Professional Documents
Culture Documents
Theory of Drying
George W. Scherer*
Central Research and Development,
E. I. du Pont de Nemours & Co.,
Wilmington, Delaware 19880-0356
This review examines the stages of drying, with the emphasis on the constant
rate period (CRP), when the pores are
full of liquid. It is during the CRP that
most of the shrinkage occurs and the
drying stresses rise to a maximum. We
examine the forces that produce shrinkage and the mechanisms responsible for
transport of liquid. By analyzing the interplay of fluid flow and shrinkage of the
solid network, it is possible to calculate
the pressure distribution in the liquid in
the pores. The tension in the liquid is
found to be greatest near the drying surface, resulting in greater compressive
stresses on the network in that region.
This produces differential shrinkage of
the solid, which is the cause of cracking
during drying. The probability of fracture
is related to the size of the body, the rate
of evaporation, and the strength of the
network. A variety of strategies for avoiding fracture during drying are discussed.
[Key words: drying, shrinkage, cracking,
models, gels.]
1. Introduction
REMOVALof liquid is particularly troublesome in sol-gel processing, because gels
tend to warp and crack during drying, and
avoiding fracture requires inconveniently
slow drying rates. However, liquid transport processes are also of importance in
other ceramic-formingoperations, includ-
A.
H. Heuer-contributing
editor
ing slip casting, tape casting, binder burnout, liquid-phase sintering, and drying of
clays. Indeed, the principles of flow in porous media are of such general interest
that they have been frequently "rediscovered" over the past 60 years, and relevant literature is found in fields including
soil science, food science, and polymer
materials science, as well as ceramics. In
most cases, liquid flows through a porous
body in response to a gradient in pressure; at the same time, the pressure
causes deformation of the solid network,
and dilatation of the pores through which
the liquid moves. In this review we analyze the interaction between flow of the liquid and dilatation of the solid in order to
predict the stresses and strains that develop during drying. Special attention is
given to the problems encountered in drying gels, but the analysis is quite general.
The driving forces for shrinkage of the
solid and the mechanisms for transport of
the liquid are discussed in Section II. The
stages of drying are outlined in Section 111,
and a model for calculation of drying
stresses is developed in Section IV. The
cause of cracking during drying and various strategiesfor avoiding fracture are described in Section V. These topics are
discussed in greater detail in a forthcoming book.'
II.
ume of liquid has been reduced by evaporation, the meniscus must become curved
as indicated in Fig. 2. The tension (0in
the liquid is related to the radius of curvature (r) of the meniscus by*
where
Fig. 1. Schematic illustration of drying process: black network representssolid phase and shaded area is liquid filling pores. (A) Before evaporation begins, the meniscus is flat. (B)Capillary
tension develops in liquid as it "stretches" to prevent exposure of the solid phase, and network
is drawn back into liquid. The network is initially so compliant that little stress is needed to keep
it submerged, so the tension in the liquid is low and the radius of the meniscus is large. As the
network stiffens, the tension rises and, at the critical point (end of the constant rate period), the
radius of the meniscus drops to equal the pore radius. (C) During the falling rate period, the liquid recedes into the gel.
Theory of Drying
January 1990
that remains there. If the pores are large,
the diffusive flux is matched by counterflow of liquid toward the interior, and no
stress develops. However, if the pores are
small enough to inhibit flow, diffusion away
from the interior can produce tension in
the liquid in that region; then the balancing compression in the solid phase (which
in principle could approach fl) can produce shrinkage. In such a situation, the
solid network plays the role of a semipermeable membrane, permitting transport in only one direction. This
phenomenon could be of importance in
clays and gels. Alkoxide-derived gels
generally contain a solution of liquids that
differ in volatility (viz., alcohol and water),
so evaporation creates a composition gradient, and osmotic flow may result.
(C) Disjoining Pressure: Disjoining
forces are short-range forces resulting
from the presence of a solidlliquid interface. The most important examples are
double-layer repulsion between charged
surfaces and interactions caused by structure created in the liquid by dispersion
forces. Liquid molecules, especially
water,43 tend to adopt a special structure
in the vicinity of a solid surface. The interaction with the surface is so strong that adsorbed layers =I nm thick resist freezing.6
As evaporation occurs and solid surfaces
are brought together, repulsive forces arising from electrostatic repulsion, hydration
forces, and solvent structure resist contraction of the gel. The pore liquid will diffuse
or flow from the swollen interior of the gel
toward the exterior to allow the solid surfaces to move farther apart. The disjoining forces thus produce an osmotic flow,
where transport is driven by a gradient in
chemical potential in the liquid phase.
