Metal Science and Heat Treatment

Vol. 47, Nos. 5 6, 2005

NANOSTRUCTURAL STATE OF ALLOYS

UDC 669.295.524

CREATION OF SUBSTRUCTURE AND NANOSTRUCTURE IN THERMOMECHANICAL TREATMENT AND CONTROL OF FUNCTIONAL PROPERTIES OF Ti Ni ALLOYS WITH SHAPE MEMORY EFFECT
S. D. Prokoshkin,1 V. Brailovskii,1 I. Yu. Khmelevskaya,1 S. V. Dobatkin,1 K. . Inaekyan,1 V. Yu. Turilina,1 V. Demers,1 and E. V. Tatyanin1
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 5, pp. 24 29, May, 2005.

The effect of various modes of thermomechanical treatment, including intense plastic deformation and postdeformation annealing, on the structure, mechanical, and functional properties of alloys based on titanium nickelide is investigated. The advantages of intense plastic deformation with annealing are shown as compared with traditional thermomechanical treatment.

INTRODUCTION Alloys with shape memory effect (SME) attract the attention of researchers, technologists, and designers due to their functional properties permitting realization of operational possibilities of structures and devices unattainable with the help of other materials and technologies [1 4]. The main functional properties of SME alloys are the characteristics of shape recovery (maximum fully reversible deformation, degree of recovery of shape), the characteristic temperatures of the range of martensitic transformations (Mi , Mf , Ai , Af determining the respective intervals of easy deformation that induces the effect of shape memory and regeneration of shape), stability of the temperatures, which is important for parts serving under conditions of heat cycles, the reactive stress (appearing under conditions of shape regeneration under external counteraction), the force characteristics of the superelastic behavior, etc. SME alloys based on titanium nickelide (nitinol) find wide application in modern engineering (aircraft, spacecraft, household, mechanical, instrument, etc.) and in medicine
1

Moscow State Institute for Steel and Alloys (Technological University), Moscow, Russia; A. A. Baikov Institute for Metallurgy and Materials Science of the Russian Academy of Sciences, Moscow, Russia; Institute for High-Pressure Physics of the Russian Academy of Sciences, Troitsk, Moscow Region, Russia; Higher Technological School, Montreal, Canada.

[1 8]. In addition to the best combination of functional properties these alloys possess a high corrosion resistance in liquids and human tissues and biological compatibility, which explains their application in medicine. The set of functional properties cannot be controlled for the solution of specific practical problems only by changing the chemical composition of alloys. Since the functional properties of SME alloys are structurally sensitive, they are controlled by various modes of heat treatment (quenching, aging, thermocycling) and thermomechanical treatment [high-temperature (HTTT), low-temperature (LTTT), thermomechanical cycling]. The treatment parameters are varied, for example, the temperature and time of the hold, the degree and temperature of deformation, as well as the phase and structural states in which the deformation in performed [9 13]. Low-temperature thermomechanical treatment with postdeformation annealing (PDA) is widely used for SME alloys based on Ti Ni due to the relative simplicity of the process and efficiency of control of the functional properties. The aim of the present work2 was to perform a comparative study of the structure and functional properties formed as a result of LTTT with traditional (e = 0.30 0.88) and intense (e = 1.9) plastic deformation and subsequent annealing in alloys based on Ti Ni.
2

E. Bastarash from the Higher Technological School, Montreal, Canada, participated in the work.

182
0026-0673/05/0506-0182 2005 Springer Science + Business Media, Inc.

