Modeling of Multilayer Drying of Polymer Films

SACIDE ALSOY, J. LARRY DUDA

Center for the Study of Polymer-Solvent Systems, Department of Chemical Engineering,

The Pennsylvania State University, University Park, Pennsylvania 16802

Received 3 August 1998; revised 23 February 1999; accepted 1 March 1999

ABSTRACT: A model was developed to predict the drying behavior of multilayer poly-
mer films on inert substrates. The model considers simultaneous heat and mass
transfer controlled by complex thermodynamic and transport properties of polymer
solutions. Key components of the model are the incorporation of the free volume theory
to predict diffusivities in each polymer layer, the use of heat and mass transfer
coefficients to describe complex transport phenomena in the gas phase, the incorpora-
tion of exact equilibrium boundary conditions at polymer–polymer interface, and the
use of the Flory–Huggins theory to describe both liquid–liquid and vapor–liquid equi-
libria. The model can be applied to guide processing, product formulation, scale-up, and
oven design. As an example, the model is applied to simulate the drying of a two-layer
coating of poly vinyl acetate (in toluene) over polystyrene (also in toluene) on a polyester
substrate. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1665–1675, 1999
Keywords: drying; diffusion; solution processing; heat and mass transfer; films

INTRODUCTION In recent years, the demand for polymer films

The drying of coated polymeric films is integral to
the production of adhesive tapes, photographic
films, and various functional coatings. Film for-
mation involves the drying of one or more layers
of polymer solutions. Each layer is produced by
casting a continuous layer of polymer solution
onto a moving substrate and drying in an oven
with forced air convection. The structure and
properties of the final product are greatly influ-
enced by the film formation. Some problems such
as phase separations, unwanted internal gradi-
ents, and various kinds of defects can be attrib-
uted to the poorly chosen drying conditions.
Therefore, a mathematical model to predict film
formation can be a useful tool for oven design,
product scale-up, product formulation, and defect
analysis.
Correspondence to: J. L. Duda (E-mail: jldche@engr.psu.edu)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 37, 1665–1675 (1999)
© 1999 John Wiley & Sons, Inc.
and coatings with unique properties has lead to
the producion of multi-layer films. Instead of ap-
plying and drying individual layers, multiple lay-
ers are formed simultaneously. Many models ex-
ist in the literature for the drying of a single layer
binary polymeric solution.1–9 There are a few
models for the drying of single layer multicompo-
nent polymeric solutions.4,10,11 However, there is
no realistic model available to describe the forma-
tion of multiple-layer coatings. The most com-
monly used approach is to treat the multiple lay-
ers as a single layer.12 However, the drying of a
multilayer film is fundamentally different than
the drying of a single layer film. Multilayer films
contain liquid–liquid interfaces where equilib-
rium behavior can play an important role in the
removal of solvents. The volume average convec-
tive velocity is not zero throughout the system as
is usually the case in a single layer. During mul-
tilayer drying, concentration jumps, and back dif-
fusion, shrinking, and swelling of each layer can
CCC 0887-6266/99/141665-11 be observed. Also, the positions of polymer– gas
1665
1666 ALSOY AND DUDA

