JOURNAL DE PHYSIQUE

Colloque C3, suppl6men-t au n 0 9 , Tome 48, septembre 1987

HIGH RESOLUTION TEM STUDY OF PRECIPITATES IN A RAPIDLY SOLIDIFIED Al-Li-Zr ALLOY

N.J.

KIM , J.M. HOWE* and E . G .

BODEN*"

Metals and Ceramics Laboratory, Allied-Signal Incorporation, P.O. Box 1021 R, Morristown, NJ 07960, U.S.A. "~epartment of Metallurgical Engineering and Materials Science, Carnegie-Mellon University, Pittsburgh, PA 15213, U.S.A. * * Applications Laboratory, Philips Electronic Instruments Incorporation , Mahwah, NJ 01430, U.S.A.

In this investigation, high resolution transmission electron microscopy and image simulations are used to characterize the atomic structure, coherency and chemistry of 6' and A1,Zr precipitates in a rapidly solidified A1-3.4Li-0.5Zr alloy. During aging, 6' precipitates around A1,Zr while maintaining coherency across the interphase boundary. Coalescence occurs when S' precipitates whose sublattices are in phase coarsen and impinge. On the other hand, 6' precipitates whose sublattices are antiphase appear not to coalesce and a layer of aluminum matrix exists between them. Deformation of the alloy results in a shearing of 6 ' precipitates which occurs in some cases, by multiple cross slip along intersecting (111) planes. Finally, the results suggest that there may be some incorporation of lithium in the A1,Zr precipitates. INTRODUCTION During aging of aluminum-lithium alloys, there is a precipitation of metastable, coherent, L1, ordered 6 ' (A1,Li) in the microstructure. This 6' precipitate suffers from its propensity to dislocation shear, resulting in a loss in ductility and fracture toughness. It has been shown that the ductility and fracture toughness of aluminum-lithium alloys can be improved by the addition of zirconium 11-51, The improvements in mechanical properties come, in part from the unrecrystallized microstructure achieved by the addition of zirconium, but are mainly due-to the effect of zirconium on modifying the precipitation behavior. Zirconium promotes the formation of a metastable, L12 A1,Zr precipitate which is isostructural with the 6' precipitate. During aging of an alloy which contains Al,Zr, 6' precipitates heterogeneously around the Al,Zr, forming so-called composite precipitates [I-81. This composite precipitate is characterized by a spherical inner core of AlaZr surrounded by an envelope of 6'. The existence of A1,Zr or composite precipitates in the microstructure has important effects on the mechanical behavior of aluminum-lithium alloys in that A1,Zr precipitates are quite resistant to dislocation shear, thereby remedying the slip localization in aluminum-lithium alloys. There have been a relatively large number of investigations on microstructural development in Al-Li-Zr alloys; however, there still is a lack of detailed knowledge of the phase transformation behavior in Al-Li-Zr alloys, e.g., formation of antiphase boundaries (APBs) during coarsening of 6 ' precipitates, interaction of dislocations with 6' and A1,Zr precipitates and chemistry of the A1,Zr

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1987352

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precipitate. This lack of understanding is mainly due to the inability of most analytical techniques to detect the structures on an atomic level. In the present investigation, high resolution electron microscopy (HREM) and image simulations have been used to perform detailed analyses of phase transformations and their consequences in Al-Li-Zr alloys.

EXPERIMENTAL PROCEDURES

An alloy of composition of A1-3.4 wt%Li-0.5 wt%Zr was rapidly quenched from the melt into continuous ribbons by the jet casting process. These ribbons were mechanically comminuted to - 4 0 mesh powder and then consolidated into bulk compacts by vacuum hot pressing followed by hot extrusion to a final rectangular shape of 63.5 mm X 10.2 mm. An extrusion was solution treated at 540C for 2 hrs., quenched in cold water and aged at various temperatures. Thin foils were obtained from the as-heat treated extrusion as well as from the gauge section of the deformed tensile specimen. TEM foils were prepared by jet polishing with an electrolyte of 33% HNO, and 67% methanol or with one of 10% perchloric acid and 908 ethanol. Conventional TEM and tilted illumination HREM observations were made using Philips CN-12 and EM400T. Axial illumination HREM study was conducted using JEOL ARM-1000. Simulate images of the precipitates and interface were calculated using the SHRLI multislice program 1 9 1 .
RESULTS AND DISCUSSION 1. 6 '/A13Zr Interface As has been mentioned in the introduction, the presence of A1,Zr in the microstructure modifies the precipitation behavior of 6' precipitates in Al-Li-Zr alloys. During aging, A1,Zr acts as a preferential nucleation site for 6' and the resultant microstructure consists of composite precipitates in which continuous envelope of 6' surrounds the core Al,Zr phase. The example of such microstructure is shown in a superlattice dark field image (Figure 1). It shows that all of the A13Zr is surrounded by 6 ' and there also is a homogeneous precipitation of 6' in the matrix. The continuous envelope of 6' around A1,Zr suggests that there is a ' lattice continuity across the S1/A13Zr interface. Gayle et al. has addressed this issue by considering the several possibilities of 6' nucleation along S1/A1,Zr and concluded that there is a continuous sublattice across the S1/A1,Zr interface and there

