15512916, 1989, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1989.tb06057.x by Czech Technical University, Wiley Online Library on [27/01/2023].
See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
journal
New York State College of Ceramics at Alfred University, Alfred, New York 14802
Chill checks of controlled depth were
produced in soda-lime-silica glass,
and an optimum humidity of 30 kPa
(300 mbar) water vapor pressure was
found to heal these checks in an an-
nealing cycle. Critical factors were
found to be afEuxing effect, having a
direct dependence on moisture, fol-
lowed by a drying operation at the
annealing temperature. A four-step
model is proposed for crack healing:
(I) exposure of the crack surface to
moisture at temperatures below TB,
( 2 )formation of a gel layer, (3) clo-
sure of the crack resulting from the
relief of stress (a minimum of 10 to
20 MPa applied compressive stress
was determined to be necessary f o r
complete closure), and ( 4 ) drying in
the presence of a controlled atmos-
phere. [Key words: cracks, soda-
lime, silica, humidity, stress.]
ENVIRONMENT has been found to have a
critical influence on crack propagation.
If fundamental crack reversibility assumed
by Griffith’ holds true, one would expect
environment to play an important role also
in the healing of cracks. In the case of a
chill check, commonly found in container
production, crack healing would lead to
direct economies. Crack closure has been
investigated by a number of
whereas the recovery of strength by crack
healing has remained less understood.
Michalske and Fuller6 evaluated possible
mechanisms for crack closure. Two mod-
els that were found necessary to explain
different cases were (1) surface adsorption
of water molecules, providing a linkage of
hydrogen bonds, and (2) formation of a
cationic bridge or a siloxane bridge. By
using these models, a successful predic-
tion of the strain energy release rate for
closure as a function of ambient humidity
C. Kurkjian- contributing editor
Manuscript No. 199143. Received May 13, 1988;
approved
.. April 19. 1989.
Preseited at the 90th Annual Meeting of the
American Ceramic Society, Cinncinnati, OH, May 4,
1988 (Glass Division, Paper No. 72-6-88).
Based on M. K. Clark’s M. S. Thesis, New York
State College of Ceramics at Alfred University, Al-
fred, NY.
Supported by the Center for Glass Research and
Engineering, Alfred University.
*Member, American Ceramic Society.
*Leitz, Wetzlar, FRG.
+SmithOptics.
Healing of Glass in Humid Environments
Mary Kay Clark Holden* and Van Derck Frechette*
was made. Seibold’ established correla-
tions between strength measurements and
healing behavior in soda-lime-silica
glass. Checks were introduced by a dry
glazier’s wheel followed by straining the
sample thermomechanically, thereby caus-
ing the checks to develop into a semiellip-
tical flaw8 and allowing control of the
check depth. Samples were then passed
through an annealing cycle with enhanced
humidities. By looking at the samples
fractographically and measuring strengths,
Seibold found an optimum humidity
for crack healing to occur at 30 kPa
(300 mbar) water vapor pressure. Quanti-
tative assessment of the strengths of the
healed specimens was a problem because
of the residual groove in the specimen left
by the glazier’s wheel. Most recently,
crack healing has been observed in geo-
logical specimens by Are Tsirk.’ The pres-
ent investigation examines the healing of
chill checks and the parameters involved
in healing.
EXPERIMENTAL
PROCEDURE AND
RESULTS
Soda-lime-silica float glass sam-
ples* (edge length of 3.18 cm and thick-
ness of 6.35 mm) were soaked at 450°C
and quenched with a metal probe to intro-
duce a thermal check; the apparatus is
shown in Fig. 1. Check depths ranged
from 191 to 900 p m . The depth was meas-
ured as the distance perpendicular to the
check surface extending from the surface
to the crack tip. The tip position was ob-
tained with an image-shearing polarizing
microscope by observation of the strain-
field birefringence. The samples were sub-
jected to an annealing cycle with enhanced
humidities. Six sets of annealing cycles
were studied to determine the optimum
cycle for healing (Fig. 2). Strength tests
Window
ifCOQQOl
Fig. 1 . Chill check apparatus.
2189
J . Am. Cerum. Soc., 72 [ I l l 2189-93 (1989)
were performed using a ring-on-ring test‘
and postmortem examination followed
using a differential interference contrast
microscope.’ Before samples underwent
fracture, they were abraded with 600-grit
silicon carbide to reduce scatter. Based on
residual check depths and the strengths at
failure shown in Table I , an optimum
tiealing cycle was determined. The critical
conditions were found to be as follows:
(1) A humid atmosphere must be
present at lower temperatures during the
heating cycle.
(2) A residual stress must be pres-
ent before the annealing cycle.
(3) The sample must remain at the
annealing temperature in the presence of a
controlled humidity for a period much
longer than that required for the relief of
stresses.
Crack closure, the disappearance of the
crack to visual examination, was distin-
guished from crack healing, in which the
original chill check was ineffective as a
crack nucleus, so that the origins of failure
in strength tests were scratches from
preabrasion. A determination was made of
the stress necessary for self-welding. Two
pieces of soda-lime-silica glass were
placed in contact. A dead weight was ap-
plied as a compressive load from 1 to
100 MPa while the glass was subjected to
the optimum healing cycle; the results are
shown in Fig. 3. At about 1 MPa, it ap-
peared that the compressive stress was not
sufficient for self-welding to occur,
whereas 100 MPa was too great a stress. It
was only in the 1 to 20 MPa range that
complete welding occurred between the
two samples. In Figs. 3(A) to (C), the
stress was applied throughout the entire
cycle; in Fig. 3(D), a high stress was not
applied until the sample reached the an-
nealing temperature, thus allowing water
- Heater coil8
Water in
Dhere Inlet
Proba
 15512916, 1989, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1989.tb06057.x by Czech Technical University, Wiley Online Library on [27/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
2190 Communications of the American Ceramic Society Vol. 72, No. 11

