JOURNAL OF GEOPHYSICAL

RESEARCH, VOL. 89, NO. B6, PAGES 4072-4076, JUNE 10, 1984

Effects of Chemical

Environments

on Slow Crack Growth

in Glasses and Ceramics

S. W. FREIMAN

InorganicMaterials Division,National Bureauof Standards

This paper presentsa review of our currentunderstandingof environmentallyinducedslow crack

growthin glasses,
singlecrystals,and polycrystalline
ceramics.
It is shownthat the rate of crackgrowthis
controlledby the chemicalactivity of the active speciesin the environmentas well as by the stress
intensityat the crack tip. A recentlydevelopedmolecularmodel of stress-induced
chemicalreaction
betweenvitreoussilica and water is described.The implicationsof this model for the effectsof other
chemicalspecieson crackgrowthare discussed.
Finally, the complications
introducedby the presenceof
grainboundariesin polycrystallineceramicsare pointedout.
INTRODUCTION

curvesrange from n = 11 for some binary glassesto n > 100

for somepolycrystallineceramics.Wiederhorn[1967] showed
that crack velocityis controlledby the rate of reactionof the
activeingredientin the environmentwith the chemicalbonds
of the solid at the crack tip. This reaction may or may not

The objectiveof this paper is to provide a current view of

the mechanismsof environmentally influenced, subcritical
crack growth in both glassesand ceramics.This review will
concentrateon various aspectsof the stress-aidedchemical
reactionwhich governsthe crackingprocess.Particular attention will be paid to recentmodelsfor stress-assisted
physical
and chemicalprocesses
whichappearto governcrackgrowth.
Before discussingcrack growth in glassesand ceramics,it

involvetheformation
ofcorrosion
produc
ts.
While reductionsin surfaceenergydue to the attachmentof

surfacegroupsto SiO2 can be considered

as the drivingforce
for thestress-enhanced
reactionat a cracktip, assuggested
by
Orowan [1944] and more recentlyby Parks [this issue],the
crack growth rate is determinedby the kineticsof the chemical process.
Reactionrate theory can be used to derive a model for
stress-assisted
crackpropagationin glassesand ceramics.Such
a derivation.forthe SiO2-H20 reaction(the specificmolecular
chemistryis describedin the next section)is shownin summary as follows (for a more detailed derivation, see Wieder-

should be said that all of these materials will be considered to

be ideally brittle, i.e., that there are no zonesof plasticdeformation at propagatingcrack tips. This assumptionhas been
shownto be valid in MgO and aluminum oxide [Lawn et al.,
1980]. Even for "softer"materialssuchas MgF 2, where dislocationsare known to be generatedaround advancingcrack
tips,fractureis stillgovernedby bond-breakingmechanisms.
Most of the crack growth data reported herein were taken
using double cantileverbeam specimensin which a constant

horn et al. [1982]):

^ generalexpression
for H20 reactingwith an Si-O bondis

loador bendingmomentis appliedto the specimen

andcrack

given by

extensionmeasuredoptically as a function of time. Crack ve-

!0cities
from10-xto 10-2 m/scanbeobtained
in thisway.

[Si-O-Si] + H20--'Z-

2[SiOH]

(1)

