Materials Science and Engineering A273 – 275 (1999) 625 – 629

www.elsevier.com/locate/msea

Characterization of a hot-rolled CuAlNiTi shape memory alloy
C. Seguı´ a,*, J. Pons a, E. Cesari a, J. Muntasell b, J. Font b
a

Departament de Fı´sica, Uni6ersitat de les Illes Balears, Carretera de Valldemossa, km 7.5., E-07071 Palma de Mallorca, Spain
b
Departament de Fı´sica i Enginyeria Nuclear, Uni6ersitat Polite`cnica de Catalunya, Diagonal 647, E-08028 Barcelona, Spain

Abstract
The changes in the martensitic transformation of a CuAlNiTi alloy hot-rolled at different temperatures have been studied
in detail, covering different aspects such as ageing in the parent phase at temperatures ranging between 250 and 350oC,
stabilisation of the martensite and betatization of the previously hot-rolled specimens. Besides the evolution of transformation
temperatures upon different thermal treatments, special attention has been paid to the changes in mechanical properties of the
alloy, such as elastic modulus and internal friction. These results are analysed in relation to the microstructural changes as
observed by transmission electron microscopy. © 1999 Elsevier Science B.V. All rights reserved.
Keywords: Martensitic transformation; Shape memory alloys; CuAlNiTi; Thermal treatments; Mechanical properties

1. Introduction
A considerable interest exists towards shape memory
alloys transforming above 100oC, because of their
prospective applications. Among the Cu-based shape
memory alloys, the CuAlNi system offers the best
potential because of the high transformation temperatures that can be chosen while maintaining a better
thermal stability than for CuZnAl. However, polycrystalline CuAlNi displays a poor ductility which
can be improved by grain refinement as achieved
through Ti and/or B additions.
Ageing in the parent phase of CuAlNiTi alloys
leads to the formation of the g2 phase which, together
with the Ti-rich X-phase [1], affect the martensitic
transformation characteristics and specially the mechanical properties such as the internal friction (IF) and
elastic modulus (E). As a matter of fact, it has been
found that the presence of X-precipitates, which are not
affected by ageing, decrease the IF maximum occurring
during the martensitic transformation; this fact has
been explained by the decreasing mobility of the parent/martensite interfaces due to grain boundaries and
fine dispersion of X precipitates [1 – 3]. As for the
g2-phase precipitates, they are known to increase the
* Corresponding author. Tel.: +34-971-173224; fax: + 34-971173426.
E-mail address: dfscsp0@ps.uib.es (C. Seguı´)

transformation temperatures due to Al depletion of the
matrix [4], but its influence on the IF and E behaviour
is largely unknown. Apart from the ageing effects both
in b and martensite, the production processes like hotrolling can influence the martensitic transformation undergone by those alloys.
In this paper we study the martensitic transformation
of a CuAlNiTi alloy hot-rolled at different temperatures. The effects of the rolling temperature will be
described, as well as the behaviour of the differently
hot-rolled alloys upon ageing both in parent and
martensite phases.

2. Experimental procedure
A polycrystalline alloy with a nominal composition
Cu -11.9% Al- 4.8% Ni- 1.0% Ti (wt.%) (nominal Ms of
100oC) was used in this study. Several ingots of the
alloy were hot-rolled in the same conditions at different
temperatures in the range between 600 and 850oC, but
a systematic study was performed on those hot rolled at
850 (alloy A) and 650oC (alloy B), which were representative of significantly different behaviours. Specimens of
those alloys were subjected to ageing at different temperatures in the parent and martensite phases performed in a melted salt bath. The martensitic
transformation was monitored by means of differential
scanning calorimetry (DSC; Perkin-Elmer DSC7) and

0921-5093/99/$ - see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 5 0 9 3 ( 9 9 ) 0 0 3 3 6 - 6