Creation of Substructure and Nanostructure in Thermomechanical Treatment

183

METHODS OF STUDY We performed LTTT in the following modes: cold rolling with changing the true deformation within e = 0.30 1.9 and postdeformation annealing in the temperature range of 200 700C. We studied the structure and functional properties of alloys Ti 50.0% Ni and Ti 50.7% Ni.3 These are typical representatives of SME alloys; the former high-temperature alloy is used as a material for temperature-sensitive elements and the latter low-temperature alloy is used in medicine. We studied the mentioned SME alloys with the help of standard methods (mechanical testing for tensile strength at various temperatures for determining the deformation behavior, differential scanning calorimetry for determining the temperatures of martensitic deformations) and special methods for determining the maximum reactive stress generated under the conditions of realization of SME in a mandrelforced specimen (the tests were performed in an original test installation developed by A. V. Korotitskii, MISiS) and the maximum reversible SME deformation by the method of bending of specimens around mandrels. RESULTS AND DISCUSSION We should differentiate between LTTT with deformation of martensite (LTTTm ) and LTTT with deformation of stable B2-austenite (LTTTa above the point Md but below the temperature threshold of recrystallization). A comparative study of LTTT with deformation of martensite and austenite was performed for alloy Ti 50.7% Ni [3, 13]. Substantial differences were established in the kinetics of structural processes that occur in heating after LTTT. In the initial state after LTTTm (e = 0.30) we observed a structure of strongly strained martensite with very high dislocation density (about 1011 cm 2 ). Directly after LTTTa (e = 0.30) the austenite had a high density of dislocations distributed uniformly or forming a substructure of a cellular type. At the same time, the dislocation density was much lower than in the case of deformation of martensite. This also led to a lower accumulated deformation energy, which is the driving force of the softening processes during the postdeformation treatment (PDT). Indeed, a comparative x-ray and electron microscopic study showed that the structural processes of postdeformation softening in alloy Ti 50.7% Ni (return, formation of cells, and recrystallization) during PDT after LTTTm developed much faster than after LTTTa . In the second case (as compared with the first one) the temperature ranges of these processes were shifted to the higher side by 50 100C. However, we did not observe substantial difference in the maximum fully reversible deformation after LTTTm and after LTTTa with annealing at 400 700C in [12, 13]. In
3

Here and below in the text the content of elements is given in atomic fractions expressed in percent.

this connection we will now consider LTTTm as the initial treatment, which is more manufacture adaptable than LTTTa and makes it possible to collect more information and obtain a wide spectrum of structures before PDT. As a result of LTTT (rolling at room temperature) of alloy Ti 50.0% Ni with low degrees of deformation (e = 0.30) a developed dislocation structure arises in martensite (see Fig. 1a). Postdeformation annealing causes reversible martensitic deformation and development of softening processes in austenite, i.e., return, formation of cells, and recrystallization (see Fig. 1b d ). In the processes of annealing at a temperature of up to 350C a return substructure and cells form in austenite [the size of the polygonal cells (subgrains) is 40 100 and 200 400 nm after PDT at 300 and 350C, respectively]. The amount of martensite formed in cooling after PDT is low and does not exceed 30%. PDT at 450C causes recrystallization of austenite with markedly increased temperature Mi , which is responsible for abrupt growth in the martensite content. It is important to note that the formation of cells in alloy Ti 50.7% Ni in PDT after LTTTm with the same degree of deformation (e = 0.30) begins only at 400C and ends fully at 450 500C, whereas recrystallization ends in PDT performed at 550 600C [3, 13]. Thus, the processes of softening in alloy Ti 50.7% Ni with nickel content exceeding the equiatomic amount are decelerated relative to the equiatomic alloy Ti 50.0% Ni, and the temperature delay amounts to 150 200C. This deceleration is explainable by the barrier action of dispersed particles of the Ti3Ni4 phase segregated in the aging alloy Ti 50.7% Ni (in contrast to the nonaging alloy Ti 50.0% Ni) [2, 3] on the migration of dislocations, subboundaries, and boundaries in austenite. Intense segregation of particles of Ti3Ni4 in the hardened alloy occurs in annealing at 350 500C [2, 3]. In the deformed alloy intense segregation of particles hindering the processes of structural softening begins earlier [3]. Growth in the degree of deformation at LTTT to e = 0.88 causes formation of nanocrystalline and amorphous structures in alloy Ti 50.0% Ni in addition to a developed dislocation substructure. PDT at a temperature of up to 350C causes cell formation, growth of grains in the nanocrystalline structure, and nanocrystallization of amorphous regions in austenite. The beginning of cell formation is noticeable already at 250C due to the high accumulated energy of deformation in LTTT with e = 0.88. After PDT at 450C austenite possesses only a recrystallized grain structure. The transition to intense plastic deformation in LTTT (e = 1.9) leads to a substantial change in the structural state and, correspondingly, in the softening processes of alloy Ti 50.0% Ni during the LTTT as compared to LTTT with e = 0.30. As a result of deformation with e = 1.9 the formed structure has a mixed nanocrystalline and amorphous nature (see Fig. 1e). The nanocrystalline regions are quite dispersed (2 8 nm) and form continuous fields or are distributed randomly in an amorphous structure. PDT at 300C causes