6 0 min. 3°~/min.
6 0 2 i n .7 3'C/min.

d.
', natural
rate \ cooling
al
v \
\
rate
\
RT I

5 50

450 , natural
-
0
\ coollng
\ rate
9
AJ
\
RT V \

time

Fig. 2. Various annealing cycles for soda-lime-s,ilica glass (( - - - ) no humidity and (-) humidity): (A) little or no closure at all humidities, (B) closure,
very low strength, (C) no closure, (D) closure, low strength, (E) and (F) closure, good strength. (B) and (D) to (F) at water vapor pressure of 30 kPa
(300 mbar) and heating rate of 3"C/min.

to reach the surfaces for reaction at lower furnace accomodated a soda-lime-silica a crack was extended by a hot-wire tech-
temperatures. The final group of experi- glass in the high-humidity annealing cycle nique. The samples were pulled open at
ments was designed to give insight into with a mechanical device to rupture the 300°, 450", and 550°C. All samples were
possible mechanisms of crack healing. A sample inside the furnace at any desired then examined using the interference con-
temperature. A notch was sawed through trast microscope. Postmortem examination
'Lakeside 70 the specimen. From the root of the notch, of the sample opened at 300°C showed the
original crack, an arrest line indicating the
point where the original crack extended,
Table I. Original Crack Depth, Residual Check Depth, and Load at Failure as a Func- and a continuation of the crack upon sepa-
tion of Annealing Cycles* ration. The sample fractured in a brittle
Original check depth Residual check depth Load at failure fashion as did the sample pulled open at
Annealing cycle (wm) (pm) WPa)
550°C after 100 min. However, the sample
Controlled humiditv 580 530 15.2 pulled open 1 min into the annealing cycle
during heating 620 450 23.6 (at 550°C) did not fracture in a brittle
cycle 440 370 23.6 fashion. This pattern is shown in Fig. 4.
552 460 15.2
To aid in the identification of a sample
Contro1led humidity 371 3 10 23.1 that would undergo a plastic deformation
during heating 560 t 25.4 during fracture, a model experiment was
cycle and 10 min 624 50 22.0 performed. This experiment consisted of
anneal 299 t 50.8 heating a thermoplastic resin' applied be-
440 I10 36.7 tween two microscope slides and allowing
Controlled humidity 589 i- 42.9 the unit to partly cool before pulling the
during heating 305 t 33.8 slides apart. The patterns formed here
cycle and 60 min 286 t 39.5 (Fig. 5) were compared with unidentified
anneal 191 t 40.0 patterns in the glass sample. Finally, a
218 t 45.1 soda-lime-silica glass sample was pulled
567 t 42.9 open at 450°C. Between the sawed notch
410 t 42.9 and the original crack tip, a tear mark ap-
664 t 49.6
peared on the surface, as shown in Fig. 6.
582 t 53.0
556 t 53.0
75 1 60 28.8
480 t 50.2 DISCUSSION
350 t 52.5 Healing of Chill Checks
Controlled humidity 648 t 49.1 Figure 2 shows that healing phenom-
during heating cycle 702 f 33.8 ena are net controlled solely by a water-
and 100 min anneal 800 t 47.4 vapor-enhanced diffusion process. A key
446 t 40.0 step in closing a crack involves the pres-
900 t 54.7 ence of water vapor at about 100°C before
Standard group* the annealing cycle. However, humidity at
1 53.0 lower temperatures alone will not close
53.0 a chill check. For a chill check to close
56.3 and heal, a vapor pressure of 30 kPA
52.5 (300 mbar) must be present during the
54.1 heating cycle and throughout the anneal-
41.2 ing cvcle as the residual stresses are re-
u ,
56.3 lieved. The optimum water vapor pressure
*Water vapor pressure uf 3 Pa and air flow of 0 14 m'/h (5 ft'/h). 'Scratch origin 'No check coincides with Seibold's finding.' Al-
 15512916, 1989, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1989.tb06057.x by Czech Technical University, Wiley Online Library on [27/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
November 1989 Communications of the American Ceramic Society 2191

