AASS, Örebro University

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1 Mobile Robotics Achim J. and Lilienthal Olfaction Lab, AASS, Örebro University 1

2 Contents 1. "Classical" Electronic Nose 2. Further Gas Sensing Technologies for Mobile Robots 3. (Signal Processing in Electronic Noses) 4. (Electronic Nose Applications) 5. Literature 2

3 1 "Classical" Electronic Nose [The electronic nose is ] an attempt to mimic the principles of smelling that gives another view on the whole scene of volatiles compared to its biological inspiration. [Röck et al. 2008] 3

4 1. Electronic Nose Definition "Classical" Electronic Nose o definition [Gardner/Bartlett 1999]» [An electronic nose is ] An instrument that comprises an array of heterogeneous electrochemical gas sensors with partial specificity and a pattern recognition system capable of recognizing simple or complex odors. 4

5 1. Electronic Nose Definition "Classical" Electronic Nose o definition [Gardner/Bartlett 1999]» [An electronic nose is ] An instrument that comprises an array of heterogeneous electrochemical gas sensors with partial specificity and a pattern recognition system capable of recognizing simple or complex odors. 5

6 1. Electronic Nose Definition "Classical" Electronic Nose o definition [Gardner/Bartlett 1999]» [An electronic nose is ] An instrument that comprises an array of heterogeneous electrochemical gas sensors with partial specificity and a pattern recognition system. 6

7 1. Electronic Nose Chemosensors "Classical" Electronic Nose o electrochemical gas sensors (chemosensors)» devices capable of converting a chemical quantity into an electrical signal large variety of different gas sensors exist (first publications date back to the 1950s)» respond to certain gaseous substances gaseous substances = true gases or liquids in their vapor phase ("volatiles")» very different from physical sensors several orders of magnitude more measurands can be detected with chemosensors GAS SENSOR TGS2440.jpg Sensors/WEB SIZE ELECTROCHEM GROUP.JPG 7

8 1. Electronic Nose Definition "Classical" Electronic Nose o definition [Gardner/Bartlett 1999]» [An electronic nose is ] An instrument that comprises an array of heterogeneous electrochemical gas sensors with partial specificity and a pattern recognition system. 8

9 1. Electronic Nose Definition "Classical" Electronic Nose o definition [Gardner/Bartlett 1999]» [An electronic nose is ] An instrument that comprises an array of heterogeneous electrochemical gas sensors with partial specificity and a pattern recognition system. 9

10 1. Electronic Nose "Classical" Electronic Nose o an array of heterogeneous electrochemical gas sensors from [Röck et al 2008] 10

11 1. Electronic Nose "Classical" Electronic Nose o an array of heterogeneous electrochemical gas sensors» with partial specificity from [Röck et al 2008] 11

12 1. Electronic Nose "Classical" Electronic Nose o an array of heterogeneous electrochemical gas sensors» with partial specificity o and a pattern recognition system from [Röck et al 2008] 12

13 1. Electronic Nose "Classical" Electronic Nose o introduced to mimic the mammalian olfactory system for smells [Persaud and Dodd 1982]» resembles the biological model receptors gas sensors (not fully selective) information about the smell is in the response signature 13

14 1. Electronic Nose "Classical" Electronic Nose o introduced to mimic the mammalian olfactory system for smells [Persaud and Dodd 1982] o offers different sensitivity characteristics than the human nose 14

15 1. Electronic Nose "Classical" Electronic Nose o introduced to mimic the mammalian olfactory system for smells [Persaud and Dodd 1982] o offers different sensitivity characteristics than the human nose» compare human and bee eyes [Röck et al 2008] from Gas Discrimination for Mobile Robots [Trincavelli 2010] 15

16 1. Electronic Nose "Classical" Electronic Nose o term electronic nose is somewhat unfortunate» sensor response patterns cannot be directly correlated with human olfactory perception» electronic nose systems applications rarely exhibit the enormously broad applicability spectrum of a human or animal nose (sensitivity, discrimination) 16

