280

Journal of Non-Crystalline Solids 125 (1990) 280-286

North-Holland

Gas transport in vitreous silica fibers

R. S t e p h e n W o r t m a n a n d J a m e s F. S h a c k e l f o r d
Division of Materials Science and Engineering. University of California, Davis, CA 95616, USA

Received 1 March 1990

Revised manuscript received 5 July 1990

Micrometer-scale fibers of vitreous silica were used to extend solubility-based gas transport measurements to lower-temperature ranges and/or gas species larger than helium. The distribution of fiber diameters established a saturation curve for
determining diffusivity from time-to-half saturation. Necessary experimental sensitivitywas provided by a differential pressure
transducer. Good agreement was demonstrated between near room temperature measurements in this study on neon and
previous high-temperature studies on millimeter-scale rod and disk specimens. Over the temperature range 0-777 C, the
solubility of neon in vitreous silica can be given by S = (6.07 1022 atoms/(m 3 atm)) exp(( + 6.70 kJ/g atom)/RT), and the
diffusivity over the range of 0-984C can be given by D = (0.997 10-8 m2/s)exp((- 41.0 kJ/g atom)/RT).

1. Introduction
A careful analysis of the solubility and diffusivity of inert gas atoms and molecules can provide
an experimental probe for structure in amorphous
solids [1]. The interstitial structure of the relatively
open silicates is especially appropriate to study by
this method [2,3]. Numerous processes of commercial importance are also closely associated with
gas transport mechanisms, e.g. the thermal oxidation of silicon [4].
Gas transport measurements generally fall into
one of two categories: (i) 'permeability-based' in
which a permeation coefficient ( K ) is measured
during the steady-state flow through a membrane
[5] or (ii) 'solubility-based' in which a solution
coefficient (S) is measured for the equilibrium
saturation of a sample in a closed chamber [1]. In
either case, a diffusion coefficient ( D ) can be
obtained from the approach to steady-state or
equilibrium. The three transport parameters are
related by the simple expression
K = DS.

(1)

A substantial amount of data has been generated for gas-in-glass systems in the past three
decades, but the vast majority has involved helium
as the gas species, due to the experimental convenience of the resulting highly permeable systems. The range of helium diffusivities in a variety
of glasses allows disks, rods, and powders with a
minimum dimension on the order of 1 m m to
provide convenient experimental times (on the
order of a few minutes to a few hours) at moderate temperatures. In order to obtain results for
larger diameter gas species (with correspondingly
smaller diffusivities), smaller sample dimensions
a n d / o r higher experimental temperatures are required. The purpose of the present study was to
develop a technique for solubility-based gas transport measurements in small diameter glass fibers.
An attractive feature of this experimental system
is the ability to use a sample geometry (the right
circular cylinder) for which precise diffusivity
solutions are available [6]. This is in contrast to
the need for a spherical approximation for
powdered samples [7].

0022-3093/90/$03.50 1990 - Elsevier Science Publishers B.V. (North-Holland)

R.S. Wortman, J.F. Shackelford / Gas transport in vitreous silica fibers

2. Experimental
2.1. Glass fiber characterization
The sample used in this study was a spun glass
fiber of vitreous silica obtained from Heraeus,
Amersil, Inc. having a labeled diameter of 4 - 8
~tm. An accurate knowledge of the distribution of
fiber diameters was of utmost importance due to
the dependence of the diffusivity measurement on
sample diameter, as is shown in section 3.1. The
diameter characterization was accomplished using
a Zeiss Videoplan Optical Analyzer.
Representative portions of the bulk glass fiber
sample were taken from ten randomly chosen
areas and mounted on glass microscope slides
with double-sided tape in as thin a layer as possible. These were then sputter coated with a thin
film of gold, a few tens of nanometers thick, to
prevent the refraction of light during optical microscopic inspection. The optical analyzer was then
used to rapidly measure independent fiber diameters and to generate distribution histograms
according to preset window parameters.
One hundred measurements were taken on each
of the ten sample slides giving a statistically significant 1000 fiber population on which to base
the study. The results of this analysis are shown in
fig. 1, as the per cent distribution of the fiber
diameters in one micrometer increments. This distribution is highly linear on a probability-log
paper plot indicating that the fiber diameter distribution is log-normal. It is interesting to note that

011,lit
G
1-2

4-5

7-8

10-11

13-14

16-17

19-20

Ranges (Microns)
Fig. 1. Distribution of glass fiber diameters in vitreous silica
sample (H. Amersil vitreous silica).
Diameter

281

a central observation in the characterization of the

interstitial structure in vitreous silica by gas transport and related techniques is that the interstitial
size can be represented as log-normal [1-3]. The
occurrence of a log-normal distribution for glass
fiber diameters can be considered just one more
example of its common appearance in 'randomly'
generated microscopic-scale geometries [8,9].

