Effect of large-strain deformation on surface remodeling characteristics in

porous materials

P. Ganguly
Schlumberger-Doll Research, Cambridge

F.-J. Ulm
Dept. of Civil and Environmental Eng., Massachusetts Institute of Technology, Cambridge

ABSTRACT: The paper develops constitutive relationships for deformation coupled surface growth/dissolution
(remodeling) in porous solids. Such phenomena have been observed in a wide range of natural and technological
processes, including corrosion in metallic materials and healing of bone and skin. In all these situations, the
surface remodeling takes place in a biochemical environment, and the combined mechanical and biochemical
effects need to be modeled for determining the remodeling characteristics. The present paper develops a consis-
tent model for exploring large-strain deformation coupled surface remodeling, and examines different conditions
that may hinder or encourage surface growth/dissolution in porous materials. It is observed that both tensile and
compressive deformation aid dissolution (or mass removal) at the material surface. Thus, concurrent deformation
can enhance the rate of corrosion in materials or cement leaching. On the other hand, suitable chemical envi-
ronments can induce surface growth. The model helps develop an understanding of the effects of these different
factors, and can aid the design of suitable environments (through alloying, changing solvent acidity/alkalinity,
surface treatments) for pre-determined surface characteristics in a variety of technological applications.

1 INTRODUCTION tissues. The load bearing capabilities of such materials

Surface modification (remodeling) of materials
through mass addition/removal is technologically sig-
nificant in a number of material applications. Gen-
erally, such remodeling occurs due to the action of
a chemical or biological agent, and is driven by
the chemical potential. Examples include corrosion/
oxidation of metals (Fontana 1986), cement leaching
(Adenot & Buil 1992), or physiological processes like
wound healing in skin and bone (Blair 1998). In most
of these processes, experimental evidence suggests
phenomenological connections between imposed
deformation (stress/strain) and the remodeling char-
acteristics. Imposed stresses have been observed to
enhance corrosion rates in metals (Liu et al. 2004) and
the influence of contractile forces generated during
skin wound healing on scar tissue formation has been
recorded (Yannas et al. 1989). Analysis of the coupling
between deformation and the remodeling rates is thus
significant.
The deformation-remodeling coupling assumes
even greater significance for porous materials, i.e.
materials with a continuous solid framework, com-
posed of struts, enclosing a large volume fraction of
pores. Many natural and technological materials are
porous, including cement, wood and the bone and skin
are profoundly influenced by the geometrical charac-
teristics of the solid struts (Gibson & Ashby 1997).
Deformation-remodeling induced local thinning of the
struts can cause catastrophic failure of porous materi-
als, with minimal changes in the macroscopic material
densities.
Modeling of deformation-coupled surface remodel-
ing has been earlier undertaken by Ulm and co-workers
(Silva & Ulm 2002, Ulm et al. 2003) in the small-
strain regime. On the other hand, elastic large-strain
deformations may govern the remodeling process in
soft materials, e.g. in healing of the skin wounds or
hypertrophy of the heart (i.e. dilation of overloaded
heart muscles, Lund & Tomanek 1978). Hoger and
co-workers (Chen & Hoger 2000, Lubarda & Hoger
2002) have modeled deformation-coupled growth in
biomaterials through a multiplicative split of the total
deformation gradient into the growth and deforma-
tion components. This approach is similar to the
multiplicative split in elasto-plastic materials (Lee
1969) and assumes a volumetric (or global-scale)
growth/removal, rather than a surface (or local-scale)
remodeling.
The present paper develops a consistent frame-
work for constitutive relationships defining large-
strain deformation coupled surface growth in porous