The dataareusuallyplottedas log V versusK, whereK is

where Z is the activated complex.As in most reaction rate

theory [Laidler, 1965], the decompositionof the activated
complexto the productsis assumedto be very rapid in composesand easeof mathematical
manipulation,crackgrowth
parison to the reversereaction'
data are often expressedas V = AK n where A and n are
constantswhich dependon material and environment.While
this expressionis easilyintegratedto calculatetimesto failure,
its theoreticalbasisis much weakerthan an expressionof the
form V = Vo exp (bK). Becauseof its common usage,how- where tis the transmissioncoefficient(for most reactionsassumedequal to 1, meaningthat every activated complexbeever,this paper will usen as a measureof the slope.)
comesa product); k is the Boltzmann constant; T is temperGENERAL CRACK GROWTH BEHAVIOR
ature; h is Planck'sconstant;AG$ is the Gibbs free energyof
V-K plots for glasses,single crystals,and polycrystalline activation;a(H20) is the activityof the water; andf is the
ceramicscan be quite complexin shape(Figure 1). Each seg- activitycoefficientfor the activatedcomplex.
ment can,however,be describedby a differentrate controlling
Combiningterms and assumingthat the crack velocityis
mechanism.Becausethey are isotropic and homogeneous, directlyproportionalto the reactionrate, we obtain
most of the work in determiningthesemechanismshas been
V = Voa(H20) exp (-AG$/RT)
(3)
performedon silicateglasses.These mechanismscan be synopsizedas follows:
There are at least two important aspectsto (3). First, note
the stressintensity factor at the crack tip and is calculated
from the load and specimendimensions.
(For engineeringpur-

f
(2)
rate=
t(-)exp(-AG:/R
T)a(H20)

Region I

Becauseslowlygrowingcracksspendmost of their growth

period in this regime,it is of primary importance.Slopesof

that the reaction rate, and thereforethe crack velocity,is proportional to the activity rather than the concentrationof
water in solution in the liquid or gas. If water vapor is assumedto behaveas an ideal gas,then

This paper is not subjectto U.S. copyright.Publishedin 1984 by

the AmericanGeophysicalUnion.

Papernumber3B1067.

"
4072

ai = P,/Po

(4)

where Po is the vapor pressureof pure water at the temperature of the experiment.In a gaseousenvironment,Pi is the

FREIMAN: SLOW CRACK GROWT[-tIN OLASSESAND CERAMICS

4073

KIC

II

Si

(1)
(2)

IB

(3)

.....
ilA

Fig. 3. Model for the stress-induced

chemicalreactionof H20 with
amorphoussilica[after MichalskeandFreiman,1982].

StressIntensity,
KI

where AS:, AE$, and A V$ are the activation entropy, activation energy,and activationvolume respectively,and d is a
dimensional parameter depending on the structure of the
vapor pressureof water,and Pi/P o is the relativehumidity. crack tip. (Wiederhornet al. [1982] usethe crack tip radius p,
For waterdissolved
in nonaqueous
liquids,Pi is the equilibri- but for valuesof p approximatelythat of the network spacing
um vaporpressureof wateroverthe solution,and P/Po is the in the solid, this term probably has little meaning.)The last
relativehumidityof the gaseousatmosphereover the solution. term is includedfollowing the approachof Charlesand Hillig
Giventhesedefinitionsand the relationshipexpressed
in (3),it [1962] and accountsfor changesin the surfaceenergyof the
becomesclear why the data of Wiederhorn[1967] and Frei- crack tip during the reaction; and V are the surfaceenergy
man [1974] obey a simple V R.H. relationship(whereR.H. and molar volume of the reactingspecieswhile and V$ are
is relativehumidity)(Figure2). The fact that crackvelocityis thosequantitiesfor the activatedcomplex,and p is the crack
dependenton relativehumidityrather than concentrationhas tip nucleus.The effectof stresson the crack tip reactionrate is
Fig. 1. Schematicof the different regionsof a typical crack growth
curvefor glassesand ceramicstestedin air, for instance.

importantimplications
for predictions
of structuralreliability. includedin the (d)-l/2KAV term.The parameterd must
It meansthat liquidssuchas siliconeoil and fiuorinatedhy- haveunitsof (length)
2 sothat d-l/2Kz hasunitsof stress.
The
drocarbonscannot be consideredinert merely becausetheir use of the activation volume in this context assumes that the
solubilityfor wateris small.Second,thisexpression
providesa tensilestressdependenceof the reactionrate can be expressed
fundamentalbasis for plotting crack velocity data as In V
versusK rather than In V versusIn K asnotedearlier.
The stressdependenceof the reaction is contained in the
AG$ term. It has beenshown[Wiederhornet al., 1980] that
thisterm can be expandedasfollows:

AG, = - TAS, + AE, - (d)- '/2K,AV, - (7*V* - 7V)/p

(5)
10-6
-_

_
--

"
=

as the negativeof the pressuredependence.