interfaces and liquid–liquid interfaces change

with time.
In the first part of this work, a model was
developed to predict the drying behavior of mul-
tiple-layer polymer solutions that contain the
same volatile solvent. It is assumed that the poly-
mers are immiscible, and the problem involves
the coupling of diffusion in two binary polymer
solutions. The most critical parameter in the
model is the mutual diffusion coefficient for each
polymer-solvent system, which usually is a strong
function of concentration and temperature. The
free volume theory of Vrentas and Duda and the
Flory–Huggins theory are utilized to describe the
influence of temperature and concentration on
the mutual diffusion coefficients.13–16 The Flory
Huggins theory is used to describe the vapor- Figure 1. A schematic of drying geometry in multi-
liquid equilibria and the liquid-liquid equilibria layer drying.
at the polymer–polymer interface. The model has
unique features that facilitate the numerical so-
lution of the governing equations. The influence of
surface tension and instabilities associated with In the second part of this paper, we discuss the
surface tension gradients are neglected as well as application of the model to a 2-layer system of
potential complications associated with polymer polystyrene-toluene and polyvinyl acetate-tolu-
relaxation and stress gradients. ene. Predictions from the model provide informa-
Casting the problem in terms of the volume tion concerning residual solvent level, tempera-
average velocity instead of the mass average ve- ture of the substrate and polymer layers, shrink-
locity significantly reduces the complexity of mod- ing and/or swelling of the films, and concentration
eling the drying process when the polymer and profiles in each layer as a function of time.
solvents have different densities and the coating
is nonreactive. To eliminate the complications as-
sociated with formulating finite elements or finite THEORY
difference grids for the case of a moving bound-
ary, different coordinate transformations for each A schematic of the drying geometry used in deriv-
layer are utilized. Also, to minimize the number ing the equations is given in Figure 1. All symbols
of finite difference equations required to describe are defined in the nomenclature section. Initially,
the very steep concentration gradients that typi- the lower and upper polymer films have a con-
cally form near the gas–polymer solution inter- stant thicknesses of L1o and L2o, respectively. The
face and polymer–polymer interface, a variable lower polymer film extends from x 5 0 to x 5 X1(t)
grid size technique was applied. Finally, an anal- and the upper polymer film extends from x 5 X1(t)
ysis of the relative rates of mass transfer com- to x 5 X2(t). The substrate is impermeable to the
pared to heat transfer indicate that temperature solvent and has a constant thickness H. The top
gradients in the polymer films and the substrate and bottom gas phases have the temperatures of
can be neglected under most drying conditions in TG and Tg and heat transfer coefficients hG and
which the resistance to heat transfer is much hg, respectively. Each layer consists of one poly-
greater in the gas phase than in the polymer or mer and the same volatile solvent.
substrate layer. This approximation was ana- Using this geometry and the notation given in
lyzed in detail by Yapel.4 As a consequence, we Figure 1, model equations can be derived for one
were able to use a UNIX-based work station to dimensional unsteady state mass transfer.
accurately describe the complex drying process.
More details concerning the numerical technique
and the approximations incorporated in the Species Continuity Equation in Layer 1
model are presented by Alsoy11 and the single
layer drying analysis of Alsoy and Duda.8
­ r j1
­t
5
­
­xS D
Dj
­ r j1
­x
j51 (1)
 MULTILAYER DRYING OF POLYMER FILMS 1667

Species Continuity Equation in Layer 2 solution and substrate are used and radiative

S D
­ r j1 ­ r j1 ­ ­ r j1
1 nÞ 5 Dj j52
­t ­x ­x ­x
In this formulation, r j1 is the concentration of the
solvent and D j is the mutual binary diffusion
coefficient in the jth layer. In this derivation, it is
assumed that the partial molar volumes of all
components are independent of the composition
so that there is no volume change on mixing. This
assumption leads to the conclusion that the gra-
dient of volume average velocity, v#, is zero in
each layer. Based on this result, volume average
velocity becomes zero everywhere within the first
polymer layer since it is zero at substrate polymer
interface and it becomes a function of time only in
heat transfer mode is neglected.
The thickness of the bottom layer, X1, changes
(2)
as solvent diffuses out of that layer into the upper
layer. Correspondingly, the position of the top gas
interface, X2, will change because of the flux of
solvent into the bottom of this layer and the evap-
oration of solvent out of the layer. The thick-
nesses of the two polymer solution layers can be
determined by the formulation of jump mass bal-
ances for the solvent at the two interfaces.
Time Dependence of Boundary Positions
dX 1
dt
5 F D j51V̂ 1 ­ r j51
~1 2 r 1V̂ 1! j51 ­x
1
G x5X1~t!
(6)

