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Intermetallics 16 (2008) 10901094

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Inuence of Be addition on orderdisorder transformations in b CuAl

a Luja n Castro a, b Fernando Lanzini a, b, *, Ricardo Romero a, c, Mar

sica de Materiales Tandil, Universidad Nacional del Centro de la Provincia de Buenos Aires, Pinto 399, 7000 Tandil, Buenos Aires, Argentina IFIMAT Instituto de F cas y Te cnicas, Argentina Consejo Nacional de Investigaciones Cient c n de Investigaciones Cient cas de la Provincia de Buenos Aires, Argentina Comisio

a r t i c l e i n f o
Article history: Received 13 March 2008 Received in revised form 18 June 2008 Accepted 22 June 2008 Available online 5 August 2008 Keywords: A. Intermetallics, miscellaneous B. Electrical resistance and other electrical properties B. Orderdisorder transformations

a b s t r a c t
The dependence of resistivity with temperature around the orderdisorder transitions is measured for bcc shape memory alloys CuAl (Be). The experimental curves are discussed in terms of the Rossiter theory, and the parameters involved in this approach are determined. The model allows calculating the variation with temperature of the long-range order degree. Whereas for the binary CuAl the kinetics of the orderdisorder transformation is rst order, the addition of Be leads to a gradual smoothing in the variation of the order parameter below the transition temperature. 2008 Elsevier Ltd. All rights reserved.

1. Introduction Cu-based shape memory alloys (SMA) belong to a group of modern materials, which have undergone an extensive study due to their interest in advanced technologies. These alloys exhibit the so-called shape memory effect which is linked to a martensitic transformation that takes place from a bcc derived intermetallic b phase (the parent phase) to one between several types of close packed structures (the martensitic phase) [1,2]. These alloys can be used as both sensor and actuators. These interesting properties joined with the relatively low production costs, made this family of alloys candidate for several technological applications [3]. Such as in other alloys based on noble metals, the phase stability is mainly controlled by the concentration of valence electrons, e/a. In the binary CuAl system, Cu and Al atoms contribute to the electronic concentration with 1 and 3 electrons, respectively. In this alloy, a disordered bcc phase is stable at high temperature in the range 1.40 e/a 1.55. As the temperature decreases, this stability range becomes smaller and a eutectoid point is reached for e/a 1.48 at 840 K. Below this temperature, the equilibrium phases are the complex cubic g phase, with stoichiometry Cu9Al4, and the disordered fcc a phase [46]. When cooling from high temperatures with relatively high cooling rates, it is possible to suppress almost entirely the precipitation of stable phases. Under such conditions,

* Corresponding author. IFIMAT Instituto de F sica de Materiales Tandil, Universidad Nacional del Centro de la Provincia de Buenos Aires, Pinto 399, 7000 Tandil, Buenos Aires, Argentina. Tel.: 54 2293 439670; fax: 54 2293 439679. E-mail address: (F. Lanzini). 0966-9795/$ see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.intermet.2008.06.009

the metastable b phase experiences some type of atomic ordering. For compositions close to the stoichiometric Cu3Al, two possible ordering mechanisms have been proposed. Soltys [7] reported the existence of two ordering reactions: the rst one from the disordered bcc A2 to a B2 (ClCs type) conguration at TA24B2 z 973 K, and a B2 / DO3 ordering at TB24DO3 z843 K. However, subsequent investigations [811] have not been able to conrm these results. In fact, XRD measurements [8] indicate the occurrence of a single transition at T z 800 K. Calorimetric and resistometric measurements [9,10] also failed to nd evidence of an additional ordering transition. Indeed, both XRD [8,11] and neutron diffraction measurements [12] indicate that the low temperature phase has DO3 character. Thus, it seems to be well established now that there is a single ordering transition from the disordered A2 to a DO3 state; as will be shown below, the results of the present work support this conclusion. Addition of small quantities of beryllium as third element stabilizes the b phase: Belkhala et al. [13] reported that, for CuAl 0.47 wt.% Be, the temperature of the eutectoid point is around 50 K lower than for the binary CuAl system. On the other hand, Jurado and co-workers [8] have studied the orderdisorder transitions in ternary alloys with low beryllium content and compositions near the eutectoid. They reported a single ordering reaction A2 / DO3 at around 800 K; besides, the ordering temperature does not vary signicantly with the beryllium content. Since the type and degree of long-range order, lro, present in the b phase inuence several properties of this kind of alloys and, in particular, the characteristics of the martensitic transformation [1,2], a deep understanding of all the aspects related to the atomic ordering is necessary.

