A Review of Optical Fibre Ethanol Sensors: Current State and Future Prospects
Abstract
:1. Introduction
2. Optical Fibre Sensing Methods
2.1. Absorption-Based Sensors
2.2. Externally Modified Interferometric Sensors
2.3. In-Fibre Grating Sensors
2.4. Plasmonic Sensors
3. Current Status and Future Prospects of Optical Fibre Ethanol Sensors
- Targeting specific applications is crucial in bringing the technology to a real-world implementation. Being a good target analyte, it is necessary to explore and realise the application-specific requirements where ethanol concentration measurement is an important parameter, e.g., in biofuel production and processing, general fuel monitoring, the food and beverage industry, the paints and varnishes industry, medical diagnostics, and in the cosmetics industry. A specific example is evident in the case of bio-ethanol production using biomasses, specifically algae. There are very stringent requirements for specific sensitivity and resolution attainment, temperature stability and selectivity for sensing purposes as well as the ability to operate in real-time, which are crucial to avoiding sample loss and long lead time offline analysis [41,62]. It is clear that optical fibre sensors have a significant role to play in providing solutions in this scenario.
- In many cases of industrial production and/or processing, high-sensitivity/ultra-low-level ethanol sensing is a fundamental requirement. Hence, many researchers have focused on improving the sensitivity of optical fibre ethanol sensors by seeking improvements in materials, coatings as well as sensor structures. However, temperature cross-sensitivity and/or cross-sensitivity caused by other chemical species in the measurand solution are also significant issues. Some researchers have formulated techniques to mitigate temperature cross-sensitivity, including an inline C-shaped open-cavity FPI [68], a combination of FP cavity and Michelson interferometry [69], micro grooved FBG [42], a combination of FBG and LPG for simultaneous temperature and RI measurement [37] and etched FBGs [84]. Cross-sensitivity due to other chemicals can be minimised or avoided by improving the selectivity of sensors and some work has also been reported for improving selectivity by modifying POF with CNTs [56], by combining interferometric and LSPR techniques [72] and by using ethanol-selective enzymes [94]. However, these sensor systems exhibit other drawbacks such as the use of specialised essential non-commercial parts, complex interrogation methods, low mechanical strength, narrow measurement range and limited sample-by-sample measurement. It is important to state here that some of those drawbacks may be irrelevant for some applications, depending on their specific requirements. Therefore, future research is likely to be focused on achieving high sensitivity combined with high selectivity and temperature compensation of optical fibre ethanol sensors.
- Reusability of optical fibre ethanol sensors, specifically when they are coated with novel 2D materials and/or precious metals, is becoming increasingly important. In the case of SPR chemical sensors, some reusability techniques are explored such as removing the immobilised histidine-tagged peptide (HP) layer using imidazole (IM) on Ni metal to regenerate the sensor surface [105], by cutting and polishing the sensor tip to regenerate the surface [106] and by exposing the sensor to ethanol for repeated cycles [107] to demonstrate the reproducibility of results.
- Distributed optical fibre sensing techniques for industrial measurement have gained significant attention during the last 10 years, which has culminated in many commercial systems becoming available (e.g., Luna [108] and OZ Optics [109]). Distributed optical fibre sensors are currently being used in several industrial applications, e.g., in oil and gas exploration, and in large structure monitoring. This technology certainly has scope for future measurements covering large scale ethanol industrial production and other chemical processing applications [110]. However, interrogation of distributed optical fibre sensors is complex and the instrumentation is currently expensive. Consequently, their uses are currently confined to a few ‘high end’ applications, e.g., where very large numbers of sensing points are required and non-optical measurement is not feasible. Research in this direction in combination with real-time, robust, sensitive and selective optical fibre ethanol sensing can help realise the Industry 4.0 requirements of real-time sensing and data collection to develop a digital twin of the facilities to predict yield and future demands of ethanol in industrial production and processing.