Fig. 1. Superlattice dark field. Aged 1 9 O 0 C / 1 6 hrs.

HREM was conducted in this study to determine the exact spatial relationship of the lattice of the 6' phase with that of the A1,Zr phase. Figure 2a is a HREM image of the alloy which shows the A1,Zr phasesurrounded by &'.The image was obtained using the (100) superlattice and transmitted beams. Tracing along the (100) superlattice planes reveals that they are continuous as they across'the interface which demonstrates that the 6' phase is coherent with the A1,Zr phase. However, it can be seen that the atom planes are slightly bent as they cross the interface. The lattice parameters of two phases are a=4.01 .& for 6' and a=4.05 .& for A1,Zr. These differences in the lattice parameters between two phases are demonstrated in the lattice image. It should be noted that in certain locations, A1,Zr precipitates do not show any structural details, as shown in Figure 2b. This abnormal behavior is similar to the observation made in the superlattice dark field in which core A1,Zr precipitates show dark contrast.

Fig. 2. Tilted beam HREM images of G'/A13zr interface: (a) coherency is maintained across the interphase boundary and (b) A13Zr does not show any structural details in this micrograph. Aged 190C/16 hrs.

2. &'/Matrix Interface Figure 3a shows a tilted beam HREM micrograph of alloy aged at 190C for 16 hours. The objective aperture was placed-to include the (100) 6' superlattice, (200) matrix and transmitted beams. As can be seen from the micrograph, the (100) superlattice fringes of spacing equal to 4.01 A, running parallel to the (200) matrix fringes of spacing equal to 2.01 A, were resolved. By following the matching of atomic planes across the boundary, it can be seen that one (100) superlattice fringe transforms to two (200) fundamental fringes as expected. One important feature observed in this alloy is concerned with the coarsening mechanisms of 6' precipitates. In an fcc alloy which has a superlattice L1, structure, there is a 50% possibility of APB formation when two 6' precipitates impinge. When they impinge they will coalesce only if their sublattices are occupied in phase; however, impinging particles whose lattices are antiphase may or may not merge and form an APB depending on their interfacial free energy and APB energy. Close examination of the lattice image in Figure 3a shows that APB formation is possible by impingement of two 6' precipitates. As shown in Figure 3a, (100) superlattice fringes of 6' precipitate A do not coincide with the (100) superlattice fringes of 6' precipitate B across the aluminum matrix. The coarsening and impingement of these two 6' precipitates may form an APB if the formation of an APB is energetically favorable. Reported data on the 6' APB energy

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Fig. 3. (a) Tilted beam HREM image of G1/matrix interface and (b) superlattice dark field. Aged 150C/2000 hrs. on (111) of 140 [Ill, 160 [12] and 195 ergs/cmz [13] and the interfacial energy between the aluminum matrix and 6' phase of 14 ergs/cm2 [ 1 4 ] , however, suggest that two impinging 6' precipitates will not form an APB because the formation of a common APB requires a higher energy than leaving a layer of fundamental phase between them. This is probably also true for the lower energy (100) APBs. In this case, two 6' precipitates will not coalesce and will be separated by a layer of aluminum matrix and the resulting microstructure will be very close to some of the 6' precipitates shown in the superlattice dark field (arrowed in Figure 3b). On ' precipitate C are shown to the other hand, the (100) superlattice fringes of 6 match perfectly with those of 5 ' precipitate A. The growth and impingement of these two 6 ' precipitates will result in a change in aspect ratio (ratio of minor axis and major axis), ranging from 0.5 to 0.8 as suggested by Kulwicki and Sanders 1151, although they reported that such encounters are quite seldom. In contrast to their observation, however, it has been found that there are a fairly large number of incidents of such encounter and coalescence as shown in Figure 3a (marked A ) .