the second and subsequent layers since there is

mass transfer through each polymer-polymer in-
terface.
An energy balance on the system must incor-
dX 2
dt F
5 nÞ 1
D j52V̂ 1
~1 2 r 1V̂ 1!
­ r j52
j52 ­x
1
G x5X2~t!
(7)

porate heat transfer from the gas above and below

the films through effective heat transfer coeffi- The boundary conditions for this model can be
cients as well as heat of vaporization of the sol- derived by assuming there is no flux of the solvent
vents diffusing out of the system, and possible into the substrate, thermodynamic equilibrium is
differences in the enthalpies of the solvent as it maintained at the interface between the two poly-
diffuses from the bottom layer to the top layer. mer solutions, and the continuity of mass fluxes
The modeling of the heat transfer process is sim- at the two moving interfaces.
plified since conduction of heat in the polymer
layers and the substrate is fast compared to the Boundary Conditions
convection of heat at the gas interfaces. Conse-
quently, the temperature is only a function of ­ r j51
1
x50 50 (8)
time and not position within the layers. ­x

x 5 X 1~t! m j51
1 5 m j52
1 (9)
Heat Transfer Equation

dT 1
dt
5
A F
h g~T g 2 T! 1 h G~T G 2 T! 2 QDĤ n1 x 5 X 1~t!
dX 1 j52
~ r 2 r j51
dt 1 1 !

1 r j51
dX 1 j52
dt
~Ĥ 2 Ĥ j51! G (3)
5 r j52 Þ
1 n 2 D
j52
­ r j52
­x
1
1 D j51
­ r j51
­x
1
(10)

dX 2
Q 5 r jn j 2 r j j52 (4) Þ
­ r j52
1
dt x 5 X 2~t! r j52
1 n 2 D
j52
­x

A 5 r sĈ spH 1 r j51Ĉ j51

p X 1~t! dX 2
2 r j52
1 5 k G1 ~P 1i
G
2 P 1b
G
! (11)
dt
1r j52
Ĉ j52
p ~X 2~t! 2 X 1~t!! (5)
The vapor pressure of the solvent in the bulk gas,
When the Flory-Huggins equation is used, Ĥj51 Pg1b is considered to be a constant input param-
5 Ĥj52 . Also, average values for densities, heat eter while the vapor pressure of the solvent at the
capacities, and thermal conductivities of polymer gas-polymer interface, Pg1i, is based on the con-
1668 ALSOY AND DUDA

centration of the solvent and the temperature at T 2 To D j51

o t
the interface using the Flory–Huggins thermody- T* 5 t* 5 (18)
TG 2 To 2
L 1o
namic model for phase equilibria. An expression
for volume average velocity is obtained by apply-
X 1~t! X 2~t!
ing jump mass balances for each polymer at the X *1 5 X *2 5 (19)
polymer polymer interface (x 5 X1(t)) and it is L 1o L 2o
given as follows:
r j51
1 r j52
1
C j51 5 C j52 5 (20)
Þ
­ r j51
1 V̂ 1 ­ r j52
1 V̂ 1 r 1o
j51
r 1o
j52

n 5D j51
2 D j52
­x 1 2 r 1 V̂ 1
j51 ­x 1 2 r j52
1 V̂ 1
n ÞL 1o
(12) n* 5 (21)
D j51
o

Initially, it is assumed that the solvent concen-

trations in both layers are constant and the tem- where Djo 5 1 is the reference diffusivity calcu-
peratures initially uniform throughout the sys- lated at initial composition and temperature in
tem. the bottom layer. In addition to these variables,
the following dimensionless groups are defined.
Initial Conditions
D j51 D j52
r j51
~0,x! 5 r j51
0 # x , X 1~t! (13) D R1 5 D R2 5 (22)
1 1o D j51
o D j51
o

r j52
1 ~0,x! 5 r 1o
j52
X 1~t! , x # X 2~t! (14) L 2o
LR 5 K 1 5 L RX *2 2 X *1 (23)
L 1o
r j51
1 ~0, X 1~t!! 5 r 1oi
j51
r j52
1 ~0, X 1~t!! 5 r 1oi
j52
(15)

