THE JOURNAL OF CHEMICAL PHYSICS 130, 234503 共2009兲

Composition dependence of glass transition temperature and fragility.

II. A topological model of alkali borate liquids
John C. Mauro,1,a兲 Prabhat K. Gupta,2 and Roger J. Loucks3
1
Science and Technology Division, Corning Incorporated, Corning, New York 14831, USA
2
Department of Materials Science and Engineering, Ohio State University, Columbus, Ohio 43210, USA
3
Department of Physics and Astronomy, Alfred University, Alfred, New York 14802, USA
共Received 23 March 2009; accepted 19 May 2009; published online 15 June 2009兲

Glass transition temperature and fragility are two important properties derived from the temperature
dependence of the shear viscosity of glass-forming melts. While direct calculation of these
properties from atomistic simulations is currently infeasible, we have developed a new topological
modeling approach that enables accurate prediction of the scaling of both glass transition
temperature and fragility with composition. A key feature of our approach is the incorporation of
temperature-dependent constraints that become rigid as a liquid is cooled. Using this approach, we
derive analytical expressions for the composition 共x兲 dependence of glass transition temperature,
Tg共x兲, and fragility, m共x兲, in binary alkali borate systems. Results for sodium borate and lithium
borate systems are in agreement with published values of Tg共x兲 and m共x兲. Our modeling approach
reveals a natural explanation for the presence of the constant Tg regime observed in alkali borate
systems. © 2009 American Institute of Physics. 关DOI: 10.1063/1.3152432兴

I. INTRODUCTION ing the number of constraints to the atomic degrees of free-

Accurate knowledge of the temperature 共T兲 and compo-
sition 共x兲 dependence of shear viscosity, ␩共T , x兲, is of critical
importance for all stages of industrial glass production.1,2 It
is also vital for our scientific understanding of glass transi-
tion and relaxation phenomena. Much effort—both
experimental and theoretical—has been invested over several
decades in the measurement, characterization, and under-
standing of the viscosity of glass-forming liquids. Extensive
sets of measured viscosity data are available for a wide va-
riety of liquids over large temperature ranges.1,3,4 While
there has been much effort to systematize this large amount
of data in the hope of uncovering universal trends,5,6 our
understanding of the mechanisms of viscous flow remains
rather poor. There has recently been growing attention and
research activity in understanding viscosity and various as-
sociated phenomena from the theoretical physics and chem-
istry communities.7–10 While the recent enthalpy landscape
modeling of Mauro and Loucks11 has enabled the calculation
of both glass transition temperature and fragility for simple
systems such as selenium, where the interatomic potentials
can be computed accurately from ab initio physics, conven-
tional atomistic modeling techniques such as molecular dy-
namics cannot access the long times required to compute
viscosity in the supercooled regime.12
In the first paper of this series,13 we presented a new
topological modeling approach that formulates shear viscos-
ity in terms of temperature-dependent constraints that be-
come frozen as the liquid is cooled from high temperature.
dom, it is possible to predict compositions with optimum
glass-forming ability; glass network topology is also respon-
sible for critical behavior in a number of mechanical and
thermal properties.25–38 While previous topological models
are formulated for zero temperature conditions, incorporation
of temperature-dependent constraints13 allows us to extend
the approach to enable calculation of ␩共T , x兲.
The glass transition temperature, Tg共x兲, and the fragility,
m共x兲, are two important parameters describing the tempera-
ture dependence of viscosity at the glass transition. Although
the glass transition temperature can be defined in many
ways, here we follow the convention of Angell39–42 by defin-
ing Tg as the temperature at which the shear viscosity is
equal to a fixed value, generally taken as 1012 Pa s:1,3
␩关Tg共x兲,x兴 = 1012 Pa s. 共1兲
With this definition, the viscosities of all glass-forming com-
positions can be mapped onto a single universal plot in terms
of Tg / T.39–42 This definition of Tg is also equivalent to the
annealing point,1 where the structural relaxation time is on
the order of 100 s. Following Angell,39–42 the fragility de-
scribes the slope of the viscosity curve with respect to in-
verse temperature at the glass transition temperature and is
defined as39–44
m共x兲 ⬅ 冏 ⳵ log10 ␩共T,x兲
⳵ 关Tg共x兲/T兴
冏 T=Tg共x兲
. 共2兲

Our approach builds on the pioneering work of Phillips and
Thorpe14–19 and that of Gupta and Cooper,20–24 who first pro-
posed treating glass as a network of constraints. By compar-
a兲
Electronic mail: mauroj@corning.com.
In our previous paper,13 we presented a new modeling
approach for the calculation of Tg共x兲 and m共x兲, starting with
the Adam–Gibbs relation.45–50 The Adam–Gibbs relation de-
scribes viscosity in terms of the configurational entropy,
Sc共T , x兲, of the melt:

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234503-2 Mauro, Gupta, and Loucks
B共x兲
log10 ␩共T,x兲 = log10 ␩⬁ + . 共3兲
TSc共T,x兲
Here, ␩⬁ is the extrapolated composition-independent infi-
nite temperature viscosity39,51 and B共x兲 is a fitting parameter.
While B共x兲 is commonly associated with the activation en-
ergy of the Arrhenius model for viscosity, Adam and Gibbs45
showed that B共x兲 is given by
sⴱc 共x兲
B共x兲 = n p⌬␮共x兲 , 共4兲
k
where n p is the number of particles in the system, ⌬␮ is the
average energy barrier for structural rearrangement, sⴱc is the
configurational entropy of the smallest rearranging region,
and k is Boltzmann’s constant. While both ⌬␮ and sⴱc are
functions of composition, Toplis52 showed that B共x兲 often
varies unappreciably within a given class of material 共e.g.,
alkali silicates兲. In our model we assume that the major com-
position dependence of Tg共x兲 is due to variations in Sc共T , x兲,
and hence we take B共x兲 as a constant. With this approxima-
tion, the glass transition temperature Tg共x兲 can be computed
relative to that of some reference composition xR; combining
Eqs. 共1兲 and 共3兲, we have
Tg共x兲 Sc关Tg共xR兲,xR兴
= . 共5兲
Tg共xR兲 Sc关Tg共x兲,x兴
According to the recent energy landscape modeling of
Naumis,53,54 the configurational entropy of a system is
largely proportional to the density of atomic degrees of free-
dom, f共x兲, i.e., the number of low-frequency “floppy modes.”
With this result, Eq. 共5兲 becomes
Tg共x兲 f关Tg共xR兲,xR兴 d − n关Tg共xR兲,xR兴
= = , 共6兲
Tg共xR兲 f关Tg共x兲,x兴 d − n关Tg共x兲,x兴
where d = 3 is the dimensionality of the network and n共T , x兲
is the average number of constraints per atom. The con-
straints per network node can be calculated by averaging
over all network-forming species i and each type of con-
straint ␣. By “network-forming species” we mean any atom
that is bound to at least two other atoms as part of the infi-
nitely large, topologically disordered glass network. Defining
Ni共x兲 as the mole fraction of network-forming species i in
composition x, we may write the average number of atomic
constraints as
n共T,x兲 = 兺 Ni共x兲 兺 wi,␣q␣共T兲. 共7兲
i ␣
The first sum in Eq. 共7兲 is over the network-forming species
i, and the second sum is over the various constraints ␣,
which may include two-body linear, three-body angular, or
higher-order constraints. Here, wi,␣ is the number of ␣-type
constraints associated with species i, and the temperature de-
pendence of the constraints is accounted by q␣共T兲, a measure
of rigidity for constraint ␣. Each q␣共T兲 satisfies the limits
lim q␣共T兲 = 1 and lim q␣共T兲 = 0. 共8兲
T→0 T→⬁
In the limit of zero temperature there is no thermal energy
available to break a constraint, so all constraints are fully
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J. Chem. Phys. 130, 234503 共2009兲
rigid 共q␣ = 1兲; in the limit of infinite temperature, constraints
are easily broken and hence do not contribute to the rigidity
of the network 共q␣ = 0兲. At a finite temperature, some fraction
of the constraints are broken while others are rigid. In this
paper we employ two forms of q␣共T兲, continuous and dis-
crete. In terms of the energy landscape approach, q␣共T兲 can
be expressed as a continuous function of temperature,55
冋 冉 冊册
␯tobs
⌬F␣ⴱ
q␣共T兲 = 1 − exp − , 共9兲
kT
where ⌬F␣ⴱ is the activation free energy for breaking the ␣
constraint, ␯ is the vibrational attempt frequency, and tobs is
the observation time. Owing to this dependence on observa-
tion time, the continuous form of q␣共T兲 contains information
on the cooling rate dependence of the glass transition.55,56 A
fast cooling rate indicates a lower tobs and an earlier onset of
the glass transition. Since typically q␣共T兲 is a rather sharp
function of temperature, it can be approximated in discrete
form with a unit step function:
q␣共T兲 = ␪共T␣ − T兲, 共10兲
where T␣ represents the onset temperature below which a
particular constraint ␣ becomes rigid. In practice, the dis-
crete form of q␣共T兲 in Eq. 共10兲 is convenient for deriving
analytical expressions for glass transition temperature, Tg共x兲,
employing Eq. 共6兲. However, as fragility is computed in
terms of a temperature derivative of f共T , x兲,13
冉 冏
m共x兲 = m0 1 +
⳵ ln f共T,x兲
⳵ ln T
冏 冊
T=Tg共x兲
, 共11兲
the continuous form of q␣共T兲 in Eq. 共9兲 is used for calcula-
tion of m共x兲. Here, m0 ⬇ 17 is the fragility of a strong liquid
such as silica.13
Application of our topological modeling approach to any
new system involves three basic steps:
共1兲 Identify and count the number of distinct network-
forming species as a function of x. By distinct, we
mean either chemically distinct or chemically similar
but having different short-range orders 共i.e., coordina-
tion number兲.
共2兲 Identify and count the number of constraints associated
with each species. Rank different constraints in terms
of their relative bond strengths 共or onset temperatures兲.
共3兲 Apply Eqs. 共6兲 and 共11兲 to calculate Tg共x兲 and m共x兲,
respectively.
In this paper, we apply our topological constraint model
for the binary alkali borate system. Equation 共6兲 is used to
provide an analytical form for Tg共x兲, and m共x兲 is computed
using the straightforward numerical calculation of Eq. 共11兲.
We show agreement between calculated and published val-
ues of Tg共x兲 and m共x兲 for both sodium and lithium borate
systems.
II. STRUCTURE AND TOPOLOGY
The alkali borate system, xM 2O · 共1 − x兲B2O3, has proved
a significant challenge for theoretical modeling due to the
234503-3 Topological model of alkali borates J. Chem. Phys. 130, 234503 共2009兲

