Water Penetration—Its Effect on the Strength and Toughness

of Silica Glass
SHELDON M. WIEDERHORN , THEO FETT, GABRIELE RIZZI,
MICHAEL J. HOFFMANN, and JEAN-PIERRE GUIN

When a crack forms in silica glass, the surrounding environment flows into the crack opening,
and water from the environment reacts with the glass to promote crack growth. A chemical
reaction between water and the strained crack-tip bonds is commonly regarded as the cause of
subcritical crack growth in glass. In silica glass, water can also have a secondary effect on crack
growth. By penetrating into the glass, water generates a zone of swelling and, hence, creates a
compression zone around the crack tip and on the newly formed fracture surfaces. This zone of
compression acts as a fracture mechanics shield to the stresses at the crack tip, modifying both
the strength and subcritical crack growth resistance of the glass. Water penetration is especially
apparent in silica glass because of its low density and the fact that it contains no modifier ions.
Using diffusion data from the literature, we show that the diffusion of water into silica glass can
explain several significant experimental observations that have been reported on silica glass,
including (1) the strengthening of silica glass by soaking the glass in water at elevated tem-
peratures, (2) the observation of permanent crack face displacements near the crack tip of a
silica specimen that had been soaked in water under load, and (3) the observation of high
concentrations of water close to the fracture surfaces that had been formed in water. These
effects are consistent with a model suggesting that crack growth in silica glass is modified by a
physical swelling of the glass around the crack tip. An implication of water-induced swelling
during fracture is that silica glass is more resistant to crack growth than it would be if swelling
did not occur.

DOI: 10.1007/s11661-012-1333-z
 The Minerals, Metals & Materials Society and ASM International 2012

I. INTRODUCTION Other applications for glass include chemical vessels, flat

GLASSES form an important class of industrial
material for a variety of reasons. Generally, they are
transparent, chemically durable, and inexpensive to
make, and they can be easily formed into flat sheets
for window panes. The most common type of glass for
window applications is soda-lime-silicate glass; over
90 pct of the glasses made today have compositions that
are characteristic of soda-lime-silicate glass. Glass is also
used in optical fibers for information and voice trans-
mission. Silica glass is the glass of choice in this
application because it has a low concentration of
scattering centers that would otherwise interfere with
light transmission. The magnitude of this application
can be sensed by the fact that enough optical fiber has
been installed in the world since 1976 to stretch back
and forth between the Earth and the Moon 160 times.[1]
SHELDON M. WIEDERHORN, NIST Research Associate, is with
the National Institute of Standards and Technology, 100 Bureau Dr.,
Gaithersburg, MD 20899-8520. Contact e-mail: sheldon.wiederhorn
@nist.gov THEO FETT, Guest Scientist, GABRIELE RIZZI,
Mathematical Technical Assistant, and MICHAEL J. HOFFMANN,
Head of Institute, are with the Institute of Applied Materials,
Karlsruhe Institute of Technology, Haid-und-Neu Str. 7, 76131
Karlsruhe, Germany. JEAN-PIERRE GUIN, CNRS Researcher, is
with the Larmaur ERL-CNRS 6274, University of Rennes 1, 35000
Rennes, France.
Manuscript submitted January 5, 2012.
Article published online September 8, 2012
screen TVs, PC monitors, bottles, fiber glass insulation,
jars, and vessels for cooking and other kitchen use.
Compositions of glasses used for these applications can
be found in Reference 2.
For most applications, glass has to maintain its
structural integrity; as glass is brittle, fracture is always a
matter of concern. For this reason, substantial amounts
of research funding are spent each year to characterize
the strength of glass, to make it stronger and to improve
its reliability. Glass almost always fails from surface
cracks. Under a large enough applied stress, a surface
crack will start to grow, slowly at first, accelerating as it
gets longer, until failure occurs. The process of crack
growth in glass has been reviewed recently by a number
of authors.[3–5] Water in the atmosphere causes crack
growth by acting as a stress-corrosion agent, attacking
strained -Si-O- bonds at the tips of cracks and causing
them to rupture. The rate of this stress enhanced
chemical reaction controls the rate of crack growth,
the higher the stress the faster the cracks grow.
Generally, two approaches have been used to improve
the strength and reliability of glasses. The first is to
eliminate surface cracks and then to protect the surface
of the glass with a polymer so that new cracks will not
be generated. This approach is used for optical fibers.
Silica glass is forced through a nozzle in a highly viscous
but fluid state, so that any damage to the glass fiber
while it is forming will self-heal. Once through the

