Thermal cycling layer by layer dip coating method
for oxazine formation on clad modified optical fiber
core
Ahmed Hasnain Jalal, Sajib Roy
Dept. of Electronics & Telecommunication Engineering
University of Liberal Arts Bangladesh
Dhaka, Bangladesh
hasnain2065@yahoo.com
sajib.roy@ulab.edu.bd
Abstract—The paper shows plastic optical fiber of 960/1000
μm Core/Cladding as an optical waveguide by removing a
portion of the cladding section of the fiber via chemical etching
and then applying dip coating method to fabricate 0.0005 M
Oxazine 170 per Chlorate on the bare core. It is then followed by
a Poly Di-Methyl Siloxane (PDMS) layer to design an opto-
chemical sensor, to be used in detection of pH- based
contaminants in air and water. The thickness of PDMS layer
varies between 130-145 μm and that of Oxazine layer varies
between 20 - 25 μm. This paper also shows a novel moisture
trapping technique, necessary to trap moisture within PDMS and
Oxazine which results in proper detection of contaminants.
Keywords—Clad-modified; PDMS; Dip coating; POF; Organic
solvent etching.
I. INTRODUCTION
The motivation behind using optical fiber as sensing
elements mainly derives from the fact that optical fibers are
light, compact, multiplexible, EMI immune and require no
electric power for sensing purpose. The purposes of this paper
this to design an opto-chemical based sensor for detecting air
or water contaminants. The opto-chemical sensor is based on
the unique ability of micro or nano-structured form to alter
their optical response in the presence of a ‘recognition
element’, the chemical adsorbent on the surface. Such sensors
can be calibrated for detection of specific chemicals, including
toxic species in both liquids and gases such as ammonia. Glass-
silica based opto-chemical sensors were developed in the early
1980s. These sensors were used for ammonia gas detection. A
sensor, Oxazine-ethanol based, was spray-coated on the
capillary tube and 60 ppm ammonia gas was detected by this
sensor [1]. The important phenomenon of this Oxazine-based
sensor was that it required moisture to detect ammonia. As a
result, without relative humidity the sensor did not work and
detection level was also very high (It is supposed to be less
than 35 ppm) [2]. Since 1990, the use of the optical methods
for gas detection has become more popular. Optical wave guide
technique was developed during this time and the principle of
the planar waveguide sensor or integrated optical sensor is
based on the optical intensity modulation technique. Such a
waveguide modified sensor, based on polyaniline /PMMA
Fahmida Alam
Dept. of Electrical & Electronic Engineering
University of Information Technology & Sciences,
Chittagong, Bangladesh
fahmida.alam0502041@gmail.com
(Poly Methyl Meth-Acrilate), detects ammonia gas at 92 ppm
[3].
Opto-chemical sensors were usually fabricated by two
ways. They are: (a) Waveguide fabrication and (b) Clad-
modified fabrication. The next section will focus on the clad-
modified fabrication technique.
II. CLAD-MODIFIED FABRICATION
Sol-gel technique is one of the popular clad-modified Silica
based fabrication techniques where transparent glasslike
material formed by synthesis of inorganic or composite
organic/inorganic networks based on the hydrolysis and
polymerization of metal alkoxides or metal-organic compounds
at lower temperature [4, and 5]. The silica glass formed by this
method is a porous matrix that contains interconnected pores
formed by a three dimensional network [5]. Another U-shaped
BCP-trapped sol-gel based sensor was also developed to detect
ammonia in air and water [6]. This U-shaped was formed in the
flame. It was observed that the sensor fabrication is not only
complicated [6] but also time consuming (it takes 14 days to 1
month to prepare sensor) [4, and 5]. Fragility is another big
issue of this sensor. This sol-gel technique usually implements
for glass fiber and the developed sensor is not as flexible for
bending as POF (plastic optical fiber) based sensor. Polyaniline
was deposited by spin coating on a clad removal part of the
fiber for the detection of HCl and ammonia vapor [7]. Another
polyaniline-based sensor was developed for ammonia detection
in standing water where 1 μm thin layer of polyaniline formed
on the 3-5 cm clad removal part of the fiber [8]. A thin layer of
Poly Di-Methyl Siloxane was used for protecting the polymer
from water. A mixture of PVC with dye materials was dip
coated onto a 10 cm length of de-clad optical fiber before being
left to cure at room temperature overnight. This sensor was
used for ammonia gas sensing [9]. Comparing with glass fiber,
clad-modified plastic fiber sensors are relatively new. For
ammonia gas detection, de-clad BCP- pH dye based sensor was
fabricated by dip coating method and fiber is mirrored with
silver paint which helped sensor to increase its sensitivity [10].