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Ethanol Measurement Techniques | Advantages | Disadvantages |
---|---|---|
Enzymatic method | Selectivity and sensitivity [6]. | Low accuracy, reproducibility and enzyme stability issues. Non-specific interference [24]. |
Raman spectroscopy | Specificity and require small sample volume [19]. | Precautionary measures required for laser use and difficulty to measure low concentrations of ethanol [18,19]. |
UV/NIR spectroscopy | Good sensitivity and less sample preparation. Non-destructive method [8]. | Complicated calibration procedures, expensive and time consuming [20]. |
Dichromatic oxidation spectrophotometry | Inexpensive, high accuracy and do not require skilled analysts [25]. | Sample loss and moderate time for analysis. Potassium dichromate oxidation: non-environmentally friendly due to the carcinogenicity of Chromium (Cr) (VI) [26]. |
Refractive index (RI) analysis | Simple and easy method [21]. | Accuracy highly dependent on temperature and not suitable for complex solvent mixtures [21]. |
Gas chromatography (GC) | High accuracy and sensitivity [10]. | Expensive instrumentation, laborious and long analysis time [27]. |
High performance liquid chromatography (HPLC) | High accuracy and reproducibility. Less time consuming in comparison to other chromatographic methods [22]. | Expensive, requiring large quantities of expensive organics. Complex to troubleshoot problems [22]. |
Pycnometry | Simple method [12]. | Long-time analysis, susceptible to error and requires experienced technicians and, hence, is expensive [12]. |
Densimetry | Rapid, accurate and simple method [12]. | Requires large sample volume and pre-treatment process [20]. |
Hydrometry | Easy to use and inexpensive [12]. | Requires large amounts of samples and is susceptible to user error [25]. |
Capillary electrophoresis | Inexpensive and quicker than HPLC [22]. | Low reproducibility issues [28]. Lower accuracy than GC and HPLC [22]. |
Colorimetric methods | Requires small quantity of sample and is sensitive [29]. | Non-selective and requires pre-distillation of sample [29]. |
Hydrogel-based and piezoresistive pressure sensors | Low cost, small size and inline process capability [23]. | Measurement uncertainty [23]. |
Sensor Design | Fibre Type | Sensitive Coating | Light Source and Detector | S * | R ** | Measurement Range | Application | Ref. |
---|---|---|---|---|---|---|---|---|
Tapered | Chalcogenide glass fibre (400 μm and 200 μm taper) | None | Infrared Light and Mercury–Cadmium Telluride Infrared Detector | - | - | 5–50% | General | [57] |
U-, Coil- and Meander-Shaped | Quartz/quartz fibre (600 μm core) | None | Deuterium Halogen Lamp, 650 nm LED, SR2000-TR Spectrometer and UV enhanced silicon Photodiode (UVS-025) | - | 10−5 RIU | 0–10% | Fuel cell concentration | [54,58] |
Straight Grapefruit type (PCF) | PCF (10 μm core and 121 μm cladding) | None | Light Source of 632.8 nm | 0.461 dB/vol% | - | 0.1–1% | Biosensing | [59] |
Tapered | Multimode (MM) Silica fibre (62.5 µm core and 125 µm cladding) | None, Graphene and GO | Tungsten Halogen Lamp and Ocean Optics USB4000 Spectrometer | 0.829/vol% for graphene-coated sensor and 1.330/vol % for GO-coated sensor | - | 5–40% | General | [35,60] |
U-bend | MM PCS Fibre (62.5 µm core and 125 µm cladding) | GO | White LED and PG2000 Spectrometer | - | - | 10–100% | General | [61] |
Tapered U-bent | MM Silica fibre (62.5 µm core and 125 µm cladding) | MoS2 | Broadband Light Source (450 to 1000 nm) Ideaoptics Instruments PG2000 Spectrometer | 0.34 (∆A%/∆C%) | - | 0–100% | Biosensing | [55] |
U-bend | MM POF (980 µm core and 1000 um cladding) | None | Tungsten Halogen Lamp, 659 nm Photodiode and Ocean Optics QE65000 Spectrometer | 817.760 O.D/RIU | 10−7 RIU | 0.005–0.05% (w/w) LOD: 9.2 × 10−7 RIU | Bioethanol production | [41,62] |
