IOURNA

Journal of Non-Crystalline Solids 151 (1992)134-142

North-Holland

~l~],ii~

L OF

i ~

Glass formation, properties and structure of glasses

in the TeO2-ZnO system
H. Biirger, K. Kneipp, H. H o b e r t and W. Vogel
Friedrich-Schiller University-Jena, Otto-Schott Institute, Jena 0-6900, Germany

V. Kozhukharov
Sofia University of Technology, 1756 Sofia, Bulgaria

S. Neov
Institute of Nuclear Research and Nuclear Energy, 1784 Sofia, Bulgaria
Received 20 March 1989
Revised manuscript received 14 May 1992

Glass formation occurs in the zinc tellurite system in the region of the eutectic (21 mol% ZnO) on the TeO2-rich side of
the phase diagram. Glasses are characterized by a high refractive index which increases with TeO 2 content. The glasses are
transmitting from about 400 nm to about 6 ~zm with O - H absorption bands at 3.3 and 4.4 ~m. Short range order of the
glasses was deduced with neutron diffraction, infrared and Raman spectroscopy by comparison with the spectra of the
synthesized crystalline a-TeO2, Zn2Te30 8 and ZnTeO 3. Glasses consist of disordered TeO4, TeO3+ 1 and TeO 3 building
units. The number of the TeO3+ 1 units is limited by ZnO addition. There is a relatively strong structural correlation
between the glasses and the crystalline compound ZnzTe30 s in accord with the phase diagram.

I. Introduction

The glass-forming range in the Z n O - T e O 2

system has been previously reported [1-3]. Detailed structure studies have employed phase
equilibrium [4] and X-ray diffraction of the compounds ~x-TeO2 [5,6], Zn2Te308 [7] and ZnTeO 3
[8]. It is known that TeO 2 in combination only
with modifiers, including ZnO, forms stable
glasses at cooling rates typical of glass preparation ( < 1 K/min). Pure a-TeO2 was obtained in
the vitreous state only by extremely high cooling
rates (> 2 X 102 K/s) [9,10].
Tellurite glasses are characterized by low glass
Correspondence to: Dr V. Kozhukharov, Private PO Box 2,
1756 Sofia, Bulgaria. Tel: + 359-2 62 441, ext. 408. Telefax:
+ 359-2 62 1042.

transition temperature, high refractive index and

high transmittance from ultraviolet to near infrared (NIR) [1,3,11-13]. There is limited knowledge of the structure of tellurite glasses. A structural model was developed from X-ray data [5-8].
This should be possible for glasses of this system
through comparison of spectroscopic data of
glasses and crystalline compounds. We used neutron diffraction, infrared and Raman spectroscopy of crystals, glasses and recrystallized glass
samples for this purpose. The structure of the
zinc tellurite glasses should be useful to evaluate
the structure of other RnOm-TeO 2 systems.
Analogous glass structure investigations have
been performed in binary tellurite systems with
V205 [14], VO 2 [15], Li20 [16], P2Os [17], B203
[18], WO 3 [19-21], MoO 3 [22] and the TeO 2B 2 0 3 - K 2 0 [23] ternary system.

