PHILOSOPHICA L M AGA ZINE A , 1999, V OL. 79, N O.

3, 549± 560

Determination of the tiling type and phason strain analysis of decagonal quasicrystals in Al± Ni± Co alloys
By R. Hory, C. Pohla and P. L. Ryder
Institut fu r Wersto physik und Strukturforschung, University of Bremen, È Germany
[Received 29 January 1998 and accepted in revised form 7 May 1998]

From high-resolution electron micrographs of the decagonal phases of the Al 72. 5 Co11 Ni16 . 5 and Al 70 Co15 Ni 15 alloys, tilings are produced by connecting prominent structural features. Indexing the tiling vertices as the projection of a ® ve-dimensional periodic lattice and investigation of the distribution of the vertices in orthogonal space gives information about the tiling model and possible phason strains. The technique also reveals domain boundaries which separate regions di ering only in the amounts of linear phason strain.

A bstract

§ 1. Introduction The structures of quasicrystals can be regarded as the intersection of a periodic structure in 3 n dimensions n 1 2 3 with the three-dimensional physical space E (Janssen 1988 ) . The n-dimensional subspace is called the internal or orthogonal space E . The well known Penrose tilings and their generalization s (Penrose 1974, Janssen 1988 ) are frequently used models for quasicrystal lattices. Elastic excitations in the physical and orthogonal spaces correspond to phonons and phasons respectively (Lubensky et al. 1985 ). The relaxation of a phason ® eld is associated with the di usion of atoms. Thus phason defects can easily be quenched into quasicrystals and are di cult to remove by annealing. In the tiling models of quasicrystallin e structures, phasons correspond to local rearrangement of the vertices, so-called phason ¯ ips (Elser 1985, Tang and Jaric 1990 ) . Â The structural changes caused by phasons in¯ uence the di raction properties of quasicrystals . A linear phason strain, for example, results in the displacement of the Bragg spots in electron di raction patterns and a change in the pro® les of X -ray re¯ ections (Lubensky et al. 1986 ) . A phason strain whose Fourier components are independent random variables is called a random phason strain and leads to a broadening or even disappearanc e of Bragg peaks (Lubensky et al. 1986 ). Other physical properties, such as the electrical conductivity or the speci® c heat, are also in¯ uenced by a phason strain (Y amamoto and Fujiwara 1995, Wang and Garoche 1997 ) . In addition, certain types of linear phason strain may transf orm the perfect quasicrystal into a crystalline approximant . Such transf ormations have been observed in various alloy systems (Hu and R yder 1994, Zhang and Kuo 1990, Cheng et al. 1992 ). The phason strain tensor can be calculated in principle from the displacements of the spots in the electron di raction patterns or from the X -ray di raction peak pro® les (Lubensky et al. 1986, Edagawa 1990 ) . However, these methods, especially the latter, provide only a mean value over a certain volume of the quasicrystal.

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R . Hory et al.

High-resolution transm ission electron microscopy (HRTEM ) allows local variations in the phason strain to be detected on a very small scale (Li et al. 1992, Jiang and Kuo 1994 ) . In the electron microscope image of a decagonal structure taken along the decagonal axis, characteristic ring features are visible, corresponding to the local decagonal arrangem ent of columns (Hiraga et al. 1991, Beeli and Horiuchi 1994 ) . In order to reveal the tiling which is characteristic of the particular quasicrystal, the ring centres must be connected by straight lines with a ® xed base length a0 . In the present paper, the tiling determined in this way is used to measure the local phason strain matrix, to detect domains with di erent phason strains and to identif y the type of tiling by analysing the distribution of the vertices in E .

