Ramarao 2003

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Moisture Diffusion Inside Paper Materials in the

Hygroscopic Range and Characteristics of Diffusivity
Parameters
a a a b
B. V. Ramarao , A. Massoquete , S. Lavrykov & S. Ramaswamy
a
Faculty of Paper Science and Engineering and Empire State Paper Research Institute , State
University of New York CESF , Syracuse, New York, USA
b
Department of Wood and Paper Science , Kaufert Laboratory , University of Minnesota , St.
Paul, Minnesota, USA
Published online: 17 Dec 2010.
To cite this article: B. V. Ramarao , A. Massoquete , S. Lavrykov & S. Ramaswamy (2003) Moisture Diffusion Inside Paper
Materials in the Hygroscopic Range and Characteristics of Diffusivity Parameters, Drying Technology: An International Journal,
21:10, 2007-2056, DOI: 10.1081/DRT-120027044
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Moisture Diffusion Inside Paper Materials in the

Hygroscopic Range and Characteristics of
Diffusivity Parameters
B. V. Ramarao,1,* A. Massoquete,1 S. Lavrykov,1

and S. Ramaswamy2
1
Faculty of Paper Science and Engineering and Empire
State Paper Research Institute, State University of
New York CESF, Syracuse, New York, USA
2
Department of Wood and Paper Science, Kaufert
Laboratory, University of Minnesota, St. Paul,
Minnesota, USA
ABSTRACT
Some current models for moisture diffusion in paper in the

hygroscopic range are analyzed. In general, two types of diffusion
models can be recognized. Models of the first type treat paper as a
homogeneous medium with moisture flux that is proportional to the
gradient in moisture content. Although useful in some instances this
approach fails frequently because it homogenizes the internal
*Correspondence: B. V. Ramarao, Faculty of Paper Science and Engineering

and Empire State Paper Research Institute, State University of New York
CESF, 1 Forestry Drive, Syracuse, NY 13210, USA; E-mail: bvramara@syr.edu.
2007
DOI: 10.1081/DRT-120027044 0737-3937 (Print); 1532-2300 (Online)

Copyright & 2003 by Marcel Dekker, Inc. www.dekker.com
2008 Ramarao et al.
dynamics and relaxation processes occurring within the paper

material. Recent studies have shown that a subtler approach
which treats paper as a composite of fibers and void spaces is more
successful at describing moisture transport dynamics. A review of
these studies along with a generalization of this approach to three
dimensions is considered here. The parameters appearing in such
models can be identified with the physical processes of diffusion
through the void space and through the fiber matrix. Diffusivities
in these individual phases are supplemented by a local kinetic
coefficient representing moisture flux interchange between the void
and fiber phases. When the local moisture exchange coefficient takes
on large values, the fibers and the void spaces are at local equilibrium
with no net exchange of moisture. Under such conditions, the model
reduces to the simpler Fickian diffusion model with nonlinear
moisture diffusivity equivalent to earlier models.
1. BACKGROUND
Moisture diffusion in paper materials under both steady and

unsteady conditions has been the subject of intensive investigations in
the past. The early works assumed a homogeneous model of paper and
determined overall diffusion coefficients for moisture in many samples.
Later works focused on identifying the important mechanisms of
transport within the paper sheets and clarifying their interactions
during steady and unsteady transport. In this article, we consider past
studies of moisture transport through paper materials under steady and
unsteady states. We consider a mathematical model of transient moisture
diffusion in paper which has been proposed and used by Bandyopadhyay
et al.[1,2] We identify the parameters of this model and how they depend
on sheet structure and fiber characteristics.
1.1. Steady State Diffusion of Moisture in Paper
Moisture can diffuse through paper by a variety of mechanisms.

Nissan[3] identified the following: water vapor diffusion through the void
spaces, moisture transport in condensed phase through the cell wall,
Knudsen diffusion through intra-fiber and inter-fiber pore spaces, surface
diffusion along the fiber-void interfaces and liquid water transport caused
by capillary action along intra- and inter-fiber pores. An in-depth review
Moisture Diffusion Inside Paper Materials 2009
of moisture transport mechanisms is provided by Hashemi et al.[4] Table 1

summarizes some of these mechanisms. Joy[5] indicated that moisture
permeability through paper is a strong function of the relative humidity.
Rounsley[6] investigated moisture diffusion through the pore space coupled
with diffusion through the adsorbed phase on the fiber surfaces.
Rounsley’s model considered moisture as diffusing through the vapor
space and simultaneously in adsorbed form on the fiber surfaces with

exchange allowed between the adsorbed and vapor phases. Rounsley’s
model for steady state diffusion contains three diffusion parameters:
diffusivity of moisture through the pore space, a coefficient for adsorption
and desorption (which he identified as a diffusion coefficient) and a
diffusion coefficient for the absorbed layer flow (surface diffusivity).
Conventional forms for the surface diffusivity were postulated and used
to solve the resulting system of equations.
Ahlen[7] measured steady moisture fluxes through paper sheets
exposed to different humidity conditions. The ratio of the moisture flux
to the water vapor concentration differential was defined as the effective
diffusivity and was determined from experimental data. This diffusivity
showed a strong increase with the average humidity of the sheet and was
also dependent upon the individual humidity values on either side of
the sheet. Ahlen proposed that these results could be interpreted by
considering the diffusivity as the sum of diffusivity through the pore
space and the diffusivity of condensed moisture through the fiber phase.
The diffusivity of water vapor through the void space will not be sensitive
to the concentration of water vapor (assuming that the pore space does not
change with sheet moisture content). For dry sheets, the water vapor
diffusivity through the void space scales with diffusivity of nonadsorbing
gas molecules in accordance with Chapman-Enskog theory. It is thus
reasonable to assume that the diffusion of water vapor is dominant
through paper under dry conditions. Ahlen’s results showed that the
effective diffusivity increased with average relative humidity above 30%
RH. This increase was interpreted as being caused by the prominence of
diffusion of moisture in the condensed form through the fiber phase (in
adsorbed and absorbed modes).
A review of some earlier results on moisture diffusion in paper
sheets has been given by Hashemi et al.[4] and also by Amiri et al.[8]
Experimental data and various correlations for moisture diffusivities in
the in-plane and thickness dimensions were presented graphically in these
works. Diffusivity correlations of Hartley and Richards,[9] Lee and
Hinds[10] and Kobari[11] obtained from analyses of paper drying
phenomena were shown. Nilsson et al.[12] reported steady state moisture
diffusivity through paper sheets at different humidities. They found
2010
Table 1. Some mechanisms for moisture transport in paper suggested by various authors.
Void space mechanisms Fiber matrix mechanisms
Molecular diffusion Rounsley, Ahlen, Surface diffusion Rounsley

of water vapor Radhakrishnan et al.,
in air Massoquete et al.,
Self diffusion Liang et al., Diffusion through Radhakrishnan et al.,
Nilsson et al. solid matrix Bandyopadhyay et al.,
(þ surface diffusion) Lescanne et al.,
Hashemi et al.
Mutual diffusion Capillary transport
in nanocapillaries
in cell wall
Knudsen diffusion
Flow under a pressure
gradient (simple
Poiseuille flow)
Slip flow
Capillary transport
in void space
Ramarao et al.
that for average humidities less than about 60%, the dependence of the
diffusivity on humidity was quite weak whereas for higher humidities it
increased strongly. Diffusivity decreased with increased sheet densities.
Nilsson and Stenstrom[13] proposed a periodic array of parallel cylinders
as a model for fibrous media such as paper and nonwoven media. They
obtained analytical solutions to Laplace’s equation in a unit cell and
determined the effective diffusivity of a nonadsorbing molecule (water

vapor). The effective diffusivity was compared with moisture diffusivity
through paper. Reasonable agreement was found when the unit cell and
the fiber were idealized to be rectangular, representing band-like fibers.
Liang et al.[14] considered steady transport of moisture and n-propanol
through pulp pads. Instead of evaluating diffusivity from experimental
moisture flux measurements, they determined transport coefficients,
which include convective boundary layer resistances with the diffusion
resistances. Their results support the broad conclusion that moisture
transport at low humidity conditions is dominated by vapor transport
through the void space whereas at high humidity conditions, transport
in the condensed phase could be significant. Liang et al. also showed
evidence that the vapor phase diffusivity decreased at high humidities
probably due to a reduction in the porosity of the sheets and increase in
the tortuosity of the pore space.
Radhakrishnan et al.[15,16] analyzed steady state moisture transport in
stacks of bleached kraft paperboard using a diffusion cup apparatus. An
effective diffusivity was defined by the ratio of the moisture flux to the total
water vapor concentration gradient and was found to be an increasing
function of average relative humidity of the stack. Considering moisture
transport to occur in two parallel pathways: one through the void space in
the form of water vapor and the other through the fiber matrix in the form
of condensed water can explain this variation as shown by them. The
resulting total moisture flux can be represented as that due to diffusion
in along the two paths as:
dc dq
jtot ¼ jp þ jq ¼ Dp p Dq ðqÞ ð1Þ
dz dz
Radhakrishnan et al. used the following equation for the diffusivity
of moisture through the fiber space based on similar forms used for
transient diffusion used in earlier work (Sec. 2.2).
Dq ðqÞ ¼ Dq0 emq ð2Þ
The effective diffusivity was defined by the following equation.
jtot
Deff ¼ ð3Þ
ðc1 c0 Þ
2012 Ramarao et al.
The effective diffusivity can also be related to the diffusivities in

the individual pathways Dp and Dq. Note that at steady state, the net
moisture flux jtot is invariant with position along the sheet’s thickness.
Thus,
djtot
¼0 ð4Þ
dz
By integrating this equation with respect to z over the sheet thickness

