Sensors and Actuators B 113 (2006) 830836

Design of a portable optical sensor for methane gas detection

Crawford Massie a , George Stewart a, , George McGregor b , John R. Gilchrist b
a

Department of Electronic and Electrical Engineering, The University of Strathclyde, 204 George Street, Glasgow G1 1XW, UK b Gas Measurement Instruments Ltd., Inchinnan Business Park, Renfrew PA4 9RG, UK Received 18 January 2005; received in revised form 11 March 2005; accepted 14 March 2005 Available online 23 May 2005

Abstract A detailed investigation has been carried out on the design of a low-cost portable optical sensor for methane detection with a sensitivity of 1% of the Lower Explosive Level (LEL) for methane (500 ppm) and able to operate in harsh environments with temperature variation between 20 and 50 C. The sensor design is based on the use of near-IR LEDs operating around the overtone absorption lines of methane at 1660 nm using a stainless steel tube to direct the light through the gas to the detectors. Various congurations of source/detector layout have been examined to provide appropriate reference and signal paths in order to achieve reliable methane detection at LEL levels in the presence of temperature variation. An optimum design has been identied using two detectors with appropriate optical ltering and with temperature stabilisation of the source and detectors. Based on this design, a prototype instrument has been demonstrated with an ultimate sensitivity of 0.2% LEL methane (100 ppm). 2005 Elsevier B.V. All rights reserved.
Keywords: Methane sensor; Optical gas sensor; Portable gas sensor; Hydrocarbon gas sensor

1. Introduction Detection of methane gas is extremely important for safety reasons in the oil and gas industries, in water treatment plants, in landll sites and in commercial or domestic environments, where methane gas may lter up through the ground and create an explosion hazard (the lower explosive limit, LEL, for methane is 5% by volume methane gas). Portable gas detectors for locating gas leaks are clearly important in a number of these applications, but must be of a low-cost design for widespread use and availability. The established method for methane gas detection is the catalytic sensor [13] which, however, is not methane-specic, as any gas whose ignition is catalysed by the pellistor will be detected. Additionally, catalytic sensors do not operate correctly in low-oxygen environments and can be poisoned. Consequently, such detector systems may require frequent functional checks. It is therefore of commercial interest to develop portable gas sensors, based on optical techniques [4]. Optical sensors,

Corresponding author. Tel.: +44 141 548 2887; fax: +44 141 548 2926. E-mail address: g.stewart@eee.strath.ac.uk (G. Stewart).

based on semiconductor sources, have the potential advantages of: (i) intrinsically safe, (ii) ability to detect a specic gas by selection of appropriate wavelengths, (iii) able to operate in zero-oxygen environment (e.g. for purging of pipe lines), and (iv) low cost of ownership, since the gas-detection principle is a physical process (not a chemical reaction), and therefore, poisoning of the sensor is not an issue (although dirt/contamination on the optics needs to be considered in the sensor design). For hydrocarbon gases, such as methane, the strongest optical absorption occurs in the mid-IR region, around 3.3 m, but the use of a broadband source in the mid-IR to detect methane [5] has cost and performance limitations. For example, a number of hydrocarbon gases have absorption bands/lines in the same spectral region, so a mid-IR system will often respond to other hydrocarbons, and hence, they are generic hydrocarbon detectors rather than methane-specic. Mid-IR detectors are relatively expensive and are often cooled [6] in order to achieve an enhanced signal-to-noise ratio, which increases the power consumptiona disadvantage for portable sensors. One way to overcome some of these problems is to operate the sensor at overtone absorption lines in the near-IR,

0925-4005/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2005.03.105

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around 1665 nm for methane [79]. In this spectral region, inexpensive LEDs and detectors are widely available, and detectors operate with low noise at room temperature (DFB laser sources are preferred [7] but are expensive for portable sensors). The chief drawback is that the absorption strength of second harmonic lines in the near-IR is at least two orders of magnitude weaker than fundamental mid-IR absorption lines. This presents a challenge in sensor design, especially when a considerable range of environmental temperature is involved. The objective of this work was therefore designing and development of an inexpensive, rugged, portable, near-IR methane sensor, with sufcient sensitivity for commercial application (<1%LEL or equivalently <500 ppm1 ), and able to operate over an environmental temperature range of 20 and +50 C. Hence, although the basic scientic principles are well-known, the practical engineering design requires a number of factors to be considered in the design including instrument size, cost, power consumption and immunity to environmental conditions.

