Dccember 1952 Thermal Stress Failure oj Pure Refractory Oxides
co5ity was then measured and the results compared with those
from the first put.
The comparison indicated that the crushing and remelting
on the average reduced the viscosity slightly. One sample
was not changed appreciably The average reduction in
viscosity was about the same as the probable error of the
me:isurements (i.e., about 4y0). On any one sample i t could
not be said with certainty that the lowering in viscosity was
due to the crushing and renielting since the difference was of
the same order of magnitude as the probable error, but the
fact that the changes were all in the same direction indicates
that the results would have been slightly better if all samples
had been crushed and remelted.
For all the data presented in this series of papers the viscos-
ity values arc least reliable for those compositions that might
develop new phases a t the temperature of the experiment.
The reasons for this are as follows: ( I ) It is possible that non-
uniformity of the melt due to the formation of crystals which
arc not detected may result in misleading data. (2) When the
sample is cooled after the preliminary melting and fining, a
Thermal Stress Failure of Pure Refractory Oxides
by BERNARD SCHWARTZ
Department of Metallurgy, Division of Ceramics, Massachusetts Institute of Technology, Cambridge, Massachusetts
An investigation was carried out to study the
thermal stress failure of three pure, dense refrac-
tory oxides, namely alumina, stabilized zirconia,
and magnesia. Thermal stress resistances were
determined by means of a direct test and by cal-
culation from the physical properties of the ma-
terial. The properties measured included
strength, elasticity, and thermal expansion. All
the tests were conducted within the temperature
range 25“ to 1500°C. For hollow cylindrical
specimens, heated uniformly from the inner sur-
face, resistance to fracture was expressed quanti-
tatively by the heat flow at steady state required
to cause fracture. This resistance was found to
b e a function of (1) the physical properties of the
material, (2) the temperature range of testing,
and (3) the temperature distribution within the
specimen.
1. Introduction
IIR desire to extend the temperature range of atomic-
T energy power systems and jet-propulsion engines has
stiniulatcd interest in the pure, dense refractory oxides
as possible structural materials. The susceptibility, however,
of these brittle ceramic materials to fractures caused by ther-
mal stresses constitutes a major problem. It was the pur-
pose of this investigation, therefore, to study quantitatix-ely
the resistance to fracture due to thermal stresses of three such
oxides, namely alumina, st abilizcd zirconia, and magnesia.
The temperature dependency of this resistance for steady
state conditions was considered primarily.
A body that is heated evenly and is free to expand (or con-
tract) in all directions will have no thermal stresses. If this
325
clear glass does not always result. In this case the crystalline
phases and the glassy phase probably would differ in compo-
sition. The remelting of the sample may not then result in a
uniform glass. (3) The possibility of the simultaneous exis-
tence of more than one liquid phase may not be completely
ruled out. In one or two instances there was some indication
that two liquid phases were present.
The general trends noted in the previous papers’s continue
to be apparent in the compositional regions covered by data
presented in Tables I, 11,and 111and pictured graphically in
Figs 1, 2, and 3.
In Pig. 1 (H) and (C) the isokoms exhibit more curvature
than is coninion in other regions of composition. The authors
doubt the reality of this. The isokoms are fairly straight a t
1500°C., but become curved at the two lower temperatues.
This whole region is one in which the isotherms, although un-
known except along the zero per cent MgO edge of the tri-
angular diagrams, are probably quite close.
The patterns of the isokoms in Pigs. 2 and 3 are logical if
one reasons from the earlier data.12 2 They require no com-
ment.
body is restrained from expanding, stresses are developed
within the mass proportional to the restraining force. When
a free body is heated unevenly, so as to set up temperature
gradients, thyma1 stresses are also produced. Under these
conditions the cooler portions of the body provide the re-
straining force for the hotter sections. The use of the term
“thermal stressing” will be meant to apply to the wse of the
free body, unevenly heated without the addition of mechanical
forces. There are other causes of thermal stresses, e.g.,
anisotropic expansion or varying degrees of elasticity of
particles within the mass. In this study, however, the bodies
are considered to be essentially isotropic, homogeneous, and
elastic.
An important tool in studying spalling resistance is a de-
pendable test. A large variety of thermal rupture tests may
be found in the literature. A complete review, however, is
beyond the scope of this paper. The tests generally appear
to fall in one of the following categories:
( I ) Cyclic heating and cooling (similar to a mechanical
loading-unloading fatigue test).
(2) Extended uneven heating (similar to a 1nechanical
stress-duration fatigue test).
(3) Uneven cooling or heating (similar to a mechanical
continuous single-loading test).
Presented at the Fifty-Third Annual Meeting, The American
Ceramic Society, Chicago, Ill., April 24, 1951 (Refractories Divi-
sion, No. 14). Received April 25, 1961; revised copy received
June 23, 1952.
This paper is based on :I tliesis submitted in partial fulfillment
of the requirements for the degree of I k t o r of Science, Massa-
chusetts Institute of Technology, Cambridge, Mass., November
1950.
The author i s no\+ senior ceramic engineer, Electronics Divi-
sion, Sylvania Electric Products, Incorporated, Woburn, Mass.
3 2 (5 Journal of T h e American Ceramic Society--Schwurtz
I
--A 1 1 :ension
Fig. 1 . Stress distribution in an infinitely long hollow
cylinder at steady state, heated from the inner surface.
( A ) Inner radius, (6) outer radius.
( 4) Iiapid lieatirig or qiicncliing (similar to a incchanical
iiqxtct test).
Several of the inethods that have been used to assess the
spalling resistance of rerractories include the following:
(I) 1,oss of weight of specimens due to thermal shock.
( 2 ) Nuniher of shocking cycles required for spalling.
( 3 ) 1,oss in strength due to thermal shock.
(4) Severity of the cwnditions required to produce spa11-
in 4.
A s carly as 1891 thermal shock resistance was correlated
with the physical properties of the material in the form of the
classical Winkelmatin and Schott equation.' The next major
devclopriient in spalling analysis may well be represented by
the equations of which pointed out the difference in
spalling caused by tensile and shearing stresses. Current
trends seem to be toward the dcvelopment of new equations
quantitatively defining conclit ions contributing to spalling.
Tlie syml)ols used in this paper include the following.
V I'oissori's ratio.
U Stress.
I.: Modulus of elasticity.
G Modulus of rigidity.
a Liurar eoeficient of thermal expansion.
Al' 'I'exnperature differewe between inner and outer sur-
faces o f a hollow cylinder.
fl ltirier radius of hollow cylinder.
B Outer radius of hollow cylinder.
S Tensile strength.
k 'l'hermal conductivity (C. G. S. units).
P 1,oad.
X Ilistanee from support to adjacent load point in a two-
point transversely loaded beam.
I' Span of beam.
I Moment of inertia.
b Width.
d Ikpth.
1 Isngth.
n Area.
II. Plan of Study
Since this investigation was concerned chiefly with the use
of pure refractory oxides for rocket liners, a test was used to
siinulate service conditions. I n this ease the greatest danger
of spalling occurs during the heating-up period. The third
type of test given in section I was selected; it was similar to the
A . Witikcltnann and 0. Schott, "Uber thrrmische Widcr-
standscoeflieicntcn vcrschicdener Gliiscr in ihrcr Abhiingigkeit
von der chcmischen Zusamtnensetzung," Ann. f'hys. Chem., 51,
730-64 (1894).
P. 1%. Norton, Refractories, 3d ed., revised, pp. 420-36.
MeGraw-Hill Book Co., lne., New York, 1949. 782 pp.;
Ceram. Abstracts, 1950, July, p. 146u.
I-01.35, No. 12
test used previously by Renfrew in this laboratory and by
Westbrook in another laboratory a t the blassachusetts In-
stitute of Technology. ISssentially a hollow cylindrical
specimen was uniformly heated in a radial direction until
thermal stresses were developed to e:ttise fracture. A further
description of the test is given in section IV (1).
This test specimen had the advantage of being amenable
to thermal stress analysis. The problem of a hollow cylinder,
heated uni€ornly from the inner surface, has been treated in
the literature.3 It has been shown 3 , 4 that fractures start at
the outer surface ends of a finite hollow cylinder. 1,imiting
the discussion to a steady state temperature distribution, the
equation selected from the literature as most appropriately
expressing the most dangerous stress is
The first expression of this equation represents the tangential
stress a t the outer surface of an infinite thick-walled hollow
cylinder heated uniformly from the iritier surface. A sche-
matic stress distribution is shoxin in IGg. 1. For brittle ceramic
materials, many tinies stronger in compression than in ten-
sion, only the tciisile stresses were considered to be significant.
For a finite hollow cylinder, however, the tendency of the free
ends to flare outward causes an aclditioiial tangential strcss at
the outer surface ends. This effect is accounted for by the
second expression in equation (1). Furthennore, only this
stress had to be considered because the axial stress at a free
end reduces to zero and the radial stresses remain relatively
small.6 This second factor was actually derived for a thin-
walled cylinder.5 I t should be pointed out, therefore, that
equation ( I) represents an approximation to the thcoretical
case of a thick-walled cylinder. I n view of the normal devia-
tions obtained in strength measurements on polycrystalline
ceramic materials, further refinements of this equation were
not considered to be necessary. To avoid further coniplexity
in equation ( I ) , the author also assumed that the physical
properties of the material did not vary with temperature in
the interval AT.
When the tensile stress equals the tensile strength of the
tnaterial, equation (2) defines the A T required for ruptuie of
the specimen.
1,rtting
and
Equation ( 2 ) may be written as
h-'= AT/S ( " C . ) (5aj
J. €1. Westbrook, "Thermal-Shock Resistance of Metitllized
Ceramics"; thesis for Doctor of Science degrcc in Metallurgy,
Massachusetts Institute of Technology, 1949.
S. Timoshenko, Strength of Materials: 11, Advanced Theory
and Problems, 2d ed., pp. 174-76, 258-64. D. Van Sostrand
Co., Inc., New York, 1949. 782 pp.
6 C. H. Kent, "Thermal Stresses in Thin-Walled Cylinders,"
Applied Mechanics (Trans. Am. Soc. Mech. Enzrs.), 53 [I31 167-
80 (1931).
I k c e m b e r 1952 Thermak Stress Failure of Pure Refractory Oxides 327

