Materials Science and Engineering A 498 (2008) 208–215

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Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

Effect of the addition of mullite–zirconia to the thermal shock

behavior of zircon materials
N.M. Rendtorff ∗ , L.B. Garrido, E.F. Aglietti
Centro de Tecnologia de Recursos Minerales y Cerámica (CETMIC: CIC-CONICET-UNLP), Camino Centenario y 506. C.C.49 (B1897ZCA) M.B. Gonnet. Buenos Aires, Argentina

a r t i c l e i n f o a b s t r a c t

Article history: Ceramics and refractories are subjected to local temperature and atmosphere gradients due to the suc-
Received 18 February 2008 cessive application of heating cooling cycles, during service. These situations originate thermal stresses
Received in revised form 21 July 2008 that cause certain degree of damage to the material defining the potential usage of the refractory. The
Accepted 25 August 2008
favorable effect of the addition of a second phase for improving the thermal shock resistance (TSR) of
dense ceramics have been proved previously. However the addition must be controlled because it can
Keywords:
excessively affect the densification and microstructure. The objective of this work is to study the TSR of
Zircon
pure zircon ceramic materials and to quantify the influence of the addition of mullite–zirconia (MZ) grains
Mullite–zirconia
Composites in a range between 15 and 45 wt.%. Cool water quenching test was carried out on slip cast prismatic bars
Mechanical properties in order to study the TSR. For the thermal shock tests temperatures differences (T) between 200 and
Thermal shock resistance 1200 ◦ C were applied. The elastic dynamic modulus (E) was evaluated by the impulse excitation technique
as a function of the temperature difference of the quenching test. The decrease in the E modulus was also
correlated with the number of thermal cycles. The materials were characterized by density measurements
and mechanical properties. The XRD and Rietveld method were employed for determining the crystalline
phase composition. Finally, the microstructure of the materials was examined by SEM. Significant changes
in the E modulus were observed for T over 400 ◦ C for all composites studied.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction erties in structural applications and as an additive to other phases

forming a composite material [5–10].
Zircon (ZrSiO4 ) is good refractory material because it does The thermal shock resistance is improved by the deliber-
not undergo any structural transformation until its dissociation ate introduction of thermal stress concentrators in the form
at about 1700 ◦ C. It exhibits many attractive properties such as of microstructural inhomogeneities in the material. Thus, the
excellent chemical stability, a very low thermal expansion coef- dispersion of zirconia grains in a mullite matrix, an improved
ficient (4.1 × 10−6 ◦ C−1 ) from room temperature to 1400 ◦ C and low thermomechanical behavior is obtained as a result of microcracks
heat conductivity coefficient 5. 1 W/m ◦ C at room temperature and formation and by the dissipation of elastic energy related to zirconia
3.5 W/m ◦ C at 1000 ◦ C. martensitic transformation [11].
Sintered zircon with high purity can retain its bending strength The first approach to determine the thermal stresses of brittle
up to temperatures of 1200 and l400 ◦ C [1]. These properties make material is the thermo-elastic theory [12,13], which is focused in the
zircon a potential candidate as a useful structural ceramic, espe- initiation of the fracture. A second approach focuses on crack prop-
cially in such fields where a sudden change of temperature may agation for conditions of thermal shock more severe than those for
occur. These materials are widely used in the steel and glass indus- crack initiation [13]. A unified theory of the thermal shock resis-
tries [2–4]. The presence of impurities decreases the dissociation tance considering the initiation and crack propagation in brittle
and usage temperatures. Moreover, pure zircon dense materials ceramics was developed by Hasselman [14] who presented analyt-
degradation by a thermal shock is sometimes the limiting property ical solutions for the extent of the crack propagation as a function
for its applications. of the severity of the thermal shock. Therefore, several theoretical
On the other hand mullite–zirconia (MZ) electrofused powders, thermal shock parameters were proposed previously [15] to predict
commercially available, have demonstrated good refractory prop- the thermal shock resistance (TSR) of a certain material. These are
functions of the global properties of the material.
The principal objective of the present work is to study the
∗ Corresponding author. Tel.: +54 2214840247; fax: +54 2214710075. influence of the added amount of mullite–zirconia on the mechan-
E-mail address: [email protected] (N.M. Rendtorff). ical properties and the thermal shock resistance of dense zircon