F. Lanzini et al. / Intermetallics 16 (2008) 10901094


In order to quantify the type and degree of lro, it is convenient to split the general bcc lattice into four interpenetrating fcc sublattices as shown in Fig. 1, and then to dene the occupation probabilities pL X for a given atomic species X (Cu, Al or Be) to be placed in the sublattice L (IIV) [1,14,15]. Whereas in the A2 conguration the atomic distribution is at random,

the DO3 ordered state is characterized by the relationship:

II III IV pI X pX pX spX

Between the various experimental techniques used to study ordering reactions in alloys, the electrical resistometry has the advantage of its relatively simple implementation and high sensibility to changes in the degree of lro. Notwithstanding, there is not a direct way to relate quantitatively the changes in resistivity to the changes in lro; it is necessary to appeal to some theoretical approach, being the best known the one due to Rossiter [16]. In this model, a simple relation between the resistivity r, the degree of lro S, and the temperature T is proposed:

polycrystalline samples used for the resistivity measurements were parallelepiped-shaped between 8 and 13 mm long and (0.2 0.4) (11.8) mm2 in cross-section. Precise dimensional measurements were performed using a micrometer and amplied images of the samples. The electrical resistance was monitored using a standard four-point probe technique. The leads and a chromelalumel thermocouple were spot welded to the sample. A constant current generator was used to drive a current of 100 mA through the sample. A Keithley 186 Nanovoltimeter measured the potential drop across the sample. The specimens were cooled to room temperature from 1000 K, within the b phase eld, at different rates just to avoid precipitation of stable phases. Typical cooling rates were in the order of 120600 K/min. Previous results on continuous cooling experiments with this family of alloys show that, for this range of cooling rates, the fraction of stable phase precipitated is, if any, completely negligible [24,25]. In order to transform the measured resistance data, R, into resistivity r, the former has to be divided by a shape factor, f:

R f

rS; T r0 0

1 S2 B 1 T 1 AS2 n0 1 AS2


In this expression, the parameter S quanties the degree of lro. It is dened in terms of the sublattice occupationspL X and their denition varies according to the particular type of ordered structure under consideration, in such a way that S 0 for the state completely disordered, and S 1 for the state completely ordered in a stoichiometric alloy. The constant A (Rossiter-constant) takes values between 1 and 1, and depends on the electronic structure of the material. The remaining constants, r0 (0) and B/n0, refer to the residual electrical resistivity and the thermal coefcient of resistivity in the completely disordered state, respectively [16]. This model has been successfully applied to various binary [17 22] and ternary alloys [23]. In the present work, we apply the Rossiter formalism to the orderdisorder transitions in CuAlBe; the main parameters of the model are determined from the experimental results, and the evolution with temperature of the lro degree is calculated.

2. Experimental details The study has been performed on samples obtained from elements of 99.99% purity. Their compositions are Cu24.7 at.% Al, Cu 22.72 at.% Al5.5 at.% Be and Cu22.19 at.% Al8.04 at.% Be. The

For the samples used in this work, f [=s, being [ the distance between the points where the voltage drop is measured, and S the (uniform) cross-section area. Even when f can be easily determined at room temperature, special care has to be paid to the possible dependence of f on the order state. From data reported by OchoaLara and co-workers [11] for Cu23.77 at.% Al2.6 at.% Be and Cu 23.18 at.% Al2.62 at.% Be, we can estimate that the relative change in lattice parameter for the A2 / DO3 transition is near 0.2%. Jurado et al. [8] report Da=az0:04% for Cu22.73 at.% Al5.5 at.% Be, Da=az0:03% for Cu22.72 at.% Al3.55 at.% Be, and Da=az0:035% for Cu23.13 at.% Al2.7 at.% Be, being Da=a aA2 aDO3 =aA2 the relative change in lattice parameter between the A2 and the DO3 structures at the transition temperature. In all cases, the dependence of the lattice parameter (and hence of the reciprocal of the geometrical factor f) on the lro degree is within the experimental uncertainty and can then be neglected. Thus, the transformation of the resistance data to resistivity values was performed dividing by a constant f fr as measured at room temperature. Before the measurements on CuAl (Be), we performed resistometric measurements on a binary CuZn alloy. As will be discussed below, the aim of this measurement was to test our experimental method and the Rossiter approach on a well-known orderdisorder transition, as is the case of the continuous A2 4 B2 transition in this system. Measurements were made on a single crystalline sample with composition Cu48 at.% Zn. As long as the ordering reaction does not involve a signicant change in lattice



Fig. 1. Disordered bcc phase (A2) and structure DO3 with order in nearest and next nearest neighbors.