X 1~0! 5 L 1o X 2~0! 5 L 2o (16) D R1r 1o

j51
V̂ 1
K2 5
X *1~1 2 r 1o
j51
V̂ 1C j51!
T~0! 5 T o (17)
D R2r 1o
j52
V̂ 1
A critical issue in this analysis is determining the K3 5 (24)
K 1~1 2 r 1o
j52
V̂ 1C j52!
initial concentrations, r j5110i and r j5210i, of the
solvent in the two solutions at the interface as
presented in Equation 15. In a typical commercial r 1oi
j51
r 1oi
j52
r 1o
j52

R1 5 R2 5 R3 5 (25)
operation, the chemical potentials of the solvent r 1o
j51
r 1o
j52
r 1o
j51

in the two solutions are not equal at the begin-

ning of the drying process. These two initial con- We obtained dimensionless forms of the heat
centrations must meet the criteria of thermody- transfer equation by combining Equations 3, 4, 5,
namic equilibrium at the interface as well as 18, and 19 as follows:
mass balance of the diffusive fluxes at the inter-
face. In this analysis, the liquid–liquid equilibria dX 1
at the polymer–polymer interface were predicted A~1 2 T*! 1 E 1 F 2B
dT* dt*
using the Flory–Huggins theory. The initial con- 5 (26)
dt* G 1 X *1
centration of the solvent on each side of the poly-
mer-polymer interface was determined by cou-
pling this thermodynamic equilibrium criteria The dimensionless groups A, B, E, F, and G are
with an analytical solution of unsteady state dif- defined as follows:
fusion in a semi-infinite composite media.11,17
~h G 1 h g!L 1o
A5 (27)
o r
D j51 j51 j51
Dimensionless Form of the Equations Ĉ p

Equations 1 through 17 are dimensionalized by

QDH n1L 1o
introducing the following dimensionless vari- B5 (28)
ables. D o r
j51 j51
p ~T 2 T o!
Ĉ j51 G
 MULTILAYER DRYING OF POLYMER FILMS 1669

h g~T g 2 T G!L 1o form of the boundary and initial conditions are

E5 (29) obtained:
D o r
j51 j51
Ĉ j51
p ~T 2 T o!
G

~Ĥ j52 2 Ĥ j51! ­C j51

F5 (30) h 5 21 50 (37)
­h
p ~T 2 T o!
Ĉ j51 G

H r sĈ sp r j52Ĉ j52

p
h 5 h# 5 0 m j51
1 5 m j52
1 (38)
G5 1 K1 (31)
r j51Ĉ j51
p L 1o r j51Ĉ j51
p
dX *1 j52 j52
During the multilayer drying, the thickness of h 5 h# 5 0 ~ r C 2 r 1o C ! 5 C j52r 1o
j51 j51 j52
n*
dt* 1o
each layer changes with time. To facilitate the
numerical solution of this problem, each phase r 1o
j52
­C j52 r 1o
j51
­C j51
2 D R2 1 D R1 * (39)
interface is immobilized by introducing the fol- K 1 ­ h# X 1 ­h
lowing coordinate transformations:
D R2 ­C j52 dX *2
x 2 X 1~t! h# 5 1 C j52n * 2 2 C j52L R
h5 (32) K 1 ­ h# dt*
X 1~t!
k G1 ~P 1i
G
2 P 1b
G
!L 1o
5 (40)
x 2 X 1~t! r 1o D o
j52 j51

h# 5 (33)
X 2~t! 2 X 1~t!
C j51~0, h ! 5 1 21 # h , 0 (41)
The new length variable in layer 1 defines a fixed
region from h 5 21 to h 5 0. Similarly, in layer 2,
C j52~0, h# ! 5 1 0 , h# # 1 (42)
the coordinates x 5 X1(t) and x 5 X2(t) are trans-
formed into a new region from h# 5 0 to h# 5 1. The
dimensionless forms of the species continuity C j51~0,0! 5 R 1 C j52~0,0! 5 R 2 (43)
equations in each layer were written as follows by
combining Equations 1, 2, 18, 19, 20, 21, 22 and 23.
X *1~0! 5 1 X *2~0! 5 1 (44)

