Ultramicroscopy 88 (2001) 6372

Structure determination and structure renement of Al2CuMg precipitates by quantitative high-resolution electron microscopy
Roar Kilaasa,*, Velimir Radmilovica,b
a

National Center for Electron Microscopy, Lawrence Berkeley National Laboratory, University of California, MS 72-215, 1 Cyclotron Road Berkeley, CA, 94270 USA b Department of Physical Metallurgy, University of Belgrade, Belgrade, Yugoslavia Received 11 February 2000; received in revised form 22 September 2000

Abstract The structure of the S-phase (Al2CuMg) precipitate in an Al matrix has been determined by using a combination of image processing, quantitative image comparison, and automatic renement of imaging and structural parameters. A method for comparing images with unknown origin relationship while quickly estimating a possible translation of the origin is outlined. The optimization algorithm used in the structure determination utilizes space group symmetry, which is deduced from the crystal-zone axis and reduces the number of free parameters. Published by Elsevier Science B.V.
PACS: 61.16.B; 61.66.D; 07.05.T Keywords: Quantitative high-resolution electron microscopy; Structure renement; Image comparison; S-phase; AlCuMg alloy

1. Introduction AlCuMg based alloys are of signicant interest for aerospace and other applications, due to their low weight, mechanical strength and corrosion resistance. Their mechanical properties are based on a dispersion of S-phase precipitates, which have the composition Al2CuMg. The crystal structure of this inter-metallic phase has been studied using dierent diraction techniques for more than ve decades. Several models have been proposed for the structure of S-phase. The rst model was given by Perlitz and Westgren (PW) [1] based on X-ray diraction. The unit cell of the PW model is shown in Fig. 1. The structure is orthorhombic with unit-cell dimensions a 0:4 nm, b 0:923 nm, and c 0:714 nm, space group Cmcm, containing 16 atoms in the ratio Al : Cu : Mg=2 : 1 : 1. Laves and Witte [2] suggested that the phase extends toward Al5Cu2Mg2, implying that equal amounts of the Cu and Mg atoms in Al2CuMg are replaced by Al. Alternatively, Nishimura [3] proposed a homogeneous S phase of composition Al13Cu7Mg8,

*Corresponding author. E-mail address: roar_kilaas@lbl.gov (R. Kilaas). 0304-3991/01/$ - see front matter Published by Elsevier Science B.V. PII: S 0 3 0 4 - 3 9 9 1 ( 0 0 ) 0 0 1 0 7 - 8

64

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

Fig. 1. Schematic drawing of the Perlitz and Westgren (PW) model of the S-phase. The three principal orientations [1 0 0], [0 1 0] and [0 0 1] are shown.

implying some degree of Mg substitution for Al. Mondolfo [4] suggested a modied PW model with slightly dierent lattice parameters (a 0:4 nm, b 0:925 nm, and c 0:718 nm). Cuisiat et al. [5] oered a model with a unit-cell dimensions identical to Mondolfos, but with space group Im2m containing only 8 instead of 16 atoms. Yan et al. [6] proposed an orthorhombic structure with space group Pmm2 (No. 25), lattice parameters a 0:4 nm, b 0:461 nm, c 0:718 nm and four atoms per unit cell in the ratio Al : Cu : Mg=2 : 1 : 1. According to the models of Cuisiat and Yan the density of the S-phase is only half that of the aluminum matrix. However, X-ray diraction experiments performed on AlLiCuMg alloys by Perez et al. [7] support the models of PW and Mondolfo. Since Al2CuMg precipitates in Al-based matrices have dimensions in the range of nanometers, they cannot be successfully investigated using X-ray diraction techniques. For nanometer scale structures, transmission electron microscopy, including nanodiraction and high-resolution imaging become indispensable tools in crystal structure determination. Accordingly, the structure of the 00 phase in Al MgSi alloys has been successfully investigated using a combination of HRTEM, electron diraction and reconstruction of exit-wave phase reconstructed HRTEM images [8,9]. Similarly, over the last few years much progress has been made in the eld of quantitative image comparison and automatic structure determination/renement in HRTEM [1013]. By building on this work, we have integrated, rened and utilized these methods in the study of the Al2CuMg intermetallic phase precipitate in Al alloys.

