On The Drying of Glassy Polystyrene

J. C. LARIAand J. V. ALEMAN
Znstituto de Plasticos y Caucho
Juan de la Cieroa 3, Madrid (6). Spain

Many commercial polymers contain water which must be

reduced to a lower level for application. The drying behavior of
polystyrene (PS), molecular weight 12,000, and flow charac-
teristics suitable for extrusion and injection molding, have
been studied. A laboratory tray dryer was used at temperatures
below the glass transition temperature of PS (To 373 K). -
Effects of air flow rate (from 0.5 to 3.5 literds), temperature
(from 323 to 373K) and relative humidity (from 0.5 to 25 per-
cent) on retained water in PS were measured, and from those
effects the effective diffusion coefficients (D) have been de-
duced as:
D(T) = Do . e - * E / R T = 3.6 x 10-5 . e - 2 W i T
In D(X%) = In D,,,o + aX% = - 19.30 + 4.0(X%)

INTRODUCTION
olymers in use normally have a certain amount of
P water which differs with polymer structure, process-
ing conditions and with polymer storage history. For
polymers to be useful, their water content generally
needs to be reduced (1, 2) to alevel whichdepends upon
the planned application. This drying process may be
carried-out to different limits according to the water-
polymer interaction characteristics (3):
Water molecules have a pronounced tendency to hy-
drogen bond: a) with themselves to form agglomerates
(pockets, etc.) and b) with polar groups of polymers to
provide strong localized bonds which change with:
i) The sorption behavior: hydrophobic polymers ab-
sorb only small amounts of water and their behavior is
thermodynamically near ideal (Henry’s law), whereas
the hydrophilic polymers absorb larger amounts of
water due to the strong interaction between their polar
groups and water.
ii) The equilibrium dfiusivity: The diffusivity of the
hydrophobic polymers (polyolefins, etc.) is independent
of the amount of water present. The not very hydrophilic
polymers (polymethacrylates, etc.) have a diffusivity
which decreases with increasing water concentration
due to preferential water association. The hydrophilic
polymers (polyamides, etc.) have a diffusivity which
increases with increasing water content, because the
absorbed water swells the polymer, making it easier for
water molecules to diffuse.
Bibliographic references on drying of polymei s, espe-
cially of polymers of major practical importance such as
synthetic fibers, etc., are rather extensive (4). Biblio-
graphic references describing the characteristics of the
drying process (drying curves, etc.) required for success-
ful operation, are scarce (2).
EXPERIMENTAL
Materials
Polystyrene (PS) was chosen as a representative
polymer to establish drying characteristics. PS has di-
electric constant of 2.5 to 3.0, sufficient to provide it
with “structural water” (5)without complications of deg-
radation which are present during the drying of more
hydrophilic polymers such as polyamides.
The material used was Styron 634 from the Dow
Chemical Company, in cylindrical shape (average radius
1.0millimeter and length 3.0 millimeters) and with flow
characteristics typical for the operations of injection and
extrusion, molecular weight of 120,000 and glass transi-
tion temperature (To)of -373K.
The process temperature was always below T , for the
PS to be in its glassy state where most viscoelastic mech-
anisms of molecular motion are frozen in (3).
Apparatus
A laboratory-scale tray dryer was constructed as
shown in Fig. 1. It allowed the use of a wide range of
process variables (2, 3): temperature, air velocity,
polymer size and shape, thickness of the drying bed,
humidity in the drying chamber, and humidity in the air
preconditioning chamber. (Care was taken to avoid dew
point temperatures below 273K, at which a small reduc-
tion in dry bulb temperature (c1o“C) provided a large
increase in the drying time needed to reach the final
polymer humidity required.)
RESULTS AND DISCUSSION
Results were plotted as percent humidity (X%) vs
time (t), and vs drying rate (Vs)
as follows:
Figure 2 shows the effect of the air volumetric flow

