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Toughening of ceramic earthenwares by quartz inclusions: An ancient

art revisited

Article in Acta Metallurgica et Materialia · August 1995

DOI: 10.1016/0956-7151(95)00006-H

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 Acta metall, mater. Vol.43, No. 8, pp. 2959-2965, 1995
ElsevierScienceLtd
~ Pergamon 0956-7151(95)00006-2 Copyright © 1995.Acta MetallurgicaInc.
Printed in Great Britain.All rights reserved
0956-7151/95$9.50+ 0.00

TOUGHENING OF CERAMIC EARTHENWARES BY

QUARTZ INCLUSIONS: AN ANCIENT ART REVISITED
V. KILIKOGLOU,G. VEKINISand Y. MANIATIS
Institute of Materials Science, NCSR "Demokritos", 15310Athens, Greece

(Received 3 August 1994; in revised form 16 December 1994)

Abstract--Since ancient times randomly distributed quartz is routinely included in ceramic earthenwares
as an aid to drying. Although it has been noticed that this practice also provides the ware with higher
capability for flaw tolerance so that a crack does not become readily unstable in the event of overloading
during service, no systematic study of the effect or a satisfactory model has been reported in the open
literature. This work reports the results of such an investigation on the influenceof grain size and volume
fraction of quartz on the elastic modulus, strength and fracture energy dissipation of such composites
based on fired clays. In addition, we have studied the fracture micromechanismsby dynamic in situ optical
microscopy and scanning electron microscopy and introduced a simple model to explain the results, based
on the local effects of the stress field of the inclusions.

INTRODUCTION significantly" the properties of dried clay from

Intentional tempering of clay--the mixing-in of other
materials--was common practice in antiquity,
especially when large vessels were to be made. Potters
had many reasons to temper; the most important
were reduction of shrinkage during drying and firing,
promotion of uniform drying of vessels and improve-
ment of thermal shock resistance during firing [1].
However, tempering enhanced the mechanical prop-
erties of the final products and, although the under-
lying details were probably not understood, the
practice was widespread which underlined its inherent
usefulness. For example, potters were aware of the
fact that tempering prevented ceramic vessels failing
catastrophically and therefore they were able to
repair pots with long cracks [2]. In modern times too
the use of tempering as a drying agent is well known
in the heavy clay industry. Sand or a "lighter" type
of clay (highly caicarous), is routinely mixed with the
base clay, up to about 20% vol. fraction. This import-
ant technological advantage of tempering is con-
sidered highly relevant to present technological needs
and is therefore at the core of this investigation.
Nevertheless, even though this practice is wide-
spread, its impact on the mechanical properties, as far
as we can ascertain, has never been properly investi-
gated. The effect of various non-plastic additives on
some physical and mechanical properties of fired
clays (earthenwares) have been reported in the litera-
ture mainly in the form of a few semi-quantitative
observations. It is generally accepted that all such
additives affect the performance of clays and ceramics
in a similar way that they affect the properties of
cements: sand with grain size 500-1000/~m and
30% vol. fraction has been reported to "increase
Fayoum in Egypt [3], while small additions of saw-
dust ( < 2 wt%) improve the compressive strength of
some non-calcereous clays from Nigeria [4]. More
relevant is a single study on archaeological pottery [5]
which considers enhancement of crack propagation
resistance but the results are mainly used to explain
pottery function.
In this paper we present the results of a systematic
study of the dependence of the elastic and mechanical
properties of such composites on size and volume
fraction of quartz and in particular the conditions
under which fracture energy is maximised. Specifi-
cally, we have studied the effect of quartz as temper,
on the fracture strength and toughness (energy dissi-
pation) of quartz-tempered fire clays, through a series
of experiments on experimental briquettes. In
addition, elastic modulus, density, shrinkage and
unfired composite properties were also determined.
EXPERIMENTAL
Processing
The experimental briquettes were manufactured
using a calcerous clay containing 15% CaO from the
area of Pikermi in Attica, Greece, normally used by
the brick industry. Such calcareous clays are known
to display excellent postfiring properties [6]. The clay
was fractionated in the laboratory and a fraction with
grain size < 30/zm was received and used as the
matrix material for all specimens. It was mixed with
naturally weathered sand (99.5% SiO2) of four differ-
ent average grain sizes: d = 750, 400, 250 and 100 pm
in volume fractions of Vr= 5, 10, 20 and 40% for
each grain size. The 750/~m-40% combination was
not included because the fired briquettes were too