Since these forces become important
when the separation between Surfaces is
small, they are most likely to be important near the end of drying of gels, when
the pore diameter may approach 2 nm.
Macey7 argues that electrostatic repulsion between particles of clay produces
tension in the liquid that draws flow from
the interior of a drying body. Even for
clays, in which these phenomena are most
evident, it has been argued8 that osmotic
forces must be less important than capillary pressure, because moisture gradients
persist in clays for long periods when
evaporation is prevented. In addition, it
has been shown that the final shrinkage
of kaolinite clay during drying is directly
related to the surface tension of the pore
liquid.9 The swelling pressure of clays in
water is < I 0 MPa,lO which is comparable
to the capillary pressure in pores with radii
>14 nrn (according to Eq. (l),assuming
yLv= 0.072 Jlm2 for water). In the case of
gels, the pores are generally smaller than
that, so capillary forces are expected to
dominate.
(0) Moisture Stress: Moisture stress
or moisture potential (y)is the partial
specific Gibbs free energy of liquid in a
porous medium, and is given byir
y=
( e x )1'
k)
(5)
where eL and V,,, are the density and molar volume of the liquid, Rs is the ideal
gas constant, T is the temperature, pv is
the vapor pressure of the liquid in the system, and po is the vapor pressure over a
flat surface of the pure liquid. In soil
science12 it is conventional to define the
moisture potential in terms of the equilibrium height to which it would draw a
column of water, so a factor of g (the
gravitational acceleration) would be included in the denominator on the right side of
Eq. (5). The moisture potential is quite inclusive, because the vapor pressure is
depressed by factors including capillary
pressure, osmotic pressure, hydration
forces, and adsorption forces. Thus, moisture potential subsumes all of the driving
forces discussed above, and can be obtained by measuring the vapor pressure
of the liquid in the system. For that reason, Zarzycki13 recommends it as the appropriate potential driving shrinkage of
gels during drying. The difficulty in implementing that suggestion is that capillary pressure gradients produce flow,
while concentration gradients (that produce osmotic pressure) cause diffusion,
so it is necessary to apply portions of the
total potential to different transport
processes. In soil science, it is customary
to assume that fluid flow is driven by the
gradient in moisture potential, but it is done
with the understanding that factors other
than capillary pressure and gravitation are
negligible.12
(A)
(B)
shrinkage.
Fig. 3. Water diffuses into the salt solution to equilibrate the concentration on either side of
the impermeable membrane; pressure il would have to be exerted on the solution to prevent
the influx of water.
unfortunately, attempts at direct measurement of the viscosity near solid surporous media obeys Darcy's la~,14~15 faces243 have been shown26 to give
incorrect results. Spectroscopic methods
which states that the flux of liquid, J, is
indicate an increase in viscosity by a facproportionalto the gradient in pressure in
tor of -3, so the effect of solvent structure
the liquid, VP,:
on the flux in gels can be substantial.
(B) Diffusion: According to Fick's
law, the diffusive flux (Jo) is proportional
to the concentration gradient (VC):27
The flux is in units of volume per area of
the porous body (not the area occupied
by the liquid) per time, PL is the force per
unit area of the liquid, q~ is the viscosity
where D, is the chemical diffusion coeffiof the liquid, and D is called the permeacient, C is the concentration, and p is the
bility and has units of area. Positive flux
chemical potential. As noted above, diffumoves in the direction of increasingly
sion can contribute to the shrinkage of gels
negative pressure (i.e., the flow is toward
in special cases (e.g., when the gel is imregions of greater tension in the liquid).
mersed in a salt solution) and may be imEquation (6)is an empirical equation derportant during evaporative drying, if a
ived from observation of flow of water
concentration gradient develops in the
through soi1,16 but it is analogous to
pores by preferential evaporation of one
Poiseuille's law for flow of liquid through
component of the pore liquid.
a straight circular pipe. This analogy has
In some cases, a gradient in concengiven rise to many models for the permetration of the solid phase can produce osability of porous media based on
motic transport (as in the swelling of some
representationsof the pores by arrays of
organic polymers28 or clay29), but it is not
tubes, many of which are discussed in the
clear whether transport occurs by diffusion
excellent texts by Scheideggerl4and Dulor flow. One can compare the fluxes givlien;l5 van Brake117 offers a critical review
en by Eqs. (6) and (8) by converting the
of over 300 such models. The most popuchemical potential gradient to pressurelar model, because of its simplicity and acvolume work, then relating the diffusion
curacy, is the Carman-Kozeny equation,
coefficient to the viscosity by use of the
which gives the permeability in terms of
Stokes-Einstein equation.1 The conclusion
the relative density and specific surface
is that flow is faster than diffusion whenarea:
ever the pore diameter is more than a few
times the diameter of the liquid molecule.