804 POLYMER ENGINEERING AND SCIENCE, AUGUST, 1981, Vol. 21, No. 72
 On the Dying of Glassy Polystyrene
Fig. I. D y i n g set-up. I) preconditioning chamber, 2 ) blower, 3)
air value, 4 ) gas meter, 5 ) heating wire, 6 ) temperature con-
troler, 7) rheostat, 8-9 thermocouples, 10-1I) on-offualues, 12)
d y i n g chamber, 13) tray, 14) scale, 15) galuanometer, 16) rub-
ber tubing.
Fig. 2 . Percent water ( X percent) a) as a function of time (t),and
b ) as a function of oolumetricjlow rate (Vd, at 353K, R . H . , = 70
percent, R.H.”(. = 2-3 percent.
rate (Vv) on the percent water (X%)at 353K, R . H . = 70
percent, R.H.Dc = 4.5 percent, Vv = 2.5 liters/s.
Figure 3 shows the effect of the temperature on the
percent water (Xpercent), and on the drying rate (Vs), at
R .H . B = 70 percent, R .H . DC = 4.5 percent, Vv = 2.5
liters/s.
As may be observed, these curves have three main
parts (2, 4):
a) A zone of transient behavior (Zone I to the right of
Zone 11, not shown in Fig. 3), of some 10 min duration,
I Taking on account only the first term of the series
I\ I /
t V,
POLYMER ENGINHRING AND SCIENCE, AUGUST, 1981, Vol. 21, No. 12
during which the polymer temperature rise to the pro-
cessing temperature takes place, and at the same time
also the constant rate of evaporation of water from the
surface of the solid polymer, through a typical process of
heat transfer in which the main transfer mechanism is
convection, since conduction and radiation are usually
negligible.
b) A Zone I1 of decreasing drying rate, of length about
1%h, during which time the elimination of the water
held by pores of all sizes takes place through a combined
process of heat transfer from the air to the solid simul-
taneous with a mass transfer from the solid to the air.
From these combined processes only it is possible to
define adrying rate “averaged” between the diffusion in
large pores (Stephan), the diffusion in pores of small
diameter (Knudsen), and the simultaneous heat transfer
process.
The drying rate in Zone I1 is non-linear (Fig. 3 ) and
becomes zero where the maximum hygroscopic humid-
ity is reached.
c) A Zone 111, of length three or more hours, in which
hygroscopic (or associated) water is eliminated, and the
drying rate decreases continuously, becoming zero
when the equilibrium humidity (X,)is reached. In this
work X, is considered to be approximately equal to the
humidity of the solid polymer at the exit of the dryer
after more than five hours operation.
Drying in Zone 111 is a combination of diffusion of
water vapor through the solid, and flow of the water
through the capillaries, in a process ruled by a general
differential equation for which only numerical solutions
are possible (4, 6). Because the flow of water in the
capillaries is small, it is usually considered that the
drying process in Zone 111 takes place only by ddFusion
of water vapor, and that (since the drying rate decreases
almost linearly: see Fig. 5 ) the “effective” diffusion
coefficient (D) is constant and obeys Fick’s law:
which for a sphere gives (7):
( n = 1):
and therefore:
For a cylinder of equivalent volume ( r = 1, L = 3 = 3r) it
is:
D = - . _1 .
2.25~’ t ln(X, - X, 6
= 0.525 X lo-’ * ( y ) (5)
805
 J . C.Laria and J . V.Aleman

The slope ( y ) is: and the lines have been extrapolated to provide the
sharp edge corresponding to the maximum hygroscopic
moisture), the agreement between the experimental
drying rate (1/A * dX/dt) and the theory (E9 8 ) being
The slope may be obtained from a plot of In (X - X,/X, - rather g o d .
X, * 7rz/6) vs time (t). The effect of water concentration on the diffusion
Diffusion coefficients computed by means o f E q 5 are coefficient was then studied. Figure 6 is a plot of the air
plotted in Fig 4. humidity (R H.Dc percent) vs the percent humidity of
Effectof temperature on these diffusion coefficients is the polymer (X percent) at 353K,R H.B = 65 percent,
described by the Arrhenius equation: V v = 2.5 liters/s.
These data were treated as in the previous case of the
D(T) = Do . e-AE'RT
= 3.6 x 105 -e-294'T (7) effect of temperature on the diffusion coefficient: from
Drying rate in Zone I11 is (see Appendix 11): the solution of Fick's law for a cylinder, the slope of the
-
In(X - X,/X, - X, 7r2/6)vs time t a t different humidities
Ps * D
V,,,,, = 0.75 * rz* - (X - X,) (8) in the drying chamber (R.H . oc percent) were deduced,
r and with them the diffusion coefficients were computed
This equation has been corroborated using the values at different humidities of the drying chamber (R H . Dc
of D,r, and X - X, of previous pages, and the densities percent), and at different percent humidities of the
of the solid polymer ps described elsewhere (8). Results polymer (X percent).
are shown in Fig. 5 (in which the points are actual data, Results are shown in Table 1 for both humidity of the
drying chamber (R.H.Dc percent) and percent humidity
(X percent). In this later case some anomalies were
observed, mostly due to the narrow interval of final
humidities attained (X percent = 0.13-0.14).
The diffusion coefficients thus obtained show a not
very pronounced increase with water content, and are
plotted inFig. 7, from which it can be deduced that they
obey (within the limits of variation of these data) the
equation
In D(X%) = In Dxsz0 + a X%
= -19.30 + 4.0(X%) (9)
The source of this behavior is provided by the non-
hydrophdic, but unsymmetrical substitutions, in the
hydrocarbon backbone of PS: the water interacts with
the polymer chains producing reorientation and chain
displacement (5), i.e., "loosening" of the structure; as a
0 20 consequence, the adsorbed water becomes more and
'PT 0.16.
2.5 26 2.7 29 29 3D 31 32 33
Fig. 4 . Effect of temperature on diffusion coefficient ( D ) at
R.H.8 = 70 percent, R.H.,,,. = 4.5 percent, Vv = 2.5 litersls.