3. Formation of APB by Slip

One of the most important consequences of 6' precipitation in aluminum-lithium alloys is the severe planar slip during deformation due to the propensity of 6' to dislocation shear. In the L1, superlattice, the unit translational vector, or slip vectors for the close-packed octahedral slip planes are twice that in the ordinary fcc lattice. It follows that superlattice dislocations in Elz tend to consist of pairs of a/2<110> type dislocations coupled together by an APB. The equilibrium width of such a superlattice dislocation is determined primarily by a balance between the line tension of the APB and the mutual repulsion experienced by the pair of same sign a/2<110> dislocations. Relatively low values of APB energy published in the literature [ll-131 suggest that the distance between dislocations might be much larger than the 6' diameter in normally aged alloy. De Hosson et al., in fact, showed that the mean jump distance of dislocation is much larger ' particle size [Ill. This means that 6' particles will be sheared off than the 6 during deformation and the restoration of order by the movement of another dislocation will not be possible. The typical example of sheared 6' particles are shown in Figure 4a. Trace analysis of this image shows that an APB has formed along (111) planes in all 6 ' particles except one (arrowed in Figure 4a) whose APB is closely parallel to a (220) plane. The formation of APBs along (220) planes is not favorable. Figure 4b is a tilted illumination HREM image of deformed alloy

Fig. 4. (a) Superlattice dark field of deformed alloy and (b) tilted beam HREM image showing the APB formation by slip. Aged 190C/16 hrs.

showing the details of such APBs. A shift of half the (100) fringe spacing is quite clearly shown. The fringes are continuous right up to the defect in most areas with the shift occuring over a very short distance (- 4 A ) . This indicates that the APB has a width of atomic dimensions. There also is a change of orientation of the APB with respect to the lattice fringes. The angle between the APB and lattice fringes is macroscopically close to 72", which is not consistent with the possible APB plane of (111). Close analysis of the fringe terminations shows that a series of steps are present. It therefore appears that this particular APB may have formed by multiple cross slip of dislocations along intersecting (111) planes.

4. Composition of the A1,Zr Phase

Although it has not been discussed until now, one of the most important questions about the precipitation phenomenon in Al-Li-Zr alloys is the possible partitioning of lithium in A13Zr phase. As has been observed in several investigations, the addition of a small amount of zirconium results in a fairly large volume fraction of A1,Zr in the microstructure. Although the phase diagram of Al-Li-Zr alloy system is not well established, such a large volume fraction of A1,Zr sbggests that there may be a partitioning of lithium in the A1,Zr. Several techniques have been used to resolve the disagreement concerning the interaction of lithium and zirconium in A1,Zr precipitates. Gayle and Vander Sande [6] suggested that the dark contrast of A1,Zr core precipitates in superlattice dark field is due to the incorporation of Li in A13Zr phase. They have calculated the structure factor as a function of Li content in the A1,Zr and proposed that the composition of A1,Zr is very close to an Al,(Li,Zr) phase whose Li:Zr ratio ranges from approximately 2:l to 1:4 depending on heat treatment and precipitation mechanism. They also reported that there is inter-solubility of A1,Zr and 6' based on electron energy loss spectrometry (EELS) result [I]. Makin and Ralph [7], however, indicate that there is negligible chemical interaction between lithium and zirconium in the precipitate. EELS study by Stimson et al. [I61 showed no detectable lFthium segregation to the semi-coherent (or incoherent) Al,Zr, but they were not able to discern the presence of lithium in coherent A1,Zr surrounded by 6' envelope. A recent study by Hono et al. [17], using atom-probe field ion microscopy (APFIM), suggests that lithium incorporation in A1,Zr is negligible.

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It has been attempted to resolve the discrepancy concerning the partitioning of lithium in A1,Zr by HREM study and image simulations. Figure 5 shows calculated images for a Sf/A13Zr interface in a [I101 orientation as a function of specimen thickness. The microscope conditions used for these calculations were: C,= 1.0 mm, Af = -50 nm and accelerating voltage of 400 keV. For simplicity, lattice parameters of 6I and A1,Zr were assumed to be same. The model for the interface is shown by the projected potentials in Figure 5. In this model, two different compositions of AIBZr precipitates were used; (a) assuming that there is no lithium in A1,Zr and (b) assuming that 60% of zirconium is replaced by lithium according to Gayle and Vander Sande [6], i.e., A13(Li0,sZr0,4).By examining the images in Figure 5, it is apparent that it is possible to distingush A1,Zr precipitates that contain Li from A1,Zr precipitates that do not, provided that the 6' precipitate does not overlap A1,Zr. Figure 6 shows an experimental HREM image of a sl/A1,Zr interface. It can be seen that the image around the center of the micrograph (circled) closely resembles the simulated image (thickness = 8.5 and 11.3 nm) and there is an absence of the strong (200) fringes around it, suggesting that there may be a partitioning of lithium in A1,Zr. This observation as well as those of Gayle and Vander Sande made in rapidly solidified high zirconium content (0.5 - 1 wt%) alloys contradict most of the early investigations made in ingot cast alloys with limited zirconium contents (< 0.2 wt%). Nevertheless, more detailed work is clearly needed to better understand this important issue.

