Unsaturated medium

Copyright 2005 Taylor & Francis Group plc, London, UK

Unsaturated poroelasticity of freezing water-infiltrated
materials with air voids

O. Coussy
Institut Navier, Laboratoire Central des Ponts et Chausses, Marne-la-Valle, France

P. Monteiro
Dept. of Civil and Environmental Engineering, UC Berkeley, United States of America

ABSTRACT: When cooled below the freezing point a water-infiltrated porous material undergoes a cryodefor-
mation resulting from various coupled and contrary actions: i) the difference of density between the liquid water
and the ice crystal and the related expulsion of some liquid water from the freezing sites; ii) the interfacial effects
between the different constituents, which govern the crystallization process in connection with the pore access
radius distribution; iii) the drainage of the liquid water expelled from the freezing sites towards the air voids;
iv) the cryosuction process, which drives liquid water towards the already frozen pores; v) the thermomechanical
coupling between the deformable porous matrix, the liquid water and the ice crystal. Here we show that air voids
act as macroscopic cryopumps, resulting in cryoshrinkage and partial melting of the ice already formed when
the cooling suddenly stops. We explain why, given the same porosity, the more narrow banded the pore access
radius distribution around a low radius, the less the strength to the frost action.

1 INTRODUCTION Irrespective of any macroscopic thermal gradient

Understanding and predicting the cryodeformation
of water-infiltrated materials is a major concern in
Food Chemistry, in Biomechanics and in Geome-
chanics in cold climates (Pingeon & Pleau 1995).
Contrarly to a natural idea, the mechanical behaviour
of water-infiltrated materials upon freezing cannot be
correlated to the sole expansion of liquid water trans-
forming into ice crystal. Actually, cement pastes still
expand when water is replaced by benzene, which,
unlike water, contracts when solidifying (Beaudoin &
Mac Innis 1974). In order to explain such unexpected
swelling ability of materials, an hydraulic pressure
effect is often invoked (Powers 1949). According to
this explanation, the expansion of water transforming
to ice crystal provokes a significant expulsion of liquid
towards the neighbouring yet unfrozen zone where it
builds up a liquid pressure provoking the most sig-
nificant expansion. However the picture is not that
simple since it has also been recognized that, upon
freezing conditions, the remaining liquid water can
also be transported towards the frozen sites (Powers
& Helmuth 1953). Indeed, at a temperature T below
the bulk freezing point Tf ; 273 K, confined water can
partially remain liquid provided that it depressurizes
with regard to the adjacent ice crystal, provoking in
turn a cryo-pumping of the distant liquid water.
the bulk cryo-deformation of porous material sub-
jected to uniform cooling eventually results from
various combined actions: i) the difference of den-
sity between the liquid water and the ice crystal;
this density difference provokes the expansion of the
solid matrix surrounding the crystal in formation, as
well as the expulsion of some liquid water from the
freezing sites towards the pores still filled by liq-
uid water; ii) the surface tension arising between the
different constituents,which eventually governs the
crystallization process in connection with the pore
radius distribution; iii) the drainage of the liquid water
expelled from the freezing sites towards the air voids;
iv) the cryosuction process, which drives liquid water
towards the already frozen sites at earlier stages of
the cooling process; v) the elastic thermomechanical
coupling between the pressurized pore space and the
surrounding solid matrix, which governs the overall
cryo-deformation. As a final result any air void acts
as an extra cryo-pump, in competition with the other
frozen sites, and tends to low down the internal pres-
surization in its influence domain of drainage. This
still rough analysis reinforces the above mentioned
explanation of the beneficial character of the air void
presence, which has been confirmed by recent experi-
ments reported in Pentalla (1998), and explored within
a promisive, yet not actually conclusive, engineering

457
Copyright 2005 Taylor & Francis Group plc, London, UK
modelling in Zuber & Marchand (2004). The paper 2.2 Unsaturated thermoporoelasticity
aims at carrying out a comprehensive approach apt to
Let ij and ij be the overall stress and strain compo-
encompass the above set of phenomena involved in
nents respectively. Further let us adopt the (zero) atmo-
the freezing porous materials. This theory is worked
spheric pressure and the related freezing temperature
out by extending the standard theory of Poroelasticity
Tf as reference pressure and temperature. The consti-
(Biot 1941, Rice & Cleary 1976) within the energy
tutive equations of unsaturated thermoporoelasticity
approach of Poromechanics (Coussy 2004). It suc-
then read:
cessfully accounts for the unexpected shrinkage of air
voids, which has been directly observed within an air-
entrained freezing cement-based material (Piltner &
Monteiro 2000).