It is interesting to notice that. In fact. The complicated microstructure of the alloys at room temperature. The same effects occur in shorter times the higher the ageing temperature. the influence of the rolling temperature on the transformation properties is predominantly due to the precipitation of the g2 phase in alloy B during rolling. Transmission electron microscopy (TEM) observations of samples in different conditions was performed using a Hitachi H600 100 kV microscope. Details on the last mentioned technique can be found elsewhere [5]. 3. Ageing in the parent phase As shown in Fig. both having similar sizes and undefined shapes. hide the contrast of the dislocations introduced by rolling. . for the present composition and according to x-ray diffraction experiments. The transformation heat remains constant up to 60 h ageing at 250oC.2. hence. Microstructure of as-received alloy B at room temperature. / Materials Science and Engineering A273–275 (1999) 625–629 626 Table 1 Transformation characteristics of as-received alloys A and B. but starts to decrease after 5 h at 300oC or 30 min at 350oC. the transformation heat Q is averaged over the cooling and heating runs and IFmax.08 0. where Em stands for the modulus value in the martensite phase and Emin is the modulus minimum) occurring during the martensitic transformation are lower in the as-received alloy B compared to alloy A. The grain size is slightly smaller for alloy B (5 – 10 mm) than for alloy A (15 – 20 mm). IFint and DE/E correspond to the heating run Alloy A Alloy B Mp (oC) Ap (oC) DT (K) Q (J/g) IFmax IFint (K) DE/E 108 164 130 193 22 29 7. The microstructure of the alloys at room temperature shows a martensitic matrix (18R structure) with intra and intergranular micrometer sized particles. Mp increasing by less than Ap thus widening the transformation hysteresis DT = (Ap − Mp). after betatization (30 min at 850°C). Thus. but the transformation in the former is spread over a wider temperature range and. Seguı´ et al.9 0. the integrated IF (IFint) has similar values for both rolling temperatures. a lower hysteresis and a larger transformation heat than as-received alloy B. 1. Fig. while 850°C lies inside the single b phase region. As it can be seen in Table 1. due to the decomposition of the b phase. and being incoherent with the martensitic matrix.C.27 0. the thin foils being prepared by double jet electropolishing in 30% nitric acid in methanol at 240 K. Results and discussion 3. in addition to the XL particles. the DSC peak temperatures obtained on cooling (Mp) and heating (Ap) will be taken as representative of the martensitic transformation temperatures.15 0. the presence of similar low density dislocation distributions in both as-received alloys is revealed. having a large number of interfaces between very small martensite plates which contain stacking faults. 3. the as-received alloy A shows lower transformation temperatures. When observing in parent phase condition (after in situ heating above the Af temperature). TEM observations confirmed the dissolution of the g2 particles in alloy B and both alloys showed a transformation behaviour very similar to the as-received alloy A.1. ageing alloy A in the b phase leads to an increase of both the forward and reverse transformation temperatures. the temperature of 650°C corresponds to the g +b region.9 6. In alloy A. Similarly. Comparison of hot-rolling at different temperatures Throughout the present work. For alloy B. the IF maximum (IFmax) and the relative modulus minimum (evaluated as DE/E= (Em −Emin)/Em. Perkin-Elmer DMA7) working in a three point bending configuration. the particles were identified from the selected area electron diffraction patterns as being X-phase (type XL) [4]. Ap increases upon ageing at 250. When treated for 30 min at 650°C. whereas in alloy B. 2(a). specimens of both alloys showed a transformation spread over a very large temperature range with very low transformation heat. 1 shows the microstructure of alloy B. g2 particles were also identified.08 dynamic mechanical analysis (DMA. 300 or 350oC (although to a lesser extent than Fig.32 0.29 0.

the images show a very finely mottled contrast. / Materials Science and Engineering A273–275 (1999) 625–629 627 Fig. big particles of g2 phase (mm sized) were observed. 4(a) and (b). 3(a) and (b). no extra diffraction spots could be observed.C. a sharp decrease on IF values and modulus minimum taking place upon ageing and no transformation occurring after 3 h ageing. Mp and DT as a function of ageing time at different temperatures for alloy A (a) and B (b). up to 10 h ageing at 250oC). which occurs after about 20 h for alloy B and 60 h for alloy A. Ageing at 350°C caused the same fine precipitation process being developed at much shorter ageing times (for instance. 2(b)). Ap. Nevertheless. after a more severe ageing of alloy A (30 min at 400°C). growth of the big g2 particles already present in the as-rolled condition has been observed. 5) (a very similar process as that reported in [6]). IFmax decreases with increasing ageing time at 250oC for both alloys. The microstructural changes occurring during ageing at 250oC have been followed by TEM. These precipitates are more densely accumulated at the B2 and L21 antiphase boundaries. For the alloy B. The transformation heat starts to decrease after 48 h ageing at 250oC. but after more prolonged ageing (50 and 85 h) small precipitates with sizes of few nm can be distinguished. a slow decomposition process being observed in both alloys.e. the images observed after 30 min at 350°C in alloy A are very similar to that obtained after 85 h at 250°C). Due to their very small size. As can be seen in Fig. At the beginning (i. in addition to this fine precipitation. Seguı´ et al. many of them near the XL particles. the fine precipitates did not grow further (they had the same size as for 30 min at 350°C) but. alloy A). 30 min and 3 h at 350°C were also studied by means of DMA. This is also shown in Fig. instead. Specimens of alloy A aged for 5 min. together with the effects of the fine precipitation process observed by TEM are the more feasible causes for the . causing a sharp increase in hysteresis (see Fig. forming a dense dispersion throughout the samples (Fig. Improvement of the L21 short range order. but they are believed to be most probably of the g-type phase. Similarly. DE/E progressively diminishes with increasing ageing time at 250oC until its apparent disappearance. 2. 5 h at 300oC or about 5 min at 350oC. but Mp shows a small increase followed by a decreasing tendency.