F. Lanzini et al. / Intermetallics 16 (2008) 10901094

parameter [26], the resistance data was transformed into resistivity values dividing by a constant geometrical factor as determined at room temperature. 3. Results and discussion Fig. 2 shows the variation of resistivity for CuAl and CuAlBe, and Fig. 3a the corresponding to Cu48 at.% Zn. Orderdisorder reactions involve a change in the slope of the curve; the critical temperatures are indicated with arrows. The resistivitytemperature curves were analyzed in the framework of the Rossiter theory by means of Eq. (1), which predicts a linear behavior of resistivity with temperature either in the high-temperature disordered state or in the low-temperature completely ordered one:

r0; T r0 0

 B T n0


r1; T

 B 1 T n0 1 A


Performing a linear t to the resistivity data well above the orderdisorder temperature, it is possible to determine both constants r0 (0) and B/n0 through Eq. (2). A similar t in the range of temperatures sufciently below the ordering one allows determining the value of parameter A, using Eq. (3) for stoichiometric alloys, or Eq. (1) with S Smax for off-stoichiometry. Once the
Fig. 3. (a) Resistivity against temperature for Cu48 at.% Zn; (b) evolution of the order parameter S as calculated from resistivity data (black dots) and from neutron scattering [20] (open circles).

former constants are determined, it is possible to invert Eq. (1), and then an expression for the variation of the order degree with temperature is obtained:


r0 0 rT B=n0 T r0 0 ArT



Fig. 2. Resistivity against temperature for (a) Cu24.7 at.% Al (the inset shows the variation of resistivity over a wider interval of temperatures, where it is appreciable the start of the martensitic transformation); (b) Cu22.72 at.% Al5.5 at.% Be; (c) Cu 22.09 at.% Al8.04 at.% Be.

In order to test the quality of this approach, we applied it to the transition A2 / B2 in Cu48 at.% Zn. This transition is a paradigmatic, widely studied, case of continuous transition, i.e., characterized by a continuous variation of the order parameter below the critical temperature. Fig. 3b shows the evolution of the order parameter against temperature as calculated from resistivity data by means of Eq. (4), with parameters A 0.36 and B/n0 2.28 108 U cm/K. In Fig. 3b are also included, for comparison, values of S as a function of temperature obtained from neutron scattering experiments [27]. As can be seen, Rossiter formalism correctly accounts for the continuous character of the transition and satisfactorily reproduces the evolution of lro below the transition temperature. Fig. 2 shows the resistivity curve for binary Cu24.7 at.% Al and two similar ternary alloys with low beryllium content. The measurements show evidence of a unique ordering transition at T z 800 K. For Cu24.7 at.% Al, the starting of the martensitic transformation at a temperature Ms z 620 K is also detected (inset in Fig. 2a). Linear ts of the resistivity curves at temperatures well above and below the ordering temperature lead to the values for the Rossiter parameters indicated in Table 1. In our analysis, we have assumed that the ordering reaction can be described by means of a unique lro parameter, S. This assumption is generally not true in ternary alloys, where the occupation probabilities for two of the three atomic species are independent. However, as long as

