Materials Science-Poland, 34(1), 2016, pp.

25-32
http://www.materialsscience.pwr.wroc.pl/
DOI: 10.1515/msp-2016-0027

Experimental and theoretical approaches on thermal and

structural properties of Zn doped BSCCO glass ceramics
H. KORALAY 1 , O. H ICYILMAZ 1 , S. C AVDAR 1 , O. O ZTURK 2,3 , A.T. TASCI 2∗

1 Superconductivity and Thermal Analysis Laboratory, Department of Physics, Faculty of Sciences, Gazi University, 06531
Ankara, Turkey
2 Department of Physics, Faculty of Arts and Sciences, Kastamonu University, 37100 Kastamonu, Turkey
3 Research and Application Center, Kastamonu University, 37100 Kastamonu, Turkey

Thermal properties of Cu–Zn partially substituted Bi1.8 Sr2 Ca2 Cu3.2−x Znx O10+δ (x = 0, 0.1 and 0.5) glass-ceramic sys-
tems have been investigated with the help of a differential thermal analyzer (DTA) by using Johnson-Mehl-Avrami-Kolmogorov
(JMAK) approximation. Non-isothermal crystallization kinetics of the samples has been tested. The calculated values of acti-
vation energy of crystallization (E) and Avrami parameter (n) ranged between 306.1 and 338.3 kJ·mol−1 and 1.29 and 3.59,
respectively. Crystallization kinetics was compared following the partial substitution, before and after Zn doping of the sample.
In addition, by using a scanning electron microscope (SEM) and X-ray powder diffractometer (XRD), structural properties of
Zn doped BSCCO glass-ceramic samples were determined. Surface morphology of the samples was studied by SEM measure-
ments. Lattice parameters and volume of the samples were calculated from the XRD measurements.
Keywords: BSCCO; Zn-doped glass-ceramics; thermal properties
© Wroclaw University of Technology.

1. Introduction materials are used in aerospace and aviation indus-

try, electronics industry, material coating technol-
Crystallization, providing transformation from ogy, production of superconducting materials and
glass to glass-ceramics, is obtained by a careful even in medicine [7, 8]. Glass ceramics, having
and appropriate thermal process program, which low thermal expansion and high transparency to the
enables nucleation and growth of crystal phases in dedicated wavelengths can be used as windows for
glass. Ceramics are polycrystalline materials hav- laser applications [9].
ing high mechanical durability and impact resis-
tance, higher refractory and lower thermal expan- A lot of additives doped to the BSCCO sys-
sion coefficient in comparison with glasses from tems and many features of this system have been
which they are produced [1–3]. These materials are investigated. Some of those studies included works
engineering materials that are used in some spe- with partially substituted Zn–Ca BSCCO systems
cial applications because of their hardness, cor- produced by solid state reaction method [10–13].
rosion resistance, oxidation, strength to corrosion The effect of Zn doping on electrical and mag-
and high temperature, dimensional stabilities, opti- netic properties of the BSCCO system has been
cal and other transmission characteristics as well investigated by Mohamed et al. [14]. Aksan et al.
as good electrical properties [4]. Some of these analyzed the effect of Zn addition to the BSCCO
applications include superconductivity, biomedi- system prepared by glass-ceramic method in order
cal applications, applications requiring high dielec- to investigate the thermal, electrical and magnetic
tric constant, material connections and substrates properties [15]. In another study, related to Zn ad-
for electronics [5, 6]. Moreover, the glass-ceramic dition, the microhardness properties of the system
were investigated [16]. In the literature there are
∗ E-mail: [email protected] no studies on Zn addition instead of Cu, showing
26 H. KORALAY et al.

