Materials Science and Engineering A 463 (2007) 27

Superplasticity in nanostructured materials: New challenges

R.Z. Valiev , R.K. Islamgaliev, I.P. Semenova
Institute of Physics of Advanced Materials, Ufa State Aviation Technical University, Ufa 450000, 12 K. Marx Str., Russia Received 14 April 2006; received in revised form 18 August 2006; accepted 19 August 2006

Abstract The discoveries made in Prof. A.K. Mukherjees laboratory in 19962001 have revealed that nanostructured metals and alloys can demonstrate extraordinary superplasticity at low temperatures and/or high strain rates. This work presents the new results on superplasticity in several nanostructured Al and Ti alloys focusing on microstructure evolution and strain hardening, as well as the challenges of their application. Grain renement in these alloys was accomplished using severe plastic deformation techniques, and subsequent superplastic deformation allowed not only to produce their efcient forming, but also to improve the ultrane-grained structure and to obtain enhanced mechanical properties of the produced articles. The results demonstrate the possibilities of new applications of superplastic forming using nanostructured materials. 2006 Elsevier B.V. All rights reserved.
Keywords: Superplasticity; Bulk nanostructured materials; Severe plastic deformation

1. Introduction Superplasticity refers to the ability of a polycrystalline material to exhibit, in a generally isotropic manner, very high tensile elongation before failure [13]. This research area has been the subject of studies of many years conducted by Prof. A.K. Mukherjee, and he has become a world authority in this research area in the last 1520 years. The main achievements in these studies by the early 1990s are presented in his excellent overview on superplasticity in metals, ceramics and intermetallics [4]. This overview also gives an idea about the outstanding contribution of its author into this research area. Almost immediately after this ne paper Prof. Mukherjee started his studies of superplasticity in nanostructured materials which was at that time a new and unexplored research eld. There were two factors that underlay these works: 1. Theoretical predictions of advanced superplasticity in materials possessing an ultrane-grained structure. It is known that superplastic ow of microcrystalline materials is often described by a constitutive equation [4,5]: =A DGb b kT d
p

where is the strain rate, D the coefcient of grain boundary diffusion, G the shear modulus, b the Burgers vector, k Boltzmanns constant, T the temperature of testing, d the grain size, p the grain size exponent (usually equal to 2), the ow stress and n is the stress exponent. Based on this constitutive law of superplastic ow, one can expect that a decrease in grain size should provide a sharp increase in superplasticity at relatively low temperatures and/or high strain rates. Therefore, this has aroused great interest in investigations of superplasticity in ultrane-grained (UFG) metals and alloys with a grain size less than 1 m. 2. New opportunities in studies of superplasticity in metallic materials have been provided by development in processing of bulk nano- and submicrocrystalline metals and alloys using severe plastic deformation (SPD) [6]. These investigations were started in two directions: rst, fabrication of large billets with submicrocrystalline structure with a grain size of less than 1 m by equal-channel angular pressing (ECAP); second, processing of nanocrystalline structures in small samples by high pressure torsion (HPT). It was demonstrated experimentally that SPD-produced alloys have a great potential for achieving enhanced superplastic characteristics at low temperatures [6,7]. As a result of the studies performed in Prof. Mukherjees lab, a series of papers were published ([810] and others), concerned with low-temperature and high-strain-rate superplasticity

Corresponding author. Tel.: +7 3472 733422; fax: +7 3472 733422. E-mail address: RZValiev@mail.rb.ru (R.Z. Valiev).

0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2006.08.121

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in nanostructured materials. These papers became widely recognized and highly cited. The present paper represents a development of these works and is focused on two topical issues concerning superplasticity in nanostructured materials: rst, microstructural aspects of the superplastic behavior of UFG materials, and second, study of the role of unusual microstructural features of superplastic nanostructured materials for their mechanical properties at ambient temperature.

Several materials were used in the investigations: Ni3 Al [8,13], as well as several Al and Ti alloys [9,10,14]. 3. Results and discussion Let us rst of all consider the microstructural aspects of superplastic behavior of the Ni3 Al nanocrystalline alloy produced by HPT. Fig. 1 shows a typical microstructure observed in Ni3 Al in the HPT-processed state. The electron diffraction pattern exhibits rings, indicating that there were many small grains with random misorientations in the selected area of view (Fig. 1b). The average grain size measured from bright eld image was 50 nm (Fig. 1a). This value was only slightly changed after annealing at T = 650 C (Fig. 2a) and the grain size did not exceed 80 nm. TEM/and high resolution TEM (HREM) observations indicated that the grains are almost free from lattice dislocations, but the grain boundaries still retained their non-equilibrium character because they are usually wavy and contained many defects, such as facets, steps and grain boundary dislocations (Fig. 2b). The diffrential scanning calorimetry (DSC) signal (Fig. 3) shows a considerable peak of heat release at temperature about 450 C. Because of very limited grain growth after heating at 650 C it appears that DSC peak is associated not with grain