§ 2. Theory
2.1. Indexing When the tiling has been produced as described above, the vertices can be indexed and `lif ted’ into the ® ve-dimension al space, for example by a technique ® rst proposed by Chen et al. (1990 ) and He et al. (1991 ) . This procedure makes use of the fact that two-dimensional quasiperiodic tilings can be represented as the projection of a periodic ® ve-dimensional lattice. 5 Let E be the ® ve-dimensional hyperspace and ei the base vectors of the lattice, with

ei

2 5

1 /2

cos

2p i 1 5 sin

,

sin

2p

i
5 1

1

,

cos

4p

i
5

1

,

4p i 1 5

, 2 1 /2 , ,
sin 2p i 1 5

E the two-dimensional physical space spanned by the base vectors

ei
and E

2 5

1 /2

cos

2p i 1 5

,
1

the three-dimensional orthogonal space spanned by the vectors

ei

2 5

1 /2

cos

4p i 1 5

,

sin

4p

i
5

1

, 21 /2 , , , , ,

where i 1 . . . 5. The projection direction is the hyperlattice unit cell diagonal d 1 1 1 1 1 . A vertex x in E can thus be assigned the ® ve indices n1 . . . n5 such that

, ,

, ,

5

x
i 1

ni ei .
may be calculated.

With the aid of these indices the projection in E
5

x
i 1

ni ei .

Tiling of decagonal quasicrystal in Al± Ni± Co
5 5

551

Since 0 (and 0 , the indexing is not unique without a i 1 ei i 1 ei further restriction, which we shall arbitrarily take to be 0<
5

ni <

4.

i 1

2.2. Phason ¯ uctuations The distribution of the vertices in the orthogonal space E may be interpreted in a variety of ways. The behaviour of the mean quadratic deviation of the points from their centre of gravity as a function of the number N of vertices,

QN

1

N

N

xi
i 1

1

N

2

N

xi
j 1

,

may give an indication of the type of tiling (Chen et al. 1990 ) . For an ideally quasiperiodic tiling, we expect Q to be independent of N, because the points are restricted to a `window’ in E . Zhang et al. (1993 ) used this criterion to demonstrate the existence of a nearly perfect Penrose tiling in decagonal A l62 Co 20 Co 15 Si3 . In the case of a random tiling, it has been suggested that Q N should increase proportionally to ln N (Chen et al. 1990 ) . Frequently, however, Q N is neither constant nor proportional to ln N. In such cases, examination of the distribution of points in E usually reveals the superposition of several groups of N points, each group being associated with a well de® ned local region of the quasicrystal. Such `domains’ , in which the phason strain is locally constant but di erent from the neighbouring domains, are not directly visible in the electron micrographs. Separate plots of Q N against N for each domain show the expected proportionalit y to ln N (or Q N constant ) . 2.3. L inear phason strain In the case of a tiling which is related to a perfect quasicrystal through a linear phason strain, the matrix S which describes this phason strain may be calculated by minimizing the function (Niizeki et al. 1994 )

F S,U

1

N

N

xi
i 1

S ui

U

2

with respect to S and U , where xi are the position vectors of the tiling vertices, xi are the corresponding vectors in E , U is the phase vector characteristic for the tiling and S the linear phason strain tensor. The solution is
S BA
1

,
S x

U

x

,
2 matrix B are given by

where the components of the 2

2 matrix A and the 3

Akj Bij

xk xj xi xj

xk xj xi

,

xj .

The angular brackets denote mean values.

552

R . Hory et al.

The magnitude of the phason strain may be represented by the ellipse associated T S S ; the square roots of the two semiaxes of this ellipse are with the matrix M equal to the principal values ¸1 and ¸2 of the phason strain. 2.4. Tiling m odels With knowledge of the phason strain matrix S and the phase vector U , the vertices of a speci® c tiling model may be calculated. Such a model is obtained by the projection of a subset of the ® ve-dimensional lattice vectors x x x in the physical space E (Janssen 1988 ). The subset is de® ned as those vectors x for which x U lies within a certain volume W (the so-called window ) in E . The well known rhombic Penrose tiling, for example, is obtained when W is de® ned as the rhombic icosahedron formed by the projection of the ® ve-dimensional unit cell (hypercube ) in E . We shall denote this window by W0 . The so-called pentagonal Penrose tiling is obtained with a prismatic window W1 having the same height as W0 and a decagonal base, the vertices of which are the projections of the ® ve base vectors and their inverses. A nother generalized Penrose tiling is obtained with a window W2 which is similar to W1 , but with a smaller decagon as base, de® ned as the area common to two pentagons, one formed by the projections of the ® ve base vectors and the other by the projections of their inverses (Niizeki et al. 1994 ) . The tiling resulting from the linear phason strain is obtained as the projection of Sx all vectors x with x U W S , where W S is the deformed window resulting from the phason strain (Niizeki et al. 1994 ) . One possible criterion for the choice of a particular tiling model is the density q of the vertices in E , which is equal to the ratio of the volume of the window in E 5 to the volume of the unit cell in E (Elser 1986 ) . Taking the lattice parameter of the ® ve-dimensio nal lattice as the unit of length, we obtain, for the window 1 2 W0 q 0 ¿ 2 ¿ / . The tilings produced by the windows W1 and W2 have the densities q 1 0. 85q 0 and q 2 0. 62q 0 respectively. When the experimental tilings are compared with those calculated using S and U , it is generally found that not all ring centres lie on the theoretically predicted positions, because of the presence of a random phason strain. A measure of the mis® t is d n /N, where n is the number of points outside the window and N the total number of points (Niizeki et al. 1994 ) .