­Cj51
2
1 1 h dX *1 ­C 1
5 *2
­ D R1
j51
­C
­h S j51

D (34)
T*~0! 5 0 (45)
­t* X *1 dt* ­ h X1 ­h
The dimensionless form of the boundary positions
­C j52
­t*
1
1
K1 F
~ h# 2 1!
dX *1
dt*
2 h# L R
dX *2
dt*
1 n* G were obtained by combining Equations 6 and 7
with Equations 18 through 21 as follows:

3
­C j52 1
5 2
­ D R2
­C j52
­ h# S D (35)
dX *1
dt* F
5 K2
­C j51
­h G h5h# 50
(46)
­ h# K1 ­ h#

Also, combining Equation 12 with Equations 19,

20 , 21, and 24, one obtains the following form of
LR
dX *2
dt* F
5 n* 1 K3
­C j52
­ h# G h# 51
(47)
dimensionless volume average velocity:
Finally, boundary conditions given by Equations
­C j51 ­C j52 39 and 40 were modified by integrating species
n* 5 K2 u h50 2 K 3 u (36)
­h ­ h# h# 50 continuity equations. Integration of Equation 34
from h 5 21 to h 5 0 and substitution into Equa-
By utilizing Equations 18 –21, 22–25 in Equations tion 39 produced the following modified form of the
8 –11 and 13–17, the following dimensionless mass transfer boundary condition at h 5 h# 5 0.
1670 ALSOY AND DUDA

E
Table I. Parameters Used in Diffusivity
d 0
dX *1
C j51X *1 d h 5 R 3C j52 Correlations
dt* dt*
21
PVAC PS
R 3 ­C j52 Parameter Toluene Toluene
2 R 3C j52n * 1 D R2 (48)
K 1 ­ h#
Do cm2/sec 4.82.1024 4.82.1024
Ea J/mole 0 0
Similarly, integration of Equation 40 from h 5 h# K11/g cm3/gK 0.00145 0.00145
5 0 to h# 5 1 and substitution into Equation 35 K12/g cm3/gK 0.000433 0.000582
yielded the following form of modified boundary K21 K 286.32 286.32
condition at h# 5 1. K22 K 2258.2 2327
Tg1 K 0 0

E
Tg2 K 0 0
d 1
k G1 ~P 1i
G
2 P 1b
G
!L 1o V̂ *1 cm3/g 0.917 0.917
C j52
K 1 d h# 5 2
dt* r 1o
j52 j51
Do V̂ *2 cm3/g 0.728 0.85
0
j 0.82 0.58