2959
2960 KILIKOGLOU et al.: TOUGHENING OF EARTHENWARES BY QUARTZ
weak to test accurately. In addition, a number of
briquettes were made from the matrix clay alone
containing no additional quartz. In this way a total
of 16 different powder mixes with all combinations of
variables were prepared. Water was added to the
mixes to provide plasticity and briquettes of size
100 × 60 x 10mm were produced by uniaxial com-
paction at a pressure of approx. 100 kPa. They were
air-dried for over 72 h at ambient temperature and
humidity and fired at 950°C in air with a heating rate
of 200°C/h and a soaking time of 1 h. This firing
schedule was dictated by previous work [6] which
showed that fine calcareous clays exhibit a homo-
geneous and reproducible cellular microstructure at
firing temperatures between 850 and 1050°C as a
result of the development of an extensive glass
filament network which is formed around the voids
created at an earlier stage by the liberation of CO2
from CaCO3. After firing, the large surfaces of the
briquettes were made parallel to approx. + 10 #m by
surface grinding with a 1200 carborundum wheel and
cut by a diamond wheel to produce test specimens of
size 10 x 10 × 60 mm.
Characterisation
Performance of structural materials such as heavy
clays is critically dependent on their mechanical
properties. Whether these clays are used in construc-
tion or in manufacturing of vessels, the properties
that are decisive in determining the material's efficacy
are its strength and, most importantly, its capacity for
absorbing energy during fracture, measured by the
fracture energy G.
The fracture energy G can be defined as the
total energy required to produce a unit area of
fracture surface. In the case of the homogeneous,
truly brittle materials, which exhibit unstable crack
propagation, it can be determined by measuring the
"critical strain energy release rate", i.e. the toughness
G1¢, given by
Gtc=KUE (1)
where K~c is the fracture toughness of the material as
measured using standard fracture mechanics methods
and E is its Young's modulus. For such materials
energy is expended in breaking atomic bonds and G1¢
can be considered to be the intrinsic fracture energy
7. In the case of composites Glc can be considered as
the fracture energy of the matrix.
By contrast, where the presence of various micro-
structures causes stable crack propagation, G cannot
be calculated using equation (1). In such cases the
total fracture energy is given by 7 -I-energy dissipa-
tion Gd. Gd is the energy dissipated during fracture
and appears on the load-displacement curve as the
region of stable crack propagation, and is best
measured by the total area under the stable part
curve.
Preliminary investigations showed that all
materials containing more than about 10% quartz
grains failed in a stable manner. Therefore, in these
cases the total energy G could be calculated as the
total area under the load-deflection curve. For spec-
imens that contained 10% or less quartz grains and
which displayed unstable fracture, their fracture
toughness K~c and Young's modulus were measured
independently, from which Glc was then calculated
using equation (1).
K~c was measured in 4-point bending of straight-
edge-notched-beam (SENB) specimens using the
analysis of Srawley [7]
3 P f ( S a - S2)x/~tF(~ )
(2)
where F(~) = 1 . 1 2 2 - 1.121~ + 3.74~ 2 + 3.873~ 3 -
19.05~ 4 + 22.55~ 5 and ~ = t/dand the dimensions S~,
$2, d, b and t are shown in Fig. 1.
The load at fracture, Pc, is determined at the
maximum point of the load~leflection curve for the
specimens. However, a notch introduced by diamond
cutting does not offer an atomically sharp crack as
assumed in the analysis. This exaggerates the value of
K~c as shown by the results of Munz et al. [8]. A
conservative value was therefore obtained by dividing
the result by a factor of 1.25.
In order to avoid loading misalignments, the spec-
imens were prepared as follows: after diamond sec-
tioning from identical fired briquettes the rectangular
beam specimens were ground parallel and polished on
a 1200 carborundum polishing wheel. Their edges
were slightly rounded to avoid stress concentrations
during loading and the notch was diamond machined
using a 0.15 mm thick wafering blade on the centre of
a surface normal to the original pressing direction. In
all cases the specimen dimensions were kept close to
10 × 10 x 60 mm. This size was chosen to minimise
shear stresses during loading while ensuring that a
statistically adequate number of quartz grains were
included in the eventual fracture surface. The notch
depth was kept close to 2 mm to avoid edge stress
effects during testing.
The testing configuration is shown in Fig. 1. A
prepared notched rectangular beam was loaded in a
self-aligning 4-point bending jig on an INSTRON
1195 100 kN testing frame at a constant loading rate
of 50#xm/min and the load was monitored as a