Equations(3) and
(5) can be combinedto yield
V = Voa(H20) exp [(-E$ + bK,)/RT]

(6)

where all of the non-stress-dependent

terms are included in
E:.

The previousderivationof the kineticsof crack growth was

completely general. No details of the chemical reaction between the environmentand the glasswere discussed.One im10-2 -

HEXANOL
HEPTANOL

**'/

i!

OCTANOL
o

DECANOL

DODECANOL

10-3-

.?.//

/!

10-4_
E

10'5-

':/

.=.

I 0.6 -

/ ?

o 10'7

SLOPE=
I/2 g.'

./

10'8

10'9
io-e

I
IO
%

"/ // ......
-- Formamide
Hydrazine

* /
I
0.4

I III

//

------N2
I

0.6

0.8

IOO

KI (MPa
m1/2
)

RH

Fig. 2. Crack velocityin sodalime-silicaglassat K t - 0.45 MPa

Fig. 4. Crack growth curvesfor amorphoussilicatestedin envi-

mTMas a functionof the relativehumidity,i.e.,activityof water,in

ronments

variousstraightchain alcohols[after Freiman, 1974].

stress-induced
reactions[after Michalskeand Freiman,1982].

whose molecular

structure

should

be favorable

to cause

4074

FREIMAN:SLOWCRACKGROWT IN GLASSES
ANDCERAMICS

portant questionis why H20 is suchan effectivecrackgrowth

agent for all silicate glasses,when the corrosion rate of a
material suchas vitreousSiO2 is extremelylow.
Michalske and Freiman [1982] have describeda specific
chemicalmechanismby which strainedSi-O bondsin vitreous
silica react with moleculesof a gas or liquid. This model for
the H20-SiO2 reactionis shownin Figure 3 as a three-step
process:

Step 1. An H:O moleculeorientsitselfwith respectto an

Si-O-Si bond at the crack tip suchthat the lone electronpair
orbitals on the oxygen of the water moleculeare aligned
toward the silicon,and hydrogenbondingoccursbetweenthe
Osinca
and the hydrogen.The strain(as muchas 20%) on the
bridgingSi-O bond clearlyenhancesthe tendencyto react at

RegionsIA and lB

The mechanismof crack growth in the steeperIA regimein

a number of glassesseemsto be similar to that in regionI, but
there is someevidencethat there are accompanyingchangesin
crack tip geometry.Work by Michalske [1983] has demonstrated the occurrenceof crack blunting and a stresscorrosion
limit in soda lime-silica glassin water, but exceptfor some
data in borosilicateglasses[Wiederhorn and Johnson,1973;
Simmonsand Freiman, 1980], determinationof a definitecrack
limit has not been extendedto other glassesor ceramics.For
instance,no evidencefor a region of increasedslopehas been

observed
for vitreous
SiO: at velocities
aslowas10-xxm/s.
A regionIB plateauin the velocityrangeof 10-x0 to 10-8

