Journal of Non-Crystalline Solids 29 (1978) 187-206

© North-Holland Publishing Company

A STRUCTURAL INTERPRETATION OF B 10 AND B 11 NMR SPECTRA IN

SODIUM BORATE GLASSES

G.E. JELLISON, Jr., * ** and P.J. BRAY

Department of Physics, Brown University, Providence, R.I. 02912, U.S.A.

Received 19 September 1977

Revised manuscript received 27 November 1977

It is shown that the B10 spectra for sodium borate glasses are sensitive to the different struc-
tural groups in the glasses. Five boron sites are inferred from the data: two 4-coordinated sites
and three 3-coordinated sites. The two 4-coordinated boron sites are identified as BO4 units
connected to all BO3 units, and BO4 units connected to one BO4 unit and three BO3 units.
The three 3-coordinated boron sites are identified as BO3 units connected to: (1) all BO3 units;
(2) a mixture of BO3 and BO4 units; and (3) all BO4 units. These five sites can be interpreted
in terms of Krogh-Moe's structural model of alkali borate glasses, wherein the fraction of each
structural group can be determined for eight sodium borate glasses spanning the compositional
range from 0 to 35 mol% Na20. The resulting fractions are consistent with Krogh-Moe's struc-
tural model.

1. Introduction

In earlier [ 1 - 1 3 ] NMR studies of structure and bonding in borate glasses, the

central transition (m = ½ ~ 1 ) of the B 11 isotope has been employed almost exclu-
sively. Because of the importance of dipolar broadening and the existence of dis-
tributions of the coupling constant Qce and the asymmetry parameter r/, only aver-
age values of the coupling constant and asymmetry parameter were obtained from
B 11 NMR. However, B 11 NMR has proved to be very useful for the determination
of N4, the fraction of 4-coordinated boron atoms. On the other hand, B 1° NMR
affords three advantages over the use of the central transition of B 11 NMR: (1)
dipolar broadening is much less important [14]; (2) the distribution of quadru-
pole coupling constants is directly obtainable from a part of the B 1° NMR experi-
mental spectrum [14]; and (3) there exists another part of the B 1° NMR experi-
mental spectrum that is sensitive to the distributions of the asymmetry parameter,
but insensitive to the distributions of the coupling constant [15]. These features of

* Based on the work performed by G.E. Jellison, Jr., in partial fulfillment of the requirements
for the degree of Doctor of Philosophy at Brown University.
** Present address: US Naval Research Laboratory, Washington, DC.

187
188 G.E. Jellison, P.J. Bray / Structural interpretation o f B l Oand B 11NMR spectra

the B 1° NMR spectrum can be employed in studying the structure of borate glasses.
Sodium borate glasses are considered in this work.
It was first proposed by Krogh-Moe [16] that alkali borate glasses with less than
33-~ mol% alkali oxide contain mixtures of the four crystalline structural groups
(boroxol, pentaborate, triborate and diborate, see fig. l a - d ) . This proposition was
advanced on the basis of a comparison of the infrared (IR) spectra of the crystalline
compounds and the glasses, which showed that the spectra of the glasses bear re-
sembances to the spectra of the crystalline compounds. Recent Raman spectra
studies by Konijnendijk [17] are consistent with the Krogh-Moe structural model.
Rhee [18] has recorded the B 11 NMR spectra of the central transition for a series
of sodium borate glasses and has measured the most probable values of the coupling
constant and the asymmetry parameter from these spectra. His results agree quali-
tatively with the results of Krogh-Moe [16], but he was unable to detect the indi-
vidual structural groupings in the glass, since dipolar broadening, as well as the dis-
tributions of the quadrupole coupling constant and the asymmetry parameter, tend
to smear out any identifiable features of the B 11 spectra. This paper presents the
B 1° NMR spectra for a series of sodium borate glasses, and shows that a feature of
the B l° spectrum can be employed to identify the different structural groups and
to determine the abundance of each group in the glasses.
The theory of B 1° NMR powder patterns is presented in ref. [19] and will there-
fore be reviewed only briefly here. Fig. 2 shows a powder pattern for B 1° NMR. It

• boron o oxygen
Fig. 1. The four crystalline structural groups found in sodium borate glasses [(a) boroxol, (b)
pentaborate, (c) triborate and (d) diborate] and two structural groups found in sodium diborate
crystal, but not found in the glass [(e) di-pentaborate, and (f) triborate with one non-bridging
oxygen]. The tetraborate group is formed by connecting one oxygen atom of the BO4 unit in
the triborate group to a BO3 unit of the pentaborate group.
 G.E. Jellison, P.J. Bray / Structural interpretation orB 10 and B 11 NMR spectra 189

o b c O e f
Fig. 2. B 1 o NMR powder pattern for t w o o f the six transitions at u0 = 7 MHz. The shoulders b
and f and the divergence c correspond to the 0 ,-, - 1 transition and the shoulders a and e and
the divergence d correspond to the 1 ~ 0 transition.

is assumed that typical values of Qcc (= 5.5 MHz) and uo (= 7 MHz, v o being the
spectrometer frequency) are employed. For higher values of/3 [/3 = vQ/Vo, vQ =
3 Q c c / 2 / ( 2 / - 1)], additional shoulders and divergences may appear [19]. The posi-
tions of the shoulders and divergences of the powder patterns may be calculated
exactly [20], since they correspond to critical points of the resonance surface
v(O, ~), where 0 and ~ are the Euler angles of the principal axis system of the elec-
tric field gradient tensor with respect to the applied magnetic field. For the features
identified in fig. 2, the expressions are:
a = - 2 +-~/3r/2 + s/32~72, (1)

b = - ( 1 + n) + ~ / 3 ( 3 - n) = + ~ / 3 = ( 3 - n)=(1 + n), (2)

c = - ( 1 - ~7) + 7 13(3 + r/) = + 2-~/32( 3 + r/)2( 1 - 7), (3)
S /32(3
d = +(1 - r/) + ~7a4t3(3 + r?)2 -- g-4 , + rT):(1 r/), (4)
e = +(1 + 7/) + 2-Z4/3(3 - r/): - 5 / 3 2 ( 3 _ rl)z(1 + r/), (5)
f = +2 + -~/3r/= - {/32r~2 . (6)

Eqs. ( 1 ) - ( 6 ) above are in units of uQ/4 with respect to v o. These equations have
been calculated to third order employing perturbation theory.