184

S. D. Prokoshkin et al.

0.2 mm

0.2 mm

0.2 mm

0.2 mm

0.2 mm

200 nm

0.2 mm h

200 nm

Fig. 1. Structure of alloy Ti 50.0% Ni subjected to LTTT and postdeformation annealing. Transmission electron microscopy: a) LTTT (e = 0.30); b ) LTTT (e = 0.30) + PDT at 300C; c) LTTT (e = 0.30) + PDT at 350C; d ) LTTT (e = 0.30) + PDT at 450C; e) LTTT (e = 1.9); f ) LTTT (e = 1.9) + PDT at 300C; g ) LTTT (e = 1.9) + PDT at 350C (dark field image); h ) LTTT (e = 1.9) + PDT at 400C.

growth of nanograins and nanocrystallization of the amorphous structure, as a result of which the grain size attains 3 20 nm (Fig. 1f ). Remnants of the amorphous structure can be seen too. Electron diffraction patterns exhibit diffracting rings corresponding to a B2 structure and consisting of very fine superimposed point reflections. Features of mar-

tensitic structure can be encountered. PDT at 330C does not cause substantial changes in the structure, but the nanograins grow, the remnants of the amorphous structure disappear, and weak reflections of martensite appear. After PDT at 350C the grain structure remains in the region of nanosizes but acquires a bimodal nature; a part of

Creation of Substructure and Nanostructure in Thermomechanical Treatment

185

the grains preserves the size of 5 25 nm and the other part grows to 30 80 nm (Fig. 1g ). Martensite forms in the larger austenite grains. After PDT at 400C (most intense from the standpoint of the combination of functional properties) the size of austenite grains increases to 20 120 nm (the major part of them has a size of 50 80 nm); the amount of martensite increases (Fig. 1h ). As a result of PDT at 500C austenite grains grow to 200 600 nm, remaining much finer than after deformation with degrees e = 0.30 and e = 0.88. Martensite forms in many grains. Treatment consisting of LTTT + PDT at 700C was chosen as the control, because the structure of austenite in this case was fully recrystallized with normal size (tens of mm) of grains of austenite transformed into martensite. It should be noted that Ti 50.0% Ni alloy (in contrast to Ti 50.7% Ni one) is prone to strong phase hardening in the course of martensitic transformations [3, 14]. Therefore, if the amount of martensite is high, the structure is characterized by a high density of phase hardening dislocations. Thus, the processes of structural changes in alloy Ti 50.0% Ni during PDT after LTTT with conventional degrees of deformation (e = 0.30 0.88) and with a superhigh degree of deformation (e = 1.9) differ. Immediately after the deformation with degree e = 0.30 we observe a developed dislocation substructure due to strain hardening. In the process of PDT such substructure acquires cells and then recrystallizes. As a result of plastic deformation (e = 1.9) the formed structure has a mixed nanocrystalline and amorphous nature. In this case PDT causes crystallization of the amorphous structure and turns it into a nanocrystalline one, and the grains of the nanocrystalline structure (formed both due to deformation and due to crystallization of the amorphous structure) grow, remaining in the nanosize range until 400C. After LTTT with e = 0.88 we observe both a developed dislocation substructure and an amorphous structure. It is obvious that each of these structures develops in PDT according to its own law until the beginning of recrystallization in the regions with cells, which wipes off the nanocrystalline structure. Let us consider the effect of the structure formed as a result of LTTT with PDT on the characteristic temperatures and on the succession of martensitic transformations in the studied alloys. Under conditions of conventional hardening and subsequent heating the processes of direct and inverse martensitic transformations occur in different succession, i.e., B2 B19 (Ti 50.0% Ni) and B2 R B19 (Ti 50.7% Ni). The presence of developed substructure in the austenite of alloy Ti 50.0% Ni after LTTT with degrees e = 0.30 and e = 0.88 and annealing at 200 500C leads to a change in the succession of the transformations, i.e., the direct transformation occurs through an intermediate R-phase. In the most hardened state corresponding to LTTT with PDT at 200 300C the range of the B2 (R ) B19 martensitic transformation is smeared toward lower temperatures. After

