Security Technology Sector

First year progress report

Author – Kshitij Aditeya Singh

Organisation – Institute of Nanotechnology

May, 2009

Executive Summary

A European Strategy on Security was adopted in 2003. The European Security and Defence policy as a part of the common Foreign and Security policy has deployed 20 missions in response to incidents. The use of various policy instruments in European Union (EU) has contributed to security of society, improving equality, human rights and good governance. The policy and missions adopted by the EU are linked to the United Nations objectives in security. The European Security Strategy aims to address the security challenges such as proliferation of weapons of mass destruction, terrorism and organised crime, energy security, cyber security, climate change, securing industrial supply chains and trade routes, and responding to natural disasters.

The rapidly changing dynamics of present times and forces in a globally integrated world are a reflection of the numerous challenges facing societies in protecting civilians and civilian infrastructure. Recent acts of aggression in London and Madrid bombings have revealed the weaknesses of security provisions in civilian zones. Risk and threats that have multiple dimensions need to be addressed for maintaining harmony and peace. The disruptions in civil society may arise from natural elements or divisive human forces. Technology can act as an enabler in assisting agencies in operational situations, where limitation of time and unknown quantity of risk presents itself. Technology research and development can enhance capabilities in supporting security missions for maintaining peace and harmony in society.

Methodology

The European Security Research Advisory Board (ESRAB) had produced a strategic framework for structuring research on technology and non-technological aspects. In a multidisciplinary approach to research aligned with strategic missions, capability development and systems development has been identified of prime importance. The technical research in ESRAB was grouped based on capability development, system development and system of system demonstration. These research areas were focused on addressing mission specific needs or multi-mission needs. The mission areas identified under ESRAB were border security, protection against terrorism and organised crime, critical infrastructure protection, and restoring security in case of crisis. A cross mission analysis was conducted as a part of the scope. The capability enhancement was focused into the following functional groups: detection, identification and authentication; situational awareness and assessment including surveillance; risk assessment, modelling and impact reduction; positioning and localisation; command and control; intervention; doctrine and operations; incident response; information management; communication; training exercise.

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Figure E.1 – Nanotechnology as an enabler of capabilities for Security Missions (Source: ESRAB)

Nanotechnology research and development can enhance security capabilities that enable critical security missions. An illustration of a capabilities enhancement by nanotechnology research is shown in figure E.1. The segmentation of nanotechnology applications for security was done based on enhancement of capabilities and missions identified in ESRAB. The mission specific capabilities enhancements are largely categorized into existing, new and advanced.

The segmentation of the security technology sector was done into four sub-sectors: ‘detection’, ‘protection’, ‘incident support’, and ‘anti-counterfeiting, authentication and positioning’. The detection sub-sector is further divided into technology segments for ‘chemical’, ‘biological’, ‘radiological and nuclear’, ‘explosive’ (CBRNE) weapons and ‘narcotics’ detection. The research and development observations in the protection sub-sector is further done by technology segments defined as ‘protection of civilians and civilian security agencies’, ‘ equipment and infrastructure protection’, and ‘condition monitoring of civilian zones and infrastructure’. The research and development observations in incident support segment have been done based on nanotechnologies relevant to ‘decontamination’, ‘forensic’ and ‘neutralising CBRNE effect’. The final segment has nanotechnologies research and development analysed based on ‘anti- counterfeiting, authentication and positioning and localisation’ (AAPL). A definition of the each of the technology segments is available from each of the sub-sector report. A visual representation of the segmentation of capabilities can be seen in Figure E.2 below.

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Segmentation

Detection

Chemical Biological Radiological / Narcotics Explosive Nuclear

Protection

Infrastructure and Personal Protection Condition monitoring equipment

AAPL

Anticounterfeiting Authentication Positioning and Localisation

Incident Response

Decontamination Forensics Neutralising CBRNE effect

Figure E.2 – Segmentation of capabilities in Security Technology Sector

The observations in each of the technology segments from the literature review were classified into the technology readiness level. These were defined into 6 levels representing research (fundamental and applied), development (prototype and field trails) and application (niche and mass deployment). Gaps in implementation and further research needs have been identified for the above technology segments that relate to specific missions. The technology segment observations have also taken interaction with aspects of commercialisation, environment health and safety issues, ethical, societal and regulatory aspects into consideration. The expert engagement process through surveys, interviews and workshops were used to validate the findings and refine the course of future work. Observations from workshop discussion were recorded and synthesized through a group of observers along with the moderator.

The methodology is limited in not being able to present an exhaustive view of all technology research and developments taking place across the world. Among other methodology challenges are balancing the width of technology monitoring and analysis, balancing knowledge representation in profile of experts engage and improving the comparative assessment between world regions taking national language publications into consideration.

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Detection

The growing threat from terror related activities to civilian security presents a significant challenge to policymakers and security agencies. The observations in the detection segment have been made with a view to assist civilian agencies and policymakers in identifying technology developments of materials and devices between 1-100 nm that may prove to be useful in safeguarding civilians by detecting substance posing a significant threat. The approach taken for detection has been that of identifying development that enable devices or instruments used in detection of different species. The risk agents have been defined in the initial part, where chemical biological, radiological dispersive devices, nuclear and explosives (CBRNE) weapons are the main focus of the detection sub-sector. The observations also address nanotechnology developments in detecting narcotics. The scientific species have then been related to specific enabling nanoscale technologies and devices integrating them. The observations are intended to provide an overview of the current state of the art and the development trajectory.

The detection of chemical weapons by identification of chemical species can be accomplished by a range of sensing methods, and instruments. The nanotechnology development mentioned in the observations for chemical weapons detection are electronic noses, conductive polymers, field effect transistors, piezoelectric sensors, field effect transistors, piezoelectric sensors, surface acoustic wave sensors, flexural plate wave sensors, sensor arrays, optical fibres, cantilever mechanism, chemiresistive action, chemicapacitive sensing and spectroscopic methods. Nanotechnology research and development for explosive detection has been observed. These observations are based on electrochemical sensing, mass based detection, optical sensing, biosensors, Terahertz detection, photoluminescence, cataluminescence, nanosensors, and nanowires based methods for explosive detection. The methods for detecting biological toxins are based on molecular recognition, self assembled bilayers, biosensors, metallic nanowires, Terahertz waves. Detection of radioisotopes based on methods based on sensor networks, radiation portal monitoring equipment, cantilever based detection, mass spectrometry, nuclear resonance fluorescence, electronic neutron dosimeter and neutron imaging camera has been mentioned. The role of radiation detection material, nanocomposites, and nanomaterials for detectors has been observed. Narcotics detection based on membranes, portable detection systems, mass spectrometry, and Raman scattering has been observed.

The nanotechnologies for various detection methods have been observed to be in different stages from applied research, to prototypes and developments that are undergoing field trials. The pace of technological developments is variable for the different detection methodologies used. Demand for specific additional research and desired functionality for detection has been

- 5 - further elaborated. Each technology segment identifies the drivers and barriers for research affecting the development of detection. The main drivers for detection research were considered as technological and social impact, while the main barriers were considered to be inadequate finance availability and insufficient technology transfer from Universities. Essential functionalities have been outlined, application specific trends and needs identified. Deployment of detection technologies, future development and factors affecting uptake and penetration has also been reported for the above mentioned detection methods. A relative comparison of regional competencies of Europe, North America and Asia has also been reported qualitative. A number of qualitative suggestions such as collaborative research, tax exemptions, technology transition and fund allocation for improvement of capabilities have also been mentioned in the technology segment.

The outcomes of the workshop on an integrated platform for CBRNE detection enabled by nanotechnology held in Dusseldorf were that technology was not sufficiently advanced to achieve a single platform for CBRNE detection. It was recommended that an integrated modular system that focuses on chemical, biological and explosive detection as one unit and radiological-nuclear detection as another unit may be a better approach. It was agreed that systems integration for CBRNE detection was a major challenge. Suggestion were made regarding producing a statement of requirements taking nanotechnology into consideration. Accuracy and reliability of measurement was considered to be the most important characteristics. Reproducibility of measurements and operating life of sensors were considered poor for a modular system. A need for greater understanding in the sensing mechanism through fundamental research was emphasised. The first application of integrated platform was expected to be transportation hubs. The demand for development and uptake of technology would be driven by the state as agreed in the expert engagement process.

While there are a number of developments going on at present for detection of different threat agents, there are a number of challenges that need to be overcome. Some of the challenges that need to be overcome are integration of a large number of sensors, high sensitivity and specific detection of toxins. The detection method observed present one advantage over another method due to a range of causal factors. A number of complimentary approaches are in practice, though integration of detection of multiple species on a single platform remains an ongoing challenge.

Incident Support

The incident support function in civilian security serves to provide relief to victims of an attack or a crime directed unknowingly or with intent against them. The responses and measures are through

- 6 - medical aid offered to victims and neutralisation of CBRNE effects. Incident support function also aims to neutralise and decontaminate the environment, civilian infrastructure and vital utilities such as water supply. Forensic analysis of evidence at crime scenes is also a vital part of this function. It aims to establish the causal link in a crime or terrorist act. Nanotechnology research and development enhancing capabilities of Incident Support have been observed.

The neutralisation of effects of chemical and biological attack on civilian population has been observed. Prophylactic antidotes for neurotoxic organosphosphorus compounds have been mentioned. Diagnosis and pharmaceutical countermeasures such as vaccines, sera and medicine have been observed as neutralisation means. A number of delivery methods of antidotes based on nanoparticles for targeted delivery, antidote carrying capacity and release has been observed for a range of methods. Improved diagnostics based on quantum dots, nano- enabled biosensors, molecular imaging and lab on a chip has been mentioned for incident support functions. The neutralisation of radiological and nuclear effects using nanosized magnetic sorbent, zircon, nanostructured sodium silcotitanate and super adsorbent polymer gels have been mentioned for environmental remediation of radio nucleotides. The use of mass spectrometry in determining environmental contamination has been reported. Biodegradable nanospeheres have been observed for removing toxins from blood stream of victims. The incident response through provision of medical aid for victims of explosions has been observed. Self assembled peptides forming nanofibrous barriers in stopping bleeding of victims has been mentioned. Research and development in nano-scale innovation is expected to enhance capabilities in surgery for victims of explosion. Bone and dental implants enabled by titanium dioxide have been reported. Nanophase materials, ceramic nanoparticles, nanocomposites and nanotubes have been reported to have applications in implants. The application of nanofibres in tissue engineering, magnetic nanoparticles as coatings on stents, carbon nanotubes based regeneration of neurons, biodegradable polymer scaffolds, and nanowires in implants are expected to benefit medical aid provided to explosion victims. The use of nanoscale silver and nanofibrous membranes provide benefits in wound care dressing.

Research and development at a nanoscale enabling capabilities in forensic analysis and criminal investigation has been observed in literature. The detection of latent fingerprints evidence and establishing an association with a crime remains of utmost importance in serving justice. The use of optical, physical, and chemical techniques has been observed for fingerprint detection. The use of quantum dots, nanocomposites, metal nanoparticles of gold and silver, metal oxide nanoparticles of titanium and zinc, nanoparticles metal sulphide of cadmium and zinc have been observed. The use of microscopy and spectroscopy methods have been observed in the analysis of forged documents, hand writing, fingerprints, damaged electronic devices, gun shot residue,

- 7 - and firearm identification. Biosensors have also been reported to have forensic applications. DNA identification has an important role in forensics with a number of developments that have been reported. Methods such as geno-magnetic nanocapture, single molecule spectroscopy, electrochemical sensors and lab-on- a- chip developments have been observed.

Decontamination of the environment and infrastructure are essential incident support function following a contamination event. A number of nanoscale materials are being researched for decontamination applications. Nanosized metal halogen adducts nanocrystals of magnesium oxide, photocatalytic titanium dioxide coatings, silica coated nanoparticles, and nanocrystalline zeolites have been observed. Photocatalytic nanowires have been mentioned for breaking down environmental toxins in the air. Silica xerogels for removing toxic gases, nanoporous keratin fibres for removing heavy metals, nanofibrous membrane for removing particulates in liquids have been mentioned as remediation measures. Nanoporous membranes for removing pores from air, nanoceramic membranes decontamination of mercury, and use of nanocrystalline silver in filters for decontamination of water has been observed as research development.

The state of research and development for neutralising effects of CBRNE, Forensics, and Decontamination range from applied research, protyping, field trials and deployed for use. The vast majority of observations are in the applied research state while some have reached field trials. Further demand for research has been reported along with the current situation in Europe through the framework projects. The drivers and barriers for research in incident support have been reported. The drivers for research were considered to be technological and societal impact. The main barriers were considered as availability of finance and intellectual property conflict. Important functionality requirements, expected development course and factors affecting the uptake of applications have also been observed from the expert engagement process. The most attractive and growth markets in the above mentioned applications were also indicated in the process. North America effort in the sub-sector was considered to be better than other world region for research, development and commercialisation for decontamination. In forensics, an area considered to be of limited research, EU was considered to at par with other world regions. For neutralising CBRNE effects, North American and EU research were considered to be at par. The potential toxicity of nanoparticles was identified as a concern requiring greater research and validation.

Protection

Nanotechnology research and development to provide protection to civilians, civilian agencies and infrastructure has been observed in the literature. The protection function is served by shields

- 8 - made out of nano-scale materials. The materials provide shielding against chemical, biological, radionucliotides, ballistic projectiles, sharp objects and electromagnetic interference. The protection of equipment and infrastructure threat agents physical, natural and electronic has been observed. The rapid proliferation of asymmetric threats has made it necessary not only to protect but also to continually monitor the condition of the environment within civilian zones and that of infrastructure. The information and communication integration with active monitoring is considered important for prevention and mitigation of the impact from threat agents.

Protective barrier suits functionalised with nanoscale material has been observed to act as a barrier against chemical and biological species. Nanoparticles of magnesium oxide in a nanocomposite membrane have been observed for enhancing protection capabilities. Nanofibres of polymer have been reported to enhance protection functionalities against CBRNE agents. Nanocomposite for body armour application, multilayer polymer thin films have been incorporated into body suits for neutralising chemical and biological agents have been reported. The use of dendrimers and electro-rheological fluids has also been mentioned for body suit applications. Research has demonstrated the effective use of carbon nanotubes as barrier to ballistic projectiles. Yarns of multiwalled carbon nanotubes have been observed to have excellent reversible damping from projectile impact making it suitable for protective vests.

Protection of infrastructure from ballistic impact and shock waves enabled by nanoscale material has been observed in literature. The use of metal foams, nanometre sized precipitates, ceramic composites have been observed to have infrastructure and equipment protection applications. Vertically aligned carbon nanotubes have been shown to demonstrate super compressible foam like behaviour, acting as energy absorbing surfaces for protection against ballistic projectiles and earthquakes. Inorganic fullerenes of tungsten and molybdenum sulphide have been mentioned to have excellent mechanical and shock resistance behaviour making them suitable for protection against ballistic impact. Protection of infrastructure against fire is possible from the benefits offered by nanoscale materials. Nanoscale layered double hydroxide, nanocomposites of silicon dioxide, nanocomposites of polymer-organoclay, nanocomposites of layered silicates, buckyball nanocomposites and bucky paper have been observed to have fire resistance properties suitable for protection applications.

Electromagnetic interference (EMI) presents a significant threat to the highly integrated information and communication networks. A number of research developments have been reported for potential application in EMI shielding. Intrinsically conductive polymers have been observed to be suitable for shielding applications. Nanoscale materials such as nanocrystalline silver coated ceneospheres, lamellar nanocomposites based on polymers such as polyaniline

- 9 - have been observed to be suitable for shielding application due to high conductivity. Organo- clays and polyaniline nanocomposites have been observed to have high conductivities and good mechanical properties. Carbon nanotubes and carbon nanofibres in polymer matrix have also shown to have excellent shielding characteristics. Vapour grown carbon nanofibres have been studied for their shielding effectiveness. Multiwalled carbon nanotubes and single walled carbon nanotubes are being researched for shielding applications against a wide range of frequencies from the electromagnetic spectrum. Silver colloid nanoparticles in protective thin films and nanoparticles of nickel and iron alloys in expanded graphite have been observed to be in an applied research stage. Nanoscale zinc oxide, carbon nano onions and detonation nano diamond composites are being researched as candidate materials for EMI shielding applications. EMI shielding using materials such as carbon matrix composites with self assembled interconnected carbon nanoribbon network have been researched for low frequency portable electronics applications. Carbon nanotubes and shape memory alloys have also been mentioned for shielding effectiveness.

Capabilities in condition monitoring of infrastructure and civilian zone environment can be enhanced through sensor networks. Nanotechnology research in sensing, information processing, communication and data transfer, storage and providing power can benefit the development of sensor networks and sensory nodes. A number of sensing mechanism based on nanoscale material and phenomena have been observed in the ‘Detection’ segment for CBRNE based on physical, chemical, optical, mechanical and electronic changes. Advancements in carbon nanotubes based transistors have been observed that may enhance capabilities processing capabilities of sensor networks. Carbon nanotubes and nanowires have been reported to have applications in communication and data transmission applications. Nanotube based antennas have been reported for communication. A range of nanooptoelectronic components are expected to add value to sensor networks. Advancements in storage are expected to benefits sensor network through the developments in IBM’s millipede technology, carbon nanotubes based NRAM, molecular memory, ferroelectric RAM, magnetic RAM, and phase change bridge RAM. Research in nanocrystalline materials and nanotubes for applications in electrodes are expected to enhance the characteristics of batteries. The use of carbon nanotubes in supercapacitors is being researched which may have potential applications for sensory nodes. The application of solar cells in power harvesting for sensory nodes is also being investigated. The application of quantum dots, carbon nanotubes, polycrystalline thin films, single crystalline thin films, organic and polymer solar cells has been observed to be under research and development. Power harvesting from mechanical vibrations using cantilever and nanowires is also being researched.

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The outcomes of a workshop on nanotechnologies enabling sensor networks for detection of CBRNE held in Dusseldorf, was that sensor networks would be valuable for trend monitoring and pattern recognition across cities and in local areas. The greatest value addition from nanotechnology to sensor nodes would be at the sensing layer. While integration of multi-channel sensors was not accomplished, novel sensors could be easily integrated with commercial off the shelf components to produce such a network. The market would be created by the state and consideration should be given to dual use for improving commercial attractiveness.

The vast majority of technological capabilities mentioned in the segment are in the applied research stage with many integration challenges to be fulfilled before the technology becomes a mainstream application for the protection of civilian and civilian infrastructure. The expert engagement process identified the main drivers for research in the protection sub-sector were considered to be technological and safety of citizens. The main barriers were considered to be availability of finance and intellectual property related conflicts. Important functionalities for each of the technology segments were identified and the applications trends noted. Relative comparison of research, EU was considered better for personnel protection while US had better instruments for commercialisation and technology transfer. Qualitative suggestions for improving research and development efficiency were mentioned as tax benefits, introducing commercialisation performance metric for academics, and promotion of scientific security enterprise.

Anti-counterfeiting, Authentication, Positioning and Localisation

Anti-counterfeiting, authentication, positioning and localisation research and development is expected to prevent crime by reducing theft of goods, property and identity. Nanotechnology developments in anti-counterfeiting are expected to improve brand protection by reduction in counterfeiting of technological goods and products. Authentication related nanotechnology research and developments are expected to enhance border security and protection against identity theft. Research enabled by nano-materials is expected to enhance positioning and localisation capabilities. The enhanced positioning capabilities are expected to improve the security of industrial supply chains from theft.

Research in nano-enabled materials, methods and devices has been observed for anti- counterfeiting applications. Nanocomposites of silicates, zeolites and luminescent nanoparticles in photopolymerisable nanocomposites have been researched as recording material for holographic security patterns. Laser surface authentication used to map the surface roughness is under field trials as a potential anti-counterfeiting technology. The physically unclonable function

- 11 - developed by Philips and magnetic fingerprinting technology based on distributing micro-nano scale magnets in non magnetic medium has been observed to offer potential advantages. Three dimensional polymer patterns on a nanoscale, metallic sub-micron rods of gold, silver and platinum, and quantum dots have been observed as nano barcodes for enhancing anti- counterfeiting features. Surface enhanced Raman scattering tags are being developed as potential solutions for anti-counterfeiting. The processing and integration of organic nanofibres, and research into multilayered nanostructures, for bank notes has been observed. Nanoclusters of metal atoms in thin films have been researched for using optical effects in anti-counterfeiting applications. Nanomaterials are being researched and patented for applications in anti- counterfeiting. Nanoscale titanium dioxide and zinc oxide are being developed for application in bank notes, birth certificates and drivers licenses. Single and multiwalled carbon nanotubes have been demonstrated as security marks. Diffractive structures for anti-counterfeiting verification have been developed in quantum dots and metallic nanoparticles. The use of gold nanoparticles as composites in security paper has also been observed. The state of research and development for anti-counterfeiting technologies range from fundamental research, applied research, prototype, field trials to commercialised.

Authentication of identify, information and communication play a vital role in preventing crime. Nanomaterials are expected to enable identity verification. Polymer nanocomposites have been observed to have application in security labelling of features such as fingerprints, photograph and signature. Quantum dot doped polymer opal composites have been developed for application as fingerprinting sensors. Optical fluorescent fibres have been developed as anti-counterfeiting technology. Quantum cryptography research is expected to enhance the safety and security of information and communication exchange. The state of enabling nanotechnologies for authentication ranges from fundamental research to field trials.

Radio frequency identification tags are expected to enhance the positioning and localisation of industrial goods by providing enhanced security for the industrial supply chain. Nanotechnology research and development can enhance the performance of RFID components. Conductor patterns based on organic insulated copper and silver nanoparticles have been experimentally demonstrated. Carbon nanotubes antennas have been researched and developed for RFID application. Printed RFID antennas produced from silver nanoparticles ink and nanowires have been observed. Position and Localisation have been observed to be at the applied research stage.

The main drivers for research in AAPL were considered to be technological, economic gain, social impact and regional policy. Brand theft, product theft and forgery were other specific drivers

- 12 - for research in AAPL sub-sector. The main barriers for AAPL were regarded as lack of supporting government policies, access to equipment and infrastructure and lack of technology transfer. Failure to integrate during field trials was regarded as a development barrier. Important functionalities for applications were identified and trends mentioned for the technology segment. Timelines for technology adoption were qualitatively presented for the research and development mentioned above. Laser surface authentication and nanocluster identification were considered closest to application, while others like holographic features were already present as applications in the market. Qualitatively research trends were mentioned to be towards intelligent materials and packaging.

Comparative World wide and EU situation: Publications and Patents

The world wide activity in security was compared using a publication database MERIT and methodology developed within the Observatory Nano project. The comparison of countries conducting security research revealed in the period from 1998 – 2007, USA (44,885) was leading the publication in applications, followed by Peoples Republic of China (26,505) and Japan (18,312). Other top 10 world leading countries for publications in security were Germany (16,577), France (10,784), United Kingdom (9,488), South Korea (7,194), Italy (6,466), India (5,762), and Spain (5,050). Worlds top ten Institutions publishing security research are Chinese Academy of Science (6,692), Russian Academy of Science (2,502), CNRS (1969), University of Tokyo (1,811), Osaka University (1,552), University of Science and Technology China, Tohoku (1,538), Tsing Hua University (1,437), Nanjing University (1,384), and CNR (1,349). A more detailed view of the research institutions and world wide countries is available from the publication report.

Within Europe security research is led by Germany followed by France, United Kingdom, Italy, and Spain. The remaining top 10 countries in Europe for security research are Switzerland (3,330), Netherlands (3,038), Sweden (2,859), Poland (2,484), and Belgium (1,964). Institutions in Europe leading publications in security research, in a European journal, during the period of 1998-2007 were CNRS (1,966), CNR (1,329), CSIC (1,322), University of Cambridge (1,135), Russian Academy of Science (925), University of Paris (834), ETH (752), University of Oxford (730), and Polish Academy of Science (723). Research collaboration leading to joint publications between EU researchers and other world regions were also observed. The collaborating regions with highest number of joint publication records were noted to be USA (6,420), Russia (1,826), Japan (1,610) and Peoples Republic of China (1,288). Other leading top 10 collaboration researchers for security were observed to be from Canada (842), India (656), Israel (572), Australia (563), Brazil (515), and Ukraine (427). A number of European framework projects have

- 13 - been observed for each technology segment which are actively pursuing security research and development. These have been mentioned in the technology segment observations.

The patent analysis was based on the European Patent Office ‘World wide patent statistical database’. It was mentioned that 5944 patent documents resulted from the classification and keyword search. A more detailed view on the methodology used is available from the patent report. The leading country in the world was considered to be ‘United States’ with 48% of the patents assigned, followed by ‘Japan’ with 18% and ‘Germany’ with 12% in third place. The combined output for European Union was mentioned to be 26% of the total security related patent documents. The correlation search in the International Patent Classification system revealed the main areas of patenting to be ‘measuring electric and magnetic variables’, ‘measuring chemical and physical properties’, ‘information storage’, ‘biochemistry, enzymeology and microbiology’, and ‘semi-conductor devices’.

Numerous challenges exist for security applications of nanotechnology. The development of capabilities enabling missions identified in the ESRAB will require overcoming the scientific and technological barriers. In addition each of the enabling nanotechnologies will have to demonstrate performance benefits at minimal costs in order for them to become mass applications. Integration of nanotechnology applications in existing systems to provide enhanced operational capabilities will be one of the biggest challenges to be overcome. The realisation of the potential offered by nanotechnologies for civilian security is expected to increase the safety and security of European citizens and also of other world regions. Future work of the ‘Security Technology’ sector is expected to take into consideration outcomes and recommendations of the European Security Research and Innovation Forum.

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Table of Contents

Executive Summary...... - 2 - Table of Contents ...... - 15 - Foreword...... - 19 - Acknowledgements ...... - 21 - 1. Detection...... - 25 - 1.1.1 Title – Chemical...... - 25 - 1.1.2 Definition of Technology segment ...... - 25 - 1.1.3 Short Description ...... - 26 - 1.1.4. State of Research and Development ...... - 31 - 1.1.5 Additional demand for research ...... - 33 - 1.1.6 Applications and Perspectives...... - 34 - 1.1.7 Current Situation within EU ...... - 39 - 1.2.1 Title – Biological ...... - 41 - 1.2.2 Definition...... - 41 - 1.2.3 Short Description ...... - 41 - 1.2.4 State of Research and Development ...... - 46 - 1.2.5 Additional demand for research ...... - 47 - 1.2.6 Applications and Perspectives...... - 48 - 1.2.7 Current Situation within EU ...... - 53 - 1.3.1 Title - Radiological and Nuclear...... - 55 - 1.3.2 Definition of Technology Segment ...... - 55 - 1.3.3 Short Description ...... - 55 - 1.3.4 State of Research and Development ...... - 60 - 1.3.5 Additional demand for research ...... - 61 - 1.3.6. Applications and Perspectives ...... - 61 - 1.3.7 Current Situation within EU ...... - 65 - 1.4.1 Title – Explosives...... - 67 - 1.4.2 Definition of Technology Segment ...... - 67 - 1.4.3 Short Description ...... - 68 - 1.4.4 State of Research and Development ...... - 75 - 1.4.5 Additional demand for research ...... - 76 - 1.4.6 Applications and Perspectives...... - 77 - 1.4.7 Current Situation within EU ...... - 82 - 1.5.1 Title - Narcotics...... - 84 -

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1.5.2 Definition of Technology Segment ...... - 84 - 1.5.3 Short Description ...... - 84 - 1.5.4 State of Research and Development ...... - 85 - 1.5.5 Additional demand for research ...... - 86 - 1.5.6 Applications and Perspectives...... - 86 - 1.5.7 Current Situation within EU ...... - 88 - 2. Incident Support ...... - 90 - 2.1.1 Title – Neutralising CBRNE effect ...... - 90 - 2.1.2 Definition of Technology Segment ...... - 90 - 2.1.3 Short Description ...... - 90 - 2.1.3.1 Response to Chemical and Biological threats attack ...... - 90 - 2.1.3.2 Response to Radiological and Nuclear weapons attack ...... - 93 - 2.1.3.3 Response to Explosive Incident...... - 94 - 2.1.4 State of Research and Development ...... - 95 - 2.1.5 Additional demand for research ...... - 99 - 2.1.6 Applications and Perspectives...... - 101 - 2.1.7 Current Situation within EU ...... - 103 - 2.2.1 Title – Decontamination...... - 104 - 2.2.2 Definition of Technology Segment ...... - 104 - 2.2.3 Short Description ...... - 104 - 2.2.4 State of Research and Development ...... - 107 - 2.2.5 Additional demand for research ...... - 109 - 2.2.6. Applications and Perspectives ...... - 109 - 2.2.7 Current Situation within EU ...... - 111 - 2.3.1 Title - Forensics ...... - 112 - 2.3.2 Definition of Technology Segment ...... - 112 - 2.3.3 Short Description ...... - 112 - 2.3.3.1 Metal Nanoparticles in Forensics...... - 114 - 2.3.3.2 Metal oxide nanoparticles in fingerprint detection ...... - 116 - 2.3.3.3 Metal sulfide nanoparticles in fingerprinting detection...... - 116 - 2.3.3.4 Microscopy and Spectroscopy...... - 117 - 2.3.3.5 Biosensors ...... - 118 - 2.3.3.6 Role of DNA in forensics...... - 119 - 2.3.4 State of Research and Development ...... - 122 - 2.3.5. Additional demand for research ...... - 123 - 2.3.6 Applications and Perspectives...... - 124 - 2.3.7 Current Situation within EU ...... - 126 -

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3. Protection...... - 127 - 3.1.1 Title - Personnel ...... - 127 - 3.1.2 Definition of Technology Segment ...... - 127 - 3.1.3 Short Description ...... - 127 - 3.1.4 State of Research and Development ...... - 129 - 3.1.5 Additional demand for research ...... - 130 - 3.1.6 Applications and Perspectives...... - 131 - 3.1.7 Current Situation within EU ...... - 133 - 3.2.1 Title – Infrastructure and Equipment ...... - 134 - 3.2.2 Definition of Technology Segment ...... - 134 - 3.2.3 Short Description ...... - 134 - 3.2.3.1 Reinforcement of structures...... - 134 - 3.2.3.2 Protection against fire ...... - 135 - 3.2.3.3 Electromagnetic shielding of information and communication equipment ...... - 136 - 3.2.4. State of Research and Development ...... - 139 - 3.2.5 Additional demand for research ...... - 142 - 3.2.6 Applications and Perspectives...... - 142 - 3.2.7. Current Situation within EU ...... - 143 - 3.3.1 Title – Condition Monitoring...... - 144 - 3.3.2 Definition of Technology Segment ...... - 144 - 3.3.3 Short Description ...... - 144 - 3.3.4 State of Research and Development ...... - 148 - 3.3.5 Additional demand for research ...... - 150 - 3.3.6 Applications and Perspectives...... - 151 - 3.3.7 Current Situation within EU ...... - 153 - 4. Anti-counterfeiting, Authentication, Positioning and Localisation...... - 156 - 4.1.1 Title – Anticounterfeiting...... - 156 - 4.1.2 Definition of Technology Segment ...... - 156 - 4.1.3 Short Description ...... - 156 - 4.1.4 State of Research and Development ...... - 162 - 4.1.5 Additional demand for research ...... - 164 - 4.1.6 Applications and Perspectives...... - 164 - 4.1.7 Current Situation within EU ...... - 165 - 4.2.1 Title - Authentication...... - 166 - 4.2.2 Definition of Technology Segment ...... - 166 - 4.2.3 Short Description ...... - 166 - 4.2.4 State of Research and Development ...... - 168 -

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4.2.5 Additional demand for research ...... - 169 - 4.2.6 Applications and Perspectives...... - 169 - 4.2.7 Current Situation within EU ...... - 170 - 4.3.1 Title – Positioning and Localisation ...... - 171 - 4.3.2 Definition of Technology Segment ...... - 171 - 4.3.3 Short Description ...... - 171 - 4.3.4 State of Research and Development ...... - 172 - 4.3.5 Additional demand for research ...... - 173 - 4.3.6 Applications and Perspective ...... - 173 - 4.3.7 Current Situation within EU ...... - 174 - References and Literature ...... - 175 -

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Foreword

The report has been written with the view to provide policy makers with analysis on the state of research and development for security applications of nanotechnology. Due to the nature of the fundamental science and engineering underlying the applications, the observations have relevance to several sectors. For instance security applications have overlap with ‘Chemistry and Materials’, ‘Energy’, ‘Information Communication Technology’, ‘Health, Medicine and Nanobiology’, ‘Environment’ and ‘Textiles’.

The security applications were related to enabling capabilities and missions based on the Strategic Research Agenda recommended by the European Security Research Advisory Board (ESRAB). Though ESRAB does not exist formally anymore, the research agenda has relevance to security. The technology segmentation has been based on applications that are relevant to ‘Civilian Security’ or also known as ‘Homeland Security’ in other world regions. The observations for civilian sector have been reported for four sub-sectors, namely detection, incident support, protection, and anti-counterfeiting, authentication, positioning and localisation (AAPL). There has been relatively greater focus on detection and incident support sub-sectors. The state of research and development are not exhaustive but aim to provide a representation of activities that have relevance to security.

The observations have been primarily made from research and development that aim to produce a device or enable instruments that address a specific security need. Where deemed necessary observations have also been made from areas of complimentary research to complete the overall picture. The sections of the technology segments reports are based on a standard template created for the Observatory Nano project in the formative stages. The standard template aims to bring scientific and technology information about an application area within the larger scope of the project.

