transformation was obviously produced
in specimen A13 with smaller hysteresis but larger enthalpy as
compared to A0 , which shows that a part of the initial stress state
caused by forging was relieved. On the other hand, in Fig. 7(b)
specimen B13 did not show any sign of transformation, during a
cooling–heating cycle between 423 and 193 K.
The significant difference between the behaviors of speci-
mens A13 and B13 is also reflected by the aspect of the respective
optical micrographs in Fig. 8. In Fig. 8(a) the structure of spec-

Fig. 9. TEM micrographs of the specimens tempered at 573 K: (a) stacking faults in specimen A13 ; (b) bainite like plate in specimen B13 ; (c) SAD pattern of specimen
A13 ; (d) SAD pattern of specimen B13 .
 L.-G. Bujoreanu / Materials Science and Engineering A 481–482 (2008) 395–403
imen A13 is obviously martensitic. In Fig. 8(b), since water
cooling was performed below 623 K and the plate-like trans-
formation product reveals internal striations [23] which seem to
be irregularly distributed and have the appearance of microtwins
[41] the structure of specimen B13 could be fairly bainitic rather
than martensitic.
The expected presences of martensite in specimen A13 and
of bainite in specimen B13 are confirmed by the TEM images
shown in Fig. 9. According to data found in literature, the stack-
ing faults [42] and selected-area diffraction (SAD) pattern [17]
from Fig. 9(a) and (c), respectively, correspond to ␤2 marten-
site, while the plate-shaped product and its SAD pattern, from
Fig. 9(b) and (d), respectively, could be ascribed to ␣1 bainite
[24].
According to Fig. 5, ␣-phase precipitation is initiated at
around 673 K and completed at 773 K therefore the specimens
tempered at these two temperatures could bring some evidence
about the course of this exothermic transformation.
The DSC charts of specimens A14 and B14 , tempered
at 673 K showed that no transformation occurred during a
cooling–heating cycle between 423 and 193 K. However, spec-
imen A14 contains austenite but, due to the large amount of
␣-phase that was observed, ␤2 should be depleted in copper
and therefore its critical temperatures would be too low.
Fig. 10. Optical micrographs of the specimens tempered at 673 K: (a) specimen
A14 ; (b) specimen B14 .
401
The micrographs of specimens A14 and B14 , (Fig. 10) reveal
the occurrence of ␣-phase but the two figures are very different.
Considering that hot pressed specimen A0 had higher stresses
in initial state, it is reasonable that A14 shows shorter ␣-phase
rods (needles) a large part of them being agglomerated along
grain boundaries that acted as stress concentrators, Fig. 10(a). On
the other hand, Fig. 10(b) shows that the former bainitic plates
became much finer, preserved their V-formation but the largest
part of them turned to ␣-phase needles. For this reason bainite
was not detected in Fig. 4(b) at the specimen tempered at 673 K.
This behavior is consistent with the TTT-diagram of the alloy
under study that shows an inflection point at 673 K where the
shortest holding periods are required for ␣-phase precipitation
[43].
The DSC charts of the specimens tempered at 773 K, during
a cooling–heating cycle between 353 and 133 K, are shown in
Fig. 11. Since incomplete exothermic peaks followed by clear
endothermic peaks are noticeable on both charts it is assumed
that a partial direct martensitic transformation occurs on cooling
and martensite reversion is produced on heating, at cryogenic
temperatures. Here again, specimen A15 with larger amount
of austenite has larger transformation enthalpy as compared to
specimen. Owing to the increase of the amount of precipitated
Cu-rich ␣-phase, austenite became richer in zinc and aluminum
and for this reason its martensitic transformation temperatures
were shifted to very low values.
Fig. 11. DSC charts recorded during a cooling-heating cycle between 353 and
133 K of the specimens tempered at 773 K, illustrating a reverse martensitic
transformation: (a) specimen A15 ; (b) specimen B15 .
402 L.-G. Bujoreanu / Materials Science and Engineering A 481–482 (2008) 395–403
Fig. 12. Optical micrographs of the specimens tempered at 773 K: (a) specimens
A15 ; (b) specimens B15 .
Fig. 12 shows the representative micrographs of the spec-
imens tempered at 773 K. Obviously ␣-phase precipitation is
more advanced than in Fig. 10 and ␣1 -bainite is no longer notice-
able but the same differences persist between the two specimens:
the ␣-phase needles are much longer and more ordered at spec-
imen B15 in Fig. 12(b) than at A15 in Fig. 12(a) and present a
Widmanstätten structure inside the austenite grains [2]. In the
micrograph shown in Fig. 12(b) one can see that the ␣-phase nee-
dles with (1 1 1) orientation intersect at about 70◦ in side area of
while those with (2 0 0) orientation at 90◦ in left side area.
4. Discussion
The constrained recovery behavior of specimen A0 can be
understood with consideration on its RT structure. According to
Table 1, it comprises ␣-phase crystallites with two orientations,
␤2 austenite and four martensite variants. When elongated to
2.38% under a stress of 250 MPa, the four martensite variants
would gradually turn to a single most favored orientation, from
the point of view of Schmid’s law and after a critical stress is
reached, stress-induced martensite is formed from austenite.
During the first heating, a1 b1 c1 , stress firstly decreases due
to thermal expansion, until As critical temperature is reached,
and then increases again, causing the occurrence of constrained
recovery SME. Since no stress drops were recorded at the end
of each of the four heating stages, it is obvious that heating
was interrupted between As and Af critical temperatures.
