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Table IV. 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
-_-_-- -
N a / P = 1.33 N a / P = 1.28 N a / P = 1.22
(El* = 5 (n)* = 6
- (? =I 7 )*
__ (Z)* = 9
(minutes)
Ortho$
-
Time of melting
~
OMT*
18.6
15
1.4
Sodium
glass?
1.1
_-pi
OMT*
13.1
-7--’
15
0.4
Sodium
glass?
0.8
OMT*
12.3
15
0.6
Sodium
glass?
0.6
,---*_--_
OMT*
6.6
15
0.6
Sodium
glass?
1.3
Pyro 8.9 3.9 3.9 7.0 2.1 2.1 6.8 1.8 1.9 3.9 1.3 1.4
Tri 9.0 16.0 15.6 7.5 9.7 10.4 6.7 6.3 8.0 44 4.2 5.0
Tetra 11.3 21.0 21.6 10.6 15.4 16.0 9.3 11.3 12.9 7.7 8.6 8.7
Penta 9.9 16.8 17.4 8.7 13.8 14.5 8.3 10.8 12.4 6.7 7.8 8.4
Hexa 8.7 12.0 12.3 8.0 11.7 11.6 8.0 8.7 10.8 6.6 6.9 8.3
Septa 7.0 9.1 9.4 7.1 9.4 9.8 7.8 8.1 6.2 5.7 8.3
High fractions and
hypob 26.6 19.8 18.7 38.0 37.5 34.8 40.8 52.4 53.4 57.9 64.9 58.6
No. of molecules per 100 phosphorus atoms
Theoretical (loo/(%)*) 20 20 20 16.7 16.7 16.7 14.3 14.3 14.3 11.1 11.1 11.1
Experimental5 36.2 23.1 22.7 29.8 18.4 19.2 28.5 16.1 17.5 20.6 14.1 14.6
* 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.
to the present data on the loss of fluorine at these temperatures not due to the presence of fluorine but to the introduction of
their melts should not contain any fluorine; indeed, some of additional Nal+ ions into the melt and the consequent in-
their experiments on the loss of fluorine from melts showed crease in Na/P ratio.
that although 4 wt% of NaF was added to the composition, Acknowledgment
only 0.01% fluorine remained in the glass. Hence, the The writers wish to acknowledge the many helpful discussions
structure breakdown observed by Williams et aZ.2(b)s (c) is with A. E. R. Westman and his continued interest.
The physical properties which affect the prop- mendations are made for the selection of ma-
agation of cracks in specimens fractured by terials for severe thermal shock, where the best
thermal shock are discussed. The driving force materials available are known to fail.
for crack propagation is provided by the elastic
energy stored at fracture. The mechanism of
energy dissipation which will tend to arrest the 1. Introduction
propagating cracks is provided by the “effective HE current theoretical treatment of the material prop-
surface energy” required to produce the newly
formed crack surfaces. An expression is derived
applicable to a body of spherical shape for the
T erties which influence the thermal shock behavior of
brittle ceramic materials generally is based on those
material properties which affect the nucleation of fracture.
mean area traversed by cracks nucleated by The procedure followed for given specimen geometry and
thermal shock. Three numerical examples are heat-transfer conditions is to calculate the resulting thermal
given for materials with widely different physical stresses. The specimen is considered to have failed when the
properties, and their fracture behavior is pre-
dicted. Good agreement with experiment was
obtained. Thermal shock damage resistance
parameters suitable for the relative comparison Received December 6, 1962; revised copy received June 12,
1963.
of the “degree of damage” to be expected in This work was based on an investigation sponsored by the
materials fractured by thermal shock are pro- United States Air Force under Contract No. AF33(616)-6806.
posed. The criteria for a low degree of A t the time this work was done, the writer was physicist,
damage are high values of Young’s modulus of Applied Research Branch, Research and Development Division,
The Carborundum Company. He is now a graduate student,
elasticity, Poisson’s ratio, and effective surface Department of Mineral Technology, University of California,
energy and low values of strength. Recom- Berkeley, California.
