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November 1963
Table IV.
535
Constitution of NaP03-NaF Glasses with N a / P = 1.4, (6) = 5,to Na/P = 1.22, (n)* = 9 (Distribution of Total
Phosphorus in Weight Percent)
Na/P = 1.4
(El* = 5
-_-_-- -
Time of melting
(minutes)
N a / P = 1.33
(n)* = 6
Sodium
OMT*
Ortho$
Pyro
Tri
Tetra
Penta
Hexa
Septa
High fractions and
hypob
15
N a / P = 1.28
(?
=I
7 )*
__
_
p
i
7--
Sodium
N a / P = 1.22
(Z)* = 9
,---*_--_
Sodium
Sodium
glass?
OMT*
15
glass?
OMT*
15
glass?
OMT*
15
glass?
18.6
8.9
9.0
11.3
9.9
8.7
7.0
1.4
3.9
16.0
21.0
16.8
12.0
9.1
1.1
3.9
15.6
21.6
17.4
12.3
9.4
13.1
7.0
7.5
10.6
8.7
8.0
7.1
0.4
2.1
9.7
15.4
13.8
11.7
9.4
0.8
2.1
10.4
16.0
14.5
11.6
9.8
12.3
6.8
6.7
9.3
8.3
8.0
7.8
0.6
1.8
6.3
11.3
10.8
8.7
8.1
0.6
1.9
8.0
12.9
12.4
10.8
6.6
3.9
44
7.7
6.7
6.6
6.2
0.6
1.3
4.2
8.6
7.8
6.9
5.7
1.3
1.4
5.0
8.7
8.4
8.3
8.3
26.6
19.8
18.7
38.0
37.5
34.8
40.8
52.4
53.4
57.9
64.9
58.6
14.3
16.1
14.3
17.5
11.1
20.6
11.1
14.1
11.1
14.6
Theoretical (loo/(%)*)
20
20
20
16.7
16.7
16.7
14.3
Experimental5
36.2
23.1
22.7
29.8
18.4
19.2
28.5
* OMT = zero melting time (see text).
1Sodium phosphate glass with ii = 4 (after Westman and Gartaganis,footnote 3(b)).
$ Orthophosphate monofluoro-orthophosphate.
5 Obtained by estimating the chain length distribution in high fractions and hypoly.
The physical properties which affect the propagation of cracks in specimens fractured by
thermal shock are discussed. The driving force
for crack propagation is provided by the elastic
energy stored at fracture. The mechanism of
energy dissipation which will tend to arrest the
propagating cracks is provided by the effective
surface energy required to produce the newly
formed crack surfaces. An expression is derived
applicable to a body of spherical shape for the
mean area traversed by cracks nucleated by
thermal shock. Three numerical examples are
given for materials with widely different physical
properties, and their fracture behavior is predicted. Good agreement with experiment was
obtained. Thermal shock damage resistance
parameters suitable for the relative comparison
of the degree of damage to be expected in
materials fractured by thermal shock are proposed. The criteria for a low degree of
damage are high values of Youngs modulus of
elasticity, Poissons ratio, and effective surface
energy and low values of strength. Recom-
New
York
mendations are made for the selection of materials for severe thermal shock, where the best
materials available are known to fail.
1. Introduction
current theoretical treatment of the material properties which influence the thermal shock behavior of
brittle ceramic materials generally is based on those
material properties which affect the nucleation of fracture.
The procedure followed for given specimen geometry and
heat-transfer conditions is to calculate the resulting thermal
stresses. The specimen is considered to have failed when the
HE
.Xi
November 1963
4?rb3St2(1- v )
7E
= radius of sphere.
Si = tensile strength.
Y = Poissons ratio.
E = Youngs modulus of elasticity.
537
15 (a) C. F. YinP and R. Truell. Scatterinp of a Plane Longitudinal Wave by a Spherical Obstacle in- an Isotropically
Elastic Solid, J . Appl. Phys., 27 [9] 1086-97 (1956).