0921-5093/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2008.08.036
 N.M. Rendtorff et al. / Materials Science and Engineering A 498 (2008) 208–215 209

materials. The elastic modulus (E) was the property chosen to ent T. Dilatometry of samples sintered at 1600 ◦ C was performed
follow the material damage. This can be done because E is related using a Netszch dilatometer up to 1400 ◦ C at a heating rate of
to the microstructure integrity, meaning the number, size and 10 ◦ C/min. The thermal expansion coefficient ˛ of these materi-
shape of cracks developed. E was measured by a dynamic method, als up to 1000 ◦ C was determined. Microstructural examination
using the impulse excitation technique (sonic velocity), that is was conducted with a scanning electron microscope SEM (Jeol
a simple and non destructive standard test [16]. In this way the JSM 6360 LV) after polishing the probes surface until to 1 ␮m dia-
severity of the treatment was studied by determining the relative mond paste. Flexural strength ( f ) was measured on the bars with
drop in elastic modulus after exposure at a given thermal cycle. rectangular section using the three-point bending test. (Universal
Also the retention of E was evaluated after application of repeated testing machine INSTRON 4483) 40 mm of span and a displacement
thermal cycles. Finally, the TSR was compared with the behavior rate of 2.5 mm/min were employed. The fracture toughness (KIC )
predicted from parameters R, R and Rst which were obtained and the fracture initiation energy ( NBT ) were evaluated by the
from the thermoelastic and energy balance theories respectively. single edge notched beam method (SENB) [10,20] using a three-
point bending universal testing machine. Samples of dimensions
(7.5 × 7.5 × 50 mm3 ) were notched with diamond saw of 0.3 mm
2. Experimental
thickness, with depth between 0.3 and 2.5 mm. The three-point test
was carried out at room temperature with a rate of 0.1 mm/min. In
2.1. Slip casting of dense zircon based materials
this method KIC is given by:
 C   C 2  C 3  C 4 
A commercial zircon powder was used as principal raw material. 3QLC 1/2
With: ZrO2 = 64–65.5 wt.%, SiO2 = 33–34 wt.%, Fe2 O3 ≤ 0.10 wt.% KIC = A0 + A1 + A2 + A3 + A4
2WD2 D D D D
and TiO2 ≤ 0.15 wt.%, specific gravity of 4.6 g/cm3 , melting point
of 2200 ◦ C and mean diameter (D50 ) of 1.5 ␮m (Kreutzonit Super, (1)
Mahlwerke Kreutz, Germany).
where Q is the load applied to the notched bar in kg, L is the span in
Electrofused mullite–zirconia was used as second raw
meters, C is the depth of the notch in meters, D is the thickness of
material. With Al2 O3 = 44.0 wt.%, SiO2 = 18.0 wt.%, ZrO2 = 39.1%
the specimen in meters, W is the width of the specimen in meters,
TiO2 ≤ 0.3 wt.%, Fe2 O3 ≤ 0.1 wt.% and Na2 O ≤ 0.2 wt.%, specific
and A0 , A1 , A2 , A3 y A4 are functions of the ratio (L/D) described in
gravity of 3.74 g/cm3 melting point of 1850 ◦ C and mean diameter
[10,21]. Eq. (1) can be approximated by the following equation:
(D50 ) of 5 ␮m (MUZR, ElfusaLT, Brazil).
√
Zircon and MZ mixtures were prepared with 0, 15, 25, 35 and KIC ∼
= f C (2)
45 wt.% (in weight basis) of MZ and were called Z0, Z1, Z2, Z3, and
Z4, respectively. Aqueous 80 wt.% suspensions of the mixtures at pH where  f is the flexural strength in MPa. The calculated values of
9.1–9.2 were prepared by adding the powder to aqueous solutions KIC , together with E, were used to estimate the surface energy for
with suitable content of dispersant (Dolapix CE64, Zschimmers and the area created by the crack propagation ( NBT ) by the subsequent
Schwartz) and NH4 OH. After mixing, the suspensions were ultra- equation [10,20]:
sonicated for 20 min. The prismatic bars 7.5 × 7.5 × 50 mm3 were 
KIC = 2NBT E (3)
produced from well dispersed suspensions by slip casting in a plas-
ter molds. where  NBT can be expressed:
Dried probes were fired at heating rate of 10 ◦ C/min up to 1600 ◦ C
for 2 h. KIC 2  2 C
NBT = = f (4)
2E 2E
2.2. Characterization techniques Finally, the critical crack length (Lc ) was estimated from Eq. (2):
 2
After drying at 110 ◦ C green density of bars was determined by KIC
Lc = √ (5)
mercury immersion. Density and open porosity of sintered sam- f 
ples were determined by the water absorption method. Theoretical
density was calculated taking into account the density of each The critical length was also proposed by Hasselman [14] in terms
component: 3.16 g/cm3 for mullite, 5.89 g/cm3 for zirconia and of the surface energy less than a constant; the values obtained by
4.56 g/cm3 for zircon. Crystalline phases formed were analyzed by the two methods differ in a constant:
X-ray difraction (XRD) (Philips 3020 equipment with Cu–K␣ radi-  EUef
ation in Ni filter at 40 kV – 20 mA). The Rietveld method [17,18], Lc = R = (6)
t 2 (1 − )
a quantitative analysis, was carried out to characterize the present
crystalline phases in the materials. The XRD patterns were analyzed This method (SENB) can only be used if the sizes of the defects
with the program FullProf, which is a multipurpose profile-fitting (pores, cracks etc.) in the microstructure of the materials are smaller
program, including Rietveld refinement [19]. The starting crystal- than Lc .
lographic data for each phase was extracted from the literature.
The dynamic elastic modulus E of the composites was measured 3. Results and discussion
by the excitation technique with a GrindoSonic, MK5 “Industrial”
model. For the TSR experiments, the water quenching method was 3.1. Characterization of the sintered Z0–Z4
used. Thermal cycles with quenching temperature differentials, T
of 400, 600, 800, 1000 and 1200 ◦ C were applied. Sintered sample In Table 1, the physical characteristics and mechanical prop-
was heated at a selected temperature in an electrical furnace in erties of the materials sintered at 1600 ◦ C–2 h are shown. All the
air atmosphere for a period of 90 min and then cooled in a water materials studied had relative densities over the 90% of the theoret-
bath at 25 ◦ C. After quenching, samples were dried at 100 ◦ C and ical and the open porosity was less than 5%. The values of the elastic
then the TS severity effect on E as well as its variation with the modulus and the flexural strength are comparable with literature
number of applied thermal cycles was determined for the differ- data [22–24].
210 N.M. Rendtorff et al. / Materials Science and Engineering A 498 (2008) 208–215