.Xi Journal of The American Ceramic Society-Hasselman Vol. 46, No. 11
thern-a1 stresses exceed the tensile strength. Based on this fore is not governed by those physical properties which affect
criterion of failure, expressions are derived for the maximum the nucleation of cracks but by those physical properties
thermal shock to which a body of given shape can be subjected which affect the propagation of cracks once nucleated.
in terms of the material properties and heat-transfer param- It is the purpose of the writer t o discuss the principal ma-
eters.’, * terial properties which affect the propagation of cracks under
Materials with good resistance to fracture by thermal shock conditions of thermal shock. From these material properties,
are characterized by high values of strength, thermal con- “thermal shock damage resistance parameters” are derived,
ductivity, and thermal diffusivity and low values of Young’s which are indicative of the relative resistance of materials
modulus of elasticity, Poisson’s ratio, coefficient of thermal to damage after fracture by thermal shock has been nucleated.
expansion, and emissivity. For the verification of the de- The application of these parameters to the design of materials
veloped theories a number of investigations have appeared for thermal shock and to the interpretation of thermal shock
in the I n the experiments accompanying the tests is illustrated.
theoretical approach the severity of thermal shock is adjusted
to the material under study. II. Theoretical Considerations
In summary, thc approach to the theoretical treatment of The energy criteria which affect the propagation of cracks
thermal shock resistance is based on the determination of the consist of (a) the elastic energy stored in the body being
physical properties and heat-transfer variables which govern fractured which provides the driving force for crack propaga-
the nucleation of fracture only. tion and (b) the various mechanisms which dissipate energy
In industry, however, particularly in the evaluation of the and which tend to slow down or to arrest the propagating
thermal shock behavior of firebrick, thermal shock tests are crack; these mechanisms can be grouped together under the
employed which are based on a constant-temperature dif- heading7 “effective surface energy.”
ference and heat-transfer mechanism. Different materials The criterion for crack nucleation or propagation is pro-
therefore are subjected to a thermal shock of the same vided by Griffith,s who states that a crack will start propa-
severity. The relative thermal shock resistance of the ma- gating and will continue to propagate as long as the elastic
terials studied is then evaluated by measuring the relative energy released from the stress field surrounding the crack is
eflect of thermal shock on the physical properties or physical as great or greater than the energy required to supply the
condition of the specimen. For instance, for a given number effective surface energy. A propagating crack which is
of cycles the percentage loss of eight,^ percentage loss of being slowed down can also derive energy from the stress
~ t r e n g t hor
, ~the change in permeability5 may be determined. wave (the kinetic energy) accompanying the crack. An
The number of cycles required to produce a given change in exact calculation of the energy balance a t any time during the
strength5 (or complete failure) or to produce a crack of given propagation of a crack in a finite body fractured by thermal
widthGmay also be determined. shock is mathematically prohibitive, if not impossible. It
These thermal shock tests do not indicate whether a given is reasonable to assume, however, that the distance (or area)
test will nucleate fracture but indicate the “degree of damage” over which the crack will propagate is directly proportional
which will result from fracture by thermal shock. The rela- to the elastic energy stored a t the time of fracture, i.e., a t
tive thermal shock resistance of the materials studied there- the time the cracks were nucleated. The same conclusion
was also reached by Kingery.lcb) Since fracture by thermal
shock generally takes place in the absence of external body
forces, the energy absorbed during the process of crack prop-
agation is supplied by the elastic energy stored in the body
only. In the following discussion, the absence of external
( a ) W. R. Buessem, “Die Temperaturwechselbestandigkeit body forces is always assumed.
keramischer Massen” (Resistance of Ceramic Bodies t o Tem-
perature Fluctuations (Spalling)), Sprechsaal, 93 [6] 137-41 The material properties which govern the elastic energy
(1960) a t fracture and their relation can be established by con-
( b ) W. D. Kingery, “Factors Affecting Thermal Stress Re- sidering a sphere subjected to thermal shock by heating.
sistance of Ceramic Materials,” J . Am. Ceram. Soc., 38 [l]3-15 At the time of maximum stress the temperature distribution
(1955).
(c) W. B. Crandall and J . Ging, “Thermal Shock Analysis of to a good approximation can be considered to be parabolic.
Spherical Shapes,” ibid., pp. 44-54. From this temperature distribution the thermal stresses can
* Listing all the references for theoretical investigations be c a l ~ u l a t e d . ~Since a t fracture the maximum thermal stress
of thermal shock resistance is beyond the scope of this paper.
The references cited should be regarded as typical examples
only.
( a ) Bernard Schwartz, “Thermal Stress Failure of Pure 6R. Fourneau, P. Lapoujade, and L. Fredholm, “fitude
Refractory Oxides,” J . Am. Ceram. Soc., 35 [12] 325-33 (1952). Comparative, Experimentale et Statistique de Diverses Mkthodes
( b ) W. R. Buessem and E. A. Bush, “Thermal Fracture of EuropCennes d’Essais de Chocs Thermiques” (Comparative,
Ceramic Materials Under Quasi-Static Thermal Stresses (Ring Experimental, and Statistical Study of Various European
Test),” ibid., 38 111 27-32 (1955). Methods of Measuring Resistance to Thermal Shock); pp.