2. Experimental
Two sets of eight samples of sodium borate glass were prepared over the com-
positional range 0 - 3 5 mol% Na20 in intervals of 5 mol% Na20. One set was pre-
pared by mixing the appropriate amounts of Fisher Reagent grade Na2CO3, H3BO3
enriched to 92% B 1° (obtained from the Oak Ridge National Laboratory) and
about 0.3 mol% MnC12 (added to reduce the spin-lattice relaxation time of the glass
samples). This mixture was heated to 1000°C for several hours and then poured
190 G.E. Jellison, P.J. Bray / Structural interpretation o r B 10 and B 11 NMR spectra

into a carbon mold at room temperature, resulting in a solid casting. The other set
was similarly made, except that the H3BO 3 was unenriched in B 1° and no MnC12
was added.
The B 1° and B 11 absorption derivatives were obtained using a Varian V4200
wide-line NMR spectrometer operating at 7 MHz for the B l° resonance, and at
16 MHz for the B 11 resonance. A Nicolet 1072 signal averager was used to accumu-
late the signals over several days for the B 1° spectra, and over several hours for the
B 11 spectra. The magnetic field was provided by a Varian V-3603 electromagnet
and VFR-2501 power supply and was swept and regulated by a Mark I Fieldial.
M1 spectra were taken at room temperature.
Calculations of the NMR lineshapes were made using a program by Taylor and
Bray [21,22]. Results were plotted on a Calcomp mechanical plotter so that the
computed spectra could be superimposed directly onto the experimental trace for
convenience in analysis.

3. Results

3.1. B 1° spectra

Figure 3 depicts the B 1° NMR derivative spectra for several Na20-B203 glasses.
The spectra of fig. 3 are distorted in two places: feature A to the left (or low-
frequency side) of Uo, and feature B centered at uo. These distortions were caused
by the magnetic field modulation and integration time constant required to see the
rest of the spectrum.
Feature A arises from the 3-coordinated boron atoms and is shown in fig. 4,
where the frequency scale is expanded and the magnetic field modulation and inte-
gration time constant have been decreased so that no distortion of the line-shape
occurs. Note that this feature changes considerably as the sodium oxide content is
increased. Feature B arises from the 4-coordinated boron atoms, which have a low
Qcc, and is seen centered about vo in fig. 3. This feature is symmetric in the region
between the highest and lowest points of the derivative spectrum. (A narrow trace
of this feature, obtained with decreased magnetic field modulation and integration
time constant, showed that it was symmetric between the highest and lowest points
of the derivative.) The dot (o) of fig. 3 shows the lowest point of the derivative of
feature B, assuming that the highest and lowest points of this feature are equidis-
tant from the baseline (using the highest point as the standard).

3.2. M e t h o d o f analysis o f the B 10 spectra

The actual lineshape for a glass involving distributions of both v o and r7 is given
by [141
1
K(u') : ? du o fd~p(uQ, r/) R(v', vQ, r/), (7)
0 0
 G.E. Jellison, P.J. Bray / Structural interpretation orB 10 and B l I NMR spectra 191

~, oO
I°V ,~
'
o
~// °/r
/

o '~'~ / o,'/

/ "2o_0 ,

' %-.-4
2 5 ; ~° Oo

3 0 .,. / " ~+'~ 30 kHz

z;

o~ >7,,
3 5/-'-" ~

Fig. 3. B l0 NMR derivative spectra for eight N a 2 0 - B 2 0 3 glasses. The computer-simulated

spectra (the darker lines in each case) were computed using the five sites characterized in table
1, with the appropriate weighting factors given in table 4. Mol% Na20 is indicated to the right
of each trace. The calibration given in the upper left-hand corner is for the glasses of composi-
tion 0, 5, 10, 15, 20, 25 and 30 mol% Na20, while the calibration given in the lower right-hand
corner is for the 35 mol% Na20 glass. Features A and B are the features of maximum distortion
due to magnetic field modulation and integration time constant for all glasses; the dot (o) repre-
sents the lowest position of feature B if these effects were not present.

Fig. 4. Experimental B l 0 derivative of the main feature (feature A of fig. 3) for 3-coordinated
boron atoms for seven N a 2 0 - B 2 0 3 glasses (solid line). The simulated spectra (circles) were cal-
culated using the five sites characterized in table 1, and the appropriate weighting factors given
in table 4.

where p(uQ, 7) is the distribution function for vQ and rl, and R(u', uO, r~) is the di-
polar-broadened shape function. It is assumed that the distribution function can be
expressed as a sum of component parts, each component part representing one site
192 G.E. Jellison, P.J. Bray / Structural interpretation o f B 1o and B 11 NMR spectra

in the glass (such as 3-coordinated boron atoms connected to all BO 3 units), i.e.

p(v~, 7) = ~piO'~, ~), (8)

where the sum extends over all possible sites inthe glass. For each distribution, Pi"
(vQ, rl), it is further assumed that the variables VQ and r/are uncorrelated; that is

Pi(V Q, 7) = Pi(V Q ) Pi (r/). (9)

This assumption is not entirely correct since r/ is a function of Vzz (the compo-
nent o f the electric field gradient tensor that has the largest magnitude in the prin-
cipal axis system) and therefore VQ. The exact correlation, however, is model-
dependent and cannot be determined experimentally.
The calculated spectra were obtained by calculating several powder patterns,
each calculated for a specific value of VQ and r/. These powder patterns were then
appropriately weighted and summed, resulting in the final calculated spectrum (see
ref. [21] and [22] for a description o f the procedure). There were five discernible
sites in the N a z - B 2 0 3 system: two sites with a low value of Qcc (corresponding to
4-coordinated boron atoms); and three sites with a higher value of Qcc, and a low
value of r/ (corresponding to 3-coordinated boron atoms). (Each site is character-
ized by a most probable value and a gaussian width for the two parameters: VQ and
r~.)
The solid wide line of fig. 3 superimposed upon the experimental spectra, and
the circles of fig. 4 superimposed upon the experimental spectra, represent com-
puter-simulated spectra obtained by using the five sites whose parameters are given
in table 1. [The most probable value and the width of the gaussian distribution of
Qee for sites 3, 4 and 5 (the 3-coordinated boron atoms) were determined in ref.
[14] and are shown in table 2.] The weighting factors used for these computer
simulations are given in table 3.

Table 1
Characterization of distributions of hamiltonian parameters for the five sites observed in
Na20-B20 3 glasses for B 10 NMR.

Site Q°c (MHz) OQcc (MHz) r~0 oH

1 0.8 0.2 0.5 0.5

2 1.5 1.0 0.0 0.5
3 a) a) 0.12 ± 0.02 0.05 ± 0.01
4 a) a) 0.26 -+0.02 0.05 ± 0.01
5 a) a) 0.08 + 0.02 0.05 + 0.01

a) The value of Qo and aQcc for sites 3, 4 and 5 vary from glass to glass and are given in table 2.
 G.E. Jellison, P.J. Bray/Structural interpretation o f B l Oand B 11 NMR spectra 193

Table 2
Experimental values of Q° c and OQcc for sites 3, 4 and 5 in sodium borate glasses (from ref.
[ 14]). Values of ~o and a.q for these sites are given in table 1.

