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Int. J. Appl. Ceram. Technol.

, 8 [1] 152–162 (2011)


DOI:10.1111/j.1744-7402.2009.02419.x

Ceramic Product Development and Commercialization

Crystal Nucleation and Growth Rates, Time–Temperature


Transformation Diagram, and Mechanical Properties of a
SiO2–Al2O3–CaO–MgO–(R2O) Glass in the Presence of
Cr2O3, Fe2O3, and TiO2 Nucleants
Mohammad Rezvani
Department of Ceramic Engineering, Faculty of Mechanical Engineering, University of Tabriz,
Tabriz 51666-14766, Iran

Vahak K. Marghussian* and Bijan Eftekhari Yekta


Ceramics Division Department of Materials, Iran University of Science & Technology, Narmak,
Tehran 16844, Iran

The crystallization of a SiO2–Al2O3–CaO–MgO–(R2O) glass in the presence of Cr2O3, Fe2O3, and TiO2 nucleants
was investigated utilizing differential thermal analyses, X-ray diffraction, and scanning electron microscope. The optimum
nu-cleation and growth rates of aluminian diopside crystals was determined for the most promising glass specimen
18 3 9
containing all three nucleants as 10 m /s and 6.1770.55 10 m/s, respectively. A time–temperature transformation (TTT)
diagram was also constructed for 82 wt% crystallization for the above glass sample and a nose time of 55 min was obtained.
The bending strength of some heat-treated specimens were also determined and were related to crystallization behavior and
microstructures. The highest strength value obtained was 16676 MPa.

Introduction

*v_k_marghus@yahoo.com Glass–ceramics are crystalline materials obtained


r 2009 The American Ceramic Society through controlled crystallization of glass in a two-step
www.ceramics.org/ACT Crystal Nucleation and Growth Rates, 153

