J O U R N A L O F M A T E R I A L S S C I E N C E L E T T E R S 2 1, 2 0 0 2, 1249 1251

Recursive packing of dense particle mixtures

J. A. ELLIOTT, A. KELLY, A. H. WINDLE Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge, CB2 3QZ E-mail: jaelool@cam.ac.uk

The quest to obtain the densest possible randomly packed arrangement of hard, geometric particles of varying shapes and sizes is an ongoing and physically challenging problem, with very wide applications in sciences and engineering. The bulk density of a packed assembly is characterized by the packing fraction, which is the ratio of the particle volume to the total occupied volume of the system. We present a straightforward recursive volume-lling model which can account for the maximum packing fractions attainable using randomly ordered mixtures of particles of discretely different sizes but similar shapes, and the relative proportions of each component required for optimum packing. We make use of existing experimental data on spherical particles where the particle size is characterized simply by the diameter, and for which a wide variety of sources are available. The model contains a single parameter x which is the maximum packing fraction attainable for randomly packed particles of a single size. For spheres, values of x between 0.6 and 0.64 have been obtained in both experiments [18] and computer simulations [9, 10]. These are 1419% lower than the closest-packed value of /3 2 0.7405, and the = cause of this discrepancy is still not well understood [11, 12]. However, it is not our intention to justify a particular value for x. Rather, by taking an experimental value for this parameter, a simple recursive interstitial lling argument can predict the total packing fraction for mixtures of particles of different sizes, and accounts closely for the existing experimental data on mixtures of spheres. Deviations from the model are due to limits on the arrangements of particles within the interstices set by the relative sizes of the components. In order to improve on the packing density for particles of a single size, it is necessary to ll the interstices between the larger particles with smaller particles without disrupting the original packing. Such arrangements are often called Apollonian packings, [13, 14] after Apollonius of Perga who studied the problem of recursively inscribed circles in two dimensions ca. 200 BCE. In fact, this is not the most efcient way to ll the gaps between the larger particles because the smaller particles do not t the interstices well. Also, there are practical difculties in constructing such tight recursive packings. In reality, the best that can be hoped for is to ll the interstices with the same efciency as the larger particles ll space.
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In the case of unit spheres, the smallest possible hole in a randomly packed structure is a triangular pore made by three spheres in contact, which has a radius of approximately 0.154. This leads to the condition that the secondary spheres should be at least 6.46 times smaller than the primary ones if they are to percolate through the packed assembly and ll all the interstices in it. This idea was suggested in passing for binary sphere mixtures by Yerazunis and co-workers, [15] and we have developed it further as follows. To illustrate our approach, let x be the packing fraction attained by randomly packing particles all of the same size and shape. Then, the free volume remaining is (1 x). Suppose now that this free volume may be packed to the same efciency by a second population of particles of similar shape. The packing fraction obtained is then given by Equation 1: Q = x + (1 x)x. (1)

Equation 1 requires not only a signicant size difference between the two sets of particles, but also that the relative volume fractions of the particles take particular values. The volume fractions for the densest total packing of the two sizes of particle will be: c1 = x/Q = x 1 = x + (1 x)x 2x (2)

and c2 = (1x)x/Q =

1x (1 x)x = . (3) x + (1 x)x 2 x

So, if x = 0.625, the experimental value for spheres found by McGeary, [5] then Q = 0.625 + 0.235 = 0.859, and the volume fractions of two components as a proportion of the total packing fraction are c1 = 0.727 and c2 = 0.273. We can now generalize this argument to mixtures with more than two components as follows. If we dene Q N as the maximum packing fraction that can be achieved using an N -component mixture of particles of different sizes then by denition, Q 1 = x. So, assuming the interstices of each particle packing are lled with the same efciency as the packing of particles of a single size, we have: Q N +1 = Q N + (1 Q N )x. (4)

Transforming this recursion relation into an explicit

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2002 Kluwer Academic Publishers

T A B L E I Comparison of predictions of volume-lling model with experimental data c1 N 1 2 3 4 Theory 1.000 0.727 0.660 0.638 Expt. 1.000 0.723 0.670 0.607 Theory 0.273 0.247 0.239 c2 Expt. 0.277 0.230 0.230 Theory 0.093 0.090 c3 Expt. 0.100 0.102 Theory 0.034 c4 Expt. 0.061 Theory 0.625 0.859 0.947 0.980 QN Expt. 0.625 0.840 0.900 0.951