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Copyright 2005 Taylor & Francis Group plc, London, UK

solid
strut
pore
space
(a)
solvent
solid strut
(b)
Figure 1. The deformation-remodeling phenomena in
porous materials at (a) macroscale, and (b) microscale. At
the macroscale, the porous structure is composed of solid
struts and the solvent filled pore space. The porous represen-
tative volume element is subjected to traction, as shown by the
block arrows in (a). The macroscopic traction is transferred
to the microscopic element (shown by the dashed rectangle
in (a)) through force balance and strain compatibility in the
structure. The microscopic element (shown in (b)) is com-
posed of a single solid strut exposed to chemical action at the
solid-solvent interface.
materials. The material is assumed to be elastic, i.e.
only geometric non-linearity in included in the model.
The porous material is treated as multiscale, and
the deformation/remodeling phenomena is modeled
at two relevant length scales (the macroscopic and
the microscopic, see Figure 1). Physically, the porous
microstructure includes individual solid struts, while
the macrostructure encompasses the representative
porous material. The mass loss/gain due to surface
remodeling is assumed to occur at the microscale, and
the effect at the macroscale is determined through con-
sistent upscaling. Such a model description defines
most surface remodeling phenomena in elastic porous
materials, and may have wide applications in structural
and bioengineering designs.
2 MICROSCALE MODEL
The representative volume element at the microscale
is shown in Figure 1b, and includes a deforming solid
strut and the solvent. Part of the solid boundary is
also exposed to chemical action through exposure to
a solvent that deposits/ removes mass from the solid.
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Copyright 2005 Taylor & Francis Group plc, London, UK
At any given time t, the mass of the solid is defined by
ms (t) and is given by
where s (t) and vs (t) are the density and the volume of
the solid strut, respectively. The rate of mass change
can be determined by differentiating Equation 1 w.r.t. t,
and applying the generalized divergence theorem (Ulm
and Coussy 2003). The rate of mass change would
include two rates, (a) due to deformation, and (b) due
to growth. The rate of mass change due to deformation
is given by
where ud is the deformation-induced velocity of the
solid particles. Assuming that the deformation is mass-
conserving, the rate of mass change given by Equation
2 is zero. Thus mass change, determined by the
growth/dissolution, is defined by the growth-induced
volume change and is given by
where ug is the growth velocity of the solid-solvent
front (positive for growth and negative for dissolution),
n is the outward normal to the front and (t) is the
area of the solid-solvent surface that is subjected to
remodeling (i.e. ug nd(t) is the infinitesimal change
in volume due to remodeling).
In the above equations, all the variables are
expressed in the current reference frame (x, t). In the
undeformed reference frame (X, t0 ), the rate of mass
change can be defined as
g
where u0 and N are the growth velocity and the outward
normal, described in the undeformed reference frame.
The volume conversion between the undeformed and
the deformed configurations is given by
where j is the determinant of the deformation gradient
tensor (f ). The corresponding surface area conversion
is defined by
where (f 1 )t is the inverse-transpose of the micro-
scopic deformation gradient tensor (f ). Since the rate
of mass change is invariant with change in reference
configuration, Equations 34 can be equated to yield
(using Eqs. 56)
Equation 7 simply states that the solid-solvent front
velocity in the current configuration would need to be
scaled by the deformation gradient (which relates the
unit vectors, x and X, in the current and undeformed
configurations) to yield the velocity measurement in
the undeformed configuration.
Volume change in the solid can be due to defor-
mation as well as mass change, and the rate of
change in volume (in the current configuration) can be
expressed as
where the first integral represents the volume change
due to deformation and the second integral that due to
growth/dissolution. The same volume change can be
expressed in terms of quantities measured in the unde-
formed configuration, through suitable transformation
of Equation 8 using Equations 57.
Note that while the deformation and growth/disso-
lution contributions can be clearly demarcated in the
current configuration, the formulation is more mixed
in the undeformed configuration as the volume change
due to growth has to account for the deformation
induced density change.
2.1 Thermodynamic considerations
The constitutive relationships for deformation coupled
growth/dissolution in the solid strut can be derived by
application of the Claussius-Duhem inequality which
states that for any process, the rate of change of
(Helmholtz) free energy (
) is equal to or less than
the external work (Pext ) provided to the system, thus
yielding a non-negative rate of dissipation D.
The external work includes work done in deforming
the solid strut, as well as the work done (or released)