heat treatment process, namely nucleation and growth. The importance of nucleation step in the whole fab-
Crystallization of glass from a small number of sites lo- rication process of the glass–ceramics in general, as dis-
cated at its surface usually results in low strength ma- cussed above, and the relative complexity and difficulty of
terials with coarse-grained microstructures. In contrast, initiation of effective volume nucleation and crystallization
efficient nucleation of crystals from numerous centers in in this system in particular, could probably explain the
the interior of glass results in fine-grained microstruc- considerable attention paid by many investigators studying
tures and consequently high-strength materials. There- the crystallization behavior and especially the nucleation
fore the role of nucleating agents in initiating glass 1–13,17–27
process in the above-mentioned system. Cr2O3 is
crystallization from a multitude of centers in reasonable one of the most studied oxides in this connection. While
time was the major factor allowing the introduction of 18
Williamson found that chromic oxide was not effective as
glass–ceramics into industrial applications. a nucleant in SiO2–Al2O3–CaO–MgO glass, Shelestak et
In recent years, the study of crystallization in 1
al. introduced Cr2O3 as an effective nucleation agent in the
glasses of the SiO2–Al2O3–CaO–MgO–(R2O, Fe2O3, 5
same glass system derived from oil shales and Omar et al.
TiO2, y) system has received considerable attention.
The practical value of research in this system stems suggested Cr2O3 as a favorable pyroxene crystalli-zation
from the fact that most of the materials produced from nucleant in quartz sand–dolomite–magnesite mix-tures. The
naturally occurring inexpensive materials such as granite, latter authors also pointed out that iron oxide by enhancing
the formation of spinel-like nuclei, may as-sist the
tuff, feldspars, clays, and so on, and glass–ceramics fabri- 6
cated from various industrial waste materials, for example, crystallization process. Davies et al. suggested that chrome
metallurgical slags, fly ashes, and so on, the disposal of ore is a better nucleant than Cr2O3 for the crys-tallization of
which is important from the point of view of environ-mental glass–ceramics derived from blast furnace slags. They also
considerations, can mainly be located in this sys-tem.
1–11 showed that using pairs of transition metal oxides is more
successful than single additions in this con-nection. Barbieri
Obviously a quite wide compositional range can be expected 17
of these glass–ceramics because of the diver-sity and quite et al. pointed out that if more than 0.5 mol% Cr2O3 is
arbitrary and uncontrolled compositions of the raw materials added to glasses of SiO2–Al2O3– CaO–MgO system, it is
used in their fabrication. However, most of the above glass– precipitated as MgCr2O4 spinel crystallites in the glass
ceramics can be located in the following compositional specimens acting as heterogeneous nucleation sites for
range: SiO2 42–52; Al2O3 5–15; CaO 22– 33; MgO 1–7; crystallization of the final diopside and anorthite phases.
Their results also showed that in the case of fine grain glass
R2O 3–11.5 (wt%). particles, surface nucleation is predom-inanted even at 5
These glass–ceramics usually contain anorthite, mol% Cr2O3 content, but for coarser particles some degree
wollastonite, diopside, melilite, and so forth, as their 22
of bulk nucleation may be observed. Karamanov et al.
major crystalline phases. It is also known that the ma-
terials containing diopside-like phases (including its recognized that Cr2O3 is a very effec-tive nucleant in high
solid solutions like pyroxenes) are usually possess iron content glasses of SiO2–Al2O3– CaO–Fe2O3 system
higher strength and hardness values.12,13 containing small amounts of PbO, ZnO, Na2O, and K2O.
Relatively suitable mechanical and chemical proper-ties They claimed that 0.7% Cr2O3 addition enhances the spinel
of glass–ceramic materials in this system have rendered them formation and consequently nucleation rate causing a higher
good candidates especially in highly wear resistant and degree of crystallization and finer structures in these glass–
chemically durable applications such as floor tiles, ar-tificial ceramics with the major crystalline phase of pyroxene.
stones, bearings, industrial pipes, pumps, and so on. Marghussian and colleagues19–21 suggested that in
On the other hand, in recent years, new applica-tions the glasses of SiO2–Al2O3–CaO–MgO–(R2O) system,
for these materials like glazes for floor and wall tiles14–16 effective nucleation may occur only by using a mixture of
have attracted considerable attention. Some other Cr2O3, Fe2O3, and TiO2. Rezvani et al.23 also intro-
applications such as high-strength biomedical ma-terials duced a combination of 3, 5, and 5 weight parts of Cr2O3,
and chemically resistant materials for immobili-zation of Fe2O3, and TiO2, respectively, as the most effec-tive
radioactive wastes have also proposed for these glass– nucleation agents in inducing bulk crystallization in these
ceramics. Obviously in the latter applications very pure
glasses. They also proposed that Cr2O3, after di-rectly
starting materials should be used instead of the
precipitating from molten glass during cooling stage as
inexpensive natural materials or industrial wastes. some form of chromium spinel crystallites, possibly
154 International Journal of Applied Ceramic Technology—Rezvani, Marghussian and Eftekhari YektaVol. 8, No. 1, 2011