2 POROMECHANICS OF FREEZING

2.1 Lagrangian porosity and saturation

When progressively invaded by ice crystal, the current
porous volume of an initially liquid water-saturated where = kk is the volumetric dilation. Properties K,
material can be split into a frozen part and a still liquid G and a are respectively the bulk modulus, the shear
one. Let then d0 by the macroscopic representative modulus, and the thermal volumetric dilation coeffi-
volume of a porous material before any deformation. cient of the solid skeleton, that is the ones related to the
Lagrangian partial porosity J related to phase J is empty porous material subjected to zero internal pres-
such that J d0 is the volume currently occupied
by ice crystal, J = C, or by liquid water L = C. The
change in partial porosities J results from two dis-
tinct processes. The first process is the invasion of
the porous volume by ice crystal. The second process
relates to the skeleton deformation, resulting from the
action of the crystal and liquid pressures onto the inter-
nal walls of the porous network. As a consequence,
noting 0 the initial overall porosity, the current par-
tial porosities J can be split into two independent
additive contributions:
The term 0 SC (resp. 0 SL ) quantifies the first pro-
sures conditions pC = pL = 0; properties bJ and NIJ
are respectively the generalized Biot coefficients and
the generalized Biot coupling moduli (see for instance
Coussy 2004), with NLC = NCL owing to Maxwells
symmetry relations, while aJ is the coefficient related
to the thermal dilation of the pore volume occupied by
phase J .
Standard upscaling methods provide the added
useful relations (Coussy 2004):
cess. It is such as 0 SC d0 (resp. 0 SL d0 ) represents
the porous volume currently invaded by ice (resp.
The above relations are the standard meso-macro rela-
remaining occupied by liquid water), yet prior to
tions ensuring the compatibility of the macroscopic
any deformation. Actually SJ can be coined as the
poroelastic constitutive equations (2) with the under-
Lagrangian saturation degree of phase J , since it
lying elastic behaviour of the solid matrix with bulk
relates to the initial overall porous volume 0 d0 ,
modulus ks and linear thermal dilation coefficient
by opposition to the Eulerian definition which applies
s . They mainly involve the bulk modulus K of the
unappropriately to the current porous volume d0
empty porous material, whose expression as a func-
[?]. The term C (resp. L ) is related to the skeleton
tion of the overall porosity can be provided by a
deformation and is such that C d0 (resp. L d0 )
double-scale upscaling procedure, as originally elab-
represents the infinitesimal volume change undergone
orated from microporomechanics considerations in
by the currently ice-filled (resp. liquid-filled) volume
Dormieux et al. (2002), and applied to cement-based
under crystal pressure pC (resp. liquid pressure pL ).
materials in Ulm et al. (2003).
Accordingly the current (Lagrangian) overall poros-
ity, which eventually concerns the skeleton only, is
consistently given by: 2.3 Liquid saturation curve
At a temperature T below the bulk freezing point
Tf ; 273 K, confined liquid water can partially remain

458
Copyright 2005 Taylor & Francis Group plc, London, UK
liquid provided that it depressurizes at pressure pL with 2.5
regard to the adjacent ice crystal at pressure pC , when
R* dSL/dR 0.9
following the linearized thermodynamic equilibrium
condition (Markov 2003): 2

1.5

0.8
where !f is the specific freezing entropy. The SL
infinitesimal work made against the interfacial 1 0.5

0.7
forces to make the inner ice-liquid water front 0.6
propagate

within a macroscopic porous volume is
pC pL dSL . Accordingly we write: 0.5
0.4
0.5
0.6 0.7 0.9
0.8
-5 -4 -3 -2 -1 0 1 2 3
(Tf T)/ T* R/R*
where U is the interface energy between all the com-
ponents per unit of porous volume. The two previous Figure 1. Left side: liquid saturation degree against dimen-
equations combine to: sionless cooling according to (10) where we let m = 0.40.9.
Right side: pore radius distribution against dimensionless
pore radius as derived from (12) for m = 0.50.9.