The technology segment reports were written as stand alone reports and have been reviewed by experts as stand alone chapters. Whilst information about other aspects such as markets, health, environmental and societal issues have been mentioned in various places, these have been covered in greater detail in other work packages of the project. Some of the information related to other aspects has been included in the perspectives on applications.

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Specific additional demand for research has been mentioned for a majority of the technology segment, while some segments give a more general view. The current state within Europe has been represented through research and development project activity in the framework programmes. A national review of the various security programmes has not been conducted, instead an EU-wide view has been provided to reflect the activities. The information is supplemented by both publication and patent analysis to give a relative comparison of activity world wide.

The analysis has been supplemented by perspectives on the applications by experts from various areas. The names of these experts involved in the survey, interview and workshop have been recognised in the acknowledgement section. The validation of the technology segment report was reviewers for accuracy and representation of the subject.

The limitation of the analysis has been mentioned in the methodology. All effort has been made to ensure the scientific validity and factual accuracy of observations recorded in the document. Further work is due to take the recommendations and outcomes of European Security Research and Innovation Forum into consideration, which is the successor body to ESRAB and builds on its work with a long term vision for security research and innovation.

K. Singh

May 2009

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Acknowledgements

The author would like to express his gratitude to the following experts who have reviewed the different security technology segment reports and validated the observations before publication.

Name Organisation and Affiliation

Professor Anja 1 Technical University of Denmark Boisen

2 Dr. Sanjay Patel Seacoast Science Inc., U.S.A.

Professor Dr. Biosafety and Biosecurity Consultant, Former ESRAB 3 Helmut Bachmayer member, Austria Professor Nikolas 4 University of Crete, Greece A. Chaniotakis Professor Seamus 5 Cranfield University, U.K. Higson

6 Valerio Pagnotta CENG, Italy

7 Dr. Richard Kouzes Pacific Northwest National Laboratory, U.S.A.

Professor Steve 8 University of Hull, U.K. Haswell Professor Anthony 9 Cranfield University, U.K. Turner School of Criminal Sciences / Institut de Police Scientifique / 10 Dr. Andy Becue University of Lausanne, Switzerland Dr. Kenneth J. 11 Kansas State University, U.S.A. Klabunde Professor Sarah C. 12 University of Iowa, U.S.A. Larsen Dr. Rutledge Ellis- Massachusetts Institute of Technology 13 Behnke and University of Hong Kong

14 Dr. J.-L. Wojkiewicz CEM- Ecole des Mines, France

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Professor L. C. 15 University of Sydney, Australia Zhang

16 Dr. Y.Q. Zhu University of Nottingham, U.K.

Dr Leonid 17 Fraunhofer IAP, Germany Goldenberg Prof. Dr. Attophotonics Biosciences GmbH 18 T.Schalkhammer and University of Vienna, Austria

19 Dr. T.Trindade University of Aveiro, Portugal

20 Dr. V. Sridhar Chonnam National University, Gwangju. South Korea

Dr. Edward A. 21 Los Alamos National Laboratory, U.S.A. McKigney

The author would also like to express his gratitude to the following experts for their input to the Security technology sector by making their informed opinions available through survey questionnaire, interviews and the Observatory Nano workshop. The output from these has been presented in the applications and perspective section of the report.

Name Organisation/ Affiliation

1 Heloisa Mariath Senior Scientific Advisor, Austria

2 Dr. Elena Lacatus Polytechnic University of Bucharest

3 Dr. Sanjay Patel Seacoast Science Inc., U.S.A.

Korea research institute of chemical technology, South 4 Dr. Jeong-O Lee Korea School of Criminal Sciences / Institut de Police 5 Dr. Andy Becue Scientifique / University of Lausanne, Switzerland

6 Dr. D. Ravi Shankaran Kyushu University, Japan

7 Keith Crandell Arch Venture, U.S.A.

8 Neil Wright C-Tech Innovation Ltd, U.S.A.

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9 Dr. Patrick Gardner Western Carolina University, U.S.A.

10 Dr. Richard Kouzes Pacific Northwest National Laboratory, U.S.A.

Professor Anthony 11 Cranfield University, U.K. Turner Prof. Dr. Attophotonics Biosciences GmbH 12 T.Schalkhammer and University of Vienna, Austria

13 Richard Palmer d30, U.K.

14 Dr. Daniel Crespy EMPA, Switzerland

15 Dr. Stan S. Swallow Intelligent Textiles Limited, U.K.

16 Dr. Christian Mittermayr Lambda GmbH, Austria

Professor Nikolas A. 17 University of Crete, Greece Chaniotakis

18 Dr. Edward A. McKigney Los Alamos National Laboratory, U.S.A.

Professor Dr. Helmut Biosafety and Biosecurity Consultant, Former ESRAB 19 Bachmayer member, Austria

20 Valerio Pagnotta CENG, Italy

21 Dr. Frank Schäfer Fraunhofer EMI, Germany

22 Dr. Gerhard Holl Bundeswehr, Germany

23 Dr Juergen Altmann University of Dortmund, Germany

24 Dr Michael Decker ITAS, FZK Karlsruhe, Germany

25 Professor Jim Darwent University of Liverpool, U.K.

Fraunhofer Center Nanoelektronische Technologien 26 Dr. Volkhard Beyer (CNT), Germany

27 Dr. Daping Chu University of Cambridge, U.K.

28 Dr Mostafa Analoui Livingston Group/Charlesson Pharmaceuticals, U.S.A.

29 Dr Donald Bruce EdinEthics, U.K.

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Professor Seamus 30 Cranfield University, U.K. Higson

31 Dr Tony Munter VTT Technical Research Centre of Finland

Professor Dr. Cees 32 VU University of Amsterdam, Netherlands Gooijer

33 Dr. T.Trindade University of Aveiro, Portugal

Dr. Rutledge Ellis- Massachusetts Institute of Technology 34 Behnke and University of Hong Kong

The author would also like to thanks Tom Crawley and Laura Juvonen from Spinverse, and Ineke Malsch from MTV for the contribution made in recording observations during the Security workshops held in Dusseldorf at the annual symposium. The author would also like to express his gratitude to all the Observatory consortium partners for the engagement and Mark Morrison for his encouragement throughout the process.

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1. Detection

1.1.1 Title – Chemical

Detection of Chemical Weapons and Industrial Toxins

Keywords: nerve agent, blister agent, electronic nose, nanosensors, chemiresistors, chemicapacitors, conductive polymers, piezoelectric, sensor array, nanomaterials, spectroscopy, field effect transistors, optical fibres

1.1.2 Definition of Technology segment

The prevention of development, production, stockpiling, and use of chemical weapons was formed in 1992 by the Organisation for Prohibition of Chemical Weapons. Sarin gas was used in Matsumoto in 1994 and in the Tokyo subway in 1995 [1]. Civilian security is also threatened by malpractices in industry and accidents that lead to release of toxic industrial chemicals. Organisation for Prohibition of chemical weapons has classified chemical weapons into three categories - schedule 1, 2, and 3. Schedule 1 chemicals (nerve agents) have very limited industrial uses. Schedule 2 chemicals (example are Amiton, PFIB, dimethyl methylphosphonate precursor to sarin) have limited legitimate use on small scale. Schedule 3 chemicals (examples are chloropicrin, hydrogen cyanide and phosgene) are those which have large scale uses. The schedules limit the use of chemicals as identified in the conventions [2].

Table CW. 1 – A complied list of most harmful and common chemical warfare agents and industrial toxic agents [2,3]

Category of Toxin Name Nerve agent Tabun, Sarin, Soman, Cyclosarin, VX, Novichok agents Choking agents Chloropiricn, chlorine, phosgene, diphosgene Blister agent Sulphur mustard, Nitrogen mustard, Lewsite, Phosgene oxime (CX) Cytotoxic proteins Ricin, Abrin Phosogene , Hydrogen cyanide, Nitrous oxide, Carbon monoxide, Hydrogen Chloride, Methyl isocynate, Mercury, Lead, Benzene Industrial toxic agents hexachloride, 1,3,5 trichlorobeneze , Dichloromethane, Chloroform

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1.1.3 Short Description

Electronic Nose - Artificial noses also known as electronic noses are used to sense the presence of toxic gases and bio agents, and convey its presence by means of an electrical signal. These artificial or electronic noses are also used in detecting explosives. A number of physiochemical approaches are used in sensing, for example measurement of changes in conductivity for metals oxides and polymers, for piezoelectric materials changes in frequency are measured and fluorescent optical fibers changes in colour are measured. Nanosensors based on the human olfactory system have been studied in the United States for molecular recognition of species, pre-processing of the neural signal and transduction of the signal. Sensors based on the electrochemical are either conductance based or potentiometric (field effect transistor). Mass change based piezoelectric sensors are quartz crystal microbalance and for surface acoustic wave devices. Optical sensors are mainly either fluorescent based optical fibers or colorimetric [4].

Conductance sensors are based on a metal oxide or a conducting polymer where binding of a compound causes a change in the resistance between two metal contacts. The main material used for metal oxide sensors are tin, zinc, titanium, tungsten, and iridium. These could be doped with palladium or platinum. A gas sensor array the size of a thumb nail size can sense industrial gases that maybe potentially toxic gases such as ammonia, formaldehyde and carbon monoxide based on oxides of tin and tungsten. Sensor layer thickness can range from 2-20nm [5]. Nanoscale tin oxide based sensors and its variations, with grain size of 8 nm, have effectively demonstrated the recognition of combustible gases such as propane, butane, LPG within their explosion limits [6].

Conductive Polymer - Conductive polymers used as sensors use a polymer to connect two electrodes. The polymer acts as the active sensing agent, the sensitivity of the sensor is higher than metal oxide sensors. The main shortcomings of these types of sensors are the complexity of fabrication and reproducibility of sensing function between batches [4,7]. The active sensor element is used to detect volatile organic compounds. Polymers such as polypyrole, polyaniline, polythiophene, and polyacetate are used due to their high sensitive to vapour and gases. Nanometre sized carbon black has also been used to make polystyrene conductive for sensing application [8]. Carbon black composite sensing arrays have been used to detect explosives and chemical warfare agent such as sarin and soman [9].

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Field effect transistors - Field effect transistors used as potentiometeric sensors have been demonstrated in detecting gases by making the gates sensitive to gases. A volatile organic compound produces a reaction in the sensing layer, which causes the physical property of the gate to change, thereby changing the threshold voltage and thus the channel conductivity. Noble metal catalysts such as platinum, palladium and iridium have been coated on metal oxide FET [10]. Nose on a chip concept of sensors arrays of polymer gated FET’s is used for sensing different odours. The sensing element is combined with a signal processing component, which is used to detect the presence of a gas, identified by a train of spikes in the frequency [11]. Methods such as statistical pattern recognition, neural networks, chemometrics, machine learning, and biological cybernetics has been used to process electronic nose data [12].

Piezoelectric sensors - Piezoelectric devices working as an electronic nose work on the basis of measuring a change in mass. Piezoelectric crystals vibrate under the influence of an applied voltage, the mass of which determines the resonant frequency. Quartz crystal microbalance (QCM) and surface acoustic wave device are used as electronic noses [7]. QCM is used in explosive detection, wherein the adsorption of a gas molecule on the surface of polymer changes the resonant frequency. Quartz crystal microbalance with immobilised nanoscaled ZSM-5 zeolite film has been developed as a sensor for nerve agent. A minimum concentration of 1 part per million (ppm) was detected using the stimulant dimethylmethylphosphonate [13].

Surface Acoustic Wave sensors - Surface acoustic wave sensors are based on acoustic waves travelling on the surface of transducers. Adsorption of a gas molecule causes a change in the mass thereby causing a change in the frequency or phase shift. The advantage with these sensors is that they are easy to fabricate, while their drawback is that they are temperature sensitive, the noise in the signal increases with decreasing size [14]. IBM has demonstrated cantilever based sensors, in ambient air to detect ethenes, alcohols, natural flavours and water vapour using optical methods [15]. Microsensor systems Inc a leading producers of SAW sensors have demonstrated the nerve gas agents and blister gas agents, with a sensitivity of 0.04 ppm in 20 seconds and 0.01 ppm in 120 seconds respectively [16]. Polymer coatings such as polysiloxane films that allow diffusion of chemical agents into the bulk of the film for optimal mass loading. These have been used both for SAW and QCM sensors [17,18]. Thin film piezoelectric acoustic sensor works on the basis of change in thickness of the gas sorption layer on the substrate. These sensors can detect chemical and biological threats with a sensitivity of 100 ppm [19,20].

Flexural plate wave sensors - Flexural plate wave sensors are similar to SAW and QCM sensors detect an agent based on mass absorbed on a coating deposited on the sensor. It is

- 27 - known to have one of the highest levels of detection sensitivity being in the range of parts per trillion (ppt) [21]. Chemical vapour detection and biosensor array based on flexural plate wave sensor has been demonstrated. A siloxane polymer coating 50nm thick is applied on the surface for the detection of specific chemical agents. A sensitivity of 10 ppm was demonstrated in the experimental study [22].

Sensor Arrays - Sensor arrays have been integrated with support vector machines for detecting organophosphate based nerve agents. Support vector machines serve the purpose of data extraction, pre-processing and classification of chemical biological agent [23]. MEMS based sensor arrays have been used to detect nerve agents such as tabun and sarin, with a sensitivity of 4 and 26 parts per billion (ppb) respectively. Blister agents such as sulphur mustard were detected with a sensitivity of 16 ppb. Oxides of tin and titanium were deposited as nanostructured thin films which act as the sensing element. These sensor arrays have demonstrated stability, high signal to noise ratio to the relevant chemical warfare agent [24].

Optical fibres - Optical fibres have been used in sensing application. The fibre is turned into a sensor by coating the end with sensing materials or by removing the cladding and coating it with the sensing material. The sensing material used is primarily polymers containing chemically active fluorescent dyes. The presence of a target agent causes a change in the polarity of the dye which further leads to a change in the wavelength [12]. These optical fibres have been used to detect explosives such as TNT at a sensitivity of 10-15 ppb, which is comparable to 1 ppb sensitivity of a dog’s nose for the same agent. The sensitivity achieved was for a closed chamber however, field trials were not as successful in demonstrating the same result [25].

Cantilevers - Microcantilevers are similar in appearance to diving boards, and are machined from silicon or other materials. The length of these can vary from 100-200 microns and the thickness between 0.3 - 1 microns. Microcantilevers offer sensitivity at least an order of magnitude higher than QCM and SAW based sensors for chemical agents sensing [3]. Piezo resistive micro cantilever based sensors have been demonstrated to have excellent detection capabilities for chemical and explosive vapour detection. The cantilevers are coated with 4nm Ti film, 20nm gold layer and 4-mercaptobenzoic acid self assembled monolayer. Detection of dimethyl methylphosphonate (DMMP), a stimulant for the nerve agents was demonstrated with parts per trillion detection capability within 10 seconds of exposure [26].

Chemiresistors - Chemiresistors are sensors that monitor a change in the resistance continuously with exposure to vapours. Carbon nanotubes have been used for organic vapour sensing. Single walled carbon nanotubes with diameter of 15-30 nm have been demonstrated as

- 28 - effective sensors for nerve gas agents Sarin and Soman. A network of films 1-2 microns thick on a polyethylene terephthalate (PET) substrate can detect traces of chemical agent vapours with a sensitivity of 25 ppm. Strong sensors responses were obtained that were not affected by environmental conditions such as air quality and humidity does not interfere significantly [27]. Single strand DNA along with single walled carbon nanotubes field effect transistors have been used to detect chemical warfare agents. These sensors have show high sensitivity and stability up to 50 cycles of operation [28]. Detection of V type nerve agent has been experimentally demonstrated using carbon nanotubes. The detection is based on enzyme catalyzed hydrolysis of nerve agents and amperometric detection of thiol containing hydrolysis product that is performed at the carbon nanotube modified screen printed electrode. The sensitivity demonstrated for such sensors is 258 ppb [29].

Chemicapacitive sensor - A chemicapacitive sensor is a capacitor that has selectively absorbing materials such as a polymer, as a dielectric. Volatile organic compounds are absorbed into dielectric, changing the permittivity leading to an increase or decrease in the capacitance. Polymer dielectrics are a type of chemicapacitive sensor that are used for detecting chemical warfare agents. These demonstrate a sensitivity of detection of 100 ppm for toxic industrial solvents and 1 ppm for chemical warfare agent as well as explosives [30]. Chemicapacitive sensors for toxic industrial chemicals have demonstrated a sensitivity of 0.0006 – 720 ppm for analyte such as carbyl for the lower limit and carbon disulphide for the higher limit [31].

Spectroscopic Methods - Nerve gas agents such as sarin, soman, tabun, and VX, along with blister agents such as mustard gas, and lewisite were compared for their detection using techniques such as gas detection tube, flame photometric detector, ion mobility spectrometer, surface acoustic wave detector, photo ionisation detector, Fourier- transform infrared spectroscopy, gas chromatography – mass spectrometry for chemical warfare agents. Similar comparative study for biological warfare agents such as flow cytometry, bioluminescence detection, lateral flow immunoassay. Figure 1 below demonstrates the shortcomings of each of these techniques for onsite detection, according to the volatility and molecular weight. Some techniques proved to be suitable in detection of certain analytes while others resulted in false positives or a slow response to the nerve agent [32].

- 29 -

Figure CW.1 – Performance of onsite chemical and biological threat detection [32]

In another study chemical warfare agents were comparatively detected by different analytical techniques such as gas chromatography–infrared detection–mass spectral detection (GC–IR– MS); liquid chromatography–mass spectrometry (LC–MS); nuclear magnetic resonance (NMR) using the nuclei H, C and P; and gas chromatography–atomic emission detection (GC–AED). It was observed in the study that each of the technique gave good identification of some of the components such as amines, phosphorous, or sulphur. Each of these techniques also missed out on several major components [33]. Separation and detection of organophosphorus type nerve agents by gas chromatography with inductively coupled plasma mass spectrometry has been demonstrated, less than 5 picogram sensitivity to river water and soil contamination [34].

Techniques such as laser photo-acoustic spectroscopy have demonstrated a detection of sarin with a sensitivity of 1.2 ppb, and with extremely low false positives of less than 1 in 1,000,000 in the presence of other trace gases [35]. Micro-X Ray fluorescence has unique capabilities suited to high throughput screening of combinatorial libraries of chemical warfare agents. High throughput screening of nerve agents such as VX has been demonstrated in nanogram quantities. These could be coupled with other spectroscopic techniques such as Raman and IR to give additional information [36]. Contamination of portable water with nerve agent Sarin can have serious consequences such as bronchospasm and even death under conditions if enough

- 30 - quantity is consumed. Diffuse reflectance infrared spectrum investigation, using nanoparticulate magnesium oxide as a preconcentration medium produced a sensitivity of 98 ppb for Sarin detection in water [37].

Laser induced breakdown spectroscopy has been used as a versatile sensory platform for detecting chemical agents, biological agents such as anthrax and improvised explosive devices. This sensory platform can be couple with robotic platforms for toxic environments and with fiber optics. The LIBS technique has demonstrated effectively to distinguish chemical agents especially in the soil [38]. Phosphorus containing nerve agent stimulant detection with LIBS has been demonstrated at a range of 20 meters [39].

Nanomaterials - Nanocomposites of tin oxide and indium oxide have been demonstrated as excellent material for semiconductor gas sensors for toxic industrial gases. Addition of additives is shown to have enhanced sensitivity and selectivity performance significantly [40]. Toxic and explosive industrial gas such as methane, butane, propane, liquefied petroleum gas, and carbon monooxide have been detected by nanostructured tin oxide sensors. The sensor arrays demonstrated have a detection capability of less than 100 parts per million [6]. Tin, Niobium and Vanadium Oxide thin films have been developed for the detection of nerve gas agents Sarin. For agglomerates of the size of 40 nm, a sensitivity of 70 ppb was demonstrated. The stability of such thin films for gas sensing applications is being further researched [41].

Challenges of chemical sensing – Integration of large number of sensors in a limited area, providing high sensitivity, and selectivity of the toxin. Another challenge is the environmental conditions, whereby it is much easier to measure parameter in a laboratory condition as opposed to ambient air or in water [4]. Shortcomings of conductive polymers are that surface morphology is not predictable, therefore the surface conductivity and the sensing function are not reproducible between batches, and more importantly it sensitivity to water vapour [4, 7]. There is no one device that meets the need of onsite detection of both chemical and warfare agents for onsite detection [32]. Shortcomings of chemical agents sensors are that no polymer coating for sensors can display complete selectivity to all possible interferents [22]. The costs of using mass spectrometry, gas chromatography, ion mobility spectrometry are expensive and not as easy to use as electronic noses [26].

1.1.4. State of Research and Development

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The sections give an overview of the technology development in relation to a specific technology. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. The technologies have been mentioned are those mentioned in the literature review for chemical detection. The scale of readiness mentioned ranges from fundamental research to mass market. The spread of research and development for a particular method indicates different applications, threat agents and devices that are being developed. A validation of their status is necessary from the economic and other technology sectors perspective. Table CW.2 gives an overview of all chemical weapon detection technologies enabled by nanomaterials.

Table CW. 2 – Comparative Research and Development Status for chemical weapons detection

Field Trials / Pilot Fundame Applied Deployed Prototyp plant ( Pre- Mass ntal Researc (Commercial e commercialisatio Market Research h ised) n) Conducti ve ƒ ƒ ƒ polymers

Field effect ƒ ƒ transistor s Piezoelec tric ƒ ƒ ƒ

Surface acoustic ƒ ƒ ƒ ƒ wave Flexural ƒ ƒ plate

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wave

Sensor ƒ ƒ ƒ ƒ arrays Optical ƒ ƒ ƒ ƒ fibres Cantileve ƒ ƒ rs Chemires ƒ ƒ ƒ istors Chemica ƒ ƒ ƒ pacitors Spectros c-opic ƒ ƒ ƒ ƒ methods Nanomat erials for ƒ ƒ ƒ detection

1.1.5 Additional demand for research

Specific research needs were mentioned in the literature relating to different detection aspects are as follows:

ƒ SWCNT based sensors for detection of nerve gas agents have to be optimised for their performance. Performance optimisation is needed for tenability, stability, detection limit and elimination of false positives [27].

ƒ No onsite detection equipment for capsaicin, lacrymating ingredient in pepper spray, and snake toxins is available. Further research is required in detection methods for these toxins [32].

ƒ LIBS – further research is needed in reducing the number of false positives and negatives. Research is also needed in refining the model to include a range of materials and selection of detection limits [39].

ƒ Research on properties of paper and its scanning through the postal system has also been suggested to protect civilians from biological or chemical attack [42].

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1.1.6 Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were observed:

• Funding research and development for detection of CBRNE and Narcotics was considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and Narcotics’ were considered technological and social impact. The technological drivers relate to cost, performance, efficiency and absence of solutions. Other secondary drivers were indicated as competitive advantage in conflict situations, safety, productivity gains and regional security policy.

• The main drivers for R&D of ‘chemical detection’ were mentioned to be ‘cost of sensors, devices and instrumentation’, ‘sensitivity’, ‘time for detection’, ‘life time of operation’ and accuracy of detection’. Other secondary drivers were identified as ‘size of detectors’, ‘mobility of detection unit’ and ‘integration of detection platform’.

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’ were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate technology transfer from Universities’. Secondary barriers indicated were ‘intellectual property conflicts’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU needs to consider dual commercial use of security technology as the market was relatively smaller than US. While trends in US are towards government driven technology that is validated, EU grants are inadequate for proving technology. It was suggested that government validation of systems was necessary as laboratory systems not scaled for field use.

• The main barriers to R&D of ‘chemical detection’ were indicated as ‘inadequate research funding’, ‘lack of skilled personnel availability’ and ‘lack of reproducible results’. Other secondary barriers were mentioned to be ‘poor detection limit’, ‘failure in integrating devices’, ‘robustness of field trials’ and ‘limited target acquisition’.

- 34 -

• The most important functionality for detection were indicated as ‘sensitivity of specie being detected’, ‘reproducibility of accurate results’, ‘retaining functionality in wide operating conditions’, and ‘long operating life with minimum maintenance’. ‘Collection and sampling’ and ‘specificity’ were considered other very important functional requirement.

• Other secondary desirable functionalities were indicated as ‘stability of detection’, ‘multifunctionality’, ‘signal transduction’, ‘minimal sample preparation’, ‘integration of detector into monitoring unit’ and ‘low cost’. ‘Reversibility’ was considered relatively less important functionality.

• The application trends were mentioned as:

- The charecteristics of a detector application are mission and scenario dependent.

- Development of portable and sensitive detection devices. There is a present lack of portable instruments with good sensing characteristics. Trend is towards miniaturising chemical sensors.

- Application development trend directed toward broad based technologies primarily for transportation hubs.

- Development of nanostructured functional materials and interfaces for high performance detection of chemical agents.

- Systems integration is a gap in technology development for detection.

- Low false positives and low false negatives are the most important application requirement.

- Response time was entirely application dependent. While in border situation 2-3 seconds response time is ideal, several seconds at the port, it should be within milliseconds in crowded locations.

- Functionalities such as detection limit are dependent on application and scenario where ppm might be adequate.

- 35 -

- Operational constraints were identified as environmental changes such as temperature, humidity and large number of interferants. Mobility of detection device, and calibration for temperature and humidity were mentioned as constraints.

- Other operational constraints were mentioned to be calibration of measurement, skills and interpretation needed from operator. The need for simpler interfaces that are tailored for operation setting was mentioned specially for less qualified operators.

- Processing constraints were identified as lack of basic understanding to control nanomaterials in a precise manner.

- Improving cost effectiveness by controlled large scale production and improve laboratory infrastructure for mass scale production.

- Long development life cycles for applications are characterised by delivering scientific results, establishing performance and establishing cost effective performance of detection technologies.

• The sensing methods for chemical detection that are presently deployed are chemicapacitive, chemiresistors, surface acoustic wave, sensor arrays, optical fibres, mass based, and spectroscopy based detection.

• Methods for chemical detection that are expected to be deployed in the next 5 years are nanomaterials based detectors, conductive polymers, field effect transistors, and piezoelectric sensors. Certain types of sensor arrays and specific optical fibres are also expected to be in the market in 5 years.

• Application issues for surface acoustic wave sensors were mentioned to be sensitivity and functionalisation. Development barriers for sensor arrays were mentioned as availability of diverse sensors at the required selectivity and sensitivity. Limitations of spectroscopy as a practical field technique were also mentioned. Reproducibility, selectivity and pattern recognition were development challenges for a majority of sensors. The factors determining the uptake of conductive polymers were mentioned as reproducibility, stability, durability and selectivity. For field effect transistors it was

- 36 -

mentioned as robustness, selectivity and sensitivity. Important factors in uptake of piezo - electric sensors were mentioned to be robustness and stability.

• Methods for chemical detection that are expected to take over 10 years to be deployed were mentioned to be cantilevers.

• The very attractive and relatively higher growth markets were expected to be sensor arrays, biosensors, surface acoustic wave, flexural plate wave, chemiresistors and nanomaterials for detectors.

• The moderately attractive growth markets were expected to be field effect transistors, piezoelectric transistors, optical fibres and cantilever based detection.

• North America was considered relatively better than Europe which was considered better than Asia for fundamental and applied research, industrial technology development and commercialisation. While Asia was considered better for cost effectiveness for technology, EU was considered better for governmental policy for innovation. Qualitative responses mentioned that EU research was complimentary to US for chemical detection. It was mentioned that Europe had existing sensor deployment relatively better than other world regions, it lacked research and development for future leadership.

• Qualitative suggestions on improvement of capabilities were :

- collaborative research between security agencies, academia and industry

- encouraging tax exemptions

- basic research to understand nanomaterials better

- technology transition from science to implemented demonstrators is gap that needs to be addressed

- creation of multinational, multidisciplinary fund for development

- creating a centre for standardised testing for different sensors

- 37 -

The theme of integrated platform for detection of chemical, biological, explosive, radiological and nuclear threats was conducted at Dusseldorf in March 2009. The following outcome and recommendations resulted from the discussion:

• Technology was not sufficiently advanced to achieve single platform detection.

• An integrated modular system that focuses on Chemical, Biological and Explosive as one unit and Radiological-Nuclear detection as a separate module is a better approach.

• One of the main weaknesses for CBRNE detection was considered to be systems integration. It was suggested that a statement of requirements to be produced taking nanotechnology into consideration.

• Accuracy and reliability of measurement was considered to be most important characteristic. Reproducibility of measurements and operating life of sensor were considered to be poor for modular systems of detection.

• The cost of false positives are very high, therefore operational definition should be developed on a case by case basis for a modular system.

• The need for greater fundamental research in understanding the sensing mechanism was emphasised.

• It was recommended that communication between materials and sensing community be improved in order to create mutual awareness of technical breakthroughs.

• The first area of application is expected to be transportation hub for such a modular system.

• Technology penetration and application driven by state for CBRNE detection.

• It was recommended that sensor requirements for the EU are critically examined.

- 38 -

1.1.7 Current Situation within EU

NANOS4 was a research and technology development project which was completed last year. The objective of the project was the development of metal oxide gas sensing system based on mesoscopic sensor. The thin film sensors were to be developed using lithography techniques, for applications in transport safety, monitoring environmental variables. TERAEYE is another framework project that aims to develop an innovative range of inspecting passive range of systems based on Terahertz wave detection. The two dimensional array of detectors are expected to detect harmful explosive, biological, and chemical agents at airports, railways hubs and civilian zones.

The following framework 7 projects have been funded by the European Commission in the Security theme that are relevant to biological threats detection:

• CBRNE related testing and certification facilities - a networking strategy to strengthen cooperation and knowledge exchange within Europe (CREATIF) was initiated early in 2009. The project aims to create a network of product testing facilities for CBRNE detection [43].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is to combine technology solutions from Detection of CBRNE, area surveillance, and check point control for additional sensitive security locations. The sensor data is expected to be integrated with communication and data module to a command centre [44].

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to chemical detection:

• European Security: High level study on threats responses and relevant technologies (ESSTRT). The support action project has provided a comprehensive overview of necessary responses to security challenges. These include technologies for detecting chemical weapons and hazardous materials at airports and travel hubs [45].

• The active terahertz imaging for security (TERASEC) project, that aims to develop terahertz detection. The detection of threats, explosives, pathogens and chemicals in person, luggage or post were the focus of the project. The Terahertz imaging systems were developed and evaluated in the 24 month period [46].

- 39 -

• Hazardous Material Localisation and Person Tracking (HAMLeT) project demonstrated an indoor security system using sensors to give real time decision information. This was done by classifying, tracking and localising potential threats. Chemical sensors were used for detection of hazardous materials such as explosives [47].

• On-line monitoring of drinking water for public security from deliberate or accidental contamination (WATERSAFE) project aimed to use nanotechnologies in sensing and detoxification to protect drinking water systems for potential terrorist attacks or accidental spillage [48].

- 40 -

1.2.1 Title – Biological

Detection of Biological threats

Keywords: anthrax, ricin, virus, bacteria, toxin, nucleic acid, biomolecular, immuno-detection, biosensors, nanowires, nanotubes, terahertz, optical methods

1.2.2 Definition

Biological threats have been defined as those viruses, bacteria and toxins which deliberately spread can cause serious harm to humans, animals and plants. 23 bacteria, 43 viruses and 14 toxins have been reported by security agencies as threats. Table BW.1 provides a list of some of these biological threats [49].

Table BW.1 – List of commonly cited harmful biological agents

Name of biological agent 1 botulinium toxin 2 shiga toxin 3 diptheria toxin anthrax - Bacillus 4 anthracis (anthrax) 5 ricin 6 ovalbumin Staphylococcal Enterotoxin B 7 (SEB) 8 Yersinia pestis (plague) 9 Variola major (smallpox)

1.2.3 Short Description

Detection of biological threats, which could be used against citizens and agricultural produce, involves the recognition of bacteria, viruses and toxins. The identification methods based on

- 41 - nucleic acid and immuno-based methods are used in detecting has been mentioned in the literature. These have also been used in food testing, clinical and environmental applications [50].