MgO Cr2O3, greatly assisted the formation of final diop- be of some scientific and especially practical value in the
side phase (as heterogeneous nuclei particles). Moreover determination of suitable heat treatment schedules for the
they suggested that the entrance of Fe31 and perhaps Ti31 crystallization of these glass–ceramics, very little informa-
cations into the structure of MgO Cr2O3 spinel tion existed on these diagrams in the above system.
crystallites, by increasing the unit cell dimensions, reduce Finally, the flexural strength of some glass–ceramic
the crystallographic mismatch between spinel phase and specimens were also measured and were related to the
the final aluminian diopside phase in ‘‘a’’ and especially crystallization behavior and microstructures.
‘‘b’’ directions, facilitating their nucleation. They also re-
ported a crystallization activation energy of 253 kJ/mol
Experimental Procedure
and Avrami constant of n 53.23 for the most promising
glass specimen (of similar composition to G–Cr3Fe5Ti5
Glass Preparation
in the present study) and proposed a two-dimensional
bulk crystallization mechanism for the specimen. A glass consisting of SiO2 52.02, Al2O3 12.85,
Despite the extensive experimental work carried out CaO 23.07, MgO 6.53, Na2O 2.66, and K2O 2.85
and numerous publications appeared on the subject of wt%, which was introduced as a suitable compo-
nucleation and crystallization of these glasses, relatively sition for making glass–ceramics in a previous investi-
few reports have been published on the subject of de- gation,23 was chosen as the base composition in this
termination of nucleation and growth rates and even less study. Various oxides were then added to this glass (in
on the determination of time–temperature transforma-tion excess of 100 wt%) in order to assess their effectiveness
(TTT) diagrams in this system. Considering the fact that in inducing bulk nucleation in this glass. Table I shows
the occurrence of an effective bulk nucleation in the the chemical composition of prepared glasses.
glasses is very crucial from the view point of ob-taining The raw materials used were reagent grade silica, a-
the desired properties we decided to study the possibility Al2O3, CaCO3, Mg (OH)2, Na2CO3, K2CO3, Cr2O3,
of application of a faster and more reliable method for the Fe2O3, and TiO2. The mixture of raw materials after
measurement of crystal nucleation rates in the above thorough mixing were transferred to an alumina cruci-ble
system and also tried to confirm the pre- and melted at 14501C for 2 h in an electric furnace. The
vious findings concerning the effectiveness of the triple melts were then cast onto preheated stainless-steel molds
nucleants (Cr2O3, Fe2O3, and TiO2)19,20,23,24 in in- and cooled naturally to room temperature.
ducing an effective bulk nucleation in this system.
Because diopside is usually the sole crystalline phase Differential Thermal Analyses (DTA)
formed in the glass–ceramics located in the similar com-
positional ranges to the specimens investigated herein, it The thermal behavior of glasses was monitored by
was also decided to construct a TTT diagram concerning DTA scans carried out using a simultaneous thermal
the crystallization of a diopside phase from the aforemen- analyzer (Polymer Laboratories STA-1640, Amherst,
tioned glasses. Despite the fact that TTT diagrams could MA). Alumina was used as an inert reference material

Table I. Chemical Composition of Glasses wt%


Oxide

Sample SiO2 Al2O3 CaO MgO Na2O K2 O Cr2O3 Fe2O3 TiO2

Gb 52.02 12.85 23.07 6.53 2.66 2.85 — — —


G–Cr3 52.02 12.85 23.07 6.53 2.66 2.85 3 — —
G–Fe5 52.02 12.85 23.07 6.53 2.66 2.85 — 5 —
G–Ti5 52.02 12.85 23.07 6.53 2.66 2.85 — — 5
G–Cr3Fe5 52.02 12.85 23.07 6.53 2.66 2.85 3 5 —
G–Cr3Ti1 52.02 12.85 23.07 6.53 2.66 2.85 3 — 1
G–Cr3Fe5Ti5 52.02 12.85 23.07 6.53 2.66 2.85 3 5 5
Base glass.
www.ceramics.org/ACT Crystal Nucleation and Growth Rates, 155