L and assuming that the fiber moisture contents on either side are given
by q1 and q0, we obtain for the effective diffusivity,
p Dq0 ðemq1 emq0 Þ
Deff ¼ Dp þ ð5Þ
m c1 c0
For details of this derivation, see Radhakrishnan et al.[15,16] and
Bandyopadhyay et al.[1,2] The effective diffusivity can be seen to be a
function of the moisture contents on either side of the sheet explicitly.
In the development above, the external surfaces of the sheets are assumed
to attain equilibrium with the local humidity conditions instantaneously.
Therefore the moisture contents q1 and q0 are those obtained at equi-
librium at the corresponding relative humidities, h0 and h1. Moreover
Radhakrishnan et al. provided a simplification of the above equation
for the effective diffusivity under the assumption of small values of the
moisture contents such that the exponentials could be linearized. The
resulting equation is
Deff ¼ Dp ð1 þ aebhav Þ ð6Þ
where hav, represents the average of the two external humidities. Values
of the coefficients in Eqs. (2) and (5) based on Radhakrishnan et al.’s data
are shown in Table 2. This table also summarizes some of the correlations
and diffusivity values for moisture in paper reported by earlier workers.
Chatterjee and Gupta[17] investigated the steady state moisture transport
in a stack of paper sheets. Recently, Gupta and Chatterjee[18] analyzed
experimental data for diffusion assuming that the fibers and the void
spaces are at local equilibrium throughout the stack.
The dependence of moisture diffusivity on sheet moisture content
seems to be quite complex and often contradictory behaviors have been
reported. Figures 1a and b show some of the correlations for moisture
diffusivity in the fiber phase as a function of sheet moisture contents.
The majority of the research seems to indicate an increase in diffusivity
as moisture content increases in the ‘‘hygroscopic’’ range. At high humid-
ities or sufficiently high moisture contents, data from various sources
indicate a saturation trend i.e., the diffusivities approaching constant
values. A rationalization of these contradictory trends can be made by

viewing moisture transport as a composite of diffusion phenomena
through the two phases viz void and fiber matrix. Diffusion through
the void space would be restricted at high moisture contents due to the
crowding of the pore space by the swelling fibers. This would increase the
tortuosity for vapor phase diffusion while reducing the pore space, both
effects tending to reduce the vapor phase diffusivity. Diffusion through

the fiber matrix (including surface and capillary phenomena) would
increase with moisture content due to increased moisture solvation or
mobility. Increased contact between fibers (reduced fiber path tortuosity)
and increased fiber space would be other contributing factors. Thus,
depending on the magnitudes of these independent effects, moisture
diffusivity can show an increase or a decrease for different paper
grades. Despite which effect dominates, it is clear that moisture diffusivity
must be bounded at sufficiently high moisture contents as shown by some
of the experimental data and correlations in Fig. 1a and also shown by
Hashemi et al.[4] and Amiri et al.[8]
1.2. Transient Diffusion of Moisture in Paper Materials
By exposing paper sheets to differential humidity conditions and

measuring steady moisture fluxes, it is possible to obtain steady state
diffusion parameters as shown in the previous section. When sheets are
exposed to changing humidity conditions, diffusion parameters obtained
from steady state measurements may or may not describe the sheet
dynamics adequately. In general, we can recognize three types of
humidity changes we expect to find in practice: step, ramp, and cyclic.
The dynamics of paper sheets to each of these changes can be analyzed
using diffusion theory as shown below.
1.2.1. Step Response
The transient sorption response to a step change in humidity can

be analyzed from the basic diffusion formulation as follows. Let us
consider a sheet of initial moisture content q0 in equilibrium at a
humidity of h0, suddenly exposed to an environment of a different
humidity, h1. The sheet responds by either adsorbing or desorbing
moisture depending upon whether h1 is greater or lesser than h0. The
sudden change in external RH can be modeled as a step change.
Figure 1 is a schematic representation of this experimental situation.
2014
Table 2. Moisture diffusivity, data, and correlations in the literature for diffusion through pore space and through fiber matrix, Dq.
Diffusivity 1012 m2s1 (except where indicated)

Sample Conditions
Authors paper grade GSM RH/q, T Dzz Dxy
Amiri et al. (q) Newsprint 48.8 6.1–50–74% 9.42 3.89

Amiri et al. Waxed board 276 6.1–50–74% 0.64 0.64
Amiri et al. Corrugated 767 6.1–50–74% 30.6 30.6
Amiri et al. Core 5.56 5.56
Westerlind et al. (q) Linerboard 150 0–50% 13.9
Westerlind et al. Linerboard 440 0–50% 19.4
Roisum (q) Board 120 0.055–0.14 3.3 109
Lescanne et al.a (q) 300 0.08 13.5 1010
120 0.10 5.5 1015
Lin (q) Kraft 0.27
Ahlenb (c) BKP mats 46 6.44 109
Nilsson et al. (c) BKP mats 812 30% 1.3 106
Ramarao et al.
Lee and Hinds 6 Ply sheets 600 Drying, 105 C Dq ¼ 1.4 1010 (q 0.15)2.2
Kobari Dq ¼ exp(3.19q/)" 27.04)
Hagglund et al.a (c) UBKP mats 431 90% 2.95 108
Lin Kraft paper Dq ¼ 2.616 1011 exp(0.5q)
Hashemi et al. BKP 50 Dq ¼ 2.95 106 exp(0.505/q)
Amiri et al. Newsprint 2.1 1010 9.5 1010
Foss et al.a Board 600 2 106
Foss et al.a 1012
Foss et al.b 3.8 1014
ten Donkelaar Corrugated Dq ¼ 1010 exp(15q)
Ramarao and Chatterjee BKP 240 50–90% 2.5 107
Radhakrishnan et al. BKP 240 Dq ¼ 2.616 1011 exp(345q/18)
6
Nilsson and Stenstrom 1.25 10
Massoquete et al. 2.5 106
Moisture Diffusion Inside Paper Materials
a
Representative diffusivity shown. Original paper contains more data at different conditions (q/RH).
b
Representative diffusivity shown. Original paper contains more data at different conditions (q/RH).
2015
2016 Ramarao et al.

Figure 1. (a) Diffusivity of condensed moisture through fiber phase in paper.

Correlations from literature shown for different moisture contents in the
hygroscopic region (approximately less than the fiber saturation points).
(1) Radhakrishnan et al.[15,16] (2) Lin[94] (3) Lee and Hind (4) Kobari. (b)
Diffusivity with moisture content on logarithmic scale. Log(Dq). Numbers on
curve as in 1(a).
Viewing the paper sheet as a homogeneous material whose diffusivity is

Dq, Fick’s law can be used as:

@q @ @ @q
¼ j ¼ D ð7Þ
@t @z q @z q @z
with initial and boundary conditions given below.
qðt ¼ 0, 0 < z < LÞ ¼ q ðh0 Þ ð8Þ

qðt, z ¼ 0Þ ¼ q ðh1 Þ ð9Þ
qðt, z ¼ LÞ ¼ q ðh1 Þ ð10Þ
In the above model the diffusivity of moisture Dq is assumed to be a

nonlinear function of the moisture content as given by Eq. (2). The
diffusivity can be determined by analyzing the response of a sheet to
step changes. Define the total amount of moisture absorbed under an
increase in humidity M(t) by
ZL
MðtÞ ¼ qðt, zÞ dz ð11Þ

0
E(t) is the ratio of the moisture gain at a chosen time to the total possible
moisture gain.
MðtÞ Mð0Þ
EðtÞ ¼ ð12Þ
Mð1Þ Mð0Þ
Assuming that the diffusivity is an increasing function of concentra-
tion, Crank has provided the following general conclusions based on
extensive numerical and experimental results. The amount sorbed [E(t)]
is directly proportional to t1/2. A plot of E against t1/2 is referred to as the
sorption (desorption) curve. Crank suggests that this curve should be
linear and the linear behavior can extend well beyond 50% of the final
equilibrium uptake value. If the sorption curve shows an inflection point,
the concentration at the boundary is no longer a constant or it implies
that the diffusivity is a function of other variables (most commonly time)
in addition to the concentration. Then the functional form of Eq. (2) does
not hold.
When the diffusivity (or the boundary concentration) is a function
of time, it is more common to replace the diffusion law by a relaxation
equation drawn from thermodynamics of irreversible processes. One such
formulation represents the moisture flux as the convolution integral of
a diffusivity function and the concentration gradient (Neogi[19,20]).
Zt
j¼ Dðt Þ rcðÞ d ð13Þ
0
where the transient process begins from an equilibrium state at time t ¼ 0.

