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Methodology for Determination of the

Maximum Packing Fraction for
Particle-Filled Polymer Suspensions
Article in Particulate Science And Technology October 2003
DOI: 10.1080/716100573

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Particulate Science and Technology, 21: 317325, 2003

Copyright # Taylor & Francis Inc.
ISSN: 0272-6351
DOI: 10.1080/02726350390240160

Methodology for Determination of the Maximum

Packing Fraction for Particle-Filled Polymer
Suspensions
TIAN HAO
RICHARD E. RIMAN
Department of Ceramic and Materials Engineering
Rutgers, The State University of New Jersey
Piscataway, New Jersey, USA
An analysis technique was developed on the basis of a modified version of Sudduths
model for calculating maximum packing fraction (MPF). Calculated MPF values
were compared with experimental values obtained with rheological methods. By
analysis of MPF data for three commercial titania powders dispersed in low
molecular weight polyethylene, a large difference was observed between the
experimental and calculated MPF values. For instance, a TiO2 P25=VF sample had
an experimental MPF of 0.15 while the calculated value was
0.8. To address this
issue, a was incorporated as a variable that would influence the packing fraction. By
studying the behavior of three different types of submicron titania, an empirical
equation was devised, that correlated a with particle size, particle size distribution,
and packing structure. This overall treatment appeared to be relevant for predicting
the a for binary millimeter steel powder mixtures. Thus, the form of this empirical
function may guide us towards developing a derivation of a quantitative expression
based on first principles.
Keywords: packing fractions, particle-lled polymer suspension, titania powders, steel powder mixtures

Introduction
The preparation of high solids loading particle-lled polymer suspensions is important to industry because of energy and cost savings derived from reduced transportation, mixing, and solvent removal (Dames et al., 2001). Determination of maximum
particle packing fraction (MPF) of particles of a given size distribution is also useful
for predicting the viscosity of such concentrated suspensions. Many researchers have
studied particle packing structure as a means of understanding how to optimize the

Presented at the 39th Annual Technical Meeting of the Society of Engineering Science, University
Park, Penn., Oct. 1316, 2002.
Support for this work was provided by the DuPont company. The authors are especially grateful to
Drs. Donald D. May, Dwight A. Holtzen, and Austin H. Reid for their valuable input on this project.
Address correspondence to Tian Hao or Richard E. Riman, Department of Ceramic and Materials
Engineering, Rutgers, The State University of New Jersey, 607 Taylor Rd., Piscataway, NJ 08854-8065,
USA. E-mail: haot@rci.rutgers.edu

317

318

T. Hao and R. E. Riman

maximum packing fraction (Cumberland & Crawford, 1987; Dextre & Tanner, 1971,
1972; Wakeman, 1975; Wise, 1952; Sudduth, 1993; Dames et al., 2001).
The packing fraction can be maximized when small particles are hierarchically
placed into interstices created by the large particles (McGeary, 1961). Relative to
mono-modal systems, the viscosity of bimodal suspensions is observed to be lower
for a wide range of particulate systems (Probstein et al., 1994). To explain this result,
it is believed that the rheological behavior of small particles functions independently
of that of the large particles. However, this hierarchic packing structure is not valid
for bimodal suspensions when the volume fraction occupied by the small particles
exceeds the interstitial volume provided by the large particles. The possible particle
packing congurations in such bimodal mixtures are complicated. The situation gets
far more complex when the particle size distribution has much more than two modes.
Sudduth (1993) proposed a method to estimate the maximum packing fraction,
Fmax, for any particle system having a size distribution without signicant particle
interactions as follows:

D
a 1
D5
1
Fmax Fult
Fult
Fmmono e
1
Fult 1
1
Fmmono

where, Fult is the ultimate packing fraction, Fmmono is the maximum monodisperse
packing fraction, n is number of different particle diameter classes in suspension
(e.g., for binary mixtures, n 2), and a is 0.268, which is a constant with no stated
physical signicance.
Sudduth obtained the value of a by tting McGearys binary particle packing
data using Equation (1). The various average particle diameters, D1 and D5, can be
dened as follows:
Pn
N Dxk
Dx Pn k1 k x
1
3
k1 Nk Dk
Sudduth calculated D1 and D5 using complex mathematical methods, which used eight
different parameters to describe the D5=D1 ratio. These parameters are not easily
determined from particle size measurements, especially with wide size distributions.
The aims of this article are to modify Sudduths model, develop a simple way for
calculating D5, and extend the capabilities of the equation for calculating the MPF
for suspensions with signicant particle interactions. Three different types of TiO2
powders were chosen, with particle sizes that span the submicron to nanometer
range. The MPF was calculated with our model on the basis of experimental particle
size measurements. The calculated MPF was compared with that obtained using
rheological methods.

Modication of Sudduths Model

For a particulate system of a relatively wide size distribution, the parameter n in
Equation (2) should be a very large number. Since Fmmono is usually larger than 0.5,
based on how particles geometrically pack together, Fult should be very close to 1.
Based on this, Equation (1) can be approximated as:

D
a 1
D5
1
Fmax 1
1
Fmmono e
4

Methodology for Determination of the Maximum Packing Fraction

319

Suppose that particles randomly pack in a highly loaded polymer suspension,

Fmmono can be either 0.639 for dense random packing or 0.589 for loose random
packing. D1 is the number average particle size that can be directly obtained from
particle size measurements. To calculate D5, a log-normal size distribution is
assumed for all of the TiO2 powders, which enables one to determine the number
average, D1, and the number geometric mean, DgN, and the geometric standard
deviation, sg. If the number distribution of a particulate system is log-normal, then
other types of weighted distributions are also log-normal and share the same geometric standard deviation as follows (Allen, 1997):
ln D1 ln DgN 0:5 ln2 sg

DgN and sg thus can be used to calculate D2, D3, and D4 using the following
transforms:
Pn
D2k Nk
ln D2 ln Pk1
ln DLS ln DgN 1:5 ln2 sg
n
k1 Dk Nk

Pn
D3k Nk
ln DSV ln DgN 2:5 ln2 sg
ln D3 ln Pk1
n
2
k1 Dk Nk

Pn
D4k Nk
ln D4 ln Pk1
ln DVM ln DgN 3:5 ln2 sg
n
3
D
N
k1 k k

where DLS is the length-to-surface average, DSV is the surface-to-volume average,

and DVM is the volume or weight moment average.
Using the same methodology outlined by Allen, the following relationship for
D5 was derived:
Pn
D5k Nk
ln D5 ln Pk1
ln DgN 4:5 ln2 sg
n
4N
D
k1 k k

Equation (5) can be combined with Equation (9) to yield Equation (10):
ln

D5
4 ln2 sg
D1

10

Equation (10) combined with Equation (4) indicates Fmax does not depend on size
but instead on the size distribution spread, as expressed by sg.

Rheological Methodology
A range of particle loadings (150 vol%) were prepared using the procedure outlined
in the following section. The viscosity of each sample was measured in a shear rate
range of 102 to 103 s1. The reciprocal viscosity against the particle volume fraction
was plotted and tted by a rst-order polynomial. This line was extrapolated to the
point where the reciprocal viscosity is zero. The volume fraction at this point was
dened as the maximum packing fraction (MPF). This is a plausible method since

320

T. Hao and R. E. Riman

the viscosity of the suspension is innity when the particle volume fraction
approaches the MPF. Thus, by denition, the reciprocal viscosity is zero at the MPF.