0022-3093/92/$05.00 1992 - Elsevier Science Publishers B.V. All rights reserved

H. Biirger et aL / Glasses in the TeO2-ZnO system

135

GFR
a

2. Experimental
Glasses were obtained with 17.4-37.2 mol%
ZnO prepared at cooling rates of 1 K / m i n and
10 K / s from batches of T e O 2 'pure for optical
purpose' and ZnO 'pro analysis' of Chemapol,
Prague, and at cooling rate > 103 K / s by roller
techniques outside the glass-forming range [3].
Batches were melted in gold crucibles at temperatures of 1133-1223 K with a melting time of 45
min. Glass transition temperature, density, refractive index and transmittance of the glasses
were measured. We calculated the partial dispersion, the anomalous relative partial dispersion
and transmittance values A~i0.5 and A~i0.1 * of
the samples. The transmittance of glasses was
determined from 185 to 900 nm, using a Specord
M40 (Carl Zeiss, Jena, Germany) spectrophotometer with optical pathlengths of 11 and 1 mm
and in the NIR with a sample thickness of 2 mm.
The standard KBr pellets technique was used for
IR measurements from 900 to 250 c m - ] using a
Perkin-Elmer, model 457 spectrophotometer.
The glasses, recrystallization products obtained by annealing at 673 K in inert atmosphere
and compounds a-TeO2, Zn2Te30 8 and Z n T e O 3
synthesized by solid state reactions, were used for
structural investigations. Crystalline phases were
identified by X-ray diffraction using standard
procedure.
Raman spectra of crystalline materials, glass
powders and glass rods were obtained using an
Ar laser (model ILA 120, Carl Zeiss, Jena,
Germany) at A = 514.5 nm and of 700 mW excitation. The experimental apparatus is described in
detail in ref. [23].
A glass of the composition 80 ml% T e O 2 and
20 mol% ZnO was melted at 1123 K in a Pt
crucible and cooled with a rate of about ~ 10
K / s for the neutron diffraction measurements.
Neutron diffraction curves of powdered glasses
were obtained by a diffractometer installed at
nuclear reactor type WVR-M (LINPH, USSR).
Experimental data were taken at increments of

~'~ 900

I I ~ l l l l l l l

~'\\\

~ 700
<
a. 500
w

I-

{2

3O0

L0

t......;.....i......i
.

60

80

100

TeO 2 (mole%)

Fig. l. Glass-formingrange (GFR) in the ZnO-TeO 2 system.

(a) Limits at cooling rate ~ 1 K/min. (b) Limits at cooling
rate ~ 10 K/s.

20 = 0.1; angular range was 20 = 4.125 at a

wavelength AN = 1.113 ,~. Radial distribution
function (RDF) could be calculated from the
diffraction experimental curve. Experimental detailes are reported in ref. [24].

3. Results

3.1. Glass formation

Glasses were obtained in the range of 20-30
mol% Z n O (100 g batches) at cooling rates of
~ 1 K / m i n . The glass-forming region of 17.2-37.6
mol% ZnO given in ref. [3] is valid for a cooling
rate of about 10 K / s . Figure 1 shows the location
of the glass-forming region in the phase equilibrium diagram [4], determinated by differertt eo01ing rates. The glass compositions prepared for
structure measurements are given in table 1. The
composition of the glasses obtained was analyzed
(TeO 2 content by a method of Browning and
Flint [25] and ZnO by complexometric titration).
The analyzed composition of glasses corresponds
to that of the batches within + 0.2 mol%.

3.2. Properties
* That is, wavelength values of inner transmittance at 50 and
10% spectral transmittance, respectively.

Refractive indices were obtained at wavelengths given in table 2. The calculated partial

H. Biirger et al. / Glasses in the T e O 2 - Z n O system

136

dispersion, relative anomalous partial dispersion

and Abbe number ( V e = n e -- 1 / n F, - nc,) are also
presented in table 2.
Transmittance in the UV-VIS spectral region
(table 2) is characterized by the )%i0.5 and Azi0.1
values evaluated from the transmittance curves
shown in fig. 2(a). A selected NIR spectral transmittance curve of a TeO2-rich glass sample is
presented in fig. 2(b). Density of the glasses as
well as linear expansion coefficient, tg and t~
(softening point) transformation temperatures of
glass samples near the eutectic composition are
shown in table 2.

Table 1
G l a s s - f o r m i n g t e n d e n c y in t h e Z n O - T e O 2 s y s t e m
Composition

Cooling rate

(mol%)

roller

copper

graphite

technique
( > 10 3 K / s )

mould
( ~ 10 K / s )

mould
(1 K / m i n )

TeO 2

ZnO

100
85

80
75
70
65

15
20
25
30
35

a)

a) O, s t a b l e glass.