0.7
so-called boron anomaly.1,57–65 In contrast to alkali silicate

Fraction of Network-Forming Species

systems, where addition of alkali invariably creates non- 0.6
Bridging Oxygen
bridging oxygen by rupturing the linkages between SiO4
0.5
tetrahedra1,66–69 and leading to an increase in floppy modes,
3
when an alkali is added to borate glass there are two possi- 0.4 Q
bilities: 0.3

共1兲 Create a nonbridging oxygen, rupturing the linkage be- 0.2

tween two trigonally coordinated BO3 groups, decreas-
0.1
ing the rigidity of the network. Q
4
Q
2

共2兲 Convert boron from a three-coordinated state to a four- 0

coordinated state, effectively increasing the rigidity of 0 0.1 0.2 0.3 0.4 0.5

the network. In this case, no nonbridging oxygen is (a) x

created.
1

Limiting ourselves to the x ⱕ 1 / 2 regime, there are four 0.9

Q
3

distinct types of network-forming nodes to consider: 共i兲 four- 0.8

Fraction of Boron Species

coordinated boron bonded to four bridging oxygens 共Q4兲, 共ii兲 0.7

three-coordinated boron bonded to three bridging oxygens 0.6

共Q3兲, 共iii兲 three-coordinated boron bonded to two bridging 0.5

oxygens 共Q2兲, and 共iv兲 the bridging oxygen itself 共OB兲. Nei- 0.4

ther nonbridging oxygens nor alkali ions are considered as 0.3

x = 1/3
4
Q 2
network formers. 0.2 Q

Properly accounting for boron speciation is especially 0.1

challenging for molecular dynamics simulations.70–72 Fortu- 0

0 0.1 0.2 0.3 0.4 0.5
nately, the random pair model of Gupta73 has proved suc-
(b) x
cessful at capturing the fraction of each boron species across
a wide range of alkali content. The random pair model is FIG. 1. 共Color online兲 共a兲 Fraction of network-forming species in the
based on the following rules for network formation: xM 2O · 共1 − x兲B2O3 system following the random pair model of Gupta 共Ref.
73兲. 共b兲 Boron speciation in the xM 2O · 共1 − x兲B2O3 system. Initially alkali
• BO4 tetrahedra occur in corner-sharing pairs, where the act to convert boron from the Q3 to the Q4 state. Further addition of alkali in
B–O–B angle within a pair is random. the x ⬎ 1 / 3 regime leads to formation of nonbridging oxygen and Q2 boron.

• Pairs of BO4 tetrahedra cannot be bound to each other.

冦 冧
3 − 2x 1
• Nonbridging oxygens occur in BO3 groups only and not , xⱕ ,
5 − 4x 3
in BO4 groups. N共OB兲 = 共15兲
21 − 28x 1 1
With the chemical formula xM 2O · 共1 − x兲B2O3 and the , ⬍xⱕ ,
31 − 38x 3 2
structural rules above, an alkali-to-boron ratio of less than
one-half 关x / 共1 − x兲 ⱕ 1 / 2, or x ⱕ 1 / 3兴 will lead to all alkali which are plotted in Fig. 1.
converting boron from three to four coordinations. Non- We consider the following types of constraints in the
bridging oxygens begin to form only at higher alkali concen- alkali borate system:
trations, x ⬎ 1 / 3. With the random pair model,73 the fraction
• ␣: B–O linear bonds. There are two ␣ constraints at
of each network-forming species is
each bridging oxygen.