Mol% Na20 Q° c (MHz) aQc c (MHz)

0 5.51 0.21
5 5.48 0.22
10 5.48 0.21
15 5.45 0.21
2o 5.41 0.21
25 5.41 0.21
30 5.37 0.23
35 5.39 0.23

3.2.1. Determination o f the parameters o f the sites shown in table 1

The d e t e r m i n a t i o n o f the distribution parameters for sites 1 and 2, which b o t h
yielded narrow lines (since Q~c was low for b o t h cases), was u n d e r t a k e n by fitting
the narrow lines o f the 5 and 30 tool% N a 2 0 glasses, respectively, since site 1 pre-
d o m i n a t e s in the 5 mol% N a 2 0 glass and site 2 p r e d o m i n a t e s in the 30 tool% N a 2 0
glass. Several distributions o f the h a m i l t o n i a n parameters UQ and r~ were postulated
and the resulting spectra were calculated using the m e t h o d presented above. Tile
calculated spectra, p l o t t e d by a Calcomp mechanical plotter, were then c o m p a r e d
w i t h the e x p e r i m e n t a l trace. Because there are no p r o m i n e n t features on the narrow
lines, several drastically different distributions fit the e x p e r i m e n t a l s p e c t r u m well.
H o w e v e r , it was clear f r o m the analysis o f the spectra that the m o s t probable value

Table 3
The fractions of sites l, 2, 3, 4 and 5 determined by the computer-fitting procedure given in
the text, for a series of N a 2 0 - B 2 0 3 glasses. The notation 74, D 4, B 3, T 3 and D 3 is explained
in table 4. The quantity 6 is the excess number of diborate borons from the predicted by the
lever rule (a negative values of 6 indicates that there are fewer diborate borons than are pre-
dicted by the lever rule). All fractions are rounded to two significant figures.

Glass Site 1 Site 2 Site 3 Site 4 Site 5 6

(T4) (D 4) (B 3) (T 3) (D 3)

5 0.05 - 0.79 0.16

10 0.10 0.01 0.58 0.30 0.01 0.01
15 0.15 0.03 0.38 0.44 0.03 0.03
20 0.17 0.08 0.16 0.51 0.08 0.08
25 0.14 0.19 0.04 0.44 0.19 0.02
30 a) 0.11 0.28 0.33 0.28 -0.08
35 a) 0.08 0.34 - 0.24 0.34 0.14

a) Borons bonded to a non-bridging oxygen have been ignored for these glasses.
194 G.E. Jellison, P.J. Bray / Structural interpretation orb 10 and B 11 NMR spectra

of the coupling constant for site 2 was considerably higher than for site 1. Theval-
ues quoted in table 1 are in no sense unique, and should be viewed simply as val-
ues that fit;they do not necessarily have any physical significance.
The determination of the distribution parameters for sites 3, 4 and 5 was made
from the large feature on the low-frequency side of uo (feature A of figs. 3 and 4).
It was assumed that all the distributions pi(pQ) and Pi(~) [see eq. (9)] were gaussian.
It was further assumed that pi(pQ) w a s the same for all three sites, but changed
from glass to glass. (This distribution was determined in ref. [14] for the same
series of Na20-B203 glasses. Note that the values change very little over the entire
compositional range.) Since site 3 is predominant in the 0 molar% Na20 glass, site
4 in the 20 tool% Na20 glass, and site 5 in the 30 tool% Na20 glass, the distribu-
tion parameters for sites 3, 4 and 5 were determined from the 0, 20 and 30 tool%
Na20 glasses, respectively. Several distributions of the asymmetry parameter were
postulated and the resulting spectra were calculated using the method presented
above. The calculated spectra, plotted by a Calcomp mechanical plotter, were then
compared with the experimental trace. The 20 and 30 tool% Na20 glasses contained
3-coordinated sites other than the predominant one, but the presence of these other
sites did not interfere with the determination of the distribution of r/, since their
intensities were low. In this way, the distribution parameters can be determined
with reasonable accuracy.

3.2.2. A ssignment o f the sites to structural groupings

Krogh-Moe's interpretation [16] of the IR spectra for alkali borate glasses states
that below 20 tool% alkali oxide, the addition of one "molecule" of alkali oxide to
boron oxide results in the formation of one triborate group (fig. lc) and one penta-
borate group (fig. lb). These groups are connected, the BO4 unit of the triborate
group being connected to one of the BO3 units of the pentaborate group, so it is
convenient to refer to the triborate-pentaborate pair as a tetraborate group. Above
20 tool% alkali oxide (up to 33~ tool% alkali oxide), diborate units will increase at
the expense of tetraborate units. Therefore, the 0 tool% Na20 glass will consist
mainly of boroxol units, the 20 tool% Na20 glass will consist mainly of tetraborate
units and the 30 mol% NazO glass will consist mainly of diborate units, according
to Krogh-Moe's model.
The assignment of the five sites to various BO3 and B O 4 units must be made,
keeping in mind that the NMR quadrupole interaction is proportional to 1/r 3,
where r is the distance between the nucleus under investigation and the charge cre-
ating the electric field gradient. Therefore, only nearest neighbors or, at most, next-
nearest neighbors need be considered.
The vastly different hamiltonian parameters listed in table 1 for the five sites can
be explained by the difference in the electronic distribution of the 3- and 4-coordi-
nated boron atoms. One effect of this difference, which has been exploited exten-
sively [1-13], is that the distribution of electrons about 4-coordinated boron
atoms in borate glasses is close to being tetrahedrally symmetric, which produces a
 G.E. Jellison, P.J. Bray / Structural interpretation o r B 1o and B 11 NMR spectra 195

weak quadrupole interaction (as measured by the quadrupole coupling constant);