1164—VOLUME 44A, MARCH 2013 METALLURGICAL AND MATERIALS TRANSACTIONS A

nozzle and sufficiently cooled, the glass is coated with a
polymeric coating to protect the surface of the fiber from
further damage. Glass fibers made in this manner are
essentially free of cracks and possess strengths close to
14 GPa.[6] This method of strengthening glass works very
well with optical fibers, but it is too expensive to apply to
glass in ordinary use, say as in wind-screens or windows
for glass doors. Flat screens on television sets and
computer monitors, on the other hand, are made by a
flow process and hence are very strong, being relatively
free from flaws, but flaws can be introduced by handling,
which reduces the strength of the glass with time.
The second approach to strengthening glass is to
apply a compressive stress to the surfaces of the glass.
This technique is most easily applied to flat glass articles
such as glass doors for dwellings and offices, transparent
panels for smartphones, and windows for automobiles.
The reason that the method works so well is that the
compressive stress keeps the cracks closed; for the glass
to fail, a high enough tensile stress has to be applied to
overcome the compressive stress in the surface of the
glass. The two methods of applying such compressive
stresses are thermal tempering and chemical tempering.
A. Thermal Tempering
In thermal tempering, the finished glass article is
heated well above the glass transition temperature
(viscosity  1012 PaÆs).[2] Both sides of the glass plate
are then cooled with a blast of cold air. A parabolic
temperature gradient develops across the thickness of
the plate as a consequence of the cooling. Until the
temperature falls below the glass transition temperature,
no stresses develop within the glass plate. As the glass
plate approaches room temperature, the material near
the outside surfaces of the glass plate stops contracting
first, because they are cooler than the glass in the center
of the plate. Continued contraction on the inside of the
plate puts the outside volume of the glass into a state of
compressive stress, while the inside is subject to a tensile
stress. During this process, the parabolic temperature
gradient is converted into a parabolic stress gradient.
Thermal tempering is an excellent way of strengthen-
ing glass. Fully tempered commercial glasses can have a
surface stress as high as 100 MPa[2] and can be four
times as strong as the fully annealed glass from which it
is made. Glasses can be thermally tempered only if it has
a high thermal expansion coefficient, such as (80 to 100)
9107/C. As silica glass has a thermal expansion
coefficient of only 5.5 9 107/C, thermal tempering is
not an effective method for improving its strength.
B. Chemical Tempering
Chemical tempering works by an ion exchange
process taking advantage of the fact that potassium
ions K+ in glass are much larger than lithium Li+ ions,
0.133 nm vs 0.060 nm, respectively.[7] The process works
by holding the glass piece in a molten bath of potassium
nitrate at a temperature slightly less that the strain point
of the glass (viscosity = 1013.5 PaÆs) for a period of
several hours. The compressive stress developed by this
METALLURGICAL AND MATERIALS TRANSACTIONS A
treatment may be as high as –700 MPa,[2] and the glass
can be as much a six times as strong as a fully annealed
glass of the original composition. For ordinary articles,
say beverage bottles, the penetration depth may be about
40 lm, but for special applications (windscreens for
airplanes, smart-phone windows, etc.) the penetration
depth may be as much as 300 lm.[2] This technique
requires mobile ions in the glass to work, so it too cannot
be used for silica glass, which contains no mobile ions.
C. Transformation Toughening
A possible way of strengthening or toughening silica
glass depends on the local expansion in volume that
occurs when water enters into the structure of silica
glass. This local expansion can be understood by
discussing transformation toughening of ceramic mate-
rials. Ceramics can be toughened if they contain a
crystalline phase that undergoes a volume increase due
to a phase transformation when subjected to the high
stresses present at the tips of cracks. The phase
transformed zone behind and around the tip of the
crack forms a compressive layer that is constrained by
the surrounding material. For the crack to move, it must
propagate against this compressive stress field; hence, a
higher stress is required to propagate the crack than in
the absence of the phase transformation.
The equation that is used to quantify this process was
first derived by McMeeking and Evans[8]:
ev  E pffiffiffiffiffiffiffiffi
Ksh ¼ 0:22 xeff ½1
1m
where Ksh is the shielding stress intensity factor, ev is the
unconstrained volume expansion of the transformed
material, E is Young’s modulus, m is Poisson’s ratio, and
2xeff is the width of the transformation zone. Figure 1
shows these terms with reference to the crack geometry.
Fig. 1—Schematic diagram of transformation toughening. As the
crack propagates, a transformation zone is formed around the tip of
the crack of width 2xeff. The volume of expansion within the trans-
formation zone creates a compressive stress on the surfaces of the
crack and around the crack tip that requires an additional applied
load for crack propagation. The toughening comes primarily from
the compression in the wake of the crack tip.[8]
VOLUME 44A, MARCH 2013—1165
 The crack-tip stress intensity factor has to be equal to
the sum of the applied stress intensity factor Kapplied and
the shielding stress intensity factor Ksh.
Ktip ¼ Kapplied þ Ksh ½2
This equation is applied in a situation for which a phase
transformation occurs around the crack tip. In silica glass,
however, a phase transformation does not occur so that
toughening cannot occur in this manner. In silica, the
volume expansion occurs as a consequence of water
penetration into the glass structure. As demonstrated by
Shelby,[9] Bruckner,[10,11] and Shackelford et al.[12] when
water enters into the structure of silica glass, the glass
suffers a small increase in volume; the volume increase is
proportional to the mass of water entering the glass.
Water entry into the silica glass structure is particularly
strong in the vicinity of a moving crack.[13,14] In studies by
Tomozawa et al.[13] and by Lechenault et al.[14] fracture
surfaces were formed by the passage of a crack through
double cleavage drilled compression specimens
(DCDC),[15–17] while the specimen was exposed to either
water or deuterium oxide. Measurements[13,14] demon-
strated that the concentration of water was significantly
higher near the fracture surface than for silica glass merely
exposed to water for a time equal to that required for the
passage of the crack through the specimen.[13,14] In the
absence of high tensile stresses at the crack tip, water
diffusion into silica glass is very slow.[18]
Three cases of diffusion in the vicinity of a crack tip
can be envisioned, Figure 2:
Case I—No load is applied to the crack and water
penetrates uniformly along the fracture surfaces and the
external surface of the specimen; swelling, as a conse-
quence of water penetration, affects the strength of the
silica glass by providing a shielding stress intensity
factor that tends to close the crack.
Case II—a load is applied to the crack, but the load is
low enough that the crack does not move; as a
consequence, there are high tensile stresses near the
Fig. 2—Illustration of water penetration into the region near a crack
tip. Each of these three cases of water diffusion at a crack tip in sil-
ica glass is discussed in the text.
1166—VOLUME 44A, MARCH 2013
crack tip that enhance diffusion at the crack tip during
the period that the load is applied to the crack. After the
crack is forced to propagate through the compression
zone (by increasing the mechanical force on the speci-
men), the stresses due to water diffusion cause an elastic
rebound (in the vicinity of the crack tip) that can be
quantified and used to estimate the mass fraction of
water in the glass and the activation volume for
diffusion of water in the silica glass.
Case III—a load is applied to the crack that then
propagates through the zone of compression surrounding
the crack tip. The shielding stress intensity factor now
causes a substantial shift of the position of the v-KI curve,
which greatly improves resistance of silica to crack
growth. Taking advantage of the shielding zone, it may
be possible to design a better glass composition that will
enhance the process of water penetration around a crack
tip and, thus, increase the toughness of the silica glass.
In this article, we review recent evidence of water
penetration in the vicinity of the crack tip and discuss
some of its consequences. We start with case I, for which
no load is applied to a surface crack, and water
penetrates into the glass surrounding the crack by
simple diffusion, thus increasing the strength of the
glass. Experiments that quantify the effect of this
process on the strength of glass have already been
carried out for silica glass.[19,20] These experiments will
be analyzed; predictions of strength before and after
water penetration agree with experimental measure-
ment, within the scatter of the measurement.
In case II, a fracture mechanics specimen (double
cantilever beam) was used for the study. A load was
applied to the specimen, which was submerged in water,
and held there for 80 days at an applied stress intensity
factor of 0.245 MPaÆm1/2. After the hold period, the
specimen was split in two and the surfaces were
examined with an atomic force microscope. Profiles of
the crack from the two fracture surfaces were shown to
match over the entire fracture surface, with the excep-
tion of the point where the crack was arrested. Down-
stream of this point, extra material was found at the
crack surface and was attributed to a volume expansion
as a consequence of elastic relaxation of a water-
penetrated zone. These conclusions will be justified and
their consequences will be discussed below.
Finally, in case III, we predict the depth of penetra-
tion around a moving crack and compare the calcula-
tion with actual measurements. Quantification of water
diffusion around the tip of a moving crack requires a full
two dimensional solution of the diffusion equation.
Within scatter, the results of the calculation agree with
the two experiments that have been carried out to date.
II. CASE I—WATER PENETRATION INTO
SILICA GLASS SURROUNDING A SURFACE
CRACK
A. Method
This is by far the simplest of the three cases shown in
Figure 2. Water diffuses into both fracture surfaces and
into the external surface on which the crack terminates.
METALLURGICAL AND MATERIALS TRANSACTIONS A
In both kinds of surface, water diffusion into the glass
causes swelling, which in turn causes a shielding stress
intensity factor Ksh at the crack tip. For diffusion
directly into the fracture surfaces, the shielding is given
by a slight variation of Eq. [1].
ev  E pffiffiffiffiffiffiffiffi
Ksh1 ¼ w xeff ½3
1m
where Ksh1 is the shielding from the crack surface and
the coefficient w is 0.255; see Appendix. On the frac-
ture surfaces and on the external surface of the glass
specimen, we assumed that water diffusion into the
glass occurs in the same way as at a stress-free, flat
surface. This assumption yields a one-dimensional dif-
fusion problem, the solution of which is a complimen-
tary error function of water concentration, Cw(z, t).
The water concentration depends on the diffusion
time, t, and distance, z, from the glass surface.
 