Fig. 3. Sample configuration of healing as a function of applied compressive stresses: (A) 1 MPa, partial
heal, (B) 10 to 20 MPa, complete heal, (C) 100 MPa, no heal, and 100 MPa, complete heal. Dead weight ap-
plied at low temperature for (A) to (C) and at annealing temperature for (D). (E) is experimental arrangement.

though humid atmosphere throughout a
10-min annealing cycle accomplished
crack closure, it did not ensure complete
healing. As the soak temperature was in-
creased, as shown in Figs. 2(D) to (F), the
chill checks healed completely. This be-
havior was shown by the increase in
strength combined with the nature of the
fracture origin.
Self-welding of Two Glass Pieces
Using the critical conditions required
for healing, two pieces of glass that previ-
ously had not been contacted could be
self-welded together, the compressive
stress between them being varied. From
Fig. 3, the 10- to 20-MPa compressive
stress is necessary for a complete self-
weld. However, when the high stress was
present throughout the cycle, there was
little or no healing. It is possible that the
heavier weight prevented water from
reaching the surface, thus hindering any
adsorption and possible chemical reactions
that occur at the lower temperatures. This
theory is supported by the complete weld-
ing that occurred when the high compres-
sive stress was applied only after the
sample had reached the annealing tem-
perature. Previously, in the chill-checked
samples, the water was able to reach the
crack surfaces at low temperatures, and
stresses were pinned until a high tempera-
ture was reached. This result again illus-
trates the necessity of the precursor step at
low temperatures in addition to a mini-
mum compressive stress of 10 to 20 MPa
for healing.
Healing Mechanism
It has now been established that
moisture is involved at low temperatures
in a precursor step and that, under residual
stresses, cracks will close. The third criti-
cal condition for healing (the extended an-
nealing cycle), provided insight on the
healing mechanism.
It was not anticipated that a crack
would close at 300°C. Therefore, when
the checked sample separated at 300°C did
not show any evidence of a heal, it was not
unexpected. There was only the original
check pattern, an arrest line, and a subse-
quent continuation of the crack separating
the sample in halves. At 550°C, the glass
sample that was pulled open at the end of
the annealing cycle also showed a brittle
fracture pattern, except that there was no