The response function D is a function of time. The above equation is also
known as the visco-elastic diffusion equation. The following equation was
given by Neogi[19,20] as a model for small solvent molecules penetrating
in polymers.
ðD0 Di Þ t=t
DðtÞ ¼ Di ðtÞ þ e ð14Þ
t
2018 Ramarao et al.
with Di representing the initial diffusivity and D0 as the long time

diffusivity.
1.2.1.1. Transient Diffusion Described by a Fickian Process

In an early work, Steele[21] determined transient moisture profiles
in dry kraft paper used for capacitors and in oil soaked samples after
subjecting the sheets to a step increase in humidity. Lin[22] analyzed these
profiles using predictions from the standard unsteady state diffusion
model with a moisture dependent diffusivity. The coefficients in the
moisture dependence of the diffusivity determined by Lin are shown
in Table 2. Lin’s model used Eq. (7) with Eq. (2) substituted for the
diffusivity and the initial and boundary conditions given by Eqs. (8)
through (10).
Roisum[23] and recently, Amiri et al.[8] modeled transient
moisture diffusion through paper rolls using the two-dimensional analog
of Eq. (7). ten Donkelaar and Jaeger[24] analyzed moisture diffusion in a
paper sheet and corrugated board assuming that local equilibrium is
established between the pore and fiber spaces. They showed that diffusion
within the pore and fiber phases can be reduced to a single transient
diffusion equation that can be approximated by Eq. (7). Further, if one
accepts the exponential relation for the diffusivity given by Eq. (2), the
model reduces to that used by Lin. All of these works are based on the
validity of the flux being represented by a single potential gradient.
Thus they can all be classified as generalized Fickian diffusion models,
although nonlinear dependence of the diffusion coefficient is allowed.
1.2.1.2. Nonfickian Descriptions of Moisture Diffusion in Paper

Paper is a porous medium and the interaction of diffusion between
the pore space and fiber space is quite complex. Consideration of this
interaction leads to a more complicated description of moisture transport
than the simple homogeneous model described in the earlier section.
Lescanne et al.[25] studied transient and steady state diffusion in paper
and concluded that moisture diffusion is definitely nonfickian at least
within the ranges of transients they studied. This is a common phenom-
enon observed with small penetrant molecules in polymeric systems.[26]
Lescanne et al.’s mathematical model idealized paper to contain
cylindrical fibers suspended in void space. Moisture diffuses as water
vapor through the inter-fiber void space (represented by the vapor
concentration, c) and also simultaneously diffuses into the fiber cell
walls in the condensed phase. Lescanne et al.’s mathematical model is
described as follows. The concentration of condensed water at the surface

of the fibers is given by qs. Accumulation of moisture within the pore
space is neglected and the continuity equation for moisture content is
given by

@qs @ dc @qs
¼ Dp ð15Þ
@t @z dqs @z
The moisture content at the surface of the fibers is assumed to be in

equilibrium with the water vapor concentration within the pore space
locally. Therefore,
qs ¼ q ðcÞ ð16Þ
The surface concentration of the fibers, qs is determined by diffusion
within the fibers. The continuity equation governing moisture distri-
bution within the fibers is given as

@q 1 @ @q
¼ rDp0 ð17Þ
@t r @r @r
The initial condition is that the entire sheet is at equilibrium with the
initial humidity condition. Therefore,
cðt ¼ 0, zÞ ¼ c0 ð18Þ
and
qðt ¼ 0, zÞ ¼ q ðc0 Þ ð19Þ
where the function q* denotes the equilibrium moisture content when
the water vapor concentration is c0 in the air. Further, the boundary
conditions are
cðt, z ¼ 0Þ ¼ c1 ð20Þ
qðt, z ¼ 0Þ ¼ q ðc1 Þ ð21Þ

and
@q @c
¼ ¼0 ð22Þ
@z @z
Note that Lescanne et al.’s model assumed that the moisture diffusivity
through the fibers Dq0, is a constant. However, experimental evidence
indicates that intra-fiber diffusivity is a strong function of the moisture
content.
Further evidence of the nonfickian nature of moisture diffusion
emerges from the work of Hellen et al.[27,28] In their work, they monitored
the diffusion of moisture and nonadsorbing butanol inside paper sheets.
2020 Ramarao et al.
They also conducted random walk simulations of a tracer molecule inside

the void space of a model fiber network. The transient diffusion model of
Hellen et al.[28] in terms of c and q is
@c @q @2 c
" þ p ¼ Dp 2 ð23Þ
@t @t @z
@q
¼ c q ð24Þ
@t
In this model, moisture conduction by the fibers in parallel with the
void space is ignored just as Lescanne et al.’s did. The exchange of
moisture between the fibers and the pore space is assumed to be by
adsorption or desorption each of which is represented as a first order
process [Eq. (24)]. Consider the sorption isotherm to be linear with the
constant of proportionality Ks. Then, by equating the kinetic constants,
to Kski and u to ki, this model reduces to Ramarao and Chatterjee’s
model. However, Ramarao and Chatterjee attributed local moisture
exchange between the fibers and the void space to a more generalized
departure from equilibrium of the local moisture concentration (i.e.,
deviation of q from q*).
Hellen et al.[27] conducted random walk simulations of tracer
diffusion through simulated fiber structures in conjunction with the
above ‘‘phenomenological’’ description. The random walk simulations
clearly show that diffusion is nonfickian when fiber and void spaces are
not in local equilibrium.
A more complete discussion of fickian and nonfickian diffusion of
moisture in paper is given by Lavrykov et al.[29]
1.2.2. Ramp Response
In many situations, paper materials are exposed to slower variations

in external humidities, which can be modeled as simple ramps.
Furthermore, equipment to investigate dimensional response to humidity
changes such as the Varidim may be unable to accomplish rapid changes
in humidity and thus unable to simulate step changes. Therefore, it is
useful to investigate diffusion under ramped changes in humidity. Two
closely related investigations of moisture sorption have been reported
by Foss et al.[30,31] from Weyerhaeuser (WTC) and by Ramarao and
Chatterjee[32] from SUNY (ESPRI). Both these groups studied transient
moisture pickup in very similar experimental set-ups. By embedding
humidity sensors in between the paper sheets, Foss et al. obtained
humidity profiles in addition to gravimetric measurements of moisture

gain. This mathematical model shares some essential features with that of
Lescanne et al. The model considered moisture transport to be occurring
through both the fibers and pore spaces with a linear mass exchange
between them. Furthermore, diffusive flux of moisture within the
fibers along the thickness dimension is also included. Their model was
solved numerically to predict moisture content profiles within the

paper sheets.
This model avoids the assumption made by earlier authors that fibers
are in local equilibrium with the pore space. Moisture encounters three
resistances as it moves through paper sheets. The first is the convective
boundary layer at the external surface of the sheet. The second is the
diffusional resistance of the tortuous pore space and third, the diffusional
resistance of the cell wall matrix to condensed moisture flow. Although
simpler diffusion models can indeed be used to describe experimental
moisture pick-up, the parameters in these models will lack general
validity (Foss et al.[30]). They extended this theory to consider simulta-
neous transport of heat and mass through paper sheets. Satisfactory
agreement was reported between model predictions and experimental
observations. In the specific mass transport model of Foss et al.,[30,31]
two critical assumptions are made that distinguish it from the later
models of Bandyopadhyay et al.[1,2,33] The first is that the mass transfer
coefficient ki; is assumed to be the harmonic mean of simple diffusional
resistances in the pore and fiber spaces. The second assumption is that the
diffusivity of condensed moisture through the fiber phase is a constant.
By comparing model predictions with experimental results for moisture
uptake dynamics, Foss et al. were able to determine the diffusivity of the
condensed moisture (Dq).[30,31] The assumption of constant value for the
diffusivity in the fibers is contradicted by experimental data for high
moisture contents. Therefore, this model can be applied if the fiber
moisture contents are not too high.
Ramarao[34] has summarized the mathematical models for both
equilibrium hysteresis and moisture transport dynamics. This article also
provided a conceptual basis for the transient transport model proposed by
Ramarao and Chatterjee[32] and used by Bandyopadhyay et al.[1,33] The
fiber mass transfer coefficient ki can be defined rigorously from local
moisture uptake if the local geometry of the pores and fibers is known.
In a more elaborate investigation of humidity transients in paper,
Bandyopadhyay et al.[1] applied the transport model developed by
Ramarao and Chatterjee[32] to humidity ramps of different magnitudes
and speeds as well as to cyclic changes. Experimental data could be
well described by the transport model, which included transport in both
2022 Ramarao et al.
the phases as well as allowing for local nonequilibrium conditions within

the sheets.
Recently, Gupta and Chatterjee[35] (see also Gupta,[36]) have reinves-
tigated the transient response of a stack of paper sheets to ramped
changes in humidity. They first determined moisture diffusivity param-
eters Dp and Dq (as in Eq. (5)) by steady state experiments following the
procedures used by Lescanne et al. Gupta and Chatterjee simplified the

model of Bandyopadhyay et al.[2] by neglecting the local moisture
exchange within the paper sheets. This forces the fibers to be always
in equilibrium with the surrounding void space. Gupta and Chatterjee
compared their model predictions with experimental moisture pick-up
data for different ramp rates and for stacks composed of different
layers. The assumption of local equilibrium of Gupta and Chatterjee[35]
conflicts with evidence for nonfickian diffusion in paper. Furthermore, the
model of Foss et al.,[30,31] Ramarao and Chatterjee,[32] Bandyopadhyay
et al.[2,37,38] all emphasize the sequential nature of the diffusional resis-
tances in pore and fiber phases inside paper. Assumption of local equili-
brium negates this and transfers the dominant resistances to the parallel
mode. Whereas this may be plausible for steady state transport (although
not necessarily true as discussed by Lavrykov and Ramarao[39]), it cer-
tainly would be violated for the transient pick up of moisture by a paper
sheet. Additionally, the approach of fibers towards local equilibrium
would depend on the speed of the humidity transients with rapid external
changes causing large deviations whereas slow changes allow smaller
deviations. Experimental results for the humidity profiles reported by
Gupta[36] show a larger departure from theoretical predictions for
faster ramps.
1.2.3. Cyclic Response
Paper materials creep under applied stress and their creep rate is
dependent upon the moisture content (or the humidity level).
Furthermore, creep is accelerated significantly when the material is
subjected to transient variations in humidity. The accelerated creep of
paper has been theorized recently to occur due to plasticization of the
fibers in conjunction with the existence of nonuniform moisture fields.
Obviously accurate estimation of the moisture fields is central to any
analysis of accelerated creep. Eusufzai et al.[40] to our best knowledge
were the first to investigate the sorption response of paper sheets to
cyclic variations in humidity with this objective. They used Lin’s
unsteady state diffusion model with the nonlinear diffusivity to describe
the sorption response of paper sheets. Different sets of parameters were

necessary to describe the paper sheet’s response to increasing or decreasing
humidity conditions. It is apparent that the single diffusivity model is
unsatisfactory in describing transient response of paper sheets to moisture
variations.
Ramarao et al.[41] developed a mathematical model of transient
diffusion in paper sheets subjected to cyclic humidity variations

considering diffusion as occurring primarily through the void space and
assuming local equilibrium of the fibers. Since moisture equilibrium in
paper shows hysteretic behavior, the response of paper sheets to cyclic
humidity has to track the evolution of the equilibrium moisture content
in addition to the transient moisture contents. Chatterjee et al.,[42]
Chatterjee and Ramarao[43] and Chatterjee[44] showed that equilibrium
trajectories for paper moisture could be followed adequately using the
theory of independent domain complexions. A later study by
Bandyopadhyay et al.[1] considered changes in humidity described by
increasing and a decreasing humidity ramps with hold times between the
up and down portions of the cycle.
In a recent work, Lavrykov and Ramarao[45] analyzed moisture
sorption under cyclic humidity conditions by focusing on the nonlinear
diffusion equation. The moisture content profiles show waves that travel
through the sheet and their exact shape and magnitude depend upon the
equilibrium hysteresis in addition to sheet parameters.
1.2.4. Same Additional Problems Using Moisture Diffusion