P/2 $2 P/2
P/2 S1 P~2
Fig. 1. Schematic diagram of the SENB fracture toughness
testing method in 4-point bending.
 KILIKOGLOU et al.: TOUGHENING OF EARTHENWARES BY QUARTZ
function of deflection. The outer loading points were
spaced at $1 = 40.8 mm and the inner loading points
had a span $2 = 20 mm. The estimated measurement
accuracy was +2.5/zm (,,,1%) for deflection
measurements and +2.5 N ( ~ 1%) for load measure-
ments. The experimental conditions used, especially
the specimen size, rigidity of frame and strain rate are
known to influence significantly the fracture
behaviour of toughened brittle materials: small spec-
imens require very low loading rates which would
enable accurate load-deflection monitoring during
crack propagation.
The calculation of Gt¢ from equation (1) and the
analysis of fracture energy dissipation requires
knowledge of the mechanical and elastic properties of
the material under identical loading configuration.
Thus Young's modulus E was measured from the
same load~leflection curve obtained from the bend-
ing experiments. This was carried out by measuring
the gradient of the curve at the stage just prior to
fracture initiation and calculating E using standard
beam deflection theory [10]. Independently, for
confirmation, E was also measured in compression
(for specifically prepared rectangular parallel sided
specimens) and by the ultra-sonic time-of-flight
method with comparable results.
Finally, transverse rupture strength (TRS) was
measured in order to obtain information on the
influence of quartz and relate the strength of
the specimens to their flaw size and fracture energy.
The tests were carried out on unnotched but identi-
cally prepared and sized specimens as used for
the SENB tests, using 3-point bending to minimise
possible misalignment effects. The calculation of TRS
was done using the standard bending mechanics
analysis
3PfSl
TRS = (3)
2bd 2
where the parameters are defined in Fig. 1.
All other loading and testing parameters were
identical to those used in the SENB tests. TRS was
taken as the average of at least seven experiments.
The variability of measurements in tempered speci-
mens was found to be significantly lower than in
untempered ones, probably due to the beneficial
presence of the equi-sized quartz inclusions.
0%.
5%
A 10%
o 0/A4 0.
Displacement
Fig. 2. Typical load-displacement curves for a series of
specimens with a range of Vf for d = 400 #m.
2961
The micromechanics of fracture were investigated
by dynamic in situ microscopy. A video camera and
colour monitor were used to observe and record
the fracture process at magnifications up to 100
times. This, in conjunction with a fast video printer
provides the possibility of monitoring the progress
of fracture and allows correlation with the load-
deflection curve in real time. In addition, scanning
electron microscopy (SEM) was used to study the
fracture surfaces and in particular the quartz-matrix
interfaces.
RESULTS AND DISCUSSION
Five typical load--displacement curves (SENB) are
shown schematically in Fig. 2 for specimens with
different Vf but same quartz inclusion size d
( ~ 4 0 0 # m ) . The shapes for other quartz inclusion
sizes are similar. As Vf increases the apparent post-
fracture behaviour of the material changes: for
Vf ~< 10% we have typical brittle ceramic behaviour
with sharp load drop at the fracture point but no
apparent energy dissipation after fracture initiation
was observed under the loading conditions used. On
the other hand, for values of Vf > 10% the material
displays pronounced crack stability giving fracture
energy dissipation as evidenced by the tail in the
curve after fracture initiation. In this case the crack
was observed to arrest soon after initial fracture and
to advance stably to the opposite edge of the speci-
men with increasing deflection. This was particularly
pronounced for Vf = 40%. SEM observations indi-
cated that crack arrest occurred at quartz-matrix
interfaces. It was also found that fracture behaviour
was independent of the quartz grain size. The
observed value of Vf for stable-unstable transition
(10--20%) is probably related to the stiffness of our
testing equipment. Nevertheless, the trend is clear: the
amount of energy dissipation during fracture
increases significantly with volume fraction.
The effect of quartz on Young's modulus is unex-
pected. Figure 3 shows that the Young's modulus
of the composites decrease significantly with increas-
ing Vf for all quartz sizes even though quartz has a
higher modulus than fireclay (Eq,ar~=80GPa,
Ec~,y= 22 GPa) and so, theoretically, the modulus of
25
I --e--- d=lOOpm
--II-- d=250pm
20
+d=4OOl.zm
d---X--
=750Hrmie
o i i i J i i i
5 10 15 20 25 30 35 40 45
Volume fraction, %
Fig. 3. Variation of Young's modulus with volume fraction
and size d of inclusions.
2962 KILIKOGLOU et al.: TOUGHENING OF EARTHENWARES BY QUARTZ

