Scripta METALLURGICA et MATERIALIA

Vol.

28, pp. 1417-1421, 1993 Printed in the U.S.A.

Pergamon Press Ltd. All rights reserved

ORIGIN OF THE TWO-WAY MEMORY EFFECT IN NiTi SHAPE MEMORY ALLOYS P.Y. Manach and D. Favier GEnie Physique et M~canique des Matrriaux (U.R.A. CNRS 793) Ecole Nationale Suprrieure de Physique de Grenoble Institut National Polytechnique de Grenoble BP.46, 38402 Saint Martin d'H~res Cedex (France)
(Received March 22, 1993)

Introduction It is now well-known that the two-way memory effect (TWME) of shape memory alloys is obtained after a thermomechanical cycling called training. Although this point is well-admitted, many controversies still subsist on the physical origin of this two-way memory effect. The explanations of the development of the TWME which are often given (1) are either the presence after training of a low proportion of local stabilised martensite in the parent phase or the presence after training of an internal stress field in the material. Recently, in a systematic study of the two-way memory effect obtained by thermomechanical training cycles under homogeneous tensile constant load, Stalmans et al (2,3) disproved these two previous explanations. Following their study, the most important effect of the dislocation arrays which are introduced during the training is not to develop internal stresses but rather to give rise to a microstructural anisotropy inducing a thermodynamic anisotropy. It means that after training, the crystallographically equivalent martensite variants are no more thermodynamically equivalent. The present paper describes some experimental results obtained by the homogeneous simple shear training of a NiTi shape memory alloy. The experiments have been specifically designed to give new comprehension elements on the existence and the nature of the thermodynamic anisotropy developed during training. Experimental orocedure The material used in this study was a commercial Ti-50.2 at % Ni alloy supplied by Cezus (Pechiney, France) in the form of 0.5mm sheet fabricated by several cold rolling steps with intermediate heat treatments at 973K for 300s in an argon atmosphere. A differential scanning calorimetry (DSC) measurement gave the transformation enthalpy AH=-17J/g and the following transformation temperatures : Ms=276K, Mf=260K, As=293K and Af=305K. The experimental study was carried out with simple shear mechanical tests on a hydraulic tension-compression device. The shear strain rate was 10.4 s-1. The temperature was controlled by a cryothermostat which regulated the temperature of a silicon oil bath, in the range of 243 to 373K. The temperature was measured by a thermocouple (accuracy 0.1K) connected to the sample and the maximum heating and cooling rate was 1K/min. The shear tests were performed on a shearing machine developed specifically for the present tests. The specimens were cut in a sheet of thickness e=0.5mm with a rectangular shape Lxl=30x18mm 2 ; the width h of the shearing zone was 3mm. Shear stresses and strains were defined by using the conventional expressions : x=F/eL and y=AL/h. To calculate the shear strain, the displacement of the grips zkL was given by a linear variable differential transformer directly connected to the grips. The accuracy of the measurement on the shear strain "/is of the order of 10.4 (4,5).

1417 0956-716X/93 $6.00 + .00 Copyright (c) 1993 Pergamon Press Ltd.