Fig. 4. Soda-lime-silica sample, 1 min at 550°C


2192 Communications of the American Ceramic Society
Fig. 5 . Thermoplastic resin sample.
arrest line and no indication of the previ-
ous crack. This result was not unexpected
since we have found that healed cracks do
not show evidence of any previous cracks.
It was between these two temperatures,
300” and 550°C (after 100 min), that the
most information was obtained. The
sample that was separated at the beginning
of the annealing cycle, shown in Fig. 4,
appeared to have fractured in a plastic
mode. This result was verified by compar-
ing the thermoplastic resin fracture pat-
tern, known to be in a plastic mode, with
that of the glass. Figures 4 and 5 show
some of the viscous flow patterns of each.
The outstanding feature in both samples is
the double tail that is formed. When a
crack surface encounters a bubble or in-
clusion in a brittle-fracture mode, one tail
is formed and referred to as wake hackle.
Figures 4 and 5 show voids with two tails.
However, as the sample remains at the
soak temperature until it is later pulled
apart in the annealing cycle, the fracture
pattern changes from one of a viscous-
flow pattern to a brittle-fracture pattern. It
H 2O
Fig. 6. Soda-lime-silica glass sample, 450°C.
appears reasonable to conclude that a dry-
ing operation is taking place at the soak
temperature. bar tho lo me^'.^ described the
release of water from high-water-containing
glasses.
The gel layer that is present early in
the annealing cycle is also present at tem-
peratures far below the annealing tempera-
ture. The behavior is shown in Fig. 6 by
the tear mark, a mark that could only be
seen in a gel system.
Model for Crack Healing
Figure 7 shows a proposed model for
crack closure and healing in soda-lime-
silica glasses.
SUMMARY
Chill checks of controlled depth were
introduced into soda-lime-silica glass.
These checks were then healed in a high-
humidity annealing cycle. The optimum
vapor pressure was 30 kPa (300 mbar),
equivalent to a 70°C dewpoint. The hu-
midity formed a gel layer at comparatively
low temperatures. Closure followed, be-
cause of the relief of residual stresses, and
GEL LAYER
H2O
15512916, 1989, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1989.tb06057.x by Czech Technical University, Wiley Online Library on [27/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Vol. 72, No. 11
this step was then followed by healing.
For complete healing to occur, a minimum
compressive stress of 10 MPa was re-
quired. Higher compressive stresses pre-
vented healing only if applied at low
temperatures. Finally, an extended anneal-
ing time was favorable for healing and
was thought to be a drying operation con-
trolled by the humid atmosphere. This
model is consistent with work done in
glass sintering .9,’0
REFERENCES
IA. A. Griffith, “The Phenomena of Rupture and
Flow in Solids,” Philos. Trans. R . Sor. London A ,
221, 163-98 (1920).
2V.M. Finkel and I. A. Kutin, “The Reversihil-
ity of Cracks in Glass,” Sov. Phys. Dokl. ( E n g l .
TransLJ,7 [3] 231-32 (1962).
’M.Schwahel, “The Effect of Electric Fields on
Crack Propagation in Glass”; Ph.D. Thesis. Alfred
University. Alfred, NY, 1978.
‘ G . B. Caso, “The Phenomenology of Electric
Field-Induced Crack Arrest and Healing”; M.S. The-
sis. Alfred University, Alfred, NY, 1982.
‘ B . Stavrindis and D. G . Holloway, “Crack
Healing in Glass,” Phys. Chem. Glasses, 241 [ I ] 19-
25 (1928).
Fig. 7. Model for crack healing: (A) adsorp-
tion and chemical reaction, (B) gel layer is
complete, (C) closure due to relief of stress,
and (D) drying of gel.