Models
The concept that transient moisture transport in paper can be

considered to occur in a dual sorption mode has found application
in models for a variety of moisture transport processes. More recent
work includes that of Hellen et al.[46] who investigated moisture transport
in different paper materials forming moisture barriers. Besides the work
of Lescanne et al., Foss et al., Ramarao and Chatterjee, and
Bandyopadhyay et al. discussed in the previous section, similar models
have been set up by Hagglund et al.[47] for analyzing moisture transport
in paper sheets.
The dual transport and sorption model can be applied to describe
the transport of liquid water in paper materials. Under Darcian flow
conditions, the imbibition of liquid water in paper proceeds in both the
pore space as well as the fiber matrix. It is known that water absorption
in paper is generally nonfickian (showing nonLucas Washburn kinetics
2024 Ramarao et al.
as it is referred to) due to the simultaneous absorption of water by the

fibers in addition to the uptake within the pore space. Recently,
models similar to the relaxation models have been applied to describe
the kinetics of liquid water imbibition.[48–50]
It is the intent of this article to provide an analysis of moisture
transport in paper in the hygroscopic range. We identify conditions
under which this model reduces to simpler versions especially for the
single dimensional cases. Their physical meaning identifies the parameters
appearing in this model and we correlate them with some papermaking
and fiber variables.
When exposed to air at a certain humidity h, paper attains an
equilibrium moisture content qsat. Obviously, for a given humidity
level, different moisture contents [qsat(c or h)] are obtained depending
upon the prior history of the sheet of paper. For our purpose here it is
sufficient to note that the dependence of the equilibrium moisture content
on humidity and on temperature can be described by the following
equation also known as the GAB isotherm (e.g., Chatterjee et al.[51]).
CG MG kG h
q ðhÞ ¼ ð25Þ
ð1 kG hÞð1 kG h þ kG CG hÞ
2. A GENERAL MODEL FOR MOISTURE

DIFFUSION IN PAPER
Ramarao et al.[41] proposed a model for diffusion along the thickness

dimension of paper to investigate the moisture sorption response of paper
sheets to cyclic changes in the humidity. This model accounted for exter-
nal surface boundary layers and diffusive transport of vapor inside the
pore space. An assumption that the fiber phase is in local equilibrium
with the water vapor content of the pore space was also made.
Subsequently, Ramarao and Chatterjee[32] and Foss et al.[30] proposed
diffusion models for moisture transport in paper, which incorporated
three key mechanisms. These included moisture transport in condensed
form through the fiber matrix along the z dimension and vapor diffusion
through the void space. A local uptake of moisture was also provided in
these models. These models have been used to describe a variety of trans-
port processes involving moisture in condensed, free liquid, and vapor
form through paper materials. Some details of the background of
these models is available in Ramarao[34] and Bandyopadhyay et al.[1,2,52]
When generalized to three dimensions, the model for diffusion can be

given as
@c
" ¼ r Dp rc þ p ki ½q ðcÞ q ð26Þ
@t
@q
¼ r Dq ðqÞ rq ki ½q ðcÞ q ð27Þ

@t
The first equation represents continuity of the concentration field

c(t, z) in the void space within the medium. The second equation repre-
sents continuity of the moisture content field q(t, z). Both these fields are
understood to be suitably locally averaged concentrations (p, the density
of the paper is included so as to maintain dimensional consistency with
conventionally accepted nomenclature for moisture content of paper—
for more details on dimensions and conversion, see the table of symbols).
Diffusive transport within the fiber phase in directions orthogonal to the
dominant direction z is averaged out and is represented by the first order
sink terms in Eqs. (26) and (27). ki is a transport coefficient representing
local moisture uptake (or release if desorption obtains), by the fibers.
In the above model, two material characteristic parameters have been
introduced: ‘‘the diffusivity of water vapor through interconnected voids
DP’’ and the ‘‘diffusivity of moisture in the condensed phase along the
fiber matrix, Dq(q).’’ When moisture adsorption occurs at the fiber/
void interfaces a functional representation of the moisture adsorption
isotherm is given by
q ¼ q ðcÞ ð28Þ
We multiply Eq. (27) by p and add to Eq. (26). The resulting

equation shown below does not have the mass exchange term.
@c @q
" þ p ¼ r Dp rc þ p r Dq ðqÞ rq ð29Þ
@t @t
The condition of continuity of moisture flux at the surface of the

sheet can be expressed by equating the convective mass flux with the
diffusive flux in the pore and fiber phases as below. The parameter kf
denotes the mass transfer coefficient and cb is the external concentration
of water vapor in the air.
@c @q
kf ðcb cÞ ¼ Dp p Dq ð29aÞ
@z @z
2026 Ramarao et al.
2.1. Assumption of Local Equilibrium [q(t, x) 5 q*(c)]
Under some situations, it may be possible that local thermodynamic

equilibrium is obtained. This condition could occur for instance under
steady state conditions if the moisture dependence of the diffusivity Dq is
weak or the fibers are reasonably thin and the sheet is insufficiently
porous.
2.1.1. Local Equilibrium Model Using Void Space

Concentration, c
Thus, Eq. (28) can be applied to the moisture content q, and since it is
a function only of the local concentration field c, we obtain

@c dq @c dq
" þ p ¼ r Dp rc þ p r Dq ðq Þ rc ð30Þ
@t dc @t dc
which reduces to

@c 1 dq
¼ r D p þ D
p q ðq Þ rc ð31Þ
@t " þ p ðdq Þ=ðdcÞ dc
This equation is mathematically equivalent to the nonlinear heat
conduction equation with the conductivity defined as
dq
Dcomp ¼ Dp þ p Dq ðq Þ ð32Þ
dc
If the isotherm is linear, i.e., the following approximation holds for
Eq. (28),
q ðcÞ ¼ q0 þ Ks ðc c0 Þ ð33Þ
the slope of the isotherm is independent of c and is given by
dq
¼ Ks ð34Þ
dc
For the steady state case, whether the isotherm is linear or not,
diffusion remains fickian as shown by setting the transient term to
vanish in Eq. (31), resulting in

dq
r Dp þ p Dq ðq Þ rc ¼ 0 ð35Þ
dc
For the uptake of moisture when the sheet is subjected to a step
change in humidity at its surface, the boundary conditions are given by
Eqs. (18) through (22). Therefore when local equilibrium can be assumed
within the paper sheet, moisture transport reduces to Fickian diffusion
in the steady state. A single diffusivity for paper sheets can be derived
which incorporates the geometric/structural aspects in addition to the
diffusivity in both these phases.
2.1.2. Local Equilibrium Model in Fiber Moisture Content: q
We can also write the equilibrium relationship (Eq. (28)) as
c ¼ cðq Þ ð36Þ
using the GAB relationship as
c
¼ Ai þ Bi c þ Ci c2 ð37Þ
q
Hence,
@c dc @q
¼ ð38Þ
@t dq @t
@c dc @q
¼ ð39Þ
@z dq @z
Substituting into Eq. (29), we obtain,
dc @q @q dc
" þ p ¼ r Dp rq þ p r Dq rq ð40Þ
dq @t @t dq
This equation can be simplified to

@q Dp ðdc=dq Þ þ p Dq
¼r rq ð41Þ
@t "ðdc=dq Þ þ p
where we have assumed the slope of the equilibrium sorption relation-

ship, dc/dq* to be a constant for simplicity. Equation (41) clearly shows
that when local equilibrium is satisfied, transient and steady state
transport of moisture are fickian processes, and the nonlinear diffusivity
2028 Ramarao et al.
is given by,
Dp ðdc=dq Þ þ p Dq
Dcomp ðqÞ ¼ ð42Þ
"ðdc=dq Þ þ p
A simpler representation is obtained if the sheet density (p) is
large compared to the first term in the denominator, i.e., "(dc/dq*). The
simplification can be represented as
Dp dc
Dcomp ðqÞ ¼ þ Dq ð43Þ
p dq
or
Dcomp ðqÞ ¼ Dc0 þ Dql emq ð44Þ
if we assume that the diffusivity of moisture through the fiber matrix can
be represented by an exponential relation as in Eq. (7). We thus note that
the complete transient diffusion model can be simplified to

@q @ @q
¼ D ðqÞ ð45Þ
@t @z comp @z
which is approximately equivalent to the simple nonlinear diffusion
models of earlier workers. The initial and boundary conditions to be
applied for a step change in humidity at the external boundary and
when external surface boundary layers are negligible are given by
Eqs. (18) through (22).
Whenever local equilibrium may be assumed, diffusion simplifies to
a single Fickian process. Local equilibrium within paper sheets
simplifies the treatment substantially for both the steady and unsteady
cases. If the sheet is subjected only to small ranges of humidity or
sufficiently slow transients, it may be useful. Rapid transients or large
swings in humidity are likely to disturb this equilibrium and result in
substantial nonfickian effects due to the interference of transport by
many mechanisms. When the boundary conditions involve convection,
difficulties occur. In the next section, we conduct a perturbation
analysis of the model to delineate the specific conditions under which
this assumption may be valid.
3. ANALYSIS OF THE GENERALIZED DIFFUSION