Table 1 Table 2
Physical and mechanical properties of the materials Initial and final crystalline phase compositions of the studied materials in wt.%

Apparent density (g/cm3 ) Apparent porosity (%) ˛ (10−6 ◦ C−1 ) Lc (␮m) Starting Final

Z0 4.1 2 5.0 103 Zircon Mullite ZrO2 Zircon Mullite m-ZrO2 t- ZrO2
Z1 4.1 2 5.0 58
Z0 100 0 0 96.5 0 3.5 0
Z2 4.0 3 5.0 76
Z1 85 9 6 83 10 7 0
Z3 3.9 4 5.0 72
Z2 75 15 10 72 15 12 ≤1
Z4 3.9 5 5.0 54
Z3 65 21 14 62 21 16 ≤1
Z4 55 27 18 45 27 27 ≤1

10 wt.%. Zircon decomposition was not completely reversible due

to the presence of impurities and the relatively rapid cooling rate
(5 ◦ C/min) and therefore ZrO2 remained after cooling.
The degree of dissociation was more important in the material
with a higher proportion of MZ. Mullite proportion did not change
during the sintering. The partial dissociation of zircon with an
increase in the amount of ZrO2 implied that a silica rich glassy phase
was present. Therefore 5–10 wt.% of this non crystalline phase was
present in the composites. The final amount of t-ZrO2 in all the
materials can be neglected.
Fig. 3 shows the evolution of the crystalline phases (estimated
using the Rietveld method) as a function of MZ addition. In this
graph the initial composition is also represented. The zircon content
decreased near 5 wt.% whereas the amount of mullite remained
unchanged with the thermal treatment. Also, a small quantity of
zircon (≤5%) decomposed to ZrO2 and SiO2 for materials with less
than 35 wt.% of MZ whereas for Z4 the dissociated amount was
Fig. 1. Complete XRD pattern of the studied materials.
almost 20 wt.% of the initial zircon.