17 1. Electronic Nose Chemosensors II "Classical" Electronic Nose, Chemosensors o What do we expect from gas sensors?» high sensitivity» large dynamic range» high selectivity / specificity to a target analyte» low cross-sensitivity to interferents» perfect reversibility of the physicochemical sensing process» short sensor response and recovery time» long-term stability» "a sensor exhibiting all these properties is a largely unrealizable ideal" [Hierlemann/Gutierrez-Osuna 2008] 18

18 1. Electronic Nose Chemosensors II "Classical" Electronic Nose, Chemosensors o What do we expect from gas sensors?» high sensitivity» large dynamic range» high selectivity / specificity to a target analyte» low cross-sensitivity to interferents» perfect reversibility of the physicochemical sensing process» short sensor response and recovery time» long-term stability» high selectivity demands a strong, irreversible interaction between sensor and target gas the human receptor cells have a lifetime of only a few weeks! 19

19 1. Electronic Nose Chemosensors II "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors» Metal Oxide gas sensors (MOS/MOX) 21

20 1. Electronic Nose MOX Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, metal oxide gas sensors (MOS/MOX)» heating element» coated with with semiconductor sensing material often tin dioxide» sensing material doped with catalytic metal additives e.g. palladium or platinum doping changes operating conditions sensor characteristics Semiconductor Coating (typically SnO 2 ) Heating Element 23

21 1. Electronic Nose MOX Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, metal oxide gas sensors (MOS/MOX)» absorption of gaseous compounds causes a change of resistance sensitivity depends on the catalytic material, operating conditions,...» sensing material is heated to 250 o C 500 o C increase rate of reactions prevent absorption of water molecules Semiconductor Coating (typically SnO 2 ) Heating Element 24

22 1. Electronic Nose MOX Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, metal oxide gas sensors (MOS/MOX)» absorption of gaseous compounds causes a change of resistance sensitivity depends on the catalytic material, operating conditions,...» sensing material is heated to 250 o C 500 o C increase rate of reactions prevent absorption of water molecules Semiconductor Coating (typically SnO 2 ) Heating Element 25

23 1. Electronic Nose MOX Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, metal oxide gas sensors (MOS/MOX)» semiconductor has sintered polycrystalline surface» voltage across heated surface electrical current through grain boundaries 26

24 1. Electronic Nose MOX Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, metal oxide gas sensors (MOS/MOX)» semiconductor has sintered polycrystalline surface» voltage across heated surface electrical current through grain boundaries» absorption of oxygen at the sensor surface increases potential barrier between grain boundaries large resistance change!» conductivity rate of redox reactions with the ambient gas 27

25 2. Electronic Nose Classical Electronic Nose, Tuning o variety of sensor specificity tuning possibilities (MOX)» different sensitive materials» different doping elements are available» different production processes different morphologies of the sensing layer» different electrodes» different filter layers» different operating temperatures 28

26 1. Electronic Nose MOX Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, metal oxide gas sensors (MOS/MOX)» pros high sensitivity (down to the sub-ppm level for some gases) usable life-span of three to five years low susceptibility to changing environmental conditions changes caused by environmental conditions are smaller than "natural" fluctuations inexpensive to fabricate currently most widely used gas sensor in mobile robotic applications 29

27 1. Electronic Nose MOX Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, metal oxide gas sensors (MOS/MOX)» pros high sensitivity (down to the sub-ppm level for some gases) usable life-span of three to five years low susceptibility to changing environmental conditions inexpensive to fabricate» cons poor selectivity combustion process not strongly selective to precise structural details of the gas molecules comparatively high power consumption due to the high operation temperature sensors have to be heated before operation (30-60 min) even more in classical e-nose applications (up to days on first use) variance of the response between individual sensors slow response slow recovery after the target gas is removed (15s to 70s) 30

28 1. Electronic Nose Chemosensors II "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors» Metal Oxide gas sensors (MOS/MOX)» Conducting Polymer Gas Sensors 32