Table 2
Physical properties and values
S a m p l e no:

Error

17.4
82.6

19.9
80.1

24.6
75.4

29.6
70.4

33.2
66.8

36.4
63.6

+ 0.1

2.1099
2,1395
2.1721
2.2071

2.0996
2.1275
2.1598
2.1937

2.08072
2.09431
2.10768
2.13867
2.17094

2.05951
2.07245
2.08516
2.11456
2.14502

2.0433
2.0682
2.0966
2.1266

2.0297
2.0538
2.0809
2.1097

0.0622
0.0350

0.0602
0.0339

0.05795
0.03227

0.05505
0.03046

0.0533
0.0300

0.0512
0.0288

18.3

18.7

19.1

19.7

20.0

20.6

0.0577

0.0553

384
399

378
393

372
385

368
380

315
328

320
335

+ 5C

Composition (tool%)
ZnO:
TeO2:

Refractive index, n
C ' (643.8 nm):
d (587.6 nm):
e (546.1 nm):
F ' (480.0 nm):
g (435.8 nm):

+ 0.00005

Dispersion
n F ' - n C':
ng-nF,:

_+0.0001

Abbe number
re:

Relative dispersion
ng - rl F,
- - :
n F, - n C,

Transmittance (nm)
A,i0.1:
A ~i0.5:

Transformation temperature (C)

tg:
ts:

Linear thermal expansion ( x 10 - 76 - l)

a:

174

170

5.54

5.53

5.51

5.49

5.48

5.46

Density (g / cm 3)
p:

_+0.01

H. Biirger et al. / Glasses in the TeO2-ZnO system

WAVELENGTH
2.5
" 100
U

Z
<

1-

137

C,um)
10

4.4

I=
5C

O-H stretch

Z
<
I,-

300

Z.O0

500

/.

Ixi000

W A V E L E N G T H ( n r n } WAVENUMBER[ern-ll
Fig. 2. Spectral transmittance curves of zinc tellurite glasses.
(a) U V cut-off net transmittance (sample thickness of 10 mm):
curve 1, 70.4TEO 2 .29.6ZNO ( m o l % ) glass; curve 2, 75.4TEO 2
24.6ZNO ( m o l % ) glass; curve 3, 80.1TeO 2.19.9ZNO ( m o l % )
glass. (b) N I R spectral transmittance curve of glass with
composition 80.1TeO2-19.9ZNO (mol%) (sample thickness of
2 mm). Abscissa accuracy is better than + 5 cm t; ordinate
accuracy and % T repeatability is better than + 0 . 2 % T ; typically limited by noise level, pen recorder dead b a n d < 0.5%.

900
700
500
300
W A V E N u 1'4 BER (cm-1)

3.3. Structural measurements

Fig. 3. I R transmittance spectra: curve 1, ct-TeO2; curve 2,

Zn2Te308; curve 3, for Z n T e O 3. ff (cm - ] ) accuracy is better
than + 1 cm 1; run-to-run abscissa repeatability after warmup of 0.005 c m - I ; ordinate accuracy and repeatability better
than 0.1%T.

For detailed I R structural study, glasses of the

composition presented in table 1 were p r e p a r e d
at different cooling rates. Glass samples recrystallized at thermal treatment of 623 K for 20 h.
These devitrificated samples as well as the crystalline compounds a - T e O 2, Z n 2 T e 3 0 8 and ZnT e O 3 were also used for the structural measurements. The I R spectra of these compounds have
been studied and results shown in fig. 3 and table
3 are in good accord with prior work [26]. The
correlation of I R spectra of glasses p r e p a r e d at
different cooling rates and the same samples after devitrification process are shown in fig. 4.

The R a m a n spectrum of a - T e O 2 has already

been published in refs. [23,27]. The structure of
oL-TeO 2 is characterized by R a m a n lines at 640
and 600 cm - ] and a deformation vibration at
about 400 cm -1 (fig. 5(a)). One can also find
these three lines belonging to the T e O 4 building
units in the spectrum of the Z n 2 T e 3 0 8 shown in
fig. 5(b) but their intensity is smaller. R a m a n
vibrations at 790, 740 and 690 c m - ] as well as
deformation vibrations at 360 and 310 c m - t were
observed. A wide accordance with the I R absorption spectra exists (see table 3) besides the band
at 790 cm -t. Well resolved R a m a n spectra of