and the sample particle sizes were in 0.45–0.55 mm where IN is the nucleation rate at a given nucleation tem-
range. The heating rate was 101C/min. perature (TN), tN is the nucleation time at TN, A1, and A2
are the area of DTA peaks after crystal growth heat treat-
X-Ray Diffraction (XRD) Studies ment at crystallization temperature (TG) for times tG1 and
tG2, respectively, and M1 and M2 are the sample masses
XRD analysis (Siemens D-500, Munich, Germany) for two DTA runs. The quantity Nq is the number of
with Ka radiation and in a 2y range from 51C to 651C nuclei quenched in the specimen before the onset of nu-
was utilized to identify and determine the content of cleation heat treatment at TN, IG, and UG are the steady
crystallized phase. Ten weight percent pure Si powder state nucleation and growth rates at TG, respectively.
was added to all samples as an internal standard. A For measuring the nucleation rate according to the above-
diopside powder obtained via crystallization of a glass mentioned method, the number of nuclei (IN tN) formed
sample with a similar composition as used in the present during the nucleation heat treatment at TN should be
investigation, was chosen as a reference material. This determined as a function of tN from DTA measurements for
material after being prepared, according to the proce-dure each tN. A plot of (IN tN) vs tN should be a straight line, its
explained in this paper, was carefully leached in HF to slope yielding the value of IN at TN. Determining (IN tN)
remove the remaining glass phase. using Eq. (1) requires three unknown parameters be known,
namely Nq, IG, and UG. The value of UG can be determined
Microstructural Examinations by the conventional method. To determine Nq and IG, three
DTA runs for an as quenched glass (INtN 50) with different
The microstructures were examined by a scanning heat treatment times (tG1, tG2, tG3) at TG are required. If A1,
electron microscope (Leica Cambridge Stereoscan A2, and A3 are the respective DTA peak areas then three
360, St. Gallen, Switzerland). Polished sections etched equations of the following type can be de-veloped for A1/A2,
in 5% HF solution for 15 s, coated with a thin gold A1/A3, and A2/A3 from Eq. (1).
layer were used for this purpose.
h p 3 3 i
A1 M1 1 3 IGtG1 þ Nq UG tG 1 I GtG1 þ Nq
Nucleation and Growth Rate Measurements
A h p
3 3 i
Nucleation: The technique commonly used to deter-mine 2 ¼M2 1 3 IGtG2 þ Nq UG tG 2 I GtG2 þ Nq
the nucleation rate is to heat the glass at a certain ð2Þ
temperature for a selected period of time, thereby devel-
oping nuclei within the glass. The glass is then heated to a
Simultaneous solution of any two of three equations for
higher temperature for a short time where detectable crys-
tals grow on the nuclei. If it is assumed that each crystal
A1/A2, A1/A3, and A2/A3 will yield the values for Nq
grows from a single nucleus and no new nuclei are formed or and IG, which can be used in Eq. (1) as constants to
dissolved during crystal growth, the number of nuclei determine (IN tN) values vs tN.
In order to determine the parameters, which should be
per unit volume of glass can be determined by counting
used in Eq. (2) above first 30 mg of the most promising glass
the number of crystals in a given volume.28–30 powder preheated for 5, 10, and 15 min at growth
DTA methods have also been utilized to determine the
temperature (TG) were subjected to DTA runs at a heating
nucleation rates in glasses.31–33 More recently a much
rate of 101C/min and the DTA peak areas A1, A2, and A3
faster and precise DTA method was introduced for nu-
were calculated. Then according to the aforementioned
cleation and growth rate measurements in glasses that
re-quires a smaller amount of sample and needs no procedure, the values of Nq and IG were determined.
In the second stage, the glass powder samples were first
special sample preparation.34,35
heated at a rate of 251C/min to the most suitable nucleation
According to this method, the nucleation rate can be
temperature of (TN) held for 1, 2, 3, and 4 h respectively,
determined as follows35:
h p I t each sample were then heated at the same rate to TG, held
M1 1 I Nt N þ 3 3 i I t
þ Nq UG t G I NtN þ Þþ Nq
G G1 1 G G1
A 1 3
ð for two different time periods of 5 and 10 min and finally
¼ h þ I t þ ð þ I t Þþ were air cooled. The above-mentioned specimens were then
M2 1 p I t i N
A2 3 NN G G2 N q U G3t G32 I NtN G G2 q subjected to DTA analysis at a rate of 101C/min. By using
ð1Þ DTA peak areas, (calculated by softwares attached to
156 International Journal of Applied Ceramic Technology—Rezvani, Marghussian and Eftekhari YektaVol. 8, No. 1, 2011