Dark field image of the small precipitates observed in a sample of alloy A aged 85 h at 250°C. The degradation of transformation characteristics observed after a severe ageing can be related to the development of the big g2 particles in both alloys. the big ones (XL and g2) cannot be overcome by the growing Fig. except for the severely aged alloys. A decrease in the IF peak values could arise from a decrease in transformed mass fraction since. the non-chemical effect seems to be overcompensated by the compositional effect as well as by the short range ordering taking place upon ageing. 5. Thus.8]. Never- Fig. in the present case. 3. Seguı´ et al. as a first approach. Because the IF peak during the martensitic transformation is due to the hysteretic movement of the parent/martensite interfaces [10]. Fig. Mp and DT upon moderate ageing. the decrease in IF is attributed to the decreasing mobility of these interfaces caused by the precipitated particles. while the finely dispersed precipitates are held responsible for the observed decrease during ageing at 250°C. theless. the fact that the transformation heat (which is considered to be proportional to the amount of transformed material) remains constant. As for the DMA results. the lower IF peaks and less pronounced modulus minimum as well as the larger temperature spread of the IF peaks in alloy B are thought to be a consequence of the big g2 precipitates always present in this alloy. / Materials Science and Engineering A273–275 (1999) 625–629 increase of Ap. the latter effect would bring about a decrease of transformation temperatures. However. The small precipitates influence the transformation in two different ways: a chemical effect (change of composition of the matrix) and a non-chemical effect related to the difficulties in the martensite/precipitate accommodation.628 C. IF peak values and relative modulus minima as a function of ageing time at 250oC for alloys A (a) and B (b). 5 K min − 1 and stress amplitude 4 MPa). IF and E modulus spectra obtained during heating after 5 min and 65 h ageing at 250oC for alloys A (a) and B (b) (runs performed at 1 Hz. . allows to discard this possibility as a general rule. as indeed observed in CuZnAl containing small g precipitates [7. the IF values depend on the amount of transformed mass in a stress oscillation cycle performed at each temperature. 4.

Adachi. D Thesis. J. Gotthardt. Sugimoto. Stoiber. K. and indeed. Hamada. [5] C. Phys. CuAlNi alloys are less prone to martensite stabilisation than CuZnAl ones. 6. in order to increase their transformation temperatures allowing martensite ageing at higher temperatures (150. 86 (1995) 176. Cesari. Sade. Ap(1)-Ap(2).C. / Materials Science and Engineering A273–275 (1999) 625–629 Fig. Van Humbeeck. 37 (1997) 1783. as seen in Fig. no noticeable stabilisation occurred in any of the alloys upon ageing up to 110°C. K. A. The shift is the higher the longer the ageing time and the higher the ageing temperature. [1] K. 1994 [4] P.C. Scripta Metall. although in this comparison. Roqueta. Metallkde. R. Garcı´a. G. 629 to martensite ageing. MTM. E. Delaey. the very different ageing temperatures have to be taken into account. 42 (1994) 453. 21 (1986) 453. Ll. [6] K. (France IV) 5 (1995) C8–835. Phys. Katholieke Universiteit Leuven. R. Reverse transformation temperature shift. K. Gue´nin. 23 (1989) 579. Lovey. causing a considerable reduction of the martensite plates size. Auguet. Komatsu. S. V. research project PB950340. L. up to 2 months at 90 and 110°C. Kamei. stabilisation actually takes place in the studied alloys if ageing is performed at higher temperatures. Y. J. Pons. Mat. This fact can limit the application of these alloys at very high temperatures. Nakamura. parent–martensite interfaces. to different ageing stages in the martensitic state. for CuZnAl it has been established that dense distributions of small g precipitates inhibit martensite stabilisation by ageing at room temperature [9]. Acta Met. Z. J.3. Eng. Sugimoto. which recovered the transformation temperatures prior . J. Tagawa. Acknowledgements The authors acknowledge the partial financial support received from the DGES. Sci. J. Cesari. References 3. [7] C. a process which is energetically expensive due to the accommodation of precipitates in the martensite phase [8]. [2] M. while the small precipitates are actually absorbed by the martensite plates when they grow. . [9] J. Kamei. It is also interesting to emphasize that. Rapacioli. Rodrı´guez. Torra. K. Sugimoto. Metals 56 (1992) 30. Cesari. Isalgue´. Akamatsu. while it seems not to be the case for the dense dispersion of very small precipitates present in the studied CuAlNiTi alloy after ageing. a temperature at which a high martensite stabilisation is usually observed in CuAlZn alloys. M. Y. Nakaniwa. Ageing in martensite Specimens of both alloys A and B were subjected. Dept. as a function of ageing time in martensite. [10] J. Scripta Metall. Specimens of alloy A were first aged for 30 min at 350oC. either in the as received condition or after one transformation cycle. Ph. [8] F. Hurtado. Seguı´ et al. Sugimoto. Scripta Mater. T. Seguı´. [3] I. 200 and 210°C). The enlargement of the transformation temperature range caused by precipitation of g2 and the decrease in strain per oscillating cycle caused by the poor mobility of the interfaces are responsible for the progressive disappearance of the E-modulus minimum. A 129 (1990) 273. E. However. The first reverse transformation measured after ageing displays a significant shift in transformation temperatures with respect to the second reverse transformation. no appreciable shift in the reverse transformation temperatures being observed in any case. Y. Japan Inst. Mat. E. D. 6. T. (France) 43 (1982) C4 – 761. and then limits the displacement of the interfaces during the oscillating stress. Man˜osa.