Table 3
IR and R a m a n frequencies of crystalline zinc tellurites
Compound

Frequencies (cm

l)

Infrared spectroscopy
a-TeO 2
ZnzTe30 s
ZnTeO 3

IR
IR
IR

775
750
765

710
685
695

660
655
670

620
600

790
790

740
-

690
690

640
640
-

600
600

.
570

.
520
-

.
480
485

400
400

340
370
-

310
-

400
400
400

360
360

310
300

Raman spectroscopy
c~-TeO 2
Zn 2Te 3O 8
ZnTeO 3

H. Biirger et aL / Glasses in the TeOe-ZnO system

138

~',

(mo e%)

Zn0 : Te0 2

ttl

u
Z
<

II-

30:70

>-

:,~."~' ~..... S ~'~"

I.--

ao : 70

.,o
z
I.LI

25:75

I.--z

I-

.....

900

:80

"""

1115:85

700

I13 0 0

500

20:80
(m01e%)

Lt.I
I--

WAVENU MBER (crn-1)

.-3

Fig. 4. Correlation dependence of IR spectra of glasses at

different cooling rates: . . . . . . , cooling rate > 103 K / s (roller
technique); - - ,
cooling rate ~ 10 K / s (copper mould);
. . . . . . , recrystallized glass sample (KBr pellets of 1 g KBr,
10 mg glass powder). Errors of the measurements are given in
fig. 3 caption.

.,0

c/

~-

WAVENUMBER (cm-1)
Fig. 6. Raman spectra of glasses cooled at ] K/min; data
errors are given in the fig. 5 caption.

=-]e 02

~ Z n2TeTO 8
z
I--

;z

lj

ZnTe 03

e~

zinc tellurite glasses cooled at 1 K / m i n are shown

in fig. 6.
Because of the similar, nearly identical scattering amplitudes of 80, 3Zn and 52Te, the method
of neutron diffraction is sensitive to light oxygen
nuclei. Therefore this method is expected to supply information about the short range order of
the vitreous network. We calculated the Fourier
transform curve, F(R), from the neutron interfer~9,10o /

,/ZnO : Te02
~

30 : 70

(m01e%)

~s~
298K

d
J

WAVE

UMBER (cm -1 )

Fig. 5. Raman spectra of polycrystalline compounds (a-c) and

(d) recrystallized sample containing 70 mol% TeO 2. ff ( c m - i )
accuracy is better than +0.2 cm-X; ordinate accuracy and
repeatability are better than 0.02% scattering intensity.
~z indicates the laser plasma line.

6'

9Q(

l-I)

Fig. 7. Experimental neutron scattering curve of glass powder

sample with composition 80TeO2.20ZnO (mol%); statistical
average error is < 2% after fourfold measurement of the
experimental points registered.

H. Biirger et aL / Glasses in the TeO2-ZnO system

(4,65)

3F

..5,,2.0,

-0[

/l/l /

'

'

'

P3'

'

'V

139

comparison of the model and experimental RDF.

A well resolved coordination maximum appears
in the RDFexp curve at R~ = 0.202 nm (P1), R 2 =
0.297 nm (P2) and two unresolved maxima at
0.385 nm (P3) and 0.475 nm (P4).

' ~

4. Discussion
4

R
Fig. 8. Neutron pair scattering function, F(R) vs. interatomic
distances, R. The values in parentheses represent the position
of the peak (in ,~). The accuracy of determination of the
position of the P1-P4 peaks is 4R ~<0.05 .~ and for peaks
P5-P9 it is 0.10 ~,.

ence function, I(Q), shown in fig. 7 which is

presented in fig. 8. Figure 7 shows the characteristic broad scattering maxima, typical for vitreous
samples. The calculation of the R D F 4~rR2p(R)
for the glass 2 0 Z n O . 8 0 T e O 2 (mol%) is described in detail in ref. [24]. The pair distribution
function, F(R),
shows nine maxima, in the range
o
up to 10 A, which are attributed to the atom
density as is illustrated in fig. 8. Figure 9 shows a
36
6.10

28

"7 24
2G

,0

g
'e

8
4
o

3~

,t

R (~ )
Fig. 9. Radial distribution function 4~rR2p(R) of the glass
investigated (curve 1), RDFcalc (curve 2) of a glass with composition 80TeO2.20ZnO (mol%) and RDFc~lc (curve 3) of
Zn2Te30 8 atomic density; quantitatively there was no registration of sharp oscillation for R values < 2 ,~, i.e., the
normalization procedure is carried out correctly.