m/s has been observedonly in binary alkali-silicateglasses

testedin aqueoussolutions[Simmonsand Freiman, 1981]. The
Step 2. Electron transferfrom the Owater
to the Si occurs authors hypothesizethat, becauseof the great solubility of
simultaneouslywith proton transfer to the Osinca.
Two new theseglassesin water at lower valuesof K, cracksgrow at a
bondsare formed,Si-Owate
r and H-Osin
a.
rate approximatingthat of the SiO: dissolutionrate. A very
Step 3. Rupture of the weak hydrogen bond between small stressis apparentlysufficientto remove corrosionprodOwatrand the transferredhydrogenoccursto yield Si-OH ucts at the crack tip and acceleratethe dissolutionprocess
surfacegroupson eachfracturesurface.
there, in preferenceto the sidesof the crack. However, effects
Note that the model does not require prior dissociationof of stressesgeneratedbecauseof a H + for Na + exchange
the water molecule,nor must reaction productsbe removed cannot be ruled out.
from the solid. Wiederhornand Johnson[1973] observeddefinite effectsof hydrogenion activity on crack growth in silica Region II
and other glasses,
suggesting
that OH- and H + ions may
This plateau appearswhen crack growth occursin an envishow a different stress-dependent
reaction rate than HO.
ronment in which the minor constituentin the liquid or gas
Theseeffectsneedfurther study,however.
controls the crack tip reaction. As the crack proceeds,the
The above model suggeststhat other environmentsshould speciesin the environment which reacts with the chemical
also enhancecrack growth in silicaif the specieshas structural bondsat the crack tip, e.g.,H20, is depletedin the vicinityof
and bonding featuressimilar to water, namely, proton donor the tip, thereby creating a concentrationgradient. As noted
sites on one part of the molecule,and lone pair orbitals on earlier, in region I the rate is controlledby the reactionrate at
another. It is likely that there are sizelimitations as well since the tip, but as the crackvelocityincreases,
the sizeof the H:O
theSi-Obonddistance
is only1.63A. It is interesting
to note depleted zone, 6, grows. At some crack velocity the rate at
the similarity of this model to that of Griggsand Blacic [1965]
which the active speciescan diffusethrough this zone to the
for the hydrolyricweakeningof quartz.
tip becomesslower than the reaction rate and hencebecomes
Figure4 showscrack growthcurvesfor amorphoussilicain the controlling step in determiningrates of growth. On the
water, ammonia (NH3), hydrazinc (NH,0, formamide basisof the use of the Stokes-Einsteinexpressionfor the dif(HCONH), and N2 gas.As will be discussed
later, the plateau fusivityof a moleculein a liquid, it was shownthat this velociin the N gascurveoccurswhencrackgrowthis controlledby ty is givenby [Wiederhornet al., 1982]
the rate of diffusion to the crack tip of the small quantity of
dissolvedwater. The absenceof this plateau in the curvesfor
Vplateau
= 6nr---ammonia, hydrazinc,and formamide leads to the conclusion
that their reaction with the crack tip bonds governs crack where k is the Boltzmann constant,T is temperature,r is the
growth ratesin preferenceto the reactionof the water present size of the diffusingspecies,Co is the bulk concentrationof
in theseenvironments.On the basisof the plateau in the crack this diffusing species,and r/ is the viscosityof the solution.
growth curves obtained in environments such as carbon Experimental data for alcohol-water solutions have verified
monoxide (CO), acetonitrile (CH3CN), and nitrobenzene the applicability of (7) (Figure 5). Becausediffusioncan also
(C6HsNO), thesedid not control crack growth,as would be take placein from the facesof a double cantileverbeam spedpredictedby the above model, sinceeach of thesemolecules men, for instance,the region II velocity is also crack front
does not meet all of the required bonding specifications.
Allength-dependentand can show a small stressintensity dethougheachcontainslone pair orbitals,nonecan donatepro- pendence,i.e.,a slopeof 2 to 6.
this site.

0.0275kT
(__) (7)

tons. It should also be noted that no direct correlations

were

found to exist betweendielectric constant or dipole moment

alone and an environment'sability to causecrack growth in
preferenceto water.
Recent crack growth data obtained on a commercialsoda
lime-silica glassshow the same trends as that describedfor
silica [Freiman and White, 1982]. There was no obvious par-

ticipationof the Na + ionsin the crackgrowthprocess.

However, preliminary data suggestthat when the Na content is
increasedsignificantlyas in a binary 33% NaeO/67% SiOe
glass,variationsin the crack growth mechanismsappear.