2. Experimental In order to produce samples with a nano- and submicrocrystalline structure, two severe plastic deformation techniques were used: HPT and ECAP. These techniques were proposed and appeared in the pioneer works on formation of UFG structure using SPD [6,7]. The principles of these techniques and their development trends can be found elsewhere [11,12]. Mechanical tensile tests of samples produced by ECAP were carried out in standard conditions, whereas small samples produced by HPT were tested on a special computerized machine [8,9]. Structural studies were performed using transmission electron microscopy (TEM) and X-ray methods.

Fig. 1. Microstructure of Ni3 Al processed by HPT: (a) bright eld image; (b) electron diffraction pattern.

Fig. 2. Microstructure of Ni3 Al processed by HPT and annealed at 650 C for 5 min: (a) dark eld image; (b) high-resolution transmission electron micrograph of a typical grain boundary.

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Fig. 3. DSC signal from Ni3 Al processed by HPT. Fig. 4. Appearance of nanostructured Ni3 Al samples prior and after tension at temperature 650 C, 1 103 , elongation 390% (a cross indicates the place where the foil was cut out for TEM) and at temperature 725 C 1 103 , elongation 560%.

growth but rather with recovery and reordering, which were revealed by X-ray analysis as well [15]. At 650 C, nanostructured Ni3 Al revealed superplastic behavior and the appearance of a Ni3 Al specimen after testing is shown in Fig. 4 in which the upper specimen is the untested one. It is apparent from Fig. 4 that the specimens exhibit very high tensile ductilities (several hundred percent elongation to failure) without visible macroscopic necking. This conrms the manifestation of superplastic behavior. However, such superplastic behavior has several unusual features. In particular, the stressstrain curves for Ni3 Al at a strain rate of 103 s1 and 650 and 725 C show an extensive region of strain hardening at both temperatures with the peak ow stress ranging from 0.9 to 1.5 GPa (Fig. 5a), which is the highest ow stress reported in the literature for the Ni3 Al intermetallic. It should be noted that superplasticity in nanostructured Ni3 Al has been observed at temperatures, which are more than 400 C lower when compared with microcrystalline Ni3 Al [16]. In order to understand the microstructure dynamics in this nanostructured alloy, special TEM/HREM investigations have

Fig. 5. The variation of true ow stress with elongation at 650 and 725 C and a strain rate of 1 103 s1 .

Fig. 6. Micrographs of nanostructured Ni3 Al: (a) TEM bright eld image after tension; (b) HREM image of twin boundaries. Note no lattice dislocations trapped by twin boundaries.

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Table 1 Mechanical properties of the alloy Ti6Al4%V ELI in the as-received state and in the state after ECAP and extrusion State Initial Processed by ECAP and extrusion Fig. 7. Semi-products out of nanostructured Ti6Al4V ELI alloy. UTS (MPa) 940 1300 YS (MPa) 840 1250 Elongation (%) 16 8

been performed where a thin foil was prepared from a gauge section of Ni3 Al sample strained about 300% (see Fig. 4). Although there is some grain growth during superplastic deformation, the grain size remained less than 100 nm (Fig. 6a). Grains were not elongated and we could not nd any evidence of large dislocation activity inside the grains even though careful HREM investigations were conducted taking advantage of annealing twins (Fig. 6b). Such twin boundaries are known to trap and retain lattice dislocations easily [17]. However, we could not detect any dislocations at these interfaces. This experiment supports theoretical calculations [9] demonstrating a difculty of accommodation for grain boundary sliding through generation of lattice dislocations in nanograins during superplastic deformation. Probably superplastic deformation of the nanomaterial occurs as a result of grain boundary sliding and some diffusional accommodation without high dislocation activity in the grains. Thus, nanocrystalline Ni3 Al processed by HPT exhibits superplasticity at temperatures which are more than 400 C lower when compared with the corresponding microcrystalline specimen. For the aims of the present work, it is quite important to mark improvement of the microstructure of the material after superplastic straining, when a homogeneous UFG structure is observed with clearly dened boundaries (Fig. 6). Similar changes were found in other nanostructured materials produced using SPD techniques as well: Ti6%Al4%V [10], Al alloys 1420 and 1421 [9,18]. Let us now consider the microstructural features and superplastic behavior of bulk billets of nanostructured Ti materials produced by ECAP. Using this approach, it was shown recently [14] that rod with a diameter of 17 mm and length over 300 mm possessing an UFG structure can be successfully produced out of a hard-to-deform alloy Ti6%Al4%V ELI using ECAP and subsequent extrusion (Fig. 7). After this kind of treatment, the mechanical strength properties of the alloy grew considerably (Table 1) as compared with the initial state, while elongation