z Hirao and Tomozawa.[20] These authors used abraded
Cw ðz; tÞ ¼ Cw0  erfc pffiffiffiffiffiffiffiffiffiffiffiffiffi ½4
2 Dw  t
The effective penetration distance for Eq. [3] is given
by[21]
pffiffiffiffiffiffiffiffiffiffiffiffiffi
xf ¼ z ¼ Dw  t ½5
where Dw is the diffusivity and t is the time for diffusion.
We now assume that Eq. [5] gives the distance r from the
crack surface to the diffusion penetration boundary,
r = xf, including the crack tip, where the diffusion
boundary now forms a cylinder-like zone around the tip
of the crack. In an earlier paper,[21] the zone was
assumed to be a circular cylinder. When Eq. [5] is used
to define the diffusion distance, the value of the shielding
from Eq. [3] is identical to that obtained by using the
entire error function in the analysis to obtain Ksh1. In
the analysis for Eq. [5], we assumed a constant concen-
tration of water from the surface to xf.[21]
The diffusivity Dw is given by the following equation:
Dw ¼ A0 expðQ=RHÞ expðDVw rh =RHÞ ;
½6
D0 ¼ Dw ðrh ¼ 0Þ
where Q is the activation energy and DVw is the
activation volume for diffusion of water in silica glass.
The diffusion process depends on temperature h in K
and the hydrostatic stress rh at the crack tip.
A solution for Ksh1 can be obtained for an edge-
cracked half-space (this is our model) by combining Eqs.
[3], [5], and [6], yielding Ksh1 as a function of Dw, t, and
water concentration. Experimental measurements of the
diffusivity and the water concentration in silica glass
may be found in Reference 18 and the conversion of
water concentration to volume expansion is found in
Reference 9.
As shown in case I, Figure 2, for an edge-cracked
specimen, a swollen layer of thickness, xeff, extends from
the surfaces of the crack and from the free surfaces
of the specimen. Expansion of the penetrated layer
along the free surface is constrained by the underlying
material. The expansion of this penetrated layer causes a
METALLURGICAL AND MATERIALS TRANSACTIONS A
negative shielding contribution to the edge crack; see
Appendix.
ev  E 1:465  b
Ksh2 ffi  pffiffiffi ½7
3ð 1  m Þ a
where a is the length of the surface crack and b is the
thickness of the diffusion layer from the free surface.
The total shielding stress intensity factor for the two
surface layers is given by adding Eq. [3] to Eq. [7].
ev  E pffiffiffiffiffiffiffiffi ev  E 1:465  xeff
Ksh ¼ 0:255 xeff  pffiffiffi ½8
1m 3ð 1  m Þ a
B. Experimental data
Strength data that can be used to test our model
have been published by Ito and Tomozawa[19] and by
rods of annealed Vycor (C7900)*,** 3 mm in diameter
*The use of commercial names is for identification only and does not
imply endorsement by the National Institute of Standards and Tech-
nology.
**Vycor glass contains about 96 pct SiO2, 3 pct B2O3 and 1 pct
Al2O3 by weight.
and 60 mm long for their study. Sixty rods were
tumbled in a small, evacuated ball mill (1 L volume)
for 2 hours, with 100 g of 600 grit SiC. After abrad-
ing, the specimens were washed in water at room
temperature, cleaned three times in an ultrasonic bath,
and then dried at 403 K (130 C) for 3 hours. A
minimum of 20 specimens were used for each four-
point bending strength measurement.
This procedure supplied a set of uniformly treated
specimens for their study. For as received strengths, one
set of specimen was tested as is. Another set was heated
in water at 361 K (88 C) for either 112 hours[20] or
240 hours.[19] All strengths were measured in four-point
bending in N2 (l). Previous experience[22] shows that
when fracture mechanics specimens are broken in N2 (l),
subcritical crack growth does not occur. The as received
strengths were 181 MPa for 112 hours[20] and 134 for
240 hours.[19] The initial size a of a crack when tested in
liquid nitrogen is given by
1h i
a¼ ðKIc =1:12rÞ2 ½9
p
where the critical stress intensity factor of Vycor KIc in
liquid nitrogen is 0.741 MPaÆm1/2.[22] For the 112 hours
exposure,[20] a crack length of 4.26 lm is obtained; for
the 240 hours exposure[19] the crack length is 7.76 lm.
In the calculations of a, we assume that shallow wide
cracks are formed by the abrasion process so that Eq. [9]
VOLUME 44A, MARCH 2013—1167