Region III

Crack growth curvesin region III are quite steep,n > 100.
Wiederhorn[1967] showedthat crack growth rates in region
III for sodalime glassare independentof water concentration.
Freiman [1974] showed that while crack growth rates in
region III are not affected by water in the environment,in
agreementwith Wiederhorn,there are effectsof the liquid in
which the water was dissolved,e.g., the chain length of an
alcohol. Similar data were subsequentlyreported by Richter
[1977]. A model explainingregionIII crack growth basedon

FREIMAN: SLOW CRACK GROWTH IN GLASSESAND CERAMICS

Concentration/Viscosity

(Kg-moles/m3/pa.s)
102

103

104

10-4

utyl (Sat.)

'_ 10-5

autyl ($%)

Ethyl
(1%)

Butyl
(1%)/Heptyl
(t.)

Butyl
(0.2%)
/
E

10-6

Decyl
(Sat.)

t Octyl
(50%)
I

10

102

103

Concentration/viscosity
(g-moles/I/Poise)

Fig. 5. Crack velocity in region II as a function of (concentration/viscosity),

as suggested
by equation(1). Data are for soda
lime-silica glasstestedin straightchain alcoholscontainingvarious
amountsof water [after Wiederhornet al., 1982].

4075

covalentto ionicbondingin the solid?What are the effectsof

strain on the bond character?Complete answersto these
questionsare not known at present.However,recentdata
obtainedon A1203(sapphire)[Michalskeet al., 1982]suggest
that this material behavesidenticallyto amorphousSiO2 in
that the sameenvironmentsthat governedcrackgrowthin the
latter alsocontrolin Al:O3 and to the samerelativedegree.In
the moreionicallybondedMgF:, however,the aboveauthors
found that ammonia no longer controls crack growth in

regionI, while acetonitrile(CH3CN) is an effectivecrack

growthenvironment
eventhoughit hasno proton-donating
capability.This behaviorsuggests
that individualatom solvation may play a part in the fractureof ionic solids.There
may be a pureelectrostatic
bondingof the solventmolecules
to the Mg and F atoms.The seeming
lack of anymeasurable
subcritical
crackgrowthin silicon,a completely
covalentsolid,

indicatesthe needfor somedegreeof chargeseparationduring

stressing.
Very few detailedcrackgrowth data existfor polycrystalline
ceramics.There are severalgeneral observationsthat can be
an electrostrictive interaction between the solid and the fluid
made,however.First, it is apparentthat grain boundarystrucat the crack tip has recentlybeen proposedby Wiederhornet ture and chemistrybecomea significantfactor in determining
crack growth rates. One can show, for instance,that MgO,
al. [1982]. Their modelis synopsized
asfollows:
which does not appear to be subject to subcriticalcrack
If we assumethat the slopeof the V-K t curve in region III
(or in region I) is determined by the stressdependenceof a growth in singlecrystal form, does undergodelayedfailure
when preparedin polycrystallineform [Freiman, 1976]. Fracreactionrate at the crack tip, then the activationvolumeA
can be taken as a measureof the stress-dependent
process. ture occursalmost exclusivelyalong grain boundaries.Other
From a physicalpoint of view, AV:[:representsthe difference polycrystallineceramicsin which subcriticalcrack growth is
observedalso exhibit primarily intergranularfailure over the
in volumebetweenthe reactantsand the activatedcomplex.It
is assumedthat the formation of chargesduring the rupture of regime in which the crack is growing slowly, even in cases
a strained Si-O bond at crack tip has a significanteffect on where there is no obviousgrain boundary phase [Mecholsky
A V:[:,suggestingthat environmentswhich can alter the mag- and Freiman, 1981]. A transition from an intergranular to a
nitude of these chargeswill influenceA V and therefore the transgranularfailure mode is frequentlyobservedat the critical flaw boundaryin thesematerials.Whether this kind of
slopeof the V-K t curve.
behavioris due to chemicaleffectsor to changesin the ability
Wiederhornet al. derivedthe followingexpressionfor
in a solid-solventsystem in which the electrostaticcontri- of the crackfront to changedirectionsat differentvelocitiesis
not known. In addition, there are effectsof grain size on the
butionsare of primary importance:
slopeof the V-Kt curvewhichare not understood.