E 0 x 0.393 0.354
1 1
2 C j51X *1 d h (49)
R 3 dt*
21

of numerical solution procedure can be found in

RESULTS AND DISCUSSION
For most commercial operations, the model pre-
dicts that the drying is initially controlled by heat
and mass transfer in the gas phase. Once this
external mass transfer resistance is not control-
ling, molecular diffusion of the solvent in the poly-
mer solutions becomes the key issue. The accu-
rate calculation of diffusion coefficients in each
layer, particularly when these coefficients are a
strong function of composition and temperature,
is very important. The Vrentas–Duda free-vol-
ume theory was used to predict self-diffusion co-
efficients that are related to mutual coefficients
through a thermodynamic factor. The free-volume
parameters used in the predictions were obtained
from Zielinski18 and are listed in Table I. In ad-
dition to mass transfer in each layer, the equilib-
rium behavior at the polymer–polymer interface
and the polymer– gas interface can play an impor-
tant role in the evaporation of the solvent.
Liquid–liquid equilibria at the polymer–polymer
interface and vapor-liquid equilibria at the poly-
mer– gas interface were predicted from the Flory–
Huggins theory.
The drying process is described by coupled non-
linear differential equations. Analytical solutions
cannot be obtained by using standard functions. A
finite difference approximation was used to dis-
cretize these equations. A variable grid was ap-
plied to generate finer mesh near the polymer
polymer and polymer gas interfaces where the
concentration gradients are steeper. The details
Alsoy (1998).11
The model is applied to polystyrene (PS), poly-
vinyl acetate (PVAC) toluene system coated on
polyester substrate. The input data used in the
simulation are listed in Table II. In the first case,
PS is the polymer in the bottom layer, PVAC is
the polymer in the top layer, and toluene is the
solvent for both layers. Since these polymers are
immiscible, the diffusion in each layer is a binary
diffusion process. The results are shown in Fig-
ures 2 through 9. Figure 2 shows the equilibrium
distribution of toluene between PS and PVAC.
The equilibrium composition of toluene in each
layer was calculated from the Flory–Huggins the-
ory by equating chemical potentials. A linear
equilibrium relationship was observed with a dis-
tribution coefficient of 0.98, since Flory–Huggins
interaction parameters of toluene in PS and in
PVAC are very similar. Consequently, the solvent
prefers each layer almost equally.
Figure 3 shows the average concentration of tol-
uene in the bottom (PS) and in the top (PVAC)
layers during the drying. Concentration of toluene
in each layer decreases very sharply within the first
15 min of drying and then it levels off because of the
increasing diffusional resistance in the polymer
films. Also, the thickness of each layer decreases
very rapidly at the beginning of the drying because
of the convective removal of the solvents from the
coating as shown in Figure 4.
The change in the temperature of the substrate
and polymer films from the initial temperature of
330 K to the final oven temperature of 353 K
throughout the drying is shown in Figure 5. The
 MULTILAYER DRYING OF POLYMER FILMS 1671

Table II. Parameters for PS/Polyvinylacetate/Toluene Test System

Initial Conditions:
Temperature 330 K
Thickness of layer 1 0.0103 cm
Thickness of layer 1 0.0229 cm
Initial composition of solvent in layer 1 0.642 g/cc
Initial composition of solvent in layer 2 0.722 g/cc
Substrate Parameters:
Heat Capacity 1.25 J/g K
Density 1.37 g/cc
Base thickness 0.00356 cm
Coating Parameters:
Heat capacity of layer 1 1.933 J/g K
Heat capacity of layer 2 1.653 J/g K
Heat of vaporization of the solvent 360 J/g
Operating Conditions:
Base side heat transfer coefficient 0.00018 W/cm2 K
Coat side heat transfer coefficient 0.00018 W/cm2 K
Bottom air supply temperature 353 K
Top air supply temperature 353 K
Mass transfer coefficient 0.31.1029 sec/cm
Mole fraction of the solvent in the gas 0

temperature goes through a minimum within 3
min of drying since evaporative cooling due to the
latent heat of vaporization is the dominant heat
transfer mechanism and then it increases to the
oven temperature asymptotically.
Figure 6 shows the concentration profiles of
toluene within the coating after 1,500, 3,000, and
6,000 seconds of drying. During that time period,
the diffusion front has penetrated throughout the
first and second layer and sharp concentration
gradients are observed near the gas interface as
the concentration of toluene at that interface ap-
proaches to zero. Also, a discontinuity in the slope
of the toluene concentration at the polymer-poly-
mer interface occurs. Figure 7 demonstrates that
even after 250 min of drying, significant concen-
tration gradients exist near the gas interface,
which indicate “skin formation” as is commonly
observed in single layer drying of polymer film.
As the drying proceeds, concentration gradi-
ents in the bottom layer near the polymer-poly-
mer interface become much more pronounced,
and the discontinuity in the slope of toluene con-