Fig. 3. Test bars (half size). Arrows indicate fracture; lines indi-
cate support and loading positions.

Potentiometer Millivoltmeter
Fig. 4. Test cylinders (one-quarter size). From left to right, speci-
Fig. 2. Thermocouple arrangement for thermal stressing test.
mens are shown alternately before and after thermal stressing test.

Ilcncc, the physical property factor K’ defines the ratio of Table I. Density and Porosity
the AT’ rccpired for thermal stress failure to the shape factor
S. The end-effect expression, although a function of a phys- Alumina Zirronia Magnesia

ical property, was included in .Srather than in K’ because its I’ycnometer dctisit y 3 .9 5.4 3.6
effect was present owing to the special case of a finite hollow Bulk density 3 .7 , i
.2 3 .2
cylinder. Ik-thermore, equation (:{), as i t is written, gives Open pores (%) 0 0 9.0
Total pores (yo) 5 .4 11
an expression for K’ that is coinmon in thermal stress equa-
tions for other shapes, such as plates and spheres.4
‘To compare only the physical properties of materials, S
w a s corrected to unity for a standard case; then Table II. Dimensions of Cylinders (cm.)
K = AT (5b) Alumina Zirconla Magnesia hl&l size

In addition to the maximum temperature gradient a speci- Outer diameter:

iiicii can withstand without fracturing, resistance to fracture Avg. 4.53 ‘4.28 4.67 5.04
Avg. deviatioii 0.07 0 . 04 0 .03
also dcpends on the ability of the material to resist the derelop- Inner-diameter :
incnt of such gradients. At steady state the temperature Avg. 2 74 2 60 2 8.1 3 to
gradient is determined by the heat flow, thermal conductivity, Avg. deviation 0 08 0 04 0 02
and ditncnsions of the system: Length Approximately 8.5 11 0

