Sie sind auf Seite 1von 6

International Journal of Trend in Scientific Research and Development (IJTSRD)

International Open Access Journal |

ISSN No: 2456 - 6470 | Volume - 2 | Issue – 6 | Sep – Oct 2018

A Comparison Study Between Two Hydrogen Sensors

Dr. Albashir Zomrawi
Assistant Professor, College of Engineering, Karary University, Khartoum, Sudan

In this research work, a comparison study has been as the sensing material. A large number of hydrogen
carried out between Palladium (Pd) coated PMMA sensors based on palladium and palladium alloyed with
(Poly Methyl Meth acryl ate) optical sensor and other metals, are reported in the literature4-14 but to
Palladium thin films sensor that have been prepared date there is no single optical sensor that has all the
on glass substrates. PMMA were sputter coated with desired characteristics (such as low hydrogen
Palladium using a sputter coating facility offered by concentration (<1%) detection in the presence of
the He riot Watt University, during sputter coating the humidity with a response time of a few seconds).
target (palladium) is showered with argon gas such Palladium has been the focus of most
mo research groups
that atoms from the target are ejected by the ionized 13, 15because hydrogen is not only highly soluble in
gas and then deposited on the PMMA substrate. palladium but palladium also shows a high selectivity
Palladium thin films have been prepared on glass to hydrogen. In the presence of hydrogen, adsorption
substrates by vaporization deposition technique with occurs on the surface16, 17 of the palladium and
annealing temperature is around 600 600◦ C. Relative hydrogen dissociates into atoms. The hydrogen atoms
inertness of the sensors to relative humidity makes it penetrate the subsurface layers of the palladium metal
specific to detect hydrogen at low concentration. and palladium hydride is formed 11, 18. The
Target environments for the proposed sensors are fuel adsorption of hydrogen in the palladium lattice leads to
cell cabinets, industrial process plants, submarines, the expansion of the lattice but is dependent on the
nuclear fuel power generation and decom
decommissioning concentration of hydrogen ogen and the working
plants. temperature [3]. Hydrogen sensors exploiting the
Palladium/Palladium Hydride reaction are affected by
Results showed that optical characteristics of the humidity, whether based on optical or
prepared sensors are highly sensitive, but their electronic/catalytic detection, which poses difficulties
properties considerably vary when the measurements for operation in field or real life conditions. Gases
conducted in vacuum or in air. In the two sensors the being monitored require pre-conditioning
pre such as
response-recovery time of Pd materials
aterials to hydrogen drying, to facilitate sampling at low humidity, and the
gas characterized to be extremely short. sensor coating requires heating to maintain it at a
constant temperature [4].
Keyword: Micro electro mechanical systems,
Palladium, Poly Methyl Meth acryl ate (PMMA), II. MECHANISMS FOR HYDROGEN SENSING
Sensor, Spectrometer, Substrates, Thin-Film.
Film. Hydrogen sensor technology needs to satisfy three
basic requirements. These requirements are;
I. INTRODUCTION sensitivity, selectivity, and specificity [7].
Hydrogen, occupies aboutmoretethan90%ofthe
atmosphere “is a highly flammable gass and will burn Different approaches used to sense and detect hydro
at concentrations aslowas4%inair [1]. It is the lightest gen. Numbers of which used in industry such as gas
of elements and the smallest molecule; le; it, ttherefore, chromatography (GC), masss spectrometry (MS),
has the greatest endency to leak. Thus,, for a process catalytic bead (CB), and therm
mal conductivity.
ss safety application, a hydro gen leakk can be more
dangerous [8].Detection
Detection of hydrogen gas has been Semiconducting metal oxidee and CB sensors are
extensively investigated with various materials 11-3used popular solid-state technollogies, these, sensors