on the other hand, the distribution of electrons about 3-coordinated boron atoms
in borate glasses, for the case when all oxygen atoms connect two boron atoms, is
close to being axially symmetric, which produces a stronger quadrupole interaction
with a low value of the asymmetry parameter. Another effect of this difference
arises front the fact that a 3-coordinated boron is in an sp 2 hybridized state, while
a 4-coordinated boron is in an sp 3 hybridized state. Therefore, the B - O bond of a
BO 3 unit can possibly have n-character, while the B - O bond of a B O 4 unit cannot
have n-character. This will strongly affect the electron concentration on the neigh-
boring oxygen atoms, which will affect the electric field gradient at the next
nearest atom (a boron atom). It seems logical, then, to consider the type of unit
( B O 3 o r B O 4 ) connected to the subject unit in the assignment of the five sites.
Retrospectively, the reason five sites were chosen can now be seen. There are at
least two possible B O 4 sites: B O 4 units connected to all B03 units and B O 4 units
connected to a mixture of BO3 and B O 4 units. (The possibility of B O 4 units being
bonded to all B O 4 units is neglected, since this possibility has never been observed
in crystalline borates.) There are three possible BO3 sites: BO3 units connected to
(1) all BO3 units; (2) a mixture of B O 3 and BO4 units; (3) all BO4 units.
This difference between the BO3 and BO4 units has also been used by Bril [23]
to explain the different Raman frequencies of boroxol rings and rings with one
(or more) B O 4 units. The boroxol rings contain n o B 0 4 units; therefore n-charac-
ter is to be expected in the B - O bonds in the ring, which will strengthen the inter-
anular B - O bonds. If the ring contains one or m o r e B O 4 units (such as pentaborate,
triborate, tetraborate or diborate groups), then there can be no n-character to the
B O bonds of the B O 4 unit, weakening these bonds. This results in the breathing
mode vibration being of a higher frequency for the boroxol ring compared to the
ring with one or m o r e B O 4 units. Therefore, the 806 cm I Raman line observed in
borate glasses is assigned to boroxol breathing mode vibrations, and the 770 cm -I
Raman line is assigned to the breathing mode of a ring with one or m o r e B O 4 units.
Sites 1 and 2 can be assigned to B O 4 units, since the value of Qc°c is low for these
sites; but there is a fundamental difference between the two sites: the value of Q°cc
for site 1 is considerably lower than Q°cc for site 2. This implies that site 1 is closer
to tetrahedral symmetry than site 2. The origin of this can be seen from X-ray dif-
fraction studies of crystalline sodium tetraborate [24] (containing all tetraborate
groups) and lithium diborate [25,26] (containing all diborate groups). The BO 4
units in sodium tetraborate are connected to four B03 units, while the B 0 4 unit in
lithium diborate is connected to three B03 units, and o n e B O 4 unit; therefore, the
electric field gradient at the site of the boron nucleus of a B O 4 unit in a tetraborate
group will be closer to tetrahedral symmetry than a B O 4 unit in a diborate group.
Therefore site 1, which has a low value of Qcc and is predominant at low sodium
content, can logically be assigned to B04 units connected to all B03 units; while
site 2, which has a higher value of Qcc and is predominant at high sodium content,
can logically be assigned to B O 4 units connected to a mixture of B03 and B O 4
units.
196 G.E. Jellison, P,J. Bray / Structural interpretation o f B 10 and B 11 NMR spectra

Sites 3, 4 and 5 are assigned to BOa units (owing to their higher value of Q°c),
but again there is a fundamental difference between the three sites, as exhibited by
the differences in the values of the asymmetry parameter (see table 1): the value of
77 for site 4 is considerably higher than the values of ~ for sites 3 and 5, indicating
that site 4 is less axially symmetric than sites 3 and 5.
The X-ray work of Mozzi and Warren [27] (as well as the interpretation of the
806 cm -1 Raman line [16]) of B20 3 glass indicates that this glass consists mostly
of boroxol rings (see fig. la). Raman studies by Konijnendijk [17] show that the
same line is present in glasses of the sodium borate system (though shifted 1 or 2
cm -I in frequency) up to approximately 20 mol% sodium oxide, indicating the
presence of boroxol groups in sodium borate glasses up to 20 mol% Na20. Site 3,
then, can be assigned to BOa units connected to three other BO3 units, since this
site is highly axially symmetric and exists predominantly at low sodium content.
The non-zero asymmetry parameter for site 3 can be attributed primarily to the
non-equivalence of the three connecting oxygens [ 15].
At higher sodium content, according to Krogh-Moe's model, most groups present
are tetraborate groups [ 16,17]. X-ray diffraction studies of crystalline sodium tetra-
borate [24] indicate that all the BO3 units of this compound are attached to one
(or two) BO 4 units and two (or one) BO3 units. Therefore, the asymmetry param-
eter for BO3 units in tetraborate groups would be considerably higher than for BO 3
units in boroxol groups. This is confirmed by NMR measurements of crystalline
sodium tetraborate [18] where ~ = 0.27 is recorded for 3-coordinated boron atoms
in tetraborate groups. The agreement between the values of ~7 of crystalline tetra-
borate and of site 4 is excellent. Therefore, site 4 is assigned to BO3 units, connect-
ed to one (or two) BO 4 units and two (or one) BO3 units, such as are found in
tetraborate groups. (It is impossible to distinguish between the two cases, since the
tetraborate group contains both.)
X-ray diffraction investigations of crystalline lithium diborate [24,25] indicate
that all BO3 units in diborate groups are connected to three BO4 units. (Sodium
diborate is not appropriate for comparison, since the crystal structure does not con-
tain diborate groups, but rather di-pentaborate groups and triborate groups with
one non-bridging oxygen [28] - see fig. le, f.) These BO3 units are therefore near
axial symmetry. Site 5, then, is assigned to BO3 units connected to three BO 4 units,
since it occurs at high sodium content, where the predominant group present in the
Krogh-Moe model is the diborate group, and since it has a low asymmetry param-
eter. However, NMR measurements of crystalline lithium diborate yield a value
[29] 77 = 0.17, which is clearly greater than the value of 77 for site 5. This is possibly
due to one B - O bond length being about 0.04 A shorter than the other two B - O
bond lengths [26] for BO3 units in lithium diborate, which would tend to increase
the asymmetry parameter. If this is the case, then the crystalline diborate groups in
lithium diborate are more distorted, owing to crystal packing requirements, than
the glassy diborate units.
Until now, Krogh-Moe's interpretation of IR data has been employed only as
 G.E. Jellison, P.J. Bray / Structural h~terpretation o f B 10 and B 11 NMR spectra 197