due to the movement of the solid-solvent interface.
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Copyright 2005 Taylor & Francis Group plc, London, UK
where d is the Eulerian strain rate tensor, and p is the
solvent pressure at the solid-solvent interface. The first
integral in Equation 11 is deformation work, while the
second part evaluates the work done as the solid front
expands (or contracts) against (or aided by) the fluid
pressure. Thus, the first term is mechanical in origin,
while the second term defines the mechano-chemical
coupling. Note that the partial pressure of the solute
in solution has been neglected in this formulation.
The change in free energy is due to free energy
change in the bulk as well as due to the chemi-
cal change (which results in mass addition/removal)
occurring at the solid-solvent surface.
where  is the difference in the chemical poten-
tial of the solid atoms (i s , where i and s
are the potentials of the atoms in solution and in
the solid, respectively), and m s is the rate of solid
mass change (per unit interface area, m s = s (t)ug n).
Thus, the first term in Equation 12 defines the free
energy change in the bulk (independent of the remod-
eling process), while the second term denotes the free
energy change due to surface growth/dissolution (i.e.
the change in potential of ion/atoms that move between
solid and solvent).
The rate of dissipation can be determined from
Equations 1012, and would include the volume and
the surface effects. The volume phenomenon is given
by Dv
while the surface phenomenon can be defined by Ds
The dissipation rates in the undeformed reference
frame can be determined from Equations 57, 13.
where f is the deformation gradient rate and is
Boussinesq tensor (which is the energy compliment to
the deformation gradient rate). The similarity between
the second terms in Equations 13, 15 is evident, and is
a result of mass conservation in the bulk, as the defor-
mation coupled surface remodeling progresses. The
surface dissipation rate in the undeformed reference
frame can be evaluated from Equation 14.
 g
where m s0 = s (t0 )u0 N is the rate of mass gain/loss
per unit interface area in the undeformed frame.
The total dissipation rate, D, is a sum of the volume
and surface dissipations given in Equations 1316.
The volume integrals given in Equations 13, 15 are
standard integrals seen in elasticity theory, and indi-
cate that the energy supplied to the solid bulk is stored
as stressstrain energy or dissipated as heat. The vol-
ume dissipations are non-negative and independent of
the surface phenomena. Given that the overall dissi-
pation is non-negative, the surface integrals given in
Equations 14, 16 must be non-negative.
Eq. (18) indicates the relationship between mass addi-
tion and the mechano-chemical conditions of the
surroundings. Following standard thermodynamic
arguments, (i s p/s (t)) can be identified as Ficks Law) may be appropriate. In terms of measur-
the thermodynamic force causing the mass change
(dms /dt). The free energy in the solid (s ) is a sum
of the elastic free energy (el ) and the chemical free
energy (gs , defined per unit mass). The free energy of
the ion (i ) is primarily composed of the chemical free
energy (gi ) of the ions in solution (Atkins 1994). The
thermodynamic driving force (in terms of per mole)
can be represented by the chemical affinity (Coussy
1995) of the deformation coupled remodeling process.
where A is the chemical affinity and Mm is the molec-
ular weight of the species involved in mass addition/
dissolution at surface. The driving force (A) for
remodeling can be decomposed into chemical and
mechanical effects. The first term in Equation 19 is
purely chemical, while the second term is primarily of
mechanical origin. The chemical contribution to the
driving force (gi gs ) arises from the difference in the
Gibbs free energy between an atom (or ion) in solution,
and that same atom (or ion) in the solid structure. The
mechanical driving force arises from the deformation
of the ions (or atoms) at the surface and the resultant
change in their potentials, and the work done due to
the expanding (or contracting) solid against the fluid
pressure.
Equation 18 can be rewritten in the standard ther-
modynamic format
Copyright 2005 Taylor & Francis Group plc, London, UK
where Jm is the molar flux
The effects of the process variables on the surface
remodeling characteristics can be estimated from
Equations 1921. Equation 20 indicates that the signs
of the driving force (A) and the flux (Jm ) must be
similar: growth (positive Jm ) can take place when the
driving force is positive, while dissolution (negative
Jm ) will result from a negative driving force. Thus,
from Equation 19, deformation and fluid pressure
would encourage dissolution at the solid surface, while
growth would be encouraged if the ions are at a lower
chemical potential at the solid surface than in the fluid.
The effect of change in driving force on the mass
flux need to be determined from a kinetic equation,
thus requiring simplifying assumptions on the rate
limiting step. Assuming that the remodeling kinetics
is governed by the diffusion of the chemical species
between the solid and the solution, a linear equation
relating the driving force and the flux (in the form of