Experimental Methods
Three kinds of titanium dioxide particulate materials, TiO2 101, TiO2 104, and TiO2
P25, were used in this study (Table 1). The rst two powders were purchased from
DuPont (Wilmington, D.E.) and the third one was from the Degussa (Port Newark,
N.J.). A low molecular weight polyethylene, Versa Flow EVTM (VF) (Shamrock
Technologies Inc., Dayton, N.J.), was used as a dispersing medium. The suspensions
were prepared by stirring the particles with VF by hand until the particles were
visibly wetted. This was followed by deagglomeration with an ultrasonication horn
for 2 min (W380, Heat Systems, Inc., Farmingdale, N.Y.). The particle size distribution of each sample was directly measured in VF with ultrasonic attenuation
spectroscopy (DT-1200, Dispersion Technologies, Mount Kisco, N.Y.). Particle size
distribution data were found to be slightly dependent on the particle volume fraction. Thus, the size data reported in this article were obtained using a particle
concentration of 5 vol%. The viscosity of each sample was measured in a parallelplate rheometer (Rheometrics ARES, Rheometrics, Inc., Piscataway, N.J.).

Results and Discussion

The particle size distribution of TiO2 P25=VF suspension of 5 vol% particles is
shown in Figure 1. This powder, as well as the other two titanias, had a log-normal
distribution. Thus, these measurements can be used to calculate D2, D3, D4, and D5
using Equations (5)(9). The number geometric mean, DgN, and geometric standard
deviation, sg, of three TiO2 samples dispersed in VF, as measured with the DT-1200,
are listed in Table 2. Among those three samples, TiO2 101 has the largest number
geometric mean and geometric standard deviation, indicating that this sample has
the broadest particle size distribution. On the basis of the data presented in Table 2,
MPF can be calculated using Equation (4). The calculated results are shown in
Table 3 on the assumption that the particles will pack in either a loose or dense
random fashion. The calculated MPF values range from 0.71 to 0.88. Note that the
calculated MPF values are all anomalously high. This is because Sudduths model
assumes there is no strong interaction between particles in the suspension. However,
this is not true, especially for the TiO2=VF systems, since particle sizes are less than 1
mm and attractive interparticle forces can dominate their behavior (Cumberland &
Crawford, 1987).

Table 1
Raw materials used in this study
Nomenclature
TiO2 101
TiO2 104
TiO2 P25
VF

Material
Titanium dioxide
Titanium dioxide
Titanium dioxide
Poly(ethylene)

Manufacturer
DuPont
DuPont
Degussa
Shamrock

Methodology for Determination of the Maximum Packing Fraction

321

Figure 1. The particle size distribution of TiO2 P25=VF versus ow suspension of 5 vol%
particles obtained with DT-1200.

The reciprocal viscosity of each sample was plotted against the particle volume
fraction to measure the experimental MPF (Figures 24). The volume fraction values
corresponding to the reciprocal viscosity of zero are dependent on the shear rate. For
example, at shear rate 1000 s1 the MPF for TiO2 101, TiO2 104, and TiO2 P25 was
0.50, 0.45, and 0.15, respectively. Not all the viscosity data collected at high shear
rate and high solid loadings were suitable for analysis. This is because the highly
loaded suspensions had a pastelike consistency and tended to extrude out of
the parallel plate at high shear rates. This phenomenon was manifested as a
discontinuity that appeared in a plot of viscosity versus shear rate. Therefore such
viscosity data were not used in Figures 24.
The experimental MPF values are very much different from the calculated values
shown in Table 3. It should be noted that the calculated MPF values are based on an
a value of 0.268. In McGearys work, millimeter-size steelspheres were used for
studying particle packing, which is a size range where attractive surface interactions
are usually negligible. Since signicant attractive surface forces are in effect with our
titania powders, a can be considered as a tting parameter to adjust our calculated
MPF values. The magnitude of this term could conceivably vary directly because of

Table 2
Number geometric mean DgN and geometric standard deviation sg
of TiO2 samples dispersed in VF

DgN (mm)
sg

TiO2 101

TiO2 104

TiO2 P25

0.430
1.90

0.293
1.58

0.053
1.76

322

T. Hao and R. E. Riman

Table 3
Calculated maximum packing fraction from Equation (4)
Sample

MPFloose

random

MPFdense

0.87
0.71
0.79

TiO2 101=VF
TiO2 104=VF
TiO2 P25=VF

random

0.88
0.75
0.82

those surface forces or indirectly because of particle size, size distribution, and
packing structure. Table 4 shows the range of a values obtained when either loose
Exp
random packing, aExp
loose , or dense random packing, adense , is assumed. The values of
Exp
a
value range from 0.04 to 0.33.
An empirical equation is proposed that ts the experimental a data shown in
Table 4. This calculated a value is termed a0 , and a0 was found to correlate with
particle size, particle size distribution, and packing structure as follows:
c

