Materials Science and Engineering A304306 (2001) 796799

Infrared absorption study of Fe2 O3CaOSiO2 glass ceramics

S. Atalay , H.I. Adiguzel, F. Atalay
Physics Department, Science and Arts Faculty, Inonu University, Malatya, Turkey

Abstract
The ceramic glasses were prepared from extra pure reagents of Fe2 O3 , CaO and SiO2 powders. The 15 g batch was melted at 1550 C
for 2 h in a platinum crucible. The glass structure was obtained by pouring the melt into a copper plate and pressing quickly by another
copper plate. The glass structure was checked by XRD. IR studies were first made in ceramic glasses for various Fe contents. The
19.5Fe2 O3 40.25CaO40.25SiO2 glass sample was annealed at 750 C under hydrogen atmosphere. In the annealed sample, new vibration
bands were observed which were absent in the untreated samples. It was observed that the new peaks are mainly due to the formation of
-CaSiO3 (wollastonite) phases. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Ceramic glass; Infrared absorption studies; XRD

1. Introduction
Hyperthermia is one of the promising approaches in cancer therapy [13]. At present, hyperthermia treatment utilizing energy sources such as hot water, infrared ray, ultrasound and microwave are clinically used. However, the technical problem with these methods is the difficulty of uniform
heating of only the tumor locally without damaging normal
tissue.
It has been reported that ferromagnetic particles can heat
the tumor locally without damaging normal tissue. These
ferromagnetic particles are easily incorporated into a tumor
and generate heat under an alternating magnetic field by hysteresis loss [3]. Konaka et al. [4] has recently showed that
glass ceramics containing -Fe can be used for hyperthermia. It is well known that IR spectroscopy has been used to
throw light on the understanding of the glass and crystalline
structure. In this study, we therefore have prepared glass ceramics containing Fe2 O3 CaOSiO2 and have investigated
the properties of its structure using IR measurements.

2. Experimental
Ceramic glasses with compositions x(Fe2 O3 )(100
x)(CaO SiO2 ), where x = 5, 10, 15, 19.5 were prepared
from chemically pure powders. Fifteen grams batch was
melted at 1550 C for 2 h in a platinum crucible. The melt
was poured onto a thick and clean copper plate at room
Corresponding author. Fax: +90-422-3410037.
E-mail address: inonu01@vm3090.ege.edu.tr (S. Atalay).

temperature and pressed by another thick copper plate.

Black shiny sheets of glasses were produced. In heat treatment, glass powder was placed in an alumina boat, and than
annealed at 750 C for 2 h under a stream of hydrogen.
The glass structure of all melted samples was confirmed
by X-ray powder diffraction measurements using Cu K radiation. In X-ray measurements, X-ray power and scanning
rate were set at 30 kV, 15 mA and 1 C min1 , respectively.
Also, the X-ray spectrum of the heat treated sample at 750 C
was obtained. The grain size, D, of -Fe was estimated from
the full-width at half-maximum (FWHM) of the diffraction
peak of -Fe after correction of instrumental broadening [5]:

(1)
FWHM cos
where is the wavelength of X-ray and the Bragg angle.
In IR measurements, 1% of the sample was mixed and
ground with 99% of KBr. Tablets for FTIR measurements
were formed by pressing the mixture at a pressure of 10 t for
10 min. The infrared absorption spectra of the glass and heat
treated samples were obtained by using a BOMEM MB 100
model infrared spectrometer in the range 4004000 cm1 .
In some IR measurements a CO2 peak around 2350 cm1
was observed. This is because tablets usually absorb CO2
during the mixing process of the sample with KBr.

D=

3. Results and discussion

3.1. X-ray results
Fig. 1 shows X-ray diffraction spectra of glass and annealed 19.50Fe2 O3 40.25SiO2 40.25CaO samples. Fig. 1a

0921-5093/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 5 0 9 3 ( 0 0 ) 0 1 5 7 2 - 0

S. Atalay et al. / Materials Science and Engineering A304306 (2001) 796799

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Fig. 1. X-ray diffraction spectrums of: (a) glass ceramics; (b) heat treated 19.5Fe2 O3 40.25CaO40.25SiO2 samples. (1) shows -Fe phase, (2) shows
-CaSiO3 phase, (3) shows Fe2 O3 phase, (4) shows Ca2 SiO4 phase, (5) shows -CaFeSiO4 phase and (6) shows FeO phase.

