Fibers and Polymers 2011, Vol.12, No.2, 233-239 DOI 10.

1007/s12221-011-0233-y

Mechanical and Structural Changes in Multimode Optical Fibers Induced by

Aging in Harsh Gaseous and Liquid Reagents
I. Severin, R. El Abdi1*, M. Poulain2, and A. D. Rujinski
Politechnic University, Splaiul Independentei, 313, IMST, 060042 Bucharest, Romania
1
Larmaur, Erl-Cnrs 6274, University of Rennes1, 35042 Rennes Cedex, France
2
Photonic Material Laboratory, University of Rennes1, 35045 Rennes Cedex, France
(Received September 24, 2010; Revised November 2, 2010; Accepted November 5, 2010)

Abstract: The increased optical fiber development for a variety of physical and chemical measurements using smart struc-
tures and sensors leads to investigate the mechanical and chemical reliability of standard commercial acrylate polymer coated
fibers. Multimode optical fiber was subjected to aggressive chemical reagents in gaseous and liquid phase, such as acetylene,
ammonia, dimethyl-sulfoxide for different durations after prior vacuum exposure. Tensile testing results were treated using
Weibull statistic. A comparison of mean failure strengths of aged fibers for similar exposure duration has revealed the highest
sensitivity to acetylene and dimethyl-sulfoxide reagents. Based on analysis of aged fiber surface morphology obtained from
Scanning Electron Microscopy, we can deduce the damage extent and the consequence on the structure of the fiber in contact
with these harsh environments.
Keywords: Optical fiber, Harsh environments, Aging, Weibull diagram, Tensile testing

Introduction environmental action, including that of water, but also to

Mechanical reliability is a major consideration in the
application of optical fibers for long-range communication,
sensor and signal processing systems [1].
Optical fiber sensors have gained much attention in recent
years for a variety of physical and chemical measurements.
For example, spectroscopic optical gas sensors employ
optical fibers (whose transmission properties are easily
exploited for remote sensing), become highly attractive for
fast, real time detection and measurement of simple
molecular gases [2,3].
Ethanol sensing is very important in many areas such as
driving, brewing and food industries, fuel or environmental
control as a few examples [4].
Optical fiber sensors for analysis of smells required in
many fields such as environmental assessments, breath
diagnosis, freshness analysis, etc [5].
Intense research has been performed to develop special
fibers for integration in smart structures to replace
conventional sensors [6-8]. The fiber transmission can be
reduced if the fiber ends are in contact with harsh
environments.
Accordingly, the issue of reliability of optical fiber becomes
methanol and other reagents, through the classical stress
corrosion phenomenon, characterized by the stress corrosion
factor nd.
Considering the numerous application fields of optical
fiber, we may wonder to what extent more aggressive
chemical reagents may influence mechanical reliability.
The aim of this study is to investigate the chemical
reliability of standard commercial acrylate polymer coated
fibers subjected to aggressive chemical reagents. Among the
chemical reagents to which can be subjected the optical
fiber, we find ammonia, acetylene, dimethyl-sulfoxide or
water. Mechanical properties of silica optical fibers exposed
for different durations at gaseous (ammonia, acetylene,
vacuum) and liquid environments (deionised water, dimethyl-
sulfoxide) were investigated by tensile tests. The effect of
reagent attacks was investigated by considering the fiber
strength during tensile tests. The surface morphology of the
broken ends of fibers was observed by Scanning Electron
Microscope and shows severe coating damage.
Experimental Procedure
Silica Fiber Fabrication