冦 冧
2x 1
, xⱕ , • ␤: O–B–O angular constraints. There are five ␤ con-
5 − 4x 3 straints at each Q4 unit to form a rigid BO4 tetrahedron,
N共Q 兲 =
4
共12兲
6 − 8x 1 1 three ␤ constraints at each Q3 to keep the BO3 unit
, ⬍xⱕ , planar, and a single ␤ constraint at each Q2.
31 − 38x 3 2
• ␥: B–O–B angular constraints. There is one ␥ constraint

冦 冧
2 − 4x 1 at every bridging oxygen.
, xⱕ ,
5 − 4x 3
N共Q3兲 = 共13兲 The bond strengths are ordered such that
10 − 20x 1 1
, ⬍xⱕ ,
31 − 38x 3 2 T␥ ⬍ Tg共0兲 ⬍ T␤ ⬍ T␣ . 共16兲

冦 冧
1 The linear bonds are strongest and freeze in at the highest
0, xⱕ , temperature. Following the structural analysis of Mozzi and
3
N共Q2兲 = 共14兲 Warren,74 the O–B–O angle poses a stronger constraint than
18x − 6 1 1 the B–O–B angle. The glass transition temperature of pure
, ⬍xⱕ ,
31 − 38x 3 2 B2O3, Tg共0兲 = 543 K, must fall between T␥ and T␤ in order to

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234503-4 Mauro, Gupta, and Loucks J. Chem. Phys. 130, 234503 共2009兲

satisfy the conditions that 0 ⬍ f关Tg共x兲 , x兴 ⬍ 3 and ⳵Tg共x兲 / ⳵x 3.5

x M2O·(1-x )B2O3
⬎ 0 at x = 0. 3.0
T >T


: B-O
2.5

Atomic Degrees of Freedom

III. GLASS TRANSITION TEMPERATURE : O-B-O
: B-O-B
2.0
Following the analysis of Sec. II, the number of atomic
T <T <T

Cooling
constraints is given by 1.5

冦 冧
12 − 6x 1 1.0
, xⱕ ,
5 − 4x 3 T <T <T
n共Tg共x兲,x兲 = 共17兲 0.5
96 − 138x 1 1
, ⬍xⱕ , 0.0
31 − 38x 3 2
T <T
in the temperature range T␥ ⬍ Tg共x兲 ⬍ T␤. Here we have as- -0.5
0 0.1 0.2 0.3 0.4 0.5
sumed the discrete form of q␣共T兲, as in Eq. 共10兲. The corre-
sponding degrees of freedom are (a) x

冦 冧
1300
3 − 6x 1
, xⱕ , 1200
5 − 4x 3 1100 T  < T g (x ) < T 
f共Tg共x兲,x兲 = 共18兲
24x − 3 1 1 1000
⬍xⱕ ,

Temperature (K)
,
31 − 38x 3 2 900

800
plotted in Fig. 2共a兲. Combining Eqs. 共6兲 and 共18兲 leads to the T  = 740 K
700
following scaling of Tg with composition: T g (x )

冉 冊
600

冦 冧
1 5 − 4x 1 500
Tg共0兲, xⱕ , T g (0) = 543 K
5 1 − 2x 3 400

冉 冊 冉冊
Tg共x兲 = 共19兲 300
T  = T 0 (0) = 328 K
1 31 − 38x 1 1 1
Tg , ⬍xⱕ , 0 0.1 0.2 0.3 0.4 0.5
11 8x − 1 3 3 2 (b) x

where Tg共1 / 3兲 is the glass transition temperature of the dibo-

FIG. 2. 共Color online兲 共a兲 Temperature and composition dependence of the
rate composition. Solving for Tg共1 / 3兲, we obtain average number of atomic degrees of freedom in the binary alkali borate

冉 冊
冦 冧
system, xM 2O · 共1 − x兲B2O3. We consider the following constraints, in order
1 5 − 4x 1 of decreasing strength: B–O linear bonds 共␣兲, O–B–O angular constraints
Tg共0兲, xⱕ ,
5 1 − 2x 3 共␤兲, and B–O–B angular constraints about the bridging oxygen. The dashed