supporting evidence; it is not central to the interpretation of the B 1° data and the
assignment of the five sites to B03 or B04 units connected to a specified number of
other BO 3 and BO 4 units. At this point, Krogh-Moe's model is taken as the basis of
the analysis; it is assumed that the four structural units o f fig. l a - d exist in the
glass. It will be seen that the B l° NMR data agree extemely well with Krogh-Moe's
model, but this does not exclude other possible structural models. The B 1° spectra
are more sensitive to differences in local structure than B 11 NMR, and present a
unique form of structural information compared to other structural tools; however,
as with all experiments employed for the determination of structure of glasses, the
B 1° spectra can be only looked on as a restraint to a proposed structural model
[301.
Given Krogh-Moe's model, there might be a tendency to extend the assignment
of the live sites to the various structural groups themselves (site 3 might be assigned
to 3-coordinated borons in boroxol rings, site 4 to 3-coordinated tetraborate borons
and site 5 to 3-coordinated diborate borons); however, this is to be undertaken with
great care as to the assumptions involved, since alternative assignments are possible.
For example, it is possible in the glass that a diborate BO 3 unit might be connected
to two BO4 units (in the diborate unit itself) and to one BO 3 unit not associated
with the diborate group. However, restrictions can be imposed, assuming that the
sodium borate glass system contains only "loose" BO 3 units (BO3 units not associ-
ated with any structural group), loose BO 4 units, boroxol groups, tetraborate
groups and diborate groups. (This is justified by the Raman studies of Konijnendijk
[17].) These restrictions are listed in table 5. If the loose units are neglected (the
Raman studies indicate that their percentages are small [17]), then the only ambi-
guity comes from sites 2 and 4. Site 1 could come only from tetraborate BO 4 units;
site 3 could only come from boroxol BO 3 units; and site 5 could only come from
diborate BO 3 units. However, site 2 could come from tetraborate BO 4 units, as well
as diborate BO 4 units, if two tetraborate groups were connected by BO 4 units. This
does not occur in crystalline sodium tetraborate [24], where aH BO 4 units are con-
nected to four BO 3 units. The ~ modification o f sodium triborate contains penta-
borate and diborate units [31 ]. Site 2 occurs in this compound, but only associated
with the diborate units. Since this is the only occurrence of site 2 in compounds of

Table 4
Symbols used to denote the fractions of borons in each structural group.

Symbol Unit Coordination Site

T4 tetraborate 4 1
D4 diborate 4 2
B3 boroxol 3 3
T3 tetraborate 3 4
D3 diborate 3 5
198 G.E. Jellison, P.J. Bray / Structural interpretation o r B 10 and B 11 NMR spectra

Table 5
Possible origins o f the five sites described in table 1

Site Loose Boroxol Tetraborate Diborate

BO 3 BO 4 BOa BO 3 BO 4 BO 3 BO4

1 X X
2 X X X
3 X X
4 X X X X
5 X X

the sodium borate system, and since site 2 occurs only in diborate groups here, it is
reasonable to rule out the possibility of site 2 coming from tetraborate BO 4 units.
The real ambiguity, then, comes from site 4, where all possibilities actually occur in
crystalline materials.

3.2.3. Assignment of weighting factors

In order to make an assignment of the proper weighting factors, five assumptions
have been made:
(1) Loose BO3 and BO4 units are neglected in this analysis. Konijnendijk [17]
indicated that there could be minor fractions of loose BO3 and BO4 units present in
the glass. In addition, ref. [15] showed that between 10 and 25% of the borons in
vitreous BzO 3 are outside the boroxol rings, though it was emphasized that this
number is not accurate. In ref. [15], it was stated that these loose BO3 units all
have bridging oxygens. Beyond that, however, nothing can be said about the
expected hamiltonian parameters for the loose BO a units. Similarly, "loose" BO4
units will have a low value of Qee"o As the loose BO3 and BO4 units have no charac-
teristic hamiltonian parameters, one is forced to neglect them.
(2) Other units that might possibly appear in minor amounts [such as di-penta-
borate units or triborate units with one non-bridging oxygen (see fig. le, f)] are
ignored.
(3) Pentaborate and triborate units (see fig. lb, c) are assumed to occur in pairs,
and will be called tetraborate groups. The Raman studies of Konijnendijk [17] indi-
cated that lone pentaborate units did not occur in the glass, supporting this assump-
tion.
(4) Site 2 is postulated to consist entirely of BO 4 units in diborate groups. As
discussed above, the X-ray diffraction studies of the crystalline materials support
this assumption.
(5) Site 4 is postulated to consist entirely of BO3 units in tetraborate groups. Im-
plicit in this assumption are the restrictions that boroxol groups are connected to
other boroxol groups or to BO3 units of tetraborate groups, and that the BO3 units
 G.E. Jellison, P.J. Bray / Structural interpretation o f B 10 and B 11 NMR spectra 199

of the diborate groups are connected to B O 4 units of the tetraborate or other

diborate groups.
Additionally, two facts should be noted: (1) the fraction of 4-coordinated
diborate borons is equal to the fraction of 3-coordinated diborate borons; (2) the
fraction of 4-coordinated tetraborate borons is equal to one-third the fraction of
the 3-coordinated tetraborate borons. The rationale for this can be seen from fig.
lb-d.
Table 3 shows the weighting fractions obtained by fitting the experimental spec-
tra of figs. 3 and 4 for the five sites whose hamiltonian parameters are listed in table
1. Fig. 5 shows feature A for the 20 tool% Na20 glass superimposed upon three
computer-simulated spectra calculated for three different weightings of the five

1.0-

09-

08-

0.7-

0.6-

05-

~ 0.5-

0.2-

01.

3 0 k Hz ~, i

I I V OI 0'.2 05 0.4 0.5 0.6 R

Fig. 5. Experimental B 1° derivative of the main feature for 3-coordinated boron atoms (feature
A of fig. 3) in the 20 mol% Na20 glass (solid line). The simulated spectra (circles) were calcu-
lated using the five sites of table 1, and three sets of weighting fractions.

Simulation Site 1 Site 2 Site 3 Site 4 Site 5 6

a 0.19 0.06 0.12 0.57 0.06 0.06

b 0.17 0.08 0.16 0.51 0.08 0.08
c 0.15 0.10 0.20 0.45 0.10 0.10

The quantity 6 is discussed in the text.

Fig. 6. Fractions of B 3 (A), T 3 (o), D 3 and D 4 (=) and T 4 (+) plotted as a function of R (=
x/(1 - x), x = molar fraction Na20). The straight line segments are plotted for the case where
the lever rule is obeyed (see text).
200 G.E. Jell&on, P.J. Bray / Structural interpretation orB 10 and B 11 NMR spectra

