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Journal of the European Ceramic Society 33 (2013) 3403–3410

A kinetic study of the quartz–cristobalite phase transition

Lucia Pagliari a , Monica Dapiaggi a,∗ , Alessandro Pavese a,b , Fernando Francescon c
a Dipartimento di Scienze della Terra, Università degli Studi di Milano, via Botticelli 23, 20133 Milano, Italy
b IDPA-CNR National Research Council, via Botticelli 23, 20133 Milano, Italy
c Ideal Standard International, C.O.E., Ceramic Process Technology, via Cavassico Inferiore 160, I-32026 Trichiana, Belluno, Italy

Received 26 April 2013; received in revised form 30 May 2013; accepted 8 June 2013
Available online 11 July 2013

Abstract
Cristobalite is a common silica polymorph in ceramics, as it can crystallize in SiO2 -rich systems during high temperature processes. Its occurrence
in final traditional ceramic bodies remarkably affects their thermal expansion, thus playing an important role in the shrinkage upon cooling. The
quartz–cristobalite transformation kinetics is investigated by in-situ isothermal X-ray powder diffraction experiments and then correlated to the
average particle size (d) of the starting quartz using a model here developed. An Avrami-like rate equation, i.e. α(t) = 1 − exp(− k × t)n , in which
the n-term is assumed to account for the dependence on the average particle size, has provided the best fitting of theoretical to experimental data,
yielding activation energy values that range from 181 to 234 kJ mol−1 , and exponential n-coefficients from 0.9 to 1.5. Ex-situ observations have
demonstrated that the formation of cristobalite from quartz after 50 min, 2, 4 and 6 h at 1200 and 1300 ◦ C, exhibits a remarkable dependence on d
of quartz, showing comparable behaviours in the case of d equal to 15.8 and 28.4 ␮m, but significant differences for d of 4.1 ␮m. The formation
of cristobalite is boosted remarkably at temperature higher than 1200 ◦ C, with an increase by weight even of 500%, with respect to its content
at lower temperature. The method of sample preparation (dry powder, wet powder and tablet of compressed dry powder) seems to influence the
results only at temperature > 1200 ◦ C and in the case of fine powder.
© 2013 Elsevier Ltd. All rights reserved.

Keywords: Quartz–cristobalite transition; X-ray diffraction; Kinetics

1. Introduction thermal dilations affect the shrinkage upon cooling of the

Cristobalite is a high temperature silica polymorph stable
in the temperature (T) range 1470–1705 ◦ C, but that also
occurs out of its field of stability as a metastable phase. The
theoretical sequence of the silica transformations upon heating
involves ␣-quartz, ␤-quartz (573 ◦ C), ␤-tridymite (870 ◦ C) and
␤-cristobalite, which has a cubic structure (1470 ◦ C). Given that
the formation of ␤-tridymite requires particular impurities to be
present,1 ␤-cristobalite can even appear at lower temperature.
Cristobalite also develops at T ≤ 1000◦ C from SiO2 glass.2
Upon cooling, ␤-cristobalite turns into its tetragonal ␣ phase at
270 ◦ C, not being able to overcome the activation energy barrier
to change into the stable silica phase. ␣- and ␤-cristobalite
have average bulk thermal expansion values of 91.7 and
6 × 10−6 ◦ C−1 , respectively.3 Such remarkably different
∗ Corresponding author. Tel.: +39 02 50315605; fax: +39 02 50315597.
E-mail address: monica.dapiaggi@unimi.it (M. Dapiaggi).
traditional ceramic bodies, especially in sanitaryware-fireclay
technology4 making extensive use of chamotte (calcined clay
or ball-clay), and plays therefore a relevant role on the quality
of the final product.5 Moreover, a controlled formation of
cristobalite is also exploited to properly “tune” the thermal
expansion of a ceramic body, in order to make it match well
with that of the glaze, thus avoiding the appearance of flaws
due to a mismatch between inner and surface. For this reason,
much interest is paid to cristobalite-involving reactions that
take place in the traditional ceramic industrial processes.6
Moreover, the stage of advancement of any high temperature
transformation, both in natural and industrial environment,
depends on the particle-size-distribution (PSD) of the involved
materials and firing-time experienced.7 Such an aspect becomes
crucial in traditional ceramic manufacturing contexts, in which
the raw materials used have undergone milling treatments to
comply with processing features of the wholesale production,
thus steering the phase composition and texture of the final
output. Even though are aware that quartz is not the only source