3.2. Crystalline phases present 3.3. Dilatometry

Diffractograms of the materials are shown in Fig. 1. For Z0 the The dilatometric curves of the Z0 and Z4 materials are shown
main crystalline phases are zircon accompanied by a little bad- in Fig. 4. The Z0–Z3 materials showed a linear expansion curve
deleyite (m-ZrO2 ) originated by the zircon thermal dissociation. with similar linear expansion coefficient, (˛ ≈ 5. 10−6 ◦ C−1 ) with
On the other hand for the composite materials the peaks of the the exception of the Z4 composition which presented a hysteresis
initial components are present: zircon, baddeleyite and mullite loop area, due to the volume change associated to the m↔t trans-
(3Al2 O3 ·2SiO2 ). In Fig. 2, a detail of the previous DRX pattern, the formation. This change is not seen in the other materials perhaps
gradual increase of the amount of the second phases (MZ) can be because of the small amount of m-ZrO2 and the presence of glassy
seen. phase covers the volume change of the m-ZrO2 grains.
Table 2 shows the initial composition of the materials before The m↔t transformation began at 1100 ◦ C on heating and indi-
processing and the final crystalline composition of the materials cated that an important content of m-ZrO2 was present. This
evaluated by the Rietvield method. Less than 5 wt.% of the zir- transition occurred when the probes were sintered and when a
con thermally dissociated during sintering at 1600 ◦ C for Z0–Z3 thermal shock test for values of T = 1000 and 1200 ◦ C was applied.
compositions, except for Z4 in which dissociation was nearly

Fig. 3. Final crystalline composition of the studied materials evaluated by the

Fig. 2. A detail of the XRD pattern of the studied materials. Rietveld method in terms of the amount of MZ powder in the initial composition.
 N.M. Rendtorff et al. / Materials Science and Engineering A 498 (2008) 208–215 211

Fig. 6. Fracture toughness KIC and initiation surface energy  NBT as functions of the
Fig. 4. Dilatometric curve of the materials sintered at 1600 ◦ C for 2 h; expansion%
amount of MZ powder in the initial composition.
as a function of temperature.

3.5. Toughness and initiation fracture energy

At 1600 ◦ C the stable phase is the tetragonal form, but on cool-
ing the monoclinic phase transformation took place in those grains Many methods are currently used to measure the fracture tough-
having a size higher than the critical one. For T = 1200 ◦ C a com- ness of ceramics materials. The SENB method is a simple and
plete transformation is expected, while a partial one will occur for inexpensive that has been positively used in several occasions for
T = 1000 ◦ C. this kind of materials [10,21].
At first glance the values of fracture toughness (KIC ) and the frac-
3.4. Elastic modulus E0 and flexural strength  f ture initiation energy ( NBT ) (Fig. 6) are similar to the ones found in
the literature for these materials [21]. The effect of the addition of
The elastic modules of the composites (Fig. 5) are similar to MZ was different for low and high proportions. An increase of the
those previously reported [1,24]. Results by the impulse excita-  NBT and KIC values is observed with the composition as showed in
tion technique are reliable and comparable with others obtained Fig. 6. With 15 wt.% of addition the fracture toughness and the sur-
by other methods such as three- and four-point bending methods face energy slightly decreased in comparison with the pure zircon
or indentation techniques [25]. material.
The influence of the addition of MZ can be described as fol-
lowing: when it acts as an additive (very low concentrations) the 3.6. Microstructure
value of the elastic modulus is slightly increased. For proportions
of the second and third crystalline phases (i.e. mullite and zirco- SEM micrographs of the five materials are shown in Figs. 7–11.
nia) higher than 15 wt.% the elastic modulus of these materials All the samples had a dense microstructure with low residual poros-
decreased almost linearly. This behavior is clearly shown in Fig. 5. ity which is similar to that reported in previous works [24]. There is
The flexural strength  f (Fig. 5) showed a gradual increase with no a preferential direction in the microstructures of these materials.
the amount of MZ in the original composition. These values are The images demonstrate that the sintering was achieved; moreover,
slightly lower than those given in the literature for pure mullite some grains are joining.
(254 MPa) [12], mullite–zirconia (about 215 MPa) [13] and pure zir- In the pure zircon material (Z0, Fig. 7) no zirconia grains can be
con (150–320 MPa for various products processed at 1600 ◦ C [14]). observed neither detected with EDAX. In the Z1–Z4 composite a
The difference may be explained by the presence of pores, microc- zircon matrix (middle gray) can be seen with zirconia grains (light
racks resulting from the zirconia transformation during cooling and
the presence of a non crystalline phase.