For the removing the cladding of the different kinds of the
fiber, different reagents and methods can be used. For this
paper, Organic Solvent Etching Technique is used.
A. Organic solvent etching for cladding removal
Usually the cladding of the POF fiber is made by PMMA
based polymer which is a thermoplastic with a softening
temperature 160°-175° F. Etching is only the realistic option to
remove the cladding of the fiber because the polymer resists
drawing partly due to latent stresses within the structure from
production and the different physical properties of the core and
cladding. PMMA is dissolved by concentrated inorganic
acid[11]. It can be dissolved by organic solvents such as
acetone, THF (Tetra Hydro-Furan) or MIBK (Methyl Isobutyl
Ketone) etc.
Fig. 1. Core and cladding etching rate by 2:1:1 proportions of THF,
MIBK and DI water
However, high concentration acetone causes brittleness and
fracture of the fiber. In order to reduce this effect a mixture of
acetone, MIBK and distilled water was used in a 3:1:1
proportion [11]. It was observed that if the POF fiber dipped
directly in the THF solution, the fiber was broken after few
seconds. To reduce this effect, DI water and MIBK are used.
In this research work, Tetra Hydro Furan-THF [(CH2)4O] was
used as a main solvent for etching the fiber. 2:1:1 THF, MIBK
and DI water solution were used for the cladding removal of
the fiber. It was observed that this proportions works well for
removing the cladding of the fiber without brittleness. Figure
1 shows cladding removal trend with this proportion, when the
solution starts etching the core.
From this plot, it is observed that cladding and core etching
rate of the POF fiber are not same. Cladding etching rate is
0.775 μm/ minute or 0.0129 μm/ second whereas core etching
rate is 1.6 μm/ minute or 0.0266 μm/ second. It is clear from
the plot that the core etching rate is almost double of the
cladding etching rate i.e. core materials are etched faster than
the cladding material.
From this experiment, cladding and core etching rates are
figured out but this method is not suitable for the removing
cladding. It is time consuming and is difficult to resist the core
etching possibility. The same solution of THF, MIBK and DI
water was used for the cladding removal of the fiber. 3-5 cm
of the plastic fiber was dipped 1 minute in this solution.
Fluorinated polymer is going to become soft after taking it out
from the solution. A lint free lens tissue (40 mm square) was
folded and gently rubbed on the 4-5 cm region several times.
After a certain period, the soft fluorinated polymers of the
fiber disappear from that region. It is necessary to measure the
diameter to make sure that the cladding is removed properly
and core was not affected. The measured diameter of the bare
core is 0.96 mm which matched with the specification sheet
provided by manufacturer- Fiber Instrument Sales, Inc. This
cladding removal technique is known as ‘Organic Solvent
Etching Technique‘. Finally, the fiber is cleaned with
Isopropyl Alcohol and DI water several times to obtain a clean
and exposed core as shown in figure 2.
Fig. 2. Before (a) and after (b) removing cladding
III. PH SOLUTION PREPARATION AND FORMATION
Oxazine 170 per Chlorate was used to make a thin layer on
the fiber. 10-5 M Oxazine 170 per Chlorate was used with
ethanol to prepare a solution [12]. In this case, water instead of
ethanol was used as a solvent. As ethanol evaporates faster
comparing with water and heating is required for fabrication,
water was used as a solvent instead of ethanol.
A. Method of pH solution preparation
Approximately 0.054 grams of Oxazine was mixed in 250
ml DI water to prepare 0.0005 M Oxazine 170 Per Chlorate
solution. Then, it was mixed properly with the stirrer in water.
After the mixing process, it was observed that particles
remained in the solution suggesting that the Oxazine did not
dissolve properly in the water. To facilitate complete dissolve
of Oxazine, ultra-sound stirrer was used for 6 times (each time
30 second). Then the solution was kept at room temperature for
1-2 hours so that the extra particles could settle down at the
bottom of the beaker. Supernatant of 100 ml of solution was
poured precisely in another beaker so that as less particles were
present in this solution.
B. pH formation technique
When compared with coating techniques, such as, spray
coating, spin coating, dip coating with chemical reaction etc.
[3, 4, 5, 13], ‘Dip Coating Method’ is easier, less expensive
and much more appropriate for the micro or nano-fabrication
on the de-clad part of the fiber. In this research work, a novel
‘Layer by Layer pH Formation Method‘ is developed and is
described which is based on thermal cycling procedure.