increasingly important as they are likely to be used in critical
applications where failure of a sensor might have dramatic
consequences for cost and/or safety. Optical fiber reliability
and expected lifetime are closely related to environment
chemical action on silica that in turn, influences fiber
strength. Previous work [9-11] has emphasized two major
mechanisms of strength degradation: aging and stress
corrosion. It has been demonstrated that silica is sensitive to
*Corresponding author: relabdi@univ-rennes1.fr
233
Silica fibers are made by drawing high purity preforms at
temperature approaching 1900 oC with a suitable set-up.
Preforms are rods in which the central part consists of a core
glass of higher refractive index while the external part is
made from glass of lower refractive index. These preforms
are prepared by a vapour phase processes in which silicon
chloride reacts with gaseous oxygen. This results in a very
high purity material which contains extremely low levels of
metal impurities and hydroxylions. Variation of refractive
index is achieved by modification of the vapour composition:
234 Fibers and Polymers 2011, Vol.12, No.2
germanium, phosphorous and fluorine can be incorporated
in this way. High quality preforms can be made using other
chemical processes, for example sol-gel. Preforms of low
melting glasses can also be prepared by inserting a high
refractive index glass rod into a tube.
Some optical fibers may also be drawn directly from the
melt using the double crucible method. Core and cladding
glasses are heated in two concentric crucibles at a temperature
for which melt viscosity of large enough. Then a step index
fiber may be drawn from the bottom of the double crucible.
An external polymeric coating is applied to protect it from
scratches, to limit chemical attack of harsh environments
and to increase its mechanical strength. Usual coatings are
acrylate resins [12,13], but other polymers such as silicones
and polyimide may be used. In spite of their hydrophobic
properties, fluorinated polymers do not make an efficient
barrier against hydrolysis and are less favourable for
mechanical properties.
Fiber Used for Testing
Standard silica optical fibers (from Verrillon Inc. [14]) of
125 µm in diameter and two layer acrylate polymer coatings
were considered as reference. The two coatings form a
polymer layer of 50 µm.
Acrylate coating is the most commonly used for standard
optical fibers. The inner layer is soft with a low glass
transition temperature Tg, and is applied onto the glass fiber
surface. It ensures protection against micro-bending and
damping of the external stresses. The outer layer has a
higher Tg, and is therefore harder, and protects the fiber
against external damage.
If the silica optical fibers offer a set of unique advantages:
lowest attenuations, good mechanical and chemical resistance,
transparency range extending from 300 nm to 2 µm, these
advantages can be called into question if the fiber
mechanical characteristics are deteriorated by severe attacks.
Tensile Testing Procedure
A Lloyds Instruments LR 50K (max. 100N) tensile bench
was used [15]. Tensile testing was performed in a controlled
environment at a temperature of 17-19 oC, 46-52 % relative
humidity and no more than 5 % humidity variation during
each series of the tensile tests.
For dynamic tensile testing, sample fibers were wrapped
three times around a cylinder pulley 65 mm in diameter. The
pulleys were covered with a powerful double faced adhesive;
Mechanical properties of the adhesive layer were important
controlling factors, as mentioned in an early paper [16]. The
dynamic tensile test consists to subject fibers to a deformation
under a constant velocity until the rupture. During the test,
the deformation and the tensile load are measured using a
dynamometric cell while the fiber deformation is deduced
from the displacement between the fixed lower pulley and
the mobile higher plat (Figure 1).
I. Severin et al.
Figure 1. (a) Optical fiber tensile set-up and (b) schematic
representation.
If generally, the tested fiber length is rather long (for
example 500 mm), for reasons of economy and time, a
sample test length of 200 mm was chosen. Test strain rates
of 20, 50, 200, and 500 mm/min were chosen. Expressed as
a percentage of the initial sample lengths, these strain rates
correspond to 10, 25, 100, and 250 %/min.
In the case of the reference fiber at least 30 samples were
tested and Weibull plots made and the nd-stress corrosion
factor calculated. In the case of samples exposed to various
substances, the same number of tests were performed,
excepting one series exposed to vacuum and tested in two
subsequent steps of 15 samples each making a total of 30.
For statistical reasons, in case of some anomalous values
in result series of the fiber strength, they were plotted and
then discarded in statistical analysis. Anyhow, we might
notice that no more than 10 % of the total series exhibited
slightly out of range values than the overall tested series.
The treatment of results is usually based on Weibull plots
despite some doubts concerning the adequacy of Weibull
distribution in tensile experiments [17-19]. Even if at least
50 samples are normally required for a reasonable estimation
using Weibull methods for our main aim of comparing
mechanical strength of fibers subjected to different aggressive
environments, the 30 samples used for Weibull treatment
appeared sufficient.
Exposure to Reactive Reagents
A sufficient fiber length for the dynamic tensile testing
was exposed to different aggressive environments for different
durations, as follows:
a) Fibers were immersed in cold deionised water for 2
respectively 18 h, and then dried in ambient conditions
for 2 days prior to tensile testing.
b) Fibers were soaked in dimethyl sulfoxide (DMSO) for
40 min, 2, 6, and 18 h, then dried ambient conditions for
2 days prior to tensile testing. Note that the dimethyl-
sulfoxide is an organosulfur compound with the
formula C2H6SO.
c) Fibers were inserted in an hermetic container and
Optical Fibers Under Harsh Environments Fibers and Polymers 2011, Vol.12, No.2 235

subjected to vacuum at 0.5 mbar pressure for 30 min

and tested in two steps: the first immediately (15
samples) and the second after one day in ambient
conditions (15 samples).
d) Fibers were inserted in an hermetic container, subjected
to vacuum at 0.5 mbar pressure for 15 min, then exposed
to acetylene (C2H2) at 1 bar pressure for 5, 36, 48, and
68 h (7 days), respectively; certain samples were tested
immediately, others after two days in ambient conditions.
e) Fibers were inserted in an hermetic container, subjected
to vacuum at 0.5 mbar pressure for 15 min, then exposed
to ammonia (NH3) at 1 bar pressure for 180 h (7.5 days)
and tested after 2 days in ambient conditions.
Results and Discussion