AVEs
- a--2
(3B)1(
1-[2)
-1--(1
-[2)'PA
(8)
r

whereNa is Avogadro'snumber,e is the unit of charge,r is the

atomic radius (contributionsdue to Si and O are calculated
separately),B is the bulk modulusof the solid, and , and
are the dielectricconstantsof the liquid and solidrespectively.
One can see that the secondterm on the right contains the
partial derivative of the solid dielectricconstantwith respect
to pressure,i.e.,the stresscontribution.A plot of log (velocity)
versusKt should have a slopeproportional to AV:[:.Figure 6
is a plot of AV$tscalculatedfrom (8) comparedto the AVStotal
determinedfron the slope of the V-Kt curve for soda limesilica glass.(A value of d of 0.5 nm was assumedfor this
calculation.While there is clearly uncertaintyin this number,
it should be correct within at least an order of magnitude.)
The correlation

between the calculated

18

Vacuum
(5)

N2(1)

o 16r

t C7H16
/

H-'141_

10

C7H16
(27)
/

Alkanes
,27,
c,0.,.o.,c,_

and measured values

suggests
the generalvalidity of the aboveapproach.
EFFECTS OF CHEMICAL BONDING AND MICROSTRUCTURE

Most ceramicmaterialsare susceptibleto crack growth in

the presenceof water. What is surprisingis that thesematerials include such diverse chemical compositionsas AI:O 3,
MgF:, ZnSe, and graphite, as well as many others. Is the
mechanismof subcriticalcrack growth the same as that describedfor SiO: ? What are the effectsof changingthe ratio of

10

12

14

16

ElectrostaticComponent of Activation Volume,

AVes,
cm3/mol
Fig. 6. ActivationvolumeVo= determinedfrom the slopeof
the V-K curve for soda lime-silica glass tested in environments
whosedielectricconstantvariesfrom 1 (vacuum)to 78 (H20) plotted
againstthe V s calculatedfrom(8) [after Wrhom t al., 1982].

4076

FREIMAN: SLOW CRACICGROWTI IN GLASSESAND CERAMICS

Freiman, S. W., and G. S. White, Effects of chemicalenvironmentson

crack growth in soda-lime glass,Am. Ceram. $oc. Bull., 61, 414,

SUMMARY

An overall picture of the complex relationship between

1982.
crack velocityand stressintensityfactor has beenpresented.It Griggs, D. T., and J. O. Blacic, Quartz: Anomalous weaknessof
has been shown that chemical reaction kinetics can be used to

explain the dependenceof crack growth rates on the activity

of a given environment. Mechanisms of subcritical crack
growth in glassesand ceramicshave been describedin terms
of models

for the stress-induced

reactions

of environments

with crack tip bonds.It has beenshownthat the tendencyof a

given substanceto participatein sucha reactioncan be predicted from knowledgeof the molecularchemistryof the environment and the bonding in the solid. While only limited
crack growth data existfor polycrystallineceramics,it is clear
that processesin these materials are dominated by grain
boundarychemistryand structure.
In closing,it is perhaps worthwhile to point out that no
mention was made in this paper of the possibleeffectsof zeta
potential on crack growth even though other authors in this
conference discuss it rather extensively [i.e., Dunning et al.,
this issue;A.M. Westwood, unpublishedmanuscript, 1983]. It
is our observation

that no clear correlation

has been made

syntheticcrystals,Science,147, 292-295, 1965.