DTA) the IN tN values vs tN were ploted. The average 1196, Norwood, MA) with a crosshead speed of 0.5
value of nucleation rate at TN was then calculated from mm/ min and according to ASTM C158-84 procedure.
the slope of the resulting straight line drawn by linear Five polished rectangular specimens (40 mm 10 mm 5
regres-sion analysis. The measured temperatures for mm) were tested to calculate each average value.
crystal nu-cleation (TN) and growth (TG) as determined
by DTA, according to a procedure to be explained in the
next sec-tion, were accurate to within 721C. Three Results and Discussion
separate spec-imens were used for each measurement.
Growth: The growth rate of crystals were calculated
DTA Results on Nucleation and Crystallization of
according to the conventional method by measuring the
Glass Specimens
dimensions of particles growing from the glass specimens.
Figure 1 shows DTA plots for some specimens
The specimens had been heat treated at TG for 3, 4, 6, and 30 and Table II summarizes the results.
min, respectively, after a 3-h nucleation heat treatment at
TN. The micrographs of polished and etched specimens were
used for the above-mentioned measurements. The diameter
of crystallized particles was then plotted versus time and the
growth rate UG was calculated from the slope of the
resulting straight line, drawn using linear regression analysis.
Three different specimens were used in this ex-periment and
the average values have been reported.

TTT Diagrams

In order to plot the TTT diagrams, first the above


glass samples after subjecting to the optimum nucle-ation
process, were held at five differing temperatures around
the optimum growth temperature (TG) for 30, 60, 120,
and 240 min and were then subjected to quan-titative
XRD analysis. The value of percent crystallized (X) were
determined for each heat treatment tempera-
ture and time by first calculating the had and hpd ratios,
h h
si si

where had hpd, hsi are the principal XRD peak heights for
artificial (fully crystalline) diopside, partially crystallized
diopside (heat-treated sample) and pure silicon powder,
respectively. The average X values were then determined
by calculating the ratio of hpd to the had for each heat
h h
si si

treatment condition using three separate specimens.


A series of X (average wt% crystallized) versus time
curves were then plotted for different crystallization
temperatures. TTT curves were plotted for differing X
values by connecting the T/t data points, where T is the
chosen crystallization temperature and t is the holding
time at that temperature to produce the required degree of
crystallization (X value).

Mechanical Properties

The three-point bending strength of specimens were Fig. 1. Differential thermal analyses traces for some glass
determined using a universal testing machine (Instron specimens. (a) G–Cr3Fe5Ti5; (b) G–Cr3Fe5; (c) G–Ti5; (d) G–Cr3.
www.ceramics.org/ACT Crystal Nucleation and Growth Rates, 157

Table II. Summary of DTA Glass Transition (T g)


and Crystallization (Tc) Temperatures
Tg (1C) Tc (1C)
Specimen (72) (72)

Gb 774 1078
G–Cr3 805 1002
G–Fe5 710 1046
G–Ti5 715 1059
G–Cr3Fe5 725 936
G–Cr3Ti1 767 1006
G–Cr3Fe5Ti5 702 903
Base glass.
DTA, differential thermal analyses.

It is clear that the specimen G–Ti5 exhibited the


highest crystallization temperature and a broad DTA
exothermic peak, indicating a weak bulk crystallization
tendency. On the contrary, specimen G–Cr3Fe5Ti5
shows a quite sharp exothermic peak and the lowest
crystallization temperature, which are the evidences for a
marked bulk crystallization tendency. The most suitable
nucleation temperature of glass specimens can be deter-
mined according to Day and Ray method24 as follows:
first the specimens are soaked at differing nucleation
temperatures (Tn) in Tg–Td range for a specified time,
where Tg and Td were glass transition and dilatometric
softening temperatures, respectively, they are then sub-
jected to DTA runs and a T c vs Tn curve is ploted, where
Tc is DTA peak temperature. The minimum of this
curve generally represents the most efficient nucleation
temperature, because the specimen soaked at the most
suitable nucleation temperature usually shows the lowest
exothermic peak temperature in DTA runs. Figure 2
depicts DTA plots for the specimen G–Cr3Fe5Ti5 ob-
tained according to the above procedure for a nucleation
time of 3 h at the indicated temperatures. A continuous
decrease in DTA peak temperature and improvement in
peak sharpness are observed upon the elevation of nu-
cleation temperature up to 7401C but higher nucleation
temperatures resulted first in the increase of peak tem-
perature and then the shortening and broadening of
peaks (despite the reduction of peak temperatures),
which are the signs of crystallization decline and even-
tually the vanishing of the peak at around 8001C. In this
way, 7401C was chosen as the most suitable nucleation Fig. 2. Differential thermal analyses traces of specimen
temperature for specimen G–Cr3Fe5Ti5. Table III de- G–Cr3Fe5Ti5 previously nucleated at the indicated temperature
picts the DTA results concerning the most suitable for 3 h.
158 International Journal of Applied Ceramic Technology—Rezvani, Marghussian and Eftekhari YektaVol. 8, No. 1, 2011