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3404 L. Pagliari et al. / Journal of the European Ceramic Society 33 (2013) 3403–3410

for cristobalite formation during ceramic production (see for

example,8 and references within), being it the metakaolinite
coming from thermal decomposition of kaolinite, still the kinet-
ics of the phase transition is an important step in the course of
understanding the kinetics and the energetics of the whole high
temperature process that generates a traditional ceramic body.
In the light of the discussion above, it is of interest to get
insight into kinetic mechanisms of the transformations of SiO2 -
based systems leading to ␤-cristobalite, and in particular, as a
fundamental reference, into the phase transition from quartz.
The aim of the present study is to investigate the
quartz–cristobalite transformation paying particular attention
to PSD of the starting quartz powders, firing-time, firing-
temperature and sample preparation. In this view, we planned
two sets of experiments:

Fig. 1. Particle size distribution of the five powder investigated.

(i) those in which measurements are carried out on samples
that have undergone annealing after thermal treatment;
(ii) those that are meant to enable the study of the reaction
kinetic parameters.
Such investigations are carried out by ex-situ and in-situ
X-ray powder diffraction experiments; the quartz–cristobalite
transformation kinetics is explored by isothermal runs and then
interpreted by a formalism here developed that uses the Avrami
model.
2. Experimental
2.1. Samples
In the present investigation five powder quartz samples pro-
vided by Sibelco were used, with different PSDs, as displayed
in Fig. 1. PSD- and micro-structure parameters are set out in
Table 1.
Given that the d-values of the quartz powders range from
4 to 29 ␮m but none of them lies in the interval 4.5–15 ␮m,
two more mixtures were prepared, by blending the two finest
raw powders: 50% SA600 (50% SA600 +50% SA250S;
d = 9.958 ␮m) and 70% SA600 (70% SA600 +30% SA250S;
d = 7.629 ␮m). The PSDs were measured as follows: first, 7 g
of sample were mixed with 40 ml of de-ionised water, 5 ml of
1% Sodium Hydroxide solution and 5 ml of 1% Sodium Hexa
meta Phosphate (Calgon) solution, in a high speed homogeniser,
at 10,000 rpm, for 1 min; then, the resultant slurry was screened
through a 125 ␮m sieve and classified, taking into account the
eventual residue found after sifting. PSDs were eventually mea-
sured by a CILAS LASER MOD 920L.
2.2. Ex-situ and in-situ high temperature experiments
We carried out three series of high temperature experiments.
The first one was meant to provide an overview on the
behaviour at non-ambient conditions of the available samples.
Ex-situ analyses were performed on samples heated in a LKN-
S86 Nannetti muffle furnace at 1200 and 1300 ◦ C (ramp time:
6 h), and then cooled slowly down to room temperature. Three
sample preparation techniques were used: (i) dry compression
to form tablets; (ii) mixing sample and water to obtain a paste;
(iii) bare powders. Altogether, 21 samples were produced, three
for each PSD. X-ray powder diffraction (XRPD) patterns were
collected by a θ–2θ Bragg-Brentano parafocusing PANalytical
X’ Pert PRO diffractometer, equipped with multi-channel X’
Celerator detector. A Cu-K␣ radiation with λ = 1.5418 Åwas
used. The optics were very simple, with a fixed divergence slit
of 0.5◦ and an antiscatter slit of 0.5◦ . Samples were ground and
then pressed in a back-loading sample holder; diffraction sig-
nals were collected from 5◦ to 80◦ 2θ, with a step size of about
0.017◦ 2θ, and a counting time of 30 s per step.
In the second series of measurements the coarsest, the
finest and the intermediate grain-size powders (SA10S,
SA600 and SA250S respectively) were used to investigate
the quartz–cristobalite transformation as a function of time-
temperature. Wet samples were chosen for such experimental
runs as they provide conditions closer to those of the industrial