Unclad Straight | MM POF (980 um core and 1000 um cladding) | Carbon Nanotubes (CNT) | Tungsten Halogen Lamp and Ocean Optics USB4000 Spectrophotometer | 0.678/vol%/0.2% | - | 20–100% | General | [56] |
U-bent | MM PCS Fibre (62.5 um core and 125 um cladding) | Gold nanoparticles on Tungsten disulphide (AuNPs on WS2) | HL200 Light source (360 to 2500 nm) and Ideaoptics Instruments PG2000 Spectrometer | 0.65 (∆A/∆C) | - | 10–80% | General | [63] |
Sensor Design | Fibre Type | Sensitive Coating | Light Source and Detector | S * | R ** | Measurement Range | Application | Ref. |
---|---|---|---|---|---|---|---|---|
Single-arm common-path interferometer | PCF (LMA-10) | None | Power Meter | - | 2.6 × 10−5 RIU | - | General | [67] |
Step structure fibre inline MI | SMF-28 (core/cladding diameter of 8.2/125 µm) | None | Broadband Light Source and Spectrum Analyser (OSA, AQ6319) | - | - | 0–50% | General | [71] |
Inline C-shaped open-cavity FPI | Fused Silica tube for C-shaped cavity and SMF-28 (core/cladding diameter of 8.2/125 µm) | None | Broadband Super-Luminescent Diode SLD (1420 nm to 1620 nm) and Spectrum Analyser (OSA, AQ6370) | 1368 nm/RIU | - | 1.333–1.365 RI | General | [68] |
Concave-core open-cavity FPI | PCF (38 µm solid core surrounded by 20 petals shaped airholes | None | Broadband Light Source (FiberLake-BBS) and Spectrum Analyser (OSA, AQ6370C) | 1635.62 nm/RIU | - | 0–19.11% | General | [36] |
LSPR-based FPI | Double-Cladded Optical Fibre (DCOF) (DCF13, Thorlabs) | Gold Nanoparticles (GNP) | Light Sources (MBB1F1, 470–850 nm and S5FC1005S, 1550 nm Thorlabs) and Spectrometers (QE65Pro and NIRQuest-512-1.7 Ocean Optics) | - | - | 30–50% | General | [72] |
Singlemode–multimode–singlemode (SMS) MMI | SMF-28 and No-Core MMF (125 um diameter) | None | SLD (1465 to 1650 nm) and Optical Spectrum Analyser (OSA Anritsu MS9740A) | 133.65 nm/RIU for 1.318 to 1.373 RI range and 390.88 nm/RIU for 1.373 to 1.420 RI range | - | 1.318 to 1.373 RI, 1.373 to 1.420 RI and E50 to pure G87 | Monitoring of gasoline/ethanol blends | [73] |
Multimode–singlemode–multimode MI | SMF and MMF | Novolac Resin | 1310 nm Light Source and Optical Power Meter | 0.028972 dBm per % v/v | - | 0–10% | Liquid phase alcohol detection | [74] |
Taper-based MZI | SMF | None | - | 28 nm/vol or 592.8 nm/RIU | - | 30–70% | General | [43] |
Michelson Interferometer (MI) | SMF | None | Broadband Light Source and Interrogator (1510−1590 nm) | 885.437 to 1067.525 nm/RIU | - | 1.3166–1.4346 RI | General | [69] |
Sensor Design | Fibre Type | Sensitive Coating | Light Sources and Detectors | S * | R ** | Measurement Range | Application | Ref. |
---|---|---|---|---|---|---|---|---|
LPG | Bare LPG | None | - | - | - | 0–100% ethanol in methanol | General | [77] |
Etched FBG | Singlemode Ge-B co-doped photosensitive fibre (Newport F- SBG -15 and cladding diameter 125 ± 1 µm) | None | Broadband Light source and Optical Spectrum Analyser (OSA) | 0.002 nm/% | - | 0–50% | General | [78] |
Microgrooved FBG | SMF (125 µm cladding diameter) with FBG of 22 µm period | None | FBG Interrogating System | - | - | Ethanol and 2.6% and 4.8% PVB in ethanol | General | [42] |
LPG | SMF-28 with 21.6 mm long LPG of 540 µm period | None | Super-Luminescent LED and OSA | 43 pm/% | - | 20–40% | Monitoring of ethanol–gasoline blends | [79] |
Encapsulated LPG | SMF-28 with 2.6 cm long LPG of 400 µm period | None | Broadband LED with centre wavelength of 1550 nm and OSA | Magnitude of 10 nm/RIU and 0.013 nm/% | - | Linear results in 0–70% for ethanol–water mixtures | Ethanol–water and gasoline | [80] |
Etched FBG | Standard SMF based FBG1300 (Central Wavelength CW = 1308.49 nm) and FBG1500 (CW = 1539.87 nm) with pitch of 902.5 nm and 1062.5 nm, respectively | None | LED1 (Superlum, Pilot2, CW = 1544.2 nm), LED2 (Superlum, BroadLighter S-1300-G-I-20 SM) and OSA (Anritsu, MS9710B) | 6.5 ± 0.2 nm/RIU (FBG1300) and 2.9 ± 0.2 nm/RIU (FBG1500) | - | 0–100% for ethanol–water mixtures | General | [81] |