45
40 11111¸

35.
~. 3 0 . Opm !
25.
¢,~ 2 0 -
't5-
10.
5-

0 5 10 15 20 25 30 35 40 45
Volume fraction, %

Fig. 5. Variation of transverse rupture strength (TRS) with

Fig. 4. SEM micrograph of the material. Debonded inter-
faces between SiO2 inclusions and the matrix are clearly
visible.
the composites should increase [11-14]. A clue to this
behaviour is presented by the SEM micrograph of
Fig. 4 which shows a debonded quartz grain in the
clay matrix. As this was observed in most of the
specimens examined it appears that the inclusions
adhere very poorly to the matrix and, in many cases,
actually debonded from it. Such debonding between
the grains and the matrix is probably the result of the
large expansion accompanying quartz transformation
which takes place at about 580°C and which exerts a
tensile stress on the surrounding matrix prior to full
densification. On cooling an equivalent contraction
occurs and, as the fired matrix is unable to follow the
contraction, the net result is debonding and separ-
ation of the two phases, although the separation is
reduced a little by the larger thermal contraction of
the matrix (~ = 9 x 10-6°C -I) than that of the quartz
(g = 1.5 × 10-6°C-'). Direct confirmation of this has
been found by SEM observations, as shown in Fig. 4,
and by densitometry which showed that total poros-
ity increases with increasing quartz size and volume
fraction [15]. Such debonding has been observed in
many industrial fireclay products with quartz as the
drying agent.
The results suggest that, as far as elastic behaviour
is concerned, the material behaves like one containing
an equivalent population of pores of effective diam-
eter equal to that of the quartz inclusions. The elastic
behaviour of such materials has been analysed by
MacKenzie [16], who showed that the Young's
modulus of a material with a Poisson's ratio about
0.3, containing a population of closed pores of con-
stant diameter, can be described by an equation of the
form
E = Eo(1 - 1.9Vf + 0.9V 2) (4)
volume fraction and size d of inclusions.
equation implies that the modulus should be indepen-
dent of the pore size (the quartz grain size in our case)
as indeed appears from our results.
The TRS, as expected, decreases significantly with
increasing Vf but, in addition, appears to decrease
with increasing inclusion size d as well (Fig. 5). The
decrease is particularly pronounced for Vr=40%
where TRS is up to 75% lower. This trend is also
obvious in the curves of Fig. 2 where materials
displaying unstable fracture generally have much
higher strength than those displaying stable fracture
behaviour.
The total fracture energy G as a function of Vf is
shown in Fig. 6. It includes contributions from both
and Gd. As no toughening was observed for Vr = 5
and 10% we only have contribution from ~, whereas
for higher Vf there is substantial energy dissipation
Gd. For such a composite, ? depends mainly on the
microstructural nature of the matrix: intrinsic
strength of crystal planes (for transgranular fracture)
or the strength of the interfaces (for intergranular
fracture) [17]. Thus, ~ for these composites would be
expected to be equal to the matrix toughness G~¢ and
be constant. Our results show this: G~¢ was found to
be approximately constant in all cases, being in the
range of 25-35J/m 2 which is reasonable for the
matrix material. Close examination of the results in
Fig. 6 for Vf = 5 and 10%, reveals that, in fact, Gic
decreases slightly, a trend which is reproducible and
has been observed for higher values of Vf as well [15].
This is probably the result of significantly increased
porosity as shown in Fig. 7 ( V f = 4 0 % and
120
80
60