29 1. Electronic Nose Conducting Polymer Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, Conducting Polymer Gas Sensors» measurand = resistance of the surface layer semiconductor thin polymer film» volatile analyte induces expansion of the polymer composite increase in electrical resistance response depends largely on the rate of diffusion of the vapour into the polymer response time between several seconds to several minutes 33

30 1. Electronic Nose Conducting Polymer Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, Conducting Polymer Gas Sensors» pros comparatively easy to prepare but conditions have to be carefully controlled and chemicals have to be suitably purified in order to achieve reproducible results wide range of materials with varying sensitivity can be synthesised can operate at room temperature low power consumption linear responses for a wide range of gases» cons sensitivity is approx. one order of magnitude lower than that of MOX sensors effects of aging sensor drift a poor understanding of the mechanism behind the conducting polymers 34

31 1. Electronic Nose Chemosensors II "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors» Metal Oxide gas sensors (MOS/MOX)» Conducting Polymer Gas Sensors o gravimetric» Quartz Microbalance sensors (QMB) 35

32 1. Electronic Nose Acoustic Wave Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, Quartz Microbalance sensors (QMB/QCM)» piezoelectronic substrate (usually quartz) application of alternating electric field generates elastic wave in the quartz crystal» coating with a specific affinity» absorbed molecules perturb the propagation of the acoustic waves due to the effect of the added mass by changing the viscoelastic properties of the coating layer» shift of the fundamental frequency of the quartz crystal measured as the output of the sensor head.jpg 36

33 1. Electronic Nose Acoustic Wave Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, Quartz Microbalance sensors (QMB/QCM)» pros rapid response time required for recovery usually shorter than for MOX sensors low power consumption long term stability, long lifetime» cons comparatively low sensitivity limited robustness to variations in humidity complex fabrication processes poor signal to noise ratio 37

34 1. Electronic Nose Acoustic Wave Sensors "Classical" Electronic Nose, Sensors used in Robotics o chemoresistors, Quartz Microbalance sensors (QMB/QCM)» pros rapid response time required for recovery usually shorter than for MOX sensors low power consumption long term stability, long lifetime» cons comparatively low sensitivity limited robustness to variations in humidity complex fabrication processes poor signal to noise ratio High Frequency Fundamental (HFF) Quartz crystals [Kreutz et al. 2006] 38

35 2 Further Gas Sensing Technologies for Mobile Robots 39

36 2. Further Gas Sensing Technologies (for Robots?) Beyond the Classical Electronic Nose o optical sensor systems 40

37 2. Optical Sensor Systems Optical Sensor Systems o measures modulation of light properties» e.g. absorption in a specific frequency range 41

38 2. Optical Sensor Systems RMLD Optical Sensor Systems o Remote Methane Leak Dector (RMLD, Sewerin)» exclusively developed for detecting methane gas, shows no cross-sensitivity to other hydrocarbons» detection principle» measurement specifications» laser specifications Transceiver Controller 42

39 2. Optical Sensor Systems RMLD Optical Sensor Systems o Remote Methane Leak Dector (RMLD, Sewerin)» exclusively developed for detecting methane gas, shows no cross-sensitivity to other hydrocarbons» detection principle TDLAS (Tunable Diode Laser Absorption Spectroscopy)» measurement specifications» laser specifications 43

40 2. Optical Sensor Systems RMLD Optical Sensor Systems o Remote Methane Leak Dector (RMLD, Sewerin)» exclusively developed for detecting methane gas, shows no cross-sensitivity to other hydrocarbons» detection principle» measurement specifications» laser specifications 44

41 2. Optical Sensor Systems RMLD Optical Sensor Systems o Remote Methane Leak Dector (RMLD, Sewerin)» exclusively developed for detecting methane gas, shows no cross-sensitivity to other hydrocarbons» detection principle» measurement specifications» laser specifications class 1 laser (no eye protection required) conical beam, width 0.56 m at 30 m 45

42 2. Further Gas Sensing Technologies (for Robots?) Beyond the Classical Electronic Nose o optical sensor systems o mass spectrometry (MS) 46