able quantities, such an equation would link the driving
force and the solid-liquid front speed (ug , ug = ug n,
given that ug is linked to Jm by Eqs. 3, 21), i.e.
The constant k would be determined by the mechanism
of diffusion and would be independent of the physi-
cal quantities defining the driving force, i.e. pressure,
deformation and chemical potentials.
Equations 1922 indicate the connection between
the remodeling kinetics and the driving force. Defor-
mation resulting in elastic free energy would encour-
age dissolution at the surface. According to Equations
1922 higher deformation strains would increase the
rate of dissolution. Thus, in deformation coupled sur-
face remodeling, surface dissolution would be higher
in regions with maximum deformation, which may be
regions of concentration of stress/strain and damage.
This synergistic linkage between deformation and
mass-loss (i.e. the weaker regions are made progres-
sively weaker due to deformation-dissolution cou-
pling) may cause localized failures, and is the cause for
concern in stress-corrosion cracking, cement leaching
and osteoporosis. In such situations, as seen in Equa-
tions 1922, the dissolution rate of the solid can be
lowered by changing the chemical potential of the ions
in solution (e.g. by changing pH) or by lowering the
fluid pressure.
The field and flux quantities in Equations 1822
have been defined in the current configuration. The
corresponding quantities in the undeformed configu-
ration can be evaluated using the appropriate volume
124
and surface area conversion relationships (Eqs. 56).
The driving force (in the undeformed configuration)
would be given by
as the chemical and elastic free energies (measured
in terms of per unit mass) are invariant with change
in configuration, and s (t0 ) = js (t). The mass flux Jm
would be defined by Equation 21, although the appro-
priate formulation for rate of mass change (Eq. 4
instead of Eq. 3) needs to be considered. Finally,
the kinetic equation relating the driving force and
the solid-liquid front motion can be rewritten in the
undeformed configuration,
g g
where u0 = u0 N, and the constants of proportionali-
ties (k and k0 ) can be related using Equations 57.
3 MACROSCALE MODEL
The formulations derived above consider the defor-
mation-remodeling occurring at a single strut in a
porous solid. In order to estimate the effect of this
phenomenon on the material characteristics at the
macroscale (porous material scale), the equations need
to be consistently upscaled. The representative vol-
ume element at the macroscale (total volume V) is
composed of a solid of volume Vs (t), and pore-space
volume of Vf (t). The rate of change of Lagrangian
porosity ( = Vf (t)/V(t0 )) can be defined as
Using Equations 59, the rate of change of porosity
can be derived from the microscopic measurements.
where J is the determinant of the macroscopic defor-
mation gradient, cs0 indicate the original solid volume
fraction, and <> indicate averaging over the appro-
priate volume. The first two terms in Equation 27 are
routine in poromechanics, and define the change in
porosity due to differences in macroscopic and micro-
scopic deformation (Coussy 1995). The third term
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Copyright 2005 Taylor & Francis Group plc, London, UK
primarily signifies the contribution of the chemical
processes (mass addition/removal) to the porosity
change.
The work done on the porous solid would include
the work done by the externally imposed tractions, as
well as the work done by the fluid pressure (on the
change in porosity). In terms of quantities measured
in the undeformed reference frame, the total external
work would be
where F and " are the macroscopic deformation gra-
dient rate and Boussinesq tensor, respectively. The
free energy can be evaluated by upscaling the micro-
scopic free energy change (Eq. 12 expressed in the
undeformed configuration).
where sv is the solid free energy per unit volume
(i.e. sv = s (t0 )s ). As in Section 2.1, the dissipation
can be divided into volume and surface components.
In this case (i.e. macroscopic analysis), the volume
phenomena include physical processes that occur in
a smeared or distributed manner, and can be deter-
mined from macroscopic or volume-averaged mea-
surements using standard poromechanics theory. The
surface phenomena involve the growth/dissolution
processes that need to be modeled in a local man-
ner. The volume dissipation Dv will be given by (from
Eqs. 2729)
where is the porosity change due to mechanical
causes only, and is given by the first two terms in Equa-
tion 27. The volume dissipation is due to mechanical
forces, and indicates that a part of the external work
done on the porous material is stored as elastic energy
of the solid structure, while another part is expended
in porosity change (against or for the fluid pressure),
assuming that the system is under equilibrium.
The dissipation at the surface involves the driving
force for the surface remodeling and the mass-flux for
the remodeling process. From Equations 2730, the
surface dissipation can be written as
 1000 for bone remodeling can be estimated to be approx.
500 from Silva & Ulm (2002). Figure 2 (evalu-
Relative dissolution rate (u0g/u0g0)