2. Preparation of the experimental data The structure of the S-Phase was imaged from two directions, the [1 0 0] zone axis and the [0 1 0] zone axis. The images were recorded on photographic lm and digitized from the negatives. The non-linearity of the lm to exposure was taken into account by taking a series of images with no specimen for dierent exposure times so to obtain the correlation between digitized image intensities and electron count. In order to reduce noise from the amorphous surface layers, the experimental images were processed using an automatic Wiener lter [14]. Subsequently templates were created by marking an area slightly larger than the size of the unit cell and regions of high similarity were found using a template matching routine that produces a cross-correlation map, where the peaks in the map mark positions of other unit cells [15]. The dimension of the unit cell was found by tting a 2D lattice to the positions of the peaks and the average unit cell images and the standard deviation images were found by extracting regions of the size of the unit cells centered on the peaks. The unit-cell images were further averaged over the symmetries of the projected

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

65

Fig. 2. Wiener ltered experimental image of S-phase precipitate in the [1 0 0] orientation (a). Average image of the unit cell (b) and standard deviation of the unit cell image (c). The intensities in 2c have been multiplied by 10 with (b) and (c) being displayed on the same gray-level scale.

S-phase structure, reducing the deviation images previously obtained by the square root of the number of symmetries used. Although these procedures were applied to experimental images obtained from two dierent zone-axis orientations, the text will concentrate on the results obtained from the [1 0 0] orientation of the S-Phase precipitate. This is because all investigated models that produced reasonable t with experiment have the same projected structure in the [0 1 0] orientation. Fig. 1 shows the Wiener ltered experimental image and the nal average image from a unit cell ([1 0 0] orientation) is shown in Fig. 2a with the standard deviation image shown in Fig. 2b.

3. Comparison to simulations Based on the various models proposed for the S-phase, image simulations were carried out for a range of thickness and defocus, and the theoretical images were compared quantitatively to the unit-cell image obtained from the experimental image. The methodology of the comparisons is outlined below. 3.1. Goodness of t criteria In order to x the origin of the experimental image with respect to the model used in the simulation, the rst comparisons were performed by calculating the cross-correlation coecient in reciprocal space based on the amplitudes of the Fourier transform of the images. The normalized cross-correlation coecient (CCC) in real space is given as P i;j I1 i; j hI1 iI2 i; j hI2 i CCC qq; P P 2 2 i;j I1 i; j hI1 i i;j I2 i; j hI2 i where Ii; j denotes the intensity in pixel i; j and hI i indicates the mean value of the image.

66

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

The equivalent expression in reciprocal space is P * h60;k60 F1 h; kF2 h; k CCC qq P 2 P 2 h60;k60 jF1 h; kj h60;k60 jF2 h; kj P 2 h>0;k>0 jF1 h; kjjF2 h; kjcosj1 h; k j2 h; k qq P P 2 2 h60;k60 jF1 h; kj h60;k60 jF2 h; kj The second equality is true for real images since in this case Fh; k F * h; k: The cross-correlation based on amplitudes alone is written P 2 h>0;k>0 jF1 h; kjjF2 h; kj CCCAmp qqP P 2 2 h60;k60 jF1 h; kj h60;k60 jF2 h; kj The cross-correlation coecient CCC(Amp) gives a value of 1 for identical images even when the two images are shifted with respect to each other. This has the advantage of being able to quickly compare images for conditions of defocus and thickness when the exact origin of the experimental image, with respect to, the simulated image is unknown. Since the cross-correlation coecient based on amplitudes alone will always be greater than the true cross-correlation coecient, it is easy to eliminate conditions that produce no reasonable t between experiment and theory. The most likely shift of the origin between the two images being compared is estimated as follows: (1) Assume the two images I1 and I2 are the same except for a change in origin. (2) This implies that I2 x; y I1 x x0 ; y y0 . In reciprocal space for an image of dimensions NM and a shift in pixels of (n0, m0) this gives the phase relationship f2 h; k f1 h; k 2phn0 =N km0 =M (3) Choose the strongest reections in the two directions for the Fourier transforms of the two images to compare and calculate the translation (n0 ; m0 ) that satises the equations
N n0 2ph f2 h; 0 f1 h; 0; M m0 2pk f2 0; k f1 0; k:

(4) Depending on whether h and k are odd or even, there is an ambiguity in the translation of N=h; M=k that one may try to resolve by considering more than 1 reection in each direction or by using a reection of the type (h; k). The algorithm used in this work included using cross terms and higher-order reections to attempt to resolve translational ambiguity. If the cross-correlation coecient based on the amplitudes of the Fourier transform indicates a possible good t, the image is shifted by (n0 ; m0 ) and the exact cross-correlation coecient is calculated. While the CCC is a good indicator of how well the patterns of the images match, the chi-square (w2 ) goodness of t parameter is a better indicator of the overall similarity of the images as it also takes into account the image contrast and the uncertainty of the experimental data. The w2 is given as 1 X I1 i; j I2 i; j2 w2 N M i;j s2 i; j where si; j gives the standard deviation for pixel (i; j) of the experimental image, N is the number of pixels in the image and M is the number of adjustable parameters. Of the models that were tested, only the PW model produced images comparable to the experimental data. Fig. 3 shows the map of cross-correlation coecients giving goodness-of-t values for the investigated range of thickness and defocus for the PW model. Although the highest obtained value for CCC (0.90) indicates a relatively good t between experiment and theory, both the value for w2 and the dierence image indicate denite discrepancies between