Fig. 3—A comparison of the strengths of silica rods tested in N2 (l)
both before and after exposure to water at 361 K (88 C). The error
bars give the standard deviation of the measurements. The dark tri-
angles are the predicted strengths after high temperature exposure.
Data are taken from Refs. [19] and [20].
for an edge crack can be used. The calculated strengths
obtained from these crack lengths after exposure are
197 MPa[20] and 150 MPa.[19] These values are the dark
triangles plotted in Figure 3. The simpler but less accurate
evaluation with the approximation in Eqs. [7] and [8] yields
slightly lower values of 196 MPa[20] and 148 MPa.[19] The
measured strengths after exposure were 205 MPa for the
112 hours exposure and 155 for the 240 hours exposure.
As can be seen from Figure 3, the increases of
calculated strengths are from 67 pct to 76 pct of the
final increase of measured strength. So, they are a bit on
the low side, but considering the scatter in the strength
(Figure 3), diffusivity (standard deviation  20 pct to
30 pct of the mean[18]), and concentration (standard
deviation  15 pct to 20 pct of the mean[18]), the
comparison between experimental strengths and calcu-
lated strengths seems to be reasonable.
C. Case II—Diffusion enhanced by an applied stress
1. Deriving the pertinent equations
In case II, Eq. [5] is used to calculate the diffusion
depth. However, because the crack tip is now associated
with high stresses, the diffusivity in Eq. [5] is considered
to be stress dependent. Substituting Eq. [6] into Eq. [5]
and rearranging terms, we obtain the following equation
for the distance at which the concentration decreased to
50 pct of maximum:
pffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffi
r1=2 ¼ Dw  t ¼ D0  t expðDVw rh =2RHÞ ½10
If Ktip denotes the stress intensity factor at the tip of a
crack, then the singular near-tip hydrostatic stress field
is given by the following equation:
1168—VOLUME 44A, MARCH 2013
Ktip pffiffi
rh;tip  rh ðKtip Þ ¼ ð2=3Þð1 þ mÞ pffiffiffiffiffiffiffiffi cosðu=2Þ ¼ 2j= r
2p r
½11
where r and u are the polar coordinates with the origin
at the crack tip, and rh,tip is the hydrostatic stress caused
by the external loading. In the crack tip region, the
diffusion coefficient is strongly affected by this stress.
Substituting Eq. [11] into Eq. [10] yields the following
equation for r1/2
pffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffi
xeff ¼ r1=2 ¼ D0  t expðDVw j=RH r1=2 Þ ½12
Equation [12] is a transcendental equation and has to
be solved by numerical methods.[23] For the purposes of
this article, a complete solution for r1/2 is unnecessary;
Eq. [12] alone will be used for comparison with
experimental data.
2. Comparison of theory with experiment
In order to investigate the effect of crack tip stress on
diffusion, we carried out the following experiment[23]:
Using a double cantilever specimen, a static load was
applied to the ends of the specimen and held for 80 days.
During this period, the specimen was submerged in
room-temperature water. The applied stress intensity
factor was low for silica glass, 0.245 MPaÆm1/2, low
enough that the crack did not move during the loading
period. At the end of the loading period, the stress
intensity factor was increased to 0.45 MPaÆm1/2; crack
growth started immediately upon increasing the load to
the crack. The specimen was then broken in two and
both fracture surfaces were examined by atomic force
microscopy (AFM).
The profiles of both fracture surfaces are shown in
Figure 4(a). The crack propagated from right to left (see
arrow), and both profiles matched over the scanned
region with the exception of a small segment down-
stream from the point of crack arrest, point a in the
figure. Over this segment, the lower and upper profiles
overlapped, indicating the presence of extra material
along the crack front that was not present over the rest
of the profile. We attributed the extra material to an
elastic stress relaxation once the specimen was broken in
two and the constraints at the crack tip were removed.
Surface displacements can be measured directly by use
of the AFM, i.e., Figure 4(a). The displacements can
also be calculated by carrying out a finite-element
analysis to determine how much surface displace-
ment should occur as a result of the relaxation of the
stress.
The profile given in Figure 4(b) is obtained from
Figure 4(a); the profile given in Figure 4(c) is a calcula-
tion using a finite-element analysis.[23] Assuming that the
strain due to water diffusion was constrained to the
cardioid shape shown in Figure 4(d) and that the crack
split the cardioid shape into equal parts when it propa-
gated, half the measured displacement in Figure 4(a)
went with each part. By comparing the results of the
finite-element analysis with the AFM measurement, we
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 4—Determination of glass expansion due to water penetration of a crack tip: (a) AFM scan of a crack tip that was held under load in
water at room temperature, Kappl = 0.254 MPaÆm1/2 for 80 days. (b) Profile of region of swelling on the fracture surface. (c) Finite-element anal-
ysis of cardioid diffusion volume subject to expansion. (d) Cardioid diffusion volume. Taken from Ref. [23].
obtained the equations shown in Figure 4, and from these
equations and the AFM measurements near the point of
crack arrest, point a, we reached the conclusion that the
penetration distance x = 80 nm and the strain within
the water penetrated region is eo = 13.7 pct. This strain
is close to the strain of 11.7 pct measured by Tomozawa
et al.[13] as a consequence of water penetration into glass
during crack growth. These values are about a factor of
50 times larger than that due to water penetration into
silica glass in the absence of an applied stress, Zouine
et al.[18] The dilatational stresses at the crack tip probably
create the extra volume needed to accommodate the
additional water molecules.
The activation volume DVw for the diffusion of water
through silica glass can be calculated from Eq. [12],
using the swelling data presented in Figure 4. For the
case of a stress-induced weak phase transformation, the