to failure remained 8%. Fig. 8 presents TEM images of the microstructure of this alloy after ECAP processing and extrusion. It can be seen that severe straining led to strong grain renement, but it is quite a complex UFG structure. The small grains are not perfect and contain many defectsmicrotwins, dislocations and others. A certain inhomogeneity of the structure can be seen, when along with grains/subgrains with a size under 100 nm larger grains with a size of 400600 nm are visible. The grain boundaries are not clearly dened and do not have a pronounced banded contrast (Fig. 8a). The UFG alloy after the conducted treatment was investigated for exhibition of superplasticity using tensile testing of the samples at a rate of 104 to 101 s1 and temperatures 500750 C. Fig. 9a shows a view of the samples after tension at a strain rate of 104 s1 and relatively low temperatures of 500800 C. It can be seen that ductility of the alloy grows noticeably with increasing temperature and during tension at 600 C the samples demonstrate a superplastic elongation of 240%. Fig. 9b displays a TEM micrograph of the alloy microstructure after superplastic straining at 600 C. It can be seen that it differs qualitatively from the microstructure of this alloy after ECAP and extrusion. In the gure, one can see distinctly ultrane grains divided by clearly dened boundaries. The grains have an equiaxed shape although the samples were subjected to signicant strains (240%). Dislocations density inside the grains has fallen noticeably and does not exceed 1014 m2 . The mean grain size totalled about 500 nm, i.e. it grew insignicantly as compared with the pre-straining state. The UFG alloy exhibits superplastic behavior also during straining at a higher rate of 102 s1 , but at a higher temperature. This strain rate of 102 s1 is the border line of the so-called high-strain-rate superplasticity which was found during straining of ultrane-grained materials [9]. The view of the samples after tension is presented in Fig. 10a. It can be seen that the alloy exhibits superplastic elongation to failure in these con-

Fig. 8. Microstructure of Ti6Al4V ELI alloy after ECAP and extrusion. TEM: (a) cross-section; (b) longitudinal section.

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Fig. 9. (a) UFG Ti6Al4V ELI samples after tension within temperature range of 500600 C at = 104 s1 , and (b) microstructures of the corresponding areas of a sample; longitudinal section, TEM.

Fig. 10. (a) UFG Ti6Al4V ELI alloy samples after tension within the temperature range of at 700800 C at = 102 s1 and (b) microstructures of the corresponding areas of a sample; longitudinal section, TEM.

ditions. The microstructure of the alloy after high-strain-rate deformation is shown in Fig. 10b. Like in the conditions of low-temperature superplasticily, a pronounced UFG structure is formed here, i.e. an improvement of the microstructure takes place while a rather small grain size is retained. As was shown recently in [19,20], a change in the morphology of the grain structure in the UFG alloy can change its mechanical
Table 2 Mechanical properties of the Grade 4 Ti rods Material Grade 4 Ti State Initial ECAP 8 passes + TMT UTS (MPa) 725 1140

behavior considerably, and ensure signicant ductility, at the same time maintaining high strength. This approach was employed recently while developing a technology for producing long-length rods of nanostructured titanium (Grade 2 and Grade 4) for medical use. With this aim in view, ECAP with subsequent thermomechanical treatment was used, including forging at superplastic regime. The view of