( 6 ) D. P. H. Hasselman, “Thermal Shock by Radiation Heat- 207-20 in Transactions of the VIIth International Ceramic
ing,’’ibid.,46 [51 229-34 (1963). Congress, London, 1960. The British Ceramic Society, Fed-
( d ) D. P. H. Hasselman and W. B. Crandall, “Thermal Shock eration House. Stoke-on-Trent. 1961. 491 D W . : Ceram. Abstr..
A. I
General equation: A =
27rStZ(1- v)b3
~~~
7NEr0.tt
.. . ~
Condition of failure: Calculated value of A greater than cross-sectional area of sphere (about 20 cmz)
Alumina reinforced by molybdenum
Material properties Porcelaint Fireclay body P fibers11
shock fracture resistancc as well as high thermal shock dam- elasticity, Poisson’s ratio, and eniissivity and high values of
age resistance. strength and thermal conductivity. Since the avoidance of
Since the probability that a crack will completely traverse fracture by thermal shock is always desired, this is the direc-
a body will depend on the ratio of the total elastic energy tion which should always be pursued first. For those cases of
stored at €racture to the cross-sectional area of the body, severe thermal shock where even in the best materials avail-
it is clear that the larger the body undergoing fracture by able fracture will be nucleated, the selection of materials
thermal shock, the greater becomes the degree of damage. should be based on a low degree of damage, which is dictated
An increase in thermal shock damage resistance therefore can by low values of strength and high values of Young’s modulus
be attained simply by decreasing the body size. of elasticity, Poisson’s ratio, and effective surface energy.
Since it has been shown that the effective surface energy The approach of a low degree of damage should always be
can play a significant role in the fracture behavior of materials accompanied, however, by a search for, or development of,
subjected to thermal shock, it is suggested that greater em- those materials which will resist the nucleation of fracture by
phasis be placed on the quantitative determination of the thermal shock.
mcchnnisrns by which energy is dissipated during crack prop-
agation In this manner, more accurate values for (rcff) IV. Summary and Conclusions
are obtained with the result that the fracture behavior of brit- The principal factors that affect the propagation and ar-
tle materials subjected to thermal shock can be predicted resting of cracks were discussed. The driving force for crack
with greater accuracy Ways also may be developed by propagation is provided by the elastic energy stored at frac-
which the effective surface energy can be increased Incor- ture. The mechanism which tends to arrest the propaga-
porating into thc brittle ceramic matrix a continuous or dis- ting crack is provided by the effective surface energy that is
persed relatively ductile phase will increase the value of required to produce the newly formed crack surfaces.
(-y.rf) and thereby can lead to an increase in thermal shock An expression was derived for the mean area over which
damage resistance. The same result is obtained by increasing cracks nucleated in a body of spherical shape will propagate.
the degree of anelasticity of the material. Of course, an This expression permits the prediction of whether failure by
increase in plasticity or anelasticity also will lead t o an in- thermal shock will be catastrophic or whether the cracks will
crease in thermal shock fracture resistancz. be arrested. Sample calculations were carried out for three
The foregoing results and conclusions should be regarded materials of widely different properties and their fracture
as valid only for the first cycle of thermal shock. It is en- behavior was predicted. Good agreement with experiment
tirely possible that crack propagation on subsequent thermal was obtained.
cycles is again governed by those physical properties which Thermal shock damage resistance parameters applicable to
affect the nucleation of fracture. Also, during the time of a comparison of the relative damage to be expected in ma-
thermal cycling, the chemical properties of the material at terials fractured by thermal shock were derived. The cri-
the tip of the crack may change, owing to the adsorption OF teria For a low degree of damage are high values of Young’s
gases on the surface This will affect the value of (reff) modulus of elasticity, Poisson’s ratio, and effective surface
and could lead to further crack propagation. During the energy and low values of strength. Examples were cited
cycling treatment, small particles of material may become from the literature and interpreted in terms of these criteria.
dislodged, enter the crack, and gradually widen the cracks For cases of very severe thermal shock for which no materials
by means of a “wedge action.” The presence of the cracks exist, in which fracture is not nucleated, it was recommended
also may affect the temperature distribution considerably. that the selection of materials be based on a low degree of
Rased on the theories advanced in this paper, two direc- damage.
tions can now be taken in the selection of materials for ther-
Acknowledgment
mal shock applications. The criterion of lack of nucleation
The writer is indebted to his colleagues in the Physics Depart-
of fracture by thermal shock dictates the selection of materials ment of The Carborundum Company for many helpful discus-
with low coefficients of thermal expansion, Young’s modulus of sions and for review of the manuscript.