where E 0 is the modulus of the uncracked solid and

Vr is the volume fraction of pores. The relation is ~ 20 ~ ~
shown superimposed on the results in Fig. 3. It is
evident that the results are consistent with this 0 5 10 ~5 20 25 30 35 40
equation especially if one takes into account the Volume fraction, %
experimental error of such measurements and the Fig. 6. Total fracture energy as a function of volume
approximate nature of equation (4). In addition, this fraction and size d of inclusions.
 KILIKOGLOU et al.: TOUGHENING OF EARTHENWARES BY QUARTZ 2963

Fig. 7. Micrograph of a specimen with Vf=40% and

d = 400 #m showing the extensive network of cracks in the
matrix.

d = 400 #m). However, the total energy of fracture

(intrinsic toughness plus energy dissipation) increases
dramatically for Vf> 10%. The influence of the
quartz inclusions is thus significant: the total energy
dissipated during fracture increases nearly 4-fold at a
volume fraction of about 20%. After the maximum,
the total energy appears to decrease slightly, probably
due to the extensive damage observed and higher
porosity present at Vf = 40%.
The micromechanisms of toughening were studied
by dynamic in situ microscopy aided by subsequent
SEM of the fracture process. Figure 8 (Vr = 40% and
d = 250 #m) presents a sequence of micrographs of a
crack propagation during loading. A number of
events can be discerned: the crack propagates by
matrix cracking or along a debonded interface and,
in the case of low volume fractions of quartz, the
crack traverses large areas of matrix material before
meeting an inclusion. For large Vf, the crack "jumps"
easily from one inclusion to an adjoining one. These
fracture processes result in crack deflection and crack
bifurcation which interact to produce "bridges"
spanning the crack surfaces, a number of which are
visible in Fig. 8. In these cases, material, cracked Fig. 8. Sequence of micrographs from an in situ experiment
showing crack deflection and bifurcation as a result of
around its boundary but wedged or pinched into both crack inclusion interaction. Vf= 40%, d = 250 pm.
crack faces, does work against friction (sometimes
involving localised crushing) as it is pulled free. The
action of such energy dissipation mechanisms are turn is balanced by a hydrostatic tensile stress on the
known to result in R-curve behaviour (increase in matrix material around them. This results in matrix
toughness) which is more pronounced for higher microdamage and tensile residual stresses in the
populations of inclusions. It is significant that such immediate vicinity of the inclusions: the "damaged
energy dissipation mechanisms have been determined zone". On firing, this damaged zone is highly suscep-
recently to be responsible for R-curve behaviour in tible to cracking and, in conjunction with matrix-in-
monolithic alumina [9]. clusion debonding, defines an "effective flaw radius",
The energy dissipation observed in our experiments re~, over which the local stress falls to the fracture
can be modelled by considering what happens to the strength af, of the dried clay. An example of such
material during preparation. We start by considering damage in the vicinity of an inclusion is shown in
the effect of drying on the matrix integrity and Fig. 9. We can get a rough estimate of reefas follows:
generation of residual stresses and microdamage in we assume (reasonably, e.g. [10]) that the magnitude
the material: before drying the two phases are in of the stress a around a rigid spherical inclusion
intimate contact with one another. During drying, under hydrostatic pressure falls off as approx. 1/r 2,
however, the matrix contracts and exerts a hydro- from ao at the interface to a at distance r from the
static compressive stress on the inclusions which in inclusion. The fracture strength ar is given by
AM 43/8--F
2964 KILIKOGLOU et al.: TOUGHENING OF EARTHENWARES BY QUARTZ
Fig. 9. SEM micrograph of an inclusion-matrix interface.
Damaged matrix in the vicinity of a quartz grain is clearly
visible.
Ee(1 - Vr) where E is the Young's modulus of the
dried matrix, e the matrix shrinkage (strain) occurring
during drying and Vt is the volume fraction of the
inclusions whose presence reduce the effective shrink-
age by a factor of (1 - Vf). The extent of the damage
zone ten will then be given by the radius over which
tr falls to the fracture stress of the dried matrix a t. To
calculate this, we carried out a separate set of
measurements on dried untempered specimens and