Laidler, K. J., ChemicalKinetics,McGraw-Hill, New York, 1965.
Lawn, B. R., B. J. Hockey, and S. M. Wiederhorn,Atomically sharp
cracksin brittle solids.An electron microscopystudy, J. Mater.
Sci., 15, 1207, 1980.
Mecholsky,J. J., and S. W. Freiman, Fractographicanalysisof delayed failure in ceramics,Fractography and Materials Science,
ASTM Spec.Tech. Publ., $TP 733, 246-258, 1981.
Michalske,T. A., Crack arrest in glass:The blunt truth, Fract. Mech.
Ceram., V, 277-289, 1983.

Michalske, T. A., and S. W. Freiman, A molecularinterpretation of

stresscorrosion in silica, Nature, 295, 511-512, 1982.
Michalske, T. A., S. W. Freiman, and B. Bunker, A chemicalapproach to predicting stresscorrosion behavior of brittle materials,
Am. Ceram.$oc. Bull., 61, 414, 1982.
Orowan, E., The fatigue of glassunder stress,Nature, 154, 341-343,
1944.

Parks, G. A., The surfaceand interfacialfree energiesof quartz, J.

Geophys.Res.,this issue.
Richter,H., The effectof different liquids on the transitionfrom slow
to fast crack propagation in soda-limeglass,in Physicsof NonCrystallineSolids,edited by G. H. Frischat, Trans. Tech. Pub.,

Aedermannsdorf,Switzerland, 1977.
between zeta or surfacepotential and the rates of subcritical
crackgrowth. There is seriousquestionwhetherzeta potentials Simmons,C. J., and S. W. Freiman, Effectsof phaseseparationon
crackgrowthin borosilicateglass,J. Non Cryst.Solids,38-39, 503measuredon bulk solidsor powderswill be similarin any way to
508, 1980.
thosewithin the small confinesof a crack tip. In addition, these Simmons,C. J., and S. W. Freiman, Effect of corrosionprocesses
on
measurementssuggestwhat has happenedto a surface after
subcriticalcrack growth in glass,J. Am. Ceram.$oc., 64, 683-686,

reaction with an environment, while we are interested in the

kinetics of the interaction process.
Acknowledgments.I thank S. M. Wiederhornand G. S. White for
their time and effort in their numerous discussions with me on this

subject.

REFERENCES

Charles,R. J., and W. B. Hillig, Symposium

on MechanicalStrengthof
Glassand Waysof ImprovingIt, p. 511, Union Scientifique
Continentaledu Verre, Charleroi,Belgium,1962.
Dunning,J. D., D. Petrovski, J. Schuyler,and A. Owens, Effects of

1981.

Wiederhorn,S. M., Influenceof water vapor on crackpropgationin

soda-limeglass,J. Am. Ceram.$oc.,50, 407-414, 1967.
Wiederhorn,S. M., and H. Johnson,Effectof electrolytepH on crack
propagationin glass,J. Am. Ceram.$oc.,56, 192-197, 1973.
Wiederhorn, S. M., E. R. Fuller, Jr., and R. Thomson, Micromechanismsof crack growth in ceramicsand glassesin corrosive
environments,Met. $ci., 14, 450-458, 1980.
Wiederhorn,S. M., S. W. Freiman, E. R. Fuller, Jr., and C. J. Simmons, Effectsof water and other dielectricson crack growth, J.
Mater. $ci., 17, 3460, 1982.

S. W. Freiman, Inorganic Materials Division, National Bureau of

Standards,U.S. Department of Commerce,Bldg. 223, Room A331,
Washington,DC 20234.

aqueouschemical environmentson crack propagationin quartz,

d. Geophys. Res., this issue.

Freiman,S. W., Effectof alcoholson crackpropagationin glass,d.

Am. Ceram. Soc.,57, 350-353, 1974.

Freiman, S. W., Effect of environmenton fracture of ceramics,Ceramurgia,2, 111-118, 1976.

(ReceivedOctober 20, 1982;

revisedMay 23, 1983;
acceptedJune 16, 1983.)