,

,

2.5. Fourier method The Fourier transf ormation of the points in E can also be used to distinguish between ideally periodic and random tilings (Joseph et al. 1997 ) . This method makes use of the fact that the sharp edge of the vertex distribution in E of a perfect quasiperiodic tiling gives rise to secondary maxima in the Fourier spectrum, whereas a random tiling produces a Gaussian distribution.

§ 3. Experimental Methods Ternary A l± Co± Ni alloys were prepared by melting the pure elements in an arc furnace under argon. The composition s and heat treatments of the alloys investigated were as follows: A l72 . 5 Co 11 Ni 16 . 5 held for 10 min at 1050 ë C, then cooled at 1 10 K min to 860 ë C and ® nally homogenized for 5 days at 925 ë C; A l70 Co 15 Ni15 , 3 days at 930 ë C Specimens for the HRTEM investigations were obtained by grinding the materials under methanol and transf erring drops of the resulting suspension onto micro-

Tiling of decagonal quasicrystal in Al± Ni± Co

553

grids. A Philips CM20( UT ) electron microscope with a point resolution of 0.19 nm operating at 200 kV was used.

§ 4. R esults
4.1. Alloy Al 72 . 5 Co 11 Ni 16 . 5 Figure 1 shows the high-resoluti on image of the decagonal phase in A l72. 5 Co 11 Ni16. 5 . The centres of the most prominent structural features (arrangements of ten bright spots in a ring ) were taken as the vertices of the tiling, which is made up mainly of pentagons and in addition thin and thick rhombi and hexa-

(a )

(b )

Figure 1. (a ) High-resolution electron micrograph of the decagonal phase in A l7. 25 Co 11 Ni16. 5 . The tenfold axis is parallel to the incident electron beam. (b ) Corresponding tiling formed by connecting the ring centres in (a ) .

554

R . Hory et al.

gons. The thin rhombi are frequently arranged in such a way that they overlap and form a ® vefold star. The projection of the tiling vertices in E is shown in ® gure 2 (a) . The projection consists of a single cluster of points with a di use boundary. A part from some scatter at small numbers, the scatter Q N is independent of N (® gure 2 (a)) , indicating that the tiling may be ideally quasiperiodic, although this conclusion is not conclusive on account of the relatively small number of vertices measured.

Figure 2. ( a) Projection of the tiling vertices of ® gure 1 onto the x± y plane of the orthogonal space. ( b) Phason ¯ uctuation Q N as a f unction of the number N of vertice (logarithmic) for the whole tiling of ® gure 1 ( b) . (c ) Orthogonal space projection of the tiling vertices from ® gure 1 ( b ) after reverse transformation and the corresponding window S W 1 . ( d ) Tiling for the quasicrystal in ® gure 1 (a ) , calculated with S and U ; ( ), experimental tiling; ( s ) , calculated tiling; ( d ) , coincidences.

Tiling of decagonal quasicrystal in Al± Ni± Co

555

The density of the points in the experimental tiling is in this case q 2 . 7 q 1 ; so the window W1 was used for the tiling model. Figure 2 (c) shows the projection in E S and the distorted window W1 af ter reverse transf ormation with the matrix S and the phase vector U . On account of the almost negligible phason strain ¸1 0 . 01; ¸2 0. 006 ) , the window is only slightly distorted. The mis® t between the experimental and calculated tilings (® gure 2 (d)) is d 0 . 26.