2.2. Gas solubility and diffusioity measurements

A gas probe system was designed and constructed after the method of Shackelford [10] to
provide a sufficiently high sensitivity pressure
measurement to allow a precise determination of
the solubility and diffusivity of gas species larger
than helium. The experimental system depends
primarily on a Validyne DP-15 variable reluctance, differential pressure transducer. The glass
fiber sample was packed into the sample chamber
after characterization and a solid copper gasket
was used between the chamber and the endcap to
ensure an adequate vacuum seal. In fact, two
types of pressure transducers were connected to
the manifold to measure the initial absolute pressure in the manifold and the changing differential
pressure between the sample chamber and the
manifold. The absolute pressure transducer was a
Bell and Howell model C.E.C. strain gage transducer with a pressure range of 0-20 psia. The
differential transducer utilized a thin magnetic
metal diaphragm between two induction coils.
Electrical output from this was connected to a
linear amplifier which stepped up the 35 mV full
scale signal to 10 V full scale. The diaphragm used
gave a full scale differential range of 5 Torr and
resulted in a sensitivity of 0.5 mTorr which corresponded to a reading of 1.0 mV.
The sample chamber and the manifold were
each contained in their own temperature-controlled environments. It was found that this configuration allowed for accurate maintenance of the
desired temperatures, and temperature fluctuations never exceeded +0.1 C.
An IBM PC computer was employed to monitor and record systematically the differential and
absolute pressure transducers and the manifold
and sample chamber temperatures. Interfacing be-

R.S. Wortman, J.F. Shackelford / Gas transport in vitreous sifica fibers

282

tween the computer and peripheral hardware was

accomplished by means of a National Instruments
General Purpose Interface Bus (GPIB) interface
card.

3. Results

3.1. Effect of fiber diameter on diffusivity analysis

The mathematics of diffusion in a right circular
cylinder has been described in some detail by
Crank [6]. The glass used in this study was of a
spun fiber type which was reduced to a chopped
fiber form for greater packing efficiency. The individual fibers were assumed to represent a right
circular cylinder of semi-infinite length, since the
aspect ratio (fiber length to diameter) of the
chopper fibers was in the range of 10 : 1 to 20 : 1.
The gas transport in a given fiber is non-steady
state diffusion in which the gas concentration at
the surface of the cylinder remains essentially
constant. If M t denotes the total quantity of gas
diffusing into the cylinder after a given time t and
Moo is the corresponding quantity after an infinite
time, then
Mt
~
Moo = n = l

4
r

exp(_Da2t).

(2)

from tabulated solutions of Bessel functions from

Selby [11].
The need to use glass fibers in the micrometer
diameter size range introduced another factor
which had to be considered, namely the effect of
fiber size variation on diffusivity calculations.
Earlier experiments using millimeter diameter glass
rods were not affected by this problem, since the
diameter variation from rod to rod was not significant. Unfortunately, fibers in the micrometer diameter size range were not as uniform, as shown
by fig. 1.
Preliminary calculations indicated that the time
to half saturation for a given experiment could
vary by several hundred percent for a variety of
possible fiber diameter distributions. To assume a
single average fiber diameter for such distributions
would lead to a correspondingly large error in the
calculated diffusivities. It was clear that an expression was needed to define the saturation in the
specific sample mixture of this study as a function
of time. This requires the use of an individual
saturation equation, of the form of eq. (2), for
each diameter range of the sample mixture.
If P, is the number per cent of a cylinder of
radius r~ in the mixture, the volume ratio of the
i th cylinder, denoted V~, to the total sample volume
is

~t n

The radius of the cylinder is r and the a~ are the

roots of

Jo(r .) =0,

(3)

Vi = ri2py ~_,ri2pi.

(5)

If S~ represents the saturation in the ith cylinder,

then

where Jo(x) is the Bessel function of the first kind

of order zero.
The per cent saturation at any given time,
t > O, for a cylinder whose initial concentration of
gas was C = 0 at t = 0 is simply

and the combined saturation, Smix, for the mixture

of cylinders would be

% saturation = ( Mt/Moo ) >( 100.

Smj = ~ S,V~.