MODEL TO PROVIDE LIMITING CASE SITUATIONS
A mechanistic picture of moisture diffusion is given in Fig. 2. We

observe that the salient mechanisms for diffusion are those through the

Figure 2. Sample schematic representation of the structure of a paper sheet

showing pore space details. Moisture transport occurring through void space
and through the fibers is shown. Local exchange of moisture due to departure
from local equilibrium is represented by the horizontal double headed arrow.
pore space, the fiber matrix and a local uptake of moisture represented by
the algebraic term in the model (Eqs. (28) and (29)). It is our desire to
analyze transient uptake of moisture by a paper sheet subjected to a
change in the external humidity conditions. The analysis we present is
largely that presented by Bandyopadhyay et al.[1]
We first scale the diffusion equations to obtain the following
nondimensional forms. In this, C and Q represent the scaled water
vapor concentration and moisture contents and and represent the
scaled time and z dimension respectively. The definitions of these
variables are provided in the table of symbols.
@C
¼ r Dp rc þ ½Q ðCÞ Q ð46Þ
@
@Q
¼ r FQ ðQÞ rQ ½Q ðCÞ Q ð47Þ
@
Considering transport in the z dimension alone, we obtain[1]
@C @2 C
" ¼ 2 þ ðQ QÞ ð48Þ
@ @

@Q @ @Q
¼ F ðQ QÞ ð49Þ
@ @ Q @
2030 Ramarao et al.
These are subjected to:

Cð ¼ 0, Þ ¼ Qð ¼ 0, Þ ¼ 0 ð50Þ
Cð, ¼ 0Þ ¼ Qð, ¼ 0Þ ¼ 1 ð51Þ
@Cð ¼ 1Þ @Qð ¼ 1Þ
¼ ¼0 ð52Þ
@ @
Equation (52) indicates that the sheet is initially at equilibrium and is
subjected to a sudden change in humidity at the external boundaries.
Assuming the sheet to be symmetric, the moisture fluxes in condensed
and vapor forms vanish at the centerline denoted by ¼ 1. If the external
convective boundary layer poses a significant resistance, the boundary
condition given by Eq. (53) must be replaced by
@C @Q
Bi ½Cb C ¼ FQ0 ð53Þ
@ @
which is the nondimensional form of Eq. (29a). In order to simplify the
analysis, we will assume that the equilibrium sorption relation is linear
for the materials. In nondimensional form, this can be expressed as
Q ¼ C ð54Þ
3.1. Case 1. 1
In this case, the fibers and the pore space are close to equilibrium
locally throughout the sheet. This will occur if
ki L2
1 ð55Þ
Dp
i.e., when the intra-fiber exchange coefficient is large or the pore diffusiv-
ity is small or the sheet is quite thick. In this case, we see that the model is
nonuniform since it reduces to the simple algebraic condition that
C 0 ¼ Q ¼ Q0 ð56Þ
and the boundary conditions can no longer be adequately satisfied.
However, this shows that when the parameter is large, the sheet
approaches equilibrium. Local equilibrium can be expected whenever the
interchange coefficient ki is large or the pore diffusion process
is substantially slow compared to local diffusion. From dimensional
arguments, we can write a general form for ki in terms of a local fiber

diameter or cell wall thickness represented by rf as
Dqav
ki ¼ $ ð57Þ
r2f
where ! is a suitable constant. Substituting into Eq. (40) provides a good

estimate of when local equilibrium will be valid in terms of intrinsic

properties as
Dqav L2
¼$ ð58Þ
Dp0 r2f
Therefore local equilibrium is likely to occur when rf is sufficiently

small for any chosen set of diffusion parameters. Thus, if the cell wall
thickness is small or for sufficiently thick sheets such that pore diffusion
occurs on a slow time scale or when pore diffusivity is very small, we can
expect local equilibrium.
3.2. Case 2. 1
Although we have assumed that the ki parameter is large in case 1, in

most paper materials, this parameter is generally small and results in local
fiber moisture uptake dominating the kinetics. Dq is many orders of
magnitude smaller than the pore diffusivity at low humidity. Since the
pore diffusivity is large, water vapor concentration within the pores
changes rapidly in response to external changes. However, a slower
change occurs due to local sorption dictated by the slow diffusion into
the fibers locally. A multiple scale analysis of the model equations shows
this situation clearly.
Let us define two time scales: a slow time scale denoted by * and a
fast time scale þ (valid for small )
¼ ¼ ki t ð59Þ
tDp
þ ¼ ¼ ð60Þ
L2
Let
C ¼ Cð , þ Þ ð61Þ
Q ¼ Qð , þ Þ ð62Þ
2032 Ramarao et al.
Expanding the C and Q functions in asymptotic series in the small

parameter as
C ¼ C0 ð , þ Þ þ C1 ð , þ Þ þ ð63Þ
Q ¼ Q0 ð , þ Þ þ Q1 ð , þ Þ þ ð64Þ
Substituting into Eqs. (48) and (49) of the model and collecting terms of
similar order of magnitudes, we obtain at the leading order,

@C0 @2 C 0
" ¼ ð65Þ
@ þ @2
( )
@Q0 @ 0 @Q
0
¼ F ð66Þ
@ þ @ Q @
subject to the standard initial and boundary conditions. We recognize

that at the leading order, the change in Q is governed by diffusion
through the fibers in the z dimension. If the humidity is not too high,
this term is likely to be very small in which case, Q0 is independent of þ
to the leading order. Referring to Eq. (65) we see that C0 changes with the
fast time scale. The change in the moisture content though will occur
fairly slowly although the change in water vapor concentration is
rather rapid. The first order problem is given by
" #
@C1 @2 C 1 0 @C 0 @C 0
" þ¼ þ ðQ Q Þ " þ ð67Þ
@ @2 @ @
( ) " #
@Q1 @ 0 @Q
1
0 @Q0
¼ F ½Q Q ð68Þ
@ þ @ Q @ @
These two problems clearly show that the moisture content changes on a
much longer time scale (*) whereas rapid changes occur within the pore
space. The long time scale is given by Eq. (61).
4. DIFFUSION PARAMETERS FOR PAPER SHEETS

AND THEIR DEPENDENCE ON SHEET STRUCTURE
AND FIBER CHARACTERISTICS
In the model for moisture diffusion in paper, there are three critical
parameters. These are: diffusivity of water vapor within the void space,
Dp, the diffusivity of condensed phase moisture through the fiber matrix,
Dq, and the local moisture interchange coefficient between the fibers
and the pores, ki. If these parameters are known for a paper sheet, the
moisture uptake and distributions in transient and steady states can be
determined by applying the model given by Eqs. (46) and (47), subject of
course to the appropriate initial and boundary conditions. In this article,
we study the parameters Dp and Dq in detail and relate them to the

structural characteristics of the paper and the fibers. An analysis of the
parameter ki requires the structure of the pore space and the fiber
matrix and has been reported elsewhere (see Lavrykov and Ramarao[39]).
4.1. Diffusivity Within the Void Space: Dp
Detailed structural reconstructions of paper sheets using X-ray

microtomography have shown that paper is a bicontinuous medium
composed of fibers and void spaces, both of which are well connected
with each other.[53–57] Moreover, the experimental data of
Radhakrishnan et al.,[16] lead to the conclusion that both phases are
percolating for moisture conduction at high moisture contents (or
RHs). In order to understand the relationship between the diffusion param-
eters and the intrinsic phase diffusivities for moisture, let us begin by
considering the case when the fiber phase is nonconducting (and also
nonadsorbing) to moisture. Diffusion in this situation becomes equiva-
lent to diffusion of water vapor through an inert porous medium of the
same structure. The diffusivity Dp can then be expressed in terms of the
intrinsic phase diffusivity Da [the diffusivity of water vapor in air] and
some geometric measures for the structure such as porosity and tortuos-
ity. The effective diffusivity of a three dimensional porous medium has
been analyzed in much detail in the literature. The following equations
have been obtained by Whitaker and co-workers based on the method of
volume averaging. If Da represents the diffusivity of water vapor in air,
the dimensionless effective diffusivity of water vapor in the void spaces
of the paper medium is given by
Dp Z
"p 1
¼Iþ ðnf þ fnÞ dA ð69Þ
Da V 2
Apq
where f is a vector field and n is the unit normal vector at the interface
between the fiber and void interface, Apq is the area of this interface.
The vector field f is harmonic and is defined within the void space.
2034 Ramarao et al.
Representation of the structure as an array of repeating unit cells can

simplify the solution of f . The differential equation to be solved is
r2 f ¼ 0 ð70Þ
in the void space, Vp. The boundary conditions to be satisfied are:

n rf ¼ n ð71Þ
Figure 3. Schematics showing different idealized configurations of the pore

space and fibers for diffusion through the void space.

Figure 3. Continued.
(continued)
at Apq with f being periodic. Example unit cells which can be used for the
paper structure are shown in Fig. 3. Note that if we define the tortuosity
as is conventionally used by
¼ "Da D1
p
ð72Þ
the tortuosity is a tensor field representing the pore space. This definition
of the tortuosity is in terms of the effective diffusivity Dp. When Dp is in
2036 Ramarao et al.

