Journal of Non-Crystalline Solids 231 (1998) 286±290

Letter to the Editors

On the structure of borosilicate glasses: a triple-quantum

magic-angle spinning 17O nuclear magnetic resonance study
Shuanhu Wang, Jonathan F. Stebbins *

Department of Geological and Environmental Sciences, Stanford University, Stanford, CA 94305, USA
Received 13 April 1998; received in revised form 19 May 1998

Abstract
17
O multiple-quantum magic-angle spinning nuclear magnetic resonance (NMR) spectra of borosilicate glasses clear-
ly resolve four oxygen peaks, corresponding to Si±O±Si, B±O±B, Si±O±B and [Si,B]±O±Na linkages respectively. The
results suggest that earlier assignment of the B±O±B and Si±O±B resonances is incorrect. In contrast to widely accepted
structural models, the high intensity of the Si±O±B resonance demonstrates a much better mixing between the three-
coordinated borons and the silica network. The implication of the mixing on the glass structure of other related systems
is discussed. Ó 1998 Elsevier Science B.V. All rights reserved.

1. Introduction used to predict many physical and chemical prop-

Boron-containing glasses (including borosili-
cate, boroaluminate and borophosphate glasses)
are among the most widely used glassy materials
with applications including glassware, glass/poly-
mer composites, nuclear waste storage materials
and high-temperature sealing glasses [1]. The
structure of these materials have been studied by
nuclear magnetic resonance (NMR) [2±12] and
Raman spectroscopy [13,14,11] for about 40 years.
As an example, 11 B NMR was ®rst used by Bray
et al. to quantify the proportions of three- and
four-coordinated borons in B2 O3 , borate and bo-
rosilicate glasses [2,3]. Their later studies led to a
structural model [5,7,8], which accurately ac-
counted for the boron speciation in sodium boro-
silicate glasses and was successful enough to be
*
Corresponding author. Tel.: +1-650 723 1140; fax: +1-650
725 2199; e-mail: stebbins@pangea.stanford.edu.
0022-3093/98/$19.00 Ó 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 9 8 ) 0 0 7 0 3 - 0
erties of alkaline borosilicate glasses (for example,
Tg , density, and thermal expansion coecient [15±
17]). One of the major assumptions in the model is
that the three-coordinated borons do not mix with
the silica network [8]. In this case, it leads to phase
separation for alkaline borosilicate glasses with
low alkaline content. The assumption is appar-
ently supported by the fact that very few crystal-
line materials contain direct linkage between
three-coordinated boron and four-coordinated sili-
con [18]. Earlier 17 O and 29 Si NMR studies also
seemed to con®rm this idea [11], although the reso-
lution of those spectra are often poor, and the ef-
fects of boron on silicon and oxygen NMR
parameters (chemical shift and/or quadrupolar pa-
rameters) are not well-understood. We report here
much better resolution 17 O NMR spectra of boro-
silicate glasses, obtained using multiple-quantum
magic-angle spinning (MQMAS) [19±21]. Di€erent
oxygen species (Si±O±Si, B±O±B, Si±O±B and
[Si,B]±O±Na) are well resolved, leading to a better
 S. Wang, J.F. Stebbins / Journal of Non-Crystalline Solids 231 (1998) 286±290 287