Values of the relative proportions of spheres cn for maximum density packings of N -component mixtures calculated from the recursive lling model, together with packing fractions, compared with experimental data of McGeary [5].

formula for Q N , we obtain: Q N = 1 (1 x) N . (5)

of the smaller components due to practical limits on particle size. This issue can be made clear using the model in the following way. From Equation 5 we can derive the inversion formula: x = 1 (1 Q N )1/N (11)

This implies Q N 1 as N independently of x, provided x 1, which is the expected asymptotic limit for a mixture with an innite number of components. In order to construct the recursively packed mixtures with a nite number of components, the relative proportions of each component cn , where c1 is proportion of the largest size component, can be calculated from the ratio of the partial packing fraction qn of component n to the total packing fraction Q N . The total packing fraction is related to the partial packing fractions of each component by Equation 6, and the values of cn by Equation 7.
N

QN =
n=1

qn .

(6) (7)

cn = qn /Q N . The values of qn must satisfy a recursion relation: qn+1 = (1 qn )x

(8)

which can be transformed into an explicit equation for qn : qn = x(1 x)n . (9)

Substituting Equations 5 and 9 into Equation 7 yields an explicit expression for cn : x(1 x)n cn = qn /Q N = 1 (1 x) N (10)

So, given Q N we can infer x from the successive orders of experimental data in addition to the rst, and use this to assess the quality of our model. Specically, we can test the assumption that x remains constant at each lling iteration. The results for McGearys data [5] are given in Table II, and it is found that the value of x obtained varies somewhat with N . In general, the values become smaller as N becomes larger. This is due to the practical limitations in obtaining monodisperse spheres with which to construct a packed assembly whose relative sizes are sufciently different that each successive level of interstices is maximally lled. The size ratios for the sphere packings of McGeary are given in Table III. In general, a size ratio of at least 10 : 1 is needed between each component for the packings to be independent, as assumed in the model. As noted by McGeary, [5] this is just above the percolation limit dictated by the triangular pore size. If the size ratio is not sufciently large then the packings will be less dense due to nite size effects at the boundaries of the interstices. So, if the largest particles are of the order of centimeters, then the smallest must be of the order of microns for a quaternary mixture. This explains why, in practice, it is rare to nd particle mixes with more than four size grades

T A B L E I I Application of Equation 8 to infer value for x from McGearys [5] maximally dense N -component sphere mixtures N 1 2 3 4 QN 0.625 0.840 0.900 0.951 x 0.625 0.600 0.536 0.530

which can be used to calculate the appropriate proportions of particles with which to construct an maximally dense randomly packed N -component particle mixture. The predicted relative proportions for binary, ternary and quaternary mixtures of spheres, calculated assuming x = 0.625, are compared with the experimental data of McGeary [5] in the rst four columns of Table I. The relative sizes of the components are not specied in our model; it is assumed that the size ratio of successive components is sufciently large so that random packing is achieved within all interstices. Although the calculations are generally in good agreement with experiment, there are some discrepancies in the relative amounts
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T A B L E I I I Size ratios of McGearys [5] maximally dense N -component sphere mixtures N 1 2 3 4 Size ratio(s) 1 1 : 77 1 : 7 : 77 1 : 7 : 38 : 316

of components, as it is not possible to ll the interstices more efciently using additional ner grades due to the inuence of non-geometric forces. It is worth noting that we have not assumed anything about the shapes of the particles involved in the recursive lling model. Thus, the arguments presented could apply equally to similar angular particles which pack randomly with a different value of x to spheres. However, it would be necessary to dene some mean size parameter for the particles, and it might be expected that the boundary effects in the interstices would have a different, possibly more severe, effect on the nested packing of particles which are not sufciently different in size. We nish by reiterating our main conclusion that it is possible to predict quantitatively both the maximum packing fraction and relative proportions of components in a mixture of particles of similar shape under the assumption of random packing by using a simple recursive procedure, provided that the relative sizes of each component are such that they pack independently.

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Received 18 March and accepted 22 April 2002

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