Journal of Non-Crystalline Solids 473 (2017) 108–113

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Journal of Non-Crystalline Solids

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

Structure and crystallization behavior of 50CuO-xTiO2-(50-x)P2O5 MARK

(x = 5–20) glasses
Liyuan Zhang, Shiquan Liu⁎
School of Materials Science and Engineering, University of Jinan, Jinan 250022, Shandong, China

A R T I C L E I N F O A B S T R A C T

Keywords: Glass samples with molar compositions of 50CuO-xTiO2-(50-x)P2O5 (x = 5, 10, 15, 20) were prepared. The
CuO-TiO2-P2O5 glass crystalline phases, characteristic thermal temperature as well as crystallization kinetic parameters were in-
Depolymerization vestigated using X-ray diffraction (XRD) and differential thermal analysis (DTA) under non-isothermal condi-
Aggregation tions. The Fourier transformed infrared spectroscopy (FTIR) results show that the glass network depolymerizes
Crystallization
with the increase of TiO2. However, TiO2 has an aggregation effect on the glass network. As a result of the
depolymerization and aggregation effects, the glass transition temperature first increases and then decreases
with TiO2. In the meantime, the glass is easier to crystallize. The XRD measurements indicate that when the
content of TiO2 is more than 10 mol%, desired CuTi2(PO4)3 phase appears in the heat-treated samples. The
crystallization kinetics of the samples was studied using the Kissinger and Augis-Bennett models. It is evidenced
that the crystallization activation energy increases with TiO2, while surface and bulk crystallization mechanisms
dominate in the sample with 5 mol and 10–20 mol% TiO2, respectively.

1. Introduction TiO2 is used as a nucleating agent in silicate glasses [12]. However,

Phosphate glasses have potential applications in batteries, laser
technologies and biology, etc. [1,2]. The basic structure unit of phos-
phate glasses is PO4 tetrahedron [3]. Various phosphate anions can be
formed by linking through covalent bridging oxygen atoms. Three-di-
mensional cross-linked network of phosphate glasses contains three
bonging oxygen atoms and this structure may change into a polymer-
link metaphosphate which includes two covalent bridging oxygen
atoms. Polymer-link metaphosphate may further transform to pyr-
ophosphate which has only one bonding oxygen atom. The actual
structure of a phosphate glass depends on the O/P ratio in its compo-
sition [4,5].
The poor chemical durability associated with the chain-like struc-
ture phosphate glasses limits the practical application of glasses in the
fields that conventional silicate glasses have been used [6]. There has
been great efforts to improve the chemical stability of phosphate glasses
by introducing suitable dopants, such as Al2O3, Fe2O3, MgO, CaO, etc.
[7–10]. These additions may not only enhance the chemical durability
of the phosphate glasses but also can impart special functions to the
glasses and expand the glass application fields. For example, with ad-
dition of CaO, phosphate glass can act as bioactive glass and phosphate
glasses containing large amount of TiO2 have shown excellent photo-
catalytic properties after heat-treatment [10,11].
there is not much literature on binary TiO2-P2O5 glasses. Binary TiO2-
P2O5 glasses could be prepared by quenching method [13]. However, it
was found that glass formation region in the binary TiO2-P2O5 system is
narrow. Alkaline, alkaline earth or transition metal oxides were added
to improve the glass forming ability of titanium containing phosphate
system [14]. More profoundly, especially founctionalized titanium
phosphate glass materials have been developed. For example, Li2O-,
CaO- and CuO-containing titanium phosphate glasses have been made
into functional porous glass-ceramics via crystallization and subsequent
acid leaching procedures. Hosono et al. prepared porous glass-ceramics
with CaTi4(PO4)6 and β-Ca3(PO4)2 phases from CaO-TiO2-P2O5 glass
and with Li1 + xTi2 − xAlx(PO4)3 and β-Ca3(PO4)2 phases from Li2O-
CaO-TiO2-Al2O3-P2O5 glass [15,16]. The porous glass-ceramics with a
skeleton of LiTi2(PO4)3 made from Li2O-CaO-TiO2-Al2O3-P2O5 glass
showed excellent exchange ability with Ag+ ions [17,18], which led to
the formation of microporous materials with AgTi2(PO4)3 and Ti
(HPO4)2·2H2O crystals. The latter materials exhibited bacteriostatic
activity and ammonia gas adsorption capacity [19]. Special attention is
given in this article to CuO-TiO2-P2O5 glasses, from which porous glass-
ceramics with a skeleton of NASICON-type crystal CuTi2(PO4)3 could be
formed [20]. The prepared porous glass-ceramics showed catalytic ac-
tivity in the oxidation of propene to acrolein [21]. It could also be used
as a solid electrolyte to replace zirconia one in oxygen gas sensors [22].