The effect of back stresses on the swelling volume is not considered.
See Reference 23 for a discussion of this point.
zone shape was derived by McMeeking and Evans.[8]
For the polar angle, u = 0, the relation between r and x
is given by r1/2 = (8/27)Æx. All of the other parameters
in Eq. [12] are known, or are experimental variables.
The only unknown is the activation volume, DVw, for
the diffusion of water in silica glass. Substituting all of
METALLURGICAL AND MATERIALS TRANSACTIONS A
the known variables into Eq. [12], we obtained
DVw = 15 9 106 m3/mol. Thus, the activation volume
for the diffusion of water through silica glass is of the
same order as the molecular volume of the water, 18 9
106 m3/mol. The method presented here is a novel way
of determining the activation volume for the diffusion of
water in silica glass.
D. Case III—Diffusion through the tip of a moving crack
in silica glass
Two experiments on silica glass[13,14] have been
carried out to show that during crack growth, water
diffuses through the crack tip and into the glass to leave
a layer of water penetrated glass at the fracture surface
of the test specimen as the crack moves on. Both studies
used the DCDC specimens[15–17] to produce fracture
surfaces that could be analyzed for water penetration
after being fractured in two. Crack growth was carried
out either in water[13] or in N2 (g) containing a high
concentration of deuterium oxide.[14] In Tomozawa
et al.[13] the water concentration was analyzed as a
function of depth using the nuclear reaction analysis
technique, whereas Lechenault et al.[14] used the neutron
reflection technique for the same purpose. Both papers
concluded that a layer of glass containing absorbed
water was present at the surface. Diffusive penetration
of water into the glass was deeper than could be
VOLUME 44A, MARCH 2013—1169
 1
C/C0
ϕ=0
t=1 s
0.5
0.3 s
0.1 s
0.01 s
0.001 s
0 2 4 6
r (nm)
(a)
Fig. 5—This figure shows (a) the concentration of water on the projected crack plain as a function of distance r from the crack tip, and the (b)
stresses on that plain as a function of r. The upper part of the figure shows the combined stresses from the Kapplied, whereas the lower part of
the diagram shows the stresses due to swelling.
explained from known values of the diffusivity at room
temperature. Both sets of authors attributed the
enhanced penetration to the very high tensile stresses
normally present at the tips of cracks in glass and the
sensitivity of the diffusivity to these stresses (Eq. [6]).
In Reference 21, a two-dimensional diffusion equation
was solved and the thickness of the diffusion layer
around the crack tip was calculated. The diffusivity was
assumed to be stress dependent (Eq. [6]), which pre-
cluded simplification of the partial differential equations
used to solve the problem. The solution of the differen-
tial equation was obtained numerically by application of
the procedure NDSolve in Mathematica,[24] as discussed
in Reference 21. Some of the results obtained in
Reference 21 are shown in Figure 5.
In Figure 5(a), we show the concentration of water vs
the penetration distance as a function of hold-time for a
static crack. The curves in the figure can be converted
into velocity curves by dividing the penetration distance,
i.e., the half height distance in the figure, by the hold
time for each curve.[21] In this way, the velocities range
from 2 9 109 m/s (the curve furthest to the right) to 1
9 106 m/s (the curve furthest to the left). An interesting
feature of these curves is the plateau at C/Co = 1, for
which the concentration is independent of the crack
velocity. Penetration distances of as much as 1 nm can
be seen on the plateau. The plateau is similar to the one
measured by Lechenault et al.[14]; however, their plateau
was larger, 4.5 nm instead of  1 nm. The size of the
plateau may depend on the position of the v–K-I curve,
which can be very different depending on whether the
test is carried out in water or N2 (g) containing water
1170—VOLUME 44A, MARCH 2013
σh σh(Ktip)
3000
(MPa) t=10-4 s
ϕ=0
2000
t=1 s
1000 σh,total
2 4 6 8
-4
10 s r (nm)
σh,swell
-1000
t=1s σh(Ktip)+σh,swell(r=0)
ε0=0.13, ΔV=15 cm3/mol
8 -2000
(b)
vapor. This difference may explain the difference
between our calculation and the measurements of
Lechenault et al.[14]
Another interesting feature of the curves in
Figure 5(a) is the dependence of the curve spacing on
hold time. At or near the plateau, C/Co = 1, the
distance between the curves is small; virtually all the
curves have the same penetration distance r. After that,
the curves fan out; the penetration distance increases as
the concentration decreases. At C/Co = 0.5, the differ-
ence between the curves marked t = 0.0001 seconds
and t = 1.0 seconds is about 1 nm, while at C/
Co = 0.9, the difference is about 3.5 nm. Such behavior
is very different from that of a complimentary error
function and is a result of the assumed exponential stress
dependence of the diffusivity.
Figure 5(b) shows the stress distribution on the
projected crack plane as a consequence of crack tip
swelling. One can see two regions of behavior, connected
by a transition between the two. The dash-dotted curve
rh(Ktip) represents the hydrostatic stress caused exclu-
sively by the crack tip, stress intensity factor Ktip
according to Eq. [11]. This stress dominates at large
distances from the crack tip. Close in to the crack tip the
stress is given by the sum of the crack tip stress and the
maximum hydraulic stress due to swelling, rh(Ktip) +
rh, swell(r = 0). The transition between these two curves
depends on the hold time: For a short hold time, the
transition between the two curves occurs at higher
stresses than it does for long hold times. The transition
distance is relatively short, regardless of the hold time.
For all hold times studied, the transition between the
METALLURGICAL AND MATERIALS TRANSACTIONS A
two curves was complete by 8 nm, which means that for
distances greater than 8 nm, the stresses around the
crack tip are controlled by the crack tip stress intensity
factor alone (Eq. [11]). This finding is consistent with the
