Referencias DECENTES

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

#1
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
MRO'12 A. J. Lilienthal (Jun 6, 2012)
#2
"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. [Rck et al. 2008]
#3
1.
Electronic Nose Definition

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
1.

[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
1.

[An electronic nose is ] An instrument that comprises an array of heterogeneous electrochemical gas sensors with partial specificity and a pattern recognition system.
#6
1.
Electronic Nose Chemosensors

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
http://www.emeraldinsight.com/content_images/fig/0870210202009.png http://www.wellgainelectronics.com/ProductImages/17e/FIGARO GAS SENSOR TGS2440.jpg
http://www.e2v.com/e2v/assets/Image/Gas Sensors/WEB SIZE ELECTROCHEM GROUP.JPG
#7
1.

#8
1.

#9
1.
Electronic Nose

o an array of heterogeneous electrochemical gas sensors
from [Rck et al 2008]

# 10
1.
Electronic Nose

with partial specificity

# 11
1.
Electronic Nose

with partial specificity
o and a pattern recognition system

# 12
1.
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
1.
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
1.
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 [Rck et al 2008]
from Gas Discrimination for Mobile Robots [Trincavelli 2010]

# 15
1.
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
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
1.
"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
1.
"Classical" Electronic Nose, Sensors used in Robotics

o chemoresistors
Metal Oxide gas sensors (MOS/MOX)
# 21
1.
Electronic Nose MOX Sensors

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 SnO2) Heating Element
# 23
1.

absorption of gaseous compounds causes a change of resistance
sensitivity depends on the catalytic material, operating conditions, ...
sensing material is heated to 250oC 500oC

increase rate of reactions prevent absorption of water molecules
# 24
1.

absorption of gaseous compounds causes a change of resistance
sensitivity depends on the catalytic material, operating conditions, ...
sensing material is heated to 250oC 500oC

increase rate of reactions prevent absorption of water molecules
# 25
1.

semiconductor has sintered polycrystalline surface voltage across heated surface electrical current through grain boundaries
# 26
1.

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
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
1.

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
1.

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
1.

o chemoresistors
Metal Oxide gas sensors (MOS/MOX) Conducting Polymer Gas Sensors
# 32
1.
Electronic Nose Conducting Polymer Sensors

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
1.
Electronic Nose Conducting Polymer Sensors

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
1.

o chemoresistors
Metal Oxide gas sensors (MOS/MOX) Conducting Polymer Gas Sensors
o gravimetric
Quartz Microbalance sensors (QMB)
# 35
1.
Electronic Nose Acoustic Wave Sensors

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
http://www.tectra.de/_icons/QMB head.JPG
# 36
1.

pros
rapid response time required for recovery usually shorter than for MOX sensors low power consumption long term stability, long lifetime comparatively low sensitivity limited robustness to variations in humidity complex fabrication processes poor signal to noise ratio
cons
# 37
1.

pros
rapid response time required for recovery usually shorter than for MOX sensors low power consumption long term stability, long lifetime comparatively low sensitivity limited robustness to variations in humidity complex fabrication processes poor signal to noise ratio
cons
High Frequency Fundamental (HFF) Quartz crystals [Kreutz et al. 2006]
# 38
Further Gas Sensing Technologies for Mobile Robots
# 39
2.
Further Gas Sensing Technologies (for Robots?)
Beyond the Classical Electronic Nose

o optical sensor systems
# 40
2.
Optical Sensor Systems

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

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
2.

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
2.

exclusively developed for detecting methane gas, shows no cross-sensitivity to other hydrocarbons detection principle measurement specifications laser specifications
# 44
2.

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
2.

o optical sensor systems o mass spectrometry (MS)
# 46
2.
Mass Spectrometry (MS)
Mass Spectrometry
o ionization of compounds
http://antoine.frostburg.edu/chem/senese/101/atoms/images/ms3.jpg
# 47
2.
Mass Spectrometry
o ionization of compounds o separation according to m/z
with electric or magnetic field
# 48
2.
Mass Spectrometry
o detection of the ions with an electron multiplier
# 50
2.
Mass Spectrometry
o detection of the ions with an electron multiplier o disadvantages for robotics

ionization unit required vacuum is required
not very convenient costly
# 51
2.

o optical sensor systems o mass spectrometry o ion mobility spectrometry (IMS)
# 52
2.
Ion Mobility Spectrometry (IMS)
Ion Mobility Spectrometry

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

ionization of compounds
2.

ionization of compounds separation of m/z
2.