It is assumed that fracture at the most critical flaw on a
fiber leads to total failure. For brittle materials as silica
optical fibers, strength results obtained from tensile tests,
present a significant scattering. Then, the statistical Weibull
method is commonly used. This method leads to obtain the
mean stress value (strength at 50 % fracture probability of
the Weibull plot), the medium stress, the Weibull slope and
the distribution of the critical flaw size in the sample. The
statistical Weibull law gives a relationship between the
probability FK of fiber rupture and the applied stress σ. The
evolution of Ln[ Ln FK)] according to Ln(σ) is called
− (1−
Weibull diagram [20,21].
The slope p of the curve Ln(σ) versus Ln σ· (where σ·
( ) ( )
is stress rate in MPa/s) is related to the dynamic stress
corrosion parameter nd [12] by the following relations
[22,23]:
Ln σ = p Ln σ· + b
( ) ⋅ ( ) (1)
Figure 2. Weibull plots for reference fiber for different velocities
with least squares fitting lines.
nd = 1--- – 1 (2)
p
where b is a constant parameter.
nd is a parameter characterizing the material capacity to
resist to a stress. The accepted stress corrosion parameter is
~20 for high strength fiber and generally between 10-20
when the fiber strength varies between 0.3 and 7 GPa. In this
case, the defect type in fiber is subthreshold and the crack
initiation is dominated by residual stresses [24].
The reference Verrillon fiber Weibull plots for four
different strain rates are given in Figure 2. We might notice
the coherent mono-modal Weibull plots (see accordingly the
linear regression represented by the least squares fitting
lines, as-indicated in Figure 2). For each velocity, we can

Results for different reagents and for different testing conditions

Table 1.

Reagent Exposure duration Testing conditions Mean failure stress (MPa)