⁎
Corresponding author at: School of Materials Science and Engineering, University of Jinan, West Campus, No. 336, West Road of Nan Xinzhuang, Jinan 250022, China.
E-mail addresses: liusq_ujn@hotmail.com (L. Zhang), mse_liusq@ujn.edu.cn (S. Liu).

http://dx.doi.org/10.1016/j.jnoncrysol.2017.08.003
Received 15 June 2017; Received in revised form 31 July 2017; Accepted 2 August 2017
Available online 09 August 2017
0022-3093/ © 2017 Published by Elsevier B.V.
L. Zhang, S. Liu
For the above phosphate glasses, their structure and crystallization
behavior are vital to the special functions of the final derived materials.
However, there still lacks a systematical study on the crystallization of
copper titanium phosphate glasses. In this work, the structure and
crystallization behavior of 50CuO-xTiO2-(50-x)P2O5 (x = 5, 10, 15, 20)
glasses have been studied.
2. Experimental procedures
Glasses with a composition (in mol%) of 50CuO-xTiO2-(50-x)P2O5
(where x = 5, 10, 15, 20) were prepared using analytic grade reagents
of CuO, TiO2 and H3PO4 (Conc. 85%). These raw materials were put
into a Teflon beaker and mixed with 30 ml water to make a slurry [23].
The slurry was evaporated and dried at 200 °C for 12 h. Then, the dried
mixture was melted in an electric furnace at 1250 °C for 1 h. Finally, the
melts were poured out and quenched into water to avoid the crystal-
lization of the melts during cooling process. The collected particles
were finally dried at 100 °C in a furnace. The as-synthesized samples
were denoted respectively as Ti5, Ti10, Ti15 and Ti20 corresponding to
the contents of TiO2.
The glass samples were thermally treated in a furnace with a
ramping rate of 5 °C/min at the glass transition points for 1 h, then at
the crystallization peak temperatures for 2 h. The heat-treated samples
were denoted as Tix-HT-T, where x stands for the content of TiO2 in the
parent glass and T represents the heat treatment temperature.
The Fourier transform infrared spectroscopy (FTIR) spectra of
samples were recorded on a Nicolet iS10 Spectrometer (Thermo, USA)
in the wave number range of 400–1350 cm− 1. The measurements were
made on glass powder dispersed in KBr pellets. The crystalline phases in
the heat treated specimens were identified by X-ray diffraction analysis
(XRD) carried out on a D8 ADVANCED diffractometer (Bruke,
Germany). The relative contents of the crystalline phases were esti-
mated using the Matrix-flushing method [24].
Differential thermal analysis (DTA) was performed on an HCT-1
(Henven, China) thermal analyzer with a heating rate of 20 °C/min in
air with an empty alumina crucible as reference. Powder samples with
particles sized 106–125 μm were applied in the DTA analysis. The glass
transition points were determined using the tangent extrapolation of
the onset of first endothermic peak on the DTA curves. To determine the
crystallization activation energy (E) of the glasses, heating rates of 5, 10
and 15 °C/min were also applied in the DTA analysis. E is calculated
based on the following Kissinger eq. [25,26]
ln (Tp2 α) = (E R)(1 Tp) + C (1)
where Tp is the crystallization peak temperature in the DTA curve; α,
the heating rate; R, the universal gas constant and C, a calculation
constant. As can be seen from Eq. (1), a plot of ln(Tp2/α) versus 1/Tp
will give a straight line, indicating that the data of ln(Tp2/α) and 1/Tp
have a linear relationship. E can then be obtained from the slope (E/R)
of the straight line. In addition, the crystallization mechanism of a glass
can be correlated with the Avrami parameter, n, which is obtained from
the eq. [27]
n = (2.5 ΔT )RTp2 E (2)
where ΔT is the width of the crystallization peak at half height in the
DTA curves.
3. Results and discussion
3.1. XRD and FTIR analysis of the as-synthesized samples
The XRD patterns of the as-synthesized samples are presented in
Fig. 1. The patterns in Fig. 1(a) consist of broad halo peaks at low
diffraction angles, which confirm the amorphous nature of the as-syn-
thesized samples Ti5 to Ti20. However, the pattern in Fig. 1(b)
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Journal of Non-Crystalline Solids 473 (2017) 108–113