sites. As can be seen, this feature is very sensitive to changes in the weighting frac-
tions.
The determination o f the fractions of the five sites by the lever rule (denoted by
B 3, T 3, D 3, T~o and D 4) - assuming only boroxol, tetraborate and diborate groups
are present - is shown by the solid line of fig. 6 plotted versusR = x/(1 - x ) ( x =
molar fraction alkali oxide). At 0 mol% Na20, 100% of the borons will be in
boroxol groups (according to the lever rule). As the mol% Na20 is increased, the
percentage of tetraborate borons will increase until, at x = 0.20, T 3 = 0.75, T~o =
0.25, and Bo3 = 0. Above x = 0.20, as x increases, the percentage of diborate groups
will increase at the expense of the tetraborate groups until, at x = ½, D 4 = Do3 = 0.5,
To3 = T~o = Bo3 = 0. Above x = ½, the diborate groups will be destroyed and 3-coordi-
nated borons with non-bridging oxygens will be created [4]. However, the rate at
which the diborate groups will be destroyed is unknown. It has been determined
emperically by Greenblatt and Bray [4] that the destruction rate of 4-coordinated
borons is 0.5 (each Na20 "molecule" added beyond the x = ½ composition destroys
half o f a BO 4 unit.) If it is now assumed that only diborate groups and BO3 units
with one (or two) non-bridging oxygens and two (or one) bridging oxygens exist
above the x = -~ composition, the fraction Do3 = D 4 will be as shown in fig. 6. This
assumption is somewhat tenuous, but since the largest mol% Na20 glass used in this
study is the 35 tool% Na20 glass, which is not far above x = ½, the effects of this
assumption are negligible.
In determining the weighting factors of table 3 for the glasses with x = 0.25 and
below, only a quantity 6 is varied, where 6 represents the fraction of diborate
borons in excess of the fraction of diborate borons expected by the lever rule, that
is,
D 3 = D 4 = D o3 +6. (10)

Now, since N4 must [2] have the value

N 4 =X/(1 --x), (11)

it is necessary that the total numbers o f 3-coordinated and 4-coordinated borons be
unaffected by the departure of the number of diborate units from the value pre-
dicted by the lever rule. Therefore,
T 4 + D 4 = T 4 + D 4, (12)
and
B 3 + T 3 + D 3 = B 3 + T 3 + D 3. (13)
But since
T 4 = T3/3, T~o = T~/3, (14)

and
D 4 = D 3' D 4 = D o3, (15)
 G.E. Jellison, P.J. Bray /Structural interpretation orB 10 and B 1 I NMR spectra 201

then eqs. (10), (120 and (13) can be solved forB3, T3,D 3, 7 "4 andD 4, yielding

B3 =Bo3 +26, T3 = To3-36, D3 =Do3 + 6 , 74 = T 4 o - 6 '

D 4 = D 4 + 8. (16)
That is, if a diborate boron is "created", then two boroxol borons must be "cre-
ated", and three tetraborate (3-coordinated) borons must be "destroyed". Fig. 5
shows the experimental spectrum of the x = 0.2 glass superimposed upon three
computer-sinmlated traces for different values of 6. Clearly, fig. 5b represents the
best fit. It should be emphasized that only the single parameter 6 is varied in ob-
taining the fit in fig. 5 ; the variations of the five-site weighting fractions given in the
caption of fig. 5 follow from eqs. (16) when/5 is varied. Fig. 6 presents as a func-
tion o f R = x/(1 - x) the values of B 3, D 3, D 4, T 3 and 74 given by eqs. (16) and the
value of 6 determined for each glass.
For the 30 and 35 tool% Na20 glasses, it was necessary to relax the condition
that N4 = x/(1 - x ) ; otherwise it was not possible to fit the central line (due to the
4-coordinated borons) and the broad line (due to the 3-coordinated borons) simul-
taneously. However, from the Raman studies of Konijnendijk [17], it is possible to
say that B 3 = 0 for these glasses. Since the total number of boron atoms is fixed for
a particular composition, it must be true that
r 3 + 7,4 + D 3 + D 4 = Toa + T~o + D o3 +Do4 = 1.00. (17)

Using the relations of eqs. (14) and (15) and setting D 3 = Do3 + 6, eq. (17) yields
g3=0, T 3 = T 3o 36/2, Da =D~ +6, T4 + T~o - 6/2,
D 4 = D ~ +6, (18)

(Note that 6 will be negative for these glasses. Also, the number of oxygens will not
be conserved by this transformation, since the condition on N4 is relaxed; this is
because non-bridging oxygens have been ignored.) Clearly, the "disassociation" of
one diborate group will "create" half of a tetraborate group. (The diborate group
has two 3-coordinated boron atoms and two 4-coordinated borons for a total of
four; the tetraborate group has six 3-coordinated borons and two 4-coordinated
borons for a total of eight.)

3.3. B 11 N4 measurements

The experimental derivative of the B 11 NMR lineshape was obtained for the pur-
pose of determining N 4. This lineshape was then integrated, using the integration
option on the Nicolet 1072 signal averager, yielding the B 11 NMR absorption pat-
tern (see fig. 7). The central peak near uo is due to 4-coordinated borons; the broad
line is due to 3-coordinated borons. The ratio of the area of the central peak (area
A of fig. 7b) to the total area is just the fraction of 4-coordinated borons (N4) in
202 G.E. Jellison, P..L Bray / Structural #zterpretation orB l 0 and B 11 NMR spectra

N4
0.5:
0,4-

.-~ 0.3-
.....................'..........................
""
0.2- ... +[,o

0.1-

(~.1 0'.2 0'.3 0[4 0'.5 ) R

l:ig. 7. B 11 NMR derivative of the absorption wave (a) and the B 11 absorption curve itself (b)
taken at v0 = 16 MHz for the 20 tool% Na20 glass. The absorption curve (b) has been displaced
to the left to get both spectra in the figure. From the absorption curve (b), N 4 can be deter-
mined as N 4 = area A/(area A + area B). In this case, N 4 = 0.25.

Fig. 8. N 4 versus R[ = x/(1 - x ) ] from B 1 ! NMR (o) and B 10 NMR (+). The straight line is
determined by summing T~O+D 4 from fig. 6. The dotted line is from 13eekenkamp [37].

the glass [13,32]. The resulting values o f N 4 are shown in fig. 8 by the circles (o)-
The B 1° values in fig. 8 are the sum of T a a n d D 4 from table 3.

4. Discussion

The assignment o f weighting fractions has been made on the somewhat unjusti-
fied assumption that all site 4 borons arise from BO3 units in tetraborate groups.
However, the comparison o f results presented here and R a m a n work presented by
Bril [23] lends this assumption a degree o f validity. The ratio of the n u m b e r o f
boroxol rings to the n u m b e r o f rings containing one or more BO 4 units is given
by

B3/3 _ I B3 (19)
3 X T3/6 + D 3 3 T3/2 + D 3

if the postulate that all site 4 b o r o n s arise from BO 3 units in tetraborate groups is
assumed. These fractions are plotted with circles in fig. 9. A similar fraction can be
o b t a i n e d from R a m a n data. Bril [23] measured the fraction o f the intensities o f
the 8.06 c m - 1 line to the 770 cm -I line. (The 806 cm - l line arises from a breath-
ing mode vibration o f the boroxol ring [16], while the 770 cm -1 line arises from a
breathing m o d e o f rings c o n t a i n i n g one or more BO4 units [17,23]). The data of
Bril, multiplied b y a normalizing factor 0.4, are plotted in Fig. 9 with crosses (the
normalizing factor is necessary to correct for differences in linewidths, scattering
cross-sections, etc.). The normalizing factor was assumed to be constant over the
 G.E. Jellison, P.J. Bray/Structural interpretation o r B 10 and B 11 NMR spectra 203