metallic properties of the BSCCO system. Copper range of 3° 6 2θ 6 70° at a scan speed of
is a fundamental element in this structure respon- 2°/min. Phase structure and lattice parameters were
sible for its conductivity. For this reason, investi- obtained by using Bruker-EVA 10.0.1.0 version an-
gation on Zn–Cu substitution is important. In this alyzing program with ICDD PDF2-2002 library.
study, thermal changes caused by copper deficiency The mean values of lattice parameters of the
have been analyzed. Bi1.8 Sr2 Ca2 Cu3.2 − x Znx O10 + δ samples were deter-
In the present work, variation in thermal mined from the high angle (0 0 1) peaks of the
and structural properties of the glass-ceramic XRD measurements. Leo EVO-40 VPX scanning
Bi1.8 Sr2 Ca2 Cu3.2 − x Znx O10 + δ system (x = 0, 0.1 electron microscope was used to determine the sur-
and 0.5) with various Zn doping levels have been face morphology of the samples. Hereafter, the pro-
studied. duced samples were named as CZn00, CZn01 and
CZn05 for simplicity.

2. Experimental 3. Theoretical background

One of common methods used for preparing As it was indicated by various authors, the
ceramic materials is the glass-ceramic method. isothermal kinetics was firstly derived by Kol-
Therefore, in this study, the amount of copper in mogorov and developed by Johnson, Mehl and
the BSCCO system was reduced by zinc doping us- Avrami. During the long development history of
ing the glass-ceramic method. High purity Bi2 O3 , this process, Erofeev and Mitskevich also gave
SrCO3 , CaCO3 , CuO and ZnO powders were used some contributions [17–21]. The volume fraction
as starting materials in the preparation of the sam- changing in time t is defined as a function of
ples. 20 g of samples for each doping level (x = 0, time as:
0.1 and 0.5) were prepared. Powders constituting  Zt Z t 
the composition were weighted and mixed in an x = 1 − exp −g Iν (( udτ )m )dt 0 (1)
agate mortar for 1 h to get a homogenous mixture. 0 t0
This final powder was put into an alumina crucible
and heated approximately up to 1150 °C for 1.5 h. Crystallization and reaction kinematics at a
The molten mixture in the crucible was taken from constant temperature were expressed by the well-
the furnace and rapidly poured between two cop- known Johnson-Mehl-Avrami equation:
per plates, which were cooled down with liquid ni-
− ln(1 − x) = (kt)n (2)
trogen, then pressed, and as a result, thick black
shiny glasses of 1 to 3 mm thickness were obtained.
Temperature dependence of k within a spe-
This cold and quick procedure was specially cho-
cific temperature range can be given by Arrhenius
sen to prevent selective crystallization. Otherwise,
equation:
partial crystallization might have occurred and as a
result, not quite amorphous samples would be ob- k = k0 exp(−E/RT ) (3)
tained. SII7300 Exstar DTA was used to determine
the thermal properties of these glass samples at var-
At the Differential Thermal Analysis (DTA),
ious heating rates (β = 5, 10, 15 and 20 K·min−1 )
heating rate (β = dT/dt) is usually kept constant
under nitrogen gas atmosphere. After this process,
during scanning. Thus, the reaction rate constant
glass-ceramic samples were obtained by sintering(k), changes with time as the temperature changes.
the glass samples in a furnace at 840 °C under an
Such cases are referred as non-isothermal condi-
oxygen flow for 120 h. tions. Temperature of a sample and heating rate are
Bruker D8 Advance X-ray powder diffractome- linearly dependent on each other as [22, 23]:
ter was used to determine the lattice parame-
ters of the samples, with CuKα radiation in the T = T0 + βt (4)
 Experimental and theoretical approaches on thermal and structural properties of Zn. . . 27

