Roadmap Report Concerning the Use of Nanomaterials in the Energy Sector

Forschungszentrum Karlsruhe

funded by the European Commission

TABLE OF CONTENTS I. Introduction .......................................................................................................................3 I.1. Objectives of the Roadmap Report............................................................................3 I.2. Guidelines for the use of the Roadmap Report..........................................................3 I.3. Overview on the Energy Sector .................................................................................8 I.3.1. Applications in the Energy Sector.........................................................................8 I.4. Relevant Nanotechnology Effects for Applications in the Energy Sector...................9 II. Nanomaterials Roadmap Analysis on the Energy Sector ...............................................10 II.1. Energy Conversion Energy Production.................................................................10 II.1.1. Solar Photovoltaics .........................................................................................10 II.1.2. Hydrogen Conversion .....................................................................................20 II.1.3. Thermoelectricity ............................................................................................24 II.1.4. Solar Thermal Energy.....................................................................................26 II.1.5. Bioenergetics ..................................................................................................28 II.2. Energy storage.........................................................................................................29 II.2.1. Rechargeable Batteries ..................................................................................29 II.2.2. Hydrogen Storage...........................................................................................40 II.2.3. Supercapacitors..............................................................................................47 II.3. Energy Saving..........................................................................................................52 II.3.1. Insulation ........................................................................................................52 II.3.2. More Efficient Lighting Point Sources.............................................................60 II.3.3. More efficient Lighting for Large Areas...........................................................64 II.3.4. Combustion.....................................................................................................72 II.3.5. Lighter and Stronger Materials .......................................................................75 III. Conclusions ................................................................................................................86 IV. Sources and References ............................................................................................87 V. Impressum..................................................................................................................88

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I.

Introduction I.1. Objectives of the Roadmap Report

This report has the objective to give an overview on the use of nanomaterials in the energy sector and has not the goal to be exhaustive. It will give to small and medium sized enterprises (SMEs) the possibility to have a concise description of the development in this sector. For this reason only some scientific details and technological explanations are presented. This roadmap report has the main purpose to help SMEs which are in the process of looking for new materials with improved properties to be integrated in their new products and to give them a first list of relevant nanomaterials they should consider depending on the industrial applications foreseen, the time to market and the R&D capacity of the company. The target group of users are SMEs, which are starting a strategic decision-making phase for new product development. The main purposes are: To give an overview on relevant nanomaterials for industrial applications in the automotive sector at short, middle and long term. To give the actual level of development of the nanomaterials and an approximate evolution of it at short, middle and long term. To be adapted to SMEs. The results are based on a database with information about more than 100 nanomaterials, which was developed in the frame of the EC-funded project NanoRoadSME. The database and the linked roadmapping tool were structured taking into account the results of a European Survey on more than 300 European SMEs, the results of several R&D surveys and industrial SWOT analysis as well as workshops and experts interviews. Technology and market driven approaches were used to gather useful data into the database. It therefore contains relevant technical and economical information on nanomaterials which have future potential use in the automotive industry. This database is a new kind of instrument for dynamic technology roadmapping. I.2. Guidelines for the use of the Roadmap Report

The report is structured in 3 different main domains of the energy sector in which nanomaterials can play an important role in the future. These domains are: Energy conversion Energy production Energy storage Energy saving For each domain, the report will give an overview of the following aspects: Information about relevant barriers in each specific domain which have to be overcome.

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 Possible solutions to overcome the barriers through nanomaterials. Presentation of relevant nanomaterials to overcome these barriers by drawing 3 figures and 1 table, which represent the nanomaterial roadmap for the specific domain of application and which give the following information: Figure 1 - the level of development of the nanomaterials and a prognosis of its evolution in the next 15 years

In order to have a quick overview of the development stage of the different nanomaterials and its evolution, five different levels of development were defined, each one corresponding to a specific color: 1. Scientific result / technology invention (TI - red) the very first steps in the development process. This is considered as true research and is often still in theory or in a test status. 2. Laboratory prototype (LP - orange) still within the research status, but moving from theoretical calculations and evidence towards a proof in reality as tests are verified and results can be seen in a laboratory. 3. Industrial demonstrator (ID - yellow) now results can be brought forward towards the industry. The purely scientific results are being applied with first applications and can be introduced to interested companies. 4. Industrialization (I green) the development is starting to prove itself, the movement and transition towards real-life applications is moving forward and there demand through the industry is beginning to increase. 5. Market entry (ME blue) the final stage in the development process. The material is now ready available for the end consumer, probably still not everywhere and at a rather higher price. These stages of development have different order of importance for SMEs depending to their position in the supply chain of nanomaterials. Three main categories can be defined: Developer of nanomaterials Producer of nanomaterials User of nanomaterials These SME types have special interests in specific nanomaterials according to their R&D budget, resources, position in the supply chain:

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Figure 1: Relevant product development stages for the different SME types