Table 1
Granulometric characterization of the starting powders. Dv  and RMS strain come from the analysis of the powder diffraction peak broadening (see the experimental
paragraph for the details).
Sample d (␮m) D50 (␮m) Mode (␮m) Dv  (nm) RMS strain (×10−4 )

SA10S 28.38 23.42 50.22 270 (3) 3.81 (5)

SA6S 24.59 17.90 34.58 251 (3) 4.06 (5)
SA12S 23.05 18.24 31.50 256.8 (1) 3.84 (4)
SA250S 15.78 10.90 23.81 230 (3) 3.72 (6)
SA600 4.135 2.689 2.787 167 (1) 3.48 (7)
 L. Pagliari et al. / Journal of the European Ceramic Society 33 (2013) 3403–3410 3405

environments. The samples were heated at 1200 and 1300 ◦ C simplicity, through a histogram composed of a set of j-bins,
for 50 min, 2, 4 and 6 h, and then annealed. Heating treat- each bearing a ξ j fraction by weight of the original material with
ments and XRPD measurements were carried out with the same average 2Dj size. Let us introduce the following definition for a
instruments and experimental set-ups reported above. generic observable F that takes the values Fj in the jth-bin:
The third set of measurements was oriented to the study 
of the reaction kinetics of the quartz–cristobalite phase tran- F= Fj × ξj . (4)
sition, by in-situ experiments. A θ–θ geometry Philips X’ Pert j
diffractometer was used, equipped with an Anton-Paar heating Assuming that the activation energy Ea is the same for any
chamber (HTK 16 MSW) and a Pt heating strip, which is able to particle size, one then can write the reaction kinetics equation
achieve a maximum temperature of ∼1600 ◦ C. Explorative heat- for the j-fraction as
ing ramps were performed on the finest and coarsest samples  
(SA600 and SA10S, respectively): the maximum temperature Ea
g(αj ; pj ) = Aj exp − ×t (5)
was ∼1300 ◦ C, and data were collected from 19◦ to 75◦ 2θ at RT
room temperature before and after treatment, and from 19.5◦ to where pj is a possible parameter depending on the
27◦ 2θ, every 50 ◦ C, until about 500 ◦ C, and every 5 ◦ C from 500 jth-bin. In some case, it may be convenient to use
to 1300 ◦ C, with a step-size of 0.03◦ 2θ and counting time of 1 ln(g(αj ; pj )) = ln(Aj )(− Ea /RT) + ln(t); the formalism we are
s/step. Such 2θ-intervals allow one to record the most intense developing does not change, and hereafter we assume to proceed
peaks of quartz and cristobalite. Isothermal kinetics experi- with Eq. (5). If one sets αj = α+j and pj = p + δpj , then from
ments were then carried out by the same diffractometer and high Eq. (5) it follows:
temperature device, and using SA600-SA10S-SA250S-samples.
Each sample was studied along three isotherms, chosen as a    
Ea
function of the preliminary ramp experiments. g(α + j ; p + δpj ) × ξj = exp − ×t× A j × ξj
XRPD patterns were collected for all of the samples, before RT
j j
and after thermal treatments. The quantitative analyses and (6)
the determination of the volume-average crystallite coherence
If one Taylor-expands in j and δpj the right-hand member of
domain size (Dv ) and root mean square (RMS) micro-strain9
Eq. (6), and
were performed by the Rietveld refinement technique combined
with the Warren-Averbach10 method (MAUD software11 and  
(i) takes into account that j j ×ξ j = 0 and j δpj × ξ j = 0;
isotropic model). For all the experiments, we were not able to
(ii) neglects the second order terms in j and δpj ;
refine the RMS strain parameter of cristobalite if its content
then it follows
was less than 2 wt.%: in such cases the too low diffraction peak
intensity did not allow the separation of the size and strain profile   
Ea
contributions. g(α; p) × ξj = exp − × t × A. (7)
RT
j
3. Kinetic theory We tried out several kinetic models,12 and chose an Avrami-
like15–17 formalism as it proved to be the most satisfactory one
The fundamental equation describing reaction kinetics, in terms of: (i) matching between observations and theory, (ii)
which is reported below12 : and consistence between the inferred Ea s versus d of quartz. In
dα this light, the reaction rate is described by the general equation
= kf (α), (1) beneath
dt
is often cast into its integral version, namely [− ln(1 − α)]1/n = k × t. (8)