Gold-coated FBG | Standard SMF and Commercial SMF FBG | Thin gold film | Halogen white light source (HL2000) and Ocean Optics Spectrophotometer (USB4000) | 2% change in absorbance per 10% change in ethanol concentration ~0.2 (∆A/∆C) | - | 0 to 99.7% ethanol in water | General | [82] |
LPG and FBG | SMF 28 | Cuprous oxide (Cu2O) | SLD, Broadband Source, OSA (AQ 6315B) and BraggMeter FS2200 SA | 0.76 ± 0.01 nm/% v/v and 0.125 ± 0.003 dB/% v/v | - | 1.5% v/v to 30% v/v ethanol in Gasoline | Quantification of ethanol–gasoline blends | [37] |
Dual FBGs integrated in fibre ring laser structure | SMF 28 for FBG | None | Broadband light source and OSA (Advantest Q8384) | - | 1.5 × 10−4 RIU | 0–14% v/v ethanol in gasoline RON | General | [83] |
Tilted FBG | FBGs and Tilted FBG with tilt angle of 6° | None | SLD, OSA and Photodetectors | - | 1.5% | 0–60% ethanol in gasoline | Gasoline quality monitoring | [84] |
Etched FBG | Singlemode Ge–B co-doped photo-sensitive fibre (Fibre Core PS1250/150; cladding diameter ~125 µm) | Graphene oxide (GO) | Broadband ASE source and OSA (JDSU, MTS8000) | 0.18 dB/percent | - | 0–100% ethanol in petrol | Ethanol detection in petrol | [85] |
Sensor Design | Fibre Type | Metal Coating | Light Source and Detector | S * | R ** | Measurement Range | Application | Ref. |
---|---|---|---|---|---|---|---|---|
Gold-coated unclad straight SPR sensor in a glass tube | NJ-PF200/300 (200 µm core diameter and 300 µm clad diameter) | Gold film | 632.8 nm He-Ne Laser (Melles Griot V05LHR15), 50 cm focal length lens and ILX Lightwave (VOMM-6722B) | - | - | 0–80% LOD: 0.5% | Ethanol content in liquor | [88] |
Gold-coated cone-shaped SPR microdevice | Single-mode GeO2 doped silica core fibre | Gold film (13 nm) | Chopped Laser Source (780 nm) and Photodetector | - | 10−2 RIU | - | General | [89] |
Dual-colour SPR sensor | Step index multimode fibre (400 µm core diameter) | Silver and gold film (10 to 70 nm) | Tungsten halogen lamp, LEDs (612 nm and 680 nm) and Photodetector | - | - | 0–50% LOD: 5.2 × 10−4 RIU | General | [90] |
Conical shape SPR sensor | 100 µm diameter optical fibre | Gold film (50 nm) | Semiconductor laser (690 nm wavelength) and PIN Photodiode | - | 2 × 10−4 RIU | 0.9 volume ratio of dimethyl sulfoxide and ethanol solution | General | [91] |
Gold-coated straight SPR sensor fixed in a glass tube | NJ-PF200/300 (200 µm core diameter and 300 µm clad diameter) | Gold film (45 nm) | LEDs (563 nm, 660 nm and 940 nm) and Photodiode | - | 10−4 RIU | 0–50% | Ethanol content in spirits | [92] |
Tapered fibre LSPR sensor | Single-mode optical fibre (SMF28e) | Star-shaped gold nano particles (80 to 120 nm) | Bromine tungsten light source (BFC-445), Monochromator (SBP500), Side window detector photomultiplier (PMTH-S1) | 1190.5 nm/RIU | - | 10–40% | General | [40] |
Double-sided metal sputtered SPR sensor (inline transmission-based scheme and reflection-based scheme) | Polymer-clad-silica (PCS) multimode optical fibre (core diameter of 200 μm) | Thin gold film (50 nm), ADH and ADH/Nicotinic acid | Halogen lamp (Ocean Optics HL2000) and Spectrometer (Ocean Optics USB4000) | - | - | 0–80% | General | [93] |
Silver-coated SPR sensor combined with ADH and ADH/nicotinic acid enzymes | PCS fibre (core diameter of 600 μm) | Thin silver film (40 nm) | AvaLight-HAL tungsten halogen lamp, Microscope objective and UV-VIS-NIR Avaspec-3648 optical fibre spectrometer | - | - | 0–10 mM | Ethanol in food and beverages | [94] |
Silver/silicon/hydrogel layered SPR sensor with ADH and ADH/nicotinic acid enzymes | PCS fibre (core diameter of 600 μm) | Thin silver film (40 nm) and Silicon (8 nm) | Tungsten halogen lamp, Microscope objective and UV-VIS-NIR Avaspec-3648 optical fibre spectrometer | 21.70 nM/mM | - | 0–5 mM | General | [95] |