Table BW.2 – A selection of detection of commonly known bacterial pathogens as cited in the journal paper [50]

Estimat ed time Sensitivit Biorecognition of assay y (no. of Specif molecules Target Type of assay (h) targets) icity Nuclei pst gene probes Yersinia 5% nuclease 2.5 h 3–30 Very c acid and primers pestis fluorogenic assay cells high Heat stable toxin E. coli PCR-ELISA; color 3.5 h 270 cfu High gene (ST-gene) amplified PCR (CAPS) Genomic DNA; E. coli Lambda phage 2 h 103 cells High Escherichia coli and Molecular combing, lambda scanning force phage , microscopy Universal and B. Multiplex PCR 3 h ND (5 ml High specific 16s subtilis, followed by gel of soil) rRNA primers Y. pestis electrophoresis and E. coli

Immun Fluorescently Salmonel Flow cytometry 40 min 103 High o- labeled MAb la cells:ml of assay typhimuri milk & s um egg Fluorescently Antibody-direct 3 h 104–105 High labeled PAb to Epifluorescent filter cfu:g 0157 antigen E. coli technique feces 0157:H7 (Ab-DEFT)

- 42 -

Table BW.3 – A selection of recognition techniques for detection of pathogenic viruses as cited in a journal paper [50]

Estimate d time Sensitivi Biorecognitio of assay ty (no. of Specif n molecules Target Type of assay (h) targets) icity Nucleic Biotinylated HIV-1 QC-PCR followed by 4h 100 Very acid primers for gag RNA:DN amplicon capture, high gene and A probe hybridization quantit internal and ative standard Luminometry control Biotinylated HIV-1 PCR followed by 3 h 20 virions Very primers for pol RNA amplicon capture and high gene colorimetry Primers for Active In situ PCR followed 4 h 100 High immediate human by in situ colorimetry early genes cytomeg alovirus (hCMV) Primers for hCMV Nested PCR followed 4 h 5 virions High immediate by gel early genes electrophoresis PCR based, digoxigenin labled Primers and Hepatitis amplicons are biotinylated C virus captured by 10–100 Very probes (HCV) biotinylated probes 3 h virions high Digioxigenin labeled riboprobe Dot blot hybridization targeting non- and coding Enterovir chemiluminescent 104–105 sequence uses detection 2.5 h TCID High Digioxigenin Polioviru Dot blot hybridization 2.5 h 103–104 High

- 43 -

labeled Vp1 ses and TCID probe serotyop chemiluminescent es detection

Fluorescein Cells Indirect 2.5 h ND High labeled human infected immunofluorescence recombinant with Fab (rFab) herpes Immun simplex o- virus assays (HSV) Fluorescein 2 h ND (less High labeled murine Cells indirect than monoclonal Ab infected Direct to HSV with HSV immunofluorescence Latex bound Cytomeg 10 min 1012 High antibody to alovirus Latex agglutination, (CMV) visual assay IgM antibody to Enzyme immuno 10 min 106 High CMV assay Antibody Immuno electron 8 h 104–105 Moder HAV microscopy virions/ml ate Radio labeled 2 h 105–106 Moder antibody HAV Radioimmunoassay virions/ml ate

Self assembled bilayers of Cu2+/L-cysteine have been coated on gold surfaces are used to detect biological agents in microcantilever sensors. Dimethyl methyl phosphonate was used as a sarin nerve gas stimulant in these tests [51].

Label free biosensors also known as optical biosensors are based on direct measurements of a change taking place during a biochemical reaction on the surface of a transducer [52]. Ricin has been detected using optical biosensors within 30 minutes to a detection limit of 10ng/ml. The advantages optical biosensors offer is rapid screening and multi-analyte detection. The main disadvantage for these sensors is the reduced sensitivity for the rapid screening assays [53].

- 44 -

Portable fibre optic biosensors have been demonstrated in the detection of Staphylococcal Enterotoxin B. These biosensors have been demonstrated in the compact, light weight portable identification system. The multi-channel identification system is based on simultaneous fluorescence immunoassays on the surface of polystyrene fibre optic probes [54].

NASA has demonstrated the nanotechnology based biosensors that can be used to detect pathogens such as anthrax. These sensors are based on carbon nanofibres and the licensed technology is being commercialised by Early Warning Inc. Electrical signals are measured in these sensors to identify the presence of a pathogen. These sensors are equipped with microfludics as well that provides the advantage of field testing, allowing detection within 30 minutes [55].

Aptamers are functional RNA oligonucleotides that are used for sensing biologicial agents. These are also DNA based. Aptamers based biosensors have been reported to be good for security applications. Aptamers based biosensors are relatively immature, in relation to immunoassays, due to the limited availability of aptamers and knowledge of surface immobilization [56]. Single walled carbon nanotubes based field effect transistors, has been demonstrated to monitor aptamers – protein affinity binding processes. These offer an advantage over immunological assays due to their small size in monitoring protein- protein interactions [57].

Array Biosensors have been used to detect targets such as staphylococcal enterotoxin B (SEB), ricin toxin, cholera toxin, mouse IgG and Bacillus globigii (anthrax spore simulant). Prototype for monitoring postal sorting machines was demonstrated to be successful. The array biosensors provide the advantage of being specific and non-destructive [58].

Inhibition of enzyme acetylcholinesterase has been the basis of detecting organophosphate compounds due to high specificity and selectivity. The development of single thiocholine enzyme based biosensor has been reported in the literature using screen printed carbon electrodes doped with cobalt phthalocyanine. The sensors were observed to be fabricated using electropolymerisation and ablation with ultrasound. Detection limits in the order of 1 * 10-17M were experimentally reported for dichlorvos, parathion and azinphos. In a separate experiment the same detection limit was reported for paraoxon. The biosensors were reported to have application in environmental monitoring [59,60].

Biosensors based on acetylcholinesterase functionalised carbon nanotubes have been demonstrated in detecting organophosphorus compounds. These sensors have shown excellent

- 45 - limits of detection (0.145 ppb), good precision, electrode to electrode stability, and reproducibility [61].

Metallic nanowires striped with gold, silver and nickel nanoparticles in a suspended format have been used to identify biological warfare agents such as anthrax, smallpox, ricin and botulinum. Each nanowire relating to a particular antibody detects a pathogen. The made advantage offered by this method of detection is the ability to have up to 100 different striped nanowires which reduce analysis time significant for multiple analytes [62].

Kane et al. have demonstrated the use of peptide bound carbon nanotubes in detecting toxins such as anthrax, and deactivating the anthrax toxin by using invisible and near infrared light. Carbon nanotubes coatings maybe applied as a thin coating on a range on surfaces [63]. SERS enhancements have been used to detect microorganisms using colloidal metal suspension [64].

Terahertz imaging has been demonstrated for anthrax stimulant bacillus cereus in postal envelopes [65]. The need for research in detection methods of biological threats was driven by the anthrax spores distribution through the postal services in the United States. Laser induced breakdown spectroscopy (LIBS) is a technique that uses light induced from a laser induced microplasma to determine the composition of the sample, based on elemental and molecular emission intensity. The main advantages of this technique are high sensitivity, selectivity and minimal sample preparation. LIBS have been demonstrated to have been effectively used in the detection of bacillus subtilis and ovalbumin. Experimental research has established the effectiveness of this method with few false positive or false negatives [66].

1.2.4 State of Research and Development

The sections give an overview of the technology development in relation to a specific technology. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. The scale of readiness mentioned ranges from fundamental research to mass market. The spread of development across the readiness level is

- 46 - an indication of various detection methods, research and development effort for different threat agents using varied biological means. A validation of their status is necessary from the economic and other technology sectors perspective. The table BW.4 below gives an overview of technology developments in relation to specific enabling technologies for biological threats detection.

Table BW.4 – Comparative Research and Development Status for category of biological threats detection

Field Trials / Pilot Fundame Applied Deployed Prototy plant ( Pre- Mass ntal Researc (Commercial pe commercialisatio Market Research h ised) n) Nucleic Acid ƒ ƒ ƒ ƒ based Sensing Immunoa ssay ƒ ƒ ƒ ƒ sensing Optical biosenso ƒ ƒ ƒ ƒ rs

Nanowire ƒ ƒ

Nanotub ƒ ƒ e Spectros ƒ ƒ ƒ ƒ copy

1.2.5 Additional demand for research

Specific research needs were mentioned in the literature relating to different detection aspects as follows:

ƒ Leveraging telecommunications in sensing of biological warfare agents has been identified as an applied research need. Linking of sensors, detectors and inspection systems into a communication and management network similar to air traffic control has been suggested [49].

- 47 -

ƒ Research on properties of paper and its scanning through the postal system has also been suggested to protect civilians from biological or chemical attack [67].

1.2.6 Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were observed:

• Funding research and development for detection of CBRNE and Narcotics was considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and Narcotics’ were considered technological and social impact. The technological drivers relate to cost, performance, efficiency and absence of solutions. Other secondary drivers were indicated as competitive advantage in conflict situations, safety, productivity gains and regional security policy.

• The main drivers for R&D of ‘biological detection’ were mentioned to be ‘cost of sensors, devices and instrumentation’, ‘sensitivity’, ‘time for detection’, ‘size of detectors’, ‘mobility of detection unit’, and ‘accuracy of detection’. Other secondary drivers were identified as ‘integration of detection platform’, and ‘life time of operation’

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’ were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate technology transfer from Universities’. Secondary barriers indicated were ‘intellectual property conflicts’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU needs to consider dual commercial use of security technology as the market was relatively smaller than US. While trends in US are towards government driven technology that is validated, EU grants are inadequate for proving technology. It was suggested that government validation of systems was necessary as laboratory systems not scaled for field use.

- 48 -

• The main barriers to R&D of ‘biological detection’ were indicated as ‘inadequate research funding’, ‘lack of reproducible results’, ‘failure in integrating devices’ and ‘poor detection limit’. Other secondary barriers were mentioned to be ‘inadequate skilled personnel’, ‘lack of equipment and testing facility’ and ‘robustness of field trials’.

• ‘Collection and sampling’, ‘integration of detector into monitoring unit’, ‘continuous operation’ and ‘specificity’ were considered important functional requirement. Other important functionality for detection were indicated as ‘sensitivity of specie being detected’, ‘reproducibility of accurate results’, ‘retaining functionality in wide operating conditions’, and ‘long operating life with minimum maintenance’.

• Other secondary desirable functionalities for detection were indicated as ‘stability of detection material’, ‘reversibility’, ‘multifunctionality’, ‘signal transduction’, ‘minimal sample preparation’, and ‘low cost’. ‘Reversibility’ was considered relatively less important functionality.

• The application trends were mentioned as:

- The charecteristics of a detector application are mission and scenario dependent.

- Development of portable and sensitive detection devices. There is a present lack of portable instruments with good sensing characteristics. Trend is towards miniaturising biological sensor systems.

- Application development trend directed toward broad based technologies primarily for transportation hubs.

- Development of nanostructured functional materials and interfaces for high performance detection of biological agents.

- Systems integration is a gap in technology development for biological detection. Along with system issues, performance issues for sensors were also mentioned.

- Low false positives and low false negatives are the most important application requirement.

- 49 -

- Qualitative responses mentioned that getting the sample into the device, concentrating and analysing is a development challenge.

- In-situ forensics application demand has been mentioned.

- Lack of data sharing from field trials has been mentioned as a constraint for example by water companies.

- Operational constraints were identified as environmental changes such as temperature, humidity and large number of interferants. Mobility of detection device, and calibration for temperature and humidity were mentioned as constraints.

- Other operational constraints were mentioned to be calibration of measurement, skills and interpretation needed from operator.

- Processing constraints were identified as lack of basic understanding to control nanomaterials in a precise manner.

- Improving cost effectiveness by controlled large scale production and improve laboratory infrastructure for mass scale production.

- Long development life cycles for applications are characterised by delivering scientific results, establishing performance and establishing cost effective performance of detection technologies.

- Nanotoxicology was considered an important issue therefore development of appropriate risk assessment methods is necessary.

• The sensing methods for biological detection that are presently deployed are nucleic acid, immunoassays, optical biosensors and spectroscopy.

• Methods for biological detection that are expected to be deployed between 5 - 10 years are nanowires, and nanotubes based sensors.

• Development challenges for immunoassays were mentioned to be field practicability, durability of sensing surface, sample handling and cost. For nanotubes sensors,

- 50 -

economical production of nanotubes was considered to a development issue to be addressed. Other development issues and critical factors for nanotubes and nanowires sensors were mentioned to be reproducibility, sensitivity, selectivity and pattern recognition. For spectroscopic techniques, miniaturising the system was considered to be the most challenging aspect.

• The very attractive and relatively higher growth market for biological detection was expected to be nucleic acid based and optical biosensors.

• The moderately attractive future growth markets for biological detection were expected to be immunoassays and nanowires.

• North America was considered relatively better than Europe which was considered better than Asia for fundamental and applied research, industrial technology development and commercialisation for the Detection sub-sector. While Asia was considered better for cost effectiveness for technology, EU was considered better for governmental policy for innovation.

• Qualitative responses indicated that US was considered to be far advanced than Europe in Biological detection. Korea, Taiwan, Japan and Singapore were conducting considerable research. Notable advances have been made in China. Research funding was mentioned to be dispersed and effort was ill directed. US was considered good for commercialisation but increasingly Asia is becoming better. It was mentioned that Europe had existing sensor deployment relatively better than other world regions, it lacked research and development for future leadership.

• Qualitative suggestions on improvement of capabilities were suggested as:

- collaborative research between security agencies, academia and industry

- encouraging tax exemptions

- basic research to understand nanomaterials better

- greater need for biochemical basic and applied research

- 51 -

- technology transition from science to implemented demonstrators is gap that needs to be addressed.

- creation of thematic networks to improve coordination of research and development activity

- development of novel solution for sample collection and identification of a wide range of threats

- creation of multinational, multidisciplinary fund for development

- creating a centre for standardised testing for different sensors

The theme of integrated platform for detection of chemical, biological, explosive, radiological and nuclear threats was conducted at Dusseldorf in March 2009. The following outcome and recommendations resulted from the discussion:

• Technology was not sufficiently advanced to achieve single platform detection.

• An integrated modular system that focuses on Chemical, Biological and Explosive as one unit and Radiological-Nuclear detection as a separate module is a better approach.

• One of the main weaknesses for CBRNE detection was considered to be systems integration. It was suggested that a statement of requirements to be produced taking nanotechnology into consideration.

• Accuracy and reliability of measurement was considered to be most important characteristic. Reproducibility of measurements and operating life of sensor were considered to be poor for modular systems of detection.

• The cost of false positives are very high, therefore operational definition should be developed on a case by case basis for a modular system.

• The need for greater fundamental research in understanding the sensing mechanism was emphasised.

- 52 -

• It was recommended that communication between materials and sensing community be improved in order to create mutual awareness of technical breakthroughs.

• The first area of application is expected to be transportation hub for such a modular system.

• Technology penetration and application driven by state for CBRNE detection.

• It was recommended the technology readiness level for biological agents should be assessed on a case by case basis for the specific threat agent and medium of propagation.

• It was recommended that sensor requirements for the EU are critically examined.

1.2.7 Current Situation within EU

TERAEYE is another framework project that aims to develop an innovative range of inspecting passive range of systems based on Terahertz wave detection. The two dimensional array of detectors are expected to detect harmful explosive, biological, and chemical agents at airports, railways hubs and civilian zones. DINAMICS is a framework 6 project that aims to develop an integrated cost-effective nano-biological sensor for detection of bioterrorist activities. The project is developing a lab on a chip device that will detect pathogens in the water supply.

The following framework 7 projects have been funded by the European Commission in the Security theme that are relevant to biological threats detection:

• CBRNE related testing and certification facilities - a networking strategy to strengthen cooperation and knowledge exchange within Europe (CREATIF) was initiated early in 2009. The project aims to create a network of product testing facilities for CBRNE detection [43].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is to combine technology solutions from Detection of CBRNE, area surveillance, and check point control for additional sensitive security locations. The sensor data is expected to be integrated with communication and data module to a command centre [44].

- 53 -

The following completed Preparatory Action for Security Research projects, were funded by the European Commission and are relevant to biological detection:

• European Security: High level study on threats responses and relevant technologies (ESSTRT). The support action project has provided a comprehensive overview of necessary responses to security challenges. These include technologies for detecting biological threats and hazardous materials at airports and travel hubs [45].

• The active terahertz imaging for security (TERASEC) project, that aims to develop terahertz detection. The detection of threats, explosives, pathogens and chemicals in person, luggage or post were the focus of the project. The Terahertz imaging systems were developed and evaluated in the 24 month period [46].

• Assessment of the quantity, identity, viability, origin and dispersion of airborne micro- organisms for application in crisis management tools (AEROBATICS) project aimed to develop a sensing system for biological threats detection. The project aimed to quantify the origin of micro-organism, analyse the micro-organism, and develop predictive model tools [68].

• Bioterrorism resilience, research, reaction-supporting activity promoting co-operation to assess the bio threat and organise a collective and comprehensive response for EU society and citizens bio security (BIO3R) project aims at improving preparedness for bioterrorism. It aimed to identify operational requirements, countermeasures against biological attack (detection and therapeutic) and resilience, ethical and legal issues [69].

• Biological Optical Detection (BODE) project aimed to address the necessities of developing a reliable and accurate detection tool for biological threats for stand-off applications using LIDAR. The project identified functional and operational requirements, proposed specifications, and produced a demonstrator [70].

• On-line monitoring of drinking water for public security from deliberate or accidental contamination (WATERSAFE) project aimed to use nanotechnologies in sensing and detoxification to protect drinking water systems for potential terrorist attacks or accidental spillage [48].

- 54 -

1.3.1 Title - Radiological and Nuclear

Detection of Radiological and nuclear weapons

Keywords: alpha particles, beta rays, gamma rays, high energy photons, high energy electrons, radiation monitoring, plastic scintillators, pure crystal scintillators, solid state devices, nuclear resonance fluorescence, nanophosphor, nanocomposite

1.3.2 Definition of Technology Segment

Nuclear weapons and radiological dispersal devices illegitimately smuggled across the European borders present a significant threat to civilian population. Radiological dispersal devices (also know as ‘dirty bombs’) are capable of dispersing highly radioactive particles over large densely populated areas. Alpha particles (equivalent of a helium nucleus), beta rays (high energy electrons) and gamma rays (high energy photons) are detected by devices to warn of the presence of a nuclear weapon or radiological dispersive device [71].

1.3.3 Short Description

International smuggling of weapons grade nuclear material presents a significant security challenge. Between 1993 and 2004, the International Atomic Energy Agency has reported 18 incidents that related to smuggling of weapons grade nuclear materials. The proliferation of nuclear weapons can take place through the borders at ports, airports, road passengers and through the postal system. A tactical or improvised nuclear weapon would be small enough to be transported in modular containers. It was reported that 25 kilograms of highly enriched uranium or 4 kilograms of plutonium-239 would be adequate for a nuclear explosive device. A significant challenge is presented by dirty bombs, which would present a significant challenge to health of civilians. Americum-241, californium-252, cesium–137, cobalt-60, iridium–192, and strontium-90 are radioactive species that could possibly be used for a dirty bomb. The radioactive isotopes californium-252 and americium–241, are used in the oil industry and smoke detectors respectively, therefore are easy to obtain for a dirty bomb [72]. Weapon grade plutonium and highly enriched uranium can also be used for radiological dispersal devices. Radiological dispersal devices can thus contain a variety of radioactive species that emit gamma rays, neutrons and/or bremsstrahlung radiation.

- 55 -

Radiation monitoring is largely done by detecting gamma rays emitted by radioactive materials. The gamma rays cover a spectrum of energies. Gamma rays passing through matter deposit a part of their energy resulting in electrons that can be detected. One method of detection of photons in a detector is a process called scintillation. Plastic scintillators, pure crystal scintillators, and solid state devices are used for detecting gamma radiation. The drawback of plastic scintillators is the low energy absorption due to the low density of the material. As a result the instruments using such detectors cannot identify the radioactive material accurately. Pure crystal scintillators and solid state devices are relatively better at absorbing all the energy of gamma rays due to their higher density and atomic number. Radioactive isotopes such as strontium-90 emit beta rays, which when shielded produce bremsstrahlung radiation which can be detected by the same methods as gamma rays. Weapon grade plutonium and highly enriched uranium are relatively less radioactive with respect to gamma ray emission in comparison to other isotopes, therefore making them more difficult to detect. Neutrons are also emitted by weapon grade plutonium, often making detection easier due to the low natural background from cosmic radiation. The neutron detectors function by detection of protons released from nuclei struck by neutrons, of fission daughters or by measuring gamma rays, electrons and other charged particles. Uranium isotopes emit alpha particles and gamma rays, and not as many neutrons [72].

A number of strategic tools are used in the detection of radiation such as radiation portal monitoring equipment, personal radiation detectors, hand held detectors and x-rays systems for imaging of shielding. Radiation detection systems can be passive or active. Passive systems for detection of radiation include radiation portal monitoring equipment, mobile systems, hand held, backpack and belt monitoring systems, all of which have been deployed. Mobile x-ray and fixed systems have been used for penetration of cargo containers for suspected cargo. Plutonium and a few other radioactive materials emit neutron and tus neutrons are of particular interest in detection applications at border crossing [73].

Radiation portal monitoring equipment has been deployed for border crossing and port application in detection of illicit nuclear material. Detectors of gamma rays based on polyvinyltoluene (PVT) and thallium doped crystalline sodium iodide have been demonstrated and deployed. For passive screening of gamma rays, the energy range of interest for detection was between 20 keV to 3 MeV [74]. A comparison of radiation portal monitoring equipment for border security was done using gamma ray and neutron detectors. A comparison of polyvinyltoluene and thallium doped crystalline sodium iodide for vehicle based radiation portal monitoring has also been evaluated in the literature. The spectral capability of NaI(Tl) is superior to PVT for isotopic identification, though the cost of NaI(Tl) has been reported to be much higher than PVT. A range of environmental and operational factors determine the suitability of a detector in different

- 56 - operating scenarios. Each detector type offers some advantages for various operating conditions of portal monitoring systems [75].

Energy based alarm algorithms with enhanced sensitivity over gross counting have been implemented for radiation portal monitoring equipment. The energy information obtained from plastic scintillators can be used to distinguish between naturally occurring radioactive material and special nuclear material. The energy based algorithm was considered to be a much desired improvement in detection over gross count algorithms. One of the main limitations of radioaction portal monitoring systems is the presence of naturally occurring radioactive isotopes that can present a significant operational challenge [73,76].

Nuclear weapons detection in transportation cargo has been demonstrated with a range of techniques, including both passive and active detection. The photo-fission of neutron emission induced by gamma rays forms the basis of one active detection approach. The technique and its effectiveness has been demonstrated for radioactive material in simulated shipping containers and air-cargo [77]. Detection of nuclear weapons in cargo has been demonstrated using a pulsed beam of neutrons, that produce fission events and detection of their fissionable material is done from the beta delayed neutron emission or beta delayed high-energy gamma radiation. This is another of the several active interrogation detection methods, and has been demonstrated for simulated shipping cargo [78].

Nuclear Resonance fluorescence, another potential active interrogation technique, has been demonstrated in the detection of isotopes of uranium in a laboratory. The basis of the method is a unique signal that is relevant to each nuclei. The technique combined with effective algorithms has been demonstrated in the laboratory as a possible method that may be applicable to detection of material in sea containers, truck containers, trucks and other vehicles [79].

Monitoring of radioactive xenon in air has been used to detect nuclear weapons explosions as part of the worldwide network of the Comprehensive Test Ban Treaty verification effort. A prototype single phoswich detector has been used to detect beta particles and gamma rays from radioxenon isotopes [80].High resolution inductively coupled plasma mass spectrometry and accelerator mass spectrometry have been demonstrated in detecting ultra low level of uranium isotopes in marine environments. The uranium isotope signature provides valuable information on origin of uranium. The method has useful applications in monitoring radioactivity in depleted uranium environments and undeclared nuclear activity or movement of nuclear material [81].

- 57 -

Detection of radioisotopes using a distributed sensor network, as opposed to central fixed systems, has been proposed and developed. These distributed sensor network, coupled with a monitoring portal has been demonstrated. The sensor array consisted of sodium iodide scintillators that were connected to a platform for processing of gamma counts. The performance of the array was reported to be higher than that of a single detector, though that is a controversial claim. The advantage of this proof of concept is that it may be inexpensive, further research is aimed at increasing sensitivity and developing an integrated platform for chemical and biological threats [71].

The use of various detectors for radioactive species has been mentioned earlier. A system for simultaneous detection of radiation species such as x-rays, gamma rays, neutrons and minimum ionising particles has been observed in the literature. The sensitivity of the scintillators in the research was achieved using nano-sized particles, dopants and extruded plastic material. Three different type of detectors have been described, which identify specie of radiation. Nano-sized particles of lithium have been used in neutron detectors. The wavelength shifting fibre absorbs scintillator light at a wavelength and re-emitting it at a higher wavelength to better match the photodetector used [82].

The use of nanoscale materials for detection of radiation is expected to overcome single crystal based detectors limitations such as size and cooling requirements to very low temperatures. Nanophosphor has been mentioned as a candidate material for scintillators and detectors. Cerium doped lanthanum halides (less than 10nm in diameter) have also been mentioned as suitable candidates for scintillators nanocomposites. Due to their brightness and short decay lifetime they are very effective in gamma ray detection. Scaling up of the synthesis of cerium lanthanum fluoride to kilogram quantities remains a further research challenge that remains to be addressed [83].

Enhanced optical properties of nanocomposites made of existing scintillator materials have been reported in the literature. The nanocomposites offer enhanced light output, decreased costs and scalability have been demonstrated at the proof of principle stage. Cerium doped lanthanum fluoride has been synthesized nanoparticles having a size of 25 -100nm, have shown a three times increase in light intensity as compared to bulk material used for scintillation. Further research in the area was identified as synthesis of nanophosphors as scintillators and their fabrication as nanocomposites. Measurement of absolute light yield and linearity of the nanocomposite were mentioned as challenges for characterization [84].

- 58 -

Solid state semiconductor detectors offer advantages over gas filled detectors and scintillator detectors due to excellent energy resolution and higher efficiency. High purity germanium detectors are the gold standard for gamma ray detection but require cryogenic temperatures. A number of semiconductors have been suggested for application such as cadmium zinc telluride (CZT), cadmium telluride, gallium arsenide, indium phosphide, mercury iodide and thallium bromide. CZT offer advantages due to its wide band gap, high resistivity and commercial availability. The higher resistivity is a desirable characteristic as it decreases noise level thus improving the resolution of detection. A synthesis process for producing nanowire arrays of CZT has been mentioned in the literature for detecting gamma ray radiation. In the process CZT was electrodeposited on a titanium dioxide nanotubular template. Stacks of CZTs with very high resistivity were fabricated and connected. It was experimentally demonstrated that the flow in the current increased when exposed to a radiation source. The potential of nanowires being used as a radiation detector at room temperature was at a much lower bias applied in relation to bulk material detectors. Very high sensitivity to radiation was experimentally demonstrated [85].

Other recent methods have been mentioned in the literature such as the Neutron Imaging Camera for detection of weapon grade plutonium at borders. The camera is based on three dimensional image tracker developed initially for applications in gamma ray astrophysics. The working principle is based on measuring the energy and position in three dimensions of the charged particles moving through the camera medium. The application was successful demonstrated to identify radiation at stand-off distances and in the presence of other background emissions [86]. An Electronic Neutron Dosimeter has been mentioned in the literature for detecting radiation. It uses scintillators on a pair of photomultiplier tube minimizing the power consumption and increasing operational times. The dosimeter has been prototyped with results exceeding electronic neutron dosimeter standards [87]. Microcantilevers were reported to detect an alpha particle as it impinges on an electrically insulated metallic surface by undergoing a deflection of a few nanometres. The particle is detected by a shift in the resonance frequency due to electrostatic forces. A single alpha particle can be detected using this method, however other conventional methods have been shown to have higher sensitivity as compared to these detectors [88].

One of the main challenges of detecting these threat radioactive materials is the shielding using lead and other dense materials for gamma rays, and hydrogenous materials for neutrons. An additional challenge is interference from medical isotopes and other slightly radioactive, but relatively innocuous materials such as smoke detectors, fertilizers, television sets, abrasives and glazed ceramics. The approach of using X-ray scanners has been used in the United States, for any shielding that may be used to hide radiological weapons. Other methods such as active

- 59 - interrogations using gamma ray and neutrons have also been reported. As mentioned above, these induce fission in uranium and plutonium, resulting in gamma rays and neutrons that are detected [72].

1.3.4 State of Research and Development

The sections give an overview of the technology development in relation to a specific technology. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. The technologies have been mentioned are those mentioned in the literature review for nuclear and radiological weapons detection. The scale of readiness mentioned ranges from fundamental research to mass market. The range of activity indicates various methods and materials being used at different stages of readiness. The table RNW.1 below gives an overview of enabling technologies for detection of radiological disperse device and nuclear weapons in relation to their development status.

Table RNW.1 - Technology and its Development Status for radiological disperse devices and nuclear weapons detection

Field Trials / Pilot Fundame Applied Deployed Prototy plant ( Pre- Mass ntal Researc (Commercial pe commercialisatio Market Research h ised) n) Radiation portal ƒ ƒ ƒ ƒ monitorin g Sensor ƒ ƒ ƒ Array Spectro ƒ ƒ ƒ metric

- 60 -

method

Nuclear Resonan ce ƒ fluroesce nce Nanomat eri-al based ƒ ƒ Detector s

1.3.5 Additional demand for research

Specific research needs were mentioned in the literature relating to different detection aspects are as follows:

ƒ Materials research needs for CBRNE sensors has been identified as developing sensors with the ability to detect and warn. Sensor capabilities to allow functionality at stand off distances in order to protect personnel in conflict situations. Enhanced understanding of the energetic behaviour of weapons and its packaging modes has been suggested. Enhanced and portable imaging techniques have been identified as a research need for civilian areas with high shipping container traffic. Integration of imaging and detection techniques with mass transportation has also been mentioned [89].

1.3.6. Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were observed:

• Funding research and development for detection of CBRNE and Narcotics was considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and Narcotics’ were considered technological and social impact. The technological drivers relate to cost, performance, efficiency and absence of solutions. Other secondary drivers

- 61 -

were indicated as operational advantage in conflict situations, safety, productivity gains and regional security policy.

• The main drivers for R&D of ‘radiological and nuclear detection’ were mentioned to be ‘mobility of detection unit’, ‘cost of sensors, devices and instruments’, and ‘accuracy of detection’. Other secondary drivers were ‘time for detection’, ‘integration of detection platform’, and ‘life time of operation’

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’ were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate technology transfer from Universities’. Secondary barriers indicated were ‘intellectual property conflicts’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU needs to consider dual commercial use of security technology as the market was relatively smaller than US. While trends in US are towards government driven technology that is validated, EU grants are inadequate for proving technology. It was suggested that government validation of systems was necessary as laboratory systems not scaled for field use.

• The main barriers to R&D of ‘radiological and nuclear detection’ were indicated as ‘lack of equipment and testing facility’, and ‘limited supporting policies’. Other secondary barriers were indicated as ‘lack of reproducible results’, ‘failure in integrating devices’ and ‘robustness of field trials’.

• Qualitative responses suggested the different approach towards funding research in radiological and nuclear weapons from different agencies. Short term 2-3 year view was detrimental to research efforts.

• The desirable characteristic of a radiological nuclear detector was mentioned inexpensive, excellent energy resolution, thermally stable, physically robust, and usable for a long operating life.

• The application trends were mentioned as:

- Radiological and nuclear detectors are physically large. Physical miniaturisation is not possible therefore improved material performance is being investigated.

- 62 -

- Increased energy analysis for radiation detection has led to higher costs. The direction of research is towards extracting more information from less expensive technological solution.

- Response time was entirely application dependent. While in border situation 2-3 seconds response time is ideal, longer at trading ports, it should be within milliseconds in crowded locations.

- Operational factors important in radiological- nuclear detection are time, distance and shielding. Time of detection is for seconds, and distance is based on packages and physical sizes of vehicles. Shielding is considered to be the main factor for planning against different scenarios.

- Results from technique such as Nuclear Resonance fluorescence were considered poor for laboratory condition. In real situations with shielding they may not produce predictable results like those from active induced fission by neutrons or gamma rays.

- One of the main application problems was considered to be absence of an accelerator which can address the lack of tunable, variable energy, continuous source of gamma rays with the right energy. The present sources are pulsed thus resulting signal to noise ratio are not feasible for application of technique.

- CeF3 material was mentioned to have been developed as proof of principle. The limitation for CeF3 was reiterated to result from the low light output. It was

mentioned that scale up to 500 gram/batch synthesis of CeF3 had been achieved.

- There are limitations in understanding of the production process.

- All detector materials show limitations and advantages over each other.

- Application areas where nanomaterials can add value would be nanoparticle inclusion in plastic for plastic scintillators.

- Nano-additives could play a role in gamma radiation detectors

- 63 -

- Nanotechnology could enhance light detection system for photo tube detection and gas detectors.

• The sensing methods for radiation and nuclear weapons detection that are presently deployed are radiation portal monitoring and spectroscopy.

• Methods for radiological and nuclear detection that are expected to be deployed after at least 5 years of development are sensor arrays for radiation detection and nanomaterials based detectors.

• The factors determining uptake of radiation detection technology are physical size, price, robustness, resolution. Response time, count rate (some scintillators are slower than others), and relationship to material properties.

• The moderately attractive future growth markets for explosives detection were expected to be radiation portal monitoring, sensor arrays for radiation and spectroscopy methods.

• Investment in technology and evaluation of product markets is important for radiation detection. One company holding sole monopoly in a market through patents is counterproductive for development in security.

• Basic research for radiation detection was perceived to be better in Europe than North America, mainly concentrated in Universities. National laboratories in US were focused on technology development and transfer for radiation detection. Europe was considered particularly weak for technology transfer.

The theme of integrated platform for detection of chemical, biological, explosive, radiological and nuclear threats was conducted at Dusseldorf in March 2009. The following outcome and recommendations resulted from the discussion:

• Technology was not sufficiently advanced to achieve single platform detection.

• An integrated modular system that focuses on Chemical, Biological and Explosive as one unit and Radiological-Nuclear detection as a separate module is a better approach.

- 64 -

• One of the main weaknesses for CBRNE detection was considered to be systems integration. It was suggested that a statement of requirements to be produced taking nanotechnology into consideration.

• Accuracy and reliability of measurement was considered to be most important characteristic. Reproducibility of measurements and operating life of sensor were considered to be poor for modular systems of detection.

• The cost of false positives are very high, therefore operational definition should be developed on a case by case basis for a modular system.

• The need for greater fundamental research in understanding the sensing mechanism was emphasised.

• It was recommended that communication between materials and sensing community be improved in order to create mutual awareness of technical breakthroughs.