4.2. Alloy Al70 Co 15 Ni 15 The high-resoluti on micrograph and the correspondin g tiling for the decagonal phase in A l70 Co 15 Ni 15 are shown in ® gure 3. In this case the tiling consists mainly of thick and thin rhombi. In addition, there are some pentagons, di erent hexagons and other polygons, but these shapes are clearly in the minority. The projection of the tiling vertices in E , shown in ® gure 4 (a ), does not display the decagonal symmetry expected for a Penrose-type tiling (Edagaw a et al. 1994, Niizeki et al. 1994 ) . Furthermore, the distribution appears to be the result of the superposition of two di erent `clusters’ of points, as indicated by the circles in the ® gure. Further investigation of the correspondence between the points in E and E shows that each cluster in E corresponds to a spatially distinct region (domain ) of the tiling (® gure 3 (b )) .

( a)

(b )

Figure 3. (a ) High-resolution electron micrograph of the decagonal phase in A l70 Co 15 Ni15 . The tenfold axis is parallel to the incident electron beam. (b ) Corresponding tiling formed by connecting the ring centres in (a ) .

556

R . Hory et al.

(c )

Figure 4. ( a ) Projection of the tiling vertices of ® ure 3 onto the x± y plane of the orthogonal space. ( b) Phason ¯ uctuation Q N as a f unction of the number of N vertices ( logarithmic) for the whole tiling of ® gure 3 (b ) ( n ) and for the marked domains separately ( s , d ) . ( c) Tiling for the domain A of the quasicrystal in ® gure 3 ( a) , calculated with S and U : ( ) , experimental tiling; ( s ) , calculated tiling.

The plot of Q N against ln N for the whole of the tiling visible in ® gure 3 is shown in ® gure 4 (b ) (full circles ) . The resulting nonlinear curve does not comply with any of the above-m entioned tiling models. However, when Q N is plotted for each domain separately (open circles and open triangles ) , straight lines are obtained, in agreement both with the random tiling model (LancË on et al. 1986, Widom et al. 1987, 1989, LancË on and Billard 1988, Strandburg et al. 1989 ) and also with the model of an energetically stabilized quasicrystal with thermal phason ¯ uctuations (Kalugin 1989 ) . In domain A the plot of Q N against N shows a slight but statistically signi® cant upward slope, indicative of a random phason strain. In the case of domain B the number of vertices is too small to allow a de® nite interpretation. However, the calculated ¸ values indicate a greater phason strain in domain B (table 1 ) . The density of vertices in the experimental tiling is q 2 . 9, that is between the values for the pentagonal and rhombic Penrose tilings. Since the number of points projecting onto the same plane in E (points for which the sum of the indices ni has

Tiling of decagonal quasicrystal in Al± Ni± Co
Table 1. Domain A B ¸1 and ¸2 for domains A and B. ¸1 0.08 0.17 ¸2 0.04 0.07

557

Table 2.
4

(R elative ) number of points of the tiling in ® gure 6 ( b ) , projecting onto each plane in E .
4

i 0

ni

Ni
313 248 180 171 244

Ni

i 0

Ni

0 1 2 3 4

0.27 0.21 0.16 0.15 0.21

the same value ) was not the same for all planes (table 2) , the rhombic Penrose tiling was chosen as the suitable model. The orthogonal space projection of the vertices af ter the reverse transf ormation S using W0 and U 0. 589 0 . 052 0 . 815 are not shown here for reasons of space. Corresponding to the weak phason strain, the window is only slightly distorted. However, a relatively large number of points were found to lie outside the window d 0 . 45; ® gure 4 (c)) .