Fig. 5. Simulated images and projected potentials of G1/A13Zr interface: (a) assuming that there is no Li in AlgZr and (b) assuming that 60% of Zr is replaced by Li, i.e., A13(~i0.6Zr0.4). CONCLUSIONS Detailed analyses of the G'/Al,Zr interface, the &'/matrix interface, formation of APB and composition of A13Zr precipitates have been studied using the techniques of HREM and image simulations. The major findings of this study are: (1) interfaces of 6' precipitates are largely coherent with A1,Zr precipitates, thereby minimizing interfacial energies associated with interphase boundaries, (2) coarsening and impingement of 6' precipitates result in coalescence when their sublattices are occupied in phase; otherwise, it appears that coalescence does not occur and a layer of fundamental aluminum matrix exists between 6' precipitates, (3) shearing of 6' by dislocations occurs on a single (111) plane in most cases; however, multiple cross slip on intersecting (111) planes has been observed to 4 ) agreement between experimental and calcuated occur in some 6' particles, and ( images of GV/A1,Zr interface suggests that there may be incorporation of Li in A1,Zr precipitates.

Fig. 6. Experimental image of 6' /~l?Zrinterface.

REFERENCES 1. F.W. Gayle and J.B. Vander Sande, p. 137 in Rapidly Solidified Aluminum Alloys, eds., M.E. Fine and E.A. Starke, Jr., ASTM, Philadelphia, PA, 1986. 2. N.J. Kim, D.J. Skinner, K. Okazaki and C.M. Adam, p. 78 in Aluminum-Lithium Alloys 111, eds., C. Baker, P.J. Gregson, S.J. Harris and C.J. Peel, The Institute of Metals, London, UK, 1986. 3. N.J. Kim and S.K. Das, Scripta Metall., 20, p. 1107 (1986) 4. F.W. Gayle, J.B. VanderSande and O.R. Singleton, p. 767 in Aluminum Alloys - Their Physical and Mechanical Properties, eds., E.A. Starke, Jr. and T.H.Sanders, Jr., EMAS, West Midlands, UK, 1986 5. N.J. Kim, R.L. Bye and S.K. Das, in this conference. 6. F.W. Gayle and J.B. VanderSande, Scripta Metall., 18, p. 473 (1984). 7. P.L. Makin and B. Ralph, J. Mat. Sci., 19, p. 3835 (1984). 8. P.J. Gregson and H.M. Flower, J. Mat. Sci. Letters, 3, p. 829 (1984). 9. M.A. OIKeefe and P.R. Buseck, Trans. Amer. Cryst. Assoc., 15, p. 27 (1979). 10. F.W. Gayle and Vander Sande, p.376 in Aluminum-Lithium Alloys 111, eds., G. Baker, P.J. Gregson, S.J. Harris and C.J. Peel, The Institute of Metals, London, UK, 1986. 11. J.Th.M. De Hosson, A. Huis in't Veld, H. Tamler and 0. Kanert, Acta Metall., 32, p. 1205 (1984). 12. B. Noble, S.J. Harris and K. Dinsdale, Met. Sci., 16, p.425 (1982). 13. M. Tamura, T. Mori and T. Nakamura, J. Jpn. Inst. Met., 34, p. 919 (1970). 14. S.F. Baumann and D.B. Williams, Scripta Metall, 18, p. 611 (1984). 15. J.H. Kulwicki and T.H. Sanders, Jr., p. 31 in Aluminum-Lithium Alloys 11, eds., E.A. Starke, Jr. and T.H. Sanders, Jr., AIME, Warrendale, PA, 1983. 16. W. Stimson, M.H. Tosten, P.R. Howell and D.B. Williams, p. 386 in Aluminum-Lithium Alloys 111, eds., C. Baker, P.J. Gregson, S.J. Harris and C.J. Peel, The Institute of Metals, London, UK, 1986. 17. K. Hono, T. Abe, D.R. Hess, H.W. Pickering, P.R. Howell, Y. Hasegawa, T. Sakurai, N. Sano and K. Hirano, p. 621 in Aluminum Alloys - Their Physical and Mechanical Properties, eds., E.A. Starke, Jr and T.H. Sanders, Jr., EMAS, West Midlands, UK, 1986.