November 1989 Communications of the American Ceramic Society
‘T. A. Michalske and E. R. Fuller, ”Closure and
Repropagation of Healed Cracks in Silicate Glass,”
J. Am. Ceram. Soc., 68 [111 586-90 (1985).
‘M. M . Seibold, “Crack Healing by Annealing
in Humid Environments”; M.S. Thesis. Alfred Uni-
versity, Alfred, NY, 1985.
*R. L. Hudson and V. D. Frechette, “Producing a
Semielliptical Flaw in a Glass Surface,” J. Am. Ce-
Ceramics Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
GaAs has been found to undergo envi-
ronmentally enhanced crack growth
in water, formamide, acetonitrile, and
methanol. I n contrast, no crack ex-
tension whatsoever was observed in
ammonia gas, N2 gas at 50% relative
humidity, or heptane. These results
are consistent with a model of electro-
static, rather then chemical, inter-
action between the environment and
the crack-tip bonds, governing the
rate of crack growth. The lack of any
water - imp u r i ty - con t r o 1I ed c ra c k
growth further suggests that it is the
dielectric constant of the liquid
medium rather than the polarizabil-
ity of an individual molecule that is
important. [Key words: gallium ar-
senide, cracks, mechanical proper-
ties, crack growth.]
NVIRONMENTALLY enhanced crack
Epropagation in brittle materials has
been the subject of investigations for
years. Although complete understanding
of the processes involved has not been
attained, substantial progress has been
made. Two models’.2 have been proposed
for the interaction of environments with
the strained bonds at the crack tip. The
R. C. Bradt-contributing editor
Manuscript No. 198266. Received July 11, 1989;
approved August 2, 1989.
Supported by the Office of Naval Research under
Contract No. N00014-87-F-0007.
’Member, American Ceramic Society.
*Morgan Semiconductors, Garland, TX. (Trade
names and companies are identified in order to specify
adequately the experimental procedure. In no case
does such identification imply that the products are
necessarily the best available for the purpose.)
ram. SOC., 64 121 C-26-C-27 (1981).
YAreTsirk; unpublished work.
‘ “ J . E . Ritter ef a l . , “Appraisal of Biaxial
Strength Testing,” J . Non-Crysf. Solids, 38-39, 419-
20 (1980).
“R. E Bartholomew, “Water in Glass”; pp. 75-L24
in Treatise Materials Science and Technology, Vol. 22.
Coming Glass, Coming, NY, 1982.
Grady S. White,* Stephen W. Freiman,* and Anne M. Wilson
first model involves the direct chemical
reaction of the environmental molecule
with a crack-tip bond in the solid through
the donation of both a proton and an elec-
tron pair to opposite sides of the strained
bond, thereby reducing the stresses needed
to break this bond and extend the crack.
The second model involves an electro-
static attraction, rather than a chemical re-
action, between the environment and the
solid, which reduces the crack-tip bond
strength. The mechanism of a stress-
enhanced chemical reaction is applicable
to oxides such as S i 0 2 and A12032and
silicate-based g l a ~ s e s whereas
,~ the
electrostatic mechanism appears to be
appropriate for materials such as MgF2.
GaAs was chosen as an interesting
material for investigation because, al-
though its bonds are approximately of the
same ionic/covalent character as S i 0 2
(~30% ionic), its chemistry is quite dif-
ferent. From a technological point of
view, GaAs is an important new material
i n the semiconducting industry and is
known to be quite sensitive to mechanical
failure during processing.
EXPERIMENTAL
PROCEDURE
Crack-growth studies on single crys-
tals of GaAs were c o n d u c t e d using
applied-moment, double-cantilever-
beam specimens4nominally 12.5 mm wide,
37 mm long, and 0.5 mm thick. The speci-
mens were cleaved from commercially ob-
tained,* Si-doped, Bridgeman-grown
wafers with (100) faces and were oriented
so that (110) cracks ran down the center of
the specimens. The Si-doped specimens
were used because the presence of Si re-
duces the dislocation density, shown5 to
be related to residual stresses that can inter-
fere with crack-growth measurements in
GaAs. Specimens were mechanically pre-
15512916, 1989, 11, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1151-2916.1989.tb06057.x by Czech Technical University, Wiley Online Library on [27/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
2193
”R. F. Bartholomew. “High-Water Containing
Glasses,” J . Non-Cryst. Solids, 56 [I-31 331-42
(1983).
”T. H. Elmer, “Sintering of Porous Class,” Am
Ceram. Soz. Bull., 62 [4] 513-17 (1983).
I4H. I . Oel, “The Sintering of Classes by the Ac-
tion of Viscous Flow and Surface Tension” (in Cer.),
Ber. Drshc. Keram. G e s . , 37 (1960). 0
cracked in a universal test machine
equipped with a Knoop diamond indentor
and were then dead-weight loaded to gen-
erate crack growth. Crack-tip positions
were measured as a function of time with
an optical microscope and filar eyepiece.
Measured crack velocities (V) ranged
from to m/s. The upper ve-
locity was limited by the rate at which the
load could be removed without twisting
the specimen and causing failure. Meas-
urements of the lower velocity in metha-
nol and acetonitrile were limited by the
evaporation rates of these liquids. In the
time interval required to make crack ve-
locity measurements of =5 X lo-’’ m/s,
the environments would evaporate from
the specimen chamber. The lower-velocity
limit in water resulted from corrosion of
the GaAs which, over the course of sev-
eral hours, made precise measurements of
the crack tip impossible.
Crack-growth curves were obtained
in at least two environments for each
specimen; this procedure was used be-
cause past experience6 has shown it to be
the most sensitive technique to evaluate
small changes in environmental effects on
crack propagation. In addition, crack-
growth curves were obtained from at least
two specimens in each environment. The
environments fell into two categories:
those that chemically decompose into both
proton- and electron-pair-donating seg-
ments and those with large dielectric
constants (i.e., that can interact electro-
statically). All environments had been
used in previous investigations of crack
growth in vitreous silica,’ single-crystal
A1203,2and single-crystal MgF,.2 There is
overlap between the two categories of
environments; e.g., water and methanol
have large dielectric constants and also
interact chemically via proton donation