43 2. Mass Spectrometry (MS) Mass Spectrometry o ionization of compounds 47

44 2. Mass Spectrometry (MS) Mass Spectrometry o ionization of compounds o separation according to m/z» with electric or magnetic field 48

45 2. Mass Spectrometry (MS) Mass Spectrometry o ionization of compounds o separation according to m/z» with electric or magnetic field o detection of the ions with an electron multiplier 50

46 2. Mass Spectrometry (MS) Mass Spectrometry o ionization of compounds o separation according to m/z» with electric or magnetic field o detection of the ions with an electron multiplier o disadvantages for robotics» ionization unit required» vacuum is required not very convenient costly 51

47 2. Further Gas Sensing Technologies (for Robots?) Beyond the Classical Electronic Nose o optical sensor systems o mass spectrometry o ion mobility spectrometry (IMS) 52

48 2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o separation of ions by m/z and mobility Strukturuntersuchungen an (C60) n +-Clustern mit der Methode der Gasphasen-Ionenchromatographie MRO'12 A. J. Lilienthal (Jun 6, [Lilienthal 2012) 1998] 53

49 2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o separation of ions by m/z and mobility» ionization of compounds Strukturuntersuchungen an (C60) n +-Clustern mit der Methode der Gasphasen-Ionenchromatographie MRO'12 A. J. Lilienthal (Jun 6, [Lilienthal 2012) 1998] 54

50 2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o separation of ions by m/z and mobility» ionization of compounds» separation of m/z Strukturuntersuchungen an (C60) n +-Clustern mit der Methode der Gasphasen-Ionenchromatographie MRO'12 A. J. Lilienthal (Jun 6, [Lilienthal 2012) 1998] 55

51 2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o separation of ions by m/z and mobility» ionization of compounds» separation of m/z» pulsed introduction to a drift region larger ions with greater collision cross section are slower due to more collisions Strukturuntersuchungen an (C60) n +-Clustern mit der Methode der Gasphasen-Ionenchromatographie MRO'12 A. J. Lilienthal (Jun 6, [Lilienthal 2012) 1998] 56

52 2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o separation of ions by m/z and mobility» ionization of compounds» separation of m/z» pulsed introduction to a drift region» detection of ion current Strukturuntersuchungen an (C60) n +-Clustern mit der Methode der Gasphasen-Ionenchromatographie MRO'12 A. J. Lilienthal (Jun 6, [Lilienthal 2012) 1998] 57

53 2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o separation of ions by m/z and mobility» ionization of compounds» separation of m/z» pulsed introduction to a drift region» detection of ion current o disadvantages for robotics» ionization unit required» ion-ion interaction causes problems in complex mixtures» drift cell with inert gas required (isolated from atmospheric air) not very convenient costly 58

54 2. Photoionization Detector (PID) Photoionization Detector (VOC monitor) o MS/IMS without m/z and mobility separation 59

55 2. Photoionization Detector (PID) Photoionization Detector (VOC monitor) o MS/IMS without m/z and mobility separation o ionization with UV lamp» max ev in RAE PIDs ( ethanol, acetone, methanol)» cannot detect methane (IP between 12.6 and 13.6 ev [URL]) o detection of current o pros» quick response to a wide range of gases» calibrated readings if there is only one, known compound o cons» not suitable for classification» too bulky (?)» expensive 60

56 3 Signal Processing in Electronic Noses 63

57 3. E-Nose Signal Processing Components of an E-Nose Approach o sampling system o sensor array (physical or virtual) o data evaluation algorithms» reference data set Tasks o detection o discrimination o identification o quantification 65

58 3. E-Nose Signal Processing Components of an E-Nose Approach o sampling system o sensor array (physical or virtual)» sensors with partial selectivity» output of sensors is usually one feature per sensor (at a time) resistance, fundamental frequency shift, etc. preferably during an equilibrium-type or steady-state-type situation» sensor array corresponds to feature space 66