Figure 3. Continued.
diagonal form, so is the tortuosity and its principal components can be

used to obtain the following relation.
"Da
Dp, ii ¼ ð73Þ
ii
where ii denotes any of the normal (xx, yy, or zz) components. Hence,
Eqs. (73)–(75) can be understood to define the effective tortuosity of the
sheet microstructure. The tortuosity is a geometric property and is
usually visualized as the length of the path taken through the pore
space to the physical thickness of the sample. However, the definition
above gives it as the solution to the Laplace equation. In the diffusion
case, the solution to Laplace equation through the microstructure
yields the tortuosity function whereas in the flow situation, one works
with either the full Navier-Stokes equation or the Stokes’ equation for
creeping flows (at low Reynolds’ numbers).
Some sample microstructures are shown in Fig. 3 for paper
materials. The effective diffusivity properties of regular cylindrical
arrays have been widely investigated and numerical and analytical results
are available for these cases. When the structure is an array of spheres or
ellipsoidal particles which are not touching (so-called unconsolidated
systems) analytical solutions are also available. For the case of
consolidated systems solutions have to be obtained numerically.
Random walk simulations of Brownian motion have been shown to be
particularly effective for this purpose. (see Goel et al.[57,58]). An interest-
ing exercise would be to compare the effective diffusivities obtained by

random walk simulations through real structures and the results from the
periodic microstructures shown in Fig. 3.
4.2. Diffusion Within the Fiber Matrix: Dq
Moisture is present in the condensed form within and on the

interfacial regions of the fiber matrix. Let us assume that it can diffuse
along the z dimension due to the moisture chemical potential gradient as
the driving force. In analogy to Eq. (73) for the void space, a relationship
between the fiber space geometry and an intrinsic diffusivity within the
fiber matrix denoted by Dqi should be present.
Z
"q 1
D q ¼ D q0 I þ ðng þ gnÞ dA ð74Þ
¼ ¼ ¼ V 2
Aqp
This equation allows us to separate the effect of the geometry of the fiber
space from the diffusion process intrinsic to the fibers. Analogous to the
void space, the tortuosity for the fiber matrix is
ð1 "ÞDq0i
qi ¼ ð75Þ
Dqi
where Dq0i represents the intrinsic diffusivity of condensed phase

moisture through the fibers in the i direction and Dqi represents an
‘‘effective’’ diffusivity of the condensed moisture due to the tortuous
nature of the diffusion path through the fibers. If the ‘‘intrinsic fiber
diffusivity’’ is known, we can determine the effective diffusivity using
random walk simulations through the fiber space similar to the void
space diffusivity. Foss et al.’s model uses this definition of the tortuosity
for the fiber matrix in addition to a tortuosity for the pore space.
2038 Ramarao et al.

Figure 4. Diffusion mechanisms inside fiber/cell wall. Three orthogonal

components are identified. Dqr —represents diffusion locally perpendicular (i.e.
radical) to the cell wall, Dqt —represents diffusion along tangential direction of
cell wall, possibly between or along microfibril lamellas as shown in inset, Dqa—
represents diffusion along the fiber axis (longitudinal).
4.3. Intrinsic Fiber Diffusivity: Dq0i
The diffusion of moisture through the fiber matrix is quite complex.

The intrinsic diffusivity Dq0i will be a property of moisture diffusion
through the cell wall. Due to the structure of the cell wall, we can expect
this to be direction dependent as shown in Fig. 4 and also concentration
dependent (i.e., on q).
4.3.1. Capillary Transport Through Nanopores in Cell Wall
The cell wall of papermaking fibers consists of structural components

(microfibrils) of crystalline cellulose embedded in a matrix. As described
by Foss et al.,[31] the crystallites in the cell wall are thought to be
interrupted locally by ‘‘amorphous’’ regions. Structurally, the cell wall
is considerably complex. Crystals of cellulose are formed into crystallites
called microfibrils, which are linked to each other forming strands. These
strands are joined to form sheet-like lamellas. The lamellar planes
are embedded in a matrix of hemicellulose and lignin material with
hemicellulose as bonding glue. Depending on the pulping, bleaching,
and refining processes used the cell wall becomes substantially porous
and swells with moisture. Delignification by alkaline pulping results in
cavities within the cell wall at least some of which survive in the final
paper. Crystalline cellulose is relatively inactive towards water molecules
and it is the amorphous cellulosic regions that are thought to absorb
water in considerable amounts. The state of moisture in the cell wall is
subject to much speculation although it is clear that it should be in the
condensed form. Water condensing inside the cell wall can also create
its own pores, which were not present in the dry state (the so-called
‘‘transient pores’’). Condensation of water inside the cell wall causes
stresses resulting in significant expansion of the cell wall in the radial
(transverse) dimension. This will yield better fiber–fiber contact at high
moisture contents and also crowd out the pore space in the sheet.
Individual pores inside the cell wall are considerably anisotropic and in
the transverse plane, their size is of the order of 10 nm.[59,60] The pore
sizes in the axial direction of the fiber seem to be much larger, of the order
of a few micrometers.[61]
As moisture condenses, it penetrates the outer surface and is
absorbed by the amorphous regions inside the cell wall. We can identify
two different models of moisture inside the cell wall. The first view is that
moisture condenses within the voids created in the inter-lamellar spaces
akin to capillary condensation. In the second model (as recently
explained by Foss et al.[31]), moisture binds with the amorphous regions
solvating their hygroscopic components forming a polymer solution.
Based on the shape of the sorption isotherm, Foss et al. proposed that
moisture inside the cell wall can reside in two forms—a solvated polymer
phase and as a free solvent phase. Other workers have also advanced
similar concepts that water exists in the cell wall in multiple phases.
Distinction between the phases is made based on their binding energies.
Bound and free water based on whether it is of the freezing or nonfreez-
ing type has been proposed by Maloney and Paulopuro[62] (see also
Karenlampi et al.[63]) Harding et al.[64] used magnetic resonance imaging
to measure the diffusion of water molecules in the intra-fiber matrix of
paper sheets. The shape of the relaxation of the resonance signal could be
best described by assuming that water in the cell wall existed in bound
and free forms and thus showed two different scales for diffusion.
Harding et al.’s model adds more complexity to our picture of diffusion
inside the cell wall by requiring it to be in two stages. Experimental
evidence from differential scanning calorimetry (DSC) measurements
seem to support this view of further distinctions in the properties of
the condensed water held within the fibers (see Maloney and
Paulopuro[62] and Karenlampi et al.[63]).
Despite which model for water is chosen inside the cell wall, the
diffusivity should be a strong function of moisture content besides
2040 Ramarao et al.
being direction dependent. If the nanocapillarity model is assumed,

moisture condenses in the pores connected together in some fashion as
a network. The pore voids would be expected to be of the scale of 10 nm
whereas in the longitudinal or axial dimension, we expect the pores to be
of upto 10 mm in size. Increasing moisture-loading results in additional
cavities or ‘‘sites’’ being loaded. When sufficient loading within the
cell-wall pore network is achieved, continuous pathways spanning the

cell wall can be expected. This will result in a sharp increase in
the conductivity of the cell wall to moisture, yielding a rapid increase
in diffusivity with moisture content of the cell wall. This model could be
thought as a ‘‘percolation’’ model for moisture diffusion in the cell wall.
Assuming that the mechanism of wicking is valid, we can write
KðSÞ
Dq0i ðqÞ ¼ ð76Þ
ðds=dpc Þ
where Dqi is the diffusivity in one of the principal dimensions of the fiber,
i, and S represents the saturation function, commonly used in capillary
flow theory. This saturation function is related to the volume fraction of
water in the porous network and thus Eq. (79) can be written in an
overall functional form as
KðqÞ
Dq0i ðqÞ ¼ ð77Þ
dq=dpc
The permeability of the network is denoted by K in the above equation.
The variable pc is the capillary pressure. If we idealize the nanopore as a
cylindrical capillary of radius rc, the capillary pressure is given by
2 cos
pc ¼ ð78Þ
rc
If the pore structure of the cell wall is known, the capillary pressure
relation can be deduced. Note that the surface tension and contact
angle shown here represent the values for condensed water inside the
nanopore of the cell wall. This could conceivably be different from the
equilibrium values of these for water on cellulose. This conceptual model
can be used for determining the dependency of the intrinsic moisture
diffusivity inside the cell wall. We further expect the pore permeability
to be a function of its surface recognizing that the nanopores probably
are bounded by the microfibril sheets. Since the microfibrillar angle could
change between fibers of different origins, we can expect the nanopore
permeability to be effected by the microfibrillar angle. Our model of
diffusion can tie in fiber micro (and nano) structural details including
their chemical composition with moisture migration properties.
Another picture of moisture transport emerges if the polymer

solution theory is assumed. As moisture condenses within the cell wall,
the sorption sites are filled with condensate. We can imagine neighboring
sites of condensate to link and form clusters whose size continues to grow
with moisture loading. We expect the clusters to percolate as loading
increases (i.e., transition to clusters with sizes which span the entire
network) at which point, the mobility of the water molecules undergoes

a rapid increase. This translates into an increase in the diffusivity. Note
that a percolation view of moisture migration will result in the diffusivity
reaching a final saturation value at high moisture contents. This has been
observed experimentally as reported by Hashemi et al.[4]
Recognizing that the cell wall of pulp fibers is a polymeric matrix
composite consisting of crystallites of cellulose embedded in hemi-
cellulose and lignin regions, it is possible to postulate that moisture
diffusivity is related to the ‘‘free volume’’ created inside the cell wall
‘‘gel’’ when water molecules ‘‘solvate’’ it. Since the cellulose crystallites
are not hygroscopic, we are obviously focusing on the so-known
amorphous portions. In this view, water molecules will ‘‘solvate’’ the
amorphous cellulose regions and create ‘‘free volume.’’ As loading of
the water molecules is increased, the solvation effect increases rapidly
due to a co-operative effect between water molecules. Free-volume also
increases leading to substantial reductions in frictional resistance to
molecular migration. This results in rapidly rising diffusivities. This
view can be substantiated based on similar theoretical developments for
the diffusion of small solvent molecules in various polymer systems.
Further, since the tendency of water to cluster is well known, the rapid
increase in mobility can be explained. Referring to Eq. (80), we conclude
that the permeability K increase yields the increasing diffusivity with
moisture content. Notice that since the permeability increase is limited
at high moisture contents, this theory would automatically provide a
limit to the diffusivity: a feature that is well observed in practice at
high enough moisture contents (see e.g., Amiri et al.,[8] Hashemi et al.[4]).
4.3.2. Phenomenological Treatment of Intrinsic Fiber Diffusion
4.3.2.1. Power Law and Exponential Description

If one is willing to ignore the internal structural details of the cell wall
and treat the diffusion in a phenomenological sense, it makes sense to
postulate that the rate of change of diffusivity with moisture content
is proportional to the moisture content itself. The basis behind this
hypothesis is that as moisture increases in the cell wall, the free volume
2042 Ramarao et al.
available for water molecules to migrate increases as does their mobility.