5-

I-

" 20
Molar % Na20
Fig. 9. Ratio of the number of boroxol groups to the number of other rings with one or mor~
BO4 units. The ckeles represent points calculated from the data presented in this paper using
eq. (19), while the crosses represent the data of Bril [23], multiplied by a normalizing factor of
0.4, and the X's represent the data of Bartoluzza et al. [34 ].

range 5 - 2 0 tool% Na20. [Bril assumed that this normalizing factor was 1 ; he did
not take into account the fact that the peak width of the 770 cm -1 line is 2.5 3
times that of the 806 cm -1 line at 15 tool% Na20 (this would yield a normalizing
factor of 0 . 4 - 0 . 3 3 , other effects being equal). His assumption was based on the
observation that the ratio of these two peak heights for Cs20 • 9 B203 is 2 : 1
(which corresponds to the ratio of boroxol rings to triborate rings [33] in crystal-
line Cs20 - 9 B203). However, he ignored any differences in the peak widths which
could affect the ratio drastically. Ideally, a computer fit should be attempted to get
the ratio of the intensities.] Another comparison can be made with the Raman data
of Bartoluzza et al. [34]. The ×'s in fig. 9 represent the ratio of the height times the
width of the 806 cm -1 line divided by the height times the width of the 770 cm-1
line. The agreement is excellent. Although other conclusions could be drawn from
this result, it is consistent with the assumption that all the site 4 borons arise from
BO 3 tetraborate units.
The assignment o f site 4 entirely to BO3 units in tetraborate groups [see postu-
late (5) above] contains a possible explanation to the observed subliquidus immisci-
bility in sodium borate glasses [35]. Shaw and Uhlmann observed that, between 7
and 24 tool% Na20, small ( 7 0 - 1 0 0 A dia.) two-phase structures were observed, if
the samples were heat-treated for approximately 30 min. The samples used in this
study were quenched in a carbon mold at room temperature, so the cooling rate
was greater than that required to see two-phase structures 70 )~ in dimnter, but
smaller two-phase structures could very well have been formed. If, in fact, very few
boroxol borons are connected to BO 4 units in the region 0 - 2 0 mol% Na20, then
204 G.E. Jellison, P.J. Bray / Structural interpretation o r B 10 and B 11 NMR spectra

the tetraborate groups would tend to be connected to each other. This would
result in phase separation - one type of region being rich in tetraborate units and
the other type of region being poor in tetraborate groups.
Below the subliquidus immiscibility region ( 0 - 7 mol% Na20), no phase sep-
aration is observed. In this region the tetraborate groups are most likely not con-
nected to one another, and are preferably connected to boroxol groups. The tetra-
borate group has six oxygens with which it can bond to other groups (see fig. lb,
c; remember that the triborate group is connected to the pentaborate group by the
BO4 unit): one is associated with a BO 4 unit, while five are associated with BO3
units. This would result in 14.3% of the site 4 borons arising from boroxol borons
connected to BO 4 units; at 5 tool% Na20, this amounts to 2.2% of the total borons
in the sample. This is within the experimental error of the present work.
Therefore, in the region 0 - 2 0 mol% NazO, assumption (5) can be reasonably
justified. However, for larger sodium concentrations, these justifications are no
longer valid. The numbers of tetraborate BO 3 units (as well as tetraborate BO 4
units) could be somewhat smaller, and the numbers of diborate BO3 and BO 4 units
could be somewhat larger.
An examination of fig. 6 shows that the fractions B 3, D 3 and l ) 4 are above, while
the fractions T a and 74 are below, the values predicted by the lever rule, in the
compositional region 0 - 2 5 mol% Na20. This would also be true if assumption (5)
were violated, since any violation of assumption (5) would tend to decrease T 3.
It can be concluded from the data of fig. 6 and the supporting arguments given
above that, in the compositional region 0 - 2 5 mol% Na20 some of the tetraborate
units predicted by the lever rule have been "disassociated" into diborate groups and
additional boroxol groups. A convenient parameter for measuring the amount of
"disassociation" is the parameter 6 used in this work, where 6 represents the num-
ber of 3- or 4-coordinated diborate borons "created" (i.e. in excess of that predict-
ed by the lever rule). Such "disassociation" was predicted by Krogh-Moe [36] in his
interpretation of melting-point depression data for melts of the Na20-B203 sys-
tem. He found that the best fit of the experimental data in the region near x = 0.2
occurred when tetraborate, boroxol and diborate units were present, and when
some of the tetraborates, which would be present according to the lever rule, were
"disassociated" into boroxol units and diborate units. Furthermore, Raman studies
by Konijnendijk [17] and Bril [23] indicate the existence of boroxol groups at 20
mol% Na20 , and IR measurements by Krogh-Moe [16] indicate tile existence of
diborate groups at the same composition. Therefore, for the compositional region
x = 0 to x = 0.2, the conclusion can be drawn that the glass is composed of the
three principal structural groups (boroxol, tetraborate and diborate), but that the
fractions of these groups in the glasses for which x = 0.10, 0.15 and 0.20 do not
correspond to the values predicted by the lever rule.
In the region x = 0.30 and 0.35, some of the diborate groups predicted by the
lever rule have been "changed" into tetraborate groups, though the numbers pre-
sented in fig. 6 could be in error. The interpretation of melting-point depression
 G.E. Jellison, P.J. B r a y / S t r u c t u r a l i n t e r p r e t a t i o n o f B l ° and B 11 N M R spectra 205

data by Krogh-Moe [36] of melts of the N a 2 0 - B 2 0 3 system in the region of x =