0’ = k AT(o/I)
for linear licat flow, and
for radial heat flow. Considering (I the heat flow per unit
inean area per length,
@ = k A T (cal./sec./cm.)
where (I now defines the heat flow per unit mean area per
length at steady \late required to cause fracture of a finite
hollow cylinder with a shape factor of unity. The Q value,
therefore, may serve as a quantitative \ d u e for ( 1 ) directly
comparing the resistanccs to fracture of materials for thermal
tensile stresses, in terms of a stcady state condition, and (3)de-
sign work in calculating the heat flow a t steady state required
to fracture a structure, by correcting for appropriate shape
factors in stress xnd heat flow equations (providing the K fac-
tor is common to the particular problem).
It appeared thnt (1 could be determined either by a direct
ineasurement or by separate measurenients of K and k. Since
extensive studies were under way in this laboratory for ac-
curate measurements of the thermal conductivity of the
(en)
oxides, the latter method was used so that only the K factor
had to 1)e determined. Two approaches were made: (1)
(611)
direct measurement of A T :~ndS by means of a thermal stress-
ing test and (2) comparison with the direct test by separately
measuring s, E , a, and U, and then calculating K .
All tests wcre conducted in the temperature range 2 5 O to
(66) 150OoC. In the tliei-mal stress failure tests the outer surface
temperature of the specimen was taken as the parameter be-
cause fracture started in this surface. An additional phase of
(7) the study was to denionstrate, by means of thermal stress
failure tests, the relation betmeen the resistance at steady
state and the resistance during transient conditions.
111. Specimens
The alumina, stabilized zirconia, and magnesia were pur-
chased from a cotnmercial source in the form of pure (less
than lyOimpurities) fused refractorq. grains. Approximately
4y0CaO was used as the stabilizer in zireonia.
By utilizing slip-casting techniques, uniformly dense speci-
mens were formed. The alumina and zirconia slips were pre-
pared according to the method described by Hauth,B and the
W. E. IIauth, Jr., “Slip Casting of Aluminum Oxide,” J . A M .
Ceram. SOC., 32 1121 394-98 (1949).
328 Journul of The American Ceramic Socie fy--Schwurtz
--
Fig. 5. Specimen carrier with furnace.
inagncsia as cast by tlic procedure used at the National
Bureau of Standards.7 Rcctangular rods were made for
elasticity, strength, and expansion tests. The rods, approxi-
niatcly 3/8 by by 5 in., were solid-cast in plaster molds.
IIollow cylinders for the thermal stressing test were also
solid-cast in a plaster mold; a brass mandrel was used, how-
ever, to form the inner surface. drying, the specimens
were prekired to 1150°C. in a laboratory gas muffle kiln. The
pieces wcrc then machined. Both ends of the cylinders XTere
cut off,leaving a 3 3/4-in. tube. The specimens were made a t
approximately the minimum lengths allowable fur use with
equation (I). ’I’he ends were used for setters in the high
firing. Three shallow notches, each l/z in. long, were cut a t
one end of each cylinder for placing thermocoiiples a t the
inner and outer surfaces, as shown in Pig. 2. The thcrmo-
couple grooves were made with large radii to avoid the forma-
tion of a serious stress concentration. Thermal stress cracks
scldoin occurred in these notches or in any consistent location,
indicating that a signifirant stress concentration w;ts not pro-
duced.
The specimens werc sintered to maturity in an alumina
catenary gas-fred kiln a t J830°C. for 3 hours. The average
fircd density and pore volumes of the fired oxides are given in
’hblc I ; the dimensions of the hollow cylinders are given in
Tablc 11. Photographs of the specimens are shown in Figs. 3
and 4.
IV. Testing Equipment and Procedure
(I) Thermal Stress Failure lest
The test apparatus consistcd essentially of a structure sup-
porting a hollow cylindrical sample about a Globar concentri-
cally, and a means of transferring the sample along the length
of the heating clement, An angle-iron frame with Transite
end pieces served as a support for the Globar and provided an
overhead track for the specimen carrier. The carrier was
a small Kanthal wire resistance furnace, in which the cylinder
was supported by two pin point setters a t each end and con-
centrically with the furnace rnuflle, as shown in Fig. 6.
Thermal stressing of the specimen was achieved by heating
with tlie Globar. The funiacc in the carrier was used to pre-
heat the system to an equilibrium temperature so that the
temperature range in which fracture occurred could be con-
trolled.
1. G. Thompson and M. W. Mallett, “Preparation of Cru-
cibles from Special Refractories by Slip Casting,” J . Research
Natl. Birr. Standards, 23 [2] 319-27 (1939); KI’ 1236; Ceram.
Abstracts, 18 [Ill 300 (1939).
VOl. 85, hTO. 12
ov I I I I I
0 100 200 300
Time (sec.)
Fig. 6. Sample thermal stressing runs an alumina specimens;
TB = 40OoC. (A) Thermal stress failure during transient state;
( B ) thermal stress failure during steady state; (C)no thermal stress
failure.
Measuring surface temperatures presented a major prob-
lem. IIoughten and Olson8 suggested the use of thcnno-
couples cemented in grooves in the surface as one of the best
methods. Very small thermocouple beads therefore were
used. After the thermocouple was cemented in the shallow
grmvc, the surface of the bead was filed flush with the speci-
men surface. The leads were located along isotherms to
minimize errors caused by conductitm. The thermocouples
were prepared with 28-gauge wire, using Chromel-Almtiel for
temperatures up to 1OOOOC. and platinum-90yo platinum-
lOyorhodium for higher tempexatures. The gradient across
the tliickness of the cylinder was measured with a differential
thermocouple, and the outer-surface temperature was
measured with a thermocouple, as shown in Fig. 2. To cor-
rect for the nonlinearity of the thermocouple curves, the
measured electromotive force of the differential thermo-
couple was added to that of the outer-surface thennocouple,
which gave the equivalent e.xi1.f. for the inner-surface tcm-
perature; AT was then obtained by subtraction. In each