ated from Eq. 33) shows that imposed deformation

= -1000
(tensile/compressive) accelerates the dissolution
100 kinetics of the strut, and the effect of deformation
increases with increasing  value. However, the rel-
= -100 ative impact of different deformation modes on the
dissolution kinetics (e.g. change per unit strain in ten-
10 sion vs. compression) depend on the chosen reference
= -10 frame, as is evident from replacing the Lagrangian
strain measure (stretch, 1 ) in Equation 33 with the
= -1 Eulerian measure, true strain ( = ln (1 )).
1
0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25
Stretch in loading direction
5 CONCLUSION
Figure 2. Effect of deformation (tension/compression) on
the dissolution kinetics for different  ( = EMm /s (t0 )A0 ).
The stretch measure is computed as the ratio of the final
length and the initial length in the loading direction. The
range of stretch values in this figure includes uniaxial defor-
mations with final lengths ranging from half to twice the
initial lengths.
4 APPLICATION
The application of the constitutive equations devel-
oped above to the deformation/dissolution of a cylin-
drical strut is explored in this section. Neglecting the
effect of deformation on the chemical free energies and
the fluid pressure, the deformation induced change in
the driving force for dissolution can be determined
from Equation 23.
0
where A and A are the driving forces for the unde-
formed and the deforming strut. Assuming that the
elastic energy of the strut is due to uniaxial deforma-
tion of an isotropic, Hookean material (Attard 2003)
and using Equation 24 to relate the driving force and
the dissolution velocities, the velocity change due to
dissolution can be defined from Equation 32.
g g0
where u0 and u0 are the dissolution velocities for the
undeformed and the deformed material (measured in
the undeformed reference frame), and 1 is the stretch
(=final length/initial length) in the loading direction.
The ratio of the elastic modulus and the chemical driv-
A consistent model for analysis of deformation cou-
pled surface remodeling in porous materials has been
developed in the present work. The phenomenon is ini-
tially analyzed at the microscopic level i.e. the effect of
deformation on surface growth/dissolution in a single
strut. It is evident that deformation (both compressive
and tensile) would encourage dissolution (and mass
removal) at the solid surface. This can accelerate thin-
ning of struts in regions of maximum deformation
or damage and can cause premature, localized fail-
ure of the porous material. The analysis was extended
to the macroscopic scale through consistent upscaling
of the microscale formulation, and the factors defining
the increase in porosity of the material was analyzed.
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