indicates that sample Ti25 was devitrified. It will not be further studied.
The FTIR spectra of the glass samples Ti5 to Ti20 are shown in
Fig. 2. From the FTIR spectrum of sample Ti5, it can be seen that there
are mainly five absorption bands at 1200 1080, 940, 760 and
525 cm− 1, respectively. The band at 1200 cm− 1 is associated with the
stretching vibration of PO2 groups [2,28,29]. The band shifts to a lower
wave number from Ti5 to T10, and disappears in the cases of Ti15 and
Ti20. The band at 1080 cm− 1 is ascribed to the asymmetric stretching
vibrations of PeO bonds in non-bridging oxygen groups [2]. And this
band shifts to lower wave numbers with increase of TiO2. The absorp-
tion band at around 940 cm− 1 is related to the asymmetric stretching
vibration of PeOeP linkages [30]. The absorption band at 760 cm− 1 is
attributed to the symmetric vibrations of PeOeP bonds [31]. The ab-
sorption band at around 525 cm− 1 can be ascribed to the deformation
modes of PeO−(PO43 −) groups [32,33] and its intensity decreases with
the increase of TiO2. The above results are indicative of the depoly-
merization of the phosphate chains [34], suggesting that the integrity of
glass network decreases with the increase of TiO2. On the other hand,
there appears a new weak absorption band at 642 cm− 1 (see the arrow
pointed band) in the cases of Ti15 and Ti20. This new band is attributed
to the TieO vibration [12]. Due to the large electric strength of tita-
nium ions, the aggregation effect of TiO2 on the glass network cannot
be neglected [29].
3.2. DTA analysis of the glasses
The DTA curves of the glasses are shown in Fig. 3. The curves dis-
play endothermic glass transition points (Tg) at 461 °C, 488 °C, 504 °C
and 493 °C, respectively. The results show that the glass transition
points of the samples first increases with the increase of TiO2 from 5 to
15%mol. This is due to the increasing aggregation effect of TiO2 on the
glass network and slow mobility of the large titanium ions, which lead
to the increase in glass viscosity and consequently the rise in the
transition point temperature [26]. With further increasing the content
of TiO2 from 15 to 20 mol%, the Tg decreases, suggesting that the de-
polymerization of the glass network became dominate.
The DTA curves show a general trend with obvious crystallization
peaks before 1000 °C, above which the crystals become to melt. The
first exothermic peaks of samples Ti5, Ti10 and Ti15 are located around
685 °C. However, the first exothermic peak of Ti20 shifts to a lower
temperature of 646 °C. In addition, from sample Ti5 to Ti10, the first
crystallization peak becomes significantly sharper and the intensity
greatly increases with the content of TiO2. Further increasing TiO2 to 15
and 20 mol%, the intensity of this peak does not change. The second
exothermic peaks of all the samples are very weak. The temperatures
for this peak of samples Ti5 and Ti10 are 800 °C and 813 °C, respec-
tively. However, it shifts to a lower temperature of around 750 °C for
Ti15 and Ti20. The third exothermic peak appears at around 985 °C for
samples Ti5, Ti10 and Ti15. However, there exists an obvious en-
dothermic peak at 948 °C for sample Ti20, suggesting the melting of
crystals formed at the lower crystallization temperatures. The following
sharp and intense exothermic peak at 961 °C indicates a recrystalliza-
tion of the melted phase. The above results indicate that the crystal-
lization of the glass samples generally became easier with the increase
of TiO2. The ease of crystallization of the glass is a result of both the
depolymerization of phosphate glass network and the aggregation ef-
fect of TiO2.
3.3. Crystallization of the glasses at different temperatures
The XRD patterns of the heat-treated samples are shown in Fig. 4. It
is can be seen that the diffraction peaks become stronger with the in-
crease of the heat treatment temperature for all the samples. For sample
Ti5, the types of the crystalline phases do not change with the heat
treatment temperature. There exist Cu2P2O7(JCPDF card No.71-2177),
Ti7O13 (JCPDF card No.71-0629), Cu3(PO4)2(JCPDF card No.80-0991),
L. Zhang, S. Liu
Fig. 2. FTIR spectra of the glass samples with different amounts of TiO2.