ease the thermocouples were placed in the same position in
regard t o the Globar.
The specimen theoretically should not have had any axial
temperature gradient. To determine actual testing condi-
tions, a zirconia cylinder was prepared with necessary ther
mocouple grooves along both inner and outer surfaces. At
approximately 4OO0C. the largest longitudinal gradient meas-
ured Irom center to end of the cylinder was 6OC. Longitu-
dinal gradients of this order were not considered to be serious
because i t has been shown5 that the stresses caused by the
longitudinal gradients are relatively small compared with the
stresses caused by the radial gradients.
For a low-temperature run, the furnace in the carrier was
not heated. The specimen was kcpt out of the hot zone while
the Globar approached its equilibrium temperature ; then the
specimen was pushed to tlie center of the Globar. Outer-
surface temperatures and AT were read alternately a t 10-
second intervals. Rupture of the specimen was determined by
an aiidible, instantaneous cracking. The response of alumina
and zirconia pieces was very sharp, whereas the fracture in
the less-dense magnesia was just loud enough to be heard
This would indicate a necessary change in technique for de-
termining the fracturing of porous bodies.
8 IT. C. IIoughten and II. T. Olson, “,Measurement of Surface
Temperatures” in Temperature, Its Measurement and Control in
Science and Industry, pp. 885-61. Reinhold Publishing Corp.,
New York, 1941. 1362 pp.
 Thermal Stress Failure of Pure Refractory Oxides
Globars
Loadlng Saddles
Knife Edges
(Alumina)
Z C “
Fig. 7. Cross-sectional view o f transverse-loading test apparatus.
For higher-temperature runs, the specimen in the carrier
was first heated by the furnace to a desired temperature. The
carrier was kept a t the center of the Globar during the whole
run because the preheated Globar required only a short time
to reach its equilibrium temperature. The remaining proce-
dure was the same as for low-ternperature runs.
A specimen was considered to reach steady state when there
was no further change in temperature distribution with time.
This condition mas approximated by the slope of the AT-time
curve of a run, as shown in Fig. 6. The departure from steady
state, therefore, vas indicated by the slope of this curve,
where a slope of zero was taken to represent the steady state.
(2) Modulus of €/asticity
The modulus of elasticity was determined by a static test,
eiiiploying tlie principle of a two-point transversely loaded
ljeani. The equipment is shown in Fig. 7. The support and
loading components used in the hot zone of the furnace were
iriadc of sintercd alumina. The design of the knife-edge and
saddle system eliminated the possibility of producing a torque
on the specimen during loading. The saddle could rotate in a
iockrt, bearing perpendicularly to the rotation around the
knife edge. The loading was done by means of a lever system
below the furnace. The two saddles were connected to the
levcr by alumina rods extending out of the bottom of the
furIKLcc.
The deflections of a specimen under load were nieasuretl a t
both points of support and a t the center of the rod. The true
deflection could then bc found by correcting for any move-
inen1 of the supports. The deflections were transmitted t o
three dial gauges (0.0001 in.) by three synthetic sapphire rods.
In making a run, the sample was heated to the testing tem-
perature and soaked for ;Iminimum of *,’2 hour. To measure
thc modulus of elasticity, ’/Z-kg. loads were applied to the
spcciineri a t 1-minute intervals. The three gauges were read
preceding each weight addition. The modulus of elasticity
was calculated from a conventional deformation equatiorig
for an elastic beam:
I’ x (31? - 4x2)
I3 = (y) 241
F. R . Seely, Resistance of Materials, 3d ed., p. 137. John
Wiley & Sons, Inc., New York, 1947. 486 pp.
329
I I I I I
Deflection ( X 0 4 in.).
Fig. 8. Elasticity curves for alumina specimen (I= 1.35 X 10 -4 in.4).
The ratio ( P l y ) was determined from the linear portion of the
load-deformation curve. Sample cun-es are shown in Fig. 8.
(3) Tensile Strength
The transverse-loading apparatus, used to nieasure elas-
ticity, was also designed to conduct continuous-loading rup-
ture tests. I’or the rupture tests, water loadiiig was em-
ployed in conjunction with the lever system. A pail replaced
the weight holder on the lelyer. A large water reservoir was
used to maintain a nearly constant pressure for the water
flow. The rate of loading was selected by adjusting the rate
of water flow through a stopcock. When the specimen broke,
the lever arm activated a solenoid water valve that automat-
ically stopped the water flow.
Before the run, the same procedure was eniployed as in the
elasticity tests. A loading rate of 100 gm. per second on the
specimen was used. After rupture, the total load was weighed
and the tensile strength was calculated from the equation.
The validity of this method for the accurate determination of
tensile strengths has recently been treated in dettil by Duck-
worth. l o
If the elastic limit of a material is exceeded, the tensile
strength calculated from equation (9) is greater than the
actual maximum stress produced to cause rupture. The ex-
tent of this error depends on the degree of inelasticity of the
material and depth of the specimen.1° For the oxides studied,
fractures were found to occur within the elastic liniit up to
approximately 1000°c. for magnesia and 12 O O O c . for a h -
mina and zirconia. Above these temperatures similar in-
elastic behavior should also occur in the thermal stressing
specimens, and therefore cornparatilye calculations should
still agree, although the absolute strength values reported
might be in slight error.
(4) Thermal Expansion
The thermal expansion equipment used has been described. *
The expansion of a &in. sample was measured directly by nieans
lo IT. H. Duckworth, “Precise Tensile I’ropcrtirs of Ceramic
Bodies,” J . Am. Ceranz. SOC.,34 [ I ] 1-9 (1951).
* F. H. Xorton, see pp. 481-83 of footnote 2.
330 Journal of The American Ceramic Society---Schwartz Vol. 35, No. 12