冉 冊
Tg共x兲 = 共20兲 line corresponds to the isostatic situation, where f = 0. 共b兲 Plot of the con-
1 31 − 38x 1 1 straint onset temperatures and Tg共x兲 for the sodium borate system. In order
Tg共0兲, ⬍xⱕ ,
5 8x − 1 3 2 to satisfy the condition that the product f关Tg共x兲 , x兴 · Tg共x兲 is a constant, the
final Tg共x兲 for the alkali borate system is given by Eq. 共23兲.
which is valid for glass transition temperatures falling in the
range T␥ ⬍ Tg共x兲 ⬍ T␤. Equation 共20兲 is plotted as the blue
f关Tg共x兲 , x兴. In Fig. 2共a兲, this is equivalent to jumping from
共gray兲 curve in Fig. 2共b兲 and shows a clear peak at x = 1 / 3.
the blue curve 共T␥ ⬍ T ⬍ T␤兲 to the green curve at higher
However, at some point the glass transition temperature will
temperature 共T␤ ⬍ T ⬍ T␣兲. When this happens, the Tg共x兲
exceed T␤, the onset temperature for the O–B–O angular
must decrease in order to achieve a constant f关Tg共x兲 , x兴 · Tg共x兲
constraints, violating our assumption of T␥ ⬍ Tg共x兲 ⬍ T␤ and
and compensate for this increased floppiness. However,
leading to a very interesting effect.
when Tg共x兲 decreases slightly below T␤ the network sud-
From Eq. 共6兲, it is clear that the product f关Tg共x兲 , x兴 · Tg共x兲
denly becomes more rigid due to a decrease in f关Tg共x兲 , x兴,
is a constant for all x. In order to satisfy this condition, there
and the Tg共x兲 must increase to compensate for this loss of
must be a horizontal jump in Tg共x兲 between the two intersec-
floppiness. The net result is a regime of constant Tg共x兲 = T␤
tion points of the blue 共gray兲 curve with the T␤ isotherm in
until enough nonbridging oxygens form to satisfy the condi-
Fig. 2共b兲, i.e., the two intersection points of Eq. 共20兲 with T␤.
tion of constant f关Tg共x兲 , x兴 · Tg共x兲 with lower values of the
Denoting these two intersection points x1 and x2, we have
glass transition temperature. Hence, the final Tg共x兲 curve for

冉
5 T␤/Tg共0兲 − 1
冊 共21兲
the alkali borate system is given by

冉 冊
x1 =

冦冉 冧
2 5T␤/Tg共0兲 − 2 1 5 − 4x
Tg共0兲, x ⱕ x1 ,
and 5 1 − 2x
31 + 5T␤/Tg共0兲 Tg共x兲 = T ␤, x1 ⬍ x ⬍ x2 , 共23兲
x2 =
38 + 40T␤/Tg共0兲
.

Physically, when Tg共x兲 increases slightly above T␤ the net-

共22兲 1 31 − 38x
5 8x − 1
Tg共0兲, 冊 1
x2 ⱕ x ⱕ .
2
work suddenly becomes more floppy due to an increase in If Tg共x兲 were to fall below T␥, there could be another

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234503-5 Topological model of alkali borates J. Chem. Phys. 130, 234503 共2009兲

850 TABLE I. Experimental values of Tg共x兲 and m共x兲 in the xNa2O · 共1

x Na2O·(1-x )B2O3 − x兲B2O3 system. The measurements of Nemilov 共Ref. 79兲 use the penetra-
800

Glass Transition Temperature (K)

tion method. Stolyar et al. 共Ref. 80兲 employed the beam bending technique,
750 and Suzuki et al. 共Ref. 81兲 used application of a compressive force.
700
x Tg 共K兲 m Reference
650
0.0249 543.6 35.1 Nemilova
600 0.0481 568.3 36.9 Nemilova
550 0.0715 593.5 39.2 Nemilova
Model Nemilov 0.0959 616.7 40.1 Nemilova
500 Suzuki Stolyar 0.1215 646.2 42.6 Nemilova
450
Moynihan 0.1379 663.9 43.1 Nemilova
0 0.1 0.2 0.3 0.4 0.5 0.1582 694.6 49.1 Nemilova
(a) x 0.1767 718.0 48.9 Nemilova
850 0.1831 717.5 51.8 Nemilova
x Li2O·(1-x )B2O3 0.1934 728.4 55.7 Nemilova
800
Nemilova
Glass Transition Temperature (K)