4.1. Glass-forming and properties

Figure 1 illustrates that the glass-forming range
in the T e O z - Z n O system is quite wide. Glass
formation limits depend strongly on the cooling
rate and melts size. The upper limit of the glassforming range at a cooling rate of ~ 10 K / s
correlates with the peritectic point of Z n T e O 3
and with the isopleth of the Zn2Te30 8 compound as well. Glasses more stable to devitrification glass are obtained in compositions situated
around the eutectic and above the liquidus line
for primary crystallization of Zn2Te30 8.
The refractive indices of the glasses increase
while the ue-values decrease with increasing TeO 2
content. Density of the glasses decreases slowly
up to 5.46 g / c m 3 with increasing ZnO.
Figure 2(a) indicates that the UV transmittance edge shifts to shorter wavelengths with
increasing of ZnO content. The transmittance in
visible spectral region of the zinc tellurite glasses
is mainly influenced by the formation of nonbridging oxygens, and the increase of the TeO e
content which leads to a shift of the UV cut-off
to longer wavelengths. These two factors operate
oppositely. The second parameter is dominant;
thus, with increasing T e O 2 and decreasing nonbridging oxygens, a long-wavelength shift occurs.
Absorption bands appear in the NIR spectral
region at 3.2 and 4.4 txm belonging to O - H
stretching vibrations, as shown in fig. 2(b). The
multiphonon absorption edge at about 6 ~ m (1660
cm -1) is determined by overtones of the T e - O
stretching vibrations at 600-800 c m - ].

4.2. Structural characteristics

It is known [5,6] that a - T e O 2 consists of T e O 4
units in the form of trigonal bipyramids. In each

140

H. Biirger et al. / Glasses in the TeOe-ZnO system

case, two equatorial and axial oxygen atoms are

located at distances of 0.191 and 0.208 nm, respectively from the Te atom. Each polyhedron is
bonded to four others. According to ref. [26], the
IR absorption bands at 780, 714, 675 and 635
S
cm-1 are assigned to the stretching vibration Veq,
veaSq, Vaxas and Vaxs, respectively, corresponding to
different Te-,O bonding lengths (see table 3 and
fig. 3).
The monoclinic compound Zn2Te30 8 investigated by Hanke [7] is of chain-like structure with
T e 3 0 8 groups built up by one TeO 4 and two
TeO3+ 1 units. In the compound, these groups are
connected by a long T e - O bond to ~[Te30 8]
chains [7]. A different distribution of the T e - O
bonding length was found. The observed IR absorption bands at 765, 685, 655 and 600 cm -~
may be assigned to T e - O stretching vibrations. In
the orthorombic compound Z n T e O 3, isolated
T e O 3 groups occur [8] belonging to different
T e - O lengths of the bond at 0.186, 0.188 and
0.190 nm. Due to the different T e - O bond
lengths, the degeneration is raised and the tellurium-oxygen stretching vibrations at 775, 700
and 660 cm-1 can be assigned to different oxygens, i.e., to vTe_ o [1-3]. Bond vibrations in the
region of 300-500 cm-~ belong to deformation.
The spectra of glasses shown in fig. 4 show
broad absorption bands between 500 and 700
cm-1 with a shoulder at 770-800 cm-n. IR spectra of fast-cooled glasses (roller technique) show
an additional broadening, a small shift and a
relative increase in intensity of the longer wavelength bands VT~_o. The broadening could be
explained by states frozen in at a higher temperature with a.large disorder, where a broad distribution of bond lengths occurs.
A better structure view of the glasses can be
obtained by taking into account the spectra of
recrystallized glasses. Absorption bands occur in
the spectra of the crystalline compounds
Zn2Te30 8 and Z n T e O 3 between 750 and 760
cm-1, as well as some deformation vibrations at
400-600 c m - k These bands give an additional
contribution to the glass spectra with increasing
the ZnO content. This leads to an intensity distribution over a broad wavelength region in the
glass spectra and the 780 cm -a band of the