estimation of the proportion of each structural 3 s delay between scans. Details about data pro-
unit in the system. In contrast to previous studies, cessing have been described in our earlier work
our results show that a large fraction of Si±O±B [24]. The shifts in the isotropic dimension are de-
exists in borosilicate and alkaline borosilicate termined by measuring the peak centers in the
glasses, which we suggest is due to a much better 1D isotropic projection, and the error bar is less
mixing between the boron and silicon networks. than 2 ppm. 11 B NMR spectra for all samples ob-
Previous structural models need to be re®ned or tained using a 0.5 ls pulse (30° tip angle for solids)
modi®ed to accurately describe these glass systems. and a 1 s recycle delay. The spectra are in good
agreement with previous studies [2,8,11] and con-
®rmed that only three-coordinated boron exists
2. Experimental procedures in B2 O3 and BS46 glasses, while 71% of boron is
four-coordinated in NBS226.
17
O-enriched silica and boron oxide were pre-
pared by hydrolyzing silicon tetrachloride or bo-
ron tetrachloride in 47% 17 O-enriched water. The 3. Results and discussion
former reaction was carried out in a diethyl ether
solvent, whereas the latter reaction was in CH2 Cl2 . The MQMAS 17 O spectrum of glassy B2 O3
The boric acid obtained was subsequently heated shown in Fig. 1 has one peak at )70 ppm. This
to 1000°C under argon for 2 h, and then quenched is, however not necessarily in con¯ict with Jellison
to room temperature to give enriched B2 O3 glass. and Bray's previous work, where the oxygens in
The borosilicate glass containing 40 mol% B2 O3 and outside of the boroxyl rings were di€erentiated
and 60 mol% SiO2 was synthesized by mixing re- [4]. For a quadrupolar nucleus such as 17 O, the ob-
agent grade H3 BO3 with 17 O-enriched silica and served shift in MQMAS is given by
heating the mixture in platinum crucible in argon 2Q
dMQMAS ˆ ÿ17=31dcs
iso ‡ 10=31diso ; …1†
¯ow at 1173 K for 2 h. The mixture was then
cooled to room temperature by removing the cru- where
cible from the furnace. A similar procedure was
used to make the sodium borosilicate glass with
Na2 O:B2 O3 :SiO2 ˆ 2:2:6. The weight loss during
the preparation was monitored, and was found
to agree well with the stoichiometry (the discrep-
ancy was at the most 2%). X-ray powder di€rac-
tion showed that all the samples are amorphous,
and all glasses are optically clear. The glass sam-
ples were doped with 1000 ppm Co3 O4 to ecient-
ly reduce the oxygen spin-lattice relaxation time
(T1 ) to about 1.5 s. For simplicity, we will use
BS46 to designate the borosilicate glass, and
NBS226 for the sodium borosilicate glass.
NMR spectra were obtained with a modi®ed
spectrometer (Varian VXR-400S) with a 17 O fre-
quency of 54.22 MHz. A 5 mm probe spinning
at 14.5 kHz was used. The shifted-echo MQMAS
pulse sequence has been described by Massiot
and Grandinetti [22], except that the reconversion
pulse is short (3.5 ls, corresponding to a selective p
pulse for oxygen) [23]. Typically 1200 scans were
accumulated for each of the 72 t1 points with a Fig. 1. Two-dimensional 17 O-MQMAS spectrum of B2 O3 glass.
288 S. Wang, J.F. Stebbins / Journal of Non-Crystalline Solids 231 (1998) 286±290
3  106 I…I ‡ 1† ÿ 3=4 CQ2 …1 ‡ g2 =3†
d2Q
iso ˆ ÿ 2
40 I 2 …2I ÿ 1† x20
is the second-order quadrupolar shift and dcs
isotropic chemical shift [24,21]. CQ and g are the
quadrupolar coupling constant and asymetry pa-
rameter, respectively. According to Youngman
[12], oxygens in boroxyl rings and those  connect-
p
ing two rings have PQ …ˆ CQ 1 ‡ g2 =3† and dcs
of 5.0 MHz, 104 ppm, and 4.3 MHz, 113 ppm, re-
spectively. Using the above equations, both sites
give resonances at )74 ppm, consistent with our
observation ()70 ppm). However, we do not see
the third resonance observed by Youngman using
double-rotation (DOR) NMR [12], even though
such a peak should stand out clearly at )60 ppm
in our MQMAS spectrum, if it exists and has been
correctly assigned. This B2 O3 spectrum serves as
the basis for spectral assignment when we analyze
the spectra of borosilicate glasses.
Fig. 2 is the 17 O MQMAS spectrum of a boro-
silicate glass with 40 mol% of B2 O3 and 60 mol%
of SiO2 . This spectrum has three peaks at )37,
)56 and )70 ppm. Based on Fig. 1, the )70 ppm
peak should be assigned to oxygens in B±O±B
linkage. The MAS dimension projection of this
peak is similar to a MAS spectrum of B2 O3 glass,
Fig. 2. Two-dimensional 17 O-MQMAS spectrum of borosilicate
glass with 40 mol% of B2 O3 and 60 mol% of SiO2 .
suggesting that the BS46 glass may contain B2 O3 -
…2† like regions. Previously, the B±O±B peak has been