If we write equation 2 in another form, we get: activation energy and R is the gas constant,
R = 8.314 J/mol·K. Similarly, k0 value can be de-
x(t) = 1 − exp[−(kt)n ] (5) termined from ln(β/T2x ) versus 1000/Tx graph. k0
can also be found from the intercept of this plot.
Time derivative of this equation is:
We can calculate the reaction rate (k) from equa-
ẋ = n(kt)n−1 (k + kt)(1 − x) (6) tion 3 which is valid for both isothermal and non-
isothermal conditions, by substituting the value
For the derivative of k with respect to time, with of the frequency factor in the equation. Accord-
help of equation 3 and equation 4, equation 7 was ing to Ozawa method derived from Johnson-Mehl-
obtained: Avrami-Kolmogorov equation:
d ln[− ln(1 − x)]/d ln β = −n (14)
    
dk dT βE
k̇ = = 2
k (7)
dT dt RT the slope of ln[−ln(1 − x)] versus lnβ graph,
If this equation is substituted in equation 6 plotted according to equation 14, gives the value
we get: of −n [24]. To obtain the Avrami parameter (n),
which is important in determination of the nucle-
n n−1
ẋ = nk t (1 − at)(1 − x) (8) ation mechanism of the samples, the crystallization
fraction equation was used [25]:
where a = (βE/RT2 ).
x = Ax /A (15)
If E/RT2  1, (at) term can be neglected. Thus,
equation 8 can be rewritten as [17]: Fig. 1 shows a DTA curve changing with tempe-
rature. Here, TStart is the beginning temperature of
ẋ = (1 − x)nknt n−1 (9) the peak, Ty is the partial temperature, Tx is the
DTA peak temperature, TFinish is the final tempe-
If this equation is rearranged according to equa-
rature of the peak, Ax is the partial area of the peak
tion 7 we get:
between TStart and Ty , A is the total area (crystal-
ẋ = Ank(1 − x) (10) lization enthalpy) of the peak between the tempe-
ratures TStart and TFinish , and Tg is glass transition
where A = [ln(1−x)] (n−1)/n . If the time derivative temperature.
of equation 9 is set to zero, by assuming that A
is constant at maximum peak temperature (Tx ), an
equation depending on (Tp ) is obtained:

ẍ = Ank(1 − x)[(β E/RTx2 ) − Ank] = 0 (11)

This equation can also be written as:

(β /Tx2 ) = C exp(−E/RTx ) (12)

where C = (ARk0 /E). The logarithm of the above

Fig. 1. DTA curve and the values determined from the
equation is: graph.

ln(β /Tx2 ) = Sabit − (E/RTx ) (13)

According to Xie and Gao, the Avrami param-
eters found from surface to inside are interpreted
If the graph of ln(β/T2x ) expression is plot- as [26]:
ted versus 1000/Tx , the slope of this graph gives
the fraction of (−E/R) and then the activation • n = 1 − surface nucleation and one di-
energy can be easily calculated. Here, E is the mensional growth,
28 H. KORALAY et al.

• n = 2 − volume nucleation and one di-

mensional growth,
• n = 3 − volume nucleation and two di-
mensional growth,
• n = 4 − volume nucleation and three di-
mensional growth.