g(α) = kt, (2) We take that the dependence on each jth-bin is transferred
to the exponential n, i.e. nj , and the equation above changes
where α is a generic coordinate that monitors the new phase accordingly into
formation (hereafter called “coordinate of transformation”, and  
for which lim α(t) = 1), t is time, f and g are some functions 1 Ea
t→∞ [ln(− ln(1 − αj ))] × = ln(Aj ) + − + ln(t). (9)
nj RT
of α, depending on the nucleation-growth model. k is the rate
constant, whose dependence on temperature is described by the Summing over all bins one has and taking into account the
Arrhenius equation: fraction by weight for each jth-bin, one has

Ea
  1
 
Ea

k = A exp − . (3) ln(− ln(1 − αj )) × × ξj = − + ln(t)
RT nj RT
j
The role of the particle size in affecting the reaction kinetics 
+ ln(Aj ) × ξj . (10)
of a powder has earlier been discussed by 13,14 and it is here
j
re-considered. The PSD of quartz is modeled, by the sake of
3406 L. Pagliari et al. / Journal of the European Ceramic Society 33 (2013) 3403–3410

Table 2
Chemical and physical characterization of the starting raw powders.
Sample % min % max % max % max % max Loss on Density Specific surface
SiO2 Al2 O3 Fe2 O3 TiO2 K2 O ignition (%) (T/m3 ) (cm3 /g)

SA10S 99.0 0.3 0.03 0.03 0.05 0.2 1.0 2800

SA6S 99.0 0.3 0.04 0.03 0.05 0.2 1.2 1900
SA12S 99.0 0.3 0.03 0.03 0.05 0.2 0.9 3500
SA250S 99.0 0.4 0.05 0.03 0.05 0.3 0.70 5700 (900)
SA600 99.0 0.5 0.06 0.03 0.05 0.3 0.5 13,800 (2800)

From Eq. (7) it finally follows: A decrease of the particle size is accompanied by an increase
of the peak’s broadening, indicating a general reduction of the
  ξj  
Ea
 crystalline domain size and increase of RMS strain. The inverse
ln(− ln(1 − α) × = − + ln(t) relationship between crystallite size and RMS strain is very
nj RT
j well known in literature in materials subjected to mechanical
 treatment.23,24
+ ln(Aj ) × ξj , (11a)
j
4.2. Characterization of the treated powders
and finally
 
Ea 4.2.1. Ex-situ experiments
(− ln(1 − α))1/n̂ = Â × exp − × t, (11b) The quantity of cristobalite obtained from the ex-situ exper-
RT
 iments at 1200 ◦ C and 1300 ◦ C for 6 h is displayed in Fig. 3, as
 where (1/n̂) = (1/n) = j (ξj /nj ) and ln(Â) = ln(A) = a function of d and sample preparation.
j ln(Aj ) × ξj are the quantities measured by isothermal exper- Figure 3A shows the results related only to experiments
iments. with the maximum temperature of 1200 ◦ C, whereas Figure
3B collates the issues from both temperatures. The formation
4. Results and discussion of cristobalite through such treatments exhibits a remarkable
dependence on both d and sample preparation. Rising tem-
4.1. Characterization of the starting powders perature by 100 ◦ C causes the amount of formed cristobalite to
increase by more than 6 times, for the sample with the small-
Tables 1 and 2 show the results of a characterisation of the est particle size, and by 2–3 times, for the coarsest one. The
initial quartz powders. The volume-average domain size (Dv ) method of sample preparation influences the final quantity of
and the RMS-strain of quartz are presented in Table 1, and can cristobalite only when the firing temperature is 1200 ◦ C, and
be directly compared with the granulometric parameters in the in particular for the finest samples: the wet sample preparation
same table. In particular, one has that the smaller d the smaller boosts cristobalite (Fig. 3A), whereas the bare and dry powders
Dv . The differences in terms of Dv  between starting powders yield the lowest amount; such difference nearly cancels out at
are expectable even by a bare inspection of Fig. 2, which shows 1300 ◦ C (Fig. 3B). This is likely ascribable to that wet prepara-
the portion of diffraction pattern wherein the main peak of quartz tion allows a better particle-particle contact, thus favouring heat
is located. transmission and solid state reactions induced thereby.