Fig. 5. Dynamic elastic modulus (E) and flexural strength ( f ) as functions of the
amount of MZ powder in the initial composition. Fig. 7. SEM micrographs of the Z0 (z: zircon, p: pore).
212 N.M. Rendtorff et al. / Materials Science and Engineering A 498 (2008) 208–215

Fig. 8. SEM micrographs of the Z1 (m: mullite, z: zircon, b: zirconia, p: pore). Fig. 11. SEM micrographs of the Z4 (m: mullite, z: zircon, b: zirconia, p: pore).

3.7. Thermal shock behavior

3.7.1. Effect of quenching temperature difference (T) on the

E1/E0 ratio.
The TS behavior of the materials was evaluated by measuring the
decrease in E1/E0 ratio where E0 and E1 are the original dynamic
elastic modulus and those values after one quenching process,
respectively. The elastic modulus decreases if any damage exists,
like new cracks nucleation or propagation of existing ones [26].
Fig. 12 shows the evolution of E1/E0 ratio with T indicating that
the degree of damage was not significant up to T = 200 ◦ C for pure
zircon and up to T = 400 ◦ C for all the composites. Thus, the Tc
of the materials was near to 200 and 400 ◦ C, respectively.
In the range of T = 800–1000 ◦ C, the degree of damage was
clearly different between materials, the performance of the com-
posite enhanced with the added amount of MZ. This result agreed
well with that reported in literature [10,27,28] where the incorpo-
ration of a second phases gave better TSR and materials with higher
Fig. 9. SEM micrographs of the Z2 (m: mullite, z: zircon, b: zirconia, p: pore).
toughness.
Most of probes dramatically failed under a thermal shock
gray– d ≤ 7 ␮m) and mullite grains (dark gray). Phase identification with T = 1200 ◦ C, which did not allow extrapolating the obtained
was carried out by EDAX. results to the actual operating conditions.
Mullite grains in the composites with more than 25 wt.% of MZ, The general tendency of TSR may be well explained and pre-
formed a nearly continuous phase. Hence it cannot be considered dicted by the classical thermal shock resistance thermoelastic
as an additive. models and Hasselman unified theory (Table 3). The observed

Fig. 10. SEM micrographs of the Z3 (m: mullite, z: zircon, b: zirconia, p: pore). Fig. 12. Effect of quenching temperature difference (T) on the E1/E0 ratio.
 N.M. Rendtorff et al. / Materials Science and Engineering A 498 (2008) 208–215 213

Table 3
Theoretical thermal shock resistance parameters

R = (Tc ) R Rst

Z0 65 0.030 3.8
Z1 81 0.019 3.5
Z2 88 0.017 4.4
Z3 101 0.014 4.9
Z4 138 0.008 5.7

behavior corresponded well with a non-static, kinetic, crack prop-

agation [13,14,26,28].