( b ) N. G. Einspruch, E. T. Witterholt, and Rohn Truell,
Scattering of a Piane Transverse Wave by a Spherical Obstacle
in an Elastic Medium, ibid., 31 [5] 806-18 (1960).
l6 M. G. Royston and L. R. Barrett, Some Observations and
Reservations on Thermal Shock Theory, Trans. Brit Ceram.
Soc., 57 [lo] 678-85 (1958); Ceram. Abstr., 1960, November, p.
271j.
D. P. H. Hasselman and P. T. B. Shaffer, Factors Affecting
Thermal Shock Resistance of Polyphase Ceramic Bodies,
Wright Air Development Division, WADD-TR-60-749 (Part
11),Contract AF33(616)-6806(February 1962). 155pp.
* The factor 2 is introduced since the quantity (ref?)
refers to
the effective surface energy of one side of the crack only.
538
and
RIII/
The parameter R can be used to compare the relative degree of damage of materials with similar crack-propagation
properties, i e . , the same values of (rcff).The parameter
R l l l l can be applied to compare the degree of damage of
materials with widely different values of (refJ,
such as brittle
and ductile materials.
111. Discussion
First, some remarks are in order concerning the use and
interpretation of thermal shock tests. As discussed in
Section I, the thermal shock resistance of a material can be
determined by two distinctly different methods By the
first method the degree of difficulty of nucleating fracture by
thermal shock is determined By the second method the
degree of damage by thermal shock after fracture has been
nucleated is measured. In reporting the relative thermal
shock resistance of various materials, it must be stated on
which basis the materials were judged. Ratings such as
poor, good, or excellent are useful only when regarded
in the proper light. Comparing materials judged on the
basis of the nucleation oi fracture with materials judged
on the basis of the degree of damage may lead to the completely erroneous selection of materials for thermal shock
applications. One of the favorite techniques of evaluating
relative thermal shock resistance is the thermal cycling of
small (approximately l/z by 1/4 by 3 in.) modulus of rupture
bars between room temperature and some other fixed temperature near 14OO0C. The strength of the bars after thermal
cycling is then compared with the original strength before
thermal cycling. It is clear that this test is useful only for
evaluating the relative degree of damage by thermal shock.
As soou as one or all of the materials being tested do not fracture, the results of the thermal cycling test become rather
meaningless, since no relative measure is obtained of the
degree of difficulty of nucleating fracture The danger
exists that the same thermal shock rating will be given to a
material in which no fracture is nucleated and to a material
which fractures very easily but in which the cracks are difficult
to detect The results of a thermal cycling test will be useful
only when used in conjunction with another thermal shock
test which indicates the relative degree of difficulty of nueleating fracture.
Since the terms thermal shock resistance or spalling
resistance are used indiscriininately to describe both the
nucleation of fracture by thermal shock and the degree of
damage by thermal shock, it is proposed here to refer to the
resistance to nucleation by thermal shock as thermal shock
fracture resistance or thermal stress resistance and to the
resistance to damage by thermal shock as thermal shock
damage resistance
Probably the most significant result of the foregoing theoretical treatment of crack propagation in a body subjected
to thermal shock is the conclusion that for a low degree of
damage there must be low values of strength and high values
of Youngs modulus of elasticity and Poissons ratio. Since
in previous theoretical treatments of the physical properties
affecting thermal shock resistance only those properties which
affect the nucleation of fracture by thermal shock were considered, most research efforts to improve thermal shock resistance have been directed toward improving strength and finding materials with low Youngs modulus of elasticity. Since
the improvement in strength which can be obtained for a
given material often is only marginal, for severe cases of thermal shock this approach frequently has led to more and more
disastrous results. In many cases it simply does not pay to
overcome the problem of failure by thermal shock by improving strength.
November 1963
%sti
(I
1/4
539
ramischen Masseii und Glasern und ihre Beziehung zur Temperatmwechselbestandigkeit von Schamottemassen (Impact
Bending Strength of Ceramic Bodies and Glasses and Its Relationshin to the Resistance to Thermal Shock of Fireclav Bodies).