• The first area of application is expected to be transportation hub for such a modular system.

• Technology penetration and application driven by state regulation for CBRNE detection.

1.3.7 Current Situation within EU

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to radiation and nuclear detection:

• European Security: High level study on threats responses and relevant technologies (ESSTRT). The support action project has provided a comprehensive overview of necessary responses to security challenges. These include technologies for detecting nuclear weapons and radiological disperse devices at airports and travel hubs. The project also investigated technologies that could develop smart containers, and border security against weapons [45].

• CBRNE related testing and certification facilities - a networking strategy to strengthen cooperation and knowledge exchange within Europe (CREATIF) was initiated early in

- 65 -

2009. The project aims to create a network of product testing facilities for CBRNE detection [43].

The following framework 7 projects funded under the security theme by the European Commission have relevance to the radiological-nuclear detection.

• Cooperation across Europe for Cd(Zn)Te based security instruments (COCAE) project initiated in 2008 is focused on spectroscopic measurements for detecting radioactivity using Cd(Zn)Te crystals [90].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is to combine technology solutions from Detection of CBRNE, area surveillance, and check point control for additional sensitive security locations. The sensor data is expected to be integrated with communication and data module to a command centre [44].

- 66 -

1.4.1 Title – Explosives

Detection of Explosives

Keywords: explosive, TNT, DNT, Semtax, RDX, Nitroglycerin, electrochemical, mass sensor, fibre optics, photoluminescence, spectroscopy, terahertz, SERS, biosensors, nanosensors, nanowires, nanotubes

1.4.2 Definition of Technology Segment

Detection of explosives in cargo, luggage, mail, vehicles, aircrafts and on personnel presents a significant challenge for civilian security. Three main means of detection are in deployment or in advanced stages of development. The first method relies on detecting traces quantities of volatile compounds of explosives, in vapour form or deposits on surfaces. The second method used is penetrating radiation that interacts with an explosive element producing a characteristic signal on the detector. The third method used combines one or more methods as platforms for detection. In this approach one detection technique compensates for the weakness of another [91].

More than a 100 explosive categories have been identified in the literature. Table EW.1 provides a list of explosives that are commonly used. The explosive characteristics used to identify the explosive are geometry, material density, elemental composition and vapour detection. The properties used for identifying explosives and drugs have been mentioned in the literature. For explosives the constituents in general has moderate carbon, high to moderate nitrogen, very high to high oxygen and very high density [92].

Table EW.1 - List of common used explosives and their chemical formula [91]

Explosive Name/contents

Standard TNT 2,4,6-Trinitrotoluene 1,3,5-Trinitro-1,3,5- RDX triazacyclohexane

PETN Pentaerythritol tetra nitrate

NG Nitroglycerin (glycerol trinitrate)

- 67 -

EGDN Ethylene glycol dinitrate

Improvised ANFO Ammonium nitrate + fuel oil

Urea nitrate Urea nitrate

TATP Triacetone triperoxide

Plastic C-4 C-4 RDX + plasticizer Semtex RDX + PETN + Semtex plasticizer

Detasheet Detasheet PETN + plasticizer

1.4.3 Short Description

There are a number of methods used to detect trace vapour such as ion-mobility spectrometry, mass spectrometry and electronic noses. Probing radiation techniques include X-ray techniques, millimetre wave imaging, terahertz technology, neutron gamma ray techniques, and nuclear quadrapole resonance. The third method uses two or more technology solutions in a complimentary way [91]. Techniques such as X- rays, gamma rays, millimetre imaging have been used for detecting explosives and weapons [92]. Based on the type of measurement obtained, explosive sensors are largely categorised into – electrochemical, mass, optical sensors and biosensors [93].

Electrochemical sensors - Electrochemical sensors convey changes in the environment through changes in current, when chemicals interact with the electrodes. Three main types of electrochemical sensors are in use namely, potentiometric, amperometric, and conductometric. Such sensors can be used for the detection of TNT in marine environments [94]. Detection of explosives has also been demonstrated with amperometric bioelectrochemical sensors [95]. These sensors have limited sensitivity, and need mobile electrolytes [93]. Nanocomposites of metal nanoparticles with carbon nanotubes solubilised in Nafion have been demonstrated for the detection of TNT and other nitroaromatic explosives [96]. Glassy carbon electrodes containing copper nanoparticles and single walled carbon nanotubes have shown a reproducible detection limit of 1 ppb. Glass carbon electrode modified by single walled carbon nanotubes has been demonstrated to detect TNT [97].

Mass based sensors - Mass based sensors generally adsorb, chemicals on to the surface and the change in mass is detected by the device. The detection of the explosive is done by a

- 68 - travelling acoustic wave or by bending of the surface. Polymer films are used in fabrication SAW sensors that are used for detecting explosives and explosive devices [98]. Sorbent coatings for SAW sensors have demonstrated a DNT detection limit of less than 100 parts per trillion [99].

Fibre optic based sensors - Fibre optical sensors have been used for detecting explosives. They rely on changes in frequency, or intensity of electromagnetic radiation for detection of explosives [93]. Explosives such as DNT and DNB have been detected at low ppb level within seconds using optical sensors that rely on changes in fluorescence properties [100]. Optic fibre based explosive detection is based on defect free zeolite film, utilises a change in sensor reflectivity on exposure. Such sensors have not demonstrated selectivity and sensing time is about 200 seconds [101].

A number of spectrophotometric methods are used for detecting explosives such as absorption based detection, photoluminescence based detection, fluorescence based detection, laser induced breakdown spectroscopy and terahertz based detection [93]. Absorption based detection based on the change in colour, has been demonstrated to detect nitrous explosives and explosive related compounds. This method has demonstrated a detection limit of 0.2 ng for DNT [102 ]. Nanosized molybdenum hydrogen bronze react with TATP to change colour from dark blue to yellow. The colour change property can be used both for titration neutralisation and for detection of explosives [103].

Photoluminescence based detection - Photoluminescence based detection, is based on monitoring the photoluminescence of a nanocrystalline porous silicon film that is exposed to an analyte in flowing air stream. Nitro aromatic compound explosives have been detected using this method [104]. Fluorescence based detection of explosives relies on quenching of fluorescence when a target molecule is acquired. The advantage of this technique is the ability to detect from a distance. Fluorescent sensory material spread over the suspected area is detected, which is illuminated with fluorescent light identifying the explosive in question. Nitro aromatic explosives have been detected with electron rich polymer semiconductors [105]. Fluorescence quenching method using pyrene as fluorophore is applied for the detection of RDX, HMX, TNT, nitromethane and ammonium nitrate [106]. Quantum dots of cadmium selnide with zinc sulphide shell have been used to detect TNT [107]. Fluorescent nanofibrous membranes prepared by electro- spinning have demonstrated very high sensitivity to trace vapours of TNT. Highly porous structures of these nanofibres have been reported to provide it high sensitivity to analytes with detection limit of 10 parts per billion [108]. Nanofibrous membranes have been reported to act as both chemiresistor sensors and fluorescence quenched sensors. These sensors based on

- 69 - conductive polymer nanotubes have uses in detection of explosive, biological and chemical agents [109].

Spectroscopic methods - Explosives have been detected using techniques such as laser induced breakdown spectroscopy. The explosive is detected by means of laser that is used to create plasma over the explosive surface. High pulsed lasers have been demonstrated to create plasma that is detected using an optical probe to determine the explosive material composition. Detection of TNT on brass and molybdenum substrates and RDX on molybdenum substrates has been demonstrated [110]. Nuclear Resonance fluorescence has been demonstrated in detection of explosives using the signatures of carbon, hydrogen and oxygen of the elements. The experimentally demonstrated technique offers advantages such as short detection times and high probability of detection [111].

Terahertz detection –Terahertz explosive sensors are based on differential absorption. A sample region is illuminated with two frequencies, chosen for a specific explosive, and to maximise the contrast between presence and absence of an explosive. This technique has been demonstrated as a detection tool for explosive and also identifying specifically the unique terahertz spectral fingerprints of TNT, TDX, HMX, and Semtax [93]. Carbon nanotubes based antennas for THz detection have been mentioned in the literature [112]. Potassium ions interaction with carbon nanotubes have shown to induce a strong dielectric response. The binding event causes the carbon nanotubes to vibrate at 0.4Tz. This effect has potentially applications as a THz detector operating at room temperature [113].

Terahertz sensing for explosives detection at airports is being developed. A product demonstrator in a portable unit with data processing has been produced [114]. Improvements in growth, design, and characterisation of low temperature grown gallium arsenide photomixers has enabled its use for sensing applications. An important component of these photomixers is nanoparticulates that reduce the charge carrier lifetime to sub-picosecond therefore allowing optical mixing to terahertz range. This approach is limited in the power output and device reliability [115]. This technique has been demonstrated in detecting bombs and explosives in envelopes, clothes, luggage and soil [116]. Terahertz method has been demonstrated to detect RDX and RDX related explosive when are covered by opaque material [117]. One of the main challenges and limitations in Terahertz in stand off detection has been reported to be environmental conditions and barrier materials as picosecond pulsed measurement cannot be accurately measured. Quantum dot based detectors have been claimed to be the detector of choice for terahertz detection. Multiband tunnelling quantum dots infrared photo detectors, with nanometre dimensions, have been produced using molecular beam epitaxy for security applications [118]. The design and characteristic of a indium

- 70 - aluminium arsenide and gallium arsenide quantum dot which respond to terahertz radiation has been mentioned in the literature [119].

Surface enhanced Raman scattering - Surface enhanced Raman scattering has been used to detect vapours of explosives. Raman systems for detecting explosives such as RDX, TNT, and PETN have been demonstrated at a distance of 50 metres and over [120]. Large enhancements of Raman signals, using noble metal nanoparticles and nanostructures have been observed for adsorbed molecules. Electrochemically roughened gold and silver substrates have been demonstrated as a field SERS sensor to detect vapour signatures of TNT [121]. Enhancement of TNT Raman signal on non-noble metal materials is being researched [122]. SERS enhancement has been demonstrated for the detection of TNT using colloidal silver suspension. High sensitivity was demonstrated in the experimental research with detection of limit at 10-15g for DNT and 10- 19g for TNT [123].

Cataluminescence - Cataluminescence is the emission of light during the catalytic oxidation of a molecule on the surface of a solid state catalyst [124]. A sensor array based on cataluminescence, using strontium, barium and aluminium carbonates as catalysts have been demonstrated for explosive gas mixtures [125].

Biosensors - Biosensors are devices that integrate a biological element on a solid state surface, enabling interaction with an analyte and signal transduction. Biological elements such as peptides, enzymes, receptors, single strand DNA [93]. Detection of TNT and DNT has been demonstrated using proteins immobilised on electrodes [126]. Immunoassays use antibodies as recognition elements in biosensors. Electrochemiluminescent immunoassays have been developed for TNT detection in which enzyme labelled antibodies are bound to paramagnetic beads on the electrode surface are used. TNT has been detected with this method in 80s to a sensitivity of 31 ppb [127]. Development and comparison of two immunoassays for detection of TNT has been based on competitive inhibition [128].

Nanosensors - Nanosensors have been mentioned to be one of the most effective platforms for detection of explosives. The most important characteristics of a trace explosive sensor are sensitivity, selectivity, reversibility and real time operation. A number of sensing elements and platforms have been mentioned for nanosensors platform such as micro-nano structures, quantum dots, nanowires, nanotubes and nanobelts [129].

Selectivity to sensors is provided by coatings such as self assembled monolayers, polymers, metal oxides and single stranded DNA. Important factors for consideration are response time and

- 71 - recovery. Self assembled monolayers of 4 mercaptobenzoic acid are good for explosive vapour detection [130]. 6-Mercaptonicotinic acid monolayer has been reported to produce good results with TNT detection [131]. Molecular imprinted polymers for the detection of TNT have also been developed and demonstrated [132].

Nanomechanical sensors have been considered an ideal platform for detection of explosives. Molecular adsorption of vapour on the surface of the cantilever, results in bending of cantilever structure, which is used to detect the presence of explosives. Piezoresistive cantilever deflection leads to a change in the resistance which is measured. Beams coated with 4-MBA have been demonstrated to detect TNT explosive vapours [133]. Nanoporus coatings tend to produce micrometer responses in the presence of vapour phase TNT and DNT. A detection limit of 520 ppt was demonstrated [134].

A number of different approaches have been considered such as thermally induced decomposition, have demonstrated a sensitivity of 40 picogram [135]. Another approach used is photo thermal deflection spectroscopy, where a bimaterial cantilever demonstrates high sensitivity to temperature changes. The bending of the cantilever results from absorbing the IR energy on the surface of the explosive molecule [136]. Amplifying fluorescence polymers have been successfully used in detection explosives. The adsorption of the explosive molecule on the surface of the polymer leads to a change in the fluorescence characteristic. AFP’s with TNT adsorbed on the surface continuously fluorescence under the ultraviolet light source. Sensors based on thin films of AFP have been commercialised by Nomadics [137,138].

Cantilever based sensors have been used in detecting explosives by identifying compounds trinitrotoluene (TNT), 2,4 dinitrotoluene (DNT); pentaerythritol tetranitrate (PETN), and hexahydro-1,3,5-triazine (RDX). TNT is a commonly used explosive and DNT remains a by product of TNT. PETN and RDX are high end explosives used for sabotaging aircrafts. The detection of the explosive vapours was demonstrated. The sensitivity of microcantilevers in detecting such explosives is approximately 14 part per trillion within 20 seconds. Active detection of explosive vapours was allowed to deposit on a piezoresistive microcantilever which has been detected using optical signals such as laser scattering [139,140,141].

Nanowires - Nanowires also provide an effective platform for sensing explosives. Interdigitated electrode capacitors modified with single walled carbon nanotube has been demonstrated to detect chemical vapours with high sensitivity. The change in capacitance is used to detect the molecules and its class [142].

- 72 -

Table EW.2– Comparative assessment of the sensor performance used for detection of explosives, as cited in review paper [93]

Explosive Sensor Type Field of application detected Detection limit

Electrochemical Soil samples RDX 0.12 ppm

Electrochemical Marine water TNT 25 ppb

Electrochemical Forensic laboratory DNB and TNT, 60 ppb for both RDX 0.2 ppm, TNT 0.11 RDX, TNT, 2,4- ppm, 2,4-DNT 0.15 ppm, Soil extract and DNT, 2,3-DNT, 2,6-DNT 0.16 ppm, 2,3- Electrochemical ground water 2,4-DNT DNT-0.15 ppm

SAW Laboratory samples 2,4-DNT

SAW Laboratory samples DNT 92 ppt

SAW Laboratory samples 2,4-DNT, TNT For detection of A low femtogram (10−15 Micro cantilever explosive vapors PETN and RDX g)

Micro cantilever TNT 520 ppt Field test (soil Optical samples) DNT 120 ppb Optical (fiber optic Ground water and based) soil extracts TNT and RDX 0.1 ppm 4 ppb for TNT vapor in air, 1.5 ppt for TNT in sea Optical water, (photoluminescence 6 ppb for picric acid in sea based) Air and sea water TNT, Picric acid water TNB, TNT, DNB, Optical (fluorescence tetryl, and 1 ppm for all these based) Laboratory samples 2,4-DNT explosives TATP and 2×10−6 mol L−1 for both Optical (fluorescence based) HMTD TATP and HMTD Optical (fluorescence based) Water samples DNP 1.0×10−6 mol L−1

- 73 -

NB 40 ppb for DNT and 17–24 ppb for Optical (LIBS) DNT nitrobenzene 0.05 ppb for both RDX and Optical fiber (biosensor) Ground water TNT and RDX TNT Electrochemical (biosensor) Laboratory samples TNT 31 ppb

Optical (immunosensor) Artificial sea water TNT 0.05 ppb Environmental Electrochemical samples and clinical (immunosensor) assay TNT 1 ppt Optical Soil and water (fluoroimmunoassay) samples TNT 450 fmol for TNT, 1 ppb for Optical (immunosensor) Laboratory samples TNT and RDX RDX

Optical (immunosensor) Seawater TNT 250 ppt 2.5 ppb in saline buffer Electrochemical and (immunosensor) Seawater TNT 25 ppb in seawater Optical (SPR based On-site detection of immunosensor) landmines TNP 10 ppt Optical (SPR based Immunosensor) Laboratory samples TNT 6 ppt

A combination of different sensor platforms and different optical modes has been suggested as an optimal method for successfully detecting explosive trace vapours. Mass, stress and thermal signals of TNT vapours measured by cantilevers are independent of one another and could provide pattern recognition. Increased selectivity and sensitivity could also be achieved by combining platforms in a single sensing unit that could measure different physical and chemical properties. An example of such a combination would be SWCNT and cantilever. A SWCNT could measure the electrical polarisation of explosive molecule adsorbed on its surface by change in capacitance. The cantilever would determine the mass and stress measurements of the same explosive molecule [129].

- 74 -

1.4.4 State of Research and Development

The sections give an overview of the technology development in relation to a specific technology. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. The technologies have been mentioned are those mentioned in the literature review for chemical, biological, explosive, nuclear, radiological, and narcotics detection. The scale of readiness mentioned ranges from fundamental research to mass market. The span of activities for a particular sensing method represents the different applications, nanomaterials used and threat agents detected. A validation of their status is necessary from the economic and other technology sectors perspective. The table EW.3 below gives an overview of the technology development in relation to enabling nanotechnologies for explosives detection.

Table EW.3 - Technology and its Development Status for category of explosive weapons detection

Field Trials / Fundamen Pilot plant ( Deployed Applied Prototy Mass tal Pre- (Commerciali Research pe Market Research commercialisati sed) on)

Electroc- ƒ ƒ ƒ ƒ hemical

Mass ƒ ƒ based Fibre ƒ ƒ ƒ optic Photolumi ne- ƒ ƒ scence

- 75 -

Spectrosc opic ƒ ƒ ƒ ƒ methods Terahertz ƒ ƒ ƒ detection Surface enhanced ƒ ƒ Raman scattering Catalumin ƒ isc-ence Biosensor ƒ ƒ s Nanomec ha-nical ƒ ƒ sensors Nanowire ƒ s

1.4.5 Additional demand for research

Specific research needs were mentioned in the literature relating to different detection aspects are as follows:

• Explosives detection in civilian zone can be done best with sensors that can be deployed in mass number are miniature in size, selective and sensitive for detection, inexpensive and can be mass produced [129].

• Low vapour pressure of the explosive molecules present a challenge in detection for collection within an acceptable detection time. The concentration of a potential explosive molecule decreases as source from the distance increases. Very low concentration of the molecule being detected provides false positives. Research is needed in nanosensors for trace explosives to integrate the sensing element, with vapour collection and pre- concentration functionality [129].

• Research specific to microcantilever detection capabilities – detection of trace amounts of multiple analytes from researching vapour concentration, controlling experimental conditions, providing a wide variety of coatings for sufficient signal variation [130].

- 76 -

• Speed of detecting is a challenge for chemical, biological and radiological exposure. This is essential for providing a response in the event of a nerve gas attack. Detection times of seconds to minutes could not only limit the inhaled quantity but also the following prophylactic action [130].

1.4.6 Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were observed:

• Funding research and development for detection of CBRNE and Narcotics was considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and Narcotics’ were considered technological and social impact. The technological drivers relate to cost, performance, efficiency and absence of solutions. Other secondary drivers were indicated as competitive advantage in conflict situations, safety, productivity gains and regional security policy.

• The main drivers for R&D of ‘explosive detection’ were mentioned to be ‘cost of sensors, devices and instrumentation’, ‘size of detectors’, ‘mobility of detection unit’, ‘life time of operation’ and ‘accuracy of detection’. Other secondary drivers were identified as ‘integration of detection platform’, ‘sensitivity’, and ‘time for detection’.

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’ were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate technology transfer from Universities’. Secondary barriers indicated were ‘intellectual property conflicts’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU needs to consider dual commercial use of security technology as the market was relatively smaller than US. While trends in US are towards government driven technology that is validated, EU grants are inadequate for proving technology. It was suggested that government validation of systems was necessary as laboratory systems not scaled for field use.

- 77 -

• The main barriers to R&D of ‘explosive detection’ were indicated as ‘inadequate research funding’, ‘lack of skilled personnel availability’ and ‘lack of reproducible results’. Other secondary barriers were mentioned to be ‘poor detection limit’, ‘failure in integrating devices’, ‘robustness of field trials’ and ‘inadequate skilled personnel’.

• The most important functionality for detection were indicated as ‘sensitivity of specie being detected’, ‘reproducibility of accurate results’, ‘retaining functionality in wide operating conditions’, and ‘long operating life with minimum maintenance’. ‘Collection and sampling’ and ‘specificity’ were considered other very important functional requirement.

• Other secondary desirable functionalities for detection were indicated as ‘stability of detection material’, ‘multifunctionality’, ‘signal transduction’, ‘minimal sample preparation’, ‘integration of detector into monitoring unit’ and ‘low cost’. ‘Reversibility’ was considered a relatively less important functionality.

• The application trends were mentioned as:

- The charecteristics of a detector application are mission and scenario dependent.

- Development of portable and sensitive detection devices. There is a present lack of portable instruments with good sensing characteristics.

- Application development trend directed toward broad based technologies primarily for transportation hubs.

- Development of nanostructured functional materials and interfaces for high performance detection of chemical agents.

- Systems integration is a gap in technology development for detection.

- Low false positives and low false negatives are the most important application requirement.

- Response time was entirely application dependent. While in border situation 2-3 seconds response time is ideal, longer at trading ports, it should be within milliseconds in crowded locations.

- 78 -

- Operational constraints were identified as environmental changes such as temperature, humidity and large number of interferants. Mobility of detection device, and calibration for temperature and humidity were mentioned as constraints.

- Other operational constraints were mentioned to be calibration of measurement, skills and interpretation needed from operator.

- Processing constraints were identified as lack of basic understanding to control nanomaterials in a precise manner.

- Improving cost effectiveness by controlled large scale production and improve laboratory infrastructure for mass scale production.

- Long development life cycles for applications are characterised by delivering scientific results, establishing performance and establishing cost effective performance of detection technologies.

• The deployment of detection methods for explosives was perceived to be:

ƒ sensing methods presently deployed are electrochemical, optical fibres, mass based and spectroscopy based detection.

ƒ methods for deployment after 5 years of development are terahertz and surface enhanced raman scattering.

ƒ methods expected to take over 10 years to be deployed were mentioned to be nanowires, nanomechanical sensors, cataluminescence, and biosensors.

• Development challenges for biosensors were mentioned to be reliability, long operating life. Cost, sample handling, selectivity and robustness are factors which would determine the uptake of biosensors. For terahertz the development challenge was considered to be cost effectiveness. SERS and spectroscopy had limitations due be being laboratory based methods. Cost and power are other issues to be addressed for spectroscopy. Nanomechanical research challenge was mentioned to be interfacing between

- 79 -

mechanical and sensing function. Sensitivity, selectivity, reproducibility and pattern recognition are factor which would determine the uptake of nanowires and nanomechanical.

• The very attractive and relatively higher growth market for explosive detection was perceived to be terahertz.

• The moderately attractive growth markets for explosives detection were expected to be electrochemical, biosensors, mass based, surface enhanced raman scattering, optical fibres, spectroscopy based detection and nanowires.

• North America was considered relatively better than Europe which was considered better than Asia for fundamental and applied research, industrial technology development and commercialisation for the Detection sub-sector. While Asia was considered better for cost effectiveness for technology, EU was considered better for governmental policy for innovation. Qualitative responses mentioned that EU research was complimentary to US for explosive detection. It was mentioned that Europe had existing sensor deployment relatively better than other world regions, it lacked research and development for future leadership.

• Qualitative suggestions on improvement of capabilities were:

ƒ collaborative research between security agencies, academia and industry

ƒ encouraging tax exemptions and basic research to understand nanomaterials better.

ƒ technology transition from science to implemented demonstrators is gap that needs to be addressed.

ƒ creation of multinational, multidisciplinary fund for development

ƒ creating a centre for standardised testing for different sensors

- 80 -

The theme of integrated platform for detection of chemical, biological, explosive, radiological and nuclear threats was conducted at Dusseldorf in March 2009. The following outcome and recommendations resulted from the discussion:

• Technology was not sufficiently advanced to achieve single platform detection.

• An integrated modular system that focuses on Chemical, Biological and Explosive as one unit and Radiological-Nuclear detection as a separate module is a better approach.

• One of the main weaknesses for CBRNE detection was considered to be systems integration. It was suggested that a statement of requirements to be produced taking nanotechnology into consideration.

• Accuracy and reliability of measurement was considered to be most important characteristic. Reproducibility of measurements and operating life of sensor were considered to be poor for modular systems of detection.

• The cost of false positives are very high, therefore operational definition should be developed on a case by case basis for a modular system.

• The need for greater fundamental research in understanding the sensing mechanism was emphasised.

• It was recommended that communication between materials and sensing community be improved in order to create mutual awareness of technical breakthroughs.

• The first area of application is expected to be transportation hub for such a modular system.

• Technology penetration and application driven by state for CBRNE detection.

• It was recommended that sensor requirements for the EU are critically examined.

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1.4.7 Current Situation within EU

TERAEYE is another framework project that aims to develop an innovative range of inspecting passive range of systems based on Terahertz wave detection. The two dimensional array of detectors are expected to detect harmful explosive, biological, and chemical agents at airports, railways hubs and civilian zones.

The following framework 7 projects have been funded by the European Commission in the Security theme that are relevant to explosives detection:

• Optical technologies for the identification of explosives (OPTIX) project was initiated in 2008 to develop a system for stand-off detection of explosives based on LIBS, RAMAN and IR [143].

• Localisation of threat substances in urban society (LOTUS) project was initiated in early 2009. The LOTUS project aims to create a system to detect the preparation of explosives and drugs during preparation and production of a terrorist plot. This will be demonstrated by detection using sensors and global infrastructure for positioning and networking [144].

• Underwater coastal sea surveyor (UNCOSS) project was initiated in 2008, aims to protect the naval infrastructure against underwater improvised explosive devices. The objective is to provide a non-destructive tool for the evaluation of underwater objects based on neutron sensors [145].

• CBRNE related testing and certification facilities - a networking strategy to strengthen cooperation and knowledge exchange within Europe (CREATIF) was initiated early in 2009. The project aims to create a network of product testing facilities for CBRNE detection [43].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is to combine technology solutions from Detection of CBRNE, area surveillance, and check point control for additional sensitive security locations. The sensor data is expected to be integrated with communication and data module to a command centre [44].

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to explosives detection:

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• European Security: High level study on threats responses and relevant technologies (ESSTRT). The support action project has provided a comprehensive overview of necessary responses to security challenges. These include technologies for detecting weapons and hazardous materials at airports and travel hubs [45].

• The active terahertz imaging for security (TERASEC) project, that aims to develop terahertz detection. The detection of threats, explosives, pathogens and chemicals in person, luggage or post were the focus of the project. The Terahertz imaging systems were developed and evaluated in the 24 month period [46].

• Secure Container Data Device Standardisation (SECCONDD) project aims to initiate standardisation of technical interface between secure container or vehicle and a data reader at a port or border crossing. The project is expected to identify any potential threats from terrorist activity or insertion of contraband goods [146].

• Transport Infrastructures Protection System (TIPS) project aimed to address security of mainline, subway and metro systems of European cities. The project addressed technological solutions for safety of passengers against explosives along with the communication infrastructure [147].

• Hazardous Material Localisation and Person Tracking (HAMLeT) project demonstrated an indoor security system using sensors to give real time decision information. This was done by classifying, tracking and localising potential threats. Chemical sensors were used for detection of hazardous materials such as explosives [47].

• Integrated system for on-line trace explosives detection in solid and vapour state (ISOTREX) project addresses trace explosive detection of high energy material. The project investigated and development an instrument for particle and vapour detection for airports, customers and central post-offices. The instrument was based on Laser Induced Breakdown Spectroscopy and IR absorption methods [148 ].

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1.5.1 Title - Narcotics

Detection of Narcotics

Keywords: cocaine, heroine, fentanyl, drugs, narcotics, spectrometry, SERS, gamma rays, neutron analysis

1.5.2 Definition of Technology Segment

The international narcotics control board has produced a list of narcotics drugs under international control that is included in Schedule I, II and IV. The exhaustive list also provides the chemical formula and its chemical content of chemical substances considered illegal and under international control. It also provides a list of those narcotic drugs that are exempt under some provisions [149]. The segment covers detection of chemicals such as heroine, cocaine and fentanyl.

1.5.3 Short Description

Fentanyl has been reported to be 40 times more potent than heroine and has been used as a narcotic. Ion selective membrane electrodes have been reported as sensors for Fentanyl. Polyvinyl chloride based membranes have been applied with negligible interference from other chemicals to detect fentanyl citrate in injections [150].

A sea portable drug detection system can enable detecting threats such as drugs, explosives, nuclear weapons and chemical weapons behind hidden compartments of maritime vessels has been mentioned in the literature. Detection of gamma ray signature of chemicals in narcotics has been demonstrated for maritime vessels using thermal neutron analysis and fast neutron analysis. This is based on characteristic gamma rays generated by elements such as hydrogen, nitrogen and chlorine capturing thermal neutrons. The man portable detection system has been demonstrated for Heroin hydrochloride, Cocaine hydrochloride, Heroin, and Cocaine [151].

Commercially available ion mass spectrometry has been reported to have applications in detection of drugs. Ions are produced through atmospheric pressure ionisation are pulsed through an electric field to a collector, during which the time of flight is measured. The advantages offered by this technique are its portability, selectivity, high sensitivity (parts per

- 84 - billion) and low cost. The detector could potentially be used as a stand alone sensor or as an online system [152].

Surface enhanced Raman scattering offers very high sensitivity to detection of drugs and narcotics molecules. Physiological fluids such as blood, urine and saliva have been used in analysis of narcotics [153]. Research in identification of cocaine, heroin, amphetamines, 1, 4- benzodiazepines and various metabolites of the drugs has been conducted using SERS with high performance liquid chromatography [154]. SERS has been combined with electrophoresis and flow injection analysis to quantitatively analyse cyanide levels [155,156].

1.5.4 State of Research and Development

The section gives an overview of the technology development in relation to a specific technology. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. The technologies have been mentioned are those mentioned in the literature review for narcotics detection. The scale of readiness mentioned ranges from fundamental research to mass market. A validation of their status is necessary from the economic and other technology sectors perspective. The enabling technologies for the detection of narcotics, in relation to its development status have been mentioned in table N.1 below.

Table N.1 - Comparative Research and Development Status for narcotics detection

Field Trials / Pilot Fundame Applied Deployed Prototy plant ( Pre- Mass ntal Researc (Commercial pe commercialisatio Market Research h ised) n)

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Membran ƒ es

Thermal neutron ƒ ƒ analysis Fast neutron ƒ ƒ analysis Spectro metric ƒ ƒ methods

SERS ƒ ƒ ƒ

1.5.5 Additional demand for research

Additional demand for research was mentioned in further development of SERS based detection of narcotics during the engagement process. Research directed towards quantitative aspects of SERS and their improvement were considered desirable [157].

1.5.6 Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were observed:

• Funding research and development for detection of CBRNE and Narcotics was considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and Narcotics’ were considered technological and social impact. The technological drivers relate to cost, performance, efficiency and absence of solutions. Other secondary drivers were indicated as competitive advantage in conflict situations, safety, productivity gains and regional security policy.

• The main drivers for R&D of ‘Narcotics detection’ were mentioned to be ‘cost of sensors, devices and instrumentation’, ‘size of detectors’, and ‘sensitivity of detection’. Other

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secondary drivers were mentioned as ‘mobility of detection unit’, ‘time of detection’, ‘life time of operation’ and ‘accuracy of detection’.

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’ were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate technology transfer from Universities’. Secondary barriers indicated were ‘access to equipments, infrastructure and manufacturing facility’ and ‘intellectual property conflicts’. Other barriers also mentioned were ‘lack of skilled personnel availability’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU needs to consider dual commercial use of security technology as the market was relatively smaller than US. While trends in US are towards government driven technology that is validated, EU grants are inadequate for proving technology. It was suggested that government validation of systems was necessary as laboratory systems not scaled for field use.

• The main barriers to R&D of ‘Narcotics detection’ were indicated as ‘inadequate research funding’, ‘failure in integrating devices’ and ‘lack of reproducible results’. Other secondary barrier was mentioned to be ‘poor detection limit’.

• The most important functionality for detection were indicated as ‘sensitivity of specie being detected’, ‘reproducibility of accurate results’, ‘retaining functionality in wide operating conditions’, and ‘long operating life with minimum maintenance’.

• Other secondary desirable functionalities for detection were indicated as ‘stability of detection material’, ‘reversibility’, ‘multifunctionality’, ‘signal transduction’, ‘minimal sample preparation’, ‘integration of detector into monitoring unit’ and ‘low cost’.

• The application trends were mentioned as:

- Development of portable and sensitive detection devices. There is a present lack of portable instruments with good sensing characteristics.

- Operational constraints were identified as environmental changes such as temperature, humidity and large number of interferants. Mobility of detection

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device, and calibration for temperature and humidity were mentioned as constraints.

- Combining SERS detection and identification of narcotics with a separation technique to address issues in reproducibility, retention of functionality and long life. In a separation coupled system, the problems associated with SERS are expected to be overcome.

- Other operational constraints were mentioned to be calibration of measurement, skills and interpretation needed from operator.