Glass transition temperatures of the samples

were analyzed by using different approaches [26–
28]. The first experimental relation between glass
transition temperature and heating rate was given
by Lasocka [29] as: Fig. 2. DTA curves of Bi1.8 Sr2 Ca2 Cu2.5 Zn0.5 O10 + δ
sample for various heating rates (a) β =
Tg = A + B ln(β ) (16) 5 K·min−1 , (b) β =10 K·min−1 , (c) β =
15 K·min−1 and (d) β = 20 K·min−1 .
where A and B are constants of a given glass
composition.
calculated using Kissinger method. In Fig. 3, the
4. Results graph of ln(β/T2x ) vs. 1000/Tx is plotted for all
samples. From the results of calculations obtained
4.1. Thermal properties by using equation 13, the initial crystallization ac-
Fig. 2 shows the DTA curve of a powder tivation energies of Bi1.8 Sr2 Ca2 Cu3.2 − x Znx O10 + δ
Bi1.8 Sr2 Ca2 Cu2.5 Zn0.5 O10 + δ glass sample at heat- compositions with increasing Zn amount x = 0,
ing rates of 5, 10, 15 and 20 K·min−1 . Data gath- 0.1 and 0.5 were found as 338.3, 312.4 and
ered from the DTA curves of other samples were 306.1 kJ·mol−1 , respectively. Variation of activa-
listed in Table 1. It is seen from the DTA curves tion energy depending on the amount of Zn dop-
that the crystallization peak temperature intensi- ing showed a decrease with the doping. Crystal-
ties increase with increasing heating rate. The crys- lization activation energy for the BSCCO system
tallization peak temperature variations depending was found between 337 and 367 kJ·mol−1 in the
on the system of doping were investigated based literature [31]. The reason for the decrease in the
on the data from Table 1. As a consequence, it activation energy is considered as the occurrence
is seen that the glass transition temperature and of instability in the samples. The decrease in the
the crystallization peak temperature are shifted to- activation energy in glass-ceramic samples makes
wards higher values with increasing Zn doping. them thermodynamically more unstable [32].
This is because separation of the peaks that are In Fig. 4, Tg versus ln(β) graph was plotted
close together becomes harder when the heating using equation 16 which gives a relation between
rate increases. Glass transition temperature ob- glass transition temperature and heating rate. A
tained from these values was in the range of 732.0 and B parameters in Table 1 were also obtained
to 769.0 K. First crystallization peak temperature from this graph. As it is seen from Table 1, the
(Tx1 ) and second peak temperature (Tx2 ), corre- A and B parameters increase with Zn doping. The
sponding to CuO phase values were obtained in the ln[−ln(1 − x)] versus ln(β) graph drawn with the
range of 741.0 to 786.1 K and 796.8 to 819.8 K, re- help of x value calculated from Fig. 2 is show
spectively. Exothermic peaks, formed around these in Fig. 5. The average values of Avrami param-
temperatures, were claimed to occur due to nucle- eter evaluated from the slope are listed in Ta-
ation [29, 30] in the BSCCO system. ble 1. The calculated n values are in the range of
According to the DTA results obtained from Ta- 1.29 6 n 6 3.59, which indicates that the crys-
ble 1, initial crystallization activation energies were tallization occurs through different mechanisms.
 Experimental and theoretical approaches on thermal and structural properties of Zn. . . 29

Table 1. DTA results of Bi1.8 Sr2 Ca2 Cu3.2 − x Znx O10 + δ (x = 0, 0.1, and 0.5) samples.

Lasocka Parameters E n
Samples Heating Rate (β) [K·min−1 ] Tg [K] Tx1 [K] Tx2 [K]
A [K] B [kJ·mol−1 ]
5 732.0 741.0 796.8
10 738.0 751.4 809.0
CZn 0 720.4 7.1 338.3 3.59
15 740.0 755.7 805.0
20 742.0 759.5 808.0
5 738.0 745.4 799.4
10 745.0 758.2 813.0
CZn 0.1 725.8 7.8 312.4 2.79
15 747.0 762.0 808.3
20 749.0 765.0 812.0
5 757.0 766.0 806.0
10 763.0 776.3 812.4
CZn 0.5 742.4 9.1 306.1 1.29
15 768.0 785.0 819.2
20 769.0 786.1 819.8

Fig. 3. ln(β/T2x ) vs. 1000/Tx graph for all samples ac- Fig. 4. Tg versus lnβ(K·min−1 ) graph of the samples
cording to Kissinger formula. according to Lasocka formula.

Avrami parameter for the reaction is approximately

(041-0932-ICDD) main and SrO (074-1227
equal to 4. According to this value of n, a vol-
ICDD) impurity phases were determined in the
ume nucleation and three-dimensional growth oc-
undoped sample. The peak intensity of the doped
curred. The value of n decreased with the increase
samples increases and other new peaks start to
in the doping concentration. Therefore, surface nu-
appear with the increase in Zn concentration. Some
cleation and one-dimensional growth of the sample
of these peaks are Bi-2201 (046-0040ICDD), CuO
were confirmed. (078-0428-ICDD) and CaSrO (048-1471 ICDD)
impurity peaks and the others are unidentified
4.2. Structural properties
impurity peaks.
4.2.1. XRD analysis In Table 2, calculated lattice parameters and
In Fig. 6, the XRD graphs of all volume values are given. The lattice parameters
glass ceramic samples are given. Bi-2212 a, b and c were calculated using the d values
30 H. KORALAY et al.