LTTT with PDT at 350 400C the transformations B2 R and R B2 separate fully from the transformations R B19 and B19 R. After LTTT with degree e = 1.9 and PDT the B2 (R ) B19 transformation is suppressed up to the annealing temperatures of 350 400C, and the temperatures of formation of the R-phase in cooling and heating are virtually constant. The R-transformations in alloy Ti 50.7% Ni are separated from the other transformations after any mode of LTTT + PDT, and the separation is higher than in alloy Ti 50.0% Ni at the same PDT mode. This seems to be promoted by the formation of the Ti3Ni4 phase, which has a rhombohedral lattice with negative rhombohedral distortion of the cube (compression over the 111 austenite axis), accompanying the annealing. The fields of elastic distortions due to the segregated coherent particles of the Ti3Ni4 phase promote formation of an R-phase, which has a positive rhombic distortion (stretching over the 111 austenite axis) [2, 3]. With growth in the PDT temperature the separation of the R-transformation becomes less manifested. Let us consider the effect of LTTT + PDT modes on the value of maximum fully reversible strain e max (where the r, 1 subscript 1 is used to indicate that the degree of shape regeneration is equal to 1), on the maximum reactive stress s max , r and on the superelastic mechanical behavior of the alloys. Decrease in the PDT temperature after LTTT increases the true yield strength of austenite and martensite and the phase yield strength of austenite and the R-phase (or the critical stress of reorientation of martensite). The variation of the phase yield strength of austenite with variation of the PDT temperature obeys the Clausius Clapeyron relation, in accordance with which the minimum stress of formation required for the beginning of martensitic transformation should lie close to the point Mi (the temperature of formation of B19 martensite in cooling) [2]. Growth in the degree of deformation during the initial LTTT of the equiatomic alloy promotes the appearance of the effect of superelasticity after PDT at low enough temperatures. In a hardened or recrystallized (as a result of PDT at 700C) state this alloy does not exhibit superelasticity. Increase in the degree of preliminary deformation in LTTT to e = 1.9 with subsequent annealing at a temperature of up to 400C lowers markedly the point Mi and widens the range of manifestation of superelasticity to lower temperatures. The observed effects are a consequence of widening of the interval between Af and M is upon growth in the retained hardening due to LTTT [1 3] (here Af is the temperature at which the reverse martensitic transformation ceases and M is is the temperature of the beginning of direct martensitic transformation under load). Alloy Ti 50.7% Ni is more prone to manifesting superelasticity, which is observed in the same and rather wide range after LTTT with deformation of degrees 0.30 and 0.77 for the same PDT temperatures.

186
max er, 1 , %

S. D. Prokoshkin et al.

10 8 6

1 2

4 2 0 200 300 400 500 600 700

tained after LTTT with e = 0.30 0.77 at PDT temperatures ranging from 400 to 500C. The alloy acquires a cellular substructure [3, 13]. The dependence of the maximum reactive stress s max for r alloy Ti 50.0% Ni as well as the dependence of the maximum fully reversible strain on the PDT temperature has an extremum (Fig. 3). The maxima on the curves e max (tPDT ) r, 1
tPDT , C

Fig. 2. Dependence of maximum fully reversible strain e max of alr, 1 loy Ti 50.0% Ni on the PDT temperature after LTTT with deformation of degree: 1 ) e = 0.30; 2 ) e = 0.88; 3 ) e = 1.9.