• The sensing method for narcotics detection that is presently deployed is spectrometric methods and bioassays for narcotics detection. Spectroscopy methods market was considered to a moderate growth market. Miniaturisation of spectroscopic methods was considered a development needs for enhanced application. Factors that would determine uptake of the technology are size, cost and sample preparation.

• Method for narcotics detection that is expected to be deployed in the next 5 years is surface enhanced raman scattering. The SERS detection market was consider a moderate future growth market.

• Method for narcotics detection that is expected to take over 10 years to be deployed was indicated to be based on membranes for detection.

• North America was considered relatively better than Europe which was considered better than Asia for fundamental and applied research, industrial technology development and commercialisation for the Detection sub-sector. While Asia was considered better for cost effectiveness for technology, EU was considered better for governmental policy for innovation.

1.5.7 Current Situation within EU

The following framework 7 project has been funded by the European Commission in the Security theme that is relevant to narcotics:

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• Localisation of threat substances in urban society (LOTUS) project was initiated in early 2009. The LOTUS project aims to create a system to detect the preparation of explosives and drugs during preparation and production of a terrorist plot. This will be demonstrated by detection using sensors and global infrastructure for positioning and networking [144].

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2. Incident Support

2.1.1 Title – Neutralising CBRNE effect

Neutralising CBRNE effect

Keywords: neutralising, CBRNE effect, prophylaxis, antidote, organophosphorous compounds, spectrometry, vaccines, sera, antinfectious medicine, drug delivery, diagnostics, nanoparticles, biosensors, radionucleotides, polymer gels, biodegradable nanospheres, nanofiber, surgery, implant, nanomaterials, nanocomposites

2.1.2 Definition of Technology Segment

The sub-segment addresses nanotechnology developments that deal with responding to an attack on civilian population. The nanotechnology developments covered in this sector are related to response measures in the event of a chemical, biological, radiological, nuclear and explosive attack in civilian zones. The technology developments considered are those that relate to responsiveness of medical action and removing contaminating species from the environment.

2.1.3 Short Description

The neutralisation of CBRNE effect has been further divided into response to chemical and biological effects, response to radiological and nuclear weapons attack and response to explosive events. In the event of a CBRNE attack in civilian zones, guidelines and emergency responses for environment, medical and administrative are well laid out.

2.1.3.1 Response to Chemical and Biological threats attack

Organophosphorous compounds are neurotoxic and have been used as chemical warfare agents. This section presents the response to a chemical and biological attack on civilian population. The severity and rapidity of the effect of the chemical warfare agents, limits the use of administering therapeutic antidotes. A typical antidote is acetylcholine receptor for atropine. A model has been developed using which the exact amount dose of human butyrylcholinesterase enzyme is required for prophylaxis against a specified dose of the organophosphate. The

- 90 - mathematical model was built upon experimental data that was derived from in-vitro methods of AChE and butyrylcholinestrase inhibition and calculation of biomolecular rates. The first part of the model predicts the exponential decay of the administered butyrylcholinestrase. The second part is a mass action model which looks at interaction of organophosphate, butyrylcholinestrase and a neural surrogate for AChE. The limitation of the approach is the lack of validation of use of such a prophylaxis in a disaster situation, and immunological reaction that may arise from repeated use of the enzyme on the individual. One of the goals would be the prevention of long term consequences of nerve agent exposure [158].

Response of engineered human skin to sulphur mustard has been studied and reported in literature. The investigation was focused on establishing the dose and time relationship of tissue. This was done by characterising response by morphology, apoptosis, ultrastructural, inflammation and basement membrane alteration. The findings are expected to help in understanding the damage mechanisms and development of enhanced countermeasures [159]. Immunochemical analysis of chemical warfare agents adducts such as sulphur mustard, lewisite and nerve agent with DNA and proteins have been reported. Mass spectrometry based methods have been observed for diagnosis and dosimetry for exposure, health survelliance and forensic purposes [160]. The mass use of prophylactic antibiotics and gas masks has been mentioned in the literature in the event of a chemical or biological threat attack. The release of toxic materials is managed by hazardous materials control system as laid out by the United Nations guidelines [161]. A Delphi study was conducted in United Kingdom, to produce consensus statements, for response and planning of biological incidents. Aspects covered were identification of risks, personal protective equipment, contamination, transmission of infection, and accessing device [162].

The process of dealing with chemical and biological threats has been identified in the literature. Six measures of alerting, detection and diagnosis, availability of pharmaceutical countermeasures such as vaccines, sera and antinfectious medicine, medical management of victims, training and information, and research and development has been mentioned in the literature. Passive and active immunotherapy and immunoprevention has been mentioned. The use of nanoparticles as vehicles for antibiotics has been demonstrated against salmonella in mice. Challenges for future development have been mentioned as protecting and selectively delivering peptides and proteins avoiding adverse reaction to the immune system [163].

Delivery of antidotes - A number of drug delivery methods enabled by nanotechnology are under development that may have potential applications for vaccines, anti-infective medicine, antibiotics, and anti-inflammatory drugs. The pace and specific nature of medical response is

- 91 - essential in addressing victims of potential attacks. Nanoparticle based drug delivery improves the stability, targeted delivery, increases the drug carrying capability and releasing for a range of drugs. They also provide the ability to carry both hydrophilic and hydrophobic molecules. Polymer based therapeutics have been mentioned to have applications in antibiotics delivery. Polymer therapeutics includes polymer drugs, polymer drug conjugates, polymer protein conjugates and polymer micelles. Nanogels based drug vehicles have also mentioned. Nanoparticles of albumin, chitosan and lectin are currently being used for drug delivery. Lipids based solid, nanostructured carriers and drug conjugates are being researched. Nanoemulsions based delivery of drugs to tumours has been reported in the literature. Experimental research on colloidal nanoparticles of gold for delivery in a number of conditions has been mentioned. Ceramic nanoparticles processed using the Sol-Gel techniques have been used for delivering drugs to tumour cells. Gold nanoparticles coated on silica also provide a delivery platform. Apatamer based drug delivery is advantageous due to high affinity and high specivity. A number of nanoparticle and aptamer conjugates are being researched. Drug delivery based on liposomes has been reported for a number of biological and pharmaceutical compounds such as antibiotics, antioxidants, vitamins, haemoglobin, ATP and genetic material. Niosomes have been reported to be advantageous for gene delivery. Polymer and phospholipid micelles are being researched for certain delivery options. Dendrimers are being used to release anti-cancerous drugs. These are also known to be effective against bacterial and viral infections. Carbon nanomaterials such as nanotubes and nanohorns are being considered and researched as delivery vehicle for improving specivity. This has been achieved by either functionalising the molecule on the surface or by means or encapsulating it in the nanotubes. Other materials and structures such as nanoscale sponges, nanoscale diamonds and thin films are also being researched for drug delivery. More details in use of these approaches and methods can be obtained from the ‘Drug delivery’ report in the ‘Health, Medicine and Nanobio’ technology sector of the Observatory Nano project.

Diagnostics - Theranostics is the field that combines drug delivery and diagnostics. Iron oxide magnetic nanoparticles offer promising applications in targeted drug delivery. Quantum dots and carbon nanotubes based sensors have been reported as the most promising nanomaterials for diagnostic applications. Sensing applications are based on the recognition of proteins, DNA, RNA and viruses. Nano-enabled biosensors offer the potential of identifying up to a hundred viruses in parallel processing. Field effect transistors based on carbon nanotubes in a hand held device has shown to detect asthama. Carbon nanofibres integrated into micro-fluidic devices have been mentioned to detect micro organisms and toxins known to cause water based illnesses. A number of other methods like immunosensors, enzymatic and viral sensors can be used in medical diagnostic of biological species. Non-invasive molecular imaging using Magnetic Resonance Imaging, Computer Tomography, Positron Emission Tomography, and Ultra Sonography.

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Nanoparticles are used as contrasting agents such as fluorescent probes. Quantum dots applications have been mentioned in the literature to have wide ranging application from contrasting agents to fluorescence applications in DNA arrays and immunofluorescence arrays. Gold, silica and magnetic nanoparticles have also been reported in the literature to have diagnostic applications. Lab on a chip has potential applications in diagnostics due to its rapid, highly sensitive and high throughput characteristics. Other technologies with relevant applications to diagnostics are Nanopore, Lab in a cell, capillary electrophoresis and microscopy related advances. A more detailed view on the applications is available from ‘Diagnostics’ report in ‘Health, Medicine and Nanobio’ technology sector of the Observatory Nano project. Anti-body based diagnostic was mentioned for small pox and other agents, where pathogen is known. The advantage of the method is that it is fast with a turn around time of 10 – 15 minutes. The drawback of this is anti-body for each pathogen is needed. Chip readouts like those of Affymetrix can be done for 100 pathogens however the turn around time is slow up to 4-8 hours [164] .

2.1.3.2 Response to Radiological and Nuclear weapons attack

Nano-sized magnetic absorbents have been mentioned in the literature to be effective at treatment of low level radioactive material. Hexacyanoferrates have been mentioned in the literature for their cesium sorption properties. The preparation of magnetite hexacynoferrate composite has been done through wet dispersion, with in-situ precipitation synthesising coating on magnetite. A particle distribution of between 8-30nm was achieved using this synthesis route [165].

Zircon and more complex ceramics pyrochlore, perovskite, and zirconolite have been proposed as forms to safely encapsulate plutonium from civilian reactors. Experimental studies have been conducted to study the irradiation damage, at a nanometre scale, caused by radioactive material in host ceramic matrix [166]. Remediation of nuclear waste and its safety has been mentioned in literatures as one of the most serious problems facing nuclear installations. The waste containing cesium and strontium ions have been dealt with using very targeted inorganic ion exchangers. The application of nanostructured sodium silicotitanate, for selective removal of cesium ions and sodium titanate for removal of strontium ions has been reported in the literature. Hydrothermal methods of processing and ion exchange mechanism have been observed [167].

Determination of environmental contamination by radionucleotides such as plutonium, uranium and americium require accurate analysis. Alpha spectrometry and inductively coupled plasma mass spectrometry has been reported in the literature as methods for environmental monitoring, nuclear safeguards and nuclear forensics for radionucleoides in picogram quantities [168].

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Inductively coupled plasma mass spectrometry has been reported in the literature for the detection of plutonium isotopes, and strontium in ground water supply. The limits of detection reported were in femtograms per ml for the radionucleotides [169].

Super adsorbent polymer gels have been reportedly developed as a response measure in the event of a radiological attack in civilian zones. The application would be done by means of a spraying device in the form of an aqueous suspension. The action of the foam takes place by absorbing the radioactive particles into the polymer structure, where they bind to the nanoparticles contained in the gel. A vacuum device is then used to remove the gel. Arragone National Laboratory in the United States has conducted field trials and removed 98% of radioactive elements from cement and 80% from building facades [170].

Biodegradable nanospheres have been reported in the literature for removing toxins resulting from a radiological and nuclear weapons attack. Poly (D, L-lactide) nanospehere 100 – 5000nm in diameter and are injected into the blood stream of the victim. The magnetic iron oxide is coated with polyethylene glycol to prevent white blood cell attack. The nanoparticles are further coated with proteins that are specific to the toxin. This method offers advantages over existing methods due to the width of toxins it can address and the short time interval they can detoxify blood. Conventional techniques in relation to filtration of blood and can be time consuming. This method for detoxifying is also to be used in treating victims of a chemical or biological attack. The theoretical and preliminary experimental data has been presented in the literature [171].

2.1.3.3 Response to Explosive Incident

The application of self assembly peptide in establishing a nanofiber barrier has been reported in the literature. This functions by means of incorporating into tissue and forming an extra cellular matrix. The method has been experimentally demonstrated in stopping bleeding without causing any secondary damage in spinal column, brain, femoral artery, liver and skin. The advantage offered in traumatic situation such as response to explosive events is the ability to stop bleeding without use of pressure, cauterization, vasoconstriction, coagulation, or cross-linked adhesives. This method for stopping bleeding is also not toxic and does not cause any immune reactions [172].

Explosives incident can result in bleeding and damage to the human body. Nanotechnology advances in surgery and wound dressing are expected to provide enhanced capabilities in attending to emergency victims of such incidents. A number of such developments have been reported in the surgery. Bone and dental damage resulting from explosions can be addressed by

- 94 - bone implants using nanophase materials along with polymers that are used to create an extra cellular matrix. Nanoscale coating of titanium dioxide are used to improve mesenchymal cell growth have been reported in the literature. Protein immobilisation on titanium implant and nanocrystalline diamonds in implants has also been reported to improve bioactivity. Implants enabled by ceramic nanoparticles are being developed for hip and knee replacements. Zirconia nanoparticles enabling such implant provide enhanced mechanical resistance and longer life. Nanocomposites formed from hydroxyapatite nanocrystals and collagen nanofibres have been mentioned as scaffolding material for bone surgery. Nanostructured titanium has been reported to improve bone adhesion and strength. Titanium nanotubes have been proposed as coatings for implantable devices.

Research and development of nanoscale material enabling implants is expected to enhance capabilities in attending victims of explosion attacks. Nanoscale calcium phosphates have been mentioned for applications as dental implant. Cartilage implants made from anodised titanium with nanopores and carbon nanotubes have been reported in the literature. Nanofibre scaffolds have been mentioned for application in bladder replacements. Polydioxanone developed as nanofibres have been mentioned for application in tissue engineering for vascular grafts. The use of magnetic nanoparticles as coating on the surface of stents in blood vessels has been reported in the literature. Regeneration of neurons using carbon nanotubes fibres has been reported in the literature, where the nanotubes act like conducting electrodes. Biodegradable polymer scaffolds for nerve regeneration have been reported to be successfully acting as extra cellular matrix for neuron growth. Nanowires with high surface area have reported applications in neural implants. Nanowires have also been suggested as retinal implants, and experimental studies have been conducted to investigate their potential neuron-nanowire interface. Nanoscale silver has been used for its antimicrobial properties during surgery in wound care dressing. Nanofibre membranes have been reported to have applications in wound care dressings. A more detailed assessment of implants and wound dressing can be obtained from ‘Surgery and Implants’ assessment in the ‘Health, Medicine and Nanobio’ technology sector of the Observatory Nano project.

2.1.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling nanotechnologies. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market

- 95 - application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. The Response to a CBRNE event has been presented as a comparative assessment of technology readiness levels in Table NA.1, NA. 2 and NA.3. The technology readiness level details for medical responses can be validated and obtained from the Health, Medicine and Nanobio Technology Sector.

Table NA.1 – Comparative assessment of Research and Development for Neutralising chemical biological attack

Field Trials / Fundame Applied Deployed Prototyp Pilot plant ( Pre- Mass ntal Researc (Commerci e commercialisatio Market Research h alised) n)

Vaccines ƒ ƒ ƒ

Prophylat ic ƒ ƒ ƒ ƒ antibiotic s Anti- infectious ƒ ƒ ƒ ƒ medicine Drug delivery based on ƒ ƒ ƒ ƒ nanoparti cles Nano enabled ƒ ƒ ƒ diagnosti cs

A comparative assessment of research and development status of enabling nanotechnologies for radiological and nuclear attack can be seen from Table NA.2 below.

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Table NA. 2 – Comparative assessment of Research and Development status of incident response to radiological and nuclear attack

Fundamen Field Trials / Pilot Deployed Applied Prototyp Mass tal plant ( Pre- (Commerciali Research e Market Research commercialisation) sed) Nanosized magnetic ƒ sorbent Nanostruc tured ƒ sodium titanate Spectrom etry ƒ ƒ technique s Super adsorbent ƒ ƒ ƒ polymer gel Biodegrad able ƒ ƒ ƒ nanospher es

A comparative assessment of research and development status for nanotechnologies enabling a response to an explosive attack can be seen from Table NA.3 below.

Table NA. 3 – Comparative assessment of Research and Development Status for explosive attack response

Field Trials / Pilot Fundame Applied Deployed Prototyp plant ( Pre- Mass ntal Researc (Commerciali e commercialisation Market Research h sed) ) Self ƒ ƒ ƒ ƒ assemblin

- 97 - g peptide on nanofibre Nano titanium dioxide ƒ coating for implants Titanium nanotube s coatings ƒ for implants Nanocom posites ƒ ƒ for bone surgery Nanoscal e phosphat ƒ e for dental implant Nanofibre s for ƒ ƒ ƒ ƒ vascular grafts CNT for neurogen ƒ eration surgery Nanowire s for ƒ implant Nanofibre membran e for ƒ ƒ ƒ ƒ wound dressing

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2.1.5 Additional demand for research

Additional research needs for diagnostics and nanotechnology that would be beneficial for neutralising CBRNE response as observed in the ‘Health, Medicine and Nanobio’ sector of Observatory were mentioned as:

• Diagnostic equipment functionality in high noise situations in accidents and emergencies.

• Improving flow characteristics in nanofluidic channels, and development of coatings for reduction of clogging.

• Improving the stability of quantum dots used in diagnostics and imaging.

• Further research on toxicity of nanomaterials used in diagnostics and imaging.

• Better (small) animal models, and adapted imaging techniques for these models, for the development of new in vivo techniques and more accurate probe development [173].

Additional demand for research in drug delivery that would be beneficial for Neutralising CBRNE response, as observed in the ‘Health, Medicine and Nanobio’ sector of Observatory were as follows:

• Fundamental research in improved understanding of the mechanisms associated with nanostructure transport across cell membranes. Understanding is also needed in interactions between these novel nanostructures and cells.

• Applied research is needed in self assembly of polymers for creation of novel structures for application in drug encapsulation and delivery.

• Research on novel nanostructures and coatings that can deliver drugs in response to changes in pH, temperature, and enzyme interaction.

• Fundamental research is needed on understanding the mechanism and method for release of drugs from delivery vehicles.

• Design and development of drugs that enhance specificity and reduce toxic side effects.

• Applied research is needed in implantable drug delivery devices and nanosensors.

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• Particles that resemble viruses for gene delivery [173].

• Further research in drug loading efficiency of nanostructures was mentioned.

• Research and development of biodegradable nanostructures.

• Further research in toxicity of nanomaterials being researched for drug delivery options.

The following research needs for drug delivery [164] were mentioned in the expert engagement process:

• Companion equipment to help monitor the effectiveness of some of the nano decontamination agents.

• Equipment that can be used to make smart materials more effective; remote tuning on charging of materials to function in multiple environments, i.e., controlled electronic assembly or disassembly.

• Encapsulation and removal of contaminants on skin, buildings and wildlife.

• Sample acquisition and preservation for future analysis and archival.

• Active indicators in smart materials to indicate type, level and extent of contamination on materials for biological or radioactive chemicals

• Storage of blood and blood products for use in disaster

• Improved shelf life is needed for long-term blood storage before deployment. This can be accomplished by nano materials for storage without the need to stabilize temperature, thus no cold chain is needed.

Additional research needs for surgery and implants that would be beneficial for neutralising CBRNE effect, as mentioned in the ‘Health, Medicine and Nanobio’ sector of Observatory were mentioned as follows:

• Research on nanocomposites that are biocompatible and suitable for bone replacement.

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• Research needs for modifying surface of implant for improving implant integration into the body. Applied research on immobilising functionalising molecules on surface of implant coatings.

• Research has been mentioned on novel polymers, polymer mixes, and self assembled compounded for implant stability, compatibility and integration.

• Research on miniaturisation of implant devices and power sources for such devices has been mentioned.

• For large extended deployments mobile manufacturing on demand for nano materials that can be placed at site [164].

2.1.6 Applications and Perspectives

The expert engagement process identified the following for the technology segment:

• Funding research for the Incident Support Sub-sector was considered more important for societal reasons than for the economy.

• The main drivers for research and development in Incident Support were considered to be technological and social impact resulting from the technology. This was followed by ethical, environment, health and safety drivers. The technological drivers are cost, performance, efficiency and absence of technological solution.

• The main drivers for research and development in neutralising effect of CBRNE incident was mentioned as severity of incident, risk posed by incident, impact of response and time taken for response to take effect.

• Main barriers for research and development for Incident Support were identified as availability of finance to early stage companies and intellectual property conflicts. Secondary barriers mentioned were access to equipment and infrastructure, inadequate technology transfer, and lack of supportive governmental policy.

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• The main barriers for research and development for neutralising CBRNE response segment were identified as inadequate research funding, robustness of field trials and availability of countermeasures and antidotes.

• The most important functional requirements were identified as effectiveness of diagnosis and reproducibility of results. The functionality following these was mentioned to be ease of administering therapeutics and drugs, and monitoring condition of victims.

• The engineered skins used to study the effects of chemical agents were considered to be a good model. The limitation in using engineered skin model is that they lack active transport and an immune system. These limitations are likely to cause a miscalculation of the rate of damage and the contribution of the immune system to respond.

• The response to threat agent needs to include an active material to either immobilize the specific agent or cause it to be expelled from the skin, in some other form than a blister.

• Nano enabled surgical tools, drug delivery based on nanoparticles, and nano enabled point of care diagnostic devices are expected to be on the market in 10 years. These were identified as attractive future markets. More need for research in drug delivery was mentioned.

• The attractive future markets were identified for self assembling peptides on nanofibres, and super absorbent polymer gels.

• In relation to Asia and North America, fundamental and applied research was considered to be at par for Incident Support.

• Potential toxicity of nanoparticles was mentioned as a concern with suitable development of appropriate precautionary measures underlined.

- Particular health concerns and potential toxicity for coated silica particles used in drug delivery were mentioned.

- Occupational exposure to crystalline silica can lead to silicosis, pulmonary tuberculosis, and chronic obstructive pulmonary disease. Further information on these aspects is available from the Health, Safety and Environment work package of the Observatory NANO.

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2.1.7 Current Situation within EU

The following framework 7 projects funded by the European Commission in the security theme are relevant to neutralising CBRNE:

• Simulation of crisis management activity (SICMA) project initiated in 2008, in producing a computer assisted decision making tool for Health Services Managers in response to crisis scenario [174].

• Identifying the needs of medical first responder in disasters (NMFRDISASTER) project coming to an end in 2009 aimed to identify the research needs of medical first responders. This relates to the use of protective equipment used in chemical and biological incidents [175].

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to neutralising CBRNE:

• The Crisis simulation project (CRIMSON) aims to research, develop and validate using virtual reality technologies to prepare security and first response organisations for urban crisis management in terrorist attack, CBRN crisis or hostage situation [176].

• Treatment initiatives after radiological accidents (TIARA) project aimed to create a European network of excellence for managing crisis after accidental or malevolent dispersal of radionuclides. The project provides information and guidelines for treatment post radiological exposure [177].

• Bioterrorism resilience, research, reaction-supporting activity promoting co-operation to assess the bio threat and organise a collective and comprehensive response for EU society and citizens bio security (BIO3R) project aims at improving preparedness for bioterrorism. It aimed to identify operational requirements, countermeasures against biological attack (detection and therapeutic) and resilience, ethical and legal issues [69].

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2.2.1 Title – Decontamination

Decontamination post incident

Keywords: environment, toxins, water supply, air, infrastructure, nanocrystals, nanometal oxides, zeolites, photocatalytic, xerogel, nanoporous membranes

2.2.2 Definition of Technology Segment

The sub-segment focus is related to decontamination of environment, infrastructure and civilian zones affected by toxins, chemical, biological and radiological species. Nanotechnology developments related to filtration of fluid medium primarily water supply and air has also been covered in the sub-segment.

2.2.3 Short Description

Nanosized metal oxide halogen adducts have been reported in the literature for high surface reactivity due to their unique surface morphology. These can be used against vegetative cells and viruses. These adducts in three nanosized metal oxides of aluminium, titanium and cerium have been mentioned for applications in decontamination and disinfection. A comparative analysis of the three oxides produced varying degree of results. The macrocrystalline counterparts of the same oxides did not produce a result [178].

Nanocrystals of magnesium oxide have been reported in the literature to absorb organophosphorus compounds. The chemisorption has been demonstrated at room temperature. The high surface area and high surface reactivity make this material suitable for decontamination of chemical warfare agents. The advantage offered by nanocrystalline magnesium oxide over activated charcoal is that it is much faster, and organophosphorus compounds are destructively absorbed while in activated carbon they are only phsisorbed [179]. It has also been reported in the literature that nanoscale powders of magnesium and calcium oxides possess antimicrobial properties. These nanocrystalline forms carry active halogens. Vegetative cells of Escherichia coli, Bacillus cereus, or Bacillus globigii were reported to be decontaminated within a few minutes and spores of spores of Bacillus within several hours. These formulations also decontaminated water carrying Escherichia coli, Bacillus cereus, or Bacillus globigii within minutes [180].

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Nanoscale Corporation has been reported to be commercialising a chemical hazard system that combines magnesium oxide and photocatalytic titanium dioxide nanoparticles. The system has been demonstrated to neutralise 99.9% of nerve gas VX within 10 minutes [181].

Bacillus anthracis attacks and Escherichia coli contamination of produce has made it necessary for the development of a decontamination method that does not rely on time consuming cell culture development. Magnetic glyconanparticles have been considered advantageous due to the pace, high acquisition of pathogens due high surface to volume ratio and due to its non- destructive nature. The functionalization of silica coated nanoparticles, was done with triazole linker in the experimental investigation. High capture and removal efficiency for bacteria were demonstrated with the carbohydrate coated magnetic glyconanoparticles [182].

Nanocrystalline zeolite surfaces have been researched for the absorption, desorption and thermal oxidation of mustard gas stimulant, 2-chloro-ethyl ethyl sulphide. The research compares the nanocrystalline zeolites, ZSM-5 (Si/Al~20) and silicalite -1 (purely siliceous form) for decontamination of chemical warfare agents. It was experimentally demonstrated that the ZSM-5 form was more reactive than the silicalite form due to a higher surface area. The absorption was suggested to take place both on the external surface and on the internal. It was shown that chemical agent was stored in a stable state in the zeolite until destruction [183].

Experimental research has been conducted to analyse the reaction of nanocrystalline NaY with dimethyl methylphosphonate (DMMP), a nerve gas stimulant. Nanocrystalline NaY with a crystal size of approximately 30nm were used investigate the adsorption and thermal reaction. The reaction and products were studied with FTIR and solid state NMR spectroscopy. Successful decomposition of the stimulant was demonstrated, and the reactivity per gram of the zeolite was reported to be similar to other studies conducted on metal oxides such as magnesium, aluminium and titanium [184 ].

The benefits of using titanium dioxide as a photo catalyst and for decontamination of environment pollutant are that TiO2 is inexpensive, non-toxic and biocompatible [185,186]. The processing of nano-sized titanium dioxide was reported in the literature to have been produced by sol-gel processing at temperatures of less than 100 degree centigrade. The thin titanium dioxide film constituted by a of particle size in the range of 3 -5 nm adhere strongly to the substrate and are photoactive. The research reported high photo catalytic efficiency in decomposing the stimulant methylene blue and heptane extracted bitumen fraction. The titanium dioxide while decomposing environmental pollutant did not promote the degradation of fibres [187]. Nano titanium dioxide particles loaded on to activated carbon fibres have been studied in the literature for air

- 105 - purification. The experimental study examined the photo degradation efficiency of formaldehyde gas. The research showed excellent decontamination effect, by the photo catalytic action of titanium dioxide and absorption of activated carbon fibers. The research also investigated parameter such as concentration of nano-titanium dioxide, ratio of nano-titanium dioxide to activated carbon fibre, drying temperature and time [188]. Materials coated with doped photo catalysts have been reported to degrade solute toxic substances such as chlorophenol and azo dyes. They can also degrade harmful gases such as acetaldehyde, benzene, and carbon monoxide in diffuse daylight within closed spaces [181].

Research and development in photocatalytic nanowires has been reported in the literature. Free standing membranes produced from titanium dioxide nanowire have been grown through a hydrothermal heating process. These membranes give a paper like appearance and are highly chemically inert, robust and can be heated to high temperatures. These can be potentially also used as a filtration membrane in gas masks allowing oxygen but blocking toxic gases. The technology is waiting to be commercialised by the University of Arkansas researchers [181].

CoOx-doped silica xerogels with high surface area have been reported in the literature for decontamination of acetaldehyde gas. The xerogel with maximum pore size of 3 nm show high catalytic activity. Carbon dioxide and traces of methane are produced as a result of air oxidation of acetaldehyde [189].

Nanoporous keratin fibers have been reported in the literature for removing heavy metal from solution. Keratin fibres are considered suitable due to their stability over a wide range of pH, toughness of the structure and high surface area. A multi-fold increase in metal uptake by the nano-porous keratin fibres was reported on alkaline ultrasonic treatment. The resulted indicated high uptake and reusability of keratin as a biosorbent [190].

The development of a fibrous membrane has been mentioned in the literature for removing particulates from liquid. Polyvinylidene fluoride nanofibers were electrospun into membranes for this application. The structural properties were related to membrane separation properties and its performance. The membranes were reported to be successful in separating 90% of the polystyrene particles from the solution. This application has potential applications in pre-treatment to minimise fouling and contamination [191].

Permeable reactive barriers have been mentioned in the literature for the remediation of ground water. Permeable reactive barriers development investigation presents methods that rely on injection and deposition of nano sized iron sulphide particles. The chemical conditions necessary

- 106 - for optimum performance were reported to be moderately alkaline to establish optimal coverage of iron sulphide in sand [192].

Nanoporous membranes have been developed using stable nickel based super alloys by researchers in Germany. The nanoporous mechanical membranes offer high structural integrity, porosity of between 30-70%, thermal and electrical conductivity and weldability. Such membranes are suitable for applications filtering bacterial spores and dust from respiratory air and gas separation. These are advantageous as they can be thermally sterilized. Design and development challenges need to be overcome for such membranes can be cost effectively used with reproducible quality [181].

Nanoceramic membranes with a mesoporous sponge structure have been developed through self assembly of monolayers. The nanosponge is produced from mesoporous silicon dioxide ceramics. The average pore size of these ceramics is 6nm and is known to remove toxins from water more effectively than activated carbon fibers. The pores are filled with the self assembly layer. Mercury is decontaminated using mercapton molecules while chelating ligands have been reported to remove chromates. The investigation conducted by Pacific National Laboratory reported to have achieved 99.9% decontamination within 5 minutes. Potential application for the technology has also been mentioned for radio nucleotides and for non-fluid medium [181].

Water borne pathogens are an important cause of infections [193]. The most commonly known pathogens are Legionella pneumophila, Pseudomonas aeruginosa and moulds [194]. Point of use filters have been mentioned in the literature as a means of providing pathogen free water [195, 196]. This is expected to reduce infections in transmission of pathogens through water used in washing hands and rinsing wounds in emergency wards [197]. Filters with inner coatings of nanocrystalline silver have been reported in the literature for decontamination of water. The research on the functionality lifetime retention of the filtering efficiency of pathogens recommended that filters should be changed every 4 weeks in high risk areas and every 8 weeks in moderate risk areas [198].

2.2.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling nanotechnologies. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been

- 107 - defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets.

The comparative assessment of research and development status for decontamination applications enabled by nanotechnology is shown in Table DE.1 below.

Table DE.1 – Comparative assessment of Research and Development status for Decontamination applications

Field Trials / Pilot Fundame Applied Deployed Prototyp plant ( Pre- Mass ntal Researc (Commerciali e commercialisation Market Research h sed) ) Nanosize d metal ƒ oxide Nanocryst als of ƒ magnesiu m oxide Magnetic glyconan ƒ oparticles Nanocryst alline ƒ zeolites Photo catalytic ƒ ƒ titanium dioxide Silica ƒ Xerogel Nanoporo us keratin ƒ fibres Polyvinyld ƒ

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ene nanofibre s PRB Iron ƒ Sulphide Nanoporo us mechanic ƒ al membran es Nanocera mic ƒ membran es

2.2.5 Additional demand for research

Further research need have been mentioned for technologies and capabilities in decontamination of people, platforms and infrastructure following an incident [199]. Further research in improvement of decontamination reactivity of NaY for chemical warfare agents was mentioned to be investigating incorporation of reactive metal ion or oxide into the zeolite [184].

2.2.6. Applications and Perspectives

The expert engagement process resulted in the following perspectives for the technology segment:

• Funding research for the ‘Incident Support’ Sub-sector was considered more important for societal reasons than for the economy.

• The main drivers for research and development in ‘Incident Support’ were considered to be technological and social impact resulting from the technology. This was followed by ethical, environment, health and safety drivers. The technological drivers are cost, performance, efficiency and absence of technological solution.

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• The main drivers for research and development in ‘Decontamination’ post incident was mentioned as decontamination effect on civilian zones and water supply, inexpensive approach to response, impact of response and time taken for response to take effect.

• Main barriers for research and development for ‘Incident Support’ were identified as availability of finance to early stage companies and intellectual property conflicts. Secondary barriers mentioned were access to equipment and infrastructure, inadequate technology transfer, and lack of supportive governmental policy.

• The main barriers for research and development for ‘Decontamination’ segment were identified as inadequate research funding, inadequate availability of skilled personnel, robustness of field trials, health effect of nanoparticles, and availability of countermeasures.

• The most important functional requirements were mentioned as ‘time taken for desorption’, and ‘high decontamination efficiency’. Other secondary functionality were mentioned as ‘biocompatability’, ‘high uptake of toxin’, ‘destructive desorption’ and ‘functionality retention for filter applications’.

• Nanoscaled metal oxides, nanocrystalline zeolites, photo-catalytic titanium dioxide, fibrous membranes, nanoceramic membranes, nanoscale coatings on filters are expected to be in the market in the next 5 years. Optimization of nanostructures and combination with other materials are factors that would determine the market uptake. For nanoscale coatings, durability of coatings and optimization of retained pore size would be the important factors for technological uptake.