2c1

a0 2c  12 c Fmonom sg

D5 =D1

c2 1

11

where
c

DgN  0:5
DgN 0:5

12

Values for a0 are shown in Table 4 for comparison; a0 values obtained using Equation
(11) for loose random packing and dense random packing are termed a0loose and
a0dense , respectively.
The empirical expression in conjuction with the modication of Sudduths
model presented in this article succeeds in predicting the MPF for a wide range of

Figure 2. Reciprocal viscosity of TiO2 101=VF suspension against the particle volume fraction. The viscosity data were obtained at shear rates of 100, 398, and 1000 s1.

Methodology for Determination of the Maximum Packing Fraction

323

Figure 3. Reciprocal viscosity of TiO2 104=VF suspension against the particle volume fraction. The viscosity data were obtained at shear rates of 100, 398, and 1000 s1.

titanias. It also maps out an opportunity for gaining a better understanding of the
packing structure of titanias by comparison of a0 with a values. Similar values of aExp
and a0 can be used to determine whether the packed structure adopts either a loose or
0
dense packed random structure. For the TiO2 P25=VF, aExp
loose is much closer to aloose
Exp
0
than adense is to adense . Thus, one may come to the conclusion that these titania
powders adopt a loose random packed structure instead of a dense random packed
structure. Similar arguments can be made for other two titania powders. The above
analysis cannot be conclusive because the data were empirically t and there was no
experimental validation of the packing structure. However, this equation may provide a sense of the form of an equation that could be derived in the future using
fundamental principles instead of tting experimental data.
To further explore the validity of Equation (11), McGearys data were
re-examined. Relative to the titania, this represents a different system since DgN

Figure 4. Reciprocal viscosity of TiO2 P25=VF suspension against the particle volume fraction. The viscosity data were obtained at shear rates of 100, 398, and 1000 s1.

324

T. Hao and R. E. Riman

Table 4
Experimental MPF values with corresponding aExp values and a
Samples

FExp
max

aExp
loose

aExp
dense

a0loose

a0dense

TiO2 101=VF
TiO2 104=VF
TiO2 P25=VF

0.50
0.45
0.15

0.047
0.223
0.280

0.078
0.325
0.331

0.066
0.236
0.260

0.072
0.257
0.282

(i.e., 1600 mm) is in the millimeter range. The binary composition was 80 vol%
3.15 mm spheres with 20 vol% 0.91 mm spheres, which results in a geometric standard deviation of 1.38. This leads to a D5=D1 of
5.4. The values a0dense 0.293, and
a0loose 0.271 were calculated using Equation (11). The a value for the loose random
packing is close to the value, 0.268, obtained by Sudduth. This suggested that
Equation (11) may be able to predict the a values based on particle size data.
However, future work will be necessary to determine if this empirical equation is
universally applicable to a wide range of particulate systems. Given that interparticle
forces are determined by variables other than particle size and size distribution, it is
likely that this equation may be limited to those systems where gravity and van der
Waals forces inuence the packing structure of powders.

Conclusions
A method developed by Sudduth for estimating the maximum packing fraction of a
particulate system of a size distribution was modied for titania powders. The
maximum packing fraction for three types of TiO2 powder dispersed in a low
molecular weight polyethylene was determined experimentally via a rheological
methodology and estimated via a modied version of Sudduths model. The large
discrepancy between the experimental data and predicted values suggests that
Sudduths model is suitable only for particle systems that are not dominated by
attractive surface forces. A further modication was introduced, which uses particle
size, particle size distribution, and packing structure as variables for the a term. This
approach was found useful for predicting the maximum packing fraction for three
types of submicron titania and a coarse binary steel powder.

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