After the first cooling under stress, c1 d1 , it is assumed that no
thermally induced martensite variants are formed at RT, since
direct martensitic transformation starts at 305 K, according to
Fig. 6(a). Therefore at the end of the first constrained recovery
tensile test, only austenite and stress-induced martensite would
be obtained. During the subsequent tests, the reversion of
stress-induced martensite occurred at the beginning of heating,
causing stress to increase.
Assuming the transitory formation of ␣1 bainite as a precur-
sor of ␣-phase precipitation, since the latter was already present
in hot pressed specimens after austenitization, no ␣1 formation is
expected with increasing tempering temperature. Accordingly,
none of the bainite peaks were indexed in Table 1 for the diffrac-
tograms of hot pressed specimens On the other hand, in the
diffractograms of B0 homogenized specimens only two marten-
site variants could be detected, in Fig. 4(b). With increasing
tempering temperature, it is assumed that firstly a large part of
martensite remained untransformed and then a small part of it
turned to bainite. Among various possible ␣1 peaks only (1̄ 1̄ 3)
was assumed to belong to bainite at the specimen tempered at
573 K, Fig. 5(b). This assumption has been confirmed by opti-
cal microscopy, Fig. 8(b) and TEM, Fig. 9(b) and (d). Further
increase of tempering temperature enabled the transformation
of bainite to ␣-phase, with the two above orientations, while
a small part of martensite remained untransformed until 773 K
where it finally turned to austenite.
The transformation enthalpies are at least double at hot
pressed specimen A0 as compared to homogenized B0 in accor-
dance with Fig. 4, where the former presents austenite that takes
part to the direct and reverse martensitic transformation, while in
the latter no retained austenite was detectable. Since A0 should
have higher dislocation densities induced by hot pressing, it is
expectable that the direct martensitic transformation on cooling
occurs at lower temperatures in Fig. 6(a) than in Fig. 6(b) [44].
This decrease of the critical transformation temperature could
also be ascribed to the presence of ␣-phase in specimen A0 ,
which depletes the austenitic matrix in copper thus increasing
its zinc content.
This behavior shown in Fig. 7 agrees with the presence of
austenite in the diffractogram corresponding to A13 in Fig. 4(a)
and to its absence in the corresponding diffractogram of B13
from Fig. 4(b). Since specimen A13 contains austenite, it is this
phase that transforms to martensite on cooling. On the other
hand, Fig. 5 has shown that during heating the presumed for-
mation of bainite could start at 573 K being enhanced by the
300 s holding. According to the TTT diagrams, the isothermal
transformation for 300 s at 573 K of a Cu–21.57 Zn–7 Al (wt.%)
SMA is too short as to allow ␣-phase precipitation [43] there-
fore this transformation can fairly be excluded in the alloy under
study at 573 K. The reason for which bainite could be detected
in specimen B13 and not in specimen A13 could be related to
the pre-existence of ␣-phase in the latter. Moreover, since the
presumed bainite peak is flatter in Fig. 5(a) than in Fig. 5(b)
one can expect that a smaller amount of transformation product
would be obtained in specimen A13 than in B13 .
 L.-G. Bujoreanu / Materials Science and Engineering A 481–482 (2008) 395–403
5. Conclusions
The Cu–21.57 Zn–7 Al (wt.%) SMA under study, in hot
pressed air cooled state, developed both tensile constrained
recovery SME and TWSME, after being trained in bending,
in spite of the pre-existence of ␣-phase. The stress developed
by tensile constrained recovery decreased with increasing per-
manent strain according to a third order polynomial fit. The
maximum stress reached 250 MPa for a permanent strain of
1.54%. After being trained by repeatedly lifting a 2.94 N load,
the alloy reproduced by TWSME a 5 mm stroke, for the duration
of 103 cycles while decreasing its As critical temperature with
5 K, from 410 to 405 K and the corresponding transformation
hysteresis with 43%.
Bainite formation, predicted by DSC, was assumed by XRD
and confirmed by optical microscopy and TEM only in homoge-
nized specimen B13 tempered at 573 K. Due to the pre-existence
of ␣-phase in specimen A13 , the bainite amount is expected to
be too low, therefore non-distinguishable, and for higher tem-
pering temperature it is suggested that transitory bainite turned
to equilibrium ␣-phase.
The stress-state induced in austenite proved to influence the
tempering behavior of the martensitic Cu–Zn–Al SMA under
study, even after heat treatments performed at temperatures as
high as 773 K. The internal stresses caused by hot-pressing and
air-cooling lowered the critical transformation temperatures of
martensite, prevented bainite formation, favored ␣-phase pre-
cipitation both along austenite grain boundaries, mostly after
673 K-tempering, and inside them, as short disoriented rods,
after 773 K-tempering. Tempering enabled the preferred for-
mation of ␣-phase according (1 1 1) and (2 0 0) orientations
characterized by intersections at about 70◦ and 90◦ , respectively.
Acknowledgements
The author wishes to thank Dr. S. Stanciu for valuable help
in casting, Dr. V. Dia for assistance in processing and Dr. M.L.
Craus for advised support in XRD study. Special thanks are
brought to Dr. T. Kikuchi for his expertise in TEM observa-
tions. Prof. G. Eggeler, Dr. A. Yawny and Dr. T. Sawaguchi are
gratefully acknowledged for the fruitful discussions. Financial
support was offered by SFB 459 and by Romanian National
University Research Council (grant A CNCSIS 275).
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