shows no clear sharp diffraction peaks confirming the glassy

nature of the sample. The X-ray spectrum of the sample annealed at 750 C under the hydrogen atmosphere shows the
existence of -Fe, -CaSiO3 , Ca2 SiO4 , CaFeSiO4 , Fe2 O3
and FeO phases (Fig. 1b). The grain size of -Fe phase was
calculated to be 40 nm.
3.2. FTIR results
The FTIR spectra of Fe2 O3 , SiO2 , CaO and -Fe are given
in Fig. 2 for the sake of comparison with that of the glasses
and the heat-treated sample. The absorption peak of SiO2

spectrum at 477 cm1 is related to a SiO vibration and the

strong peak at 1109 cm1 is related to an OSiO vibration.
FTIR spectra of ceramic glasses with compositions
x(Fe2 O3 )(100 x)(CaO SiO2 ) are shown in Fig. 3.
Fig. 4 shows the FTIR spectrum of glassy samples of
19.5Fe2 O3 40.25CaO40.25SiO2 and the sample annealed
at 750 C under a hydrogen atmosphere. The main features of the FTIR spectra of ceramic glass are the appearance of resonance peaks at 415600 and 7501170 cm1 .
Comparing Fig. 3 with Fig. 2, we think that the strong
absorption bands at 415600 and 7501170 cm1 mainly
occur due to SiO and OSiO vibrations, respectively.

Fig. 2. Infrared absorption spectra of crystalline Fe2 O3 , CaO, SiO2 and -Fe samples.

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S. Atalay et al. / Materials Science and Engineering A304306 (2001) 796799

Fig. 3. Infrared absorption spectra of x(Fe2 O3 )(100 x)(CaO SiO2 ) ceramic glasses.

The peaks at 14621700 cm1 show the existence of a CaO

phase in the structure. Weak but clear peaks at 2868 and
2932 cm1 show the formation of an -Fe phase. The peaks
at 33613844 cm1 are mainly due to an Fe2 O3 phase.
Fig. 3 indeed shows the effect of Fe2 O3 addition in the
FTIR spectrum of the glass ceramics. Close examination
of Fig. 3 reveals that the vibration bands shift from 500
to 513 cm1 , 625 to 700 cm1 and 985 to 955 cm1 , and
intensity decreases as Fe2 O3 content increases. The shifting
of absorption peaks towards to lower wave number indicates

the increase in the band length. When Fe2 O3 content in the

glass is higher than 10% there is no example of splitting
into two components of the SiO stretching vibration at
975 cm1 region. Therefore, the presence of more Fe in the
glass seems to cancel the tendency of the glass to display a
second band around 7501170 cm1 .
The infrared spectrum of the heat-treated sample shown
in Fig. 4b reveals some new bands at 480, 516, 567, 644,
688, 819, 907, 952, 1027, 1079, 1620, 1645, 3237, 3412,
3472, 3549 and 3738 cm1 , which were absent in the glassy
samples. The presence of bands at 1620, 1645, 2855, 2922,
3237, 3412, 3472 and 3549 cm1 is assigned to the presence of an -Fe phase in the crystalline sample. A direct
comparison between the FTIR spectra of the heat-treated
sample and IR peaks of -CaSiO3 at 452, 471, 508, 566,
642, 680, 904, 925, 964, 1019, 1056, 1087 cm1 [6] and IR
peaks of -Ca2 SiO4 at 496, 520, 565, 819, 859, 953 cm1
[7] with the IR peaks at 480, 510, 567, 644, 686, 907, 952,
1020 and 1082 cm1 confirms the existence of a -CaSiO3
phase in the structure. The peaks at 567, 819 and 953 cm1
are due to the -Ca2 SiO4 phase. The bands at 480 and
3738 cm1 could indicate the presence of Fe2 O3 in the
structure.

4. Conclusion

Fig. 4. IR absorption spectra of: (a) glass; (b) heat treated sample.

FTIR absorption spectra have been shown to be capable of

providing characterization of glass and crystalline samples.
In the IR spectra of glassy samples, absorption bands occurs
mainly due to SiO2 , CaO, Fe2 O3 and -Fe phases. In the

S. Atalay et al. / Materials Science and Engineering A304306 (2001) 796799

heat-treated sample, new bands were observed which were

absent in the untreated samples. It was found that the new
peaks are mostly due to the -CaSiO3 phase. This is also
shown by XRD measurements. Also, IR results showed that
-Fe starts to form in the glass production process and that
annealing increases the grain size of -Fe.

Acknowledgements
Partial support from Inonu University research fund is
gratefully acknowledged.

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