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

increasingly important as they are likely to be used in critical Silica fibers are made by drawing high purity preforms at
applications where failure of a sensor might have dramatic temperature approaching 1900 oC with a suitable set-up.
consequences for cost and/or safety. Optical fiber reliability Preforms are rods in which the central part consists of a core
and expected lifetime are closely related to environment glass of higher refractive index while the external part is
chemical action on silica that in turn, influences fiber made from glass of lower refractive index. These preforms
strength. Previous work [9-11] has emphasized two major are prepared by a vapour phase processes in which silicon
mechanisms of strength degradation: aging and stress chloride reacts with gaseous oxygen. This results in a very
corrosion. It has been demonstrated that silica is sensitive to high purity material which contains extremely low levels of
metal impurities and hydroxylions. Variation of refractive
*Corresponding author: relabdi@univ-rennes1.fr index is achieved by modification of the vapour composition:
233

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

We might notice [22. The nd is a parameter characterizing the material capacity to statistical Weibull law gives a relationship between the resist to a stress. For brittle materials as silica with least squares fitting lines.5 mbar pressure for 15 min. The accepted stress corrosion parameter is probability FK of fiber rupture and the applied stress σ.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). Results and Discussion It is assumed that fracture at the most critical flaw on a Figure 2.23]: the coherent mono-modal Weibull plots (see accordingly the linear regression represented by the least squares fitting Ln σ = p Ln σ· + b ( ) ⋅ ( ) (1) lines. the defect type in fiber is subthreshold and the crack The slope p of the curve Ln(σ) versus Ln σ· (where σ· ( ) ( ) initiation is dominated by residual stresses [24]. then exposed to acetylene (C2H2) at 1 bar pressure for 5. Then.Optical Fibers Under Harsh Environments Fibers and Polymers 2011.– 1 (2) mean stress value (strength at 50 % fracture probability of p the Weibull plot). then exposed to ammonia (NH3) at 1 bar pressure for 180 h (7. exceeding reference Tested after 1 day in ambient air 5205 Ammonia 180 h.2 235 subjected to vacuum at 0. subjected to vacuum at 0.12. certain samples were tested immediately. strength results obtained from tensile tests. under 1 bar Drying 2 days 4805 Acetylene 5 h. 48. under 1 bar Drying 4 days 4811 60 h.5 mbar Immediate testing 5305 /max. e) Fibers were inserted in an hermetic container.5 bar Drying 2 days 5376 48 h. optical fibers. For each velocity. and 68 h (7 days). present a significant scattering. subjected to vacuum at 0. Weibull plots for reference fiber for different velocities fiber leads to total failure. we can Results for different reagents and for different testing conditions Table 1. under 1 bar Immediate testing 4604 168 h.21]. is stress rate in MPa/s) is related to the dynamic stress The reference Verrillon fiber Weibull plots for four corrosion parameter nd [12] by the following relations different strain rates are given in Figure 2. 36. the distribution of the critical flaw size in the sample. This method leads to obtain the nd = 1--. case.5 days) and tested after 2 days in ambient conditions. 6115. 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. In this Weibull diagram [20.3 and 7 GPa. the medium stress. the Weibull slope and where b is a constant parameter. under 1 bar Drying 2 days 5256 . as-indicated in Figure 2). Vol. under 0. d) Fibers were inserted in an hermetic container. others after two days in ambient conditions.5 mbar pressure for 15 min. respectively. No. the statistical Weibull method is commonly used. The ~20 for high strength fiber and generally between 10-20 evolution of Ln[ Ln FK)] according to Ln(σ) is called − (1− when the fiber strength varies between 0.

the stress corrosion subsequent to acetylene exposure seems to favour extrinsic parameter was calculated at a value of d 14 for the n = defects and broaden distribution (see 48 h. Note that the mean stress (Table 1) polymer interface level. After 48 h aging duration. (b). (a). The R2 correlation coefficient 2 days comparing to 60 h. Humidity influence results and using equations (1). Figure 3.99 and shows that the corresponding effect is noticed. testing immediately). to a certain exposure time the acetylene molecule appears For all the other tests. For short durations. . (2). the coating is detached from the fiber exposure. Severin et al.2 I. and (c) aging duration 48 h. When measures the degree to which two things vary together. Comparing the results (Figure 4-acetylene reagent) we The acetylene attack is rather severe and after an aging might notice an interesting opposite effect following gaseous duration of 48 h. Aging fiber in acetylene reagent (aging durations in day (d) or hour (h). deduce the mean failure stress σ. (d) and (e) aging duration 7 days. Figure 2). Magnification of the fiber shows that this one seems to affect progressively leading to the mean strength is composed of two concentric parts: the glass core and the decrease and a broader distribution with more and more glass cladding (Figure 5(b)).62. we Figure 5. (7 days) an unexpected less severe our case it is equal to 0. and leads to less severe decrease of is obtained at 50 % cumulative failure rate. In this sense we might consider the variables ( (σ) and ( σ· ) ) closely vary together in the Ln Ln hypothesis of a mutual compensating effect meaning that up same direction (Figure 3). testing after reference fiber (Figure 3). for a strain rate V equal to 200 mm/min. Figure 4. the reactive acetylene molecules (Figure 5(a)). the mean strength. pressure in bar). the mean failure stress σ is evident extrinsic defect populations (slope for aged fibers is equal to 5568 MPa ( (σ)=8. Stress corrosion parameter.236 Fibers and Polymers 2011.12. For example. Acetylene effects. For prolonging the exposure. Vol. Table 1 gives the testing conditions less reactive. Figure 5 gives the acetylene aging effects for durations of Acetylene Reagent Effects 48 h and 7 days. Based on these Ln smaller than that of the non aged fibers). No. due to a partial polymerization at the silica- and the mean failure stress.