Reference (strain rate 200 mm/min) 5568
DMSO 40 min Drying 2 days 5422
2h Drying 2 days 5226
6h Drying 2 days 5118
18 h Drying 2 days 2858
Deionised water 2h Drying 2 days 5324
18 h Drying 2 days 5458
Vacuum 30 min under 0.5 mbar Immediate testing 5305 /max. 6115, exceeding reference
Tested after 1 day in ambient air 5205
Ammonia 180 h, under 1 bar Drying 2 days 4805
Acetylene 5 h, under 0.5 bar Drying 2 days 5376
48 h, under 1 bar Drying 4 days 4811
60 h, under 1 bar Immediate testing 4604
168 h, under 1 bar Drying 2 days 5256
236 Fibers and Polymers 2011, Vol.12, No.2
Figure 3. Stress corrosion parameter.
deduce the mean failure stress σ. For example, for a strain
rate V equal to 200 mm/min, the mean failure stress σ is
equal to 5568 MPa ( (σ)=8.62, Figure 2). Based on these
Ln
results and using equations (1), (2), the stress corrosion
parameter was calculated at a value of d 14 for the n =
reference fiber (Figure 3). The R2 correlation coefficient
measures the degree to which two things vary together. For
our case it is equal to 0.99 and shows that the corresponding
variables ( (σ) and ( σ· ) ) closely vary together in the
Ln Ln
same direction (Figure 3).
For all the other tests, Table 1 gives the testing conditions
and the mean failure stress. Note that the mean stress (Table 1)
is obtained at 50 % cumulative failure rate.
Acetylene Reagent Effects
Comparing the results (Figure 4-acetylene reagent) we
might notice an interesting opposite effect following gaseous
exposure. For short durations, the reactive acetylene molecules
seems to affect progressively leading to the mean strength
decrease and a broader distribution with more and more
Figure 5. Acetylene effects; (a), (b), and (c) aging duration 48 h, (d) and (e) aging duration 7 days.
I. Severin et al.
Figure 4. Aging fiber in acetylene reagent (aging durations in day
(d) or hour (h), pressure in bar).
evident extrinsic defect populations (slope for aged fibers is
smaller than that of the non aged fibers). Humidity influence
subsequent to acetylene exposure seems to favour extrinsic
defects and broaden distribution (see 48 h, testing after
2 days comparing to 60 h, testing immediately). When
prolonging the exposure, (7 days) an unexpected less severe
effect is noticed. In this sense we might consider the
hypothesis of a mutual compensating effect meaning that up
to a certain exposure time the acetylene molecule appears
less reactive, due to a partial polymerization at the silica-
polymer interface level, and leads to less severe decrease of
the mean strength.
Figure 5 gives the acetylene aging effects for durations of
48 h and 7 days.
The acetylene attack is rather severe and after an aging
duration of 48 h, the coating is detached from the fiber
(Figure 5(a)). Magnification of the fiber shows that this one
is composed of two concentric parts: the glass core and the
glass cladding (Figure 5(b)). After 48 h aging duration, we
Optical Fibers Under Harsh Environments
can observe a swelling of the coating (Figure 5(c)). This
coating damage becomes more accentuated when the aging
duration is high (7 days, Figure 5(e)).
DMSO Reagent Effects
The behaviour of fibers soaked in DMSO reagent (Figure 6)
shows that: for short immersion times the mean strength
decreases (in comparison with the non aged mean strength
fiber), but maintains a mono-modal steeper plot; increasing
the exposure duration determines more and more important
mean strength decrease and extrinsic defect populations lead to
excessively broad multimodal distribution and in particular for
the 18 h exposure duration.
We can note that fiber that is electrostatically charged
attracts dust from the laboratory atmosphere (Figure 7(a)).
Under DMSO attack, the two coatings dissociate one from
Figure 6. Aging fiber in DMSO reagent for different aging
durations.
Figure 7. DMSO effects; (a) and (b) aging duration 40 min, (c) and
(d) aging duration 18 h.
Fibers and Polymers 2011, Vol.12, No.2 237
the other, and create also a circular crack around the fiber
(Figure 7(b)). The coating can be partially detached from
fiber by a longer aging duration of 18 h (Figure 7(c)) or it is
completely removed (Figure 7(d)).
Compared to the effect of water for similar immersion
times (18 h) (Figure 8) we might notice that the DMSO
reagent appears more aggressive than deionised water.
Longer immersion in water (18 h compared to 2 h) leads to a
curing effect at crack tips, slightly increasing the mean
strength, in line with our previous reported observations [24].
That was not the case for DMSO with prolonged exposure
leading to irreversible fiber failure.
Vacuum Effects
Subjecting the fiber to low vacuum during 30 min (Figure 9)
an increase of the strength was noticed for fibers immediately
tested (Ln(σ) higher than 8.6 MPa). Due to environmental
humidity absorption, we can note a slight decrease below the
reference values up to a mean strength of 5 % lower as
compared to the non aged fiber mean strength. The broader
Figure 8. Comparison with deionised water effects (aging
durations in h (h)).
Figure 9. Vacuum effects for different aging durations.
238 Fibers and Polymers 2011, Vol.12, No.2
Ammonia effect in comparison with other reagents
Figure 10.
(aging durations in day (d) or hour (h), pressure in bar).
Figure 11. Ammonia effects. Aging duration 7 days.
distribution appeared more unexpected, seeming that the
fiber is more sensitive to gaseous water molecules than to
water in liquid phase (comparison with results for aging in
water (18 h)). We may suppose the experimental procedure
consisting of preliminary vacuum prior to air exposure probably
influence the humidity reactivity favouring extrinsic defects
appearance.
Aging in Ammonia Atmosphere
Finally, the ammonia effect for an exposure of 7 days
(Figure 10) appears more aggressive than the acetylene for
the same exposure (7 days) but less aggressive than the
DMSO (aging during 18 h). For an aging in ammonia, the
mean strength decreases again in comparison with the non
aged fiber strength, but the Weibull plot presents moreover a
mono-modal distribution quite similar to those of acetylene
one (aging during 7 days).
We notice that the ammonia effect is less disastrous than
that of the DMSO solution (Figure 11).
I. Severin et al.
Conclusion
This paper examines the degradation of optical fiber
submitted to different harsh environments. Optical fiber will
not only fail when it is subjected to mechanical stress but
strength loss can also occurs when fiber is exposed to
sustained stress in liquid or gaseous environments.
Water is known to be a factor of the propagation of cracks
at fiber glass surfaces because it makes it much easier to
break the Si-O bonds which build the vitreous network. But
if aging in water decreases the fiber strength, its effect is less
severe than that of DMSO, of acetylene or of ammonia. On
the other hand, water molecules in gaseous phase appear
more reactive that those in liquid phase.
While silica optical fiber was more severely damaged by
DMSO solution, the fiber could be pulled out from the fiber
polymer coating (the coating peels off) and then the acrylate
coating appeared ineffective protection from severe chemical
damage. Consequently, it does not ensure mechanical stability
in extreme conditions and SEM observations were consistent
with mechanical measurements.
Acetylene action is more complex because a prolonged
aging duration (7 days) can lead to a less severe effect than a
small aging duration and after a certain aging time, acetylene
molecules appear less reactive, maybe due to a partial
polymerization at the silica-polymer interface level. Polymer
coatings suffer damage and swelling was observed.
For acetylene and DMSO environments, the use of
hermetic optical fibers is advised. Such fibers are designed
to improve aging behaviour and to avoid acetylene and
DMSO diffusions through the glass surface and coating
damages.
Acknowledgements
The authors express their gratitude to Verrillon, Inc. (North
Grafton, MA) for technical assistance and for material
support.
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