3.7.2. Effect of the number of quenching cycles on the E/E0 ratio

for different T
The effect of the repeated cycles at T = 800 ◦ C for the different
compositions is shown in Fig. 13 as the change of the E/E0 ratio
being E0 and E the elastic modulus for original and quenched sam- Fig. 14. Evolution of E/E0 ratio with the number of thermal cycles at T = 1000 ◦ C
ples, respectively, with the numbers of quenching cycles. There was applied for the different materials.
a rapid E/E0 drop after few cycles, and then a gradual reduction up to
achieve a practically constant value with increasing the number of
cycles. This is a typical behavior previously reported in the literature modulus E0 which is lower relative to T = 800 ◦ C. The remain-
[9]. All the composites (Z1–Z4) retained about 80% of the E0 at n = 10 ing E/E0 for Z3 and Z4 were 60% and 70% respectively. The lower
cycles showing the main microstructure degradation occurred by degree of damage with increasing MZ was probably due to the par-
applying three thermal cycles. The effect on the elastic modulus of tial occurrence of martensitic transformation during the thermal
cracks and microcracks was reviewed by Bradt and latter by Stiffler treatment using a T = 1000 ◦ C.
and Hasselman [30,31]. Generally the resulting elastic modulus is a The mismatch between the thermal expansion coefficients of
function of the number and lengths of the cracks, so the decrease in the different phases introduces micro-cracks in the grain bound-
the elastic modulus after a thermal shock is directly related with the aries. Moreover, microcracks developed during the processing by
nucleation and propagation of the cracks in the material. The crack the martensitic transformation. Contrarily to an intuition thought,
growths if elastic energy originated by the thermal shock is bigger an increase in the number of the micro cracks improves the TSR of a
than the energy required to create the new surface of the cracks. certain material, because the elastic energy provided by the thermal
Thus, Figs. 13 and 14 show that after two or three cycles, the elastic shock is divided into a greater amount of cracks. Thus the energy on
modulus did not decrease with the next thermal shock test which each crack becomes not large enough to create a new surface, and
means that the energy provided by the thermal shock was not high the cracks can not propagate. This is might be the reason why the
enough to propagate the existing cracks. A higher addition of MZ addition of micro crack “generators” improves the TSR. And in fact
caused a better TSR. For the pure zircon material (Z0) the reduc- the addition of MZ accomplishes this requirement in the two ways,
tion in E/E0 was almost twice as that of the composites, indicating due to the mismatch of the thermal expansion coefficients of the
a greater degradation. However, E/E0 remained unchanged for n new phases and the volume change associated with the zirconia
cycles higher than four cycles proving that no greater crack prop- transformation.
agations occurred. The thermal shock behavior for T = 1000 ◦ C of
the different materials is shown in Fig. 14. The E/E0 ratio followed 3.7.3. Theoretical thermal shock resistance parameters
a similar variation with the number of cycles applied to the one The thermoelastic approximation proposed by Kingery estab-
observed in tests with T = 800 ◦ C (Fig. 13). But in this case the Z0, lishes that the fracture will occur when the thermal stress equal
Z1 and Z2 materials retained a similar E, close to 50% of the original or overcomes the fracture strength of the material [28,15]. There R
and R parameters are defined, for h = ∞ and h = constant (h = heat
transference coefficient), respectively:

f (1 − )
R= (7)
E˛
kf (1 − )
R = Rk = (8)
E˛
where  f is the flexural strength,  is the Poisson ratio, E is the elastic
modulus, ˛ is the thermal expansion coefficient and k is the thermal
conductivity. The R parameter is the critical thermal difference for
the crack initiation Tc .
The energy balance approximation was developed by Has-
selman [14] and establishes that a sample will fracture if the
thermoelastic energy is superior to the energy required for the
creation of the crack surfaces. Assuming that the only energy trans-
ferred is the elastic energy from the thermal stresses. The following
expressions are deduced for the R and R parameters:

E
Fig. 13. Evolution of E/E0 ratio with the number of thermal cycles at T = 800 ◦ C R = (9)
applied for the different materials. f 2 (1 − )
214 N.M. Rendtorff et al. / Materials Science and Engineering A 498 (2008) 208–215

 Uef E nia particles because it also increased with the amount of

R = Uef R = (10)
f 2 (1 − ) MZ.