• Nanoprous keratin fibres and nanoporous mechanical membranes are expected to take up to 10 years. For mechanical membranes, factors such as avoidance of clogging, compromise between activity and longevity would be important.

• Nanoscaled metal oxides, photo catalytic titanium dioxide, xerogels were considered to be nanomaterials with very attractive and relatively higher growth future markets for products.

• Nanocrytalline zeolites, nanoporus keratin fibres, nanomaterials for membranes and coatings were considered moderately attractive growth market for future products.

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• North American research, development and commercialisation efforts were considered better than Europe which was considered better than Asia for the technology segment.

• Potential toxicity of nanoparticles was mentioned as a concern with suitable development of appropriate precautionary measures underlined.

2.2.7 Current Situation within EU

Nanosecure project mentioned in the Detection sub-sector is also relevant to decontamination of airborne substances. Detoxification of airborne borne substances is being researched in the project. DINAMICS is an ongoing European Commission project, the aim of which is the development of a lab on a chip device, for detection of pathogens in water supply. The project has relevance to decontamination sub-segment in Incident Support. Research has been funded in the EU through both national and pan-European projects to develop nanotechnologies for the incident support functions.

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to decontamination:

• The Crisis simulation project (CRIMSON) aims to research, develop and validate using virtual reality technologies to prepare security and first response organisations for urban crisis management in terrorist attack, CBRN crisis or hostage situation [176].

• On-line monitoring of drinking water for public security from deliberate or accidental contamination (WATERSAFE) project aimed to use nanotechnologies in sensing and detoxification to protect drinking water systems for potential terrorist attacks or accidental spillage [48].

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2.3.1 Title - Forensics

Forensics

Keywords: crime, fingerprint, finger mark, detection, identification, forgery, nanoparticles, nanocomposites, metal oxide nanoparticles, metal sulphide nanoparticles, DNA, biosensors, microscopy, spectroscopy, lab on a chip

2.3.2 Definition of Technology Segment

The sub-segment cover all enabling nanotechnologies that assist in criminal investigations and identification of criminals and means used to commit the crime. The scope of the assessment has been on materials and methods used in detecting fingerprints, forgeries, and weapons used in committing crimes.

2.3.3 Short Description

Forensic investigation deal with scientific analysis of evidence left at a crime scene in order to determine establish means used, time of crime and the person involved in the crime. A fingerprint is considered as extremely vital evidence that establishes an association between a suspect and a criminal act. There are three types of fingerprints are found at a crime scene - visible, indented and latent. The first ones are those that are visible formed in blood, grease, oil or paint. Such marks are generally easy to detect. Indented or plastic marks are produced when fingers are in contact with malleable materials such as candle wax, putty or wet paint. Latent fingerprints are the most common and challenging to detect as they are invisible. Optical, physical and chemical techniques are used to detect latent fingerprints. Fingerprint detection can be done by means of a number of techniques. Each technique offers an efficiency advantage relevant to the application. The advantage of a technique depends on the type of surface where the fingermark is left, whether it is porous, semi-porous or non-porous. It depends on the composition of the secretions, whether they are eccrine or sebaceous. It also depends on the time for which the fingermark has been left on the surface and whether or not the surface has been wet [200].

The visible fingerprints can be easily detected, photographed and documented. The latent fingerprints are difficult to detect. Fingerprints are formed primarily from perspiration. A typical fingerprint contains water, organic and inorganic chemicals such as amino-acids, salts, glucose,

- 112 - peptides, salts, lactic acid, ammonia, riboflavin, and lipids, due to a mix between eccrine and sebaceous secretions. The chemical residue hardens when the water evaporates, making it possible to detect fingermarks years after their deposition [201]. Nanoparticles based detection were recently developed to detect the residues of latent fingerprints and provide a good contrast between the residue and the underlying substrate.

A number of methods have been used in detecting fingermarks. The method based on photoluminscent detection of latent fingerprints has been mentioned. In this method quantum dots are bound to fingerprint residues, following which they are illuminated with the appropriate spectrum of light and the fingerprint is detected by fluorescence. Cadmium sulphide, cadmium selenide or indium phosphide quantum dots with diameter less than 10 nm have been attached to latent fingerprint using encapsulating agents such as fatty acids or amino acid components. The excitation of the quantum dot is carried out using a laser of near ultra-violet wavelength [202].

Fluorescent nanoparticles for detecting latent fingerprints have been developed by the University of Sunderland. They are processed as sol-gel particles in the presence of derivates of fluorescent dye. Nanoparticles of cadmium sulphide and cadmium selenide showing intrinsic fluorescence can also be used. The processed nanoparticles are spherical in shape with diameters ranging between 30 - 500 nm. Fluorescent dyes of Texas red-labeled gelatin have been used in the process of developing the nanoparticles. Hydrophobic molecules such as phosphatidylcholine and phosphatidylethanolamine are coated on to the nanoparticles. Texas Redporcine thyroglobulin conjugate embedded in sol-gel derived nanoparticles have been shown to bind latent fingerprints [203]. Latent fingerprints have been visualized using hydrophobic silica based particles in forensic analysis. Both nano scaled and micro scaled particles have been synthesized, the nanoparticles being applied in an aqueous solution to fingerprints while microparticles (aggregates of nanoparticles with an average diameter of 27 microns) are used as dusting agents. The synthesis route described in the literature, mentions the production of colored and fluorescent agents, also colored and magnetisable particles embedded in the agents. Carbon black and titanium dioxide has been used as embedded particles [204].

The small size of nanoparticles enables the detection of fingerprint sub-structure with greater detail and accuracy, in comparison with larger particles used in the traditional powdering on crime scene. The technique is advantageous due to a better definition of fingerprints recorded from crime scenes. The technique improves the sensitivity and consequently increases the chance to detect very faint fingermarks, and by the same way increase the possibilities to find a link with criminals or suspects. Lipid sensitive dyes have been used for imaging and documenting

- 113 - fingerprints in a method and apparatus developed by Ciencia Inc. Exposure to light brings about fluorescence when lipids are bound to the residue of a latent fingerprint [201].

The use of silicon dioxide based nanocomposites has been mentioned in the literature for the latent fingerprint detection. The experimental study has demonstrated the fabrication of sensitising ligands and silicon dioxide based xerogels. The highly fluorescent photo-stable europium metal ions/sensitizer complex into the nanopores of the xerogels. The novel doped xerogels were reported to detect unfumed fingerprints on surfaces such as metal foils, glass, plastic, coloured paper, and organic materials. The advantages offered by the doped nanomaterials are distinct fluorescent characteristics, quick prototyping, cost effective fabrication, and nanoparticle surface customisation for tagging of fingerprints [205].

2.3.3.1 Metal Nanoparticles in Forensics

Multi-metal deposition (MMD) is a technique that can efficiently detect fingerprints on a wide range of substrates, as well as old and fresh fingermarks, even if they have been wet [206]. It consists in a two-step process in which gold nanoparticles are first deposited onto the secretions, before being covered by silver through a chemical deposition performed in solution. Gold nanoparticles have been reported in the literature as intermediaries, for latent fingerprint detection. The MMD technique has further been modified to improve the operational limitations of multiple immersion baths for gold nanoparticle. Successful demonstration of detection of fingermarks was achieved using gold nanoparticles functionalized with molecular hosts bearing organic dyes [207]. Another modification consisted in replacing the silver deposition step by a second gold deposition, on the gold nanoparticles, leading to an alternative MMD formulation which constitutes a serious alternative to the classical method [208]. Luminescent techniques are considered beneficial due to high sensitivity and their ability to remove the colour of the background material on which the fingerprint is formed. A modification of the original two step process has been reported in the literature for fingerprint detection, in the first step colloidal gold particles are deposited onto the fingerprint, and in the second step zinc oxide covers the gold nanoparticles (instead of silver for the classical MMD). A luminescent fingermark is obtained due to the in situ–formed zinc oxide nanoparticles. Luminescent nanoparticles offer advantages over other deposition material such as silver or functionalised gold nanoparticles. Zinc oxide is used due to its photo-luminescent capabilities, which when excited with UV luminescent (300-400nm) in visible range (~ 580nm) due to defects in the structure [209].

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Figure F.1 – Schematic diagram of the multimetal deposition process for fingerprint detection [207]

Experimental studies have been performed on detection of latent fingerprints using lipophilic and polycationic chitosan polymer. Gold nanoparticles treated with chitosan have been used to attach it with lipids in the latent fingerprints. The research was mainly aimed at understanding the mechanism of detecting latent fingerprints using gold nanoparticles. Two approaches were used, in the first one, gold colloids were capped with chitosan. In the second approach fingerprints were pre-treated with chitosan, which was followed by immersion in a gold colloidal solution, and addition of mono sodium glutamate to agglomerate the gold nanoparticles. Reproducible results could lead to its potential use in forensic detection of fingerprints [210].

The application of gold nanoparticles using lipophilic interactions between fatty acids of latent fingerprints has been reported in the literature [211].Gold nanoparticles of size 1-3 nm, stabilized with alkanethiol have been synthesized and characterized [212]. Gold nanoparticles functionalized with anti-body of cotinine, have been demonstrated in detecting fingermarks as well as giving information whether the person was a smoker or a non-smoker. This was done by pipeting the nanoparticle-anti-cotinine conjugate onto the fingerprint, following which a fluorescent agent was added and the fingerprint imaged. Lack of fluorescence would confirm absence of cotinine and that the individual was non-smoker [213].

Gold and silver nanoparticles have been demonstrated to detect latent fingerprints on non-porous surfaces. Interaction of the oleylamine gold nanoparticles with the fatty acids in the latent fingerprints causes them to deposit on the surface. These were reported to be advantageous over conventional powder as they produce sharper patterns and do not stain the background of the non-porous material [214].

Other techniques such as gas chromatography, mass spectrometry, infrared spectro-microscopy and micro-X-ray fluorescence have been used in analyzing the finger mark composition [215, 216, 217].

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2.3.3.2 Metal oxide nanoparticles in fingerprint detection

Metal oxide nanoparticles have found applications as pigments or colorant, fluorescent agent and as fingerprinting powder. Titanium dioxide particles with particle diameter of 21nm have been reported in suspension for the detection of fingerprints on porous and non-porous surfaces [218]. Titanium dioxide nanoparticles in methanol provided good results for fingerprint detection in blood on non-porous and semi-porous surfaces. The results of the research were reproducible for both old and new fingerprints [219]. For fingerprint detection on dark adhesive surfaces, titanium dioxide nanoparticles suspended in a surfactant solution has been mentioned as the most optimum method [220]. The use of suspended titanium dioxide nanoparticles for developing latent fingerprints on wet surfaces has been reported in the literature. According to the authors, the quality of fingerprint detection mainly depends on the way the surface has been touched and the time the contact with the surface lasted [221]. Research on a highly fluorescent dye was conducted that is absorbed onto nanoparticles of titanium dioxide, for detection of latent fingerprints on non-porous surfaces. The research produced better results than conventional fluorescent powders, due to a better quality of latent fingerprint details and contrast produced by the nanoparticles and the reduced background developed [222].

Nanostructured zinc oxide was demonstrated to produce fluorescent recognition of the latent fingerprint marks on non porous surfaces such as glass, polyethylene and aluminum foil. The latent fingerprints were visualized when ultraviolet light was directed towards the surface [218]. Europium offers a narrow emission band and long excited life’s in relation to organic fluorescent that have short excited lifetimes and broad emission bands. This presents an advantage in detecting fluorescence on difficult surfaces. Experimental research has demonstrated the use of europium oxide nanoparticles that are functionalized with amines. The nanoparticles target carboxylic acid constituent of the latent fingerprints, which are subsequently detected using photoluminescence [223].

2.3.3.3 Metal sulfide nanoparticles in fingerprinting detection

Nanocrystals and nanocomposites of cadmium sulfide have been applied in detecting fingerprint marks on soft drink and aluminum foil. The nanocrystals were capped with dioctyl sulfosuccinate in heptane or hexane, which detected the fingermarks by intense luminescence under near ultraviolet light. The disadvantage this presents is that unfumed prints on metal, glass and plastic cannot be adequately developed [224]. Dendrimers with terminal amine groups have been research as reagents for fluorescent cadmium sulphide–dendrimer nanocomposties. The amine group reacts with carboxylic acids found in deposits of fingermarks. Luminescence showed the

- 116 - presence of fingermarks on aluminium foil, polyethylene and paper. The disadvantage of the process was reported to be long immersion time required for development on paper surfaces [225]. CdS with carboxylate terminal functionalisation have been used for fingerprint detection [ 226]. Zinc Sulfide capped cadmium selnide nanocrystals have been used in fingerprint detection. These bind to the amino acid component of the fingerprint residue. Fluorescent CdSe/ZnS stablised with octadecaneamine, have been used in detecting latent fingerprints on silicon wafers and paper. The results on silicon wafer had detailed marks detection whilst on paper they were not obtainable due to high background fluorescence [211]. One the main disadvantages of using cadmium if the health risk posed by the material. One of the main risks posed along with the toxicity is the half life in the human body which is reported to be nearly 30 years [227].

2.3.3.4 Microscopy and Spectroscopy

Forensic digital imaging spectrograph developed by MS Macrosystems is used in both large- and micro-scale document examinations. Two-dimensional and three-dimensional imaging is used for analysis in the digital imaging spectroscopy hardware. Forged documents examined by forensics experts for establishing authenticity use this tool to objectively compare physical parameters. Small differences between inks and papers can be identified by the application of spectral imaging technology and advanced processing. It can also reveal any information that has been removed. The advantages of this technique are the nondestructive evaluation of documents and three dimensional high resolution color imaging [228]

Scanning Probe Microscopy (SPM) is useful for characterizing surfaces based on topographical features and physical and chemical properties. It has been used for non- destructive evaluation of forged documents and applications in micro-nanometre resolution of latent fingerprints. Forensic Science applications of scanning probe microscopes (including atomic force microscope) has been mentioned in the literature [229]. Fingerprints were detected under air or liquid with no discernable difference using an AFM. Successful development of two overlapping fingerprints was also demonstrated. Analysis of thin layer of pen ink on the surface of a paper document was conducted. The profile of the line was observed to have an average height of 200nm. Writing history on a sample can be verified using this information obtained from the AFM. The main disadvantages of this technique are the long time taken for data acquisition and small area of the scan. Analysis of single bits in electronic devices has also been performed using Scanning Probe Microscopy. Recovery of raw data from damaged specimen has been demonstrated by Forensic Science Services. Information was recovered from sim cards recovered from the site of London bombings despite the strong vibrations from the shock waves [230].

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Scanning electron microscopes (SEM) play an important role in forensic examinations. Extremely good depth of focus and high to low magnification of SEMs are considered useful for a range of applications and materials. It has been used in gunshot analysis, firearm detection, identification of gemstones and jewellery, examination of paint particles and fibres, handwriting and print examination, counterfeit bank notes, trace comparisons, examination of non-conducting materials, and high resolution surface imaging. SEM identifies the particles due to their high contrast with the stub background in the analysis of specimen stubs obtained from gun shot residues. Bullets fired from the same gun have been identified from the marks left from the barrel and the firing pin, in test conducted to compare bullets. SEM provides an advantage over optical microscopy due to their high depth of focus in such forensic examinations. In addition, the backscattered electron detector in SEMs can enhance markings on the bullets and suppress the detection of dust particles. The literature points towards an Electron microscopy investigation conducted into metal nanoparticles of gun shot residues. The investigation determined the method of formation of the nanoparticles and proposed a method for the synthesis. The additional information obtained from synthesis is expected to assist in solving crime through forensic examination [231]. Variable pressure scanning electron microscopy along with energy dispersive X-ray has been successfully demonstrated as analytical tool in diagnosis of electrocution cases. In an accidental death caused by electrocution by means of histological examination of the skin and identifying titanium metallization [232].

Desorption electrospray ionization is a detection that is used in forensic examination of surfaces. The advantage of the technique is that is can be used at distances up to 3m with no need for sample preparation. The technique is also rapid, highly sensitive and selection. Trace amount of a wide range of chemical can be detected in nanogram quantities such as drug formulations, illicit drugs, organic salts, peptides and chemical warfare agents. In this process the analyte ions generated by the interaction of charged particles and neutral molecules on the surface are analysed by the mass spectrometer. This disadvantage of this technique it is constraints faced when limited access to sample. It was shown in experimental studies that illicit drugs were identified with high level of sensitivity and selection. The technique also showed a high throughput rate for the samples [233].

2.3.3.5 Biosensors

Biosensors are used in forensics to solve crimes and identify perpetrators. Prostrate specific antigen (PSA) has been used to confirm the presence of semen, and absence of sperm in sexual assault cases. The use of PSA is forensic analysis has a different set of requirements than used

- 118 - in clinical samples. The challenge for detection lies in detecting samples contaminated by other bodily fluids, lack of the sample or the need to extract the sample from different fabrics. Nanoparticles and nanostructures are used to enable the analyte detection [234]. Biobarcode arrays have been mentioned, where magnetic particles coating is where the PSA to PSA anti- bodies binding takes place. Nanoparticles probes coated with anti-body and strands of DNA barcode are applied in bind to the immoblised PSA [235]. Surface enhanced Raman scattering has been used for the detection of PSA in sandwich immunoassays to a concentration of 1 pg/ml. Gold nanoparticle probes are attached to antibodies that are labeled with Raman dyes [236]. Nanostructure based assays have been regarded robust for PSA detection due to being label free and inexpensive. Cantilever can be used for PSA detection in resonance response variation and bending of the cantilever. An electrical measurement of changes in resonant frequency of cantilever has been mentioned, when binding of PSA with its antibody takes place [237]. Anti bodies coated on silicon nanowire field effect sensors have been reported in the literature, for highly sensitive detection of PSA. The transduction of the signal in the nanowire takes place when the PSA - antibody binding takes place on the surface of the nanowire [238].

2.3.3.6 Role of DNA in forensics

A need for developing cost effective, rapid and precise methodology for detecting DNA has been mentioned in the literature. DNA based identification plays an important role in forensics. Gold nanoparticle conjugates with DNA are fabricated via gel electrophoresis, are used for precise identification of target DNA samples. The mean particle diameter of gold nanoparticles was reported as 10 nm. The quantitative analysis was done to produce a linear correlation between target DNA and conjugate groupings [239]. DNA extraction, quantitation, amplification and separation can be performed on microfabricated devices. The analytical microchip has numerous advantages such as fast processing times, reduced reagent used, sample handling and use. Reduced sample handling leads to a reduction in contamination of the sample. The increase in efficiency is attributed to reduced sample volumes that are in nanolitre range and high surface area to volume. The low cost of these devices make them an ideal platform for DNA forensic analysis. A review by Horseman et al. has looked at the different methods applied at each of the stages in the analysis. Modular, single and integrated systems for sample analysis have been reported to be in a development stage [240].

An identification method for analyzing molecules based on cantilevers has been developed by Intel. The method is used in the identity verification of criminal investigations and for forensic examination. It is also referred to as DNA testing. The method is based on the identification of target molecules (also known as analyte) by the use of probe molecules that bind to the analyte.

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A deflection in the cantilever takes place if a binding between probe and analyte takes place. The cantilever is balanced using a magnetic force, and therefore the detection is based on this counterbalancing force. Oligonucleotides-nucleic acid and protein/peptide antibodies have been successfully demonstrated probe analyte combinations [241]. A method for detecting target nucleic acid has been patented by Integrated Nanotechnologies. Oligonucleotide probes are integrated are integrated into an electrical circuit in such a manner that they are not in contact with each other. The complimentary target nucleic acid joining the two probes bridges the gap, resulting in a flow of current through the probes [242].

A method for application in forensics has been developed for genomagnetic nanocapture (GMNC). Magnetic nanoparticles are functionalised with molecular beacons in this method. The method is advantageous as molecular beacons offer high sensitivity and selectivity along with excellent separation capability of magnetic nanoparticles. The GMNC was fabricated using the magnetic nanoparticle as carrier, which was coated which was then functionalised with a DNA probe for recognition and collection. An illustration and an example is shown in the figure below. The experimental investigation was performed using samples containing cancer cells, random DNA and proteins. It was effectively used in separation, and collection of trace amounts of DNA/mRNA strands with a single base difference. The efficiency was reported to be over 90% DNA collection [243].

Figure F.2 – A). Schematic diagram of genomagnetic nanocapture, Representations are 1. Magnetic nanoparticle, 2, silica layer, 3 Biotin-avidin linkage, 4 molecular beacon DNA probe B). TEM image of a silica-coated magnetic nanoparticle with a diameter range of 28 nm [243]

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DNA electrochemical sensors have application in forensics. The detection methodology used by electrochemical sensors is fundamentally based on hybridisation. The advantages offered by electrochemical sensors for forensic applications are they are cheap, simple, reliable, sensitive and selective for genetic identification. A number of electrochemical methods have been reported in the literature based on impedance of voltametry. Gold nanoparticle based electrochemical chip for DNA identification has been reported [244]. Electrochemical assays based on tracer quantum dots of ZnS, CdS, PbS, and CuS have also been reported [245]. The main disadvantage of electrochemical DNA sensors is the need to label the and also in some instances providing lower sensitivity. A metal sulphide (Cadmium or Lead) based detection of DNA provides attomolar sensitivity of the targeted DNA [246].

Single molecule spectroscopy has been reported to have applications in forensic analysis. The technique offers ultrahigh sensitivity to detect molecules hidden condensed matter. Single molecule spectroscopy has been used for DNA fragment sizing in forensic applications. Fluorescent tags incorporated by a species provide physical information such as size, surface area, volume and reactivity. Distribution of fluorescent tags on a specie is identified by measurement of fluorescent burst size of particles. Identification in forensics is done using information that is provided by distribution size of fragments achieved by restriction digest of DNA. This technique offers advantages over gel electrophoresis such as high sensitivity as picogram mass is needed as opposed to nanograms, shorter time scale being in minutes as opposed to hours, and the ability to work with super coiled DNA [247].

Lab-on-a chip is considered to be a very useful for forensics due to its high sensitivity, high specificity and portability. Lab on a chip devices offer the potential of high performance analysis of substances rapidly by conducting sample preparation, injection, sampling, mixing, chemical reactions, product separation, detection and collection on the same chip. To ensure its disposability, they are made out of polymer, glass or hybrids of polymer-glass and silicon-glass. A number of factors have to be considered in the design namely miniaturization, integration of the different functional elements and low cost of the commercial devices. The device is capable of handling numerous biological samples such as DNA. The advantages offered by the technique are the reduction in process steps and the ability to make a number of analytical measurements. Picolitre volumes of oligonucliotides have been experimentally separated and analysed in glass micro fluidic chip. Capillary electrophoresis on the microfluidic chip was demonstrated to shorten the separation time by one order of magnitude in relation to traditional capillary electrophoresis [248]. Lab on a chip can be used in a number of relevant applications including identifying DNA profiles and explosives at the incident site. The quick results, reliability and sensitivity of capillary electrophoresis based method offers significant advantages for explosives analysis. The pace of

- 121 - information analysis can act as an effective decision making tool in conducting on site forensic analysis by agencies [249].

2.3.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling nanotechnologies. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. A comparative assessment of research and development of nanotechnologies enabling forensics is shown in Table F.1 below. A validation of readiness level against other technology sector applications for the method, material and device is necessary. The nanotechnologies are primarily focused on evidence analysis mainly through investigation of fingerprints, documents, gun shot residue, explosive residue and DNA.

Table F.1 – Comparative assessment of Research and Development status for nanotechnologies in Forensics

Fundam Field Trials / Pilot Applied ental Prototyp plant ( Pre- Mass Researc Deployed Researc e commercialisation Market h h ) Nanoparticl es for ƒ fingermark detection

Fluorescen ƒ t particles

Nanocomp osites for ƒ latent prints

- 122 -

Gold and silver ƒ ƒ nanoparticl e Titanium dioxide ƒ ƒ nanoparticl es Zinc oxide nanoparticl ƒ ƒ es Nanocrysta ƒ ls Dendrimer ƒ s SPM for document ƒ analysis SPM for explosive ƒ specimen SPM for ƒ fingerprints Biosensors ƒ ƒ ƒ ƒ in forensics DNA in ƒ ƒ ƒ ƒ forensics Lab on a ƒ ƒ chip

2.3.5. Additional demand for research

The following areas of specific research have been identified in the literature for incident support functions:

- The role of doped nanocomposites in improving latent fingerprint detection has been mentioned in the literature [205].

- 123 -

- Further research for multi-metal deposition process and detection of fingerprints using photoluminescence has mentioned the improvement of zinc oxide deposition process by avoiding thickening of the ridges. Further research is to be conducted on different surfaces such as coloured and illustrated paper. This is expected to be extended to banknotes, which present a significant challenge due to the complex printed patterns. The technique is also to be proven for other non-porus surface and compared with other methods such as cyanoacrylate fuming [209].

- Further research in gold nanoparticles capped with chitosan has been mentioned in the literature. Research is required into the mechanism of enhancement, and optimisation of treatment time to obtain improved results [210].

- Increases in sensitivity and variety of DNA target detection with electrochemical DNA sensors based on metal sulphides have been mentioned in the literature [246].

- Improved technological capabilities for forensic identification of trace hazardous substances has been mentioned [250].

2.3.6 Applications and Perspectives

The expert engagement process resulted in the following perspectives for the technology segment:

• Funding research for the ‘Incident Support’ Sub-sector was considered more important for societal reasons than for the economy.

• The main drivers for research and development in ‘Incident Support’ were considered to be technological and social impact resulting from the technology. This was followed by ethical, environment, health and safety drivers. The technological drivers are cost, performance, efficiency and absence of technological solution.

• The main drivers for research and development in ‘Forensics’ was considered to be ‘severity of incident’, ‘accuracy of forensic examination’ and ‘inexpensive approach to analysis’.

- 124 -

• Main barriers for research and development for ‘Incident Support’ were identified as availability of finance to early stage companies and intellectual property conflicts. Secondary barriers mentioned were access to equipment and infrastructure, inadequate technology transfer, and lack of supportive governmental policy.

• The main barriers for research and development for ‘Forensics’ was considered to be ‘inadequate research funding’ and ‘health effects of nanoparticles’.

• The most important functional requirements were mentioned as ‘limit of detection’, ‘High sensitivity’, and ‘ease of prototyping’. Important functionalities were mentioned to be ‘fluorescent characteristics’, ‘time taken for data acquisition and signal processing’, ‘range of substrates’, ‘physical parameters for definition’, and ‘non-destructive analysis of forensic documents’.

• It was mentioned that visible fingermarks can be of poor quality while latent fingermarks of excellent quality once detected.

• A visible fingermarks can also be greatly enhanced with subsequent treatment for example in the case with blood fingermarks.

• The formulation of multi-metal deposition photo-luminescent zinc oxide has application limited to non-porous surface.

• The most widely currently used techniques were mentioned as are chemical ones namely, 1, 2-Indanedione, DFO, ninhydrin (for porous surfaces), cyanoacrylate fuming with dye (for non-porous surfaces), vacuum metal deposition, among many others.

• FTIR spectroscopy was also mentioned to be used for detecting fingermarks by chemical imaging, as well as micro X-ray. These however were not used in routine processes.

• Metal nanoparticles, colloids for fingerprint detection and fluorescent dyes are presently in the market. The nanomaterials were mentioned to be attractive growth market for applications.

• Fluorescent nanoparticles and metal oxide nanoparticles are expected to be in the market in the next 5 years. These nanomaterials were considered attractive growth markets for future application.

- 125 -

• Quantum dots, metal sulphide nanoparticles and lab on a chip are expected to take up to 10 years to reach the market. These were also considered to be attractive growth market for the future.

• Other qualitative issues identified were the need to reduced prices of nanomaterials for forensic application, development of synthesis and functionalisation protocol, application protocols for users, ability to apply forensic technique at the crime scene.

• Additional policy measures were suggested for long term R&D strategy and support for University researchers creating start up companies. Other ideas suggested were improving the efficiency of existing techniques using nanomaterials.

• Potential toxicity of nanoparticles was mentioned as a concern, specific concerns were mentioned for cadmium based powders. Health and safety issues are expected to become important especially for application at the crime scene.

• The field of forensics was mentioned to an area of limited research spread out across world in national laboratories and Universities. EU was mentioned to be at par with North America and Asia in forensics. The recent years have witnessed a growth in publications from China for forensic applications.

• A notable qualitative interaction was mentioned to be the negative impact of that patenting may have in forensics. The increased protection of research limits enabling capabilities and thus prevents deterrence of crime. Increased sharing of research results through laboratories to implementation by civilian agencies would have a beneficial impact on society through reduction of crime.

2.3.7 Current Situation within EU

A 3-years project funded by the Swiss National Science Foundation has been mentioned in forensics. The aim of the project is to develop new efficient fingermark detection techniques based on functionalized and luminescent nanoparticles. The project is being implemented in the context of fingermark detection by chemical methods. The project has commenced in 2009 and is expected to go on till 2012 [251].

- 126 -

3. Protection

3.1.1 Title - Personnel

Protection of Personnel

Keyword: textiles, vests, protective gear, ballistic projectiles, nanoparticles, nanomaterials, fibres, oxides, body armour, Kevlar, carbon nanotubes, fullerenes, dendrimers, polymer nanofibres, shield

3.1.2 Definition of Technology Segment

The ‘Protection of Personnel’ sub-sector segment would cover the developments under textiles and protection systems against chemical, biological, radiological, nuclear and explosives. The sub-segment would also cover developments in protective clothing against knives, projectiles, and firearms.

3.1.3 Short Description

Protective clothing is based on barrier suits that are either full barrier impermeable suits or permeable adsorptive suits. Functionalised activated charcoal has been reported to been used for adsorption. The main disadvantage of charcoal for protective applications is its heavy weight and moisture retention in barrier suits [252]. DS2 is used in the United States as a decontamination agent against nerve gas. The disadvantage of this solution is that it is highly toxic, very corrosive and release toxic by products. These are also not active against biological agents. A number of other agents have been developed for decontamination of nerve agents, blister agents and blood agents. Chemical such as b-cylcodextrin (b-CD), o-iodosobenzoic acid (IBA), polyoxometalates, peroxides, oximes, chloramines and metal nanoparticles have been mentioned to be suitable [ 253 , 254, 255, 256, 257]

Nanoparticles of magnesium oxide were mentioned in the literature to have been mixed with a range of polymer solutions to produce nanocomposite membranes. A relative experimental comparison of paraoxon hydrolysis under ultraviolet light produced the best results from polysulphone. A further relative comparison of charcoal with nanoparticles produced a 60%

- 127 - hydrolysis result for magnesium oxide nanoparticles membranes. Magnesium oxide nanoparticles were loaded up to 35% into the nanofiber, were demonstrated to be twice more reactive than charcoal [258].

Nanofibres offer high specific area, low fibre diameter, potential to include active chemistry, filtration, layer thinness and high permeability [259]. The nanofibres can be incorporated into cloths which serve the purpose of enhanced protection against aerosol. The nanofibres also serve as carriers of active functionality that can detoxify the warfare agent without adding extra weight to the cloth. Functionalising the appropriate catalyst on the surface of the nanofiber has been mentioned in the literature as a suitable approach to detoxification [260]. Polymer nanofibre membrane was reported to have been produced using the electro spinning technique. These nanofibres were reported to be functionalised with activated granular carbon as catalyst. The catalyst provided good performance for paraoxon, an organophosphorus model for sarin, which was used in the experimental study [261].

Protective gear for civilian security organisation forms an important part of protection in hazardous situation they may find themselves in the line of duty. Protective equipment is expected to provide light weight gear which will allow extreme mobility and high degree of protection. Body armour composed of nanocomposites is expected to become routine. The use of Kevlar in helmets is an example of such light weight protection. Body armour is also expected to provide protection against any chemical and biological warfare agents used in civilian zones. Multilayer polymer thin films have been mentioned for use in body suits that would neutralise the effect of chemical or biological agents. The use of dendrimers has been mentioned for detoxifying the effects of mustard gas. The use of electrorheological fluids which changes its rigidity in response to an electric charge has been suggested for protection application. An electric charge in such passed through the fluid in between layers of fabric arranged like a deck of cards could be a potential solution [262].

Protective vest, shields, barriers, and explosion proof blankets against bullets, sharp objects and explosive devices are necessary for the protection of civilian security agencies. Research in Australia has examined the potential of using carbon nanotubes against ballistic impact. A comparative study of bullet impact on carbon nanotubes with both ends fixed and one end fixed was performed for different radii. The study was performed using a piece of diamond with varying velocities at different positions on the nanotubes. The absorption efficiency was reported to high for fixed ends nanotubes, and lowest middle point of the nanotubes [263]. Yarns of multiwalled carbon nanotubes have been produced with yarn strength greater than 460 MPa. These have shown to be as strong as existing bullet proof vest and with 48% reversible damping. These offer

- 128 - high thermal, creep resistance, chemical resistance and a substantial increase in yarn strength on incorporation into a polymer matrix [264].

3.1.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling nanotechnologies for protection. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. Table PP.1 below provides an overview of the development for the protection of personnel.

Table PP.1 – Comparative assessment of Research and Development status Protection of Personnel

Field Trials / Pilot Fundame Applied Deployed Prototyp plant ( Pre- Mass ntal Researc (Commerciali e commercialisation Market Research h sed) ) Nanoparti cles of ƒ magnesiu m oxide Nanofibre ƒ s Polymer thin films ƒ for body suits Dendrime ƒ rs CNT for ƒ ballistic

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absorptio n

3.1.5 Additional demand for research

The following additional demand for research has been mentioned in the literature:

ƒ Catalysts functionalised on nanofibres membrane provide a means for detoxifying chemical warfare agents. Research has been mentioned in the literature to be conducted for different catalysts for a range of chemical and biological agents that could be reduced using protective wear. Further development work has also been mentioned in brining the different nanofibre layers to form a woven textile media as a protective garment. Such a protective garment is expected to offer additional comfort through exchange of moisture in relation to charcoal impregnated suits [261].