srmax P ,
1600 1200

and s max (tPDT ) correspond to the same temperature ranges r of PDT. Growth in the degree of deformation in LTTT from 0.30 to 0.88 increases the value of the maximum reactive stress developed by the alloy after optimum PDT. The transition to LTTT with e = 1.9 makes it possible to obtain very high values of s max (over 1400 MPa, Fig. 3) afr ter PDT. Thus, the best combination of functional properties of alloy Ti 50.0% Ni (maximum values of e max and s max ) is r, 1 r formed as a result of thermomechanical treatment including LTTT with intense plastic deformation (e = 1.9) and causing the formation of a nanocrystalline structure (with the mean grain size of 50 80 nm) as a result of PDT at 400C. Realization of this high set of functional properties combining the highest values of reversible strain and reactive stress can be explained by special features of the nanocrystalline structure that appears in annealing after intense plastic deformation. Annealing at 400C after LTTT with e = 1.9 ensures a very high value of conventional (dislocation) yield strength of austenite due to formation of nanosize grains with specific fineness (50 80 nm). The growth in the dislocation yield strength promotes prevention of conventional plastic yield due to deformation inducing the shape memory effect and thus increases the margin of fully reversible strain. On the other hand, the dislocation yield strength serves a measure of maximum reactive stress. At the same time, when describing the entire cycle deformation shape recovery and deformation generation of reactive stress we should take into account the resistance to the inverse motion of interphase and intercrystallite boundaries that are carriers of reversible strain. The nanostructure formed as a result of LTTT with e = 1.9 and PDT at 400C does not contain a developed dislocation structure. In this connection, barriers hindering the inverse motion of carriers of reversible strain within grains are virtually absent, which ensures the fullest realization of shape recovery or reactive stress. PDT at higher annealing temperatures causes grain growth, the corresponding softening, and lowering of the set of functional properties. Decrease in the PDT temperature to 350C suppresses the martensitic transformation proper due to the too fine grain size of austenite despite the fact that it causes higher hardening of austenite than PDT at 400C. It has been shown in [15] that martensitic transformation in a Ti Ni alloy is suppressed when the grain size is less than 50 nm. For example, the maximum fully reversible strain after LTTT with e = 1.9 and PDT at 350C is much lower than after PDT at 400C at the same value of maximum reactive

1
800

2
400 0 200

300

400

500

600

700

tPDT , C Fig. 3. Dependence of maximum reactive stress s max of alloy r Ti 50.0% Ni on the PDT temperature after LTTT with deformation of degree: 1 ) e = 0.30; 2 ) e = 0.88; 3 ) e = 1.9.

As we have mentioned, the most important characteristics of the shape memory effect are the maximum fully reversible strain e max and the reactive stress s max . r, 1 r The maximum value of the fully reversible strain e max of r, 1 alloy Ti 50.0% Ni subjected to LTTT with optimum annealing exceeds considerably the value of e max after control r, 1 treatment (PDT at 700C) (Fig. 2). Growth in the degree of deformation in LTTT within e = 0.30 0.88 does not increase the maximum fully reversible strain of alloy Ti 50.0% Ni; after LTTT with e = 0.30 and PDT at 300 and 350C with e = 0.88 and PDT at 350 and 400C the maximum value of fully reversible strain e max = 6.5 7.0% r, 1 (Fig. 2). It is obvious that this is a limit for the given alloy, which can be realized by creating in it a developed cell-type substructure of austenite. At the same time, the transition to intense plastic deformation and to nanocrystalline structure in the case of LTTT with e = 1.9 and PDT at 400C increases e max to 8% (Fig. 2). r, 1 The dependence of the maximum fully reversible strain on the temperature of PDT for alloy Ti 50.7% Ni also has an extremum. The maximum value of e max = 8 9% is atr, 1

Creation of Substructure and Nanostructure in Thermomechanical Treatment

187

stress. Further decrease in the PDT temperature causes formation of still finer austenite grains and partial preservation of the amorphous structure, which manifests itself in a decrease in both the reversible strain and the reactive stress. Comparison of the values of maximum fully reversible strain of alloys Ti 50.0% Ni and Ti 50.7% Ni after LTTTm with conventional length of the yield plateau on the stress strain curves (stretching at room temperature) and of their changes at different temperatures shows that the length of the stage of easy deformation characterizes the margin of fully reversible strain accurately enough only in the case of initial recrystallized austenite grains in alloy Ti 50.0% Ni. The initial austenite can be in the state of considerable residual substructural hardening (LTTT + PDT at t < 400C, both alloys) or its structure can be fully cellular after undergoing strain aging (LTTT + PDT at t = 450 500C, alloy Ti 50.0% Ni). Then the fully reversible strain continues to be accumulated in the region behind the yield plateau too, until the dislocation yield point of the hardened austenite or martensite is surpassed. Finally, in the case of recrystallized or cellular austenite of alloy Ti 50.0% Ni (the inclined area) the dislocation yield point is attained within the area. CONCLUSIONS 1. Low-temperature thermomechanical treatment including intense plastic deformation and postdeformation annealing at 400C yields a nanocrystalline austenite structure with grains 50 80 nm in size, which ensures the best combination of functional properties in alloys of the Ti Ni system with shape memory effect. 2. Using LTTT with degree of deformation e = 1.9 and PDT at 400C we have obtained the highest values of fully reversible strain (8%) and reactive stress (over 1400 MPa) in the equiatomic alloy Ti 50.0% Ni. REFERENCES
1. T. W. Duering, K. N. Melton, D. Stockel, and C. M. Wayman (eds.), Engineering Aspects of Shape Memory Alloys, Butterworth-Heinemann (1990). 2. K. Otsuka and C. M. Wayman (eds.), Shape Memory Materials, University Press, Cambridge (1999).