is a macroscopic state equation of the current cool-
ing Tf T , which can be determined either by
dielectric measurements, NMR or thermocalorimetry
(Fen-Chong et al. 2004). State function (9) is well
captured by function in the form (Coussy 2005):
where T is a characteristic cooling related to the
porous material.
At the pore scale, according to Young-Laplace rela-
tion the pressure difference pC pL , and consequently
the current cooling, is related to the current access
radius r to the freezing pores, depending on the com-
plex geometry of the specific porous network at hand.
Accordingly, we write:
where CL stands for the interface energy between the
liquid and the crystal. Combination of (7), (10) and
(11) provides:
Relation (12) associates the current saturation degree
SL with the largest access radius r of the yet unfrozen
pores. A quantity of main interest is dSL /dr, which is
strongly related to the pore radius distribution. Actu-
ally dSL /dr quantifies the contribution of pores having
r as access radius R to the total liquid saturation. Fig-
ure 1 shows various pore access radius distributions
r dSL /dr and the associated liquid saturation curve
(10). For 1 > m > 0.5 the pore access radius distribu-
tion exhibilts a maximum and the closer m to 1, the
more narrow banded the distribution is. By opposition
for m < 0.5 there is no maximum and the pore access
radius distribution spread widely over the whole range
of possible values.
3 CRYODEFORMATION
3.1 The hydraulic diffusion equation
When subjected to cooling below the atmospheric
poing Tf some liquid water is expelled from the freez-
ing sites towards the neighbouring capillary pores still
filled by liquid water. The resulting liquid pressure
gradient causes a flow in order to restore a uniform
liquid pressure within the porous material. The amount
of liquid eventually expelled depends on how con-
stitutive equations (2) and mechanical equilibrium
combine so that the liquid-solid thermodynamic equi-
librium condition (7) is constantly met everywhere. We
derive hereafter the corresponding hydraulic diffusion
equation along these requests.
Using water and constitutive equations (4)(5),
together with (7), the total water mass currently con-
tained in the infinitesimal element is expressed in the
form:

459
Copyright 2005 Taylor & Francis Group plc, London, UK
where J (resp. J0 ) are the current (resp. at atmo-
spheric pressure) mass density of constituent J , and
where we note:
and:
where, noting KJ the bulk modulus of constituent J ,
MJ and M are defined by:
Term v relates to the pore volume change due to
the change in ice saturation and to the associated
liquid-crystal mass density difference. Term v relates
to the source term due to the deformation of the
porous volume, whose above expression eventually
holds irrespective of the phase tranformation. In (15)
the term factorized by Sf accounts specifically for the
porosity change due to the microcryosuction process,
that locally adjusts the liquid and crystal saturation
degrees in order to meet at any time the liquid-crystal
equilibrium condition (7).
In the absence of body forces the overall momentum
equation reads:
Use of relation = 12 + t relying the strain to
the displacement into constitutive equation (3), and
substitution of the resulting stress expression in (17),
result in Navier equations:
where K, G and s are assumed constant with regard to
space. For irrotational displacement fields such as the
ones we will explore later on, similarly to the liquid sat-
urated case we follow Detournay & Cheng (1994) and
we let = 0 in (18), which subsequently integrates
in the form:
460
Copyright 2005 Taylor & Francis Group plc, London, UK
where f (t) is an unknown time function. Substituting
(19) in (15), while using again liquid-crystal equilib-
rium condition (7) and compatibility relations (6), v
is written in the form:
where C is a poroelastic property defined by:
Non uniform pressure fields induce water flows in
both ice and liquid form. However, when compared
with the usual cooling timescales, ice flow occurs so
slowly that we can disregard any ice flow. Assuming
in addition that Darcys law governs the liquid water
flow, the fluid mass flow vector is written:
where L (T ) is the viscosity of liquid water, L
being the reference viscosity at T = 0, while the func-
tion (T ) accounts for the temperature dependence
of the viscosity of supercooled water. An operational
expression is (Grant 2000):
Furthermore is the constant intrinsic permeability,
while (SL ) is the relative permeability accounting for
the change in the porous volume offered to the liquid
flow. An expression that can be consistently used in
association with expression (10) of the capillary curve,
that is referring to the same m, is (Luckner et al. 1989):
Overall water mass conservation combined with
Darcys law (22) finally provides:
Substitution of (14) and (20) into (25) furnishes the
general hydraulic diffusion equation, where unknown
function f (t) remains specific to the problem at hand.
3.2 Cryoshrinkage of freezing materials Mechanical boundary conditions (26), displacement
with air voids and stress expressions (29) and (30) eventually
provide:
We consider now a water-air-infiltrated material,
whose air voids are much larger than the water-filled
pores of the surrounding porous matrix. An embryo
of such a porous material is afforded by considering a
spherical air void of radius R, embedded in a spherical
shell of porous material of outer radius R + L, so that
distance L scales the spacing between two adjacent
air voids. This embryo of porous material is subjected
to an uniform cooling T = Tf T > 0. On the outer and:
radius r = R + L, the radial stress rr is zero and there is
no liquid flow. In addition the air void is at zero (atmo-
spheric) pressure, and the radial stress rr is also zero
on the air void surface r = R. When the liquid enters
the air void, it becomes no more confined so that it
instantaneously freezes. Similarly the non confined ice
crystal so formed within the air void remains at (zero)
atmospheric pressure. The liquid within the shell, still
confined but immediately in contact with the crystal Making use of (31) into (20), and substituting the
already formed on the air void surface, depressurizes, resulting expression for v into (25), while considering
in order to meet the liquid-crystal equilibrium condi- a constant cooling rate such as:
tion (7), the latter requiring pL = Sf (Tf T ) since
pC = 0 on r = R. As a final result, the distant liquid
water within the porous shell is driven to the air void
which eventually acts as a cryo-pump. Accordingly
the mechanical and hydraulic boundary conditions are diffusion equation (25) to be solved with boundary
finally written in the form: conditions (27) specifies in the form:

and:

Due to the problem symmetry the only non zero

displacement component is the radial displacement:

Substituting (28) in (19), using liquid-crystal equilib-

rium condition (7) and integrating, we get:
where % is a constant poroelastic property defined by:

and where:

For the problem at hand state equation (3) and (19)

combine to give the radial stress rr in the form:

461
Copyright 2005 Taylor & Francis Group plc, London, UK
Accounting both for the progressive transformation of
liquid water into ice and for the overall local mechani-
cal equilibrium of the porous matrix, the left hand side
term in (34) relates to the liquid pore pressure change
related to the capacity of the porous material to store
water, owing to the relative deformability of its con-
stituents. The first term on the right hand side in (35)
relates to the source of liquid pressure due to the liquid
water flow. The remaining terms account for the vari-
ous sources of liquid pressure due to cooling: i) !
for the liquid pressure source due to the liquid-crystal
density difference and to the amount of liquid finally
expelled from the freezing sites; ii) !T for the liquid
pressure source due to the relative thermal dilations
of all the constituents; iii) !!f the liquid depressure
source due to microcryosuction, which drives liquid
water to the already frozen sites within the porous
matrix, in competition with macrocryosuction, which
drives liquid water towards the air void.
Solving (35) with boundary conditions (26)(27)
with the data detailed in Coussy (2005), Figure 2
shows the predicted cryoshrinkage of the air void
plotted against the dimensionless time t T /T , when
the cooling is suddenly stopped at time tstop = T /T.
After the cooling stop, the liquid pressure tends to
decrease everywhere, and to finally become uniform,
and equal to the liquid pressure (27) prevailing at the
void surface. This is achieved through a liquid flow
occurring from the porous shell towards the air void,
and which is partly supplied by the partial melting of
the already frozen sites. This partial melting is required
in order that the crystal pressure eventually goes down
to zero in order to meet the liquid-crystal thermo-
dynamic equilibrium condition (7). Accordingly, the
cryoshrinkage of the air void observed in Piltner &
Monteiro (2000) after stopping the cooling can be only
due to the simultaneous liquid and crystal depressure
generated by the air void, which acts as a cryopump.
By contrast, in the absence of any air void, there is
no macroscopic cryopump to compete with the micro-
scopic cryopumps constituted by the already frozen
pores, neither an expansion reservoir to welcome the
extra liquid water expelled from the freezing sites. As
a consequence the deformation rapidly turns out to be
a cryoexpansion, which stops with no further cooling
(dashed lines in Figure 2). Interestingly, at low cool-
ings the cryoexpansion is lower for narrow banded
distributions of the access pore radius (m = 8) than
for wide distributions (m = 5), being possibly nega-
tive in the former case due to the thermal contraction.
At larger coolings, which become close to the charac-
teristic cooling, the cryoexpansion suddenly increases
for narrow banded distributions, overpassing the one
obtained for wide distributions. This is due to the com-
pared availability of pores that can eventually freeze
at the same time and to the compared further density
of simultaneous microscopic cryopumps. Actually, the
462