a-TeO 2 occurs only as a shoulder of the broad

600-700 cm -1 band. The spectra of the glass
containing 85 mol% T e O 2 can be described
mainly by that of oL-TeO/. We find an additional
small intensity in the spectrum of the devitrificated sample in the region from 400 to 550 cm-1.
The influence of Zn2Te30 8 dominates in the
spectrum of the recrystallized glass with 35 mol%
ZnO and 65 mol% T e O 2 whereas in the sample
with composition 30 mol% ZnO and 70 mol%
TeO 2 some influence of ot-TeO 2 is observed. It
was established that the bands at 790, 720, 660
and 600 cm -~ belong to et-TeO 2, while those at
about 750, 680, 525 and 480 cm -1 belong to
Zn2Te30 8.
The Raman spectra of the crystalline samples
of o~-TeO 2, Zn2Te30 8 and Z n T e O 3 represent
the basis of the Raman spectroscopic discussion
of the zinc tellurite glasses. As in Zn2Te308, the
Raman lines at 790 and 690 c m - 1 as well as those
at 400 (very weak), 360 and 310 cm-1 were also
observed in the spectrum of Z n T e O 3. The relative intensity of the Raman lines in the devitrified
samples at 640 and 400 cm -1 increase significantly with increasing T e O : content. At the same
time, the lines at 790 and 690 cm -1 exhibit a
small shift to shorter wavelengths, i.e., the 690
cm-~band changes to the known 640 cm-~ band
of the a-TeO 2 (see fig. 5(d)). According to refs.
[26,27], the observed vibrations in the spectrum of
cx-TeOz at 640 and 400 cm-1 are typical for T e O 4
building units. The lines in the Z n T e O 3 spectrum
at 790, 690, 360 and 310 cm -1 refer to the existence of TeO 3 units. The additional Raman line
at 740 cm -~ occurring in the spectrum of
Z n z T e 3 0 8 can be related to the formation of
TeO3+ ~ ** units. A corresponding shift of the
band at 790 cm-~ towards 740 cm-~ is ascribed
to coordination evolution from TeO 3 to TeO3+~
which can also be seen in fig. 5(c) and fig. 5(d).
Figure 6 shows the polarized Raman spectra of
70, 75 and 80 mol% TeO 2 glasses. Raman spectra show characteristic broadening compared with
crystalline samples shown in fig. 5. In the crys-

** It is conditionally accepted that one T e - O bond length is

> 2.2 A.

H. Biirger et al. / Glasses in the TeO2-ZnO system

talline sample, three bands in the region of the

deformation vibration from 310 to 400 cm -1 superpose to one broad band in the glass. The
bands at 640 and 740 cm-1 overlap and can also
include parts of the vibrations appearing in crystalline samples at 790 and 690 cm-1. The spectra
of glasses suggest the presence of TeO4, TeO3+ t
and T e O 3 building units, considering the Raman
spectra of the crystals. The intensity of the band
at 740 cm-1 decreases with increasing T e O 2 content (see fig. 6(b) and fig. 6(c)) compared with the
intensity of the band at 640 c m - l ; for 80 mol%
TeO2, the 640 cm-~ band dominates. Simultaneously, the broad band in the region of deformation vibration shifts to slightly higher wave number. This could be explained by a stronger influence of the band at 400 cm-1, appearing in the
spectra of ot-TeO 2 by contrast with that of 360
and 310 cm -1 in the Zn2Te30 8 compound.
Neutron diffraction was carried out to define
short range order up to ~ 6 .& (0.6 nm) of glass
investigated. The first peak, P1, can be interpreted as distribution of T e - O and Z n - O interatomic distances, i.e., first coordination sphere of
TeO 4 and ZnO 6 building units. Determination of
the theoretical positions of P1 gives 0.203 nm in
good accord with the experimental value of 0.202
nm (fig. 9, curve 1). One cannot recognize a
greater change of the tellurium-oxygen coordination from this peak. The T e O 4 polyhedra are
easily deformed and exhibit strong dynamics of
both Te-Oax bonds. An elongation of over 0.22
nm undoubtedly exists because of the lack of a
centre of symmetry of the T e O 2 units. This is in
accord with coordinations 3 + 1 for Te atoms at
RTe_ o from 0.208 to 0.298 nm and 3 for RTe_ o >
0.298 rim. It is of interest to know how the
Te-Oax bonds influence the R D F curve. The
influence can be clearly seen in the RDF~xp curve
as a broad distribution of the T e - O distances in
the region between 0.22 to 0.3 nm. The value of
the T e - O coordination number calculated from
P1 at 0.202 nm is 3.35. This leads to the result
that approximately 35% of the Te atoms build
T e O 4 groups and 65% of them build TeO3+ 1
plus T e O 3 groups. The position of the first maximum (P1) of the RDF~xp curve compared with the
RDFcalc curves gives good conformity but a strong