AFM observation that displacements around the tip of
an emerging crack are all in the elastic region for
distances greater than 10 nm.[25]
III. DISCUSSION
A. Chemical Reaction or Water Penetration?
Water is a well-known stress-corrosion agent for
glasses, which causes delayed failure in glass and a
loading rate dependence of the strength. Without the
water present, shortened lifetimes and lower strengths
would not be experienced by glass. The dominant belief
is that stress corrosion in silicate glasses is chemical in
nature. Water reacts chemically with the strained Si-O
bonds at crack tips causing them to rupture, with the
production of two Si–OH groups on the fracture surface
of the glass. As the Si-O bonds rupture, the crack
advances and the rate of crack motion is related to the
rate of the chemical reaction. The kinetics of such bond-
breaking chemical reactions have been discussed and a
substantial literature exists on the subject detailing the
types of interactions that are believed to occur. Recent
reviews[3–5] clearly describe the experiments and the
experimental results that support the chemical model of
crack growth.
The present paper gives a very different view of how
water reacts with glass. We look at the possibility that
water not only acts as a stress corrosion agent but also
can act as potential toughening agent for silica glass, a
situation that is probably unique in the stress corrosion
literature. The diffusion of water into the silica glass is
analyzed and its potential action as a swelling agent is
described. The mechanisms of the two processes are
believed to be totally different. As a stress-corrosion
agent, water reacts chemically as soon as it comes in
contact with the Si-O bond. The rate of reaction in
region 1[3–5] is determined entirely by chemical reaction
rate theory.[26,27] Diffusion within the glass structure
never enters the picture.
As a toughening agent, the water must diffuse into the
glass structure and cause the glass to swell. The process
for the diffusion of water into the silica glass structure is
not simple because it involves both (1) the migration of
water molecules through the glass structure and (2) a
reaction of the water molecules with the glass.[28] The
effective diffusion coefficient is a parameter that is
determined by both of these processes,[28] and thus, it
describes the effective diffusion rate of water through
silica glass. To complicate the situation even further, the
parameters that control the rates of diffusion and
chemical reaction depend on the local temperatures
and stresses in the silica glass near the crack tip. The
crack-tip stresses can be very high (GPa range) and can
change very rapidly with distance from the crack tip,
further complicating the situation. A complete two-
dimensional diffusion problem at a crack tip in silica
METALLURGICAL AND MATERIALS TRANSACTIONS A
glass has been solved and the concentration and strain
profiles determined,[21] The interaction between the
crack motion due to the chemical reaction rate at the
crack tip and the enhanced stress at the crack tip are
taken into account in the solution.
B. Water Penetration: Case I
In the current paper, we explored the possibility that
water diffusion into the surface of silica glass can
produce stresses that are high enough to significantly
affect the strength and toughness of glass. Three types of
experimental data were analyzed; each showed that the
volume expansion associated with the diffusion of water
into silica glass surfaces provides a plausible explanation
for experimentally observed increases in the strength
and toughness of silica glass. In the first experiment,
case I, the strength of silica glass was enhanced by
soaking it in hot water for extended periods of
time.[19,20] We showed that swelling of the glass surface
provided a reasonable explanation for the change in
strength. Calculating the strength from an edge crack,
we accounted for 67 pct to 76 pct of the strength gain
due to surface swelling. As the cracks in the surface of
the glass were more likely elliptical cracks than edge
cracks, we feel that the comparison provided a semi-
quantitative explanation for the strength. The problem
of elliptical cracks in a silica glass surface will be treated
in a subsequent paper.
C. Water Penetration: Case II
Here, we explored the possibility that water diffusion,
enhanced by stresses at the crack tip, could explain the
swelling observed at the tip of a crack held at an applied
stress intensity factor of 0.245 MPaÆm1/2 in water for
80 days.[21,23] After the hold period, crack tip profiles
were obtained from each of the fracture surfaces. The two
profiles matched perfectly except at the point of crack
arrest during the hold period. There, extra material was
observed (Figure 4). We assumed that the apparent extra
material was the result of swelling of the glass as a
consequence of water penetration into the near crack tip
region of the specimen. By measuring the surface lift at the
point of crack arrest with an atomic force microscope and
analyzing the surface lift by finite-element analysis, we
concluded that the water penetrated a distance of 80 nm
into the glass from the crack tip and that the volume strain
at the end of 80 days was 13.7 pct. From these results and
an analysis of the diffusion problem at a crack tip, we
found that the activation volume DVw for water diffusion
in silica glass was 15 9 106 m3/mol. The method used
here is a novel technique of determining activation
volumes for diffusion.
D. Water Penetration: Case III
In the final experiment, we used a two-dimensional
finite-element analysis of the diffusion of water at the tip
of a moving crack to obtain concentration, stress, and
displacement distributions around the crack tip. Two
sets of data[13,14] were compared with our theoretical
VOLUME 44A, MARCH 2013—1171
analysis of the diffusion problem. The data set obtained
by Tomozawa et al.[13] used the method of nuclear
reaction analysis to measure the depth of penetration of
water into the glass, whereas the data obtained by