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Results The thcrmomechanical training consists in 20 sequences, each of them composed fLrSfly of a heating to 363K (>Af) without applied load, followed by a cooling to 285K (>Ms) and secondly by an isothermal deformation up to a shear strain of y=5% followed by unloading, Fig.1. The isothermal deformation involves the stress-induced martensitic transformation and the heating produces the one-way shape memory effect ; it should be noted that the subsequent cooling is not sufficient to produce the martensitic transformation. The deformation is always evaluated between the current state and the initial state before any test ; therefore the deformation at the starting point of each isothermal loading curve is the residual deformation after the shape memory effect has occurred. The evolution of the residual deformation is relatively weak, the value being equal to 0.2% after the fast cycle and to 0.475% after the twentieth cycle. The critical stress to induce the martensitic transformation is about 45MPa after the fast cycle and reaches 68MPa after the last one. The maximum stress corresponding to y=5% is of the order of 90MPa for the last cycle. The TWME obtained by this training is represented on the straintemperature curve Fig.5.a ; in this first case, its value is equal to 2.8%. In order to characterise the trained material, the sample was then subjected to a unique centred superelastic cycle in an initial austenitic state at T=313K between 7=5% and "/=-5%, Fig.2. The TWME was then measured to check that it has not been erased by the superelastic cycle, Fig.5.b. On the same sample, a second identical training was then performed, the shearing direction being reversed ; the stress-strain curves during the training are presented Fig.3, the deformation being still estimated between the current state and the initial state before any test of the fast training. The observed mechanical behaviour is different from the one observed during the first training, i.e. the material shows a cyclic softening behaviour, the critical stress to induce the martensitie transformation being about -80MPa for the first cycle and -64MPa for the last one. Similarly, the stress corresponding to 7=-5% decreases as a function of the number of training cycles ; for the last cycle, this value is equal to -92MPa, i.e. the behaviours during the stabilised last cycles of both trainings are very similar. For the last cycle, the residual deformation after the shape memory effect has occurred is -0.5%. Once again this value is close to that obtained during the first training. The TWME developed by this second training is presented Fig.5.c. As after the fast training, a superelastic centred cycle was performed between 7=-5% and 7=5% in an initial austenitic state at T=313K, Fig.4. The TWME after this superelastic cycle is presented Fig.5.d. Discussion The main advantage of simple shear mechanical tests is that they allow to study cyclic or reversed deformations and ensure (if the condition width<<length is fulfilled (6)) that the deformation is homogeneous throughout the gauge length. Compared to push-pull tests, it is possible to get really symmetric cyclic tests because the shearing of the same isotropic specimen in the two opposite directions is indeed equivalent. If asymmetrical cycle is obtained, it is only due to the thermomechanical history. This is not the case for push-pull tests for which the tensile and compressive behaviours may differ even for an isotropic material (7). For shape memory alloys, a last advantage of studying TWME in simple shear is that there is no artefacts due to thermal dilatation. I~volution of the TWME. Our discussion is first focused on the values of the TWME developed by the two previous u'ainings, i.e. on the strain-temperature curves of Fig.5.a and Fig.ft. The "INVMEobtained after the first training is 2.8% which gives a ratio with respect to the imposed deformation of 56%. After the second training, the TWME is 2.6% ; this value is a few lower than the first one but of the same level. This result shows that it is possible to train in another direction, a specimen which has been previously trained in a first direction, the discrepancy between the two obtained TWME being weak. The second point concerns the stability of the obtained TWME. After one superelastic cycle the TWME is still present but significandy lowered, Fig.5.b and Fig.5.d. The loss of the TWME is not very high, about 22% for the first training and about 16% for the second one. It should be noted lastly that the stress during the superelastic cycle is too high to have no influence on the magnitude of the TWME and secondly that this loss could bc

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certainly decreased by increasing the number of training sequences. However, the TWME loss is low enough to consider that the behaviour observed during the superelastie cycle is characteristic of the trained material. ~ld~Lliff,.~. The presence of residual martensite in the parent phase is less and less considered as the main origin of the TWME. Indeed, the training produces an increase of the stabilised martensite but those martensite remnants which subsist above Af can be removed by an overheating at higher temperature, without a significant effect on the magnitude of the TWME. This results have been firstly established by Contardo et al (8) on a CuZnA1 sample trained by bending and established by Stalmans et al (3) on NiTi sample trained by tension. In the following, this hypothesis is no more considered. All the other hypotheses are based on the fact that during training, there is a progressive development of dislocation arrays (1). If it is assumed that these dislocations have created an internal stress field, then, during cooling, this stress field should prevent the self accommodation of martensite variants and produces in that way a macroscopic deformation, i.e. the TWME. A way to check the existence of this field is to analyse the experimental results obtained during the superelastic cycles. Indeed, according to Patel et al (9) and to Ortin et al (10), during a superelastic deformation the local value of the required stress to induce the martensitic transformation is detemained by a local thermodynamic balance. From a macroscopic point of view, if an oriented internal stress field exists, the external stress required to induce the martensitic transformation during this superelastic cycle has thus to be lower for the training direction than for the opposite one. This is well observed after both trainings on Fig.2 and Fig.4. However, this conclusion assumes that the frictional energies are the same for all the martensite variants. One way to estimate the various energetic terms which are involved in the thermodynamic balance is to express the total external stress as the addition of two partial stresses, the In,st one being reversible and the second one being irreversible of frictional (10,11) or hysteretical type (12). The estimated reversible stress contribution is plotted using dashed line on the curves of Fig.2 and Fig.4 ; for deformations between 7=-3% and %'=3% the reversible contribution is estimated by the line obtained in drawing the average of the loading and unloading branches. Between 7=3% and y=5% (respectively y=-3% and y--~5%), it is assumed that the hysteresis (or frictional) contribution is constant during the martensitic transformation. In both cases, the shapes of the superelastic cycles are highly asymmetrical. However, if the TWME was only due to the existence of an internal stress field, this field should only increase the level of the reversible stress in the opposite direction compared to the trained direction. Indeed, internal stresses act like steady obstacles which favour the deformation in a specific direction and impede the deformation in other directions. Furthermore they do not create any friction between the martensite variants ; this means that we should get the same hysteresis for the positive and negative deformations. The curves of Fig.2 and Fig.4 show that the average value of the reversible stress contribution is nearly symmetrical in both cases, the discrepancy between positive and negative values being less than 10MPa. This result shows that internal stresses exist and that they may participate weakly to the development of the TWME ; however the fact that the width of the loops of the superelastic cycles is highly asymmetrical shows that they are not the main phenomena. An other explanation consists of considering that these dislocation arrays are not only a source of internal stresses. From the shape of the reverse cycle, we may suggest that these dislocations create an important friction for the variants which have not been activated during the training. In order to form during cooling, the disadvantaged variants have to overcome this friction energy. It becomes thus thermodynamically more difficult to obtain during cooling the self accommodation of the martensite variants ; the thermodynamic anisotropy suggested by Stalmans et al lies in the development during training of friction barriers which are not the same for all martensite variants. This effect contributes significantly to the TWME. Conclusion From a study of the TWME developed by thermomechanical training in simple shear of a NiTi shape memory alloy, the following results have been established : 1) if a specimen has been ftrstly wained in one direction, it can be retrained in another direction without any significant incidence on the magnitude of the TWlVIE ;