Table III. Results of DTA Crystallization Tempera-


tures (Tc) After a 3 h Hold at Nucleation Temperature
(Tn)
Specimen Tn (1C) Tc (1C)
G–Cr3 840 973
G–Fe5 755 942
G–Ti5 760 1025
G–Cr3Fe5 765 926
G–Cr3Ti1 807 993
G–Cr3Fe5Ti5 740 885
DTA, differential thermal analyses.
Fig. 3. Scanning electron micrograph of specimen G–
Cr3Fe5Ti5 nucleated at 7401C for 3 h and subsequently heat
nucleation and crystallization (growth) temperatures of treated at 8851C for 4 min.
some specimens. It can be seen that the crystallization
temperatures represented in Table III are lower than the
values summarized in Table II. This can be explained by 20 3
IG first were calculated as N 5 4.5 10 /m and
16 3 q
the effect of nucleation heat treatment, which by pro- ob-
IG 57.4 10 /m /s. The value of IN then was
viding much greater population of nuclei (more efficient tained from the slope of a straight line representing the
nucleation) reduced the crystallization temperature. It is
variation of (IN tN1Nq) vs tN. Figure 6 exhibits the above-
interesting to note that the specimens G–Ti5 and G– mentioned line, the slope of which gives the value of
Cr3Fe5Ti5 show again the highest and lowest crystalli- nucleation rate at 7401C as I740 53.107 0.18 1018/m3/s. It
zation temperatures, respectively. In this way specimen should be mentioned that in the generalized DTA method
G–Cr3Fe5Ti5 was selected as the most promising glass– used in this study, even in the case of overlapping I and U
ceramic specimen and the optimum crystal nucleation and curves, quite reliable results could be obtained.35 It is also
growth temperatures for it determined as 7401C and interesting to compare the value of nucleation rate
8851C, respectively. The details of nucleation process determined in this study with results of other
and crystallization kinetics of a glass possessing this investigators. The crystal nucleation rate in glasses
com-position have been discussed previously23,24 and the investigated in this work in comparison with the
crystal nucleation and growth rates of the latter glass nucleation rate of LS2 (Li2O 2 SiO2) glasses, for
along with its TTT diagram will be discussed here.

Crystal Growth Rate

Figures 3 and 4 depict SEM micrographs of the


random sections of the most promising glass specimen
after a 3-h nucleation at 7401C and growth of 4 and 6
min at 8851C, respectively. The diameter of crystal-
lized particles versus time, ploted utilizing the data ob-
tained from random sections of the heat-treated
specimens is shown in Fig. 5. The slope of the result-
ing straight line, giving the growth rate, was calculated
as UG 5 6.1770.55 10 9 m/s.

Crystal Nucleation Rate


Fig. 4. Scanning electron micrograph of specimen G–
The nucleation rate was determined by the DTA Cr3Fe5Ti5 nucleated at 7401C for 3 h and subsequently heat
method as described above, the average values of Nq and treated at 8851C for 6 min.
www.ceramics.org/ACT Crystal Nucleation and Growth Rates, 159