This conjecture is supported by the fact that moisture softens the cell wall
polymers substantially and lowers the glass transition temperature. If one
assumes that this co-operative effect of softening and increased mobility
is proportional to the moisture content, a power law description for the
diffusivity is suitable. Thus, we can write
dDqi ðqÞ
¼ qn ð79Þ
dq
This equation when integrated yields

Dqi ðqÞ ¼ þ qnþ1 ¼ þ Dq0 qm ð80Þ
nþ1
where is the diffusivity through the cell wall under completely dry
conditions and Dq0 and m are redefined constants in accordance with
the above relation. The coefficient Dq0 is identified as the diffusivity at
a fixed value of the moisture content. Perhaps a good fixed point for q on
the sorption isotherm would correspond to the moisture content at
saturation, namely at 100% RH when the fiber can be taken to be at
its fiber saturation point. If the moisture diffusivity at this point is known,
Dq0 may be estimated for further purposes easily. Ahlen’’s steady state
diffusion experiments described in Sec. 2 indicated that under dry
conditions i.e., at asymptotically zero relative humidity conditions, the
diffusion of moisture through paper sheets is only in the water vapor
form. That is, the pore diffusion mechanism dominates. This is supported
by the experimental observation that the ratio of the moisture diffusivity
to that of the nonadsorbing gas molecules (Ar or nitrogen) is in the
correct ratio according to Chapman-Enskog theory assuming gaseous
diffusion. Hence, we may conclude that the dry diffusivity contribution
denoted by in Eq. (83) is negligible and it can be simplified to
Dqi ðqÞ ¼ Dq0 qm ð81Þ
The above equation can also be supported by the observation that the
dependence of paper’’s electrical conductivity on moisture content
assumes a similar power law form (see e.g., Baum[65]).
m
q
¼ ð82Þ
0 q0
Earlier work for the fiber diffusivity Dq was based on Eq. (3) used
by Ahlen and also by Radhakrishnan et al.[16] The intrinsic fiber wall
diffusivity Dq has been modeled by an exponential function as given by
Eq. (2).
A theoretical basis for the exponential model [Eq. (2)] was provided
by Chatterjee and Gupta[66] who postulated that the diffusivity represents
the number of pathways available for transport at any chosen moisture

level. They further assumed that the increase of these pathways with
moisture loading is proportional to the existing number of pathways.
Thus,
dDq dNp
Np ð83Þ
dq dq
resulting in
Np ¼ Np0 expðmqÞ ð84Þ
which yields Eq. (2) since Dq is proportional to Np. This model is

conceptually simple and is physically plausible. Note that this model
predicts a nonvanishing fiber diffusivity at zero moisture content i.e., in
the dry state. Since this is contrary to Ahlen’’s experimental results one
may postulate that the initial diffusivity Dq0 is small (at least a few orders
of magnitude smaller than Dp).
If the revision given by Eq. (84) is assumed, the effective diffusivity is
given by:
Dq0 ½qmþ1
0 qmþ1
1
Deff ¼ Dp þ ð85Þ
ðm þ 1Þ ðc0 c1 Þ
where c0 and c1 are the water vapor concentrations on either side of the
paper sheet. By nonlinear fitting procedures, the three parameters Dp, Dq0,
and m in this equation can be determined. Simple nonlinear fitting
methods for experimental diffusivity data and estimation of these
parameters have been discussed by Gupta and Chatterjee[18] and by
Lavrykov et al.[29]
The models described above are inconsistent since the predicted
diffusivity increases unboundedly with moisture content. This certainly
is not physical. If one accepts the capillary wicking model or a perco-
lation explanation for the dependence of the diffusivity on moisture
content, the increase in diffusivity must be bounded. Experimental data
for the diffusivity reported and reviewed by Hashemi et al.[4] as well as
2044 Ramarao et al.
Amiri et al.[8] indicate that moisture diffusivity does reach a maximum

value at high moisture contents.
4.3.2.2. Exponential with Saturation

In order to account for the fact that moisture diffusivities should
be bounded at high moisture contents, we may propose the following

form:
Dq ðqÞ ¼ Dq0 eð=qp =qÞ ð86Þ
where qp represents a critical moisture content beyond which the

diffusivity (or analogously the mobility of the phase) behaves quali-
tatively differently with increasing moisture content. When q is greater
than qp, the incremental change to the diffusivity begins to decrease. This
equation can be placed into the form quoted by Hashemi et al.[4]
5. EFFECT OF PAPERMAKING PARAMETERS ON

MOISTURE TRANSPORT IN PAPER SHEETS
A knowledge of the effect of typical papermaking variables on

moisture migration is necessary to understand how the moisture response
may be estimated and more importantly controlled in the final product.
Knowing how moisture transport is affected will help in tune the
papermaking process to achieve optimal production.
Moisture transport in paper can be considered by using the
effective diffusivity Deff as a composite parameter. Understanding how
the components of Deff change as papermaking variables are altered will
enable us to estimate moisture migration and its effects in paper.
5.1. Effect of Sheet Density—Achieved by Refining,

Wet Pressing, Calendering
The first critical parameter effecting moisture diffusivity is sheet

density. However, since paper sheets could be substantially hetero-
geneous due to flocculation and such effects, sheet density is to be
considered only in an averaged sense. The effect of local heterogeneities
such as density variations on transport is a subject of substantial interest
although it does not seem to have been investigated in detail. Some recent
investigations have been reported by Hashemi et al.[67]
It is well established that the effective diffusivity decreases as a

function of sheet density.[13,68,69] The major cause seems to be the
sharp decrease in porosity and increase in tortuosity of paper sheets
resulting in small values of the pore diffusivity component, Dp. Higher
levels of wet pressing or vacuum application and calendering of the sheets
can cause higher sheet density.
Fiber refining seems to have an important effect on the overall or

effective moisture diffusivity, Deff Massoquete et al.[69] report diffusivity
measurements for bleached kraft softwood pulps refined to different free-
ness levels in a Valley beater. Their sheets were subjected to a spectrum of
different humidity conditions. The pore diffusivity Dp determined by
them showed a uniform decrease with refining levels. In a parallel inves-
tigation, Ramaswamy et al.[70] and Goel et al.[58] analyzed the three
dimensional structure of paper sheets using X-ray Microtomography.
A large number of tomographed cross section images were prepared
and the paper sample’’s interior void space was digitally reconstructed.
This technique allowed the actual measurement of the void space topol-
ogy inside paper sheets to about 1–4 mm resolution. The pore space was
found to be substantially interconnected even at this resolution. The
reconstructed images showed that porosity of samples decreased with
refining levels not unexpectedly. A combination of tortuosity and poros-
ity yields small pore diffusivities for paper sheets with refined pulps as
opposed to unrefined pulps. Goel et al.[57] confirmed this behavior
by conducting Brownian motion random walk simulations of tracer
molecules within the pore structure.
Massoquete et al.[69] analyzed effective diffusivity data to estimate the
diffusion parameters for moisture in condensed phase through the fiber
matrix. Note that moisture diffusivity in the condensed phase is a strong
function of moisture content [as discussed in Sec. 5.3]. Thus the para-
meters of the diffusion function can be estimated from the effective
diffusivity formula by a nonlinear fitting procedure. Their data and
estimates do not provide any evidence for a strong dependence of
the fiber effective diffusivity parameters on pulp refining levels. This indi-
cates that the change in fiber tortuosity with refining or density
increases does not contribute to fiber diffusivity. It is possible that
the interconnections between the fibers are already strong enough
for moisture transmission and that further increases in say the
RBA (relative bonded area) do not contribute to increasing diffusivity.
This is a little surprising and probably merits further inquiry with
more exact experimental tools. One technique that has been
proposed is NMR imaging of moisture diffusion (see Liesen et al.,[71]
Harding et al.[72]). Since the MRI technique performs best at high
2046 Ramarao et al.
moisture contents, this is likely to provide a reliable measure of

condensed phase diffusion.
5.2. Effect of Chemical and Structural

Characteristics of Fibers
There is sufficient data in the literature for us to draw some broad

conclusions and estimate how the nature of the fiber changes moisture
transmission response of paper sheets. First we note that the morphology
and chemical nature of the fiber in its native state is a critical factor in
determining its behavior in the papermaking process. Therefore, factors
such as its conformability, swelling, fines and surface structure tend to
dictate the nature of the formed sheet. Thus the critical parameter Dp
representing diffusion of water vapor in the void space is affected by
the nature of the fibers indirectly but significantly. For instance, papers
containing TMP or other mechanical pulps are generally more porous
and bulky leading to higher Dp values. Similar remarks would be true for
recycled paper sheets made of kraft fibers. In brief, we can expect that any
parameter, which tends to make the sheets more porous, bulky or pore
space less tortuous tends to increase pore diffusivity. Pore diffusivity is
expected to increase with higher lignin content fibers (high yield pulps) or
mechanical pulps.
Condensed phase diffusivity is a different issue altogether. In order to
project the effect of the nature and composition of fibers on Dq, one has
to refer to a theoretical model. In fact, all the models suggested in Sec. 5.3
will lead to similar conjectures although differences in the magnitudes
may persist. For example, a typical high yield fiber is more rigid and
nonporous. The cell wall may not contain a substantial nanoporous
network as can be expected for a bleached kraft pulp. In such a case
internal migration of moisture may be hindered because the wicking
mechanism may be inoperative or substantially slowed. Note here that
for the wicking mechanism to convey moisture, both the wetting
characteristic and the permeability of the nanoporous structure must
be favorable. Since high yield fibers contain significant lignin, both of
these factors would be affected adversely. On the other hand, it is possible
that the surface adsorption and surface diffusion of moisture is higher for
lignin containing pulps. Therefore, one would expect some type of a
cross-over of mechanisms of diffusion between fibers pulped by different
processes.
Another significant feature of diffusion inside fibers is the orientation
of the microfibrils along the lamellae in the cell wall. One would expect
that for acute microfibrillar angles, moisture diffusion inside the cell
wall is enhanced along the axial direction of the fibers as shown in
Figs. 4 and 5. Diffusion in other orthogonal directions may not be
affected (along the thickness) or adversely effected (along the radial
dimension) by this angle. Furthermore, the water absorbing capability
of the fibers themselves can be expected to be critical. Whether one views
this from an increased free volume point of view or due to increased