3. V. Brailovski, S. Prokoshkin, P. Terriault, and F. Trochu (eds.), Shape Memory Alloys: Fundamentals, Modeling and Applications, ETS Publ., Montreal (2003). 4. V. A. Likhachev (ed.), Materials with Shape Memory Effect, Vol. 4 [in Russian], NIIKh SPbGU, St. Petersburg (1998). 5. S. D. Prokoshkin, V. G. Pushin, E. P. Ryklina, and I. Yu. Khmelevskaya, Application of titanium nickelide based alloys in medicine, Phys. Met. Metallogr., 97, Suppl. 1, 56 96 (2004). 6. E. P. Ryklina, I. Yu. Khmelevskaya, S. D. Prokoshkin, et al., The nickel-titanium device with SME for emergency interruption of blood flow, Mater. Sci. Eng., A378, 519 522 (2004). 7. E. P. Ryklina, I. Yu. Khmelevskaya, and S. D. Prokoshkin, Use of thermomechanical treatment of titanium nickelide for creation of medical implants and instruments, Metalloved. Term. Obrab. Met., No. 5, 3 7 (2004). 8. E. P. Ryklina, I. Yu. Khmelevskaya, S. D. Prokoshkin, et al., A device for emergency stopping of bleeding fabricated from titanium nickelide with reversible shape memory effect, Metalloved. Term. Obrab. Met., No. 8, 3 6 (2004). 9. S. D. Prokoshkin, T. V. Morozova, L. M. Kaputkina, et al., Anisotropic dilatometric effects in titanium nickelide after HTTT and their interrelation with the effect of shape memory, Fiz. Met. Metalloved., 81(2), 141 148 (1996). 10. S. D. Prokoshkin, L. M. Kaputkina, T. V. Morozova, and I. Yu. Khmelevskaya, Dilatometric anomalies and the effect of shape memory in titanium-nickel alloy subjected to low-temperature thermomechanical treatment, Fiz. Met. Metalloved., 80(3), 70 71 (1995). 11. I. Yu. Khmelevskaya, M. I. Lagunova, S. D. Prokoshkin, et al., Dilatometric and structural study of high-temperature changes in the shape of Ti Ni-based alloys heated after LTTT, Fiz. Met. Metalloved., 85(5), 71 78 (1998). 12. S. D. Prokoshkin, I. Yu. Khmelevskaya, V. Brailovski, et al., Structure and strain curves of Ti Ni alloys subjected to LTTT with postdeformation heating, Fiz. Met. Metalloved., 91(4), 104 112 (2001). 13. S. D. Prokoshkin, I. Yu. Khmelevskaya, F. Trochu, et al., Thermomechanical treatments and their influence on the microstructure and stress/strain diagrams of Ni Ti shape memory alloys, Can. Metallurg. Quart., 43(1), 95 108 (2004). 14. S. D. Prokoshkin, A. V. Korotitskiy, V. Brailovski, et al., On the lattice parameters of phases in binary Ti Ni shape memory alloys, Acta Mater., 5(15), 4479 4492 (2004). 15. V. Brailovski, I. Yu. Khmelevskaya, S. D. Prokoshkin, et al., Foundations of heat and thermomechanical treatments and their effect on the structure and properties of titanium nickelide-based alloys, Phys. Met. Metallogr., 97, Suppl. 1, 3 55 (2004).