31 indicates that these two groups (tetraborate and diborate) are present. In addi-
tion, IR [16] and Raman [17] studies indicate that these two groups are the only
major components of the glass in this region. In particular, the components of crys-
talline sodium diborate (the di-pentaborate and the triborate with one non-bridging
oxygen, see fig. le, f) have been ruled out, since the NMR spectra indicated that no
BO 3 units with one or two non-bridging oxygens were present. Therefore, the tetra-
borate and diborate groups are the only major components of the glasses for which
x = 0.30 and 0.35; however, as mentioned above, the fractions T 3, T 4, D 3 and D 4
do not correspond to values predicted by the lever rule. In particular, the lever rule
would predict T 3 = T 4 = 0 for the x = -~glass. By interpolation, T 3 = 0.27, and 7`4 =
0.09 at x -- -~, which are clearly not zero values. The main consequence of the
"changing" of diborate groups into tetraborate groups for the glasses with x = .30
and 0.35 is that N 4 will fall below the x / ( 1 - x ) curve. Fig. 8 shows two indepen-
dent measurements o f N 4 : (1) using B 11 NMR [shown by the circles (©) of fig. 8,
described above); and (2) using B 1° NMR (N4 = 7"4 + D 4, shown by the crosses (+)
of fig. 8]. The solid line of fig. 8 is obtained by summing T~o + D~ (obtained from
the lever rule) of fig. 6. The agreement of both methods is excellent; both methods
indicate that the value of N 4 lies below the x / ( 1 - x ) curve for the glasses with x =
0.30 and 0.35. Also :ncluded in fig. 8 is the theoretical curve forN4 (shown by the
dotted line) from Beekenkamp [37]. As can be seen, the experimental data points
lie substantially above this theoretical curve.
The conclusions above on fractions T 3, T 4, D 3 and D 4 for the glasses with x =
0.30 and 0.35 are highly dependent on assumption (5). Any deviation from this
assumption would tend to decrease T 3 and 7-4 and increase D 3 and D 4, resulting in
a larger value of N4. Therefore, any deviation from this assumption could not be
too large without creating a disagreement with the B lj NMR N 4 measurements.

5. Summary

Here, B I° NMR has been used to study glasses of the sodium borate system. The
analysis of these spectra that five sites are present in the glasses: two 4-coordinated
and three 3-coordinated boron sites. The 4-coordinated sites can be further distin-
guished as BO 4 units with (1) all BO 3 units attached, and (2) a mixture of BO 3 and
BO 4 units attached. The 3-coordinated sites can be distinguished as BO 3 units with
(1) all BO 3 units attached, (2) a mixture of BO 3 and BO 4 units attached and (3)
all BO 4 units attached. Krogh-Moe's model can then be invoked, and the fractions
of the three major structural groups (boroxol, tetraborate and diborate) can be
obtained. The fractions thus obtained indicate that the lever rule is violated prin-
cipally at the 20 and 35 mol% Na20 compositions, which agrees with the interpre-
tation of melting-point depression data of Krogh-Moe [36]. The B 11 N M R N 4 mea-
surements agree within experimental error with B l° N4 determinations.
206 G.E. Jellison, P.J. Bray / Structural interpretation o r B 10 and B 11 NMR spectra

Acknowledgement

This research was supported by the National Science Foundation Materials

Science Program DMR 72-03023-A06.

References

[1] A.H. Silver and P.J. Bray, J. Chem. Phys. 29 (1958) 984.
[2] P.J. Bray and J.G. O'Keefe, Phys. Chem. Glasses 4 (1963) 37.
[3] S.G. Bishop and P.J. Bray, Phys. Chem. Glasses 7 (1966) 73.
[4] S. Greenblatt and P.J. Bray, Phys. Chem. Glasses 8 (1967) 213.
[5] H.M. Kriz, M.J. Park and P.J. Bray, Phys. Chem. Glasses 12 (1967) 45.
[6] H.M. Kriz and P.J. Bray, J. Non-Crystalline Solids 6 (1971) 27.
[7] P.J. Bray, Interaction of Radiation with Solids (Plenum Press, 1967) p. 25.
[8] P.J. Bray, Magnetic Resonance (Plenum Press, 1970) p. 11.
[9] P.J. Bray, Proc. 10th Int. Congr. Glass, Kyoto, Japan (Ceramic Society of Japan, 1974)
section 13,p. 1.
[10] K.S. Kim and P.J. Bray, J. Non-metals 2 (1974) 95.
[11 ] K.S. Kim and P.J. Bray and S. Merrin, J. Chem. Phys. 64 (1976) 4459.
[12] K.S. Kim and P.J. Bray, Phys. Chem. Glasses 15 (1974) 47.
[13] W. M/iller-Warmuth, W. Poch and G. Sielaff, Glastech. Ber. 43 (1970) 5.
[14] G.E. Jellison, Jr. and P.J. Bray, Solid State Commun. 19 (1976) 517.
[15] G.E. Jellison, Jr., L.W. Panek and P.J. Bray, J. Chem. Phys. 66 (1977) 802.
[16] J. Krogh-Moe, Phys. Chem. Glasses 6 (1965) 46.
[17] W.L. Konijnendijk, Thesis, Philips Res. Rep Suppl. No. 1 (1975); W.L. Konijnendijk and
J.M. Stevels, J. Non-Crystalline Solids 18 (1975) 307.
[18] C.H. Rhee, J. Korean Phys. Soc. 4 (1971) 51.
[19] G.E. Jellison, Jr., S.A. Feller and P.J. Bray, J. Mag. Res. 27 (1977) 121.
[20] J.F. Baugher, P.C. Taylor, T. Oja and P.J. Bray, J. Chem. Phys. 50 (1969) 4914.
[21] P.C. Taylor and P.J. Bray, Lineshape Manual (1969) unpublished;
P.C. Taylor and P.J. Bray, Bull. Am. Ceram. Soc. 51 (1972) 234.
[22] P.C. Taylor and P.J. Bray, J. Mag. Res. 2 (1970) 305.
[23] T.W. Bril, Thesis, Technological University Eindhoven (1975).
[24] A. Hyman, A. Perloff, F. Mauer and S. Block, Acta Cryst. 22 (1967) 815.
[25] J. Krogh-Moe, Acta Cryst. 15 (1962) 190.
[26] J. Krogh-Moe, Acta Cryst. B24 (1968) 179.
[27] R.L. Mozzi and B.E. Warren, J. Appl. Cryst. 3 (1970) 251.
[28] J. Krogh-Moe, Acta Cryst. B30 (1974) 578.
[29] J.F. Baugher, H.M. Kriz, P.C. Taylor and P.J. Bray, J. Mag. Res. 3 (1970) 415.
[30] D.L. Griscom, Proc. Alfred Conf. on Boron in Glass and Glass Ceramics (Alfred, N.Y.,
1977) p. 1.
[31 ] J. Krogh-Moe, Acta Cryst. B30 (1974) 747.
[32] M.E. Milberg, J.G. O'Keefe, R.A. Verhelst and H.O. Hooper, Phys. Chem. Glasses 13
(1972) 79.
[33] J. Krogh-Moe and M. Ihara, Acta Cryst. 23 (1967) 427.
[34] A. Bartoluzza, B. Righetti and S. Schiavina, Lincei-Rend. Sci. Fis. Mat. Nat. 53 (1972)
421.
[35] R.R. Shaw and D.R. Uhlmann, J. Am. Ceram. Soc. 51 (1968) 377.
[36] J. Krogh-Moe, Phys. Chem. Glasses 3 (1962) 101.
[37] P. Beekenkamp, Phillips Res. Rep. Suppl. No. 4 (1966).