5.41 Å and the parameter c increases from 30.78 to

30.82 Å. Related to these parameters, lattice vol-
ume increased from 897.55 to 902.34 Å3 [33].

4.2.2. SEM analysis

Surface structure of the samples was examined
based on the SEM images (Fig. 7). Crystallization
of the sample increased with the increase of Zn
doping. Therefore, needle-like and flaky-like grains
occured. As can be seen in Fig. 7, the needle like
grain morphology of the samples became dominant
with doping. The Bi-2223 phase is believed to be
the source of the needle-like grains. In all the sam-
Fig. 5. ln[−ln(1 − x)] versus ln(β) graph for the sam- ples, the needle-like grains are more dominant than
ples. the flaky-like grains. According to our previous
study, energy dispersive spectroscopy (EDS) re-
sults showed that Zn concentration increased with
decreasing Cu and Ca concentrations but reduction
in Cu dopant was more dominant [34]. Namely,
Cu atoms were replaced by Zn atoms in the crys-
tal structure.

5. Conclusions
In this work, variation in thermal properties
of a glass-ceramic Bi1.8 Sr2 Ca2 Cu3.2 − x Znx O10 + δ
system with various Zn doping has been studied
with a differential thermal analyzer (DTA) by using
Fig. 6. XRD patterns of the samples. Johnson-Mehl-Avrami-Kolmogorov approxima-
tion. Non-isothermal crystallization kinetics of the
samples has also been investigated. As it is clearly
and (h k l) parameters by assuming orthorhombic
seen from the DTA results, the crystallization
symmetry for Bi1.8 Sr2 Ca2 Cu3.2 − x Znx O10 + δ glass-
peak temperature is shifted to higher temperature
ceramic structure, employing the least-squares
values with the increasing heating rate. The reason
method and using the data extracted from the
of this can be explained as follows: the energy
XRD measurements. The accuracy in determining
required for crystallization at lower heating rates,
the lattice parameters was ±0.005 Å. The lattice
occurs at lower temperature values. However, the
parameters a, b and c increase with doping of
energy required for the nucleation is increased
Zn. The lattice parameter a increases from 5.40 to
quickly at higher heating rates. Accordingly, the
crystallization temperature increases. The decrease
Table 2. Lattice parameters a, b, c and volume (V) val- in the activation energy of crystallization with
ues of all samples.
increasing Zn doping is caused by the replacement
Samples V(Å3 ) a(Å) b(Å) c(Å)
of Cu atoms removed from the crystal structure
by Zn atoms incorporated into the structure, and
CZn00 897.55 5.40 5.40 30.78
because of the changes in the binding distances
CZn01 899.50 5.41 5.40 30.79 of adjacent atoms in the crystal structure. The
CZn05 902.34 5.41 5.41 30.82 rearrangement of the atoms in the amorphous
 Experimental and theoretical approaches on thermal and structural properties of Zn. . . 31

the ions in the structure is decreased. For this

reason, the quality of the samples in terms of
thermal properties decreased with increasing
the doping concentration. When the contri-
bution rate of the samples increased, Avrami
parameters, which were calculated from crys-
tallization peak areas of DTA curves, de-
creased. According to the obtained Avrami
parameters, surface nucleation occurred as the
doping amount increased. The XRD analysis
showed that the lattice parameters a, b and c
(a)
increased with Zn concentration. SEM results
showed enhanced crystallization of the sample
with increasing amount of Zn doping.
Acknowledgements
The authors thank the financial support for this work
through the Scientific Research Projects (BAP 05/2011-47)
Foundation of the Gazi University Ankara.

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