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2) the presence of an internal stress field after lr~ining has only a weak influence on the development of the TWlvIE. As it has been previously suggested by Stalmans et al (3), the dislocation arrays introduced by training create not only internal stresses but also a thermodynamic anisotropy. Our results show that this anisotropy is due to the friction energy which is after training no more equal for all martensite variants.

The authors are grateful to the STPA (Service Technique des Programmes Ah-onautiques) of the French Minisu'y of Defence France, for financinl support on the contract 90-96011-(X)-471-75-96. The authors acknowledge E. Ranch from G6nie Physique et M6canique des Mathiaux and Y. Liu, P.G. McCormick of the University of Western Australia for useful discussions. ]~eferences 1. I. Perkins and R.O. Sponholz, Metall. Trans., 15A, 313 (1984). 2. R. Stalmans, J. Van Humbeeck and L. Delaey, Acta Metall. Mater., 40, 501 (1992). 3. R. Stalmans, J. Van Humbeeck and L. Delaey, Acta MetaU. Mater., 40, 2921 (1992). 4. P.Y. Manach and D. Favier, Proc. Int. Conf. on Martensitic Transformations, (1992). 5. P.Y. Manach, thSse de doctorat, Insfitut National Polytechnique Grenoble, France, (1993). 6. E. Ranch and C G'SelI, Mater. Sci. Engng., A111, 71 (1989). 7. Y. Liu and P.G. McCormick, Proc. Int. Conf. on Constitutive Laws for Engng. Mater.,(1990). 8. L. Contardo and G. Gu6nin, Acta MetalL Mater., 38, 1267 (1990). 9. J. R. Patel and M. Cohen, Acta Metall., 1,531 (1953). 10. J. Ortin and A. Planes, Acta MetaU., 37, 1433 (1989). 11. K. Otsuka, C.M. Wayman, K. NakaJ, H. Sakamoto and K. Shimizu, Acta Metall., 24, 207 (1976). 12. D. Favier, P. Gu61in and P. PSgon, Proc. Int. Conf. on Martensitic Transformations, 559 (1989).

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FIG.I : First training ; shear stress-shear strain curves obtained at Tffi285K during isothermal shearing tests.

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FIG.3 : Second u'ninlng in the opposite direction ; shear stress-shear strain curves obtained at T=285IC

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NiTi SHAPE MEMORY

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FIG.4 : Shear stress-shear strain curve obtained after the second training at T=313K during a superclastic simple shear cycling between y=-5% and 7=5%.

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FIG.5 : Shear strain-temperature curves obtained in simple shear during a thermal cycling between T = 253K and 363K a) after the first training, b) after the first supcrclasfic centred cycle, c) after the second training and d) after the second supcrclastic centred cycle.