YS (MPa) 545 940

(%) 32 19

(%) 52 42

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co-workers and students Rajiv Mishra, Sam McFadden, Alla Sergueeva, Nathan Mara. This work was supported in part by the Russian Foundation for Basic Research and project #3208p by the International Science and Technology Center (IPP-DOE program). References
[1] T.G. Langdon, Metall. Trans. A13 (1982) 689701. [2] O.A. Kaibyshev, Superplasticity of Alloys, Intermetallics and Ceramics, Springer-Verlag, Berlin, Germany, 1992. [3] T.G. Nieh, J. Wadsworth, O.D. Sherby, Superplasticity in Metals and Ceramics, University Press, Cambridge, UK, 1997. [4] A.K. Mukherjee, in: R.W. Cahn, B. Haasen, E.J. Kramer (Eds.), Materials Science and Technology, Plastic Deformation and Fracture of Materials, vol. 6, Weinheim, New York, USA, 1993, pp. 407460. [5] R.S. Mishra, T.R. Bieler, A.K. Mukherjee, Acta Metall. Mater. 43 (1995) 877891. [6] R.Z. Valiev, A.V. Korznikov, R.R. Mulyukov, Mater. Sci. Eng. A168 (1993) 141148. [7] R.Z. Valiev, O.A. Kaibyshev, R.I. Kuznetsov, R.Sh. Musalimov, N.K. Tsenev, DAN SSSR 301 (4) (1988) 864866 (Reports of the Academy of Sciences of the USSR). [8] S.X. McFadden, R.S. Mishra, R.Z. Valiev, A.P. Zhilyaev, A.K. Mukherjee, Nature 398 (1999) 684686. [9] R.S. Mishra, R.Z. Valiev, S.X. McFadden, R.K. Islamgaliev, A.K. Mukherjee, Philos. Mag. A81 (2001) 3748. [10] A.V. Sergueeva, V.V. Stolyarov, R.Z. Valiev, A.K. Mukherjee, Mater. Sci. Eng. A323 (2002) 318325. [11] R.Z. Valiev, R.K. Islamgaliev, I.V. Alexandrov, Prog. Mater. Sci. 45 (2000) 103189. [12] R.Z. Valiev, Y. Estrin, Z. Horita, T.G. Langdon, M.J. Zehetbauer, Y.T. Zhu, JOM 58 (4) (2006) 3339. [13] R.Z. Valiev, C. Song, S.X. McFadden, A.K. Mukherjee, R.S. Mishra, Philos. Mag. A81 (2001) 2536. [14] I.P. Semenova, L.R. Saitova, G.I. Raab, A.I. Korshunov, Y.T. Zhu, T.C. Lowe, R.Z. Valiev, Mater. Sci. Forum 503504 (2006) 757 762. [15] J. Languillaume, F. Chmelik, G. Kapelski, F. Bordeaux, A.A. Nazarov, G. Canova, C. Esling, R.Z. Valiev, B. Baudelet, Acta Metall. Mater. 41 (1993) 29532962. [16] R.Z. Valiev, R.M. Gayanov, H.S. Yang, A.K. Mukherjee, Scripta Metall. Mater. 25 (1991) 19451950. [17] A.P. Sutton, R.W. Balluf, Interfaces in Crystalline Materials, Claredon Press, Oxford, UK, 1995. [18] R.K. Islamgaliev, N.F. Yunusova, R.Z. Valiev, N.K. Tsenev, V.N. Perevezentsev, T.G. Langdon, Scripta Mater. 49 (2003) 467472. [19] R.Z. Valiev, A.V. Sergueeva, A.K. Mukherjee, Scripta Mater. 49 (2003) 669674. [20] R.Z. Valiev, Nat. Mater. 3 (2004) 511516.

Fig. 11. (a) ECAP-processed billets (length 150 mm), (b) billets at the rst stage of thermomechanical treatment by forging (length about 700 mm), (c) billets after the second stage of treatment (length 1000 mm) and (d) billets at the nal stage of treatment (length 1500 mm).

the rods is presented in Fig. 11, and Table 2 gives also data on the tensile mechanical properties of the produced articles, where UTS is ultimate tensile strength, YS is yield stress, stands for elongation and stands for reduction area. These results testify that the specied treatment led to a signicant enhancement of strength as well as achievement of high fatigue strength, which is of high importance for advanced applications in orthopedics, traumatology and stomatology. 4. Concluding remarks The investigations conducted in 19962001 in Prof. A.K. Mukherjees laboratory yielded convincing evidence of extraordinary superplastic behavior of nanostructured materials when elongations of hundreds and thousands of percent were observed at relatively low temperatures and high strain rates. One of the important features of superplastic behavior of nanostructured materials is improvement of their granular structure associated with formation of a typical UFG structure with equiaxed grains and clearly dened grain boundaries. As shown in the given work, this is true not only for pure metals, but for alloys as well, which is important for enhancing their mechanical properties. This approach has been used for development of a technology for producing long-length rods of nanostructured Ti with very high mechanical properties. Acknowledgements The authors (R.Z.V. and R.K.I.) warmly acknowledge their nice collaboration of many years with Prof. Mukherjee and his