2. Theoretical description of absorption from near-IR LED sources We assume that the LED has an intensity distribution I(), with wavenumber , as illustrated in Fig. 1(a). If the total intensity emitted by the LED is designated by I0 , then dening a normalised f (v) = I (v/I0 ), we can write:

I0 =
0

I ()d = I0
0

f ()d

(1)

Fig. 1. (a) General intensity distribution of LED against wavenumber; (b) simple block approximation for the intensity distribution of the LED along with multiple absorption lines; (c) effect of strong absorption on LED source distribution.

where
0

f ()d = 1.

If the output of the LED is passed through an absorbing gas in a cell of length l, and assuming that the absorption is weak and does not change the source distribution, the output intensity from the cell is given by: I = I0 exp{eff Cl}

(2)

where the effective absorption coefcient is dened by: eff = N0

0

()f ()d

(3)

here, () is the absorption cross-section per molecule of the gas, N0 = 2.5 1019 molecules/cm3 is the atmospheric concentration of molecules at 25 C, and C is the gas concentration fraction (C = N/N0 , 0 < C < 1, C = ppm/106 or Cl = (ppm m)/106 , with N as the concentration of gas molecules per unit volume). Note that Eq. (3) represents the
For methane, concentration in ppm is given by multiplying the percentage of LEL by 500.
1

overlap integral between the source distribution and the absorption cross-section prole. Absorption data and spectral line positions in the nearIR are available on the Hitran database [10,11] for methane (CH4 ), but not for other hydrocarbon gases, such as, ethane (C2 H6 ), propane (C3 H8 ) and butane (C4 H10 ), which are important to consider in the design of a methane-specic sensor, as discussed later. Spectral line positions for these gases were, therefore, measured experimentally on a spectrometer, and are shown in Fig. 2. For methane, Fig. 2 shows the absorption lines around 1660 nm, with the P, Q and R branches. The Q branch contains a number of individual lines which are not resolved in this diagram; the strongest is the Q6 line at 1665.5 nm with an absorption of = 0.25 cm1 at the line centre [7]. The Hitran database [10,11] provides information on line strengths, and gives an integrated line strength2 of S = 5.172 1020 cm2 molecule1 cm1 for all the methane lines between 1637 nm (2 = 6107 cm1 ) and 1697 nm (1 = 5891 cm1 ).
2

The line strength is dened by S =

()d.
0

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Fig. 2. Measured absorption bands and line spectra in the near-IR for several hydrocarbon gases.

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We can quickly estimate the effective absorption coefcient with the above data by assuming an idealised spectral distribution, as shown in Fig. 1(b), for an LED with 60 nm spectral width and centred on 1667 nm. In this case, f (v) = 1/(v2 v1 ), and the integral in Eq. (3) takes the simple form: eff N0 = (2 1 )
2

()d =
1

N0 S (2 1 )

(4)

Substituting values gives an effective absorption coefcient of 0.006 cm1 or, from Eq. (2), approximately 0.15% change in light intensity on passage through a 10 cm cell length with 50%LEL methane (approximately 40 times weaker than using a narrow-linewidth laser source centred on the Q6 line). However, the effective absorption coefcient can be improved by appropriate ltering of the LED, blocking spectral regions that are not affected by gas while targeting strongly absorbing regions, such as the central Q-band lines. Effective absorption coefcients for ltered sources can be estimated as above, using the HITRAN database which provides individual line strengths (hence, the integrated line strength for all lines within the bandwidth of a lter through summation). For example, for 20 and 7 nm lters, both with centre wavelength on the Q6 line at 1665.5 nm, the integrated line strengths are S20nm = 2.65 1020 and S7nm = 2.14 1020 cm2 molecule1 cm1 , giving effective absorption coefcients of 0.0092 cm1 and 0.0212 cm1 , respectively. The theoretical plot of Fig. 3 for lters, centred on 1665.5 nm, shows the marked effect on the effective absorption coefcient, as the lter linewidth is reduced due to the dense spacing of lines within the Q-band. In practice, the lter tolerances, angular alignment and temperature effects, all become more critical, as the lter linewidth is reduced, and hence, a compromise is often necessary between sensitivity, cost and stability of the nal instrument. With these considerations in mind, a 7 nm width was used in this work, as discussed later in Section 3. This

is predicted to give 0.6% change in light intensity on passage through a 12 cm cell length with 50%LEL methane and similar values were obtained in practice. It should be noted that the above theoretical description is based on the condition that Cl 1 for each absorption line within the spectral bandwidth considered. For high concentrations and/or long path lengths, the strongest absorption lines may deplete the available light intensity at their respective wavelengths, as shown in Fig. 3(c), and the LED intensity distribution is no longer constant along the cell; so, as a result, the absorption signal does not change linearly with concentration. However, the work here is concerned with obtaining sufcient sensitivity for LEL levels of methane, so the assumption of Cl 1 is justied, as for the strongest Q6 line with = 0.25 cm1 and 100%LEL (5% methane) in a 12 cm length cell, we have Cl 0.1.