(7)
However, this conclusion applies only to
situations such as flow within a clay body
The factor of 5 is an empirical correction
(where tension in the liquid is produced
for the noncircular cross section and nonby disjoiningforces), where there is a gralinear path of actual pores. This equation
dient in concentration of solid phase. Flow
is reasonably successful for many types
cannot reduce a concentration gradient in
of granular materials, but it often fails, and
the liquid phase. For example, if a gel is
should be applied with caution.
immersed in a salt solution, flow of the soThe proportionality of the flux to the
lution into the pores does not affect the
pressure gradient is obeyed by many
difference in salt concentration between
materials, including those with pores
the bath and the original pore liquid; that
smaller than 10 nm, as in porous
can be achieved only by diffusion. SimiVycort718 and alkoxide-derived gels.19
larly, if evaporation creates a concentraEven in unsaturated bodies (i.e.,where the
tion gradient in the pore liquid, flow from
pores contain both liquid and gas),
the interior of the gel cannot eliminate it;
Darcy's law is obeyed1420 as long as the
only interdiffusion within the pores can do
liquid phase is funicular (i.e., interconnectso.
ed); if the liquid is pendular (i.e., isolated
in pockets), it can only be transported by
Ill. Stages of Drying
diffusion of the vapor. The permeability of
The stages of drying were clearly
unsaturated materials is a strong function
discussed in the classic work of
of liquid content and shows considerable
Shewmd30-3260 years ago. Several texts
hysteresis as the liquid content is raised
provide qualitative descriptions of the
and lowered.
phenomenology and detailed discussion
In gels the pores are so small that a
of the technology of drying,%-%The scienlarge portion of the liquid may be in structific aspects are discussed in several very
tured layers within =1 nm of a solid surgood reviews (e.g., Refs. 8 and 36) and
face, so the effective viscosity may be
in the series of books called Advances in
greater than in the bulk liquid. The reDr~ing.37~38
duced mobility in such lavers can be
demonstrated. using nuclear magnetic
(1) Constant Rate Period
resonancgl or optical s p e c t r o ~ c o p y , ~ ~ ~The
~ ~ first stage of drying is called the
constant rate period (CRP), because the
rate of evaporatlon per unit area of the dry+Corning Glass Works Corning NY
ing surface is independent of time 7,8 The
January 1990
evaporation rate is close to that from an
open dish of liquid, as indicated, for example, by Dwivedis data for drying of alumina ge1.39 The rate of evaporation, V , , is
proportionalto the difference between pv
and the ambient vapor pressure, pA:
(9)
where k is a factor that depends on the
temperature, draft, and geometry of the
system. The vapor pressure of the liquid
is related to the capillary tension (P) by
-)
The fact that the evaporation rate is similar to that of bulk liquid indicates that the
vapor pressure reduction is insignificant
during the CRP. However, in some gels
the pores are so small that a significant
reduction in pv could occur; moveover,
the composition of the liquid in the pores
could change with time if the initial liquid
is a solution. The latter factors have been
proposed to explain the absence of a CRP
for an alkoxide-derived silica gel.4W
It seems reasonable to conclude that
the surface of the body must be covered
with a film of liquid during the CRP, because the proportion of the surface covered by menisci shrinks faster than the
total area, so the rate would decrease as
the body shrank if evaporation occurred
only from the menisci. However, Suzuki
and MaedaQ proved that the evaporation
rate can remain constant even when dry
patches form on the surface of the body.
There is a stagnant (or slowly flowing)
boundary layer of vapor over the drying
surface, and if the breadth of the dry
patches is small compared to the thickness of the layer, diffusion parallel to the
surface homogenizes the boundary layer
at the equilibrium concentration of vapor.
This would certainly be expected in gels,
where the expanse of dry solid phase between menisci would be on the order of
nanometers. Therefore, transport of vapor
across the boundary layer obeys Eq. (9),
and the rate of evaporation per unit area
of surface is constant, whether or not there
are small dry patches.
Evaporation causes cooling of a body
of liquid, but the reduced temperature
leads to a lower rate of evaporation, and
this feedback process equilibrates when
the drying surface reaches the wet bulb
temperature (T,). As indicated by Eq. (9),
V , increases as PA decreases, so T,
decreases with the ambient humidity. The
exterior surface of a drying body is at the
wet bulb temperature during the CRP.3
The surface temperature rises only after
the rate of evaporation decreases (in the
falling rate period discussed in Section Ill
Theory of Drying
(2)). For alkoxide-derived gels the vapor
pressure must be kept high to avoid rapid drying, so the temperature of the sample remains near ambient.