@ IJTSRD | Available Online @ | Volume – 2 | Issue – 6 | Sep-Oct

Oct 2018 Page: 329
International Journal of Trend in Scientific Research and Development (IJTSRD) ISSN: 2456-6470
employ heated catalysts to sense hydro dro gen. They Semiconductor (MOS), CB, electrochemical, and
require e heating to about 300°C to eenable surface Surface Acoustic Wave (SAW W) technology are used
actions that promote hydro ggen sensing. in the industry for several al years. Micro electro
Electrochemical sensors are basedd on known mechanical systems (MEMS) MS) and nanotechnology-
electrolytic reactions of hydro gen. Sens
nsors based on based devices for the measurrement of hydro gen are
catalytic combustion are generally non specific, there cent developments. Th hese developments are
electrochemical hydro gen sensors with liquid or solid mainly driven by the dem mands of the fuel cell
type electrolytes having leakage issuees. The hydro industry. Solid-state approacaches are gaining rapid
gen sensors based on thermal conductivvity, CB, metal popularity with in the industrry due to their low cost,
oxide, and electrochemical technologiesies require the low maintenance, replacemeents, and flexibility of
presence of oxygen for sensor operati ation. Oxygen multiple installations with min
plays a crucial role in promoting the ggrain boundary
formation in metal oxide sensor sand elect
electron transfer ‘Hydrogen-Specific
Specific Palladium-Based
Palladium Sensors are of
reactions in electrochemical sensors. three major classes of palladium-based
palladium hydrogen
sensors’ [3]. The most popular class of palladium-
The most promising solid-state technoology is based based sensors is based on palladium resistors. A thin
on a hydrogen-specific material, palla alladium, which film of palladium deposited between two metal
does not require oxygen for operatioon. Palladium- contacts shows a change in conductivity on exposure
based sensors are gaining wide popuularity in the to hydrogen due to the phase transition in palladium.
industry due to their reliability and highh specificity to The palladium Field- Effect Transistors (FETs) or
hydrogen. capacitors constitute is the second class, wherein the
sensor architecture is in a transistor mode or capacitor
APPROACHES TO configuration. The third class of palladium sensors
HYDROGEN SENSING includes optical sensors consisting of a layer of
Number of traditional approaches caan be used to palladium coated on an optically active material that
detect Hydrogen, these may include: transforms the hydrogen concentration to an optical
a. Thermal Conductivity (TC): is the most widely signal.
applied measuring principle for the determination
of hydrogen. The measuring principle is based on V. TYPES OF PALLADIUM HYDROGEN
the differences in thermal conductivity of the SENSORS
gases to be measured. A Thermal Conductivity Several types of palladium-based based hydrogen sensors
Detector (TCD) measures the concentration of a have been reported in the literature. The most notable
gas in a binary gas mixture by measuring the ones are based on Pd thin-film film resistors, FETs, Pd
thermal conductivity of the sample gas and nano wires, Pd nano particle networks, Pd nano
comparing it to the thermal conductivity of a clusters, and Pd nano tubes. Palladium Field-Effect
selected reference gas [7]. Sensors: ‘Hydrogen sensors based on the “field effect”
b. Gas Chromatography (GC): is also another widely of palladium have been investigated extensively in the
applied measuring principle for hydrogen literature’ [9]. ‘The field effect results due to the rapid
detection. The disadvantages of G Care long dissolution
tion of hydrogen in the palladium surface
response times (minutes) due to the arranged in a Pd–SiO2–Si Si configuration. The sensor
chromatography, time-intensive
intensive sample relies on an electric field resulting from the charge
preparation, consumable (carrier and calibration transfer between palladium and hydrogen on its
gases), and lab or-intensive
intensive handling procedures. surface. The FETs’ [7] and ‘metal–insulator–
An advantage, however, is the ability to measure semiconductor (MIS)’ [10] are the two major types of
other gases such as nitrogen, oxygen, and carbon device structures that have been studied for palladium-
dioxide in the presence of hydrogen. But, this adds based hydrogen sensing. Palladium is catalytically
time to the total analysis [7]. active, permeable to hydrogen, and can be readily used
in FET and MIS devices.
IV. SOLID-STATE APPROACHES S TO HYDRO a. Palladium-BasedBased Resistors: ‘Thick-
‘Thick and thin-film
GEN SENSING palladium-based
based resistors have been reported for
A wide variety of solid-state sensors based on hydrogen sensing’ [6]. The thick-film
thick device uses
hydrogen-specific palladium, Metal Oxide printed palladium paste on a ceramic substrate in