assumed to appear at around )56 ppm [11,12],
iso is the
which is inconsistent with the absence of such a
resonance in 17 O MQMAS spectra of either B2 O3
glass, or sodium borate glasses (spectra not shown
here). The )37 ppm peak is due to Si±O±Si, which
has been previously observed in many other glassy
iso 's
and crystalline materials [25±27]. The )56 ppm
peak, which was previously assigned to B±O±B
[11], must then be attributed to Si±O±B. Our new
assignment is supported by the relative intensities
observed for the three peaks. According to stoichi-
ometry, there exists about the same amount of Si±
O±Si and B±O±B (one should note that boron is
three coordinated and silicon is four-coordinated).
Assigning the Si±O±B peak to either Si±O±Si or B±
O±B would lead to a large discrepency from the ac-
tual stoichiometry. Also, this peak does not exist
in borate or silicate glasses [28], thus is more likely
to be associated with both boron and silicon. Our
assignment, however, suggests that an assumption
that NMR parameters for oxygens in Si±O±B are
similar to those for the oxygens in Si±O±Al [11]
is incorrect. Further quantum calculations are
needed to account for the large di€erence.
The large Si±O±B intensity observed in our ex-
periment shows that the silicon and boron net-
works are better mixed than expected [5,7,8,11].
According to earlier models [5,7,8,11], the BS46
glass phase-separates into regions highly enriched
either in silicon or in boron. Such a model would
not lead to a large fraction of Si±O±B linkages.
More likely, the system is phase-separated into sil-
icon-rich phases containing a large proportion of
boron, and boron-rich phases with a large fraction
of silicon. In addition, we cannot rule out another
possibility that the system is heterogeneous only at
a nanometer scale. Such an assumption would give
randomly mixed boron- and silicon-rich regions a
few nanometers in size.
The relatively good mixing between boron and
silicon networks has an implication on the struc-
ture of other boron-containing glasses. In Fig. 3,
the MQMAS 17 O spectrum of NBS226 glass is
shown. According to Bray's model [8], the sam-
ple should be composed of reedmergnerite groups
(116 Na2 O á B2 O3 á 8SiO2 ) and diborate groups
 S. Wang, J.F. Stebbins / Journal of Non-Crystalline Solids 231 (1998) 286±290
Fig. 3. Two-dimensional 17 O-MQMAS spectrum of sodium bo-
rosilicate glass (NBS226).
(Na2 O á 2B2 O3 ), leading to about 42% Si±O±Si,
30% Si±O±B and 22% B±O±B. Our experiment,
however, show that the B±O±B content must be
much smaller as only one contour level is observed
for the B±O±B peak. This seems to indicate that
diborate groups, or other species with abundant
B±O±B linkages, may be much less in abundance
[11] when the alkaline content is moderately high.
A separate experiment on a glass of diborate
composition (Na2 O:B2 O3 ˆ 1:2) gives a single
MQMAS peak at )62 ppm and further con®rms
this conclusion. On the other hand, the smaller
than predicted concentration of B±O±B sites sup-
ports a model with considerable mixing between
silicon and boron networks. This model is consis-
tent with our earlier conclusion that three-coordi-
nated borons mix with the silica network.
However, re®nement and modi®cation to Bray's
model would not be conclusive until more sodium
borosilicate glass compositions are studied.
Fig. 3 also contains a peak centered at about
)22 ppm in the isotropic dimension, which, from
previous work, is clearly assignable to non-bridg-
ing oxygens. It is not yet known, however, whether
this includes both B±O±Na and Si±O±Na sites, or
only the latter. Experiments on binary borate
glasses would make the assignment much less un-
ambiguous.
289
4. Conclusions
In summary, our study shows that 17 O NMR is
a powerful method for obtaining information
about the connectivities among di€erent net-
work-forming cations. However, one must use
caution in interpretation of conventional MAS
NMR spectra, due to the poor resolution one
can achieve. Higher-resolution techniques such as
MQMAS should be used when possible. We have
shown that this technique is capable of separating
the resonances from oxygens in Si±O±Si, B±O±B,
Si±O±B and [Si,B]±O±Na. Based on the MQMAS
spectra, we reassigned the Si±O±B and B±O±B res-
onances, and concluded that three-coordinated
borons can be incorporated into the silica net-
work. The results raise the challenge for a re®ned
or modi®ed structural model for boron-containing
glasses.
Acknowledgements
We thank Dr Zhi Xu for collecting X-ray pow-
der di€raction data on all the samples. This work
was supported by the National Science Founda-
tion, grant NSF DMR 9626735.
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