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
2.

ionization of compounds separation of m/z pulsed introduction to a drift region detection of ion current
2.

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
2.
Photoionization Detector (PID)
Photoionization Detector (VOC monitor)

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

o MS/IMS without m/z and mobility separation o ionization with UV lamp
max. 11.7 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
Signal Processing in Electronic Noses
# 63
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
3.

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
3.

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
Electronic Nose Applications
# 72
4.
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
4.
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
4.
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
4.
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
4.
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
4.
o for application the sensitivity of the electronic nose to the target substances and to potential interferents has to be known
# 79
4.
o for application the sensitivity of the electronic nose to the target substances and to potential interferents has to be known
[Rck et al. 2008]

# 81
Literature
# 84
4.
Literature
Literature
o [Pearce et al. 2003]
Handbook of Machine Olfaction Chapter 4
# 85
4.
Literature
Literature
o [Pearce et al. 2003] o [Rck et al. 2008]
Electronic Nose: Current Status and Future Trends, Chem. Rev. 2008, 108, 705-725
# 86
4.
Literature
Literature
o [Pearce et al. 2003] o [Rck et al. 2008] o [Hierlemann/Gutierrez-Osuna 2008]
Higher-Order Chemical Sensing, A. Hierlemann and R. Gutierrez-Osuna. Chem. Rev. 2008, 108, 563-613.
# 87
4.
Literature
Literature
o o o o [Pearce et al. 2003] [Rck et al. 2008] [Hierlemann/Gutierrez-Osuna 2008] [Gardner/Bartlett 1999] Electronic Noses Principles and Applications, J. W. Gardner and P. N. Bartlett. Oxford Science Publications, 1999.
# 88
4.
Literature
Literature
o o o o [Pearce et al. 2003] [Rck et al. 2008] [Hierlemann/Gutierrez-Osuna 2008] [Persaud and Dodd 1982]
Analysis of Discrimination Mechanisms in the Mammalian Olfactory System using a Model Nose. Nature, 1982, 299, 352355.
o [Kreutz et al. 2006]

High Frequency QuartzMicro Balances: A Promising Path to Enhanced Sensitivity of Gravimetric Sensors. Sensors 2006, 6, 335340.
# 89
Mobile Robotics Olfaction Lab, Achim J.and Lilienthal AASS, rebro University
# 90

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Mobile Robotics Olfaction Lab, Achim J.

and Lilienthal AASS, rebro University

MRO'12 A. J. Lilienthal (Jun 6, 2012)

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Definition

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Definition

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Definition

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Chemosensors

"Classical" Electronic Nose

respond to certain gaseous substances

very different from physical sensors

http://www.e2v.com/e2v/assets/Image/Gas Sensors/WEB SIZE ELECTROCHEM GROUP.JPG

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Definition

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Definition

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

"Classical" Electronic Nose

from [Rck et al 2008]

"Classical" Electronic Nose

from [Rck et al 2008]

"Classical" Electronic Nose

o and a pattern recognition system

from [Rck et al 2008]

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

"Classical" Electronic Nose

from Gas Discrimination for Mobile Robots [Trincavelli 2010]

"Classical" Electronic Nose

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Chemosensors II

"Classical" Electronic Nose, Chemosensors

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Chemosensors II

"Classical" Electronic Nose, Chemosensors

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose Chemosensors II

"Classical" Electronic Nose, Sensors used in Robotics

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose MOX Sensors

"Classical" Electronic Nose, Sensors used in Robotics

sensing material doped with catalytic metal additives

Semiconductor Coating (typically SnO2) Heating Element

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose MOX Sensors

"Classical" Electronic Nose, Sensors used in Robotics

sensing material is heated to 250oC 500oC

Semiconductor Coating (typically SnO2) Heating Element

MRO'12 A. J. Lilienthal (Jun 6, 2012)

Electronic Nose MOX Sensors

"Classical" Electronic Nose, Sensors used in Robotics