0 Zirconia \
0 Magnesia
F
0
0 400 800 I200
Temp. rC.)
0 400 800 1200
Temp (“CI Fig. 10. Tensile strength curves.
Fig. 9. Modulus of elasticity curves.

Table V. Tensile Strengths (Ib./sq. in.)

Table 111. Modulus of Elasticity ( X 1O6 Ib./sq. in.) Temp (“C) Alumina Zirconia Magnesia
Temp (“C.) Alumina %irconia* Magnesia 25 21,000 20,000 14,000
200 20,500 10,800 14,200
25 51.0 21.5 (24.5) 30.5 400 1.5,000 17,500 15,200
200 50.0 20.3 (24.1) 30.5 600 17,000 17,000 16,000
400 49 2 2 0 . I (23 9 j 30.0 800 19,500 16,000 14,200
600 49 0 19.8 (23 2) 29.5 1000 20,000 14,800 11,500
800 48 2 22 0 27 5 1100 18,000 13,500 10,000
1000 45.0 19.9 21.0 1200 15.500 12.100 8,000
1200
:300
37.1
28.0
16.0
11.8
10
4 1300 ;
11 BOO ;
10 200 6 ,000
1400 7,300
*Values in parenthese? ohtainrd from tests run on sprcimenq
first heated above 800°C.

investigators” in this laboratory have measured the moduli of

Table IV. Poisson’s Ratio, v rigidity of the materials used.

V. Discussion of Results
Maguesia 25 30.5 11.2* 0.36
500 29.8 10.9 .36 (I) Physical Properties
900 24.8 9 5 .33
1000 21.2 8.0 .33 ( A ) Moddzts of l<Zasticity: Representative results of the
1100 16 5 5 6 .47 modulus of elasticity tests are presented in Table IT1 and are
Alumina 25 51.0 21.3t .20 shown graphically in Fig. 9. The experimental points on the
Zirconia 25 24.5 9.5t .29 curves represent an average of a minimum of three determina-
tions.
*Obtained by Wygant, footnotc reference l l ( a ) . The temperature dependency of the moduli of elasticity
tObtained by a static test on the equipment of Ilcw, footnote
refercnce l l ( b ) of the three oxides appeared similar to that described for
polycrystalline metals.12 With increasing temperature the
moduli first decreased almost linearly and then dropped off
more rapidly a t a critical temperature. The more rnpid fall-
of a telescopic system, sighting through tubes in the furnace ing off of the curve a t high temperatures has been attributed
walls on the ends of the specimen. The furnace was of the to increased slip a t grain boundaries, in contrast to single
Globar muffle type, equipped with an aiitomatic program con- crystals that hold the linearity approximately to their inelting
troller set for a heating rate of ’4OC. per minute. points.12 The effect of slip, or transient creep, on static
measurements of elastic constants should be considered. The
(5) Poisson’s Ratio apparent strain at any time interval was a measurement of
I’oisson’s ratio, defined as the lateral unit contraction per the instantaneous elastic deformation plus the creep. The
unit elongation, is given by thc equation* effect of this slip on the apparent elastic constant depended on