@ IJTSRD | Available Online @ | Volume – 2 | Issue – 6 | Sep-Oct

Oct 2018 Page: 330
International Journal of Trend in Scientific Research and Development (IJTSRD) ISSN: 2456-6470
a four- resistor net work. Two opposed resistors to cheek its crystallization. The coated glass substrate
are covered
overed to isolate them from the ambient (Palladium thin films) placed inside the developed
atmosphere. ‘The exposure of the uncovered polymer square test chamber of 50 mm square base
resistors to hydrogen results in a change in and of 75 mm height with the top removable cover.
resistivity of the thick-film
film material and a shift in The effective volume of the chamber was 187500
the balance point of the bridge, which can be mm3; it has an inlet to allow the test gas to flow in.
scaled to the hydrogen concentration.
ntration. The thin
thin- White photo diode that represent
esent the
t light source used
film device is equivalent in design to the thick in the sensor,
film; here, much thinner films (typically vacuum
deposited) are used as the resistors. Thin Thin-film CCS Spectrometer used to measure
m transmitted light
palladium detectors have been prepared by while vacuum unit used to evacuate the test chamber.
depositing palladium through electron beam The gauge pressure utilized to measure the current
evaporation’ [11], ‘RF magnetron sputtering’ [5], pressure of the chamber.
‘micro con-tact printing’ [12], and wet
electrochemistry. Most palladium resistors have Cylinder of hydro gen gas of a known con cent ration
fouling issues on the palladium surface due to assisted the flow through th he test chamber during
impurities and pollutants in, or reaction with the measurement. t. Recorded data can be processed by a
air. The fouling on the palladium surface can be PC as illustrated in the figure.
reduced by the addition of a second metal (alloy)
to palladium.
b. B. Palladium-Coated Fiber Optic Sensors: A
fiber optic hydro gen sensor consist sofa
palladium coat in gat the en do fann optical fiber
that senses the presence of hydro gen en in air. When
the coating reacts with the hydro ggen, its optical
properties are changed. Light from a central
electro-optic control unit is projected
ected down the Fig.1: Palladium thin films sensor component
optical fiber where it is either reflected
ected from the
sensor coating back to central opticaltical detector or
is transmitted to another fiber er lea
leading to the
central optical detector. A chhange in the
afetyby removing all electrical poower from the
test sites and reduces signal-process ssing problems
by minimizing electromagnetic inn te reference.
The fiber optic hydro gen sensor scan be
fabricated using a palladium-coated
coated single
single-mode Fig.2: Palladium thin films sensor setup
tapered optical fiber . The attenuation
enuation change of
the fiber-mode when the device was exposed to On the other hand, Palladium coated (PMMA)
hydro gen is used to detect and measure hydro gen optical sensor set up consisted of two gas cylinders
concentration in gaseous atmospheres. ; a pure hydrogen cylinder and a carrier gas
cylinder which contained either nitrogen or air. The
VI. EXPERIMENTAL SETUP coated PMMA substrate was placed inside a blacked
The Palladium thin films sensor system consists basic out stainless steel
eel chamber in which the gases were
ally of seven components including chhamber, white mixed. Transmission was measured using an Ocean
photo diode, spectrometer, vacuum unit, gauge Optics S2000 spectrometer and reflection was also
pressure, cylinder of hydro gen gas, annd computer as measured using an Ocean Optics USB 2000
shown in schematic ally in figure(1 (1). Figure (2) spectrometer. In all the experiments the light source
illustrates the sensor setup . used was a white tungsten halogen
ha lamp. Figure (3)
A sample of Palladium coated glasss slide sensor hereunder, shows a schematic diagram of PMMA
prepared first to detect hydro gen, andd te
tested by X-ray optical sensor set up.