Copyright 2005 Taylor & Francis Group plc, London, UK
2.5
with no air void
2 m=8
with air void
1.5
103
1 m=5
Cryodeformation
0.5
0
m=5
-0.5
-1 m=8 cooling stops
-1.5 0 0.5 1 1.5
Dimensionless time
Figure 2. Volumetric air void cryodeformation, that is
3u(R,t)/R, plotted against dimensionless time. By opposition
to cryoexpansion, cryoshrinkage is negative.
liquid water mainly transforms to ice when the temper-
ature is equal to the crystallization temperature suited
to the pores having the access radius the most fre-
quently encountered. This explain why, given the same
porosity, the resistance to frost action of high strength
concretes is observed to decrease when exhibiting pore
radius distributions more narrow banded around a low
radius.
REFERENCES
Beaudoin, J.J. & MacInnis, C., 1974. The mechanism of frost
damage in hardened cement paste. Cement and Concrete
Research 4, 139147.
Biot, M.A., 1941. General theory of three dimensionnal
consolidation. Journal of Applied Physics 12, 155164.
Coussy, O., 2004. Poromechanics, John Wiley and Sons.
Coussy, O., 2005. Poromechanics of freezing materials,
submitted.
Detournay, E. & Cheng, A. H.-D., 1994. Fundamentals
of Poroelasticity, Comprehensive Rock Engineering, ed.
Hudson J., Pergamon Press.
Dormieux, L., Molinari, A., Kondo, D., 2002. Micromechan-
ical approach to the behaviour of poroelastic materials,
Journal of Mechanics and the Physics of Solids 50 (10),
22032231.
Fen-Chong, T., Fabbri, A., Guilbaud, J.P., Coussy, O., 2004.
Determination of liquid water content and dielectric con-
stant in porous medial by the capacitive method. Accepted
for publication, Comptes Rendus de lAcadmie des Sci-
ences, Comptes-Rendus Mcanique, Vol 332, 639645.
Grant, S.A., 2000. Physical and chemical factors affecting
contaminant hydrology in cold environment, US Army
Corps of Engineers, ERDC/CRREL, TR-00-21.
Luckner, L., van Genutchen, M.Th., Nielsen, D.R., 1989. A
consistent set of parametric models for the two-phase flow
of immiscible fluids in the subsurface, Water Res. Res.
25 (10), 21872193.
Markov, I.V., 2003. Crystal growth for beginners, 2nd edition,
World Scientific.
Penttala, V., 1998. Freezing-induced strains and pressures in
wet porous materials and especially in concrete mortars,
Advn. Cement. Bas. Mat. 7, 819.
Pigeon, M., Pleau, P., Durability of concrete in cold climates,
Modern Concrete Technology, E & FN Spon, 1995.
Piltner, R., Monteiro, P., 2000. Stress analysis of expansive
reactions in concrete, Cement and Concrete research 30,
843848.
Powers, T., 1949. The air requirement of frost-resistant con-
crete, Highway Research Board, PCA Bulletin 33 (29),
184211.
Powers, T., Helmuth, R.A., 1953. Theory of volume changes
in hardened Portland cement paste during freezing,
463
Copyright 2005 Taylor & Francis Group plc, London, UK
Proceedings, Highway Research Board, Bulletin n 33,
Portland Cement Association, Vol. 32, 286297.
Rice, J.R. Cleary, M.P., 1976. Some basic stress diffu-
sion solutions for fluid-saturated elastic porous media
with compressible constituents, Journal of Geophysical
Research 14, 227241.
Ulm, J.-F., Constantinides, G., Heukamp., F.H., 2003. Is
concrete a poromechanics material? A multiscale inves-
tigation of poroelastic properties, Material and Struc-
tures/Concrete Science Engineering 37 (265), 4358.
Zuber, B., Marchand., J., 2004. Predicting the volume insta-
bility of hydrated cement systems upon freezing using
poro-mechanics and local phase equilibria, Materials
and Structures/Concrete Science Engineering, 37 (268),
257270.