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

67

Fig. 3. Map of the cross-correlation coecient (a) as a function of thickness and defocus for the PW model. Best agreement (CCC=0.90) is found for a thickness of 11.2 nm and a defocus of 10 nm. Average experimental image (b); corresponding best match simulated image (c); dierence image between experiment and simulation (d) together with the color scheme used for expressing the dierence between the two images in units of the standard deviation of the experimental image.

experiment and theory. In addition the associated defocus is quite far from the defocus value of about 70 nm obtained from the experimental data. This led to a search for an alternative model for the structure of the S-phase. Because of the supportive evidence from X-ray data, electron diraction, EDS microchemical analysis and previous studies of the S-phase structure, it was concluded that any proposed structure should have the stoichiometry Al : Cu : Mg of 2 : 1 : 1, lattice parameters similar to those originally reported by Perlitz and Westgren [1] and space-group Cmcm. Thus a new model was introduced, referred to as the RaVel model, where the Cu and Mg exchange position within the structure. It should be noted that this leads to inter-atomic distances between Al and Mg of the order of 2.5 A, which are smaller than those found in other Al and Mg intermetallic compounds such as Al5Cu6Mg2 [16], Al4MgY [17], Al3Mg [18] and the original P/W model for S-phase [1]. In these structures bond distances between Al and Mg are around 3 A. However, since the covalent radii of Al and Mg are 1.25 and 1.36 A, respectively, the bond length in the proposed model can still be considered realistic. In order to compare the t between theory and experiment for the two models, the Cu/Mg sites were switched gradually by testing the structure as PW1x RaVelx where x 0 gives the PW model (all Cu and Mg on the original sites) and x 1 gives the RaVel model (all Cu and Mg atoms switched). Fig. 4 shows the surface of the ln(w2 ) t for the investigated range of defocus (+20 to 110 nm) and thickness (1.6 to 16 nm) for the PW model (a) and for the RaVel model (b) while Fig. 5 gives the lowest value for w2 and the cross-correlation coecient as a function of x. As can be seen

68

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

Fig. 4. Surface plots showing values for the goodness of t for the investigated range of thickness and defocus for the PW model (top) and the RaVel model (bottom). In order to show more clearly the dierence between the ts for the two models, the natural log of chisquare is shown.

Fig. 5. Chi-square and cross-correlation coecient plotted as a function of x where the structure is modeled as PW1x RaVelx . The abrupt change in best t for x 0 happens because the optimum conditions change from around a thickness of 5.6 nm and a defocus around 85 nm to a thickness of 11.2 nm and a defocus of 11 nm.

from Fig. 5, a complete exchange of Cu and Mg gives the best t. Using a parameter grid sampling of 2.5 nm in focus and 0.4 nm in thickness, the best match between the experimental image and the computed image for a complete exchange of Cu and Mg, but without any change in atomic positions, gave a crosscorrelation coecient of 0.9955 and a w2 of 2.76.

4. Rening the imaging parameters and the specimen thickness The next step was to rene the foil thickness and the imaging parameters. This was done through an automatic renement procedure employing simulated thermal annealing [19]. An eective energy for the

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

69

conguration of adjustable parameters was dened as E w2 X Ie i; j Ic i; j2 1 N M i;j s2 i; j e

where M is the number of adjustable parameters. Simulated thermal annealing starts with an initial dimensionless temperature T0 and an initial guess for the adjustable parameters {xi }. A new set of parameters {x0i } is produced and the new conguration is always accepted if DE Ex01 ; x02 ; . . . ; x0n Ex1 ; x2 ; . . . ; xn 50. Otherwise the new conguration has a probability P of being accepted, where P eDE=T . After a given number of successful transitions to a lower energy (or a predened maximum attempts), the temperature is lowered by a given amount and the system gradually approaches its nal temperature. In this fashion, the hope is that the system moves towards its ground state, the set of parameters that minimizes the conguration energy. The parameters that were used in the renement procedure were specimen thickness, objective lens defocus, spread of defocus due to chromatic aberration and spatial incoherence of the electron beam (convergence angle). Table 1 shows the nal values at the end of the renement. It should be noted that the value for defocus is in agreement with the value of 73 nm that was obtained by taking the Fourier transform of the amorphous region adjacent to the precipitate and estimating the defocus from the contrast transfer of the objective lens.