Lechenault et al.[14] used the method of neutron reflec-
tion to calculate the penetration of deuterium oxide into
silica glass. The data given by Tomozawa et al. suggest a
shallow penetration of water into the glass surface,
about 2 nm; the theoretical prediction suggested a half-
height penetration distance of 2 nm to 4 nm depending
on the crack velocity. Our theoretical analysis is
consistent with the data collected by Tomozawa et al.
The experimental results obtained by Lechenault et al.
predict a concentration profile consisting of two parts: a
plateau extending about 4.5 nm from the glass surface
followed by an exponentially decreasing concentration
beyond the plateau. The same sort of curve is predicted
theoretically, but the plateau only extends about 1 nm
from the free surface and the half-height distance
extends about 1 nm beyond the plateau. The decay is
not exponential but can probably be approximated as
such. The Tomozawa et al. curves give no indication of a
plateau, perhaps because the technique used for the
analysis of the water concentration was incapable of the
fine resolution needed to observe this detail. The
differences between the Tomozawa et al. and the
Lechenault et al. data may be a consequence of the fact
that different glasses were used in the two studies, or
that some characteristic of the glasses differed, for
example, the fictive temperature. Also, the Tomozawa
et al. experiments were carried out in liquid water,
whereas the Lechenault et al. experiments were carried
out in N2 (g) containing a high concentration of
deuterium oxide. As the v-KI plots for these two
environments are also different, this difference may
Fig. 6—Crack growth curves. The v-Kappl was obtained from Ref. [29]; calculation of v-Ktip was from the shielding stress intensity factor Ksh in
Ref. [21]. (a) v-Ktip as a function of swelling strain eo. (b) v-Ktip as a function of activation volume, DVw. The most likely swelling strain and acti-
vation volume were 13 pct and 15 9 106 m3/mol, respectively.
1172—VOLUME 44A, MARCH 2013
have had an effect on the concentration profiles for the
two environments. Clearly, additional experimentation
will be needed to clarify the measured differences in
concentration profile.
E. Effect of Crack Tip Shielding on the v-Kappl Curves
One of the more important findings of the article is
the level of the crack tip shielding that develops as a
consequence of swelling. This effect was quantified and
discussed in Reference 21. In that article, the effective
shielding stress intensity factor Ksh was calculated from
the solution of the diffusion problem and added to the
applied stress intensity factor Kappl to yield the crack tip
stress intensity factor Ktip for each value of the crack
velocity; i.e., Ktip = Kappl + Ksh. The curves shown in
Figure 6[29] were then plotted. The shift in the position
of the v-KI curve was about 0.15 MPaÆm1/2 for the most
likely curves, which are shown by the heavy dashed
line, and the experimental v–Kappl curve, which is
shown by the solid line. Shifts of this magnitude in the
position of the v-Ktip curve amount to a difference of
about 30 pct in load-carrying ability of the silica glass.
To date, little is known about the dependence of the v-
Kappl curve on the structure of the silica glass or how
the glass structure affected the swelling and, hence, the
degree of shielding for the glass structure. Additional
experiments in this area might prove to be very fruitful
for producing glasses with greater resistance to crack
growth.
One final comment should be made in the discussion
of water as a toughening or strengthening agent for
silica glass. The method we discuss is shielding of the
crack tip as a consequence of a volume expansion in
the glass when water diffuses into the glass structure.
METALLURGICAL AND MATERIALS TRANSACTIONS A
The predicted strengths, surface displacements, or water
penetration into the glass were of the same magnitude as
those measured experimentally. Based on this observa-
tion, we feel that the suggested toughening or strength-
ening process plays an important role in the crack
growth process. However, we feel it is also important to
note that this process does not exclude other toughening
or strengthening processes from occurring at the same
time. Crack tip shielding by water penetration is based
on fracture mechanics and, hence, is by its nature a
subset of the theory of elasticity. Therefore, other elastic
processes can occur simultaneously with the water
penetration and swelling process; the effect of these
processes must then be added to the swelling process to
assess the total effect. Thus, we might have bond-
breaking mechanisms that differ from the chemical one
suggested early in this article.[19,20] We might also have
other types of shielding, such as crack tip bridging by a
precipitate from the crack tip solution.[19,20,30,31] Each
potential mechanism would have to be tested separately
to assess the probability of its participation in the
toughening process; this has not been done to date.
APPENDIX
Shielding Stress Intensity Factor for the Crack-Face
Swelling Zone
In a finite-element study, the diffusion problem for
water-soaked specimens was solved for a semi-infinite
crack in the half space. Figure A1(a) shows the water
concentration contours near the end of a semi-infinite
crack. In Figure A1(b), the local water concentration C,
normalized on the maximum value at the crack surfaces
C0, is plotted vs the crack tip distance. It can be seen that
the zone size ahead of the tip is reduced. There is also a
height reduction visible near the tip (x = 0). Fig-
ure A1(b) gives the concentration profiles for the x-
direction ahead of the crack tip and in y-direction for a
large crack-tip distance xfi-¥ and x = 0.
From the stress intensity factor evaluation by ABAQUS
6.2 a shielding coefficient of w = 0.255 was obtained in
Eq. [3]. For a circular diffusion zone, McMeeking and
Evans[8] found w = 0.25. Although the zone shape
around the tip deviates from a circular cylinder, the
resulting stress intensity factor is hardly affected.