Fig. 3. Wt% of cristobalite after the ex-situ test conducted at 1200 ◦ C (A) and
Fig. 2. The main peak of quartz for the five starting powders under investigation. at 1300 ◦ C (B). B shows again results at 1200 ◦ C as a comparison.
 L. Pagliari et al. / Journal of the European Ceramic Society 33 (2013) 3403–3410 3407

A 15

wt% Cristobalite
10

)
m
4.135

(µ
ze
15.78

Si
in
ra
28.38

G
of
n
52min 2h 4h 6h

ea
Time

M
B 60

wt% Cristobalite
40

20

0
)
m

4.135
(µ
ze

15.78
Si
in
ra

28.38
G
of
n

52min 2h 4h 6h
ea

Time
M

Fig. 4. Amount of cristobalite formed at 1200 ◦ C (A) and 1300 ◦ C (B) applying
the maximum temperature for different times.

Fig. 4 concerns the cristobalite formation in the finest, coars-

est and intermediate size samples at 1200 ◦ C and 1300 ◦ C, as a
function of time.
At 1200 ◦ C, the amount of cristobalite is in general small, but
a remarkable increase occurs in the finest sample only, and after
6 h of treatment. At 1300 ◦ C the effect of the firing time seems to
be modest after 52 min, regardless of the average particle size.
Fig. 5 shows the Dv of the samples, i.e. the difference
between the crystalline domain size of quartz before and after
high temperature treatment, as a function of the amount of cristo-
balite formed at 1200 ◦ C and 1300 ◦ C. At 1200 ◦ C (Fig. 5A), all
the coarse samples show a negative value for Dv , and therefore
they exhibit a larger average crystallite size after heating (grain
growth is well known to be promoted by high temperatures).
However, all samples with a small d (below about 16 ␮m) have
a smaller average crystallite size after heating, showing there-
fore that the reactions occurring on cooling have an influence
on the coherence of the domains that tend to break due to the
volume difference of the involved polymorphs. At the highest
temperature (1300 ◦ C, Fig. 5B), this is again true, but the sam-
ple with a d of about 25 ␮m lies somehow in between the two
different behaviours.
The difference between the initial and the final strain of quartz
(RMS) was also determined, but it is not here reported for
the sake of brevity. Such difference is negative for all of the
samples explored, proving the occurrence of residual stress in
Fig. 5. Relationship between Dv of quartz and the amount of cristobalite
formed at 1200 ◦ C (A) and 1300 ◦ C (B).
quartz undergone high temperature treatment. The fine samples
are those least affected, alike the crystallite size.
Both Dv and RMS strain do not show any dependence
on the method of sample preparation.
4.2.2. Heating ramp experiments
In-situ heating ramp experiments on the finest and the coars-
est powders were performed, reaching about 1300 ◦ C (details
on the procedure can be found in the experimental section). The
coarsest sample (SA10S), of which Fig. 6A shows the diffrac-
tion patterns in the interested thermal range, starts to transform
into cristobalite at 1250 ◦ C, and at 1300 ◦ C about 2.70% of this
latter is formed.
The finest sample (SA600) gives at the end of the heating
ramp about 40.6% of cristobalite, which starts to form at about
1190 ◦ C (see Fig. 6B). As expected, this hints a relevant role is
played by the particle size, in quartz–cristobalite conversion.
4.2.3. Isothermal kinetics analyses
On the basis of the ex-situ and in-situ experiments dis-
cussed above, we have chosen the temperature values at
3408 L. Pagliari et al. / Journal of the European Ceramic Society 33 (2013) 3403–3410