@ IJTSRD | Available Online @ | Volume – 2 | Issue – 6 | Sep-Oct

Oct 2018 Page: 331
International Journal of Trend in Scientific Research and Development (IJTSRD) ISSN: 2456-6470
The carrier gas was constantly cycled through the 0.3,-0.2and-0.1bar. Frequency y against Trans mitted
chamber and the system was allowed to equilibrate light intensity graphs were produced
prod for each reading.
to this environment and the different concentrations The six graphs were then com mbined to get her in one
of hydrogenn gas were introduced in the system. The diagram with a back ground d graph representing-0.7
concentration of hydrogen and the level of relative pressure without Hydro gen.
humidity were monitored and controlled by using
MKS 1179A mass flow controllers. After each Figure (4) and figure (5) beloww represent the resultant
different hydrogen concentration, the sensor was combinedgraphsPd1 and Pd2 for fo both sample tests.
allowed to recover to initial condition in the carrier
gas. Transmission and reflection spectra were
recorded for each cycle of hydrogen and also a time
acquisition spectrum was recorded to investigate the
behavior of the sensor over time under the influence
of varying hydrogen concentration and varying
concentration of Relative Humidity.

Fig.4: Combined graphs of the first sample.

Fig.3: Experimental set up of Palladium coated

PMMA optical sensor.


In palladium thin film sensor, two testes
tes were carried
out to examine the sensors. In both testts, results were
obtained through adopting the following steps:
a. Opening the test chamber to place the palladium
thin film sensor on the sensor holder and close it. Fig.5: Combined graphs of
o the second sample.
b. The necessary light source was then directed by
optical fiber and allowed to pass through the From figures (4) and (5) obtain edbove it can be noted
sample to the spectrometer. that by increase con cent rati
ation of hydro gen gas in
c. The rotary pump then switched on to evacuate the the test chamber, transmitted
itted light is also increased
test chamber to about -0.7 bars. that means the palladium th hin film sample success
d. Next, the hydrogen gas of a known con cent rate fully detect hydro gen gas.. Also, it can be noted that
ion allowed topass from the cylinder through the the suitable wavelength that can be used to detect
special inlet to the test chamber by opening the hydro gen gas is a visible anda in the regionof500-
cylinder valve. 650nm.
e. Test chamber pressure measured by observing the
gauge pressure. For Palladium coated PMMA optical sensor a plot of
f. Spectrometer was then detected and analyzed transmitted spectral power against wavelength for
transmitted signals and sent the data to the varying concentration of relative humidity ranging
computer. from 0 to 100% plotted as shown in figure (6). The
response of the sensor to relative Humidity was
Numbers of measurements were carried out in invariant as there was no change in transmitted
different pressures. Six readings weree observed for spectral power for the different concentrations of
each sample test includingpressuresoff-0.6,-0.5,-0.4,- Relative Humidity.

@ IJTSRD | Available Online @ | Volume – 2 | Issue – 6 | Sep-Oct

Oct 2018 Page: 332
International Journal of Trend in Scientific Research and Development (IJTSRD) ISSN: 2456-6470
This research work compares between Palladium (Pd)
coated PMMA (Poly Methyl Meth acryl ate) optical
sensor and Palladium thin films sensor that have been
prepared on glass substrates. After analyzing
analyzi results of
each experiment carried out it was found to be that
optical characteristics of the prepared sensors are
highly sensitive, but their properties considerably vary
when the measurements conducted in vacuum or in air.
In the two sensors the responsense-recovery time of Pd
Fig. 6: The spectral power distribution at each materials to hydrogen gas characterized to be
extremely short.
Relative Humidity concentration.