Y = (E/2G) - 1
Poisson’s ratio therefore may be determined either by direct
measurement or by calculation from the moduli of elasticity
and rigidity. The 1:ittcr method was selected because the
modulus of elasticity was determined in this study and other
* 1‘. B. Seely, see p. 24 of footnote 9.
(10)
“ ( a ) J. 17. Wygant, “Elastic and Flow Properties of Dense,
Pure Oxide Refractories,” J . A m . Ceranz. Soc., 34 [12] 374-80
(1951).
( b ) K.J. Ilcw, “Ihmping Capacity Mcasurrments on Refrac-
tory Oxides Under Varying Stress and Temperature Conditions”;
thesis for Doctor of Sciencc degree in Ceramics, Massachusetts
Institute of Technology, 1950.
12 C. Zener, Elasticity and Inelasticity of Metals, p. 24. Univ.
of Chicago Press, Chicago, 1948. 163 pp.
I)ecexnhcr 1953 Thermal Stress Failure of Pure Rejructory Oxides 33 1
Table VI. Linear Coefficients of Thermal Expansion
( x10--6/OC.) f
l'etnp. ("(2.) Alumina Zirconia Magnesia

25 5.5 6.7 10.0

200 5.8 6.7 18.4
400 A.. .
_i 10. 6 13.4
so0 6.8 11.0 14.8
800 7.3 9.7 15.0
1000 8.5 12.0 15.7
1200 9.5 13.0 15.7
1300 10.0 9.0 15.7

Table VII. Thermal Stress Resistance at Steady State

AT for
Temp. fracture K* Kt (cal./k,tC./ (I* 01'
("C ) PC ) ("(2.) ("(2.) cm./sec.) (cal./cm./sec.)

Alumina ( S = 0.82)
200 85 104 103
__
390 6.5 79 75 0.0239 1.8 1.7
590 65 79 76 ,019 1.5 1.4
815 85 104 92 ,016 1.6 1.5
970 60 73 86 ,014 1.1 1.2
1000 75 91 83 ,014 1.3 1.2
1000 60 73 72 ,014 1.0 1.0
1200 50 61 70 ,014 0.84 0.98
1410 110 135 130 ,013 1.7 1.7

Zirconia ( S = 0 . 9 1)
190 185 204 177 Temp. ("C.)
205 116 127 172
3tL5 100 110 113 0050 0 55 0 57 Fig. 1 1. Thermal expansion curves.
.545 93 106 115 0029 0 51 0 83
865 85 94 107 0046 0 43 0 49
915 95 105 102 0046 0 48 0 47
970 55 61 92 0045g 0 27 0 41
1060 55 fil 73 0044 0 27 0 33
12:30 105 1I f i 100 00435 0 50 0 43
Magnesia ( S = 1 . 0)
:MI 50 50 45 .029$ 1.4 1.3
970 (55 65 45 ,014 0.91 0:fi3
1300 90 90 100 ,012 1. 1 1 .2
* Values obtained from thermal stressing tests.
t Values calculated from physical propert-ies.
1 Persorial cotiixnuiiic.:Ltiori from M. Ad:tms, Ceramics Labo-
ratory, Mass:~cliusett s Iiistit utc: oi Tcchnology, September 1050.
8 Isxt rapolated d u e s . Magnesia' uo
tlic teinpcrature, stress, and rate of loading. At low tenipera-
Zirconia
tures the rate o f loading and magnitude of stress had a negli-
I I
gible effect. Abow approximately 100OOC. for magnesia 1 I I

Oh0 600 1000 I400

and 1200OC. for alumina and zirconia the rate of loading did
influence results, and increasingly with larger stresses and
higher temprrntures. It should be recognized, therefore, that
the moduli of elasticity reported here correspond to specific
testing conditions.
Temp. ("C.)
Fig. 12. Thermal stress fracture resistance o t steady state. ( N o t e Curves
represent values calculated from physical properties and points are results
o f thermal stressing tests.)

The modulus of elasticity of zirconia showed an anomalous

behavior. Moduli values of newly formed specimens followed
the lower curve in Fig. 9 until approximately 80U0C., where a
discontinuity occurred. When the same specimcns were re-
tested below this temperature, or fresh specimens were first
hcated above 80OOC. and then tested at lower temperatures,
the vahies followed the upper curve continuously.
After heating above 8OO"C., the material changed its
color from light orange to brown. T o check for it phase in-
version, light and dark saniples of the zirconia were analyzed
by X-ray diffraction. The two patterns appeared to be identi-
cal, revealing approximately less than 10% of the monoclinic
form of zirconia in the predominating cubic structure. Al-
though not detected, small amounts of the zirconia may still
have been undergoing a phase inversion. A petrographic ex-
amination of thin sections of both types of samples showed
high birefringence, extinction under crossed Nicols, and pro-
nounced grain boundaries. For predominately cubic struc-
tures, extinction under crossed Nicols suggested that the crys-
tals might have been in a very strained condition, which also
may have led to the anomality in elastic behavior.
(H) Poisson's Ratio: Poisson's ratio was calculated, ac-
cording to equation (lo), to be approximately 0.35 for magne-
sia a t temperatures up to 1000°C. At higher temperatures
the increasing inelasticity of magnesia made further evalua-
tions dubious. Since Poisson's ratio was found to be nearly
constant for temperatures below plastic regions for magnesia,
values for alumina and zirconia were determined only at 25OC.
and were also considered to be constant, The results are
given in Table IV.
332 Journal of The American Ceramic Society-Schwartz Vol. 35, No. 12

t
z
2
u)
z
W
t-

z
2
rn
u)
W
a
a
TEMPERATURE 8

W
f
a:
3
Fig. 14.
AT/t (“C./sec.)
Effect of transient temperature distributions on ATrequired
for thermal stress failure.