C. Layer by layer pH formation method
A supernatant 100 ml of Oxazine 170 per Chlorate solution
was poured into a 250 ml of beaker (shown in figure 4(a)). The
beaker was kept on a heater. If the solution was heated more
than 200° F, the particles of the Oxazine and the fiber were
burnt and a layer of the particles was formed on the solution as
depicted in figure 3 (b). This clad-modified sensor would not
function properly as the particles on the fiber also be burnt
(figure 3 (c)). It was also observed that 0.0005 M solution
worked properly for a thin layer of the Oxazine on the fiber.
Fig. 3. (a) and (b) Burning particles in the solution. (c) Burning particles
on the fiber
The sensor part of the fiber was dipped in 0.0005 M solution
around 170-180° F temperature till the amount of the solution
reach at half (50 ml) in volume as shown in figure 4 (c). The
sensor was taken out from the solution (a thin layer of the
particles formed on the solution as figure 4 (e)) for a minute
and it was observed that a non-uniform, very thin layer formed
on the de-clad part of the fiber as figure 4 (d). The fiber is
subsequently dipped in the same solution at room temperature
around 12 hours later, and the result is a thin layer (20-25 μm
width) of Oxazine 170 per Chlorate on the exposed core part of
the fiber as shown in figure 4 (f) . Due to heating, the fiber was
bent in U-shape permanently which increases the sensitivity of
the fiber. Finally, the fiber is kept couple of hours at the room
temperature and a thin layer of 20-25 μm Oxazine 170 per
chlorate was coated on the fiber as shown in figure 4 (f).
IV. PDMS FORMATION
After removing the cladding and formation of the pH
indicator on the un-clad region of the fiber, the sensor was
cured at room temperature around 15 minutes. Then, the sensor
was dipped in 10:1 PDMS and curing agent solution for 2-5
minutes and heated at 170-180° F couple of hours till the
PDMS layer cured and dried up properly. It was observed that
the sensor didn‘t perform well and sometimes it showed no
Fig. 4. pH formations on the core of POF fiber (a) 100 ml Oxazine 170 per
Chlorate-water solution, (b) Heating the solution with fiber at 170˚-180˚
F, (c) Solution was reduced down to half in volume, (d) Un-uniform layer
on the core after taking out the solution, (e) Particles formed on the
solution and (f) A uniform 20-25 μm layer Oxazine on the bare core of the
fiber after 12 hours dipping in the subsequent solution at room
temperature
intensity variation even in high concentration ammonia
environment.
Another sensor without PDMS layer, made by same
procedure, was kept above the high concentration (28%
solution) ammonia in air and it was observed that there is no
intensity variation. Then, the same sensor was dipped in water
and ammonia was added and after sometimes (within 30
seconds), the intensity gradually decreased in blue light region.
Besides, it was also observed that the sensor with PDMS layer
didn’t show intensity variation in water environment. From
these experiments, it was predicted that the oxazine might
require moisture to sense contaminants. Now the Poly Di-
Methyl Siloxane (PDMS) is a gas permeable membrane which
allows gas to pass through it and protects the pH indicator from
the liquid. As Oxazine 170 per chlorate is soluble in water, this
coating of the PDMS membrane protects oxazine. To solve this
problem, an idea was established that if water particles can be
placed between PDMS and oxazine, the sensor would be
working. Besides, heating was the cause of evaporation of
water or moisture from the sensor. As a result ‘Heating Curing
Method’ was opting and newly proposed ‘Moisture Trapping
Method’ was introduced for the PDMS formation. After
formation of oxazine on the cladding removal part, it was just
kept at the room temperature for the normal curing for the
couple of hours. Then, the sensor was dipped in the water
around 1 minute and was dried up 1 minute in air. Basically,
this 1 minute was spent for removing extra water particles from
the body of the sensor. If any visible extra water particles were
there, that was removed by lint free lens tissue. Then, the
sensor was dipped in 10:1 PDMS and curing agent solution and
hung vertically in the room temperature so that the extra PDMS
could fall down due to gravitational force. After 2-3 days, it
was observed that PDMS layer was cured and 130-145 μm
PDMS layer was formed on the oxazine.
V. IMPLEMENTATION OF THE FABRICATED OPTICAL FIBER
SENSOR
The fabricated sensor was employed in the stagnant,
dynamic water and air mediums to detect ammonia
contaminants. Results of these experiments can be found in
[14, 15].