FPI-based LSPR sensor | Double-Cladded Optical Fibre (DCOF) (DCF13, Thorlabs) | Gold Nanoparticles (GNP) | Light Sources (MBB1F1, 470–850 nm and S5FC1005S, 1550 nm Thorlabs) and Spectrometers (QE65Pro and NIRQuest-512-1.7 Ocean Optics) | - | - | 30–50% | General | [72] |
Curved D-type SPR sensor integrated with microfluidic chip | Multimode fibre (core diameter of 62.5 μm and cladding diameter of 125 μm) | Gold thin film | Tungsten halogen lamp (LS-1, Ocean Optics), Photoluminescence spectrometer (Triax 320) and Photomultiplier (R5108, Hamamatsu Photonics)3. | 3.12 × 10−5 RIU 1 | - | LOD: 0.06% or 600 ppm | General | [38] |
U-bent LSPR sensor based on a graphene (G) and silver nanoparticles (AgNPs) structure | Plastic Optical Fibre (POF) with 1 mm diameter | PVA/G/AgNPs @ Ag thin film (3, 5, 6, 7 and 10 nm) | Light source (380 nm to 780 nm) and PG2000 spectrometer (Ideaoptics Instruments) | 700 nm/RIU | - | 1.330–1.3567 | General | [96] |
Samarium doped chalcogenide optical fibre SPR sensor (Ag/MoS2 monolayer/perfluorinated (PF) homopolymer layer/polythiophene (PT) layer) with angular interrogation technique | Samarium doped chalcogenide core/polymer clad | Ag (42 nm) MoS2 (0.71 nm) PT (~7 nm) | Laser diode and photodetector | 177.18°/RIU (for ethanol in water) and 182.821°/RIU (for methanol in water) | - | Ethanol–water, methanol–water and ethanol–methanol binary mixtures LOD: 5.04 × 10−6 RIU (at ethanol in water) to 4.8 × 10−6 RIU (at methanol in water) | General | [97] |
Au nanofilm–graphene D-type SPR sensor | POF (1 mm diameter) | Au and graphene | Light source (380–78 nm) and spectrometer (PG2000) | 1223 nm/RIU | - | 1.3330–1.3657 ethanol solutions | Specificity bioanalysis | [39] |
Cavity-coupled conical cross-section gold nanohole array LSPR sensor | Multimode optical fibre (Corning Infinicor SX + 50/125) (core diameter of 50 μm and cladding diameter of 125 μm) | Photoresist (30–40 nm) Au (90 nm) | Broadband halogen light source and spectrometer (StellarNet, Inc.) | 653 nm/RIU | - | - | RI sensing | [98] |
Sensor Type | Advantages | Disadvantages |
---|---|---|
Absorption-based sensors | Easy, simple, versatile and low-cost design. Ease of implementation. Reproducibility. | Fragility due to deformation of fibre. Low selectivity without a sensitive film. |
Interferometric sensors | Robust and easily implemented. Multimode Interferometers: Easy design, flexible structure and reproducible. Sensitive. | Costly, precise and delicate design procedures for most interferometric techniques. Multimode Interferometers: non-periodic spectrum and, hence, difficult signal demodulation. Hydrogel-based FPI: difficult reproducibility. |
Fibre grating sensors | Adjustable structure design. FBG and LPG: When combined, can be used for simultaneous temperature and RI measurement. | Require expensive interrogation systems. FBG: Fragile due to fibre etching for RI measurements and temperature crosstalk. LPG: Complicated signal demodulation. |
Plasmonic sensors | Accuracy. High sensitivity. | High processing requirements in terms of uniformity and thickness consistency of metal coating. |
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Memon, S.F.; Wang, R.; Strunz, B.; Chowdhry, B.S.; Pembroke, J.T.; Lewis, E. A Review of Optical Fibre Ethanol Sensors: Current State and Future Prospects. Sensors 2022, 22, 950. https://doi.org/10.3390/s22030950
Memon SF, Wang R, Strunz B, Chowdhry BS, Pembroke JT, Lewis E. A Review of Optical Fibre Ethanol Sensors: Current State and Future Prospects. Sensors. 2022; 22(3):950. https://doi.org/10.3390/s22030950
Chicago/Turabian StyleMemon, Sanober Farheen, Ruoning Wang, Bob Strunz, Bhawani Shankar Chowdhry, J. Tony Pembroke, and Elfed Lewis. 2022. "A Review of Optical Fibre Ethanol Sensors: Current State and Future Prospects" Sensors 22, no. 3: 950. https://doi.org/10.3390/s22030950