Obviously direct measurement of the nucleation


rates is a much accurate and reliable method for deter-
mination and evaluation of the effectiveness of glass
nucleators in comparison with indirect methods like
utilization of the DTA exo-peak temperature, height,
sharpness, or activation energy for crystallization.
It seems that the method, which have been utilized
in this study as a fast and relatively easy method for
measuring the nucleation rate, has not been
appreciated enough so far and the authors hope that the
suitability and reliability of the method, reconfirmed
Fig. 5. Diameter of crystallized particles versus holding by this work, could perhaps help its more appreciation
time at 8851C after a nucleation step at 7401C for 3 h. and use in the future.

which a large amount of I and U data are avail-


TTT Diagrams
able29,34,36 is higher by nine orders of magnitude.
Barbieri et al.17 have reported the crystal nucleation The XRD patterns of glass specimens after the heat
rate of a glass with an approximately similar composi- treatment for different time periods at 8851C are shown
tion to the glass investigated in the present study. The in Fig. 7. All specimens were nucleated of 7401C for 3 h
comparison of the crystal nucleation rates of the two before the heat treatment at 8851C. An aluminian diop-
glasses reveals that the nucleation rate in the present glass side is the single phase identified in the patterns (for
is two orders of higher magnitude. Therefore, it can be comparison of relative intensities, 10 wt% silicon pow-
suggested that in the glasses investigated here a much der was added to all XRD specimens). Figure 8 shows X
efficient bulk nucleation mechanism had been operative. (percent crystallized) versus time curves for different
Considering the fact that in the present study crystallization temperatures calculated according to the
a combination of three oxides, namely Cr2O3, Fe2O3, procedure explained above. It seems that 75–82% is an
and TiO2 was used instead of singly used Cr2O3 nuc- approximate practical range in which a rela-tively high
leant in some studies (including the work of Barbieri amount of crystalline material (and good strength) can be
and colleagues) our previous claims concerning the obtained in reasonable time. Eighty-two weight percent is
effectiveness of the triple nucleants in inducing bulk almost the upper value of the
nucleation in the glasses of this system was confirmed.
These claims were substantiated by reduced values of
activation energy for crystallization and lower DT values
(DTA exo-peak shifts upon changing the glass sample
particle sizes)19,20,23,24 that are consistent with the
results of the present work.

Fig. 7. X-ray diffraction patterns of glass specimens after a two-


stage heat treatment, 3 h at 7401C and 0–240 min at 8851C,
showing an aluminian diopside as the main crystalline phase. (1)
Fig. 6. Number of nuclei (INtN1Nq) as a function of nucleation 0 min; (2) 30 min; (3) 60 min; (4) 120 min; (5) 180 min; (6)
time (tN) at 7401C. 240 min.
160 International Journal of Applied Ceramic Technology—Rezvani, Marghussian and Eftekhari YektaVol. 8, No. 1, 2011

Fig. 8. Percent crystallized (X) versus time curves for


different temperatures. (a) 8851C; (b) 8651C; (c) 9051C; Fig. 10. Scanning electron micrograph of the glass
(d) 9251C; (e) 8451C. specimen G–Cr3Fe5Ti5 nucleated at 7401C for 3 h and
soaked at 8851C for 3 h.
range. Figure 9 exhibits the TTT diagram for 82 wt%
crystallized sample.
It can be concluded that the nose temperature, at Microstructural Investigation
which the time to obtain a certain amount of
crystalline phase is minimum, is close to 8851C for 82 Figures 10 and 11 exhibit the SEM microstructures
wt% crys-tallization. This temperature was determined of G–Cr3Fe5Ti5 and G–Ti5 specimens after a heat treat-
before, as the optimum crystallization temperature ment at their respective nucleation and crystallizations
utilizing DTA methods. temperatures for 3 h. The most promising specimen (G–
The nose time for 82 wt% crystallization was Cr3Fe5Ti5) reveals an apparently well-crystallized glass–
55 min, which is relatively short for this high crys- ceramic, comprised of fine flaky particles. This is
tallization value. It is also interesting to note that a rel- consistent with the previous results reporting an Avrami
constant of around 3 for the same specimen indicating a
atively small change in the crystallization temperature,
for example 7201C, nearly doubles the required hold- two-dimensional bulk crystallization.24 Specimen
ing time to obtain the same 82 wt% crystallization.
These findings could be especially explored for the
im-provement of the technology of glass–ceramics of
this system if the nucleation agents proved here to be
the most effective in this connection were used.