Fig. 3. DTA curves of the glass samples with different amounts of TiO2.
CuO(JCPDF card No.80-0076), Ti(PO3)3(JCPDF card No.82-1178),
TiO2(JCPDF card No.71-1167) phases. The relative contents of the
identified crystalline phases are listed in Table 1. The data indicate that
Cu2P2O7 is the major phase and the content of Cu3(PO4)2, Ti(PO3)3 and
TiO2 phases increases with the heat treatment temperature, while the
Ti7O13 phase greatly decreases in Ti5-HT-985. As can be seen from
Fig. 4(b) the phase of Ti7O13 disappears in sample Ti10-HT (Table 2).
Instead, a new phase which is indexed to CuTi2(PO4)3 (JCPDF card
No.84-1355) appears in sample Ti10-HT-982 with a content of 8.2%.
This phase significantly increases with the increase of TiO2 and be-
comes the second main phase in samples Ti15-HT-686 and Ti15-HT-760
and the main phase in sample Ti20-HT-646. These results imply that the
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Journal of Non-Crystalline Solids 473 (2017) 108–113
Fig. 1. XRD patterns of the as-synthesized samples with different
amounts of TiO2.
increase of TiO2 promoted the crystallization of CuTi2(PO4)3. It is also
noted from the XRD results that heat-treatments performed at lower
temperatures help to reduce the types of crystals formed. In addition, it
can be seen from Table 3 and Table 4 that the content of CuTi2(PO4)3
phase decreases with the increase of the heat-treatment temperature.
Therefore, the heat-treatment of samples containing 15–20 TiO2 at re-
latively low temperatures facilitated the crystallization of the Cu-
Ti2(PO4)3 phase.
3.4. Crystallization kinetics of the glasses
Considering the importance of the formation of desired crystalline
phases in the functionalization of CuO-TiO2-P2O5 glasses, discussed
below are the crystallization kinetics of the glass samples. The discus-
sion is only based on the first crystallization peaks in the DTA curves
obtained with different ramping rates. Fig. 5 presents the ln (Tp2/β)
against 1/Tp curves of the samples. The correlation coefficients of linear
fitting the data are 0.9950, 0.9915, 0.9894 and 0.8990 for samples from
Ti5 to Ti20, respectively. The calculated activation energy for the
crystallization and the Avrami parameter (n) are summarized in
Table 5.
It can be seen that the crystallization activation energy increases
with the content of TiO2. Since the XRD results demonstrated that all
crystallized samples exhibited multi-phase crystals, the crystallization
activation energy reflects the energy barrier that the overall crystal-
lization needs to overcome. However, Ti20 has the largest E value,
lowest crystallization temperature and highest amount of CuTi2(PO4)3
phase. The XRD results (see Tables 3 and 4) also suggest the crystal-
lization of CuTi2(PO4)3 phases in samples Ti15 and Ti20 are highly
sensitive to the heat-treatment temperature, while the other main phase
(Cu2P2O7 and Cu3(PO4)2 in the cases of Ti15 and Ti20, respectively)
varies much less with the increase of the heat-treatment temperature.
These results may suggest that the crystallization of CuTi2(PO4)3 phase
needs a relative low activation energy.
It is well known that the crystallization of glasses involves nuclea-
tion and crystal growth stages [35]. Nucleation can occur on the surface
or in the bulk of the glass, resulting in surface or bulk crystallization.
The Avrami parameter, n, based on the Eq. (2) can be an indication of
the crystallization mechanism of a glass. An n value close to 1 denotes a
surface crystallization while a value of 3 implies a bulk crystallization
[26,36]. The Avrami parameters presented in Table 5 show that n first
increases significantly from 1.79 to 2.77 from Ti5 to Ti10, then it de-
creases slowly with the increase of TiO2. The results suggest that sample
Ti5 may have dominant surface crystallization along with bulk crys-
tallization, while other samples may mainly have bulk crystallization.
This variation in the crystallization mechanism with the increase of
TiO2 is a result of the depolymerization of the phosphate glass network
and the aggregation effect of TiO2.
L. Zhang, S. Liu Journal of Non-Crystalline Solids 473 (2017) 108–113