l-
a
LT
A (11) Thermal Expansion: The thermal expansion curves
of alumina, stabilized zirconia, and magnesia are shown in
W Fig. 11. The linear coeflicients of thermal expansion, cal-
a culated from the slopes of these curves, are given in Table VI.
2 The erratic behax-ior in the expansion of the stabilized zir-
W conia also indicates the presence of some of the monoclinic
k form.
(2) Thermal Stress Failure Tests
( A ) Tkevmal Stress Resistance at Steady State: The results
obtained for the resistances of the oxides by both methods of
approach used are given in Table VII. In Fig. 12 the Q
values calculated from the physical properties are shown as
continuous curves. Tlie respective @ values obtained from
the thermal stress failure tests are represented as points.
The results show that the thernial stressresistanceof the three
oxides was temperature dependent. This is riot an entirely
INNER OU~ER new concept, as the themial sliock sensitivity of silica at cer-
SUR FACE SURFACE tain temperatures, owing to its inversions, has long been
( B) known. For alumina, however, there were no drastic prop-
erty changes to arouse suspicion of increased spalling sensitiv-
Fig. 13. Schematic temperature and stress distribu- ity for any particular temperatiire. The existence of such
tions in a hollow cylinder. ( A ) Heated from inner sur- regions appeared to depend on the relative clianges of all the
face; ( 8 ) heated and then cooled from outer surface. physical properties with changes in temperature. The coef-
Solid lines = steady state; dashed lines = a transient
condition. ficient of thermal expansion increased, and the thermal con-
ductivity and strength decreased with increasing tempera-
tures, thereby contributing to a continuously decreasing re-
sistance. With rising temperatures, however, this trend was
abated by a decreasing modulus of elasticity. Below 1000OC.
(C) Tensile Stxngtk: The tensile strengths of alumina, changes in expansion and thermal conductivity appeared to
stabilized zirconia, and magnesia, as measured in the trans- be the most influential factor. Decreased strength contrib-
verse rupture test, are given in Fig. 1 0 and ‘Rablc V. The uted to a maximum dip in the Q-temperature curve.
values agree generally with those found in the literature, with Finally, the increasing plasticity a t high temperatures caused
the exception of the lower strengths obtained for alumina at a reversal in the thermal stress resistance trend. This rapidly
temperatures below 1000°C. -1drop in the strength of increasing resistance at high temperatures suggests that there
alumina at approximately 500°C., indicated by the data of might be a critical temperature above which no cracking
Stavrolakis’8 and Iiy~chkewitsch,’~ was found to exist should occur; i.e., the stresses developed should be sufficiently
Zirconia showed a similar dip in its strength curve, which oc- relieved by plastic flow to prevent fracture. This tempera-
curred at about 300OC. ture region, however, was beyond the tempcrature limit of the
testing equipment for the oxides studied.
The general analysis applied to alumina was also indicated
1 3 J. A. Stavrolakis and 1‘. 11. Sorton, “Mcasuremcnt of Tor-
by the results for stabilized zirconia. The modulus of clastic-
sion I’roperties of Alumina and Zirconin at Elevated Tempera- ity of the zirconia spedniens, which were not reheated, was
tures,” J . A m . Ceram. Soc., 33 191 2fi3-68 (1950). used in the calculation of Q because the thermal stressing
l4 Eugen Kyschkewitsch, Oxydkcramik dei Einstoffsysteme
specimens corresponded to this condition. The anomalous
vom Standpunkt der l’hysikalischen Chemie, p 9 1. Springer-
Verlag, Berlin, 1948. 280 pp.; Cernni. Abstracts, 1949, Oct., p. behavior of this property was, therefore, reflected by de-
233g creased resistance above 800 “C.
December 1952 Thermal Stress Failure of Pure Refractory Oxides
Since a sufficient number of thermal stress failure tests with
alumina and zirconia established agreement between both
testing methods, only a few runs were made with magnesia.
A similar pattern was obtained for the thermal stress resist-
ance of magnesia. The upward swing in the resistance
started at the lowest temperature for the three oxides, owing
to the most plastic nature of magnesia. 3f00re’~suggested
that this condition might exist because magnesia has a cubic
structure and therefore many slip planes. Wygant,“ (a) cor-
relating the crystal structure of the refractory oxides with
their flow properties, found that a t 1300°C. and 1800 lb. per
sq. in. magnesia showed a creep rate more than twenty times
that of alumina, which has a hexagonal structure. This be-
havior is probably largely responsible for the difference in
slopes of the Q-teniperature curves of these two materials at
high temperatures.
An examination of Fig. 12 shows that a generalized com-
parison of the thermal stress resistances of different materials
is not necessarily rigid unless the temperature rebfion of frac-
ture is specified. For example, the order of decreasing
resistance at 1000°C. was alurniua, magnesia, aiid zirconia.
At 1300°C. the order became magnesia, alumina, and zir-
conia.
( B ) Spallbip Dit~’Z?zgTransient Stute: Spalling in serx-ice
may often occur during the building up of temperature gradi-
ents (i.e., transient or unsteady state). The steady state,
however, is important in that i t may represent the minimum
or maximum limiting condition for the stresses that cause
failure, depending on the shape and the mode of heating or
cooling a specimen.
For the hollow cylinder heated from the inner surface, the