where  f is the flexural strength,  is the Poisson ratio, E is the

elastic modulus, and Uef is the surface effective energy. 4. Conclusions
For the conditions used in this work it is reasonable to assume
that the influence of the Biot (h = ∞) can be neglected to calculate The influence of mullite–zirconia grains (MZ) on thermal shock
R in the first model. Since materials studied can be taken as family resistance of Zircon based composites prepared by slip casting has
of materials, the thermal conductivity (k) and surface energy (Uef ) been studied. When MZ proportion is over 25 wt.% it cannot be
are expected to be similar. Then the analysis can be reduced using considered as a simple additive.
Eqs. (7) and (9). The partial zircon decomposition occurred during the sinter-
The unified theory of thermal shock fracture initiation and crack ing being the degree of dissociation more important at high MZ
propagation in brittle materials [14] includes the parameters men- addition. Therefore, the composites and also the samples prepared
tioned before, and defines a new parameter, the thermal stress crack from the pure zircon had a zirconia content slightly higher that the
stability parameter (Rst ). The Rst parameter depends on the fracture expected from the started compositions. Consequently the zirconia
surface energy (), the elastic modulus (E) and the linear thermal content reached up to 22 vol% and the samples contained a minor
expansion coefficient (˛), or in terms of the fracture toughness (KIC ) amount of non crystalline phase.
once a crack has been initiated, thermal shock failure is controlled Addition of MZ grains increased zirconia content of sintered
by the nature of the crack propagation through the material. This composites, which probably reduced zircon densification result-
parameter can be used to predict the behavior of materials with ing in an increase in porosity. Moreover, the volume change of
sufficiently long cracks under severe thermal stresses. the zirconia phase transformation which is the cause of microcrak-
ing formation increased the porosity with increasing MZ addition.

1/2 KIC The local differences in thermal expansion coefficients probably
Rst = = √ (11)
˛2 E 2E˛ contributed to microcraking. Therefore, initial elastic modulus E0
linearly reduced with MZ due to the changes in composition and
Table 3 shows the values of the approximations calculated for also to a slightly higher porosity. Whereas the strength of the com-
the materials. According to Hasselman [14] the first model (R) is posites increased with the incorporation of zirconia, connecting
applicable to brittle materials where the crack initiation is deter- mullite grains (SEM).
mining in the TSR behavior. The R predicted, that TSR improved The KIC and  NBT of 15 wt.% MZ composites were a little low
with a major addition of MZ, showing the increase of Tc Thus, the relative to that of pure zircon whereas further MZ addition resulted
thermoelastic model correlated satisfactorily well with the exper- in a considerable increase in KIC , reaching KIC for 45 wt.% of MZ twice
imental data of E1/E0 ratio vs. quenching temperature difference the initial value of that of pure zircon.
(T) and the number of quenching cycles for T = 800 and 1000 ◦ C. The thermal shock behavior of composites was typical of the
The second approximation (R ) is valid where the initiation brittle ceramic materials. The Tc of the composites is between
of the cracks is unavoidable. In our materials, R does not cor- 200 and 400 ◦ C.
relate the TSR behavior with the increase of MZ. This fact was The damage of the quenched samples was satisfactorily evalu-
expected because of the inverse proportionality of this parame- ated by a dynamic elastic modulus measurement.
ter with square of the mechanical strength property that increased The addition of MZ provided an increase in the TSR As expected,
with the amount of MZ in the material as seen in Fig. 5. the thermal shocks made with temperatures near the martensitic
The microstructure of any ceramic material exhibits grains, transformation (T = 1000 or 1200 ◦ C) caused a more important
pores, grains boundaries, microcracks and other defects especially damage.
materials obtained by slip casting. But the extent and length of Such improvement corresponded well with an increase in KIC
the cracks must be considered. The SEM micrographs clearly show and high surface energy  NBT for fracture propagation. In addition
that these materials exhibited defects or microcracks, inherent to the effect of the dispersion of an appropriate content m-ZrO2 grains
the processing, and others due to the presence of m-ZrO2 and its (microcraking, branching, etc.) was favorable.
martensitic transformation. The microcracks and residual stress are The thermoelastic approximation (R) and the unified theory (Rst )
mainly generated by the thermal expansion mismatch between zir- predict the experimentally observed thermal shock behavior of
conia particles and zircon–mullite matrix. Zircon and mullite have these dense zircon–mullite–zirconia composites.
similar thermal expansion coefficient. These microcracks increase
with MZ addition. However, these defects are in all the cases smaller
References
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