F. Lanzini et al. / Intermetallics 16 (2008) 10901094 Table 1 Composition of the alloys, ordering temperatures and values obtained for the Rossiter parameters CCu (at.%) 75.3 71.78 69.77 CAl (at.%) 24.7 22.72 22.19 CBe (at.%) 0 5.5 8.04 TA2 /DO3 (K) z810 z815 z820 A z0 z0.53 z0.75 B/n0 (U cm/K) 1.96 (3) 108 2.04 (2) 108 2.47 (3) 108


beryllium content is low, our ternary system can be treated as a quasi-binary one; this hypothesis is additionally justied since Be atoms distribute uniformly among the different sublattices [8]. Consequently, the order parameter S is dened in terms of the occupation probabilities for Al or Cu atoms. Furthermore, we will assume that S is dened in such a way that takes a maximum value of 1, independently of composition. The detailed way in which S is dened is not crucial in the analysis performed here, but affects the numerical value of the Rossiter-constant, A. In Fig. 4a the evolution of S with temperature for Cu24.7 at.% Al is shown. As can be seen, at the transition temperature, the order parameter experiences an almost sudden change from the value 0 in the disordered state to its maximum value. This discontinuity is characteristic of the rst order kinetics of the ordering reaction. On the other hand, the variation of the order parameter for Cu 22.19 at.% Al8.04 at.% Be (Fig. 4c) shows a continuous increment below the orderdisorder temperature. This behavior resembles that observed in CuZn (Fig. 3b), and is distinctive of a continuous

transition. Finally, for Cu22.72 at.% Al5.5 at.% Be (Fig. 4b) an intermediate situation occurs: there is a discrete jump in the order parameter at the transition temperature followed by a smooth increase as the temperature is reduced. This is an outstanding result if we take into consideration that previous works with this family of alloys [8] seem to indicate that the transition is rst order in the whole range of compositions studied here. This conclusion has been partially supported by arguments based on the Landau theory of phase transitions: according to some analysis based on this theory, the A2 / DO3 transition is necessarily rst order [10,28]. However, this assertion has been questioned by other authors [29,30]. In fact, calculations made within the BraggWilliams Gorsky approximation [14], and in the tetrahedron approximation of the cluster variation method [29], show that, for certain values of the interaction parameters, the A2 / DO3 transition could be second order. These calculations seem to be in accordance with the present results.

4. Conclusions Electrical resistivity is a very sensitive indicator of the degree of long-range order present in a given alloy system. We have shown that, when resistivity data is analyzed in the framework of the Rossiter formalism, it is possible to calculate the evolution of the lro degree in a very simple way. Results obtained by applying this method to the well-known A2 4 B2 transition in CuZn agree quite well with those obtained with more elaborated techniques. The remarkable advantage of this method is the comparatively easier implementation of resistometric techniques as compared to other methods (for example, X-ray or neutron diffraction). Also, it is worth noting that the rate of data acquisition is higher for an electrical resistometry measurement than for an X-ray or neutron diffraction measurement: this is a very important advantage when working with metastable phases, where it is generally necessary to use high cooling rates in order to avoid phase decomposition. In this work, the temperature dependence of resistivity for a set of CuAl and CuAlBe alloys has been measured. Orderdisorder temperatures were determined from these measurements: ordering temperatures are around 800 K and do not show a signicant dependence on composition. The changes in resistivity were related to changes in the degree of long-range order by means of the Rossiter formalism; the main parameters involved in this theory were determined (Table 1), and the resistivity variation was transformed into changes in the order parameter S. The A2 / DO3 transition in Cu24.7 at.% Al has rst-order character: the lro parameter S suffers a nite jump, reaching its maximum value in a small interval of temperatures below the transition (Fig. 4a). The magnitude of this discontinuity becomes smaller as small quantities of beryllium are incorporated (Fig. 4b), and the maximum degree of order is attained after a subsequent cooling of about 300 K. With further increase in the beryllium content (Fig. 4c), traces of a discrete step in the order parameter do not remain, and the transition is seemingly a continuous one. This last result is in contradiction with previously published ones; complementary investigation will be necessary in order to clarify this point.

Acknowledgements The authors acknowledge the nancial support of the Agencia n Cient ca y Tecnolo gica, Conicet, Secretar a Nacional de Promocio cnica (UNCentro), Argentina and Comisio n de de Ciencia y Te cas de la Provincia de Buenos Aires. We are Investigaciones Cient thankful to Dr. A. Planes for providing the alloys used in this work.

Fig. 4. Evolution with temperature of the order parameter as determined from resistivity measurements for: (a) Cu24.7 at.% Al; (b) Cu22.72 at.% Al5.5 at.% Be; (c) Cu22.19 at.% Al8.04 at.% Be. Insets: comparison with the XRD data extracted from Ref. [8] (open symbols).


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