ƒ Further development for magnesium oxide nanoparticle based nanofibre membranes to degrade mustard agents and biological warfare agents has been mentioned in the literature [258].

ƒ Bullet impact of carbon nanotubes under different loading conditions has been mentioned as a research need for application such as bullet proof vests and explosion blankets [263].

ƒ Further research and development has been mentioned for operational effectiveness and capability of first responders for reducing injury and loss of life. Research areas include protective clothing for first responders, monitoring performance and health, integrating sensors and communication devices [199].

• Active decontamination materials to protect responders from threats [164] were mentioned in the engagement process as:

- Chemical: Nano barrier materials that can be applied and do not require PPE suits.

- 130 -

- Biological: Encapsulate to protect responders from contamination at the site of attack and prevent spread.

- Radioactive: Barrier that can be applied to reduce or eliminate exposure of responders and subsequent cleanup crews.

3.1.6 Applications and Perspectives

In the expert engagement process for the technology segment the following perspectives were observed:

• Funding research and development for Protection sub-sector was considered important both for the European society and the economy.

• The main drivers for R&D in ‘Protection’ sub-sector were considered to be technological, and environmental, health and safety (EHS). The technological drivers are primarily related to cost, performance, efficiency, and absence of solution. Secondary drivers were related as productivity gains, and competitive advantage in conflict.

• The drivers for R&D in ‘Personnel Protection’ segment were considered to be ‘safety of citizens and civilian agencies’, ‘protection against risk agents’, and ‘effectiveness of countermeasures’.

• The main barriers for ‘Protection’ sub-sector were considered as ‘intellectual property conflict’ and ‘availability of finance’ for start-ups. Other secondary barriers were considered as lack of supportive government policies, lack of tax incentives, access to infrastructure, and inadequate technology transfer.

• The barriers for R&D in ‘Personnel Protection’ segment were mentioned to be ‘inadequate skilled personnel’, ‘health effect of nanoparticles’, ‘lack of research funding’, and ‘lack of integration of nanomaterials into products’.

• The most important functionality was mentioned to be ‘low weight of protective clothing’. Other desirable functionalities were mentioned as ‘non-toxicity’ and ‘non-corrosiveness’, ‘ability to functionalise catalyst on fibre surface’ and ‘freedom of movement’ for the protection solutions.

- 131 -

• The application trends for protective textiles was mentioned as follows:

- For first responder markets, the trend is towards personnel area networks and integrating sensors into textiles. The technology readiness is relatively mature and expected to be deployed in the market over the next 2-3 years.

- Demand for technology is driven by security agencies for textiles and protective equipment. Anti-ballistic functionalities drive research and development for protective gear.

- The first responder and dual application markets are fragmented. They are small and deployment times are very long.

- Cost effectiveness can be improved by legislating functionality. This is also expected to improve the fragmentation in the marketplace. Cost effectiveness was also suggested to be improving scale up through partnerships in manufacturing.

- Operational constraints were mentioned to be speed of deployment and discreteness of protective functionality.

- Product driven focus developing cost effective technological solutions was mentioned as an important issue for processing and manufacturing. Emphasis was given on technological solution that adds to the product benefits.

- Product acceptance in the market place was mentioned as to be considerably challenging. As incumbent products are averse to change, generating opinion leaders was considered to be vital.

- For some applications it is expected that commercialisation would be in other markets and then followed by security.

- Nanofibres and carbon nanotubes based vests were considered to be very attractive high growth potential markets.

• In relation to US for ‘personnel protection’ segment, EU was mentioned to be better at fundamental and applied research. US was mentioned to be better at commercialisation,

- 132 -

technology transfer, routes to market, and ‘supporting mechanisms’. EU was mentioned to be lack of resources for commercialisation and technology transfer. A notable trend mentioned was the changes in the Asian market, particularly innovative chemistry research being published from India.

• Other qualitative suggestion for changes were suggested as follows:

- improving tax benefits for R&D for security applications

- enhancing academic focus on commercialisation in EU

- introducing a commercialisation performance metric for academics contributing to research ratings

- promoting scientific defense enterprise that promotes development and validation of concept

- specification generation through collaboration with security enterprise as a non- competitive activity

3.1.7 Current Situation within EU

The following framework 7 projects funded by the European Commission in the security theme are relevant to personnel protection:

• Identifying the needs of medical first responder in disasters (NMFRDISASTER) project coming to an end in 2009 aimed to identify the research needs of medical first responders. This relates to the use of protective equipment used in chemical and biological incidents [175].

• Advanced first response respiratory protection (FRESP) project was initiated in 2008. The aim of the project is to develop nanoporous adsorbent for respiratory protection of first responders. The research and development of protection would cover a wide range of chemical toxic and biological agents [265].

- 133 -

3.2.1 Title – Infrastructure and Equipment

Infrastructure and Equipment Protection

Keywords: reinforcement, mechanical strength, EMI shielding, carbon nanotubes, inorganic fullerenes, ceramic composites, nano- layered double hydroxide, nanoclays, buckypaper, buckyball, conductive polymers, nanofibres, carbon nano onions, metal nanoparticles, fillers, dielectrics

3.2.2 Definition of Technology Segment

The technology segment is expected to cover research and development in applications that are related to reinforcement of structures, construction, areas of mechanical strength, and robustness of protection. The section also covers nanotechnological development that would enable the prevention against fire. Electromagnetic shielding of critical communication and information infrastructure would be covered under the technology analysis in this segment.

3.2.3 Short Description

The technology analysis is further been done based on protection by reinforcement of structures, protection against fire and electromagnetic shielding of information and communication infrastructure. A short description of the developments is available from the subsequent sub- sections.

3.2.3.1 Reinforcement of structures

Protection of critical infrastructure against explosions and natural disasters are of primary important in order to retain organisational functions of civil society. Enhanced safety and security of constructions through incorporation of nanomaterials can be achieved. Products such as safety glasses, plating, concrete reinforcement, fire protection and self healing are additional security features. Metal foams have been mentioned in the literature for protection against ballistic projectiles. Aluminium foams sandwiched between steel plates have shown to have high tolerance to shock waves [266]. Nanometre sized precipitates are reported to increase the strength of steel alloys making them suitable for ballistic impact applications. The material

- 134 - demonstrates very high strength, hardness, ductility, toughness and good corrosion resistance [267]. Ceramic composites backed by metal layers have been used in ballistic armour applications. Function grade material with nanoscale coating was used to enhance the weakness at the interface of composite and metal. It was demonstrated to have enhanced ballistic resistance [268].

Vertically aligned carbon nanotubes have been shown to have super compressible foam like behaviour. These nanotubes fabricated through the chemical vapour deposition process show very high compressive strength, recovery rate, sag factor and excellent breath ability. These have foams have demonstrated greater compressibility and pressure resistance than polymer foams, while offering chemical resistance similar to metal foams. The experimentally demonstrated prototype is expected to be used in energy absorbing surfaces for earthquake and explosion protection [269].

Inorganic fullerenes such as tungsten and molybdenum sulphide have been demonstrated to have excellent antishock behaviour with the ability to handle upto 25GPa. The close cage structure of inorganic fullerenes provides it very high mechanical strength and shock resistance behaviour. The fullerenes when combined in a metal, alloys and polymers can be used in applications for protection against explosive ballistic projectiles [270].

3.2.3.2 Protection against fire

Fire resistant coatings have been mentioned in the literature. Nanometer scale layered double hydroxide (LDH) and nanoscaled titanium dioxide have been mentioned in the literature for fire resistance coating. Experimental studies performed have investigated the effects of nano-LDH and nano-titanium dioxide in improving fire resistance and anti aging properties of coatings. The coatings were shown to have great improvements in properties though by addition of nano scale additives [271]. The improvement of acrylic nanocomposites with nanoscale silicon dioxide has also been studied in fire resistant properties of flame retardant coatings. The nanoscale silicon dioxide enhances the anti-oxidation, char accumulation and char structure. The fire protection properties of acrylic nanocomposites have been reported to be better than conventional acrylic resin [272]. Acrylic nanocomposite coating containing nanoclays have been developed for fire protective coatings. The influence of nanoclays on properties was studied using scanning electron microscopy and fire tests. Nanocomposite coatings with 1.5% nanoclay have demonstrated good fire resistance and aging [273].

- 135 -

A comparative study of fire resistance of polymer nanocomposites filled with organoclays, polyhedral silsesquioxanes and carbon nanotubes has been mentioned in the literature. The experimental study using TEM showed that good dispersion of fillers improve flame retarding ability but failed in flammability tests. It was demonstrated that best results were obtained using a combination of flame retardants and Nanofillers [274]. Polymer and layered silicate nanocomposites have been experimentally studied, and shown that indefinite protection against fire could not be achieved. A number of approaches were suggested for improving fire retardancy like improving coupling of silicate layers in the char, incorporating additional additives as second layers of defence, to improve the effectiveness [275].

Buckyball nanocomposites have been investigated for their flame retardant properties. Dispersion of buckyballs in a polypropylene matrix was studies using TEM. The presence of C60 demonstrated to have a marked increase in the flame retardant properties of the nanocomposites. The flame retardancy was found to increase with the increase in increasing loading of the C60 in the polymer matrix. The mechanism of the buckyballs for trapping the free radical has been proposed [276].

Buckypaper is another name for carbon nanotubes membrane, which is made up of tangled carbon nanotubes ropes. The bucky paper was incorporated on the surface of polyhedral oligomeric silsesquioxane and glass fibre composite to experimentally study the fire resistance. The buckypaper was shown to have effectively reduced flammability for covering glass fibre composites. The advantages offered by the buckypaper are its thermal stability and ability to act as a barrier in reducing the degradation of products [277].

3.2.3.3 Electromagnetic shielding of information and communication equipment

Electromagnetic interference (EMI) is a well known problem for security electronic equipment. In a highly integrated information and telecommunications networked society, electromagnetic pulses or fields could be present a threat to the security of vital networks. Electromagnetic pulses may have their origin in thermonuclear explosions or an electromagnetic bomb. A number of different materials are under consideration and are being researched to protect devices and networks from EMI.

Electromagnetic radiation is also a by product of the vast increase of 1-5 GHz consumer electronic applications that interfere with large and critical systems. The need for protection from EMI has thus become an essential functional need of critical electronic and communications

- 136 - equipment. Literature has reported the most cost effective commercially available to be magnetic fillers and dielectrics [ 278, 279]. Intrinsically conductive polymers have been considered as protection against EMI due to their high conductivity, environmental stability and simple synthesis methods [280]. Electromagnetic shielding properties of polyaniline and polyurethane nanocomposites were optimised by modelling using a genetic algorithm and then experimentally tested. EMI shielding obtained attenuation higher than 40 or 80dB based on application in the microwave band [281]. Intrinsically conductive polymers are applied in form of thermoplastic polymer thin films such as polyvinyl chloride and polystyrene [282]. The synthesis and characterisation of nanocrystalline silver coated fly ash cenosphere particles are used in producing conductive polymer composites for EMI shielding has been mentioned in the literature [283].

In order to improve the performance and properties of intrinsically conductive polymers, lamellar nanocomposites based on conductive polymers like polyaniline have been reported in the literature. An investigation into the thermal, mechanical, electrical and microwave radiation absorbing properties of conductive polymers have been studies. Nanocomposites of polyaniline and organoclays doped with dodecylbenzenesulphonate have been experimentally studied. The nanocomposites showed to have high conductivities and good mechanical properties for conducting composites. These nanocomposites were shown to act effectively against radiation between 8 -12 GHz. These could be potentially used in antistatic packaging layers as well [284].

EMI shielding has been experimentally demonstrated using nanocomposite comprising of carbon nanotubes and carbon nanofibres in a polymer matrix. Carbon nanofibres of diameter 100-200nm in diameter and 30-100 µm length, with carbon nanotubes with 10-20 nm diameter and 5 -20 µm were used in the experimental research in a polystyrene matrix. A relative comparison of carbon nanotubes composite, nanofiber based composite and the combination of the two materials was done in experimental research. Electrical conductivity of the filler material, shape, size, and distribution in the matrix determine the electromagnetic shielding of the device. EMI shielding effectiveness for commercial applications has been mentioned in the literature as 20 dB. This was successfully demonstrated by nanocomposites containing 10 wt% of carbon nanofibres and a minimum of 1wt% carbon nanotubes. Other advantages offered by these nanocomposites are the light weight, low cost and excellent mechanical properties [285]. Vapour grown carbon nanofibres (VGCNF) in a polymer matrix have been investigated for their effectiveness in shielding and the relationship with processing variables. The effect of frequency (8 -12.5 GHz) was related to electrical characteristic like impedance. The research concluded that all VGCNF reinforced composites can find applications in electromagnetic shielding applications [286].

- 137 -

The mechanical, electrical, thermal, and electromagnetic shielding properties of multiwalled carbon nanotubes embedded in rubber sheets have been investigated. The amount and alignment of nanotubes determined the shielding effectiveness. These nanotubes demonstrated effective shielding for the range between several hundred MHz upto 1GHz. Due to shielding effectiveness of above 60dB these are expected to be used in a number of industrial electrical equipments [287]. Multiwalled carbon nanotubes have been demonstrated for their electromagnetic shielding in liquid crystal polymers and melaine polymer matrix. The highest shielding effectiveness at 60 dB experimentally demonstrated is suitable for industrial scale applications. The higher aspect ratio carbon nanotubes demonstrated higher shielding effectiveness and are considered suitable for use in conductive filler in plastic package [288]. Single walled carbon nanotubes in polymer matrix have been reported in the literature for EMI shielding applications. The highest shielding effectiveness demonstrated was 49dB at 10MHz for 15 wt% SWCNT. A shielding effectiveness of between 15-20 dB was observed for 500MHz –1.5 GHz frequencies [289].

Sol-gel based coatings have been mentioned in the literature for electromagnetic wave shielding coatings. These are composed of ultra fine metal particles in a silicon dioxide matrix. Silver colloid particles 10 nm in diameter were used with TiOxNy-ATO particles to obtain a protective film. The electromagnetic shielding effect depends on the surface conductivity which in turn is affected by the electric conductivity of the material and structure of the particles. The experimental research demonstrated that the surface conductivity of the film can be controlled by controlling the shape of the nanoparticles [290]. Nanoparticles of nickel and iron alloys were mentioned in the literature to be dispersed in expanded graphite for electromagnetic shielding applications. The alloy nanoparticles showed high shielding effectiveness for low frequency. Expanded graphite is electrically conductive, and shows good shielding effectiveness at high frequencies. The material thus demonstrated high shielding effectiveness for a wide range of frequencies [291].

Electromagnetic wave absorption has been mentioned in the literature using nano tetrapleg zinc oxide as absorbent and epoxy resin as binder in a coating. The nano tetrapleg zinc oxide coatings were observed to have excellent absorption for wave band between 15 -18 GHz [292]. Carbon nano onions (average particle size of 4 -7 nm) and detonation nano diamond are considered to be a candidate material for applications of electromagnetic shielding. Nanocomposites of carbon nano onions have been experimentally shown to attenuate electromagnetic shielding radiation for 12- 230 THz. It has also been mentioned that through mixed use of carbon nanomaterials, further enhanced shielding can be achieve for a spectral range of ultraviolet to terahertz and microwave [293].

- 138 -

Electromagnetic shielding in the low frequency range (30 kHz - 1.5GHz) has been experimentally demonstrated using carbon matrix composites with self assembled interconnected carbon nanoribbon network. These were fabricated using low cost natural materials such as rice husks as source for carbonaceous sources and transition metals as catalysts. The composites with carbon nanoribbons were show to have higher electromagnetic shielding value and higher electrical conductivities, than composites without carbon nanoribbons. Low frequency shielding has important applications for portable electronic devices that are used by civilian security agencies [294].

Carbon nanotubes and shape memory alloy composites have been developed for electromagnetic shielding applications. The shielding effectiveness of the composite was shown to have a dependency on the content of the nanotubes and the thickness of the composites. Three frequency bands 8-26.5 GHz (K band), 33-50 GHz (Q band) and 50-75 GHz (V band) were used for the experimental studies, with the highest frequency demonstrating the highest shielding efficiency [295].

3.2.4. State of Research and Development

This section provides a comparative assessment of research and development status of enabling nanotechnologies for protection. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. A comparative assessment of research and development status of nanotechnology development for protection application of infrastructure, information and communication equipment has been shown in Table EIP.1 below.

Table EIP.1 – Protection of equipment and infrastructure

- 139 -

Field Trials / Pilot Fundame Applied Deployed Prototy plant ( Pre- Mass ntal Researc (Commercial pe commercialisatio Market Research h ised) n)

Metal ƒ foams

Ceramic composit ƒ es for armour CNT in compres sible ƒ foams

Inorganic fullerene s for shock ƒ protectio n

Nanoscal e LDH ƒ for fire protectio n Nanoscal e Titanium dioxide for fire ƒ resistanc e coatings

Nanoscal ƒ e silicon

- 140 -

dioxide

Nanoclay nanocom posites ƒ

Buckybal l Nanoco mposites ƒ for fire protectio n CNT Membran e for fire ƒ protectio n

Magnetic fillers ƒ and dielectric s for EMI

Nanoco mposites ƒ for EMI shielding Carbon nanotube ƒ s for EMI Carbon Nanofibr ƒ es for EMI Metal Nanopart ƒ icles for shielding

- 141 -

Nanoco mposites of carbon ƒ nano onions Carbon nanoribb on ƒ network for shielding CNT and shape memory ƒ alloy composit e

3.2.5 Additional demand for research

The following additional demand for research was mentioned in the literature:

ƒ Further research for carbon composites with a carbon ribbon matrix for electromagnetic shielding has mentioned optimisation by manipulating the nanostructures through changing the experimental parameters such as sintering temperature and impregnation of transition metal [294].

ƒ Research need has been mentioned in the development of design requirements and additional physical protection measurements to counter threats against critical infrastructure such as government building and transportation hubs [199].

3.2.6 Applications and Perspectives

In the expert engagement process for the technology segment the following perspectives were observed:

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• Funding research and development for Protection sub-sector was considered important both for the European society and the economy.

• The main drivers for R&D in ‘Protection’ sub-sector were considered to be technological, and environmental, health and safety (EHS). The technological drivers are primarily related to cost, performance, efficiency, and absence of solution. Secondary drivers were related to productivity gains, and competitive advantage in conflict.

• The drivers for R&D in ‘Equipment and Infrastructure Protection’ segment were mentioned ‘protection against sabotaging agents’, ‘information networking reliability’ and ‘protection of information and communication infrastructure’.

• The main barriers for ‘Protection’ sub-sector were considered as ‘intellectual property conflict’ and ‘availability of finance’ for start-ups. Other secondary barriers were considered as lack of supportive government policies, lack of tax incentives, access to infrastructure, and inadequate technology transfer.

• The barriers for R&D in ‘Equipment and Infrastructure Protection’ segment were mentioned as ‘inadequate research funding’, and ‘lack of product integration’.

• The most important functionality were identified as ‘fire resistance’, ‘aging resistance’, ‘thermal stability’, ‘longevity of production’, ‘resistance to forced damage’, ‘weight of structure’, ‘electromagnetic shielding effectiveness’, ‘range of frequencies shielded’ and ‘surface conductivity of shielding agent’. Secondary functionalities desirable were mentioned as ‘barrier to degradation products’, ‘strength of structure’ and ‘wear and tear resistance’.

3.2.7. Current Situation within EU

No specific EC framework projects associated with nanotechnology applications in equipment and infrastructure projects were observed.

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3.3.1 Title – Condition Monitoring

Condition monitoring of civilian zones and critical infrastructure

Keywords: sensor, sensory networks, civilian zones, monitoring, temperature, light, vibration, sound, chemical species, trace vapours, radiation, sensing, processing, storage, memory, communication, information transfer, carbon nanotubes, graphene, nanowires, interconnects, transistors, power supply, semiconductors, quantum dots, energy, cantilever, solar, light harvesting

3.3.2 Definition of Technology Segment

Sensory networks and nodes provide platform for continuous monitoring of physical and environmental variables affecting important infrastructure in civilian zones. The section aims at assessing nanotechnology development which would enhance protection capabilities through continuously monitoring the condition of infrastructure and providing information about its status or any disruption in activity.

3.3.3 Short Description

The advancements in wireless communications and integrated circuit have made the development of sensory networks possible. A network of sensors to monitoring environmental conditions and presence of threatening agents could be used in the protection of infrastructure. These sensors could detect temperature, light, vibration, sound, chemical species, trace vapours and radiation. The concept of a sensor web has been reported in the literature. This sensor web has been proposed to comprise of three layers, sensing, communication and information. The sensor web provides functional characteristics such as interoperability between platforms, low cost, reliability, scale up, and high resolution. The multimodal information obtained from the earth observatory system is expected to considerable enhance data processing capabilities for accurate analysis and decision making [296].

A sensor node comprises of a sensing unit, a processing unit, a power unit and a transceiver unit. The sensor unit further is comprised of the sensor and an analog to digital converter. The processing unit serves the function of working with other units on assigned sensing tasks. The transceiver unit serves the purpose of connecting the node to the network. The power unit

- 144 - supported by power scavengers such as solar cells serve the purpose of providing functioning power to the sensor node. Networking of such sensor nodes is an important aspect of these sensor nodes, has important implication for civilian security such as target imaging, instruction detection in sensitive locations and surveillance by detecting ambient conditions or presence of objects [297].

Figure CM. 1 – A schematic diagram of sensor node [298]

Sensing - The use of carbon nanotubes as a sensing element has been mentioned in literature. A number of examples of such sensors are mentioned in the Detection section of civil security. The use of electrical and mechanical properties has been made in creating the smallest ‘balance’ that by mounting a single particle at the end of carbon nanotubes. On application of an electrical charge the carbon nanotubes vibrates like a spring and mass of the particle is calculated using changes in the resonant vibration frequency [299]. This remains an example of physical sensing. Nanobarcodes comprising of 50nm cross section cylindrical rods can be coated with analyte specific entities, for detection of complex molecules such as DNA [ 300, 301]. Chemical sensors based on carbon nanotubes have been demonstrated in the detection of NO2 or NH3 by signalling a change in the electrical resistance of the carbon nanotubes [302]. Titania nanotubes sensors have been reported in the literature to have been incorporated in a wireless sensor network for the detection of hydrogen [303].

Processing - Carbon nanotubes based transistors are expected to become an important component of the processing unit in sensor nodes. IBM has developed and successfully demonstrated using multiwalled carbon nanotubes or single walled carbon nanotubes, as channels for field effect transistors. The current flowing through the nanotubes can be changes by

- 145 - a factor of 100, 000 by changing the voltage [304]. NEC has reported developing a method of positioning the CNT which allow electrons to flow 100 times fasters than silicon and reduce the power consumption by a factor of 20 [305].

Communication and Data transmission – The transfer of information maybe obtained Microwave amplifiers are used in wireless communication are expected to form an important part of the transceiver unit. CNT cathode developed thin film fabrication techniques have demonstrated stable current densities in excess of 100 mA/cm2, which is the current density necessary for amplifiers [306]. Excellent RF properties of nanotubes and nanowires have been successfully demonstrated to have been integrated with wireless communication. The advantage of this approach of using carbon nanotubes as an antenna is that it can communicate with the sensing unit without have to use interconnects fabricated using lithography [307, 308]. Another advantage of the nanotubes antenna is that it can serve as an excellent impedance matching circuit to receive signals. Optoelectronic communication of information can be achieved through the use of nanooptoelectronics, diffractive optical elements, optoelectronic transducers and photonic components. Opotoelectronic components are composed of quantum wells, quantum dots, and photonic crystals. A more detailed view on the research and development in the optoelectronic communication maybe obtained from the ICT Technology sector of the Observatory Nano project.

Storage - The storage unit of such a sensory network is expected to benefit from the improved storage capacity. The millipede technology demonstrated by IBM can hold up to a trillion bits per square inch, 20 times more information than the most dense information storage available. The millipede works by punching thousands of indentation using nanosharp tips, which represents bits. Ultra fine tipped V shaped silicon cantilever produced by surface silicon micromachining. The millipede technology is expected to pack 10-15 GB of data [309]. CNT based memories developed by Nantero have reported a 10GB memory. The NRAM offers advantages such as non-volatility, high speed and price of a dynamic memory is expected to be a better candidate than other memories. The nanotubes are sprinkled on silicon wafer, where the nanotubes are balanced on the ridges of silicon. A change in the electrical charge can swing the nanotubes in one of two positions representing a zero or one state. Another advantage offered by this memory is the low power consumption required to change the state due to the small size of the nanotubes [310]. A number of memory storage technologies are being developed that may have a potential application in sensory network such as Molecular memory, Ferroelectric RAM, Magnetic RAM, Phase Change Bridge RAM. A more detailed view of these developments and other storage developments can be obtained from the Memory sub-sector of ICT Technology Sector in the Observatory Nano project.

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Power Supply - The supply of power to sensory nodes is of utmost importance for continuous condition monitoring of critical infrastructure. The use of nanocrystalline material and nanotubes has been mentioned in the literature to improve power density, lifetime, and power charge/discharge rates of batteries. Nanotubes as a replacement in the graphite-lithium electrode of portable batteries are expected to improve performance by increasing performance due to higher surface area. Nanocrystalline materials have been mentioned as potential material for separator plates due to the foam like structure which can hold more energy [311]. Other materials are being considered are transition metal oxides of cobalt, zinc, iron and copper for electrodes in lithium ion batteries. The surface electrochemical reactivity is improved by nanoparticles thereby improving the performance of lithium ion batteries [312]. Experiments have reported a 600% increase in reversible energy capacity. Material for cathode based on carbon nanotubes, titanium dioxide, and vanadium oxide have been mentioned in the literature [181]. Super capacitors have been suggested as power units for such the sensory node due to their high energy storage density and high power density. Carbon nanotubes increase the surface area of the capacitors exponentially and thus are an ideal candidate material. Low resistivity, high stability and narrow distribution of mesoporous size also make carbon nanotubes ideal for super capacitors [313].

Solar cells based on quantum dots have been mentioned to be suitable material for energy scavenging applications for sensory nodes. CdS quantum dots have been demonstrated to self assemble on the surface of nanocrystalline titanium dioxide and light harvesting electrode has been fabricated from P25 particles using a pressing method. The method was mentioned to have caused some loss in performance of the CdS coating though it was considered to be a suitable option for low cost manufacturing [314]. A number of materials are being considered and developed in photovoltaic, such as silicon based, polycrystalline thin film (copper indium diselnide and cadmium telluride), single crystalline thin film, dye sensitised thin film, organic and polymer solar cells. A more detailed view on the developments is available from the technology sub-sector of photovoltaics in Technology Sector Energy of the Observatory Nano project.

A number of other methods have been suggested in the literature based on solar power, thermal gradients and fluid flow [315]. Mechanical vibrations have been harnessed through piezoelectric for transforming vibrations to electrical energy. Lead zirconate titanate (PZT) has been reported in the literature for harvesting energy from vibrations. A thin film lead zirconate titanate MEMS device has been developed. The device resonates at specific frequencies of an external vibration source. The cantilever has a PZT/Silicon nitride bimorph structure with a proof mass attached to its end. The platinum/titanium electrode was reported to be patterned on top of a sol-gel coated PZT thin film. A spiral design for the cantilever has been proposed and demonstrated for

- 147 - compactness, lower resonant frequency, and a minimum damping coefficient. The device was shown to demonstrate a continuous supply of 1 µW of continuous power [316]. An array of zinc oxide nanowires have been reported in the literature for harnessing energy from mechanical vibrations. The nanowire array is placed below zig-zag metal electrode with a small gap. The piezoelectric semi-conducting coupling converts mechanical energy to energy. The device has shown to produce high power density in relation to other microgenerators [317]. A more detailed view of the technology research and development of the power supply are available from the ‘Power’ sub sector of the ICT Technology Sector in Observatory Nano project.

Role of Sensor Networks in Emergency Response - The role of sensors in emergency response has been reported in the literature. The protocol design, application development and security model has been mentioned to address the resource limitations of sensor nodes and network. Some of the problems the architecture named ‘Code Blue’ aims to address are robustness of signals received from sensors and communicated to the device, routing of signal data to multiple nodes, and prioritisation of critical data flow over communication networks. Security of wireless communication is expected to be enabled by providing enough computational power at nodes allowing them to use dynamic cryptography protocols. The ability to locate the node and sensory devices play an important role. In the event of serious causalities being brought in to medical facilities, the facilities are overwhelmed with decision making at demanding times. Sensory networks can be used for patient triage and tracking, temporary storage of patient information, simultaneous monitoring of physical variables and tracking first responders in providing trauma care to victims [318].

3.3.4 State of Research and Development

A comparative assessment of technology readiness levels has been done in Table CW.1 below for nanotechnologies enabling sensor nodes. The sensing layer and its various developments have been covered and comparatively assessed in the ‘Detection’ sub sector. Other technological developments for processing, storage, transmission, communication and data transmission, and power supply have been mentioned.

Table CW. 1 – A comparative assessment of Research and Development status of enabling nanotechnologies in Condition monitoring of infrastructure and civilian zone environment

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Field Trials / Pilot Fundame Applied Deployed Prototy plant ( Pre- Mass ntal Researc (Commercial pe commercialisatio Market Research h ised) n) CNT based transistor ƒ s for processi ng CNT ƒ cathodes CNT ƒ antenna Nano- optoelect ƒ ronics Millipede ƒ memory CNT based ƒ ƒ memory Molecula ƒ r memory Ferroelec ƒ tric RAM Magnetic ƒ RAM Phase Change ƒ bridge RAM Nanocrys talline materials ƒ for batteries Nanotub e for ƒ electrode s

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Transitio n metal ƒ oxides Super capacitor ƒ s Quantum dot solar ƒ cells Thin film solar cells for ƒ sensory nodes Mechani cal vibration s from ƒ cantileve rs for power supply Nanowire array for ƒ harnessi ng power

3.3.5 Additional demand for research

ƒ Research and development has been mentioned in the literature to develop, functionalities of sensory nodes and sensors as follows [313] :

- Programmable sensors with multisensing functions

- Wireless sensors with mobility

- Sensors with devices responding to stimuli

- Sensors with long and short range communication capability

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- Database built into sensory nodes

- Reducing interference in the transmission unit of the sensory node

- Eliminating noise from unwanted atoms or molecules in the sensing unit through improved design

- Multiple attribute sensing has been suggested as a desirable function.

- Integration of various different sensors in one platform has also been mentioned as a further research need.

- Interoperability of the sensor network and between sensor networks making it easy for sensors to communicate with each other has been proposed as a research need

- Deployment of sensors in uncertain and hostile environments may lead to loss in functionality. Further research has been proposed for sensors to provide information about its failure.

- Integration of nanoelectronics with sensing element through electrical contacts has been mentioned as a research challenge.

ƒ One of the main limitations of sensory nodes in sensory networks is the low computational capability, power availability and bandwidth limitations. Further research is needed in enhancing performance of sensor networks in responding to emergencies and medical disasters. Further research is also needed in taking prototype sensors to deployment in clinical settings [318].

3.3.6 Applications and Perspectives

In the expert engagement process for the technology segment the following perspectives were observed:

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• Funding research and development for Protection sub-sector was considered important both for the European society and the economy.

• The main drivers for R&D in ‘Protection’ sub-sector were considered to be technological, and environmental, health and safety (EHS). The technological drivers are primarily related to cost, performance, efficiency, and absence of solution. Secondary drivers were related as productivity gains, and competitive advantage in conflict.

• The drivers for R&D in ‘Condition monitoring’ segment was mentioned as ‘information networking reliability’ and ‘protection of information and communication infrastructure’.

• The main barriers for ‘Protection’ sub-sector were considered as ‘intellectual property conflict’ and ‘availability of finance’ for start-ups. Other secondary barriers were considered as lack of supportive government policies, lack of tax incentives, access to infrastructure, and inadequate technology transfer.

• The barriers for R&D in ‘Equipment and Infrastructure Protection’ segment were mentioned as ‘inadequate research funding’, ‘lack of equipment and testing facility’ and ‘lack of product integration’.

• The most important functionality were identified as to be ‘information processing’, ‘information storage’, ‘power supply consistency’, ‘memory non-volatility and high speed’, ‘lifetime of operation of filters’, ‘operational capability retention in wide ranging conditions’, and ‘wireless connectivity of sensor nodes’.

• Other secondary functionalities of interest were identified as ‘sensor characteristics’, ‘current density in circuits’, ‘Long and short range communication’ and ‘minimum maintenance’ and ‘low power consumption’.

The theme of enabling nanotechnologies for sensor networks enabling CBRNE detection was the topic of discussion at the Observatory Nano Symposium held in Dusseldorf in April 2009. The following outcomes and recommendations were observed:

• Sensor networks would be valuable for trend monitoring and pattern recognition, either globally across the city or in small local areas.

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• Greatest value addition for sensor networks would be in sensing layer of the sensor nodes. Other nanotechnology research and development in information processing and communication, and for energy has different drivers. These could be incorporated in future.

• Integration of multichannel sensor array has not been accomplished as yet.