,

,

§ 5. Discussion The above examples show how an analysis of the projections of the vertices of an experimentally determined decagonal tiling in the orthogonal space can provide quantitative inf ormation about the phason deformation. The anisotropic distribution of the points in E was found to be due to the presence of domains di ering in their amounts of phason strain. The introduction of a phason strain in an ideal quasicrystal leads to the formation of periodic regions, so that the vertices in regions with di erent phason strains form di erent tilings. Nevertheless, no structural boundaries can be seen between the domains. One method of revealing such domains is to insert the A mman lines (for example Li et al. (1994 )); another, as shown in the present paper, is to examine the distribution of points in perpendicula r space. A nother point which is worthy of discussion is the relatively large mis® t between the experimental and calculated lattices in the case of the alloy A l 70 Co 15 Ni 15 . The mean square scatter of the vertices of the domain A in the orthogonal space clearly increases linearly with ln N (® gure 4 (b )), which is characteristic for two-dim ensional random tilings (Henley 1988 ) . However, the HRTEM image shows the projection of the three-dim ensional structure. In this connection, R itsch et al. (1996 ) have shown recently that the internal vertices of hexagonal tilings could not be determined uniquely because of contrast changes caused by phason ® ips in the stacking direction. Further, Henley (1991 ) has pointed out that random tiling models for stacked axial quasicrystals should also have a random component in the stacking direction. The entropy of a quasicrystal model in which a two-dimensional random tiling

558

R . Hory et al.

con® guration is simply repeated in the stacking direction would be proportional to the layer area, whereas it should be proportional to the volume to stabilize the quasicrystallin e equilibrium phase. A random stacking of random-tilin g planes would, however, lead to a great number of stacking faults, that is phason ¯ ips in the stacking direction. A s R itsch et al. (1996b ) showed, this would lead to a change in the contrast of the ring centres, with a consequent reduction in visibility or even extinction of the vertices. This would explain the fact that the observed vertex density (2.9 ) is less than the theoretical value q 0 3 . 08 . The introduction of stacking faults may thus lead to a more random arrangement of the ring centres, which would explain the observed divergence from the calculated tiling. The Fourier method of Joseph et al. (1997 ) was also applied to the two alloys investigated in the present work. Figure 5 (a ) shows the result for the alloy A l72 .5 Co 11 Ni 16 .5 and ® gure 5 (b ) that for the alloy A l70 Co 15 Ni 15 . In ® gure 5 (a ) the central peak is surrounded by a minimum, and there is an indication of a ® rst subsidiary maximum, whereas in ® gure 5 (b ) the Fourier amplitudes are quite random outside the main maximum . This would appear to con® rm the conclusions drawn from the above analysis, although the results for the `ideally quasicrystallin e’ phase are not as clear as those of Joseph et al. (1997 ) for the Ni-rich decagonal phase of the A l± Co± Ti system.

Figure 5.

Fourier transformation of the distribution of points in E for (a) A l72. 5 Co 11 Ni16. 5 (® gure 2 ( a )) and ( b) A l70 Co 15 Ni15 (® gure 4 (a ) , domain A ) .

Tiling of decagonal quasicrystal in Al± Ni± Co

559

In an earlier investigation of decagonal A l 70 Co 11 Ni19 , annealed at 1050 ë C for 12 h, Ritsch et al. (1996a ) used both the perpendicular space projection and scaling by a factor ¿ (`semi( de ) composition’ ) to demonstrate that the structure corresponded to an almost perfect Penrose tiling. Edagawa et al. (1994 ) investigated the type and perfection of the tilings of various decagonal phases in the A l± Ni± Co system by projection of the vertices into perpendicula r space and comparing with the acceptance domains for di erent tiling models. The same method was used by Hiraga et al. (1996 ) to demonstrate the high degree of perfection of the decagonal phase in A l71. 5 Ni23 .7 Fe4 . 7 . The present authors (R yder et al. 1998 ) have applied the methods described above to the analysis of the decagonal phase in A l70. 5 Mn 16 . 5 Pd 13 . A CKNOWLEDGEMENTS This work was supported by a grant from the Deutsche Forschungsgemeinschaf t. R eferences Beeli, C., and Horiuchi, S., 1994, Phil. Mag. B, 70, 215. Chen, H., Burkov , S. E., He, Y., Poon, S. J., and Shiflet, G. J., 1990, Phys. Rev. L ett., 65,
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