930

915

900
T (°C)

885

870

855
1.7 1.9 2.1 2.3
Log t (min)
Fig. 11. Scanning electron micrograph of the glass specimen
Fig. 9. Time–temperature transformation diagram for 82 G– Ti5 nucleated at 7601C for 3 h and soaked at 10251C for
wt% crystallized sample. 3 h.G, glass; C, crystal.
www.ceramics.org/ACT Crystal Nucleation and Growth Rates, 161

G–Ti5 on the other hand demonstrated little ability for face crystallization. Quite large crystals growing from
bulk crystallization and showed a marked tendency for the glass surface are clearly observable in the micro-
surface crystallization (Fig. 11). This is also consistent structure of the latter specimen.
with other experimental results represented above, re- The glass–ceramic G–Cr3Fe5Ti5, on the other hand,
garding the highest crystallization temperature and rel- demonstrates a well-crystallized glass specimen, densely
atively broad DTA peak of this specimen. populated with tiny flaky crystals, with the size of 1–2
mm. It can be expected that a glass–ceramic
Mechanical Properties demonstrating such microstructures would show quite
high bending strength values. In fact, the measured av-
Table IV depicts the strength values for some spec- erage bending strength of 166 MPa for the above spec-
imens. The comparison of the flexural strength values imen is relatively high in comparison with the values
represented in this table with the crystallization temper- reported by other investigators,7,12,13,21,27 which are
atures of Table II, reveals an inverse correlation between mainly in the range of 60–140 MPa.
the values of strength and DTA crystallization (exother-
mic) peak temperatures. Considering the fact that higher
DTA crystallization temperature usually indi-cates a Conclusions
relatively weak bulk nucleation and crystalliza-tion
ability, it can be deduced that the glasses exhibiting The nucleation rate of an aluminian diopside, as the
higher DTA exothermic peak temperatures are less likely sole detectable crystalline phase, was determined for
to develop sufficient crystalline material and would a glass composition located in SiO2–Al2O3–CaO—
possess higher amounts of glass phase. MgO–(R2O) system and nucleated by various amounts of
Moreover, insufficient number of nuclei in the bulk Cr2O3, Fe2O3, and TiO2 oxides. A relatively high value,
glass allows the formed crystals to grow to larger sizes. In at the order of 1018 m3/s, was obtained for the most
extreme cases, these specimens would remain more or promising specimen, in optimum nucleation tem-perature
less glassy with occasional large crystals nucleated and of 7401C indicating the existence of a great ability for
grown from the surface. Obviously, such specimens bulk nucleation in this specimen. The growth
lacking the hindering effect of embedded crystals on rate of diopside crystals in this glass was also
growing cracks (crack pining, deflection, etc.) usually measured as U 56.17 10 9 ms at 8851C.
would be weak. In some cases, when sufficient stress is A TTT diagram was also ploted for the 82 wt%
developed between the growing large crystals and glass crystallization in this glass, giving the minimum re-
matrix (e.g. due to the thermal expansion differences), the quired condition of crystallization (nose condition) as
glass–ceramic would be weaker than the parent glass. The 55 min at 8851C, which is a quite short time for this
extremely low value of flexural strength of the glass– high crystallization value. The bending strength value
ceramic G–Ti5 may probably be explained by the was also determined for this glass–ceramic as 16676
existence of some conditions like those mentioned above. MPa, which is relatively high for these type of glass–
Figure 11 demonstrates a typical example of sur- ceramics.
Finally, on the basis of the above findings the use
of the triple nucleants and the heat treatment procedure
Table IV. Bending Strength Values for Some explained here are strongly recommended for glass–
Specimens ceramics of similar compositional ranges in order to
Bending strength obtain fine grained and strong glass–ceramics.
Specimen MPa
G–Cr3 135711 References
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