59 3. E-Nose Signal Processing Components of an E-Nose Approach o sampling system o sensor array (physical or virtual)» output of sensors is usually one feature per sensor (at a time)» sensor array corresponds to feature space o data evaluation algorithms» data analysis using e.g. pattern recognition tools 67

60 4 Electronic Nose Applications 72

61 4. Electronic Nose Applications Application Areas o food and beverage control ( human sense of smell) o fire warning ( human sense of smell) o pollution monitoring ( human sense of smell)» environmental monitoring o detection of hazardous substances and explosives (security macrosmatic mammals such as dogs) o disease diagnosis» lung cancer» bacteria in blood o etc. 73

62 4. Electronic Nose Applications Application Areas o food and beverage control ( human sense of smell) o fire warning ( human sense of smell) o pollution monitoring ( human sense of smell)» environmental monitoring o detection of hazardous substances and explosives (security macrosmatic mammals such as dogs) o disease diagnosis» lung cancer» bacteria in blood o etc. 75

63 4. Electronic Nose Applications Environmental Monitoring o detection of toxic compounds in the ambient atmosphere» at concentrations which will not have an immediate effect but are a longterm danger for human health carbon monoxide, nitrogen oxides, sulfur oxides, volatile organic compounds, ammonia, ozone, and particulate matter» compounds that are simply unpleasant 76

64 4. Electronic Nose Applications Environmental Monitoring o detection of toxic compounds in the ambient atmosphere o analytical instruments do not allow dense, continuous sampling o however, using e-noses is very challenging» complex mixtures» low detection thresholds» sampling (where? when?) samples must be representative and independent of variable ambient conditions knowledge of spatial and time patterns of concentrations is important» changes in temperature and humidity sample pre-treatment and parametric compensation 77

65 4. Electronic Nose Applications Environmental Monitoring o detection of toxic compounds in the ambient atmosphere o analytical instruments do not allow dense, continuous sampling o however, using e-noses is very challenging» complex mixtures» low detection thresholds» sampling (where? when?) samples must be representative and independent of variable ambient conditions knowledge of spatial and time patterns of concentrations is important» changes in temperature and humidity sample pre-treatment and parametric compensation 78

66 4. Electronic Nose Applications Environmental Monitoring o for application the sensitivity of the electronic nose to the target substances and to potential interferents has to be known 79

67 4. Electronic Nose Applications Environmental Monitoring o for application the sensitivity of the electronic nose to the target substances and to potential interferents has to be known [Röck et al. 2008] 81

68 5 Literature 84

69 4. Literature Literature o [Pearce et al. 2003]» Handbook of Machine Olfaction Chapter 4 85

70 4. Literature Literature o [Pearce et al. 2003] o [Röck et al. 2008]» Electronic Nose: Current Status and Future Trends, Chem. Rev. 2008, 108,

71 4. Literature Literature o [Pearce et al. 2003] o [Röck et al. 2008] o [Hierlemann/Gutierrez-Osuna 2008]» Higher-Order Chemical Sensing, A. Hierlemann and R. Gutierrez-Osuna. Chem. Rev. 2008, 108,

72 4. Literature Literature o [Pearce et al. 2003] o [Röck et al. 2008] o [Hierlemann/Gutierrez-Osuna 2008] o [Gardner/Bartlett 1999] Electronic Noses Principles and Applications, J. W. Gardner and P. N. Bartlett. Oxford Science Publications,

73 4. Literature Literature o [Pearce et al. 2003] o [Röck et al. 2008] o [Hierlemann/Gutierrez-Osuna 2008] o [Persaud and Dodd 1982]» Analysis of Discrimination Mechanisms in the Mammalian Olfactory System using a Model Nose. Nature, 1982, 299, o [Kreutz et al. 2006]» High Frequency QuartzMicro Balances: A Promising Path to Enhanced Sensitivity of Gravimetric Sensors. Sensors 2006, 6,

74 Mobile Robotics Achim J. and Lilienthal Olfaction Lab, AASS, Örebro University 90

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