Fig. 7. Application of the Avrami equation for the intermediate grain-sized

sample (SA250S), heated at 1550, 1575 and 1600 K.

temperatures. As demonstrated, the data can be fitted nicely with

Fig. 6. Diffraction patterns at increasing temperatures collected in the little angle
range which contains the main peaks of both quartz and cristobalite. A refers to
the coarsest sample (SA10S) and B to the finest provided powder (SA600).
which to carry out isothermal measurements to investigate the
quartz–cristobalite reaction kinetics, using the finest (SA600),
the coarsest (SA10S) and the intermediate (SA250S) grain-size
samples.
By way of example, Fig. 7, which refers to SA250S but is rep-
resentative also of the other samples, reports the three isotherms
investigated; they trend linearly and are nearly parallel to each
other, thus suggesting that the reaction mechanism is indepen-
dent of temperature, over the explored range, for each sample.
Moreover, the first data points, referred to the lowest tempera-
ture, follow a trend with different slope with respect to the higher
an Avrami-type model; this means that the formation of cristo-
balite starts with an induction time (necessary for the growth of
critical-sized nuclei, which later start to grow into proper crys-
tals), followed by an acceleration period. The induction time is
strongly temperature-dependent: it is longer at lower temper-
ature, but considerably decreases with increasing temperature.
The different slope in the data with the lowest temperature may
therefore be due to this reason.
The kinetic exponent n ranges from 0.89 to 1.49 (see Table 3):
from,18 fractional n-values hint at diffusion-controlled crystal
growth, or processes involving complex size and shape particle
distributions for reactants and transformation products.
In particular, as to n one observes that:
1 SA250S and SA10S give ns close to each other, with n
around 1;
2 SA600 yields ns about 1.5, save for T = 1500 K. This brings
to light that the finest sample exhibits a remarkable sensi-
tivity to T, as proven by that a 25 K-shift is sufficient to
affect the kinetic exponent. Taking into account Eq. 11a, it
is likely that an effect related to the size-classes gives rise
to such discrepancy with respect to what occurs at higher
temperatures;

Table 3
Results from the kinetics experiments.
Sample Average grain size d (␮m) Working T (K) n n ln(k) (s−1 ) A (s−1 ) Ea (kJ mol−1 )

1500 1.15 −9.37 193(73)