steady state distribution for any given A T represented the
condition of maximum tensile stress a t the outer surface.
Fig. 13 ( A ) illustrates this point by showing schematically the
difference in the stress distribution for a steady state and a
transient state temperature distribution for the same AT.
Any transient state AT therefore should be greater than the
steady state AT required to cause thermal stress failure in the
same temperature range.
Thermal stress failure runs were made to determine the
necessary AT to cause fracture at various transient tempera-
ture distributions. The departure from steady state was rep-
resented by the slope of the AT-time curve (AT/t) at the
time of fracture. The results of these tests are shown in Fig.
14.
’The Poisson-Fourier equation, expressing temperature as a
function of radius and time only, states that the rate of tem-
perature change varies directly with the thermal diffusivity
of the material. The material with the highest thermal dif-
fusivity therefore should approach its steady state tempera-
ture distribution the fastest during transient heating. Fitz-
simmons’G found the thermal diffusivities of the three oxides
at -1-00°C. to be as follows: magnesia 0.031, alumina 0.023,
and zirconia 0.006 sq. cm. per second. This sequence is also
indicated by Fig. 14.
‘These results show the importarice of considering the shape
of a specimen and the mode of stressing in a thermal stress
failure analysis. Determining whether or not the hollow
cylinder would fail in the thermal stressing test was inde-
pendent of the rate of heating, in that failure could not occur
16 C. 13. Moore, “Some Iqactors Afkctirig Spalling of Fire-Clay
Brick,” Trans. Brct. Ceram. Soc., 48 [ 5 ] 176-85 (1949); Ceram.
Abstracts. 1950., ”Tan.. D. 8h.
l6 E. S. Fitzsimmons, “Thermal Diffusivity of Refractory
Oxides,” J. Am. reram. Soc., 33 [ l l ]327-32 (1050).
333
unless a temperature gradient equal to or greater than the
AT required for failure at steady state was achieved. There
are exceptions to this generalization, such as that due to
stress-duration cffects.17 Furthermore, a high thermal dif-
fusivity permitted a faster attainment of the maximum ther-
mal stresses for any given AT, although a high thermal eon-
ductivity contributed to a high spalling resistance.
The opposite case, when a steady state temperature dis-
tribution represents a minimum dangerous stress distribution,
may be illustrated in the thermal stress failure of the hollow
cylinders by first heating them uniformly and then cooling
from the outer surface. The transient temperature curve
then would have the steeper slope near the cooler surface
and, accordingly, a bg-eater tensile stress at the outer sur-
face,18as shown in Fig. 13 ( B ) . The investigations of Nor-
ton2 and Howie l 9 show that the spalling of brick is another
example; i.e., in the heating or cooling of a brick the shearing
or tensile stresses near the surfaces depend on the steepness of
the temperature gradient in these sections. In these cases
the respective curves for Fig. 14 should have negative slopes,
with the steady state AT a Inaximum. High diffusivities, then
permitting a rapid approach to the steady state, decrease
susceptibility to spalling during transient heating.
VI. Summary
The thermal stress analysis of hollow cylinders, heated uni-
formly from the inner surfaces in a radial direction, showed
that the thermal stress resistance of a material a t steady state
was expressed by the maximum heat ilow possible without
rupturing the piece. Furthermore, this heat-flow value rep-
resented the maximum dangerous stress condition for any
practical temperature distribution of a given AT and there-
fore could scrve as a guide in design work.
Since the refractory oxides studied behaved essentially as
homogeneous, elastic, and isotropic bodies, it was possible to
calculate the thermal stress resistance of the materials from
their physical properties. The close correlation of these re-
sults with the values obtained from thermal stressing tests
substantiated the analysis presented for the behavior of the
oxides.
I t should be emphasized that the thermal stress resistance
of a material could not be judged on the basis of any one prop-
erty, but only by the relative values of all pertinent properties.
High strengths, high thermal conductivities, low elastic con-
stants, and low thermal expansions Contributed to good ther-
mal stress resistance. These relationships for a material mere
not constant, but varied with temperature. The resistance of
alumina, stabilized zirconia, and magnesia decreased with in-
aeasing temperature until minima were reached at approxi-
mately 130Oo, I loo”, and 1000”C., respectively. Above
these sensitive regions, a continuing rise in resistivity was
found for each material. This trend was attributed to the
increased plasticity of the oxides a t high temperatures.
Acknowledgment
The author wishes to express his sincere appreciation for the
valuable suggestions and guidance given by F. IF. Norton aiid for
the financial assistance provided by the Bureau of Kaval Ord-
nance Contract NORD 9661.
l7 0. H. Clark, “Resistance of Glass to Thermal Stresses,” J .
Am. Ceram. Soc., 29 [ 5 ] 1:33-38 (1946).
la C . 13. Kent, “Thermal Stresses in Spheres and Cylinders
Produced by Temperature Varying with Time,” A p p l i e d Mech-
anics (Tyans. Am. Soc Mech. Engrs.), 54 [I81 185-96 (1932).
l9 T. W. Howie, “Spalling of Silica Brick.” Trans. Brit. Ceram.
Soc., 45 [2] 45-69 (1946); Ceran-t. Abstracts, 1946, Nov.. p. 195.