5. Rening the structure Once the imaging parameters were determined as accurately as possible, the fractional coordinates of the atoms in the unit cell were rened. In order to keep the space group of the structure it was necessary to modify the algorithms such that only the positions of the atoms in the motif are varied. In order to do so, the unit cell was transformed into a new unit cell given by the transformation matrix T that relates the new and the old axes of the unit cell. The relationship between the old and the new axes is given as 0 01 0 1 0 1 a a 0 1 0 B 0C B C B C @ b A T @ b A where T @ 0 0 1 A: c 1 0 0 c0 The symmetry operators for the space-group Cmcm with respect to the new unit cell were subsequently transformed according to the operations T 0 0 SR USR U 1 ST UST USR 1a0 where U T 1

Table 1 Initial P/W and rened RaVel atomic positions of Al2CuMg Atom Initial-PW x Cu Mg Al 0 0 0 y 0.072 0.778 0.356 z 0.25 0.25 0.056 Rened-RaVel x 0 0 0 y 0.765 0.074 0.362 z 0.25 0.25 0.056

70

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

Table 2 Al2CuMg interatomic distances for the Perlitz/ Westgren (P/W) model and the RaVel model Atom Cu in 4(c) Surrounding atoms 2 4 1 2 1 2 1 1 2 1 2 2 1 2 2 4 Al in 8(f) Al in 8(f) Mg in 4(c) Mg in 4(c) Cu in 4(c) Cu in 4(c) Al in 8(f) Al in 8(f) Al in 8(f) Mg in 4(c) Mg in 4(c) Mg in 4(c) Cu in 4(c) Cu in 4(c) Al in 8(f) Al in 8(f) PW atomic distance (nm) 0.251 0.254 0.272 0.276 0.251 0.254 0.277 0.277 0.291 0.295 0.315 0.303 0.272 0.276 0.295 0.308 Rened atomic distance (nm) 0.300 0.304 0.285 0.269 0.300 0.304 0.278 0.278 0.300 0.248 0.261 0.261 0.285 0.269 0.248 0.261

Al in 8(f)

Mg in 4(c)

SR and ST are the rotation and the translation parts of the symmetry operator matrix. a0 is a translation of the origin, which in this case is 0. It should be noted that an arbitrary shift of the origin results in a system that no longer can be described by the same spacegroup. Only three atoms are unique with the rest being symmetry related. The initial positions for the RaVel model are taken from the coordinates given in the literature for the PW model. These coordinates with respect to the transformed cell are shown below in Table 1. The y-coordinates of the Cu and Mg atoms are special and cannot be varied. Changing these would result in more atoms in the unit cell than physically possible. The starting point for the structural renement is shown in Fig. 5. The results obtained from the structural renement are shown in Fig. 6 and the rened positions are shown below. In order to assign error estimates on the values, one should explore the behavior of chi-square as a function of the adjustable parameters. This is a non-trivial computational task and no such attempt was done. Based on the rened atom positions given in Table 1, it is possible to dene coordination and interatomic distances in the Al2CuMg phase. These are given below in Table 2 together with the values dened by PW [1].

6. Discussion The results from a on quantitative comparison between the experimental and theoretically calculated images from postulated models together with the renement of the atomic positions and imaging parameters point towards a new model for the S-phase precipitate Al2CuMg in Aluminum. Previous X-ray diraction [7] and electron diraction [20] experiments are in agreement with the spacegroup Cmcm and report lattice parameters close to those obtained in this work, a 0:403 0:001 nm, b 0:930 0:013 nm, and c 0:708 0:01 nm. Although the results obtained from the X-ray and electron diraction experiments cited above were used to support the PW model, we believe that the sensitivity of these methods were insucient to distinguish between the PW and the RaVel model for the nanometer sized S-phase precipitates.