3. Portable sensor design options Various LED and detector congurations were considered in the development of the near-IR portable methane detector, all based around the same gas detection cell, as shown in Fig. 4. The cell consists of a 12 cm long polished stainless steel tube with an internal diameter of 1 cm, providing a sealed volume through which gas can be drawn. The multiple reections from the polished walls of the tube cell provide a light pipe that guides light from the source to the detector, greatly increasing the amount of light reaching the detector and increasing the effective absorption path length of the cell. For all cases, a phase-sensitive detection (PSD) method was used for signal extraction to attain a small detection noise-bandwidth of 1 Hz. By 1800 out-of-phase pulsing of the LEDs (or inversion of one output signal for the single LED/two-detector system), an active (gas) signal and a reference signal is created consisting of pulses of similar magnitude but opposite phase. The two signals are appropriately scaled and summed, giving a xed DC level (with no target gas present in the cell). When gas is present, the signals will be unbalanced, giving an output at the pulse modulation frequency (1 kHz), and hence, the PSD produces an output voltage related to the gas concentration. The rst design considered was based on a dual LED single detector system, as shown in Fig. 4(a). Here, one of the LEDs is chosen to emit at wavelengths outside the absorption band of the target gas (methane), and provides the optical reference signal to compensate for changes in optical intensity due to dirt or condensation, etc., in the cell, since both LEDs will be affected in a similar way. Experimental tests on this conguration, however, revealed problems in sensor operation over the required temperature range. This arises from the different temperature coefcients of the two LEDs (which are, of necessity, different models, since they operate at different wavelengths), which can lead to false signals from temperature change. Fig. 5 shows the temperature

Fig. 3. Effective absorption coefcient as a function of lter line-width for lters centred on 1665.5 nm.

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Fig. 6. (a) Photograph of a standard detector and the lensed detector; (b) comparison of absorption from 100% methane using lensed and unlensed detectors for single and double path length congurations.

Fig. 4. Various congurations for source/detector layout in the sensor cell. (a) Dual source, single detector; (b) dual source with stabilisation detector; (c) folded path; (d) single source, dual detector.

characteristics of the two LEDs used, namely, Hamamatsu L8245 (1650 nm) and L7866 (1300 nm reference), giving temperature coefcients of approximately 0.0372 dB/ C for L8245 and 0.0242 dB/ C for L7866. One possible solution to this problem is to introduce a second detector, as

Fig. 5. Relative radiant output against ambient temperature for Hamamatsu LEDs L8245 (1650 nm active LED) and L7866 (1300 nm reference LED).

shown in Fig. 4(b). This second detector, positioned at the LED end of the cell, monitors the output of both LEDs (in an area shielded from gas). If there is any intensity difference between the LEDs, the stabilisation detector circuitry feeds a signal back into the reference LED-drive circuitry to adjust the drive current and compensate for the intensity difference. By using this process, the output of both LEDs can be maintained at the same intensity. However, for this system to operate correctly, the two detectors will have to track each other with temperature, and because the detectors are at opposite ends of the cell, this is not easily achievable. Also, the number of components and cost is increased with this approach. Because temperature drift may be a problem and absorption by the gas is very weak in the near-IR, it is clearly benecial if the absorption signal can be improved through an increased path-length without having to change dimensions of the stainless steel cell (and the nal instrument). Hence, the conguration shown in Fig. 4(c) was investigated, where the detector and the source are positioned at the same end of the cell, with a mirror at the opposite end of the cell, apparently doubling the available path length. Experiments were carried out on this layout, using a standard G8421-03 InGaAs photodiode as the detector, and then repeated with a G842103 photodiode that used a lens instead of a window on the photodiode can, as shown in Fig. 6(a). The mirror used was a 15 60 mm concave mirror from Edmund Scientic. Results

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from tests are shown in Fig. 6(b), where it can be seen that very little improvement was observed for the standard detector, but the lensed detector showed an increase by a factor of 1.7. The reason for these results lies in the acceptance angles of the detectors. The lensed detector mainly accepts light that has travelled directly down the cell and back again. However, the unlensed detector will pick up a substantial amount of back-scattered light from inside the cell which does not have a large path-length through the gas. The nal conguration and the one considered to be the best option is illustrated in Fig. 4(d), consisting of a single LED and two detectors, each with a narrowband spectral lter to create reference and active channels. The active lter is chosen to have a spectral distribution over a strongly absorbing region of methane absorption lines, whereas the reference lter has a spectral distribution outside the absorption lines. As discussed in Section 2, the narrowband lter used for the active channel will also increase the effective absorption coefcient, thereby increasing the measured absorption. Moreover, this conguration uses two detectors of the same model number and at the same position within the cell. Common changes in detector performance with temperature will tend to cancel, when the reference and active signals are compared, and hence, temperature sensitivity should be less of a problem than a dual LED system. We shall now discuss the experimental design and test of this system in some detail.

