NATO's Science for Peace and Security Programme for Peace and Security (SPS) ... E.Llobet, A.Abdelghani, International Journal of Nanotechnology, 2013 Functionalized MWCNTs for vapor

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NATO

Science for Peace and Security (SPS) Programme

Workshop on CBRN Defence – 22-24 October 2013 – Brussels

Emerging Security Challenges Division

NATO

Brussels, Belgium, 22-24 October 2013

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MULTISENSING PLATFORM FOR WARFARE AGENT DETECTION (MPWAD)

Project Reference: SFP 984511

Kick-off meeting: 3-6 October 2013, Tarragona, Spain

Prof. Eduard Llobet, Tarragona, Spain. (NPD)

Prof. Adnane Abdelghani, Tunis, Tunisia. (PPD)

Dr. Alexander Mozalev, Czech Republic . (Co-Director)

Dr. Alexander Vergara, BCI-UCSD, United States of America. (Co-Director)

Mr. Marc Delgado, Sensotran, S. L., Spain. (End User)

Mr. Drew Barnett, Elintrix, USA, (End User)

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General Overview: Warfare Agent Detection

- Warfare Agent (WA) detection techniques are based on semi-

analytical methods (time consuming, expensive) such as :

-Flame photometry,

-Mass spectrometry

- Photo-acoustic infrared spectroscopy,

Gas/Vapour Microsensors are an emerging technology for

detecting WA

- Most popular transduction methods are electrical.

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Project Objectives

- Development of an innovative multi-modal sensing approach for

warfare agent detection.

What will be achieved :

-Development of new strategies for the functionalization of

nanomaterials

-The gas sensors integrating the array will be multi-parameter: D.C.

resistance, A.C. impedance, photoluminescence, and response to

temperature modulation

- Coupled to a Ion Mobility spectrometer

- A pre-concentrator unit will be also integrated to improve (i.e., lower)

the limit of detection of our proposed sensor system.

- Development of a pre-commercial prototype system and test it in a

controlled facility..

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Novelty in the project

- Development of multisensing platform based on Nanostructered

materials (MOX and CNTs) with pre-concentrator for rapid warfare

agent detection

Sample

conditioning

and delivery

Hybrid sensing module: MOX, nanotubes,

nanodots, nanoneedles, CNTs and IMS

Pump, micro

preconcentrator, mass

flow meter and split

valves

Sensor data

fusion and

pattern

recognition

DMMP

DMF

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Functionalized MWCNTs for vapor detection

CNT Sensor

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SEM image of O xygen plasma treated MWCNTs

TEM image of O xygen plasma treated MWCNTs

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HR-TEM image of a metal decorated MWCNT

dint ≈ 3.21 nm

dext ≈ 14,37 nm

I.Hafaid, H.Baccar, E.Llobet, A.Abdelghani, International Journal of Nanotechnology, 2013

Functionalized MWCNTs for vapor detection

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I. Hafaid, A. Abdelghani, E. Llobet,

Sensors and Actuators B 182 (2013) 344

Functionalized MWCNTs for vapor detection

Plasma treatment and

metal decoration

helps tuning the

response of MWCNT

sensors

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Nanostructured MOXs: Nanowires grown by AA-CVD

Intrinsic (a) and

functionalized

samples with gold (b),

platinum (c), and

gold/platinum (d)

W(OPh)6 (acetone);

HAuCl4·3H2O,

H2PtCl6·xH2O,

(methanol) At 350-

450ºC

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Nanostructured MOXs: Nanowires grown by AA-CVD

0 5000 100002,0x10

5

4,0x105

6,0x105

8,0x105

1,0x106

1,2x106

without RH

10 % RH

25 % RH

50 % RH

80 % RH

Re

sis

tan

ce

, O

hm

Time, s

Metal decoration of MOX nanowires leads to

tuning of sensitivity, lowering humidity cross-

sensitivity

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Nanostructured MOXs employing smart anodization

A. Mozalev, E. Llobet, et al. Int.

J. Hyd. En. 38 ( 2013 ) 8011

Nanotube and

nanocolumn sensors

employing PAA as

template

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Odour delivery system

Flow in

Sensors

chamberSensor

electronics

Computer-

microprocessor

Flow out

Analogue

signal

Digital

signal

Sample

visualization

Odour delivery system

Flow in

Sensors

chamberSensor

electronics

Computer-

microprocessor

Flow out

Analogue

signal

Digital

signal

Sample

visualization

Signal processing

Odour delivery system

Flow in

Sensors

chamberSensor

electronics

Computer-

microprocessor

Flow out

Analogue

signal

Digital

signal

Sample

visualization

Odour delivery system

Flow in

Sensors

chamberSensor

electronics

Computer-

microprocessor

Flow out

Analogue

signal

Digital

signal

Sample

visualization

Data-driven computational

formalisms

Algorithm development: Sensor array optimization and

pattern recognition

Pre-concentration for improved

LOD and ameliorated selectivity

Vergara, Mozalev,

Abdelghani, Llobet et al.

Anal. Chem., 84 (2012)

7502

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Criteria for Success

- Demonstrator prototype for detecting CWAS is available at the end of

the Project

- The detection limits attained by the project are below those offered by

conventional IMS Techniques

- At least two different warfare agents can be selectively detected by

the systems and methods developed in the project

Strengths:

- Complementarity between different partners.

- Use of MOX and CNTs as recognition element.

- Use of different transduction techniques

- Use of pre-concentrator to enhance sensitivity.

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Project outcome

-Technology transfer to Mediterranean countries

-Training of young scientist from Mediterranean countries

- Monitoring air pollution (interesting for ANPE in Tunisia)

- Detection of dangerous gases (e.g., neurotoxic, carcinogenic)

- Prevent public security from terrorist attacks.

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Way Forward – SPS CBRN

What research in CBRN Defense requires urgent and substantial

attention?

• Intelligent materials for the detection of CWAs and bio-hazards

What should be the focus of the SPS Programme in CBRN Defense?

• Supporting research on different technologies. Promoting the convergence

of technologies for developing rugged systems than could be operated in-

field. Benchmarking activities.

Ideas for potential SPS activities in the CBRN field

• NATO could support international conferences to raise awareness among

the scientific community and the general public about the importance of

CBRN defense.