0.2111 732.8 57.4

750 0.2214 732.8 57.3 Nemilova
0.2242 735.3 59.2 Nemilova
700
0.2364 734.9 57.1 Nemilova
650 0.2505 738.9 61.7 Nemilova
0.2733 736.2 59.9 Nemilova
600
0.2999 737.7 62.1 Nemilova
550 0.3018 742.6 60.7 Nemilova
500
0.3268 737.5 61.4 Nemilova
Model Kodama 0.3567 732.5 66.3 Nemilova
Chryssikos Moynihan
450 0.3615 727.8 69.3 Nemilova
0 0.1 0.2 0.3 0.4 0.5
0.0490 600.4 38.5 Stolyar et al.b
(b) x
0.0941 643.1 40.6 Stolyar et al.b
0.1297 692.0 47.4 Stolyar et al.b
FIG. 3. 共Color online兲 Composition dependence of glass transition tempera- 0.1343 689.1 47.8 Stolyar et al.b
ture for the 共a兲 sodium borate and 共b兲 lithium borate systems. The solid lines
0.1878 738.6 65.6 Stolyar et al.b
show the predicted Tg共x兲 using the topological model with temperature-
dependent constraints. Experimental data points 共Refs. 78–83兲 are provided 0.2111 747.2 66.3 Stolyar et al.b
in Tables I and II. 0.2242 749.2 70.4 Stolyar et al.b
0.2373 750.5 70.2 Stolyar et al.b
0.2524 749.9 73.0 Stolyar et al.b
horizontal jump in Tg共x兲 at lower temperatures. However, as 0.2581 748.8 74.2 Stolyar et al.b
shown in Fig. 2共b兲, Tg共x兲 remains above T␥ for the entire 0.2619 748.5 73.5 Stolyar et al.b
composition range of interest 共x ⱕ 1 / 2兲. Here, we have esti- 0.2923 746.9 79.8 Stolyar et al.b
mated T␥ based on the Vogel temperature of pure B2O3, T␥ 0.3037 744.6 84.9 Stolyar et al.b
0.3152 740.7 84.3 Stolyar et al.b
⬇ T0共0兲 = 328 K.75 We base this approximation on the violet
0.3200 737.6 84.5 Stolyar et al.b
curve in Fig. 2共a兲, which shows that pure B2O3 loses all
0.0445 586.2 ¯ Suzuki et al.c
configurational degrees of freedom at T ⬍ T␥. In other words, 0.0896 627.9 ¯ Suzuki et al.c
the B2O3 network is isostatic at T = T␥, i.e., f共T␥ , 0兲 = 0. Such 0.1352 684.3 ¯ Suzuki et al.c
vanishing of the topological degrees of freedom can be as- 0.1813 732.8 ¯ Suzuki et al.c
sociated with the Vogel temperature T0共x兲 at which the vis- 0.2279 741.2 ¯ Suzuki et al.c
cosity of a supercooled liquid diverges.1,48,76,77 0.2752 741.4 ¯ Suzuki et al.c
In Fig. 3 we compare our model result of Eq. 共23兲 to a
Reference 79.
published experimental values of Tg共x兲 for the sodium borate b
Reference 80.
c
and lithium borate systems. The published data are also sum- Reference 81.
marized in Tables I and II. The agreement between predicted
and measured values of Tg共x兲 is truly remarkable, especially Tg, as in Eq. 共1兲, the lithium borate data of Kodama and
since there is only one free parameter in Eq. 共23兲, the Kojima82 and Chryssikos et al.83 are, respectively, based on
O–B–O constraint onset temperature T␤. Based on the ex- dilatometry and calorimetry. Also, the critical temperature
perimental data in Tables I and II, we estimate T␤ = 740 K for the immiscibility dome is higher in lithium borates than
for the sodium borate system and T␤ = 760 K for the lithium in the sodium borate system.84,85 With Eqs. 共21兲 and 共22兲 and
borate system. This difference is partly due to the effect of these values of T␤, the iso-Tg regime falls between 共x1 , x2兲
changing alkali and partly because the experiments used for = 共0.19, 0.41兲 for the sodium borate system and 共x1 , x2兲
fitting the sodium borate model employ a different definition = 共0.20, 0.40兲 for the lithium borates.
of Tg compared to those used for fitting the lithium borate The presence of an iso-Tg regime in both of the alkali
model. Whereas all three sets of sodium borate borate systems is testament to the importance of including
measurements79–81 are based on a viscometric definition of the temperature dependence of constraints when constructing

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234503-6 Mauro, Gupta, and Loucks J. Chem. Phys. 130, 234503 共2009兲

TABLE II. Experimental values of Tg共x兲 and m共x兲 in the xLi2O · 共1 100
− x兲B2O3 system. Kodama and Kojima 共Ref. 82兲 measured glass transition x Na2O·(1-x )B2O3
90
temperature using differential thermal analysis. Here we estimate values of
Tg共x兲 from their Fig. 5 共Ref. 82兲. The measurements of Chryssikos et al. 80
共Ref. 83兲 were made using differential scanning calorimetry. All of the re-
70
ported compositions are nominal compositions. Values of fragility are esti-

Fragility
mated from their Fig. 4 共Ref. 83兲. 60

x Tg 共K兲 m Reference 50

40
0.00 518 ¯ Kodama and Kojimaa
0.02 528 ¯ Kodama and Kojimaa 30
Model Nemilov
0.04 543 ¯ Kodama and Kojimaa Stolyar Chryssikos
20
0.06 558 ¯ Kodama and Kojimaa 0 0.1 0.2 0.3 0.4 0.5
0.08 598 ¯ Kodama and Kojimaa x
(a)
0.10 618 ¯ Kodama and Kojimaa
90
0.12 638 ¯ Kodama and Kojimaa
x Li2O·(1-x )B2O3
0.14 673 ¯ Kodama and Kojimaa 80
0.16 693 ¯ Kodama and Kojimaa
0.18 723 ¯ Kodama and Kojimaa 70
0.20 748 ¯ Kodama and Kojimaa
60