Shielding Stress-Intensity Factor for the Swelling Zone

IV. SUMMARY from the Free Surface
In this article, we explored the effect of crack tip In a finite body, a diffusion and swelling layer of same
swelling on the strength of glass. We found that swelling thickness b and volume strain ev extends from the free
due to water penetration into the silica glass can explain surface, see Figure A2. The contribution of this layer to
several experimental observations reported on the the shielding stress intensity factor can be computed as
strength of silica glass and the structure of crack tips
in silica glass.
1. Silica glass increases its strength when soaked in
hot water.[19,20] In this article, we have shown that y
the strength increase can be explained by swelling 0.1
0.2
of the glass around the crack tip, which imposes a
shielding stress intensity factor Ksh on the crack.
0.5
2. Because of a stress-enhanced diffusion coefficient, 0.8
the size of the swelling zone in the vicinity of a
crack tip is greater for a crack under an applied C/C0=1
Crack
x
stress than for one held free of any stress. a
3. For a moving crack in silica glass, the shielding (a)
stress intensity factor is approximately 1
0.15 MPaÆm1/2, depending on the crack velocity, the
activation volume, and the strain increase due to C/C0

water penetration. This shielding process is suffi- y-direction

x→−∞
cient to account for a 30 pct increase in strength
when failure occurs as a consequence of subcritical y-direction
x=0
crack growth. 0.5
4. AFM profiles across points of crack arrest under
load indicate an overlap of the images from oppo-
x-direction
site fracture surfaces, presumably due to swelling of x>0
the glass that has absorbed water into the glass
structure.
0
5. The activation volume DVw for the diffusion of 0.5 1 1.5
water through silica was determined to be 15 9 x/√D t ,
×
y/√D t×

106 m3/mol. (b)

6. The exploration of glass compositions that can take
advantage of crack tip swelling as a means of Fig. A1—Water diffusion through crack surfaces of a semi-infinite
improving their mechanical behavior has yet to be crack: (a) contour lines for constant water concentration and (b)
carried out. concentration profiles in length and height directions.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 44A, MARCH 2013—1173

 4 stress free silica specimens,[18] or at fresh fracture
∞
h√a surfaces in silica glass,[13] using the relation between
b concentration of water in silica and volume expansion
3 found in Reference 9.
x
σn
2

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1174—VOLUME 44A, MARCH 2013 METALLURGICAL AND MATERIALS TRANSACTIONS A