Nanomaterial developers have special interests in materials which are at the development level of scientific result / technology invention or laboratory prototype. As these companies have their own research and development laboratories they are interested in further developing and finding solutions. They are technology driven and used to finding technological solutions. At the same time they have the brain power, equipment and potential for this type of work. Producer of nanomaterials focus on materials which are at the laboratory prototype, industrial demonstrator or industrialisation level. These companies are not interested in further developing nanomaterials but rather have competencies in the production and manufacturing. The focus moves away from development technologies towards manufacturing technologies. Process knowledge and facilities are most important. On top of that these SMEs have a network of recipients and the focus is moving towards customers. User companies of the nanomaterials may only be interested in nanomaterials which are at the industrialisation or market entry level. They do not have the interest or the potential to develop or produce nanomaterials. These SMEs are customer focused and provide the end consumer with solutions to their problems. They do this with the support of nanomaterials that can be purchased and integrated into their value adding processes.

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Table 1 - the timeframe of possible industrial applications in this domain with perspectives at short (0-2 years), middle (3-5 years) and long term (6-10 years)

Figure 2 - the nanomaterial costs and its possible evolution at short, middle and long term (when available)

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Figure 3 - the market size of the nanomaterials (when available)

For each relevant nanomaterial, detailed information like a short material description, improved properties, advantages/disadvantages of the nanomaterial, barriers for the development as well as specific applications for each category are given. Finally a list about companies and organisations (if available) active in the specific areas is presented.

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I.3. Overview on the Energy Sector The main challenges for the application of nanomaterials in the energy sector are the improvement of the efficiency, the reliability, the safety and the lifetime as well as the reduction of costs. In order to give a clear overview and description of the industrial sector, three different levels have been defined in the project: Level 1: Domains of application Level 2: Products in these domains of application Level 3: Nanomaterials used in the products or having the potential to improve the weaknesses of existing products I.3.1. Applications in the Energy Sector Three main domains of application can be identified in the energy sector (Figure 2): 1. Energy conversion / production 2. Energy storage 3. Energy saving In each domain of application different products can be identified in which nanomaterials play at present or have the potential to play in the future an important role. The SWOT analysis will present the link between the three.

Figure 2: Main domain of application for nanomaterials in the energy sector

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The most promising application fields for the energy conversion will be: photovoltaics (solar cells), hydrogen conversion (fuel cells), thermoelectricity (themoelectronic devices). For energy storage the most promising application fields will be: rechargeable batteries supercapacitors. For energy saving the interesting application fields will be: insulation (aerogels, smart glazes, nanofoams) more efficient lighting (LEDs, OLEDs). I.4. Relevant Nanotechnology Effects for Applications in the Energy Sector

Nanoparticles are especially relevant for the energy sector because of their specific properties. Nanoparticles present large surface area which leads to high reactivity with low material quantity and brings advantages in the following domains: o Better catalysts Higher reaction rates Lower processing temperatures Reduced emission Need for less material o Improving combustion processes Higher efficiency Lower processing temperatures o Energy storage applications E.g. hydrogen storage E.g. electrodes for lithium batteries Nanoceramic membranes for lithium batteries o Energy transformation/conversion/production E.g. electrodes for fuel cells Higher absorption rates for light in solar cells Tuned the spectral absorption of light by the dimension of the absorbing nanoparticles Anti-reflection coating of glass cover of sun collectors and photovoltaic units Composite materials integrating nanoparticles (e.g. nanotubes) have the potential to present improved mechanical properties combined with a reduced weight. Lighter materials for automotive or airplanes applications will reduce the energy consumption.

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II.

Nanomaterials Roadmap Analysis on the Energy Sector

II.1. Energy Conversion Energy Production In the domain of energy conversion the following applications and products can be listed (Figure 3).

Figure 3: Applications and products in the domain of energy conversion

II.1.1. Solar Photovoltaics (1) Barriers to overcome: Construction and mounting technology Reducing of the production costs, i.e. costs for surface production (cells) Improving of the efficiency Reliability (degree of reliability) Toxicity (2) Possible solution through nanomaterials: Efficiency of silicon solar cells improved by: Applying thin films (porous and non-porous), which have low defect density and high level of cristallinity Cost effective solar PV Thin layer of active material on a cheap substrate such as plastics.

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Organic Grtzel cells Nano-crystalline Dye Sensitised Solar Cells (DSC) - Research work is focused on the optimisation of cells with a standard photoelectrode design. The challenge is to increase the efficiency of the cell. Higher absorption rates for light in solar cells Tuned the spectral absorption of light by the dimension of the absorbing nanoparticles Replace liquid electrolyte with a conducting polymer or inorganic material Anti-reflection layers with a nanoporous or moth structure Flexible solar cells Light absorption nanomaterials (e.g fullerenes) combined with plastic electronic to develop semiconductor polymer photovoltaics (a) Level of development of the nanomaterials

Figure 4: Expected time frame for the development of nanomaterials in the Solar Photovoltaics segment.

(b) Time frame of possible industrial applications

Table 1: Possible application: of nanomaterials in the Solar Photovoltaics segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

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(c) Cost comparison Market size:

Figure 5: Expected costs of nanomaterials within the Solar Photovoltaics category (20062015).