SA600 4.135 1525 1.47 1.37 −9.28 411.83
1550 1.49 −8.87
1550 1.06 −9.22 181(78)
SA250S 15.78 1575 1.04 1.01 −9.16 115.7
1600 0.94 −8.78
1600 1.07 −9.51 234(191)
SA10S 28.38 1650 0.92 0.96 −8.44 3710.79
1680 0.89 −8.78
 L. Pagliari et al. / Journal of the European Ceramic Society 33 (2013) 3403–3410
Fig. 8. Arrhenius plot for SA250S, starting from the values of k obtained from
the application of the Avrami model.
3 the average grain size influences n so as to lead to two distinct
kinetic classes: the one including SA250S and SA10S, and
the other SA600;
4 n seems to exhibit an inverse dependence on d.
Fig. 8, which represents the Arrhenius plot for the inter-
mediate particle-sized powder again, shows a reasonably good
correlation (R2 = 0.84, which is similar for the other two sam-
ples) that allows one to determine the pre-exponential parameter
A and the apparent activation energy Ea of the phase transition
process.
The activation energies change from 181 to 234 kJ mol−1 ,
which are in keeping with literature values for such a kind of
processes (19–22,25 just as few examples). The Ea ’s are similar
to each other, and almost undistinguishable if one takes into
account the uncertainties, determined by the errors propagation.
In this view, the grain size seems not to significantly influence
the activation energy of the transition process, as shown in
Fig. 9, in agreement with the assumption of the model here
used that takes Ea as independent of the size-class. The
Fig. 9. Apparent activation energy as a function of grain size.
3409
Fig. 10. Amount of cristobalite after the isothermal analyses for the three sam-
ples investigated.
A-pre-exponential coefficients exhibit a remarkable scattering,
without any apparent correlation to d.
After cooling to room temperature, full-range diffraction data
were collected and then analysed with the Rietveld refinement.
Fig. 10 shows the amount of cristobalite crystallized after each
isotherm. As seen before, the sample with the smaller grain
dimension (SA600) reacts more easily: cristobalite forms at
lower temperatures with respect to the other samples and in
larger quantities upon the same applied conditions.
At a given temperature the amount of cristobalite formed
increases upon decreasing the grain size of quartz involved. The
more the particle size increases, the more the temperature nec-
essary to crystallize cristobalite is higher and the less is the
tendency of this phase to form. The latter aspect is shown by
that the slopes of the linear interpolations of cristobalite versus
T for each sample in Fig. 10 decrease as a function of d.
By way of example, at 1250 ◦ C and α = 0.2, the α(t)-curves
of SA600-SA250S-SA10S intersect each other at ∼1000, 700
and 1200 s, respectively; at t = 500 s and α = 0.2, they require
temperatures as large as 1300, 1290 and 1320 ◦ C, respectively.
5. Conclusions
The present study has been undertaken with the aim to elu-
cidate the kinetics of the quartz–cristobalite phase transition
which occurs during the production of many ceramic materi-
als. In particular, the attention has been focused on the effects
of size reduction on the cristobalite formation at high tempera-
tures, considering both the obtained quantities of that phase and
the kinetic process of the transformation. On the ground of the
results discussed in this paper, the following conclusions have
been achieved:
1 high temperature promotes cristobalite crystallization and the
method of sample preparation influences the amount of its
formation (wet samples show larger amounts of cristobalite),
but only at comparatively low temperature, i.e. 1200 ◦ C. This
is reflective of a kinetic effect;
3410 L. Pagliari et al. / Journal of the European Ceramic Society 33 (2013) 3403–3410
2 the formation of cristobalite is always favoured by a small
grain size of the starting powder, in keeping with that gener-
ally the smaller the particles, the more easily a transformation
takes place;
3 the Avrami model proves that the exponential term, n, is
related to the average particle size of starting quartz, whereas
the activation energy, Ea does not seem to depend on d of
the powders on study;
4 we observed n-values ranging from 0.89 to 1.49, according to
the rule that the smaller d the larger n. Ea has average value
of ∼203 kJ mol−1 .
Therefore, it is unarguable that the particle dimensions of the
starting powder plays a crucial role in the cristobalite forma-