Figure 3. Average concentration of toluene in poly-

Figure 2. Equilibrium distribution of toluene be- styrene (bottom) and polyvinyl acetate (top) layers as a
tween polystyrene and polyvinyl acetate layers. function of time.
1672 ALSOY AND DUDA
Figure 4. Dimensionless thickness of polystyrene
(bottom) and polyvinyl acetate (top) layers as a function
of time.
centration at that interface is more prominent
(Fig. 7). The flux of the solvent is continuous
across the polymer–polymer interface as dictated
by the boundary condition. The discontinuity in
the concentration gradients result from unequal
diffusion coefficients on each side of that inter-
face. This is illustrated in Figures 8 and 9 in
which diffusivity profiles are plotted at each grid
point through bottom and top layers. In these
figures, the diffusivity profiles correspond to the
same time for which the concentration profiles are
presented in Figures 6 and 7. In the early stages
of drying, the difference in diffusivities at the
polymer–polymer interface is only about one or-
der of magnitude. However, as the solvent con-
centration decreases, the difference between
Figure 5. Temperature of the polymer films and
substrate as a function of time. Bottom layer is PS/
Toluene and top layer is PVAC/Toluene.
Figure 6. Concentration profiles of toluene in poly-
styrene (bottom) and polyvinylacetate (top) layers after
1,500, 3,000, and 4,500 sec of drying.
these diffusivities approaches to 5 orders of mag-
nitude after 250 min of drying. Diffusivities in the
top layer (PVAC) are higher than those one in the
bottom layer (PS). The strong concentration and
temperature dependency of the diffusion coeffi-
cients in each layer shown in Figures 8 and 9 do
suggest that the sequence of the polymer layers
would have an effect on the residual amount of
solvent. To examine that effect, the top and the
bottom layers are switched while all other condi-
tions maintained the same as listed in Table II.
The influence of the order of the polymer layers
on the drying process is demonstrated in Figures
10 –14 for the case of PS as the top layer. Figure
10 shows the comparison of residual amount of
toluene for two cases when PS is the polymer in
Figure 7. Concentration profiles of toluene in poly-
styrene (bottom) and polyvinylacetate (top) layers after
7,500, 10,500, and 15,000 sec of drying.
 MULTILAYER DRYING OF POLYMER FILMS 1673

Figure 8. Diffusivity profiles in PS/Toluene (bottom Figure 10. Influence of the sequence of the polymer
layer) and PVAC/Toluene (top layer) coatings after layers on the total residual toluene.
1,500, 3,000, and 4,500 sec of drying.
surface, indicating strong diffusional resistance
and, as a result, skin formation that slows down
the bottom and in the top layers, respectively.
the removal of the solvent. Also, the diffusivity
During the initial stages of drying, residual
profiles shown in Figures 13 and 14 indicate that
amount of toluene is the same for both cases since
diffusivities in the top layer (PS) are lower than
drying is controlled by external conditions that
the diffusivities in the bottom layer; as a result
are held constant in each case. However, at later
diffusional resistance and the total residual
stages of drying, the total residual amount of
amount of toluene in the second layer are higher
toluene is lower when PS is the polymer in the
compared with the previous case where PS is the
bottom layer and PVAC is the polymer in the top
bottom layer. It is also noticed that the disconti-
layer because of the reduction of the skinning
nuity in the slope of the concentration of toluene
effect . This phenomena can be more clearly seen
is more modest since the difference in the diffu-
in Figures 11 and 12, which show the concentra-
sivities at the polymer polymer interface is only
tion of toluene in each layer at different times.
one order of magnitude.
These figures illustrate that concentration gradi-
ents are much sharper near the polymer film gas
interface and it is uniform in the lower layer both
CONCLUSION
at the early and the later stages of drying. Figure
12 shows that sharp concentration gradients still
The model presented here can be applied to a
exist even after 250 min of drying near the free
large number of processes that involve the drying

Figure 9. Diffusivity profiles in PS/Toluene (bottom Figure 11. Concentration profiles of toluene in poly-
layer) and PVAC/Toluene (top layer) coatings after styrene (top) and polyvinyl acetate (bottom) layers af-
7,500, 10,500, and 15,000 sec of drying. ter 1,500, 3,000, and 4,500 sec of drying.
1674 ALSOY AND DUDA