• Novel sensors could potentially be integrated with commercial of the shelf component to achieve such a sensor network.

• The market for civilian security application would be created by the state.

• Investment would be independent of technology domain and more sensitive to capability enhancement.

• Emphasis on dual use application was suggested to improve commercial attractiveness.

• Life cycle analysis of the material and nanomaterial for scenario dependent applications should be conducted on a case by case basis.

3.3.7 Current Situation within EU

AMICON is a European Network of Excellence that brings together players in the field of Radio Frequency Micro-Electromechanical Systems and Radio Frequency Microsystems. The project targets research, education and applications aspects. The project aims to merge MEMS technologies with Information Communication technologies. PHOREMOST was an FP6 project that aimed to create a network of excellence that will address near and long term needs of photonic functional components enabled by nanotechnology. Both the projects have relevance to the Condition Monitoring of Infrastructure in the protection segment of the Technology Sector. The European Commission funded Mobi-Health project looked at communication technology for providing a continuous monitoring of trauma patients outside hospital environments. The framework 5 project aimed to create a third generation network for monitoring purposes was expected to save lives, generate vital medical research data and reduce medical services costs.

The following framework 7 projects have been funded by the European Commission in the Security theme that are relevant to condition monitoring:

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• Seamless communication for crisis management (SECRICOM) has been initiated in 2008 for the development for a reference security platform as an interoperable system on the existing communication network [319].

• Security System for maritime infrastructure, ports and costal zones (SECTRONIC) project initiated in 2008, focuses on critical maritime infrastructure namely, passenger and goods transport, energy supply and port infrastructure [320].

• Novel intruder detection & authentication optical sensing technology (IDETECT 4ALL) project initiated in 2008 focuses on the need for alerting technology for surveillance and intruder detection for critical infrastructure [321].

• Autonomous maritime surveillance system (AMASS) project initiated in 2008 focuses on security of critical maritime areas using active and passive sensors linked to a network. The project addresses illegal immigration, drug and weapons trafficking [322].

• Suspicious and abnormal behaviour monitoring using a network of cameras & sensors for situation awareness enhancement (SAMURAI) project was initiated in 2008. The project aims to develop and integrate monitoring systems based on cameras and sensors for critical infrastructure site [323].

• Localisation of threat substances in urban society (LOTUS) project was initiated in early 2009. The LOTUS project aims to create a system to detect the preparation of explosives and drugs during preparation and production of a terrorist plot. This will be demonstrated by detection using sensors and global infrastructure for positioning and networking [144].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is to combine technology solutions from Detection of CBRNE, area surveillance, and check point control for additional sensitive security locations. The sensor data is expected to be integrated with communication and data module to a command centre [44].

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to condition monitoring:

• Vital Infrastructure threats and assurance (VITA) project has delivered an assessment of threats and protection of highly networked infrastructure. The initial assessment of threats

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and proof of concept demonstrator were achieved for critical infrastructure in the 18 month period [324].

• Highway to Security: Interoperability for situation awareness and crisis management (HITS/ ISAC) project objective was to enable information analysis and fusion from numerous sources across borders to detect and provide early warning for suspicious activities such as communication and movement of goods. The focus of the 18 month project was prevention, prediction, interoperability and information sharing [325].

• Mobile Autonomous Reactive Information system for urgency situations (MARIUS) project aimed at developing a autonomous command post which can be deployed for monitoring during and after a crisis. The system is expected to integrate information processing from sensors and communication capabilities as a generic crisis management solution [326].

• Protection of Air Transportation and Infrastructure (PATIN) project aimed to ensure the protection of air transportation system and critical ground infrastructure and security networks against terrorist attacks. The project addressed issues such as interoperability, crisis management and optimisation of networks [327].

• Surveillance of Border Coastlines and Harbours (SOBCAH) project aimed to demonstrate a real time, user friendly, high automated surveillance systems for ports and borders. The demonstration would be based on the architectural solutions for most advanced sensors and networks [328].

• Transport Infrastructures Protection System (TIPS) project aimed to address security of mainline, subway and metro systems of European cities. The project addressed technological solutions for safety of passengers against explosives along with the communication infrastructure [147].

• Wireless Interoperability for Security (WINTSEC) project aimed to study the standardised internetworking layer at the core network level. The objectives were to achieve interoperability in public and governmental security domain [329].

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4. Anti-counterfeiting, Authentication, Positioning and Localisation

4.1.1 Title – Anticounterfeiting

Anti-counterfeiting

Keywords: brand theft, forgery, holographic features, nanocomposites, carbon nanotubes, quantum dots, organic nanofibres, laser surface authentication, SERS, physically unclonable function, nanobarcodes, diffractive nanostructure, nanocluster, nanomaterial, anti-counterfeiting

4.1.2 Definition of Technology Segment

The anti-counterfeiting sub-segment covers the methods, techniques, devices, structures and nanomaterials that help in the protection of the supply chain of industrial and consumer goods. The nanotechnology developments in this segment aim to address brand theft and prevention of intellectual property theft.

4.1.3 Short Description

A number of anti-counterfeiting technologies are being developed to counter theft of brand and intellectual property. This section will observe the technology developments addressing the increasing problems. Nanotechnology methods such as holographic features, laser surface authentication, physically unclonable functions, magnetic fingerprints, nanobarcodes, surface enhanced Raman scattering have been mentioned. Nanomaterials such as carbon nanotubes, quantum dots, organic nanofibres are being developed for anti-counterfeiting applications. The development of nanostructure, nanoscale features and nanoscale clusters to enhance the security of supply chains.

Holographic features - Holographic patterns provide security features both overt and covert to bank notes and credit cards. Application of holography has also been suggested for art. Nanozeolites have been used in photopolymerisable recording material for security application. [330]. The addition of inorganic additives has improved the properties of holographic polymers

- 156 - that can be used for new photonic applications. The working principle of holographic recording is the photo-induced modulation of the refractive index. This results from the variation in material composition and density from photopolymerisation of nanocomposite and diffusion of components from exposure to interference patterns. Experimental research has demonstrated nanocomposites consisting of acrylate polymers and organically capped inorganic nanoparticles as a medium for holography. Nanoparticles of SiO2 ,TiO2 and ZrO2 were used in the study. Phololuminiscent nanoparticles of non-oxide semiconductors cadmium sulphide and zinc selnide were also used. The research had investigated the preparation, properties, holographic performance, and the polymer-nanoparticle structure. The nanoparticles of SiO2 were observed to be the most effective in producing low scattering and highly selective holograms [331].

Experimental research has demonstrated the possibility of using luminescent nanoparticles in photopolymerisable composites for holographic security technology. Lanthanum phosphate, with an average size of 7nm, doped with cerium and terbium has been used as nanoparticles. Two dimensional gratings have been recorded in the nanocomposite. Photoluminescence of these nanoparticles within homogenous polymer film has been measured under ultraviolet light excitation. The advantage of the luminescent nanoparticles is that they provide an additional level 3+ of security for the hologram [332]. Experimental synthesis of fluorescent ZrO2:Eu nanoparticles have been reported in the literature. These spherical nanoparticles 4nm in size can be easily dissolved in organic solvent and can be used to produce holographic gratings [333]. Progress in holographic imaging has demonstrated a 164nm resolution using a table top extreme ultraviolet laser. The experimental research was demonstrated on a photo resist of PMMA 120 nm thick, the image of which was digitised using an AFM. The results demonstrated an improvement by a factor of two in the lateral resolution [334].

Laser surface authentication - In laser surface authentication a laser is used to examine the map of the surface roughness of an object using diffused scattering of a focused laser. The obtained code is thereafter stored in a database that can be accessed at a later date. The code of surface roughness is similar to iris scans and fingerprints, the probability of two codes matching was demonstrated to be 10-72 for paper and 10-20 for matt finished plastic cards and coated cardboard paper [335]. The advantages of the Laser Surface Authentication technique is that surface roughness of a surface cannot be replicated therefore a high level of security is offered to products, as compared to holograms and watermarks. Other advantages offered by the technique are robustness against wear and tear, low cost of hardware, 100% accuracy, highly unique features, covertness of the feature, speed at which scanning takes place on a production line, and the overall low cost due to absence of chips. One of the main disadvantages is that it cannot be used on transparent and reflecting surfaces, and the acceptable alignment limit is 1mm [336].

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Ingenia Technologies is commercialising the solution for the substrates such as paper, plastic, metals and ceramics. The solution is aimed for integration into product, packaging, and transportation stages of 37 supply chains. The implementation of the technique is expected to target the brand theft and the forgery market. The development challenges of the technology are the scanning apparatus and the design of codes database [337].

Physically unclonable function (PUF) – The anti-counterfeiting technology is being developed at Philips Research for applications in optical devices, integrated circuits and S-RAM devices. PUF comprises of two components, a physical protection layer and a cryptic layer. The physical layer has a unique fingerprint, similar to LSA, and serves to protect the digital signature. Due to the physical and cryptic layer, the solution is tamper resistant as verification of both layers is essential. The fingerprint is printed on the surface of the packaging or the product which can be then verified. The benefits offered by the technology are its tamper resistant nature, covertness of the feature, ease with which it can be evaluated and non-reproducibility. The PUF could potentially be embedded in RFID tags with digital signatures, thereby making the features physically unclonable. S-RAM PUFs are also being developed by Philips [338].

Magnetic fingerprinting – Magnetic fingerprints are being developed and commercialised by Singular ID as tags for products for which illegal counterfeits are being produced. The unique fingerprints are created by distributing micro to nanoscale magnets in a non-magnetic matrix material. The specific process used to synthesize magnetic nanoparticles depends on the application and specification of the tag. Porous materials such as aluminium oxide can be used as the matrix material and nickel based magnetic material are deposited through the pore structure. The electroplating process used creates a random pattern and a unique magnetic signature [339]. The unique signatures are read using GMR head scanner to obtain information which is stored into a database. The magnetic material can be embedded in materials such as metal, plastics and glass. The covert security features provide additional security to products in the pharmaceutical, medical, engineering component, and bank cards. The tags are being produced for anti-counterfeiting and brand security for automotive, fashion and pharmaceutical markets [340].

Nano barcodes- Three dimensional nanoscale data encryption key, similar to barcodes has been proposed in a filed patent. It consists of three dimensional polymer patterns in tens of nanometres, of poly (methylmethacrylate) on silicon substrates as tri-dimensional barcodes. Cross-linking the polymer using ultraviolet light provides a high durability material. Nano-imprint lithography is used to generate the pattern on the surface. A number of dimensional coding arrangements have been suggested – two dimension, two and a half dimension, three

- 158 - dimensions, three and a half dimension and four dimensional code. A high resolution charged coupled device camera fitted with an infrared filter is used to detect the reflection from silicon surface using a laser in the infra-red range. The advantage that nanometre scale features provide are the difficultly of being identified and even more difficult to duplicate such features. The application of these features can be with banknotes, security papers, art, jewellery and gem stones [341].

NanobarcodesTM particle system is being developed and commercialised by Oxonica. These barcodes consist of striped submicron scale metallic rods. The barcodes use the difference in reflectivity of gold, silver and platinum. These codes are read through an optical microscope using proprietary software. A combination of one thousand metallic rods can be used to generate a trillion unique codes. These barcodes can be applied in distinct surfaces such as those present in inks, adhesives, laminates, paper, packaging, and films. They also find application in textiles, thread and glass [342].

Surface enhanced Raman scattering tags – The unique spectra generated by Raman scattering of substances can be utilised as an identification tool. SERS tags developed by Nanoplex technologies use the principles of Raman scattering for identification purposes. The SERS tag consists of metal nanoparticles, SERS reporter and, eventually, a coating material like silica. Gold and silver nanoparticles are mainly used in SERS tags. These find applications in bank notes, paper, packing, clothing and pills. The advantages offered by the technique difficultly in reproducing due to infinite combinations, covert security feature, non-toxic, and multifunctionality. One of the main disadvantages of the technique is the weak signal from the tag that can be improved using surface enhancement by adjusting the type of substrate [342].

Quantum dots as barcodes for identification – A method for identifying and locating products using quantum dots has been patented. Quantum dots fluoresce and produce characteristic emission based on their composition and size. In the patented method quantum dots of one or more particle size distribution are utilised as barcodes. The intensity of the emission at a fixed wavelength can be varied to produce a binary or higher coding scheme. Quantum dots of semiconductors for group II-VI, III-V, and IV are suitable for the identification application. Semiconductor materials such as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, GaN, GaP, GaAs, GaSb, InP, InAs, InSb, AlS, AlP, AlSb, PbS, PbSe, Ge and Si were considered to be suitable for application as quantum dots. The security tag can be used for consumer items such precious jewellery, vehicles, and confidential paper [343 ].

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Organic nanofibers - Organic nanofibers have been suggested for application in banknotes. Gas phase synthesis of functionalised organic nanofibres from organic precursors has been mentioned in a filed patent. These organic nanofibres have been reported to have novel optical properties such as pre-determined fluorescence under UV excitation [ 344]. Gain and lasing of self assembled nanofibres have been studied experimentally, which was shown to be dependent on the structure of the fibres [345].

Nanostructures - Anti-counterfeiting patterns have been produced for banknotes by depositing adapted multilayered nanostructures. These structures produce different effects when interacting with light such as change of luminosity and change of color which are used in security applications in bank notes and credit cards. Experimental studies were conducted on concave or convex structures of insect wings to study the effect [346].

Nanoclusters - Nanoclusters are assemblies of atoms or molecules that are covalently or non- covalently bonded with largest overall dimension in the nanoscale [347]. They have novel physical and chemical properties, which can be used for security applications. Clusters of metals deposited on a substrate at a nanometric distance (5-500nm), from a wave reflecting layer can act as a nanoresonator. Sensors and devices are based on surface enhancement of light absorption. This technique forms the basis of producing thin film for anti-counterfeiting applications, which is based on characteristic colours and special optical effects. This has formed the basis of commercial products through Brandsealing which uses the patented cluster technology to produce optical coding. These spectroscopic properties of the optical code are authenticated using a reader. This technology has been considered by the authors to enhance the security feature of threads in bank notes and much better than holograms for authentication of new currency [348].

Nano-coloured materials in combination with active and sensory color-changing nano-features and interactive properties are one of the promising concepts of Attophotonic’s nanotechnology applications. By using multiple reactive nano-layers and nano-structured surfaces the Attophotonics® Biosciences GmbH creates a wide range of colours using resonant nanoclusters. The layers are designed to specifically reflect some spectral sub-fraction whereas other electromagnetic waves are absorbed efficiently. Based on the particular nanostructure the surfaces shines and even sparkles in a well defined colour-pattern. The innovative products are manifold reaching from novel smart surface materials for design to films, foils, pigmented inks and printed labels visually indicating the identity, quality and status of packed products [349].

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Diffractive nanostructures - Diffractive structures are useful for application in anti-counterfeiting and brand protection. Structures of parallel lines with spacing of over 100nm are made up of material with high refraction index surrounded with low refraction index material. In order to enhance the color effect, a layer of chromophores and fluorophors materials such as quantum dots and metallic nanoparticles have been mentioned. The device is to be used in form of transferable labels and tags for banknotes, credit cards, passports and brand protection applications. These have been mentioned to be better than optical variable devices, optical variable ink, diffractive optical image wave device [350]. Diffractive optics based devices enabled by nanomaterials have been reported in a filed patent for application in authentication and security. A number of materials such as epoxy, acrylate, polycarbonate, UV-curable sol-gel material, silicon oxide, carbide, diamond, carbon, carbon derivative, magnesium fluoride, ZnO, ZnS, and/or titanium oxide have been indicated for use in the diffractive layer. Nanoparticles with a high refractive index have been used in polymer matrix. For the mirror layer, metallic nanoparticles have been suggested for use within metallic alloys. The application of the diffractive optic device has been suggested for banknotes, credit cards, passports and for brand protection [351].

Inexpensive and an easy to manufacture security packaging material and paper based on micro- nanostructure have been reported in a filed patent. The packaging carries the micro- nanostructures act as diffractive optical elements. The micro-nanostructures are embossed on to the surface. A laser beam diffracted from the structures is used to detect the security feature. The application of this method has been suggested for consumer applications such as electronics goods and medicine [352]. Experimental research has been shown to demonstrate layer by layer self assembly of gold nanoparticles on cellulosic fibres, wood and bacterial cellulose as substrate. Gold nanoparticles of 15-100nm in size could be modified by silica shells to enhance optical properties of the nanocomposite. The development will have applications in the security paper synthesis [353].

Verify First Technologies have filed a patent for security documents, have described two security features on a printable substrate, one that is on the substrate and the other partially or completely embedded in the first feature. The first security feature has nanostructures for trapping printing matter for latent copy-void warning message. The second security feature is also nanostructured configured for forming pixel pattern on digital document reproduction. Thermochromic ink is partially arranged in the pattern of the first nanostructure. This technology is expected to act as security features for bank cheques, stocks and bond certificates [354]. A prior art by the same organisation has demonstrated nanopatterns with different nanostructures such as polygons, circles, ovals, crosses, and alphanumeric characters [355].

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Confocal type laser profile microscope, have been demonstrated in measuring the thickness of films posted on passports [ 356]. Spectral information based on color of an object captured on to a database has been described in a filed patent. The spatial analysis software along with the apparatus is used to compare unique patterns [357].

Others Nanomaterials - Nanosized titanium dioxide and zinc oxide have been demonstrated as ultraviolet blockers by the Canadian Bank note company, in enhancing security features of documents such as birth-certificates, driver’s license, travel documents and bank notes. The patent describes the method of producing a transparent window on a security document, including a transparent ultraviolet blockers, and printing an invisible ultraviolet fluorescent ink. The authentication of the document is done using ultraviolet wavelengths of light [358].

Single walled and multiwalled carbon nanotubes have been demonstrated in a security mark comprising of multiple layers. The identification information is contained with the patterned layers composed of conductive material. The conductive layer is made from carbon nanotubes with diameter in the range of 0.5 nm - 15nm. Antimony Tin-Oxide has been alloyed with carbon nanotubes to produce conductive layers. The conductive layer is patterned to form resistors by printing with conductive ink. The code in the conductive layer is read by a reader which identifies an object, based on its conductivity. The application has been envisaged in prevention of counterfeiting of products and security cards [359].

4.1.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling nanotechnologies. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. The spread of technology readiness indicates the research and development focusing on different materials and application for a given technique. Table AC.1 below shows a comparative assessment for Anti- Counterfeiting sub-segment.

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Table AC.1: Anti – Counterfeiting Comparative Research and Development Status

Fundam Field Trials / Pilot Deployed e-ntal Applied Prototy plant ( Pre- Mass (Commerci Researc Research pe commercialisatio Market alised) h n) Holographic feature ( ƒ ƒ ƒ ƒ Nanocompos ite) Laser Surface ƒ ƒ ƒ Authenticatio n Physically Unclonable ƒ function Magnetic ƒ ƒ fingerprinting Nanobarcod ƒ ƒ ƒ es

SERS tag ƒ ƒ ƒ

Quantum ƒ dots Organic ƒ Nanofibres Nanostructur ƒ es

Nanocluster ƒ ƒ ƒ

Nanomaterial ƒ ƒ s Diffractive Nanostructur ƒ ƒ es

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4.1.5 Additional demand for research

Further materials and applications research for the anti-counterfeiting, authentication, positioning and localisation have been mentioned as:

ƒ Research is needed in controlling and modulating the organic nanofibres self assembly process for enhanced application performance in authentication [345].

4.1.6 Applications and Perspectives

The expert engagement process identified trend for anti-counterfeiting as:

• Main drivers for research and development are technological, economic gains, social impact and regional policy Technological drivers are principally identified as cost, performance, efficiency and absence of a solution.

• Brand Theft is considered important driver for R&D in anti-counterfeiting.

• Main barriers for research and development were identified as lack of supporting governmental policies, access to equipment and infrastructure as well as inadequate technology transfer.

• Failure to integrate during field trials was considered a development barrier. Limited supporting policies were also considered as a barrier for technology segment.

• The technological segment represents an economic implication for society with a justice related dimension to it as well.

• The attractive application research area was ‘Intelligent materials and packaging’. Automated packaging for product identification along with back tracing combined with sensory features was suggested.

• The most important functionalities were identified as ‘accuracy in identification’, ‘not easily reproducible feature’, ‘multifunctionality of identification tag’, ‘portability of identification unit’, ‘uniqueness’, ‘ease of integration’ and ‘long operating life’

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• The holographic features for anti-counterfeiting applications are currently on the market.

• Laser Surface Authentication and Nanocluster based identification is expected to be in the market in the next 5 years. Both the technology solutions were considered attractive growth markets.

• Nanobarcodes, SERS tags and nanostructured security features are expected to appear on the market in the next 10 years. Nanostructured security features were considered to be very attractive higher growth markets in relation to Nanobarcodes and SERS tags.

• Other qualitative information suggested that there should be ‘greater emphasis on creating company awareness of product security features’, ‘improving international laws to dealing with fraud’ and ‘more emphasis on technological development than basic research for authentication’.

• Based on the application, the potential toxicity of nanomaterials should be considered. Cadmium compounds were mentioned to one of the most severely regulated materials.

4.1.7 Current Situation within EU

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to explosives detection:

• Secure Container Data Device Standardisation (SECCONDD) project aims to initiate standardisation of technical interface between secure container or vehicle and a data reader at a port or border crossing. The project is expected to identify any potential threats from terrorist activity or insertion of contraband goods [146].

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4.2.1 Title - Authentication

Authentication

Keywords: authentication, biometric, fingerprint, retinal, nanocomposites, opal, nanostructured material, polymer nanocomposites, opal, nanofibre, quantum cryptography

4.2.2 Definition of Technology Segment

The authentication technology segment would cover applications of nanotechnologies in verification of individual identity using fingerprints, retinal, facial and hand features. The technology segment would cover nanotechnology developments for identity verification and security of information and communication.

4.2.3 Short Description

Research and development addressing the verification of identify and security of information and communication has been observed in this section. The use of nanomaterials in identity verification has been done demonstrated through its use in nanocomposites and protection of information and communication through quantum cryptography.

Nanocomposites – Biometrics are viewed to be vital in identification of a person’s identity. Biometrics encompasses recognition method for human fingerprinting, iris and retinal, facial and hand features. Polymer nanocomposite material based on multi-dyes has been reported in literature for application in security labelling. Polymer multiphase nanostructured materials have been reported in the literature as a medium for recording biometric information. Fluorescent dyes with non-overlapping absorption and emission spectra have been used to record information by photo-bleaching of the dyes. Design, synthesis and fabrication of two different approaches – full color and monochromatic spatial arrangement of three biometric features, photograph, fingerprint and signature was demonstrated. The dyes used were anthracene, 4-amino-7-nitrobenzo-2-oxa- 1, 3-diazole (NBD) and Nile Blue. The size of the An labelled core was reported to be 450nm, dye labelled layer as 15 nm and spacer layer as 160nm. Destructive readout using a low power laser was used to examine the information recorded on to the nanostructured material. The advantage of this approach is the longevity as the destructive readout can be used on a daily basis for 4 years of image being accessed [360, 361].

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Opal based nanocomposites - Iridescence of stacked silica spheres known as natural opals is caused by interference of light with lattice planes [362, 363]. An industrially scalable approach for producing opals from polymer has been mentioned in the literature. Quantum dot doped polymers opals have been created for security applications by compression moulding of flexible films. Experimental research has demonstrated nanoparticulate carbon black in elastomeric opals produces remarkable change in colour under compression loading [364].

Nanotechnology based platforms of P-Ink and Elast-Ink have been mentioned as commercially viable options for authentication technology. Active color tuning of opal has been utilised in these technology solutions. One solution reversibly shrinks or expands on removal or application of a voltage to a metallopolymer opal. Opal embedded in a matrix of polyferrocencylsilane gel is termed as P-Ink. The other solution is based on studying the reversible dimensional changes of an elastomeric opal that change based on application or removal of a mechanical force. Composite opal formed by combing opal with synthetic rubber, which when dissolved leaves a network of voids in a rubbery matrix known as elastomeric inverse. Due to the highly porous structure, and the color shift observed with increasing pressure can be utilised as a highly fingerprinting sensor for use in forensics, biometric security and authentication [365].

Optical Fibres - Optical fluorescent fibers randomly arranged have been suggested as a solution for anti-counterfeiting by Tracer Detection Technology Corporation. The fibers provide a constantly moving a non-repeating target, making counterfeiting difficult. A unique algorithmically generated code printed with the fibers, add to the security feature. The code optically read has mentioned the possibility of generating a duplicate is 1 in 1015. The advantage this technique offers over other is due to the difficultly in producing the same fluorescent dichroic fibers, producing the same emission behaviour at the detector wavelength, fibers of same length and shape. Other alternatives to fluorescent markers have been suggested as nanocrystalline materials, carbon nanotubes, fullerenes, dendrimers, nano-intermediaries and nano-composites. Fluorescent nanoparticles such as quantum dots, fluorescent polymer particles, silica coated fluorescent polymer particles, dye loaded latex nanobeads, and iron oxide nanoparticles have been mentioned. The application has been reported for pharmaceutical, designer and branded clothing [366].

Quantum cryptography – Quantum cryptography is based on the quantum mechanics principles of uncertainty and entanglement. Two known approaches are considered for quantum cryptography. The first approach is that using polarisation of photons, where the polarised photons representing bits of information. The vertical polarisation represents a zero state and horizontal polarisation represents one state. The information which is encrypted as diagonal

- 167 - polarisations is used as an encryption method. The second approach used is that of entangled photons, where the entanglement property utilises to transfer cryptic information. In this method both the sender and receiver get one photon from the entangled pair. Due to pairing of entangled photons the measurements of polarisation of light provides the same output at both ends. The measurements are added to give a string of zero’s and one’s to get the key [367]. The research on quantum cryptography has been successfully demonstrated in transferring funds between the Vienna City Hall and the Bank of Austria. Entangled photons have also been sent over a distance of 100 km by researchers at Northwestern University [181].

4.2.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling nanotechnologies. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets. The spread of development indicates the different methods and materials being researched and developed of the application. A comparative assessment of nanotechnologies enabling Authentication has been shown in Table AU.1.

Table AU.1 – Authentication enabling nanotechnologies

Field Trials / Pilot Fundame Applied Deployed Prototyp plant ( Pre- Mass ntal Resear (Commercial e commercialisatio Market Research ch ised) n)

Nanocomp ƒ -osites

Opal based ƒ ƒ ƒ Nanocomp osties

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Optical ƒ fibres

Quantum cryptograp ƒ ƒ ƒ hy

4.2.5 Additional demand for research

The following additional demand for research was mentioned in the literature:

ƒ Applied research is needed to demonstrate material characteristic to hone color switching times, wavelength tuning range and mechanical strength for opal based P-Ink and Elast- Ink authentication solution. The applications have to be further supplemented by demonstration as a scaled up pilot plant [365].

4.2.6 Applications and Perspectives

The expert engagement process identified trend for authentication as:

• Main drivers for research and development are technological, social impact and regional policy. Technological drivers are principally identified as cost, performance, efficiency and absence of a solution.

• Forgery is considered important driver for R&D in authentication.

• Main barriers for research and development were identified as lack of supporting governmental policies, access to equipment and infrastructure as well as inadequate technology transfer.

• Failure to integrate during field trials was considered a development barrier.

• Application trend is towards enhanced and secure identity documents as well as finger print detection.

• The attractive application research area was ‘Intelligent materials and packaging’.

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• The most important functionalities were identified as ‘accuracy in identification and authentication’, ‘not easily reproducible feature’, ‘multifunctionality’, ‘uniqueness’, ‘ease of integration’ and ‘long operating life’

• Nanostructured polymer films are expected to be on the authentication market in the next 5 years. The market is expected to be attractive growth market.

• Other qualitative information suggested that there should be ‘more emphasis on technological development than basic research for authentication’.

• The debate on privacy versus security is an important one for the authentication technology segment.

4.2.7 Current Situation within EU

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to authentication:

• European Security: High level study on threats responses and relevant technologies (ESSTRT). The support action project has provided a comprehensive overview of necessary responses to security challenges. The technology development is expected to address personal identification through biometrics solutions for documentation by improving false rejections and acceptance [45].

• Towards a network for testing and certification of biometric components and systems ( BioTesting Europe) project aimed to set up a European Network of testing and certification for biometric components [368].

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4.3.1 Title – Positioning and Localisation

Positioning and Localisation

Keywords: positioning, localisation, radio frequency identification, carbon nanotubes, nanowire, supply chain

4.3.2 Definition of Technology Segment

The positioning and localisation segment would cover all enabling nanotechnologies that would enhance capabilities in positioning and localising of goods and objects.

4.3.3 Short Description

Position and Location of industrial and consumer goods is vital in ensuring the security of supply chains. Radio Frequency identification tags have been centre of focus of development. The use of metal nanoparticles and carbon nanotubes has been observed for their functionality enhancing capability.

Radio frequency Identification (RFID) - Radio frequency identification tags are being used for surveillance and logistics applications. RFID work on identification of low frequency and high frequency, it consist of readers, transponders, and host systems [369]. The fabrication of RFID components such as capacitors, inductors, circuits and interconnects need low resistance conductors. The literature points towards a novel process for producing low resistance conductors patterns. These patterns are produced from solutions of organic-encapsulated silver and copper nanoparticles that can be printed and annealed [370].

Carbon nanotubes are being researched as suitable antenna elements for RFID tags. The high conductivity and length of nanotubes make them suitable for between 50 GHz and 1 THz wireless communication. One of the major limitations and subject of study is the achieving wireless communication of antenna with other nanometric components. Development of vertically aligned CNT based switches for RF-MEMS has also been mentioned in the literature. While striction remains a problem, CNT’s overcome these due to dramatically reduced surface area and charging effects in dielectrics [371]. The use of carbon nanotubes in an inductively couple antenna with RFID has been experimentally demonstrated [372].

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RFID embedded in paper has been considered as one of the best organic substrates due to its cheap processing, similar dielectric constant as air and its ability to embed nanoscale additives. These can also be coupled with sensors and batteries as actives tags in multilayers for security applications [373]. Method for producing silver nanoparticle (2-5nm prepared from toluene) based inks and nanowires (75nm in diameter) have been reported in the literature. These are considered suitable for applications such as printed RFID antennas [374].

4.3.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling nanotechnologies. Fundamental Research is defined for this purpose as research with no particular goals of commercialisation. Applied Research is defined as research conducted in academia and industry directed towards a specific purpose and application. Prototype has been defined as Applied Research or Fundamental Research that has found a potential market application. Technologies that are in the field trial state are defined as those that are in the process of commercialisation, and are being tested. Deployed nanotechnologies are those that have found an early stage market. Mass Market has been defined as those technologies that have been adopted by large population and are attractive high growth markets.

A comparative assessment of enabling nanotechnologies for positioning and localisation is shown in Table PL.1 below.

Table PL.1 – Positioning and Localisation

Fundame Applied Prototy Field Trials / Pilot Deployed Mass ntal Researc pe plant ( Pre- (Commercial Market Research h commercialisatio ised) n) RFID enabled by metal ƒ nanoparti cles RFID enabled ƒ by CNT

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4.3.5 Additional demand for research

The following additional demand for research was mentioned for positioning and localisation applications:

ƒ Further research is need in transmission of microwave signals in nano-antennas and nano-switches enabled by carbon nanotubes. New communication architecture has been suggested in literature for secure communication. CNT based devices are suggested to increase rate of data transfer on mobile phones, providing high efficiency, low cost and miniaturised broadband capabilities. W-band based security systems, enabled by nanoscale components, will improve evaluation and avoiding collision with obstacles in aircraft paths in difficult weather conditions [371].

ƒ Further research for integration of carbon nanotubes into RFID tags has been mentioned in the literature. Optimising layer by layer self assembly to optimise capacitance has been indicated. Research has also been suggested in fabrication parameters with sensing performance [372].

ƒ Tracking and tracing of substances and vehicles are considered to be important capabilities. Research in developing capabilities for automated observation and monitoring of substances and objects has been mentioned [199].

4.3.6 Applications and Perspective

The expert engagement process identified the following trends:

• Main drivers for research and development are technological, economic gains, social impact and regional policy

• Theft is considered important driver for R&D in positioning and localisation.

• The technological segment represents an economic implication for society. RFID technology presents a privacy related issue as well.

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4.3.7 Current Situation within EU

SELECT NANO was a framework 6 project that aimed at the development of multifunctional nanoparticles using a process of Sonoelectrochemistry. The network of excellence aimed to synthesise, scale up and apply the nanoparticles for detecting and authenticating articles using printing conductive labels and coding information based on the printed pattern. The PEARL (privacy enhanced security architecture for RFID tags) project is aimed at developing tools and methodologies for RFID systems, while preserving user privacy. The ongoing project aims at modelling relevant privacy and security policy as well as developing protocol for RFID environments. The project also looks at integration of RFID tags and developing back office support system applications.

The following Preparatory Action for Security Research Funded projects were funded by the European Commission and are relevant to positioning and localisation:

• Advanced space technologies to support security operations (ASTRO +) was a 15 month project aimed at transverse technology analysis, definition with end user and demonstration of mission concepts. The project demonstrated imagery intelligence facility, communication and tracking of vehicles and security personnel [375].

• People real-time observation in buildings: Assessment of New Technologies (PROBANT) in support of surveillance and intervention operations, project aims to develop, integrate and validate technologies for crisis intervention and surveillance situations. The technologies validated by PROBANT would be used by civilian agencies in threat detection during hostage situations, kidnapping and hijacking to obtain images in real time [376].

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