Previous experiments showed that in the presence of REFERENCES

1. Al basher Zomrawi, A.. M. Awadelgied,
Awadelgied S. F.
relative humidity there is a 50% change in intens
intensity of
Abdalah, K. Al Naimee, (2016), “Palladium Film
the transmission signal and it is difficult to distinguish
Chemical Sensor”, International Journal of
between hydrogen detection and relative humidity.
Results also showed that the proposed sensor operates Innovation in Science and Mathematics Volume
unaffected by the relative humidity concentration. A 2, Issue 2, ISSN (Online): 2347–9051.
possible explanation for the observed results was that 2. Cassidy, J., Pons, S. and Janata, J. (1986),
the polymeric material used as the substrate, despite “Hydrogen response of palladium coated
having hydrophilic carbonyl groups, suspended gate field effect transistor”, Analytical
8), 1757, 1986.
Figure (7) represents the transmitted and reflected 3. Lewis, F. A., “The Palladium Hydrogen System”,
spectral power distribution of a PMMA substrate Academic Press, London, 1967.
sputter coated, and illuminated using a white tungsten
halogen light source. The sensor was initially 4. M.A.Nabeerasool1, P. J. Scully1, J. Vaughan1, R.
subjected too N2 to obtain a baseline, and then exposed Maier21ThePhoton Science Institute, the
to varying concentration of H2 while recovering in the University of Manchester.
carrier gas after each change in hydrogen 5. Oh, Y.-s., Hamagami, J. -i., Watanabe, Y.,
concentration. The sensor had a low detection limit of Takata, M. and Yanagida, H.(1993), “Palladium
0.35% H2. However the sensitivity limited by the thin film hydrogen detector”, Journal of the
mass flow controller
ontroller and by the working temperature. Ceramic Society of Japan, 101(1174), 618–620.
The sensitivity of the sensor depended on the surface
to volume ratio and it was observed that at at1% H2 the 6. Pitts, J.R., Liu, P.,, Lee, S.-H.
S And Tracy,
sensor was at least twice as sensitive in reflection C.E.(2000), “Interfacial in stabilityin hydrogen
(526 AU/%) as in transmission (219 AU/%). Further sensors”, Pro- ceedings of the DOE Hydrogen
experi ments shown that the sensor works faster in air Program Review, Available at http://www1.eere.
than in nitrogen, Energy. Gov/hydrogen and fuel cells/pd
7. Ram B. Gupta (2009), “Hydrogen
“ Fuel
Production, Transport, and Storage”. Edited by
Taylor & Francis Group, LLC.
8. Ram B. Gupta (2009),(2009) “Hydrogen Fuel
Production, Transport, and Storage”. Edited by
Taylor & Francis Group,, LLC-2009.
9. Robins, I., Ross, J. F. and Shaw, J. E. A. (1986),
Fig.7: (a) transmitted spectral power distribution and “The logarithmic response of palladium-gate
(b) reflected power distribution of a Palladium metal” insulator-silicon
silicon field-effect
field transistors to
coated PMMA exposed to varying concentration of hydrogen, Journal of Applied Physics, 60(2), 843.

@ IJTSRD | Available Online @ | Volume – 2 | Issue – 6 | Sep-Oct

Oct 2018 Page: 333
International Journal of Trend in Scientific Research and Development (IJTSRD) ISSN: 2456-6470
10. Salomon’s son, A., Eriksson, M. and Dan net UN, 12. Villatoro, J., D´ iez, A., Cruz, J. L. and Andre’s,
H. (2005), “Hydrogen interaction with platinum M.V., (2001), “Highly
Highly sensitive optical hydrogen
and palladium metal–insulator–semiconductor
semiconductor sensor using circular Pd-coated
Pd single mode
devices”, Journal of Applied Physics, 98, 014505. tapered fiber, Electron”, 37, 1011.
11. Thomas, R. C. and Hughes, R. C. (1997), 13. Wolfe, D. B., Love, J. C.., Paul, K.E., Chabinyc,
“Sensors for Detecting Molecular Hydrogen M. L. And Whit esides, G. M., (2002),
Based on Pd Metal Alloys”, Journal of “Fabrication
Fabrication of palladium-
palladium based microelectronic
Electrochemical Society, 144(9), 3245. devices by micro contact printing”, Applied
Physics Letters, 80, 2222.

@ IJTSRD | Available Online @ | Volume – 2 | Issue – 6 | Sep-Oct

Oct 2018 Page: 334