(4)

Equation (2) was evaluated to determine the

effect of the number of summation terms on the
accuracy of the final results varying both the time
and the radius. It was found that Mr~Moo is
sensitive to small values of t and large values of r
and, by using the first ten roots of eq. (3), sufficient accuracy could be obtained for the study.
The roots to the Bessel function were obtained

4 exp(_D, 2t )
n=l

(6)

ri Otn

(7)

Therefore, combining eq. (5) with eq. (6) yields the

overall equation for the saturation of a mixture of
cylinders of different diameters:

/=1

n=l ri tn

[ Y"ri2pi JJ"
(8)

R.S. Wortman, J.F. Shackelford / Gas transport in vitreous silica fibers

3.5
3

;~E8

2.5

1.5

2 ~
Q

0.5
0
0

500

1000

1500

2000

2500

3000

3500

4000

Half Saturation Time (secorlds)

Fig. 2. Saturation curve for vitreous silica fiber sample of fig. 1,

based on eq. (8). The diffusivity corresponding to a given
experiment is determined by the half saturation time, i.e. the
time in which the gas pressure in the sample chamber has
dropped by one-half relative to the overall pressure drop
occurring at steady-state (see fig. 3).

The only necessary piece of experimental information required to determine the diffusivity of a
gas species in a given sample mixture is the time
required for half of the total amount of dissolved
gas to diffuse into the sample. This can be obtained from a continuous plot of pressure change
over time during the experiment.
The experimental results for the sample fiber
mixture of this study (fig. 1) were examined. Only

283

the diameter ranges that contained > 0.2% of the

fibers were used. This resulted in 12 ranges between 2 and 14 ~tm and represented 99.6% of all
fibers.
A computer program was written in BASIC
utilizing eq. (8) and the diameter distribution of
fig. 1 to calculate mathematically a diffusivity
corresponding to a time to one-half saturation, as
shown in fig. 2. (A tabular list of half saturation
times and corresponding diffusivities for the fiber
sample mixture was also generated.) It should be
noted that the use of fig. 2 is valid for any
non-reactive gas diffusing in the experimental fiber
mixture represented by fig. 1.

3.2. Neon transport in vitreous silica fibers

Since a new gas probe system was designed and
constructed for this study, a trial run was made to
check the accuracy of the new differential pressure
transducer and to become familiar with the increased sensitivity of the system. Helium was used
as the diffusing species and the sample chamber
was packed with 1.06 mm diameter glass rods
made of vitreous silica from Heraeus Amersil,
representing the same material as the glass fibers
except for the diameter. The size of the rods and
the significant permeability of helium in vitreous

0
-0.2
-0.4
-0.6
-0.8
-1
o=

-1.2
-1-4
-1.6
-1-8
-2
-2.2
-2.4
-2.6

]
0

i
40

J
80

,
1 20

i
1 60

200

240

TI rr~ e ( r n f n u t e s )

Fig. 3. Typical pressure versus time experimental result (for neon in vitreous silica at 33.5 o C). The total pressure drop indicates the
solubility of neon, and the diffusivity can be obtained from the time required for one-half the total pressure drop using fig. 2.

R.S. Wortrnan, J.F. Shackelford / Gas transport in vitreous silica fibers

284

silica resulted in an experimental temperature

range from 99 to 231C giving total saturation
times from approximately one to twelve hours.
Excellent agreement was obtained between the
results of this trial run and the previous solubility
data of Shackelford, et al. [12] and the diffusivity
data of Swets et al. [13].
The ability to measure gas solubility and diffusivity in glass fibers was demonstrated with neon,
for which practical experimental times could be
obtained at near-ambient temperatures.
Because of the careful control of the gas flow
during initial pressurization to avoid valve seat
contamination, a longer gas inlet time was required. This was important to track in that, during
the measured 30 s of gas introduction, the sample
began absorbing atoms that were not being measured by the subsequent pressure drop. Shackelford [10] outlined the correction needed to compensate for this 'pre' loading.
A typical pressure-versus-time experimental result is shown in fig. 3. The total pressure drop was
used to calculate solubility, and the time-to-half
saturation (half the total pressure drop) was used
to calculate diffusivity by use of fig. 2. Table 1
lists the solubility and diffusivity data that were
obtained in this study. The temperature range was
that which allowed the sample to saturate in from
1 to 12 h. Figure 4 compares the solubility data

Temperature
(C)
0.0
30.0
31.0
33.5
35.0
39.5
42.0
46.0
46.0
46.0
49.5

I / T x 103
(K a)

S x 10 -23
( a t o m s / m 3 atm)

D x 1015
(m2/s)

3.660
3.300
3.289
3.263
3.247
3.200
3.175
3.135
3.135
3.135
3.100

13.300
9.000
9.630
7.340
8.310
7.160
8.570
7.480
7.080
6.480
7.710

0.475
0.814
0.736
1.940
1.020
0.712
1.490
1.550
1.710
1.900
1.800

10 25

E
E

1024

03

E
O
v

03

1 023

1 /Tx 1 0 3 ( K -1)
Fig. 4. The solubilityof neon in vitreoussilica from the current
study on micrometer-scale fibers (closed circles) compared
with the results of Shackelford et al. [12] on millimeter-scale
rods (open circles).

from this study to that of Shackelford et al. [12]

on vitreous silica rods of between 1 and 6 mm in
diameter.
Figure 5 compares the diffusivity data of this
study to that of Frank et al. [14] obtained in a
permeation-based experiment on approximately 1
mm thick disks.