141

discrepancy exists in the region of 0.25-0.45 nm.

The peak at 0.297 nm (P2) belongs essentially to
the O - O distances. These are found in the model
curves R D F (e~-TeO 2) at 0.283 nm and RDF
(ZnO) at 0.335 nm. Both parts superimpose in
the glass and lead to a strong contribution in the
region from 0.279 to 0.325 + 0.04 nm. Additionally, in the RDFexo curve, unresolved peaks appear at R ~ 0.385 nm and R ~ 0.475 nm belonging to T e - T e , T e - Z n , O(secondsphere)--O , Z n - Z n
and Te(secondsphere)-O pair distributions. Curve 3
of fig. 9 is compared with the R D F curve and
indicates analogous structure groups. There
should also be chain-like structures mainly with
TeO3+ 1 building units in the glass with composition ZnO 20, T e O 2 80 mol%, in accord with the
chain-like structure ~[Te30 8] of Z n 2 T e 3 0 8 which,
according to Hanke [7,8], includes one TeO 4 and
two TeO3.. 1 polyhedra. There is no significant
difference between TeO3+ l and T e O 3 groups
because they are relatively unstable configurations.

5. Conclusion

It has been shown that glass formation in the

Z n O - T e O 2 system depends strongly on the cooling rate, especially in the TeOz-rich region. Optical properties, density, linear thermal expansion,
transmittance in the U V - V I S and NIR regions of
the glasses show that the zinc tellurite glasses are
of super dense flint type with good spectral transmittance. Structural information has been obtained especially about structural changes as a
function of glass composition, by means of IR
and Raman spectroscopy as well as neutron
diffraction study of the Z n O - T e O 2 glasses. Characteristic vibration frequencies of the appropriate
crystalline compounds were helpful for interpretation of glass IR and Raman spectra. TeOz-rich
glasses are characterized by T e O 4 building units
in analogy to ot-TeO 2. The influence of TeO3+ 1
structural groups increases with increasing ZnO.
This leads to a characteristic band in the Raman
spectra at 740 cm -1 caused by Z n z T e 3 0 8 and to
a typical deformation vibration in the region from
450 to 550 cm-1 in the IR spectra. This result is

142

H. Biirger et al. / Glasses in the TeO2-ZnO system

also supported by the RDF curves computed

from neutron diffraction data, which show that
the O - O pairs at distances greater than 0.22 nm
are fixed, thus causing an increase of asymmetry
in the basic building units. The glass structure
becomes increasingly ZnzTe3Os-like with increasing ZnO and consists of a ~[Te30 8] chain-like
structure with TeO3+ t and TeO 4 groups. The
reason for the change of tellurium-oxygen coordination polyhedra is the lack of a centre of
symmetry in the TeO 4 building units. This leads
to a dynamic relation of the Te-Oax bonds. The
glass network is built up mainly by distorted
TeO3+ t and TeO 4 groups, the contribution of
which is a function of the composition.

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