DMSO Reagent Effects Compared to the effect of water for similar immersion The behaviour of fibers soaked in DMSO reagent (Figure 6) times (18 h) (Figure 8) we might notice that the DMSO shows that: for short immersion times the mean strength reagent appears more aggressive than deionised water. (a) and (b) aging duration 40 min. Comparison with deionised water effects (aging durations in h (h)).Optical Fibers Under Harsh Environments Fibers and Polymers 2011. This the other.6 MPa). increasing curing effect at crack tips.2 237 can observe a swelling of the coating (Figure 5(c)). . The broader Figure 6. Figure 8. Aging fiber in DMSO reagent for different aging durations. 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. mean strength decrease and extrinsic defect populations lead to That was not the case for DMSO with prolonged exposure excessively broad multimodal distribution and in particular for leading to irreversible fiber failure. Vacuum effects for different aging durations. No. and create also a circular crack around the fiber coating damage becomes more accentuated when the aging (Figure 7(b)). decreases (in comparison with the non aged mean strength Longer immersion in water (18 h compared to 2 h) leads to a fiber). Subjecting the fiber to low vacuum during 30 min (Figure 9) Under DMSO attack. (c) and (d) aging duration 18 h. Figure 5(e)). The coating can be partially detached from duration is high (7 days. but maintains a mono-modal steeper plot. DMSO effects. in line with our previous reported observations [24]. Figure 9.12. slightly increasing the mean the exposure duration determines more and more important strength. the 18 h exposure duration. Vol. We can note that fiber that is electrostatically charged Vacuum Effects attracts dust from the laboratory atmosphere (Figure 7(a)). Figure 7. fiber by a longer aging duration of 18 h (Figure 7(c)) or it is completely removed (Figure 7(d)). Due to environmental humidity absorption. the two coatings dissociate one from an increase of the strength was noticed for fibers immediately tested (Ln(σ) higher than 8.

B: Chemical. Tanaka. Matsumoto. 2005. T. and D. and Bioelectronics. Mater. But if aging in water decreases the fiber strength. B. International DMSO (aging during 18 h). Sensors aged fiber strength. Belgium.. Ammonia effect in comparison with other reagents While silica optical fiber was more severely damaged by Figure 10. Mitsubayashi. (North fiber is more sensitive to gaseous water molecules than to Grafton. and R. 1. 139. seeming that the The authors express their gratitude to Verrillon. Proc. Vol. water molecules in gaseous phase appear more reactive that those in liquid phase. the use of hermetic optical fibers is advised. 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.2 I. 30 (Figure 10) appears more aggressive than the acetylene for (2009). Aging in Ammonia Atmosphere 2. Polymer coatings suffer damage and swelling was observed. Figure 11. Johnstone. 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. No. Ammonia effects. Inc. Petrovich. Chemical. N. For an aging in ammonia. W. and Y. Chang. Austin. H. Consequently. We may suppose the experimental procedure consisting of preliminary vacuum prior to air exposure probably References influence the humidity reactivity favouring extrinsic defects appearance. water (18 h)). 20 (2005). 146. the ammonia effect for an exposure of 7 days Richardson. Moodie. 5855. J. but the Weibull plot presents moreover a Actuat.12. Chem.475. Sensors Actuator. P. Fibres Sensors. We notice that the ammonia effect is less disastrous than 6. the same exposure (7 days) but less aggressive than the 3. MA) for technical assistance and for material water in liquid phase (comparison with results for aging in support. Hashimoto. E. 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. pressure in bar). DMSO solution. Finally. Phys. M. 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. K.238 Fibers and Polymers 2011. Nagamura. For acetylene and DMSO environments. (aging durations in day (d) or hour (h). Severin et al. A. H. Acknowledgements distribution appeared more unexpected. 193 (2003). Biosensors one (aging during 7 days). Cheung. V. Brakel. 77. Chen and T. it does not ensure mechanical stability in extreme conditions and SEM observations were consistent with mechanical measurements. the Conference OFS 17. mono-modal distribution quite similar to those of acetylene 5. Berghmans. of acetylene or of ammonia. T. 17th International Conference on Optical that of the DMSO solution (Figure 11). Aging duration 7 days. its effect is less severe than that of DMSO. maybe due to a partial polymerization at the silica-polymer interface level. C. Kon. acetylene molecules appear less reactive. mean strength decreases again in comparison with the non 4. 253 (2010). Conclusion This paper examines the degradation of optical fiber submitted to different harsh environments. On the other hand. Such fibers are designed to improve aging behaviour and to avoid acetylene and DMSO diffusions through the glass surface and coating damages. p. and D. SPIE. F. A. . 110 (2002). Bruges. 19.

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