Figure 14. Diffusivity profiles in PS/Toluene (top

Figure 12. Concentration profiles of toluene in poly- layer) and PVAC/Toluene (bottom layer) coatings after
styrene (top) and polyvinylacetate (bottom) layers after 7,500, 10,500, and 15,000 sec of drying.
after 7,500, 10,500, and 15,000 sec of drying.
a dryer design that best meets the demands of the
process.
of multiple layers. The two-layer example pre-
sented here illustrates the insights that can be NOMENCLATURE
attained through such an analysis. The model can
establish a framework for the design and optimi- C Dimensionless concentration
zation of drying conditions. Optimization involves Ĉp Specific heat capacity (J/g K)
choosing an objective function such as final resid- D Mutual diffusion coefficient (cm2/sec)
ual solvent level, maximum temperature, and Do Reference diffusivity calculated at initial
subjecting the model to a set of constraints such composition and temperature in the first
as operability limits of heaters and fans, zone layer (cm2/sec)
size, spacing of nozzles, limits in partial pressure h Heat transfer coefficient (W/cm2 K)
of solvent, or temperature at which coating is H Thickness of the substrate (cm)
stable, solubility, or skinning factor, economic fac- ki Mass transfer coefficient of component i
tors, etc. For drying equipment that has already (sec/cm)
been built, drying conditions can be found that Lio Initial thickness of layer i (cm)
meet the objectives and the constraints. For the Pii Partial pressure of component i at the in-
design of new dryers, a model can be used to find terface (g/cm sec2)
Pib Partial pressure of component i in the gas
phase (g/cm sec2)
t Time (sec)
T Temperature (K)
To Initial temperature of the substrate and
polymer film (K)
T* Dimensionless temperature
t* Dimensionless time
vÞ Volume average velocity (cm/sec)
v* Dimensionless volume average velocity
V̂i Partial specific volume of component i
(cm3/g)
Xi(t) Thickness of layer i (cm)
Xi* Dimensionless thickness of layer i

Figure 13. Diffusivity profiles in PS/Toluene (top Greek Letters

layer) and PVAC/Toluene (bottom layer) coatings after
1,500, 3,000, and 4,500 sec of drying. DĤvi Heat of vaporization of component i (J/g)
 MULTILAYER DRYING OF POLYMER FILMS 1675

ri Mass density of component i (g/cm3) 6. Vrentas, J. S.; Vrentas, C. M. J Polym Sci B: Polym
rio Initial mass density of component i (g/cm3) Phys 1994, 32, 187.
rioi Initial mass density of component i at 7. Cairncross, R. A.; Jeyadev, R.; Dunham, R. F.;
polymer polymer interface (g/cm3) Evans, K.; Francis, L. F; Scriven, L. E. J Appl Poly
h Dimensionless length variable Sci 1995, 58, 1279.
h# Dimensionless length variable 8. Alsoy, S.; Duda, J. L. Drying Technol 1998, 16,
mi Chemical potential of component i 15.
9. Gutoff, E. B. Drying Technol 1996, 14, 1673.
10. Cairncross, R. A.; Francis, L. F.; Scriven, L. E.
Subscript/Superscript AIChE J 1996, 42, 55.
11. Alsoy, S. PhD Thesis, Modeling of Polymer Drying
g Lower side gas stream and Devolatilization Processes, The Pennsylvania
G Upper side gas stream State University, University Park 1998.
j jth layer 12. Blandin, H. P.; David, J. C.; Vergnaud, J. M.; Illien,
s Substrate J. P.; Malizewicz, M. J Coating Technol 1987, 59,
27.
13. Vrentas, J. S.; Duda, J. L. J Polym Sci 1977, 15,
REFERENCES AND NOTES 403.
14. Vrentas, J. S.; Duda, J. L. J Polym Sci 1977, 15,
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Drying of Coated Films, University of Minnesota, 18. Zielinski, J. M. PhD Thesis, Free Volume Parame-
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