Fragility
0.22 753 ¯ Kodama and Kojimaa
0.24 758 ¯ Kodama and Kojimaa 50
0.26 763 ¯ Kodama and Kojimaa
0.28 763 ¯ Kodama and Kojimaa 40

0.00 ¯ 33 Chryssikos et al.b

30
0.02 ¯ 35 Chryssikos et al.b
Model Chryssikos
0.06 ¯ 37 Chryssikos et al.b 20
0.08 ¯ 36 Chryssikos et al.b 0 0.1 0.2 0.3 0.4 0.5

Chryssikos et al.b x
0.10 634 37 (b)
0.12 ¯ 37 Chryssikos et al.b
0.15 699 ¯ Chryssikos et al.b FIG. 4. 共Color online兲 Composition dependence of fragility in the 共a兲
0.16 ¯ 44 Chryssikos et al.b sodium borate and 共b兲 lithium borate systems. The solid lines show the
0.18 ¯ 47 Chryssikos et al.b predicted m共x兲 using the topological model with temperature-dependent
constraints. Experimental data points 共Refs. 79, 80, and 83兲 are provided in
0.19 ¯ 51 Chryssikos et al.b
Tables I and II.
0.20 752 60 Chryssikos et al.b
0.21 ¯ 55 Chryssikos et al.b
0.25 770 61 Chryssikos et al.b ⌬F␣ⴱ = − kT␣ ln共1 − 2−1/␯tobs兲. 共24兲
0.30 770 ¯ Chryssikos et al.b
This leaves us with one unknown parameter, ␯tobs, which can
0.35 757 ¯ Chryssikos et al.b
be adjusted to study the cooling rate dependence of Tg共x兲 and
0.48 699 ¯ Chryssikos et al.b
other properties. Since we are concerned with composition
a
Reference 82. rather than cooling rate dependence, we consider a constant
b
Reference 83.
value of ␯tobs = 103 for all calculations in this paper. The
value of ␯tobs = 103 is obtained by fitting to the published
topological models of glass-forming systems. Indeed, this value of fragility for pure B2O3, m共0兲 = 32 共our reference
should be a universal phenomenon since iso-Tg regimes can composition兲.86 Additional investigation is required to deter-
occur in any glass-forming system when Tg共x兲 reaches some mine a more precise form of Eq. 共9兲.
constraint onset temperature. Combining Eq. 共11兲 with the Tg共x兲 in Eq. 共23兲, we can
calculate the fragility numerically. As shown in Fig. 4, the
qualitative trend of the computed m共x兲 is in good agreement
IV. FRAGILITY with published experimental values. Because of the large
values of fragility for alkali-rich compositions, there is con-
As we have just shown, the discrete form of q␣共T兲 in Eq. siderable uncertainty in both the experimental and theoreti-
共10兲 is convenient for obtaining accurate analytical forms of cally calculated values of fragility. It is interesting to note
Tg共x兲. In practice, we find little difference between analytical that m共x兲 continues to change during the flat Tg共x兲 = T␥ re-
calculations of Tg共x兲 using the discrete form of q␣共T兲 and gime owing to the changing slope of f关Tg共x兲 , x兴 as the num-
numerical calculations of Tg共x兲 using the continuous form of ber of each species evolves with x. Fragility peaks at the
q␣共T兲 in Eq. 共9兲. However, calculations of fragility involve diborate composition, x = 1 / 3, which marks the onset of non-
taking the derivative of f共T , x兲 and hence require use of the bridging oxygen.
continuous q␣共T兲. When converting between discrete and
V. DISCUSSION
continuous forms of q␣共T兲, the free energy activation barrier,
⌬F␣ⴱ in Eq. 共9兲, can be computed directly from the onset In this work we have generalized the notion of bond
temperature, T␣ in Eq. 共10兲, by constraints for finite temperature conditions. Using the well-