0 81
o 1 2 3 + L 5 6 (hours)
Fig. 5. D y i n g rates computed (-) and experimental (----)at Fig. 6 . Effect ofair humidity (R.H.,,,. percent) on percent water
R.H.8 = 70 percent, R.H.,,. = 4.5 percent, V, = 2.5 litersls. ( X percent) at 353K, R.H.8 = 65 percent, Vv = 2.5 litersls.

806 POLYMER ENGINEERING AND SCIENCE, AUGUST, 1981, Vol. 21, No. 12
 On the Drying of Glassy Polystyrene
Table 1. Eff- of Water Content on the DHluslon CoeHclent
R.H.N D .10-7 X percent
twmnt) (mYh) (4 h)
22 0.35 0.142
17 0.35 0.135
13 0.47 0.136
8 0.21 0.136
4.5 0.31 0.130
more mobile (local cooperative vibrations of only a few
structural units are sufficientfor the water molecules to
diffuse) increasing the diffusion coefficient.
This is evidenced by the fact that in the activation
energy of PS (AE = AH - TAS)both the latent heat of
sorption and the differential entropy of sorption de-
pends on moisture content, the entropy component
being larger than the enthalpy one (TAS > AH)(5).
The heat of sorption (AH)comprises the energy of
attachment of the sorbed molecules to the polymer, the
mutual interaction between sorbate molecules, and the
energy of reorientation caused by penetration of the
water molecules into the polymer, plus the sorption of
water upon water which occurs as polymer sites are
occupied. For PS (5) these forces will increase with
increasing sorption, and AH increases to a value not
greatly different from zero. At the beginning of the
process AH is several calories less than the heat of con-
-
densation, which is -10.2 kcal/mole (3), indicating
that initially the water is rather weakly sorbed (held in a
not very highly ordered form), and then more strongly
with the formation of water-water contacts, making the
sorbate to begin to resemble liquid water only at higher
water contents, i.e., at the beginning of the process the
diffusion in PS is slower than in “truly” hydrophobic
polymers, and then it becomes faster.
The entropy difference (AS)consists of: i) a thermal
part, related to the specificheat, and thus to AH, and ii) a
configurational term, the importance of which decreases
as sorption increases, because the configurational en-
tropy depends on the number of sorption sites available
to the water, which for PS are presumably low (5). Both
components of AS increase with increasing moisture
content.
-15 1 t
-20 t dx
-30
0.10 0.11 0.12 0.U 0.11
X(X)
Fig. 7.Effect ofwatercontent (X percent and H.H.ucpercent)on
the dlffusion coefficient of polystyrene at 3535 R.H.L, = 65
percent, V v = 2.5 literls. -
POLYMER ENGlNHRlNG AND SClENCE, AUGUST, 1981, Yo/. 21, No. 12
Consequently, not only the diffusion coefficient but
also the activation energy are concentration dependent,
the simple Eq. 7 does not hold and, instead, the dHu-
sion coefficient should be expressed as:
D = DO(T) - JX%, T ) (10)
where Do is the diffusion coefficient at zero water con-
centration (corresponding to D(T) in E9 7).
The changes in macromolecular configurations which
“plasticize” the structure of the polymer are not instan-
taneous effects, but the result of long range relaxation
processes (onlya very small change in penetrant concen-
tration is needed to change the relaxation time by sev-
eral orders of magnitude), and therefore the diffusion
coefficient is history dependent. These long term
molecular motions slow down the rate of equilibrium
approach, and therefore also modify the sorption and
diffusion behavior. Therefore, the processes of diffusion