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

71

The cross correlation coecient (CCC) measures similarity of patterns and is an incomplete measure of the goodness of t. The match between the experimental image and the simulated image can better be expressed using chi-square, w2 , which is a measure of the dierence between the two images, taking into account dierences in image mean, image contrast and the uncertainty of the experimental data. There is often a discrepancy between the contrast in simulated and experimental images, sometimes by as much as a factor of 3 or higher [11]. While the cross-correlation coecient only measures pattern similarity and is thus insensitive to the overall contrast, chi-square is highly sensitive to image mean and contrast dierences. Thus it is often not possible to obtain a low value for chi-square even when the patterns match extremely well. In this work, the relative large uncertainty of the experimental data due to the small number of available unit cells probably contributes to the low value for chi-square. Similarly, applying a Wiener lter to the experimental image eects the signal-to-noise ratio and consequently chi-square. Any eect of tilt that also in principle could eect our results was taken out by the averaging over the 2D symmetries of the unit cell. Alternatively, the tilt could have been included as adjustable parameters to be rened. The nal value for w2 of 1.004 after renement of imaging and structural parameters states that the calculated image ts the experiment within the uncertainty of the experimental data points (the pixel values of the experimental image). This does not exclude all other models since one cannot prove that there does not exist another model which also agrees with the experimental data. Likewise, the coordinates for the rened structure all have associated uncertainties. In principle these could be determined by examining the values of w2 as a function of all parameters (and their uncertainties) that determines the experimental image. If there were only a single coordinate to be rened, the uncertainty in the coordinate would be estimated by examining w2 as a function of the coordinate. Since the goodness of t parameter w2 depends on all coordinates simultaneously and the theoretical image is known only to the accuracy of the input parameters (such as accelerating voltage and spherical and chromatic aberrations of the objective lens), the determination of the uncertainties in the given quantities becomes a non-trivial computational task and is outside the scope of this paper.

7. Conclusions By careful analysis of experimental images taken of S-phase Al2CuMg in aluminum and by comparing these images to image simulation while using automatic techniques for rening structural parameters and imaging parameters, it is believed that a new model, with space group Cmcm (No. 63, Pearson symbol oC16) and lattice parameters: a 0:403 0:001 nm, b 0:930 0:013 nm, and c 0:708 0:01 nm, ts the experimental data better than any previously suggested model. This model is based on the model given by Perlitz and Westgren, but diers in an exchange in the positions of the Mg and Cu atoms. The initial atomic coordinates have been further rened while preserving the symmetry of the space group. These new coordinates lead to a new set of proposed bond distances for Al2CuMg. Integrating the transformation of the symmetry operators as a function of the zone axis simplies the inclusion of symmetry constraints in the automatic renement procedure. Likewise, by comparing images in reciprocal space and investigating the phase relationship between strong Fourier components of the two images it is possible to quickly determine if the two images are similar and to estimate possible translational shifts of one image with respect to the other.

Acknowledgements This work is supported by the Director, Oce of Energy Research, Oce of Basic Energy Sciences, Materials Sciences Division of the US Department of Energy under Contract No. DE-AC03-76SF00098.

72

R. Kilaas, V. Radmilovic / Ultramicroscopy 88 (2001) 6372

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] H. Perlitz, A. Westgren, Ark. kemi Mineral Geol. 16B (1943) 1. F. Laves, H. Witte, Metallwirtschaft 15 (1936) 15. H. Nishimura, Mem. Colloid Eng. Kyoto, Imp. Univ. 10 (1937) 18. L.F. Mondolfo, Aluminum Alloys}Structure and Properties, Butterworths, London, 1976 p. 497. F. Cuisiat, P. Duval, R. Graf, Scr. Metall. 18 (1984) 1051. J. Yan, L. Chunzhi, Y. Minggao, J. Mater. Sci. Lett. 9 (1990) 421. J.I. Perez-Landazabal, M.L. No, G. Madariaga, J. San Juan, J. Mater. Res. 12 (1997) 577. H.W. Zandbergen, S.J. Andersen, J. Jensen, Science 277 (1997) 1221. S.J. Andersen et al., Acta Mater. 46 (1998) 3283. A. Thust, K. Urban, Ultramicroscopy 45 (1992) 23. M.J. Hytch, W.M. Stobbs, Ultramicroscopy 53 (1994) 191. W.E. King, G.H. Campbell, Ultramicroscopy 56 (1994) 46. H. Zhang et al., Ultramicroscopy 57 (1995) 103. R. Kilaas, J. Microsc. 190 (1998) 45. S. Paciornik, R. Kilaas, J. Turner, U. Dahmen, Ultramicroscopy 62 (1996) 15. S. Samson, Acta Chem. Scand. 3 (1949) 809. O.S. Zarechnyuk, M.E. Drits, R.M. Rykhal, V.V. Kinashibalo, Russ. Metall. 5 (1980) 214. H.L. Luo, C.C. Chao, P. Duwes, Trans. AIME 230 (1964) 1488. A. Thust, M. Lentzen, K. Urban, Ultramicroscopy 53 (1994) 101. A.K. Gupta, P. Gaunt, M.C. Chaturvedi, Philos. Mag. A 55 (1987) 375.