3.
Results
We present here the Raman spectra recorded at different temperatures on
one of the samples we have investigated in this work:
a 35 mol% Na2O21 mol% B2O344 mol% SiO2 glass, measured at
298, 793 and 1298 K (Fig. 3(a–c)).
Wave numbers in the 550–850 cm1 region are typical of ring
breathing modes, thus one can find here the lines characteristic
of metaborate rings (around 630, 770 and 808 cm1), and of other
borate- and borosilicate-ring-unit groups [26]. In particular, peaks
around 580 and 630 cm1 probably correspond to the breathing
mode of borosilicate reedmergnerite-like and danburite-like rings,
respectively [4,27]. Other Authors [4,17] assigned to the breathing
mode of reedmergnerite rings the intense Raman peak near 500
cm1. However, we measured again in this work the Raman spectrum of
crystalline reedmergnerite, on a Dara - I – Pioz, Tien Shan
(Tadzhikistan) sample, also taken from the Mineral Collection of
the Paris VI University. In our spectrum (Fig. 1(c)), the most intense
200 400 600 800 1000 1200
520 cm-1
I / a.u.
cm
-1
586 cm-1
BO4-
tetrahedron
SiO4
tetrahedron
Reedmergnerite
ring
abc
Fig. 1. Reedmergnerite structure: (a) Reedmergnerite-like
½(Na2OB2O38SiO2) unit [2]. This chemical formula holds only for isolated
(or ‘loose’) units of this kind. (b)
Schematic view of reedmergnerite network. Charge compensators are not
shown in this view. The dotted circles highlight a reedmergnerite ring, the
composition of which is
½(Na2OB2O36SiO2). (c) Raman spectrum of crystalline reedmergnerite.
200 400 600 800 1000 1200
I / a.u.
cm
-1
SiO4 614 cm-1
tetrahedron
Danburite
ring
BO4-
tetrahedron
abc
Fig. 2. Danburite structure. (a) Danburite-like isolated unit (composition:
Na2OB2O33SiO2). (b) Schematic view of danburite network. Charge
compensators are not shown in
this view. The dotted circles highlight a danburite-ring, the composition of
which is CaOB2O32SiO2 (or Na2OB2O32SiO2). (c) Raman spectrum of
crystalline danburite.
D. Manara et al. / Journal of Non-Crystalline Solids 355 (2009) 2528–2531
2529
LETTER TO THE EDITOR
line is at 586 cm1, and not at 515 cm1 like in [4]. Consequently,
we believe that the line observed around 500 cm1 should be assigned to Si–
O–Si bending, as in [28], and we used one more line
centred at 586 cm1 in our spectral fitting.
The nature of the Raman active mode (or modes) observed at
630 cm1 is still being debated. In order to develop a more general
approach, we postulate here that the breathing modes of two kinds
of ring exist within this spectral domain, danburite-like units and
metaborate rings. By fitting the 630 cm1 Raman peak under this
hypothesis, one can observe that a narrower line would correspond
to the breathing mode of danburite-rings, the intensity of which
decreases at high temperature (Fig. 3(b) and (c)). This assumption
is in agreement with the results of Parkinson et al. [15], who
showed that danburite tends to decompose at high temperature,
increasing the volatility of borosilicate glasses with high danburite
content. More details about this Raman study are reported elsewhere [27].
4. Discussion
To see how these remarks change the definition of R*, we reproduce here
the calculations of Yun and Bray [2,3]. These authors assume that for 0 6 R 6
0.5 all the Na2O added to the glass leads to
the formation of diborate units of formula Na2O2B2O3. For
R > 0.5 each additional Na2O destroys a diborate unit that reacts
with the SiO2 available to form two ‘‘isolated” reedmergnerite
units. The system composition, specific to the molar content of
B2O3 is,
B2O3 þ RNa2O þ KSiO2: ð1Þ
For R P 0.5 we define
ð2Þ
R ¼ 0:5 þ m:
The addition of m Na2O to a Na2OB2O3SiO2 system with R = 0.5 can
then be written:
0:5ðNa2O 2B2O3Þ þ mNa2O þ KSiO2 ! ð0:5 mÞðNa2O 2B2O3Þ
þ 2mðNa2O B2O3 8SiO2Þ þ ðK 16mÞSiO2: ð3Þ
This process continues until total exhaustion of the SiO2 available.
This point is reached when the right-hand-side (rhs) coefficient of
SiO2 in Eq. (3) equals zero, i.e. for m = K /16. From Eq. (2) this
corresponds to the critical value R* = 0.5 + K/16. For R > R*, all the
additional Na2Os depolymerise the glassy network. However, if
one considers in Eq. (3) the reedmergnerite rings formula,
Na2OB2O36SiO2, silica exhaustion condition becomes m = K /12,
leading to R* = 0.5 + K/12. If, in addition, also the formation of danburite
units (Na2O?B2O3?2SiO2) is taken into account, then Eq. (3)
becomes,
0:5ðNa2O 2B2O3Þ þ mNa2O þ KSiO2
! ð0:5 mÞðNa2O 2B2O3Þ þ mðNa2O B2O3 6SiO2Þ
þ mðNa2O B2O3 2SiO2Þ þ ðK ð4
8mÞSiO2: Þ
In Eq. (4) we postulate that a
reedmergnerite unit has the same
probability to be formed than a
danburite unit has. In this case
we obtain R* = 0.5 + K/8. This
equation can be easily modified if dif
ferent probabilities for reedmergnerite
and danburite units are to
be taken into account.
Finally it is hard, with the experimental
data available, to deter
mine which kind of borosilicate units
are formed. We suggest then
to rewrite Eq. (3) in a more general
form, by introducing a param
eter N indicating the average number
of SiO2 units included i