cluster mobility, the conclusion would be the same.
6. SUMMARY AND CONCLUSIONS
Moisture transport in paper materials tends to be quite complex and

occurs by a number of mechanisms. These include diffusion as vapor in
the void space and diffusion/migration through the bulk of the fiber cell
wall. It is possible to group all the diffusion mechanisms into two groups,
identifying each one as occurring through the void spaces or the fiber
matrix. Thus, the internal void/fiber structure of these materials becomes
a critical factor in determining transport.
Insofar as transport through the void space is concerned, a variety
of theoretical techniques are available for study. These include pore-
network models and Brownian motion random walks if the exact
three-dimensional structure can be characterized. By using X-ray and
other microtomographic techniques (e.g., based on synchrotron radia-
tion), it is possible to determine the void space and fiber structure of
paper for this purpose.
Figure 5. Schematic representation of the internal structure of the fiber cell wall
showing microfibrillar lamellas and configuration for water migration.
2048 Ramarao et al.

Figure 6. Schematic showing a microfibril lamella with pores and amorphous

regions. Both participate in moisture sorption: the former by capillary conden-
sation and latter by solvation. Microfibril strands are represented by the
cross-hatched areas.
Transport through the fiber matrix is dominant at higher moisture

contents. Diffusivity through the cell wall can be expected to be aniso-
tropic and intimately influenced by the ultra-structure of the cell wall, its
porosity, the connectivity of the nanopores inside it and the availability
of water reactive (amorphous) sites. The connectivity of the fiber network
and its overall volume fraction probably are secondary influences on this
transport. MRI techniques have provided some fascinating glimpses into
how this transport can be studied. More work on characterizing the
dependence of intra-fiber moisture transport on the cell wall chemical
nature and physical structure needs to be done.
NOMENCLATURE
p1 Partial pressure of water vapor at relative humidity

h1 [p1 ¼ h1psat(T )] (Pa)
psat Saturation vapor pressure of water in air (Pa)
T Temperature of air (K)

q Moisture content of paper, kg of water/kg dry paper
c Water vapor concentration in paper, kgmol/m3 void
space volume (c ¼ hps/RT )
j Moisture flux (subscripts tot—represents total,
p represents flux through the void space as water
vapor, and q represents flux through fiber matrix

as condensed phase)
qsat Saturation or equilibrium moisture content of paper
sheet (or fibers), usually given by the equilibrium
relation [as in Eq. ]
CG, MG, kG Constants in the sorption isotherm equation
[Eq. (25)]
ki Coefficient denoting exchange of moisture between
fibers and pores, shown in Eqs. (26) and (27)
Ai, Bi, Ci Constants in isotherm equation representing c as
a function of q [Eq. (37)]
Dcomp Composite diffusivity, defined in Eq. (42)
Bi Biot number defined as kfL/Dp
Dp Diffusivity of water vapor through pore space,
m2 s1
Deff Effective moisture diffusivity, defined as a combina-
tion of water vapor and condensed moisture, Eq. (3),
m2 s1
Dq Diffusivity of condensed water through fiber space,
m2 s1
Dq0 Diffusivity of condensed water through fiber space
at dry condition q ¼ 0, Eq. (2) m2 s1
D 0, D i Diffusivity parameters corresponding to initial and
final diffusivities in Eq. (14)
m Exponent in diffusivity definition, Eq. (2)
z Thickness dimension of paper sheets, m
hav Average humidity across a paper sheet or sample, %
a Parameter appearing in correlation for diffusivity,
Eq. (6)
b Parameter appearing in correlation for diffusivity,
Eq. (6)
L Sheet thickness, m
T Time, s
M Total moisture gained by sheets defined in Eq. (11)
t* A relaxation parameter appearing in Eq. (14)
r Radial dimension within fibers
2050 Ramarao et al.
Ks slope of isotherm (¼ dq*/dc)

0 Parameter used by Hellen et al., as defined in Eq. (24)
0 Parameter used by Hellen et al.

" Paper porosity
Density of paper sheets

kiL2/Dp
Dimensionless time, tDp/L2
$
Dimensionless distance, z/L

ACKNOWLEDGMENTS
We would like to acknowledge the support of the US DOE and

AFPA through a grant from the Agenda 2020 Industries of the Future
program to University of Minnesota and SUNY ESF. Support of the
USDA through a grant to SUNY ESF under the NRI CGP is also
acknowledged.
A number of the ideas described here followed discussions with many
colleagues to whom we are grateful including: Dr. K. Niskanen, KCL,
Helsinki Finland, Dr. C. Bronkhorst, LANL, Albuquerque NM,
Prof. S. Chatterjee, SUNY ESF, Syracuse NY and Prof. C. C. Habeger,
IPST, Atlanta GA.
BVR also would like to acknowledge the contributions of former and
current students and research associates including H. Radhakrishnan,
A. Eusufzai and Dr. A. Bandyopadhyay. SR would like to acknowledge
the contributions of former and current students and associates including
A. Goel, M. Gupta, Dr. S. Huang, L. Wang, and A. Cooper.
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This article was downloaded by: [University of California Santa Cruz]

On: 25 November 2014, At: 13:42

Drying Technology: An International Journal

Moisture Diffusion Inside Paper Materials in the

To link to this article: http://dx.doi.org/10.1081/DRT-120027044

PLEASE SCROLL DOWN FOR ARTICLE

Moisture Diﬀusion Inside Paper Materials in the

B. V. Ramarao,1,* A. Massoquete,1 S. Lavrykov,1

Some current models for moisture diﬀusion in paper in the

*Correspondence: B. V. Ramarao, Faculty of Paper Science and Engineering

DOI: 10.1081/DRT-120027044 0737-3937 (Print); 1532-2300 (Online)

2008 Ramarao et al.

dynamics and relaxation processes occurring within the paper

Moisture diﬀusion in paper materials under both steady and

1.1. Steady State Diﬀusion of Moisture in Paper

Moisture can diﬀuse through paper by a variety of mechanisms.

Moisture Diffusion Inside Paper Materials 2009

of moisture transport mechanisms is provided by Hashemi et al.[4] Table 1

space and simultaneously in adsorbed form on the ﬁber surfaces with

Void space mechanisms Fiber matrix mechanisms

Molecular diﬀusion Rounsley, Ahlen, Surface diﬀusion Rounsley

Moisture Diffusion Inside Paper Materials 2011

determined the eﬀective diﬀusivity of a nonadsorbing molecule (water

2012 Ramarao et al.

The effective diffusivity can also be related to the diffusivities in

By integrating this equation with respect to z over the sheet thickness

Moisture Diffusion Inside Paper Materials 2013

values. A rationalization of these contradictory trends can be made by

effects tending to reduce the vapor phase diffusivity. Diffusion through

1.2. Transient Diﬀusion of Moisture in Paper Materials

By exposing paper sheets to diﬀerential humidity conditions and

1.2.1. Step Response

The transient sorption response to a step change in humidity can

Diﬀusivity 1012 m2s1 (except where indicated)

Amiri et al. (q) Newsprint 48.8 6.1–50–74% 9.42 3.89

2016 Ramarao et al.

Figure 1. (a) Diﬀusivity of condensed moisture through ﬁber phase in paper.

Viewing the paper sheet as a homogeneous material whose diﬀusivity is

with initial and boundary conditions given below.

qðt ¼ 0, 0 < z < LÞ ¼ q ðh0 Þ ð8Þ

Moisture Diffusion Inside Paper Materials 2017

In the above model the diﬀusivity of moisture Dq is assumed to be a

MðtÞ ¼ qðt, zÞ dz ð11Þ

where the transient process begins from an equilibrium state at time t ¼ 0.

2018 Ramarao et al.

with Di representing the initial diﬀusivity and D0 as the long time

1.2.1.1. Transient Diﬀusion Described by a Fickian Process

1.2.1.2. Nonﬁckian Descriptions of Moisture Diﬀusion in Paper

Moisture Diffusion Inside Paper Materials 2019

described as follows. The concentration of condensed water at the surface

The moisture content at the surface of the ﬁbers is assumed to be in

qðt, z ¼ 0Þ ¼ q ðc1 Þ ð21Þ

2020 Ramarao et al.

They also conducted random walk simulations of a tracer molecule inside

1.2.2. Ramp Response

In many situations, paper materials are exposed to slower variations

Moisture Diffusion Inside Paper Materials 2021

humidity proﬁles in addition to gravimetric measurements of moisture

solved numerically to predict moisture content proﬁles within the

2022 Ramarao et al.

the phases as well as allowing for local nonequilibrium conditions within

procedures used by Lescanne et al. Gupta and Chatterjee simpliﬁed the

1.2.3. Cyclic Response

Cð, ¼ 0Þ ¼ Qð, ¼ 0Þ ¼ 1 ð51Þ