10-8

Table 1
Neon solubility and diffusivity in the vitreous silica fiber
sample of fig. 1

10-10

G"
E

10-12

a
10-14

10-16
0

1 / T x 10 3 (K "1)
Fig. 5. The diffusivity of neon in vitreous silica from the
current study on micrometer-scale fibers (closed circles) compared with the results of Frank et al. [14] on millimeter-scale
disks (open circles).

R.S. Wortman, J.F. Shackelford / Gas transport in vitreous silica fibers

4. Discussion
In fig. 4, the two data sets are seen to be fit by
a single plot of the Van't Hoff-form, namely
S = S Oe - 6 " j R r ,

(9)

where S is the number of gas atoms dissolved per

unit volume at one atmosphere gas pressure, So
the pre-exponential constant, AH s the enthalpy of
solution, R the universal gas constant, and T the
absolute temperature. The simple Van't Hoff fit
gives a value of So = 6.07 1022 a t o m s / ( m 3 atm)
and AHs = - 6 . 7 0 k J / g atom, in comparison with
the values of So = 2.89 1023 a t o m s / ( m 3 atom)
and AH~ = - 8 . 1 4 k J / g atom obtained by Shackelford et al. [12]. Figure 4 illustrates that the
solubility data of this study on micrometer-scale
fibers (closed circles) are consistent with the previous study on millimeter-scale rods [12]. To our
knowledge, the current data are the first such
quantitative results on neon near room temperature and provide a corresponding refinement for
the neon-vitreous silica system, given the much
wider experimental temperature range of the combined data set.
The two data sets in fig. 5 are seen to be fit by
a single plot of the Arrhenius-form, namely
D = D O e -A'%/Rv,

(10)

where D is the diffusivity, D O the pre-exponential

constant, A H D the activation energy for diffusion,
and R T the same as for eq. (9). The simple
Arrhenius plot gives values of D O= 0.997 10 -8
m2/s and A H D = 41.0 k J / g atom, in comparison
with the values of D o = 2.21 10 -8 m2/s and
A H D = 47.6 k J / g atom obtained by Frank et al.
[14]. Because of the wide experimental temperature range represented by the two data sets of fig.
5 and the visibly steeper data set (i.e., higher
AHD) of Frank et al., some consideration was
given to the possibility that the diffusivity data
could be more closely fit with a modified Arrhenius
equation of the form
D = DoTe - A ~ / R r ,

(11)

where the pre-exponential T term comes from

absolute rate theory, as discussed by Shelby [15].
The use of eq. (11) did not provide an improve-

285

ment in the quality of fit, leading to a conclusion

that, for the data at hand, the simple Arrhenius
plot of fig. 5 is adequate. Figure 5 illustrates, as
did fig. 4 for solubility, that the diffusivity data of
this study on micrometer-scale fibers (closed
circles) are consistent with the previous study on
millimeter-scale disks [14]. Again, we believe the
current data are the first available near room
temperature.

5. Summary and conclusions

In order to apply solubility-based gas transport
measurements to lower temperature ranges a n d / o r
gas species larger than helium, a refined experimental system was constructed. Micrometer-scale
fibers of vitreous silica were used as a specimen.
The inherent distribution of glass fiber diameters
had to be carefully characterized, with the specific
log-normal distribution of the sample establishing
a saturation curve for determining diffusivity from
the measured time-to-half saturation. The necessary experimental sensitivity was provided by a
differential pressure transducer. The ability to
measure solubility and diffusivity in the glass fibers
was demonstrated using neon gas. Good agreement was found between the results of this study
near room temperature using the micrometer-scale
fibers and previous, high-temperature studies on
millimeter-scale samples. Over the temperature
range of 0-777 C, the solubility of neon in vitreous silica can be given by
S = (6.07 1022 a t o m s / ( m 3 atm))
exp((+6.70 kJ/g atom)/RT).

(12)

Over the temperature range of 0-984 C, the diffusivity of neon in vitreous silica can be given by
D = (0.997 10-s m2/s)
exp((-41.0 kJ/g atom)/RT).

(13)

This work was supported by NSF Grant DMR85-05636. Les Gehman was instrumental in writing the data acquisition program and Brian Brown
aided in the programming and discussions of the
mathematical aspects of the study.

286

R.S. Wortman, J.F Shackelford / Gas transport in oitreous silica fibers

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