4. Design and test of the dual detector system The dual detector system was constructed, using a single Hamamatsu L8245 LED and two Hamamatsu InGaAs PIN photodiodes, G8371-01. In the design, a number of factors need to be considered carefully, including: (i) the wavelength and bandwidth chosen for the lters to create the active and reference channels, and (ii) temperature stability of the sensor. For the active lter, the target wavelength should be within the dense Q-band absorption line structure, centred on 1665.5 nm (see Fig. 2), with a narrow bandwidth of a few nanometres or less (see Fig. 3). However, in practice, other factors limit the choice in lter specications, for example, cost of manufacture, temperature effects on the centre wavelength, tilt sensitivity, etc. The cost of manufacture increases with narrowing bandwidth and tighter tolerances. The manufacturing tolerances are important because if the lter bandwidth is sufciently narrow, for example 3 nm, and the tolerance on the lter centre wavelength is sufciently large, for example 1.5 nm, then some lters within a batch production may include very little of the Q-band absorption lines. For our sensor, the specication chosen for the active lter had a centre wavelength of 1665.5 1.5 nm with a bandwidth of 7 0.15 nm. This was found to provide a reasonable compromise in terms of tolerances, cost, and temperature sensitivity, and gives considerable improvement in absorption over a non-ltered LED (see Fig. 3), but is still wide enough to have a satisfactory performance if the

lter is manufactured at the edge of the central wavelength tolerance. Similar concerns apply for the reference lter, but an additional point to be considered is the behaviour of the LED spectral distribution with temperature. If the position of the reference lter is badly chosen, a situation similar to the dual LED set-up could arise, where the active and reference channel behave very differently with temperature. To be safe, the reference lter was chosen to have its centre wavelength close to that of the active lter (1670 1.5 nm), but far away enough and with a sufciently narrow bandwidth (3 nm) to avoid the Q-band absorption lines. In order to make the sensor methane-specic, and to avoid cross-sensitivity to other gases, it is also important that the wavelengths chosen for both the active and reference LEDs lie outside the absorption lines or bands of other hydrocarbon gases (ethane, propane and butane) that may be present when monitoring gas leaks in domestic or commercial environments. Careful examination of the experimentally-measured spectral data of Fig. 2 shows that the choice of wavelengths for the LEDs (1665.5 and 1670 1.5 nm) does avoid absorption by the other gases and this was conrmed through independent tests performed during the design stages of the sensor. As noted, temperature stability is important to minimise drift and false alarms. To improve the temperature characteristics of the sensor, the two detectors were housed in a single aluminium block to increase the thermal mass and ensure the same temperature at both detectors. The block was heated using a 5.6 , 0.5 W resistor to raise the temperature above ambient to 35 C and was maintained at this temperature by a control circuit using a thermistor sensor. Also the cell was sealed using sapphire windows which also shield the LED and detectors from the cooling effect created when gas is drawn through the cell. Fig. 7 shows the fully assembled prototype portable sensor. For the instrument, the electronic gain was set so that 01 V range corresponded to 0% to 100%LEL methane.

Fig. 7. Photograph showing the fully-assembled prototype portable methane sensor.

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Johnstone of Strathclyde University are gratefully acknowledged.