VI. CONCLUSION
Plastic fiber fabrication is relatively new idea in the sensor
fabrication arena. The fabrication process of this sensor is
novel, simple, inexpensive and effective. An easy and novel pH
formation technique is introduced in this paper. The advantage
of this ‘Layer by layer pH Formation Technique’ is that the
oxazine 170 per chlorate forms on the de-clad part of the fiber
by heating and cooling process and as a result, the fiber is
formed in a U-pattern that increases sensitivity [6]. Moreover,
this technique is suitable for micro or nano-fabrication to
develop the sensor in a compact form. It was observed that
Oxazine 170 per chlorate requires moisture to detect ammonia.
A novel ‘Moisture Trapping Technique’ was applied to trap
moisture within PDMS and oxazine. The entire fabrication
process is less time consuming and cheap comparing with the
other fabrication techniques.
ACKNOWLEDGMENT
We would like to offer our sincerest gratitude towards Dr.
George A. Nnanna and Dr. Zahid Hasan Mahmood for their
support on the completion of this paper.
REFERENCES
[1] J. F. Giuliani, H. Wohltjen, and N. L. Jarvis, "Reversible optical
waveguide sensor for ammonia vapors," Optical Letters, vol. 8, pp. 54-
56, 1983.
[2] Brian Oram, “Nitrogen-Ammonia in water”, Center for Environmental
Quality Environmental Engineering and Earth Sciences, Wilkes
University, 1999.
[3] A. Airoudj, D. Debarnot, B. Beche and F. Poncin-Epaillard, “A new
evanescent wave ammonia sensor based on polyaniline composite”,
Talanta, vol. 76, pp. 314-319, 2008.
[4] Shiquan Tao, “Optical fiber chemical sensor with sol-gel derive
refractive material as transducer for high temperature gas sensing in
clean coal technology”, Final scientific /technical report, Project ID
number: DE-FC26-04NT42230, Institute for Clean Energy Technology,
Mississippi State University, 2006.
[5] Wenqing Cao, and Yixiang Duan, “Optical fiber-based evanescent
ammonia sensor”, vol. 110, pp. 252–259 , Sensors and Actuators B ,
2005.
[6] Shiquan Tao, Lina Xu and Joseph C. Fanguy, “Optical Fiber ammonia
sensing probes using reagent immobilized porous silica coating as
transducers”, Sensor and Actuator B, vol. 115, pp. 158-163, 2006.
[7] Jianming Yuan, and El-Sherif, M.A.,” Fiber-optic chemical sensor using
polyaniline as modified cladding material”, vol. 3, pp. 5-12, IEEE
Sensors Journal, 2003.
[8] Sistla S. Shastry, Abdeq M. Abdi and A. G. Agwu Nnanna,
“Investigation of Fiber Optic Sensor for Monitoring of Ammonia”, vol.
6, pp. 55-59, ASME, 2008.
[9] C. Malins, M. Landl, P. Simon and B. D. MacCraith, “Fibre optic
ammonia sensing employing novel near infrared dyes,” vol. 51, pp. 359-
367, Sensors and Actuators B, 1998.
[10] Jokin Moreno, Francisco J. Arregui and Ignacio R. Matias, “Fiber optic
ammonia sensing employing novel thermoplastic polyurethane
membranes”, vol. 105, pp. 419-424, Sensors and Actuators B, 2005.
[11] D. F. Merchant, P. J. Scully and N. F. Schmitt, “Chemical tapering of
polymer optical fibre”. Pp. 365-371, Sensors and Actuators A, 76, 1999.
[12] J. F. Giuliani, H. Wohltjen, and N. L. Jarvis, "Reversible optical
waveguide sensor for ammonia vapors", Optical Letters, vol. 8, pp. 54-
56, 1983.
[13] Abliz Yimit, Kiminori Itoh and Masayuki Murabayashi, “Detection of
ammonia in the ppt range based on composite optical waveguide pH
sensor”, Sensor and Actuator B, vol. 88, pp. 239-245, 2003.
[14] A. H. Jalal, S. Roy, and M. A. Ahad, “Comparative analysis of the
performance of polymer based opto-chemical sensor in detecting
ammonia in diverse mediums”, IEEE southeast conference, page 1-4,
2013.
[15] A. H. Jalal, S. Roy, and M. A. Ahad, Evanescent-based clad modified
polymer Optical Fiber Sensor for Ammonia gas detection”, in
proceedings of ICERIE-2013, SUST, Bangladesh.