which take place in rigid polymers, like the PS below its
To, are difficult to describe by a simple generalized form
of Fick‘s law with constant boundary conditions and
diffusion coefficients which are a function only of con-
centration, as the ones proposed for the polyamides (X%
= 0.1 - 10.0)(9, 10).
The controlling structural characteristic is the free
volume; it has thus been used to explain and compute
(11) the combined effect of concentration and tempera-
ture on the diffusion coefficient, though the use of it to
rationalize diffusion data below Tomay be questionable.
There is to date no method available which allows an
entirely satisfactory description of the effect of concen-
tration on the diffusion coefficient of polymers.
APPENDIX
Drying Rate in Zone III
Drying rate is defined (being x = X - X, = non-
equilibrium moisture content) as:
which combined with Ficks law (dxldt = -D d2ddP)
gives:
dx
Vmn = -PS * D * (A-1)
For a sphere with constant surface concentration, and
considering only the first term of the series (n = 1) (12):
x = (X - Xe).= (X, - X,) * 2 e - ‘
-- n’.D.t
(A-2)
and therefore:
a7- = (x, - x,) *
2
.e
-=
‘ (A-3)
0.15
Substituting it into Eq A-1 gives:
807
 1.C . Laria and 1.V. Aleman
X,. = initial humidity W,- W,s
Using the average moisture content x = -L l x , * d, it X
r X% = percent water = -* 100
can be written (12): W,
6 n*.D.r X = water content = W, - W,
x = (X - X,) = (X(, - X,) e
7 -e ry (A-5)
XIls = dry basis water content =
X
-
xs
and therefore: V,, = air velocity in the drying chamber
VIr = air volumetric flow rate
dX
V,, = drying rate =
A.bt
A = total area of solids = S,, * N,
which substituted intoEq A-4 provides the value of the S,, = area of one particle
drying rate: N,, = number of particles =
w,
-
WIP
R. H. % = relative humidity (%)
R H. = relative humidity (%) at room conditions
R. H.a% = relative humidity (%) in the preconditioning
and for a sphere of volume equivalent to the cylinder chamber
used (Vculindpr = 2.25Vxiih~w): R.H.,,(.% = relative humidity (%) in the drying
chamber.
V,.I,I, = 0.75 * T’ * -
r’ (X - X,) (A-8)
REFERENCES
ACKNOWLEDGMENT 1. J. V. Aleman, RAPRA Translations, No. 1787, London
(1972).
Construction of the experimental set-up was carried 2. J. V. Aleman, Reo. Plast. Mod., 232, 509 (1975).
out in cooperation with Messrs. H. Adabbo and 3. J. Crank, C. S.Park, eds., “Diffusion in Polymers,”Ch. Sand
P. Puente, chemical engineer on study-leave from the 8, Academic Press (1968).
4. 0. Krischer, W. Kast, and K. Kroll, “Trocknunstechnik,”
University of Mar del Plata (Argentina), and technical Springer-Verlag (1978).
engineer of the Instituto the Plasticos y Caucho (Madrid) 5. A. G. Day, Trans. Faraday SOC., 59,1218 (1963).
respectively. 6. S. Whitacker, IEC Fundam., 16, 408 (1977).
7. D. Stockburger and F. R. Faulhaber, Chem. Eng. Technol.,
NOMENCLATURE 41,4S6 (1969).
8. W. Patnode and W. J. Scheiber,J. Am. Chem. Soc., 61,3449
W,, = initial weight of solids (1939).
W, = final weight of solid 9. G. Voghlaender-Tetzner, Chem. Eng. Technol., 43, 260
W I p = weight (polymer + water) of one (average of i1971).
ten) polymer particle. 10. E. Meier, Chem. Eng. Technol., 41, 472 (1969) and 42,20
(1970).
W, = weight of the “completely dried” polymer.
11. H. Fujita, Adu. Polym. Sci., 3, l(1961).
W, = total weight (polymer + water) at a given time 12. W. Jost, “Diffusion in Solids, Liquids and Gases,”
X, = equilibrium humidity = W, - W, Academic Press (1960).

808 POLYMER ENGINEERING AND SCIENCE, AUGUST, 1981, Vol. 21, No. I2