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234503-7 Topological model of alkali borates
established Adam–Gibbs theory45 and the recent energy land-
scape modeling of Naumis,53,54 we relate the temperature-
dependent floppy mode density to the shear viscosity,
␩共T , x兲, obtaining a simple explanation for the striking uni-
versal scaled viscosity plot of Angell.42 Our model is clearly
a simplification of a complex fluid; to understand its appli-
cability and limitations it is useful to examine the assump-
tions involved.
First, we have taken simplifying expressions for the tem-
perature dependence of the bond constraints, q␣共T兲. We have
employed two distinct forms for q␣共T兲, the continuous form
in Eq. 共9兲 derived from a simplified energy landscape
approach55 and the discrete form in Eq. 共10兲 employing a
unit step approximation. With the discrete model, a bond
constraint becomes rigid suddenly as the temperature is de-
creased below a certain onset temperature T␣. On the other
hand, in the continuous model a bond constraint stiffens
gradually over a range of temperatures. While the discrete
form of q␣共T兲 is useful for deriving analytical expressions for
the composition dependence of glass transition temperature,
Tg共x兲, the continuous form must be used for accurate calcu-
lation of fragility, m共x兲. In practice, we have found that there
is little difference between computed values of Tg共x兲 using
the discrete and continuous forms of q␣共T兲, but the fragility
calculations are sensitive to the tails of the q␣共T兲 functions.
Additional work is required to assess the validity of Eq. 共9兲
and its application to the sub-Tg regime where thermal his-
tory plays a strong role.
Second, the counting of constraints from medium- and
long-range interactions has been approximated by counting
over the nearest neighbors only. This needs further examina-
tion, particularly in relation to the reported “intermediate
phase” behavior where medium-range ordering is of critical
importance.87,88 Boolchand and co-workers89–92 demon-
strated a link between the self-assembled intermediate phase
and nanoscale phase separation. The iso-Tg phenomenon re-
ported in this paper may also be indicative of such nanoscale
phase separation.
Third, in the calculation of Tg共x兲, we have assumed that
the parameter B共x兲 of the Adam–Gibbs relation is constant
with respect to composition. This assumption may not be
strictly valid, especially for application over a wide range of
compositions, and hence the dependence of B共x兲 on compo-
sition should be explored more thoroughly from both theo-
retical and experimental perspectives.
Fourth, we have neglected temperature-dependent
changes in the short-range atomic level structure of the liq-
uid, such as the temperature dependence of four-coordinated
boron in alkali borate glasses.57
Despite these limitations and assumptions, we have
shown that the calculated composition dependence of glass
transition temperature and fragility agrees remarkably well
with experimental measurements across a wide range of al-
kali content. The substantial agreement between our model
and the experimental measurements indicates that the above
assumptions are reasonable. While not capturing every detail
of these complex liquids, the topological model in this paper
apparently captures the most important aspects governing
Tg共x兲 and m共x兲. We also note that our modeling approach is
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J. Chem. Phys. 130, 234503 共2009兲
not limited to these two parameters. In fact, a similar ap-
proach could be used to calculate the composition depen-
dence of other viscosity reference points such as the strain
point and softening point. With this approach the entire equi-
librium viscosity curves of these systems can be computed.
Our approach gives a natural explanation for the con-
stant Tg共x兲 regions observed in the alkali borate systems,
since the condition of Eq. 共6兲 can only be satisfied with a
“horizontal jump” in Tg共x兲 as in Fig. 4共b兲. If Tg共x兲 were to
increase above the constraint onset temperature, the network
would become more floppy, driving the Tg共x兲 downward.
However, when Tg共x兲 falls below the constraint onset tem-
perature, the network becomes more rigid, driving the Tg共x兲
upward. The net result is a region of constant Tg共x兲 in com-
position space. This should be a general phenomenon for any
glass-forming liquid when the Tg共x兲 reaches a constraint on-
set temperature.
VI. CONCLUSIONS
Topological modeling of glass networks is useful for
predicting trends in thermal and mechanical properties. We
have extended the concept of rigidity to finite temperatures
and related it to a temperature-dependent floppy mode den-
sity. The floppy mode density is used to calculate configura-
tional entropy associated with atomic rearrangements and to
determine viscosity in the vicinity of the glass transition tem-
perature. Our modeling approach allows for derivation of
simple analytical expressions for the scaling of glass transi-
tion temperature with composition, Tg共x兲, and provides a
natural explanation for horizontal jumps in Tg共x兲, a possible
cause of phase separation behavior. Fragility, m共x兲, can be
computed using a straightforward temperature derivative of
the floppy mode density.
Our approach, accounting for the temperature-dependent
nature of constraints, enables the calculation of Tg共x兲 and
m共x兲 for a variety of systems, specifically demonstrated in
this paper for the binary alkali borate system. The Tg共x兲 cal-
culation is insensitive to the particular form of q␣共T兲 and
demonstrates good quantitative agreement with experiment.
On the other hand, the m共x兲 calculation depends on the de-
tails of q␣共T兲 and is 共currently兲 useful for determining quali-
tative trends. A more accurate model of q␣共T兲 is necessary to
obtain a quantitatively accurate model of m共x兲.
This work represents an intermediate level of approach
between traditional atomistic simulation techniques such as
molecular dynamics and other more empirical macroscopic
modeling. While the topological modeling approach does not
capture the minute level of detail as molecular dynamics, it
focuses on the most relevant aspects of the interactions to
enable accurate prediction of property scaling with composi-
tion. We do not, however, consider the modeling approach of
this paper as a replacement for atomistic simulation tech-
niques such as molecular dynamics. Rather, we consider both
approaches as providing critical pieces of a larger whole.
Only when systems are modeled on multiple scales does the
complete nature of glass-forming systems become clear. In
particular, molecular dynamics can be useful for providing
key inputs into a topological model, such as identifying the
234503-8 Mauro, Gupta, and Loucks J. Chem. Phys. 130, 234503 共2009兲

43
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