References
[1] P.T. Mosely, B.C. Toeld (Eds.), Solid-State Gas Sensors, Adam Hilger, Bristol, 1987, pp. 1750. [2] P. Krebs, A. Grisel, A low-power integrated catalytic gas sensor, Sens. Actuators B: Chem. 1314 (1993) 155158. [3] H. Debeda, L. Dulau, P. Dondon, F. Menil, C. Lucat, P. Massok, Development of a reliable methane detector, Sens. Actuators B: Chem. 44 (1997) 248256. [4] P.T. Mosely, J.O.W. Norris, D.E. Williams (Eds.), Techniques and Mechanisms in Gas Sensing, Adam Hilger, Bristol, 1991, pp. 234259. [5] A. Krier, V.V. Sherstnev, Powerful interface light emitting diodes for methane gas detection, J. Phys. D: Appl. Phys. 33 (2000) 101106. [6] C.H. Wang, J.G. Cowder, V. Mannheim, T. Ashley, D.T. Dutton, A.D. Johnson, G.J. Pryce, S.D. Smith, Detection of nitrogen dioxide using a room temperature mid-infrared InSb light emitting diode, Electr.Lett. 34 (3) (1998) 300301. [7] B. Culshaw, G. Stewart, F. Dong, C. Tandy, D. Moodie, Fibre optic techniques for remote spectroscopic methane detectionfrom concept to system realisation, Sens. Actuators B: Chem. 51 (1998) 2527. [8] G. Stewart, C. Tandy, D. Moodie, M.A. Morante, F. Dong, B. Culshaw, Design of a bre optic multi-point sensor for gas detection, Sens.Actuators B: Chem. 51 (1998) 227232. [9] G. Whitenett, G. Stewart, K. Atherton, B. Culshaw, W. Johnstone, Optical bre instrumentation for environmental monitoring applications, J. Opt. A: Pure Appl. Opt. 5 (2003) S140S145. [10] L.S. Rothman, C.P. Rinsland, A. Goldman, S.T. Massie, D.P. Edwards, J.-M. Flaud, A. Perrin, C. Camy-Peyret, V. Dana, J.-Y. Mandin, J. Schroeder, A. McCann, R.R. Gamache, R.B. Wattson, K. Yoshino, K.V. Chance, K.W. Jucks, L.R. Brown, V. Nemtchino, P. Varanasi, The HITRAN molecular spectroscopic database and HAWKS (HITRAN atmospheric workstation, 1996 edition, J. Quant. Spectrosc. Radiat. Transfer 60 (5) (1998) 665710. [11] L.S. Rothman, R.R. Gamache, A. Goldman, L.R. Brown, R.A. Toth, H.M. Pickett, R.L. Poynter, J.-M. Flaud, C. Camy-Peyret, A. Barbe, N. Husson, C.P. Rinsland, M.A.H. Smith, The HITRAN database, 1986 edition, Appl. Opt. 26 (19) (1987) 40584097.

Fig. 8. Time response of the instrument to 1.6%LEL and 50% LEL methane.

To further improve the stability of the reading, output signals were averaged over 32 samples through software ltering. A time response trace of the instrument output for 1.6%LEL (800 ppm) and 50%LEL methane is shown in Fig. 8. The magnitude of change for 1.6%LEL is 40 mV, and the change in signal for 50%LEL is 580 mV. The ultimate sensitivity of the detection system is limited by the signal to noise ratio and was determined to be 0.2%LEL (100 ppm).

5. Conclusion In this paper, we have described in detail the design and construction of a low cost, rugged, portable, methanespecic sensor. The optical sensor has potentially a low cost of ownership compared with the standard pellistor sensor and the component cost is relatively low through use of standard LEDs and detectors operating in the near-IR region around 1660 nm. However, due to the low absorption from overtone absorption lines in the near-IR, the main challenge is to achieve the required sensitivity over a wide temperature range of 20 C to +50 C and the best design option for achieving this has been identied. A prototype instrument has been constructed with a sensitivity down to 0.2%LEL (100 ppm). The knowledge gained from this investigation provides a good basis for the development of portable sensors for other hydrocarbon gases such as ethane, propane and butane and for the development of portable laser-based systems for higher sensitivity.

Biographies
Crawford Massie graduated with a BSc(Hon) in Physics from the University of Paisley in 1998, and an MSc in Lasers & Optoelectronics from the University of St. Andrews in 1999. He worked as a patent analyst with Derwent Information before taking up an Associate Post with Gas Measurement Instruments (GMI) Ltd. under the Knowledge Transfer Partnership (KTP) programme with the University of Strathclyde, in 2002. George Stewart is currently a Reader at the University of Strathclyde, Glasgow. He was awarded a BSc Degree with First Class Honours in 1974, and a PhD degree for research on integrated optics in 1979, both from the University of Glasgow. He was appointed as a Research Fellow at the University of Glasgow until 1985, and then joined the Photonics Group at Strathclyde University to work on bre optic components, sensors and bre lasers. Dr. Stewart is the primary author of ve chapters in various specialist textbooks and is author/co-author of more than 100 technical and scientic papers in the eld of bre and integrated optics.

Acknowledgments The authors gratefully acknowledge the nancial support provided through a Knowledge Transfer Partnership (KTP3876) between The University of Strathclyde and Gas Measurement Instruments Ltd. Assistance provided by Professor G Duxbury in obtaining spectral data for gases and technical discussions with Professor B Culshaw and Dr W