tion. This is reasonable and confirms what one could expect if it
is kept in mind that stronger reactivities are usually associated
to finer materials. The results of the present work have impor-
tant implications from a practical point of view and so must be
taken into account: on the basis of the conclusions here reported,
industries could indeed choose the most appropriate raw mate-
rials and the most convenient conditions at which these powders
should undergo, in order to obtain the desired final product.
Acknowledgements
This work was supported by Sibelco, which provided the
samples for the research. An Acknowledgment is also due to an
anonymous referee who helped improving the paper.
References
1 Palmer DC. Stuffed derivatives of the silica polymorphs. In: Silica: physical
behavior, geochemistry and materials applications; vol. 29 of Reviews in
Mineralogy. 1994. p. 83–122.
2 Gupta TK, Jau-Ho J. Origin of cristobalite formation during sintering of
a binary mixture of borosilicate glass and high silica glass. J Mater Res
1994;9(4):999–1005.
3 Fei Y. Thermal expansion. In: Ahrens TJ, editor. Mineral physics and crys-
tallography: a handbook of physical constants, vol. 2. 1995. p. 29–44 [AGU
Reference Shelf].
4 Njoya D, Hajjaji M, Njopwouo D. Effects of some processing factors
on technical properties of a clay-based ceramic material. Appl Clay Sci
2012;6:5–66, 106–113.
5 Shackelford JF, Doremus RH. Ceramic and glass materials. New York:
Springer; 2008.
6 Sao O, Ozgur C. Investigation of a high stable ␤-cristobalite ceramic pow-
der from CaO–Al2 O3 –SiO2 system. J Eur Ceram Soc 2009;29:2945–9.
7 Bernasconi A, Diella V, Pagani A, Pavese A, Francescon F, Young K,
et al. The role of firing temperature, firing time and quartz grain size on
phase-formation, thermal dilatation and water absorption in sanitary-ware
vitreous bodies. J Eur Ceram Soc 2011;31(8):1353–60.
8 Ferrari S, Gualtieri A. The use of illitic clays in the production of stoneware
tile ceramics. Appl Clay Sci 2006;32:73–81.
9 Snyder RL, Jaroslav F, Bunge HJ. Defect and microstructure analysis by
diffraction; vol. 10 of international union of crystallography, monographs
on crystallography. Oxford: Oxford Science Publications; 1999.
10 Warren BE. X-ray diffraction. Reading, MA: Addison-Wesley Publishing
Company; 1969.
11 Ferrari M, Lutterotti L. Method for the simultaneous determination of
anisotropic residual stresses and texture by X-ray diffraction. J Appl Phys
1994;76(11):7246–55.
12 Khawam A, Flanagan DR. Solid-state kinetic models: basics and mathe-
matical fundamentals. J Phys Chem B 2006;110(35):17315–28.
13 Koga N, Criado JM. Influence of the particle size distribution on the CRTA
curves for the solid-state reactions of interface shrinkage. J Therm Anal
1997;49(3):1477–84.
14 Koga N, Criado JM. Kinetic analyses of solid-state reactions with a particle-
size distribution. J Am Ceram Soc 1998;81(11):2901–9.
15 Avrami M. Kinetics of phase change: I. General theory. J Chem Phys
1939;7:1103–12.
16 Avrami M. Kinetics of phase change: II. Transformation-time relations for
random distribution of nuclei. J Chem Phys 1940;8:212–24.
17 Avrami M. Granulation, phase change and microstructure. Kinetics of
phase change. III. J Chem Phys 1941;9:177–84.
18 Galwey AK, Brown ME. Thermal decomposition of ionic solids; vol. 86
of studies in physical and theoretical chemistry. Amsterdam: Elsevier;
1998.
19 Gualtieri A, Bellotto M, Artioli G, Clark SM. Kinetic study of the kaolinite-
mullite reaction sequence. Part II: Mullite formation. Phys Chem Miner
1995;22(4):215–22.
20 Dapiaggi M, Artioli G, Righi C, Carli R. High temperature reactions in
mold flux slags: kinetic versus composition control. J Non-Cryst Solids
2007;353(30–31):2852–60.
21 Hu AM, Li M, Mao DL. Crystallization of spodumene-diopside in the
las glass ceramics with CaO and MgO addition. J Therm Anal Calorim
2007;90(1):185–9.
22 Gualtieri AF, Gemmi M, Dapiaggi M. Phase transformations and reaction
kinetics during the temperature-induced oxidation of natural olivine. Am
Mineral 2003;88(10):1560–74.
23 Criado JM, Gonzales M, Real C. Correlation between crystallite size and
microstrains in materials subjected to thermal and/or mechanical treat-
ments. J Mater Sci Lett 1986;5:467–9.
24 D’Incau M, Leoni M, Scardi P. High-energy grinding of FeMo powders. J
Mater Res 2007;22:1744–53.
25 Dos Santos DS, Dos Santos DR. Crystallization kinetics of Fe–B–Si metal-
lic glasses. J Non-Cryst Solids 2002;304(1–3):56–63.