Her. Deut Keram. Ges., 18 Ill] 465-89 (1937); Cevam. Abstr:,
17 [ll]354 (1938).
26 Shuzo Kato and Hiroshi Okuda, Relations Among Porosity,
Thermal Shock Resistivity, and Some Physical Constants of
Porcelain. N a ~ o v a Komo Giiutsu Shikensho Hokoku.. 8 .151.
37-43 (1659); d & m . Ab%., 1959, November, p. 287a.
zGH. M. Richardson, Choice of Refractories for Linings of
Blast Furnaces; pp. 13540 in Transactions of the VIIth
International Ceramic Congress, London, 1960. The British
Ceramic Society, Federation House, Stoke-on-Trent, 1961.
491 pp.; Ceram. Abstr., 1962, August, p. 204s.
27Y.Baskin, C. A. Arenberg, and J . H. Handwerk, Thoria
Reinforced by Metal Fibers, Am. Ceram. SOC.Bull., 38 [7]
34548 (1959).
28 J. R. Tinklepaugh, Metal Reinforcement and Cladding
of Cermets and Ceramics; pp. 170-80 in Cermets. Edited by
J. R. Tinklepaugh and W. B. Crandall. Reinhold Publishing
Corp., New York, 1960. 239 pp.; Ceram. Abstr., 1961, April,
p. 105a.
29 J. R. Tinklepaugh; private communication.
540
Table I.
Calculation of Area Traversed by Propagating Cracks ( A ) and Prediction of Type of Failure for Spheres 2 In. in
Diameter Fractured by Thermal Shock
27rStZ(1- v)b3
7NEr0.tt
.. . ~
Condition of failure: Calculated value of A greater than cross-sectional area of sphere (about 20 cmz)
General equation: A
Material properties
Youngs modulus ( E )
dyne cnir2 (psi)
Poissons rate ( u )
Effective surface energy
( Y r f i ) (ergs cm-*)
Calculated area traversed by
single crack ( A ) (cnia)*
~~~
Fireclay body P
Porcelaint
1.38 X loQ
(20,000)
2.07 X 1012
(30 X lo6)
0.25
2
10q
1.05 x 103
Complete failure
Complete failure
Yes
3.45 x 103
( 5001
3.45 x loll$
(5 x 106)
0,253
2
1.38 x 109
(20,000)
3.45 x 1012
(50 X 106)
0.25$
108
1033
4.0
Cracks arrested
Cracks arrested
Yes
1.22 x 10-2
Cracks arrested
Cracks arrested
Yes
t Footnote l(c).
$ Assumed values.
Footllotc 21.
I Footnote 28 and R. S.Truesdale, J. J. Swica, and J. R. Tinklepaugh, Metal Fiber Reinforced Ceramics, Wright Air Development
Center, WADC-TR-58-452, Contract AF33 (616)-5298 (December 1958). 36 pp.
IV.
The principal factors that affect the propagation and arresting of cracks were discussed. The driving force for crack
propagation is provided by the elastic energy stored at fracture. The mechanism which tends to arrest the propagating crack is provided by the effective surface energy that is
required to produce the newly formed crack surfaces.
An expression was derived for the mean area over which
cracks nucleated in a body of spherical shape will propagate.
This expression permits the prediction of whether failure by
thermal shock will be catastrophic or whether the cracks will
be arrested. Sample calculations were carried out for three
materials of widely different properties and their fracture
behavior was predicted. Good agreement with experiment
was obtained.
Thermal shock damage resistance parameters applicable to
a comparison of the relative damage to be expected in materials fractured by thermal shock were derived. The criteria For a low degree of damage are high values of Youngs
modulus of elasticity, Poissons ratio, and effective surface
energy and low values of strength. Examples were cited
from the literature and interpreted in terms of these criteria.
For cases of very severe thermal shock for which no materials
exist, in which fracture is not nucleated, it was recommended
that the selection of materials be based on a low degree of
damage.
Acknowledgment
The writer is indebted to his colleagues in the Physics Department of The Carborundum Company for many helpful discussions and for review of the manuscript.