determined the Young's modulus, the linear shrink-
age and the fracture stress. The results are shown in
Table I.
Using these results we calculate that a o ~
7 0 ( 1 - Vt). Matrix damage due to a stress a thus
becomes negligible when tr equals the fracture
strength, at = 8.4 MPa at r = reg from which the total
damaged area can be calculated. The values of Vf and
d define the number of inclusions N, intersecting the
fracture surface from which the total damaged area
can be calculated. The values for N, re~ and the ratio
A,~/A (where A is the actual fracture surface) for
Vr = 5, 10, 20 and 40% and for a nominal inclusion
size (400#m) are tabulated in Table 2. The table
shows that, at volume fractions up to 10%, the
effective damage area is a fraction of the total fracture
area providing limited crack deflection and energy
dissipation. At volume fractions greater than about
10% the individual stress fields of the inclusions begin
to interact strongly with the crack producing exten-
sive microcrack networks (Fig. 9), encouraging crack
deflection and bifurcation which increases energy
dissipation. At Vt> 20% the individual stress field
zones cover the whole of the specimen cross-sectional
area and thus the toughening effect at these levels of
Vf is constant. Adding more than about 20%
Table 1. Properties of dried matrix material (average of three
measurements)
Young's modulus, E (GPa) 3.37 _+0.4
Transverse rupture strength, TRS (MPa) 12.6 _+1.5
Estimated tensile strength, o'f (MPa)t 8.4 _+1.5
Ultimate compressivestress, UCS (MPa) 12.9 +_1.5
Linear shrinkage:~, e (%) 2 + 0.2
tCalculated as = TRS/1.5. 3~Untildry.
Table 2. Calculated values of N, deer,Acfr/A and d~aWspecimens with
inclusion size 400/am. Values for other inclusion sizes are similar
Damage zone Effectiveflaw
Number of radius r~ radius, rna.
Vr (%) particles(N) (/am) A,et/A (/am)
5 40 562 0.40 424
10 80 547 0.75 518
20 159 516 1.33 1872
40 318 447 1.99 6972
inclusions will not offer any further toughening but
will only serve to decrease the strength.
The variation of T R S with microstructure is con-
sistent with the previous model. Using the basic linear
elastic fracture mechanics equation for the fracture of
brittle materials, Klc = atsx/na, where a is the half-
diameter of the largest enclosed flaw, and taking
trts ~ TRS/1.5 [11] and K~c and E from the present
results, we find that the calculated flaw radius raw
(given in Table 2) is very close to ten as long as
Vf~< 10%. The value of rnaw for Vr~> 20% is much
larger probably due to the large overlap of the
individual stress fields.
F r o m our results, it appears that a volume fraction
of quartz inclusions around 20% is an optimum level
for toughness as G is maximised at the expense of a
reduction in T R S of about 40%. These results are
valid for the materials prepared in this work: hand-
pressure fabrication without pressure compaction etc.
Nevertheless, they reflect a definite trend on the
mechanical properties of such tempered earthen-
wares. The results may be different if the specimens
were to be prepared by uni-axial or even isostatic
compaction or extrusion as used in modern heavy-
clay industries. This is being investigated at present.
CONCLUSIONS
The incorporation of a random dispersion of
quartz inclusions in earthenwares (tempering)
appears to be an effective way of increasing the
toughness of the brittle matrix offering substantial
flaw tolerance. The mechanism of toughening is
frictional energy dissipation as a result of crack
deflection and bifurcation. This is aided by weak
interfaces and localised matrix damage introduced
during drying and firing. As a result, Young's modu-
lus and transverse rupture strength decreases but
toughness increases 4-fold compared to untempered
material. In the system studied here there appears to
be an optimum volume fraction of inclusions which
is independent of inclusion size around 20% above
which no further increase in toughness is found. The
results can be explained by considering the extent of
microdamage introduced in the matrix during drying
and firing due to the presence of the quartz
inclusions.
Acknowledgements--We would like to express our gratitude
to Professor M. F. Ashby for his incisive and helpful
comments and suggestions. We would also like to thank
Professor G. Tsamasfyros of the National Technical
 KILIKOGLOU et al.: TOUGHENING OF EARTHENWARES BY QUARTZ
University of Athens for permission to use his laboratory
equipment.
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