Fig. 4. XRD patterns of the heat-treated samples.

Table 1
Relative contents (%) crystalline phases in Ti5-HT samples.

Sample Cu2P2O7 Ti7O13 Cu3(PO4)2 CuO Ti(PO3)3 TiO2

Ti5-HT-686 47.19 ± 0.05 28.40 ± 0.11 9.37 ± 0.08 7.47 ± 0.02 5.77 ± 0.04 1.80 ± 0.02
Ti5-HT-800 40.02 ± 0.03 33.37 ± 0.09 10.27 ± 0.06 5.88 ± 0.02 7.87 ± 0.04 2.59 ± 0.02
Ti5-HT-985 53.96 ± 0.04 6.08 ± 0.10 16.37 ± 0.07 6.63 ± 0.01 12.23 ± 0.04 4.37 ± 0.01

Table 2
Relative contents (%) crystalline phases in Ti10-HT samples.

Sample Cu2P2O7 Cu3(PO4)2 Ti(PO3) CuO TiO2 CuTi2(PO4)3

Ti10-HT-684 56.14 ± 0.07 17.60 ± 0.13 12.62 ± 0.08 8.12 ± 0.03 5.52 ± 0.03 –
Ti10-HT-813 50.35 ± 0.03 21.40 ± 0.06 16.91 ± 0.03 5.76 ± 0.02 5.58 ± 0.02 –
Ti10-HT-982 54.72 ± 0.03 15.52 ± 0.07 12.09 ± 0.03 5.41 ± 0.01 4.06 ± 0.02 8.20 ± 0.03

Table 3
Relative contents (%) crystalline phases in Ti15-HT samples.

Sample Cu2P2O7 CuTi2(PO4)3 CuO Cu3(PO4)2 Ti5O4(PO4)4

Ti15-HT-686 52.59 ± 0.08 39.96 ± 0.08 7.45 ± 0.03 – –

Ti15-HT-760 58.06 ± 0.07 33.90 ± 0.07 8.04 ± 0.03 – –
Ti15-HT-985 54.55 ± 0.03 7.23 ± 0.04 5.96 ± 0.02 20.42 ± 0.06 11.84 ± 0.04

Table 4
Relative contents (%) crystalline phases in Ti20-HT samples.

Sample CuTi2(PO4)3 Cu3(PO4)2 Cu2P2O7 CuO TiO2

Ti20-HT-646 43.15 ± 0.10 40.52 ± 0.18 9.76 ± 0.11 6.57 ± 0.04 –

Ti20-HT-748 37.25 ± 0.07 48.35 ± 0.14 10.41 ± 0.07 4.01 ± 0.04 –
Ti20-HT-961 10.35 ± 0.03 41.61 ± 0.05 32.19 ± 0.04 5.63 ± 0.02 10.22 ± 0.02

4. Conclusions
Glasses with nominal compositions of 50CuO-xTiO2-(50-x)P2O5
(x = 5, 10, 15 and 20) have been successfully prepared by melting and
water quenching technique. The FTIR measurement results indicate
that the glass network depolymerized with the increase of TiO2.
However, TiO2 has an aggregation effect on the glass network. It is
evidenced that the glass is easy to crystallize and the content of desired
CuTi2(PO4)3 phase in crystallized samples increases with the increase of
TiO2. In the meantime, the dominant crystallization mechanism turns

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L. Zhang, S. Liu Journal of Non-Crystalline Solids 473 (2017) 108–113

Fig. 5. ln (Tp2/β) versus − 1/Tp curves correspondent to the crystallization peak 1 of Ti5 (a) Ti10 (b) Ti15 (c) and Ti20 (d) glasses.

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