The tension in the liquid is supported by
the solid phase, which therefore goes into
compression. If the network is compliant,
as it is in alkoxide-derived gels, the compressive forces cause it to contract into the
liquid and the meniscus remains at the exterior surface, as indicated in Fig. 1(B). In
a gel, it does not take much force to submerge the solid phase, so the capillary
tension is low and the radius of the meniscus is much larger than the pore radius.
As drying proceeds, the network becomes
increasingly stiff, because new bonds are
forming and the porosity is decreasing; the
meniscus deepens and the tension in the
liquid rises correspondingly. Once the radius of the meniscus becomes equal to
the radius of the pores in the gel, the liquid exerts the maximum possible force.
That marks the end of the CRP: beyond
that point the tension in the liquid cannot
overcome further stiffening of the network,
so the meniscus recedes into the pores,
leaving air-filledpores near the outside of
the gel (Fig. 1(C)). Thus, during the CRP,
the shrinkage of the gel is equal to the volume of liquid evaporated; the meniscus
remains at the exterior surface, but r
decreases continuously. This behavior is
illustrated by the data of Kawaguchi et d . 4 3
for alkoxide-derived gels; equivalent
results have been reported for particulate
gels made from fumed silica.44
The end of the CRP is called the critical
point (or leatherhard point, in clay technology), and it is at this point that shrinkage
virtually stops. At the critical point, the radius of curvature of the meniscus is small
enough to enter the pores, so the capillary tension is found from Eqs. (3) and (4):
Fig. 4. After the critical point, the liquidlvapor meniscus retreats into the pores of
the body. In the first falling rate period, liquid
is in the funicular state, so transport by fluid
flow is possible. There is also some diffusion
in the vapor phase.
(3)
Theory of Drying
January 1990
raise the energy of the system, because
(1)
Pressure Distribution
We need to express in terms of the tension in the liquid using a constitutive equation for the network. Various authors have
done this by using empirical (nonlinear
elastic) equation~7~12
or by assuming elastic behavior with the solid and liquid
phases compressible57P or incompressible,63!a or allowing the network to be
purely V ~ S C O UorSviscoelastic.66-70
,~~
For
the sake of discussion, we will employ the
simpler elastic analysis. When the network
is assumed to be elastic, Eq. (13) has the
mathematical form of the diffusion equation. For the CRP it is appropriate to introduce the boundary condition that the
flux at the exterior surface is constant:
P-(P>
(18)
10
=;/a/;.
(3) Diffusion
If the pores contain a solution of liquids
with intrinsic diffusion coefficients D, and
D2, then diffusion contributes to the transport and the diffusion term must be added to the flow term. Then Eq. (13)
becomes72
h=
K i
-v. - VP
+ ( I -@)V.
V.
Fracture
January 1990
Theory of Drying
(22)
which means that the drying front becomes smoother (w decreases) as the
drying rate increases. Thus
oc
= pRwl/2a (VE)-1/4
(23)
u,
= uXwl/2a (VE)3/4
11
(241
Fig. 6. Drying behavior of flat plate: (A) normalized pressure (P/PR)in liquid versus reduced
time (0 = th) at several locations in the plate (exterior surface at z/L = 1 and midplane at ziL = 0);
(B)normalized stress (ox/PR)versus reduced time at same locations as in (A); (C) pressure distribution at several times during CRP (KO,);(D) normalized stress distribution at same times as
in (C); (E) normalized pressure distribution at several times during FRP (@>OR); (F) normalized
stress distribution at same times as in (E). From Ref. 63.
12
VI. Conclusions
Although the principles of drying have
been recognized for decades, the means
of calculating drying stresses and strains
have been developed relatively recently.
The stresses result from a gradient in the
pressure in the liquid in the pores of the
drying body. The stress increases with
the drying rate and the size of the body,
and is inversely related to the permeabil-
January 1990
ity of the structure. It is the latter factor that
makes gels so much harder to dry than
conventional ceramics: their small pores
result in very low permeability. Fracture
may result from the action of drying
stresses on preexisting flaws, but in many
cases seems to result from flaws generated by the irregularity of the drying front
as it enters the body at the critical point.
Unfortunately, many of the physical
properties needed to predict failure (e.g.,
permeability and critical stress intensity
of wet bodies) have not yet been
measured.
A variety of strategies have been devised to avoid fracture during drying.
These include strengthening of the solid
network by aging or chemical additives,
increasing permeability by increasing
pore size, and reducing capiliary pressure by increasing pore size, reducing interfacial energies, or drying under
supercritical conditions. Each of these approaches involves some tradeoff (for example, in processing time or sintering
temperature), so the best method must
be chosen by regarding the process as
a whole.
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