Material costs:

Figure 6: Expected market size of nanomaterials belonging to the Solar Photovoltaics category (2006-2015).

(d) List of the nanomaterials in the Solar photovoltaics sector 1. Core shell nanoparticle This type of nanoparticle consists of a core surrounded by one or more shells. The core can consist of an inorganic particle or of a magnetic particle below 100 nm in diameter. The shell can consist of a metal, an organic or ceramic material. Properties which are improved may include electrical, optical and magnetic properties. Applications include diagnostics in life sciences, biomedical and food, coatings and paints, electronic equipment, catalysts, biocides and nanotextiles. Disadvantages: - some are poisonous Possible application: Solar cells Time Scale: Long term (6-10 years) - 12

Description: This nanomaterial could be used in solar cell applications possibly in the long term. 2. Fullerenes Fullerenes are a carbon configuration where the atoms form more or less spherical cages also known as Buckminster-fullerenes or as Bucky Balls. C60, consisting of 60 carbon atoms in pentagon and hexagonal arrangement, is the best known fullerene but there are a several other fullerenes with e.g. 20 or 70 carbon atoms. Similar to carbon nanotubes there exist single wall fullerenes, termed cages and multiwall fullerenes termed onions. Description of material properties which have been improved: Inertness The pure fullerene is chemical and physically very stable and not reactive [Knupfer 2001]. The pure fullerene is insoluble in water but soluble if the molecule is modified. Electrical It can carry up to six additional electrons without braking up their bonds. Diffusion Fullerenes show a high diffusion coefficient on plane substrates. This is the reason why fullerenes are assigned the potential to build up self-assembled nanostructures [Interview Harneit 2004] Advantages: A variety of modifications are possible, which alter its chemical and optical behaviour. For example the solubility in water can be modified by attaching molecules to the fullerenes. Its optical characteristics can be changed by applying an atom or a molecule inside of the fullerene. The pure fullerene is chemical and physically very stable and not reactive [Knupfer 2001]. It can carry up to three additional electrons without destroying. Due to its symmetry it is interesting as model system for research. Building blocks for complex nanoscale systems [Sawamura 2002]. High diffusion mobility on plain surfaces can be used to investigate self-organization of divices higher complexity. In summary the reason for the scientific attention on fullerenes is less their potential for technical applications as that they serve as subject of investigation to gain fundamental chemical understanding [Interview Harneit 2004, Interview Lebedkin 2004] Disadvantages: Production of pure fullerenes is very expensive and very slow. Toxicity to human body is under discussion [Sayes 2004]. Another problem for the application of fullerenes is their lack of chemical stability against UV-Irradiation in the present of oxygen [Interview Harneit 2004]. Possible application: Photovoltaic energy supply Time Scale: Middle term (3-5 years) Description: Due to the fact that they can carry six electrons without braking up their bonds they are interesting as electron acceptors in complexes for example for solar cell applications..

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[Peumans 2001, Wang 2004] Photovoltaic properties of fullerenes are also under investigation with a view to applications in artificial photosynthesis [Imahori 2003]. The development of solar cells based on fullerenes is most advanced, and might give rise to a mass product within the next five years. [Interview Harneit 2004] Infineon has already realized a prototype based on chemically modified fullerenes. Here, the fullerenes are mixed with organic light-absorbing molecules and serve as an ultrafast electron acceptor. The cell efficiencies are still well under 5% and will only find a market if the production costs can be made sufficiently low. The most remarkbale feature of Infineon's results is that they have managed to enhance the stability, and thus the lifetime, of these cells by a factor of hundred or so by using new encapsulation techniques developped for organic light emitting diodes (OLEDs), another emerging product in organic electronics. The development of solar cells based on fullerenes is most advanced, and might give rise to a mass product within the next five years [Interview Harneit 2004]. Problem for the application of fullerenes is their lack of chemical stability against UVIrradiation in the present of oxygen [Interview Harneit 2004]. 3. Indium Phosphide [InP] thin films Highly amorphous Indium Phosphide thin films obtained from nanostructured particles or wires with enhanced semiconductivity and photoelectric properties than the crystalline InP. It can be used in solar energy conversion applications and circuitry. Description of material properties which have been improved: Semiconductor with enhanced photoelectric properties compared to its non-amorphous counterpart. Advantages: Due to their good properties they offer advantages for space applications Improved power/weight ratios Better radiation resistances compared to silicon solar cells Disadvantages: Can be toxic to the environment Expensive to produce Possible application: Photovoltaic solar cells Time Scale: Short term (0-2 years) Description: They have direct energy bandgaps, high optical absorption coefficients and good values of minority carrier lifetimes and mobilities making them excellent materials for making high efficiency solar cells. 4. Metal ceramic nano nanocomposite (coating) This type of nanocomposite coating consists of highly dispersed metal and ceramic nanoparticles. Metal and Ceramic both make up a considerable share of the material volume. Dielectric properties are mainly improved at the moment. Biocompatibility, Piezoelectricity, Fracture Toughness, thermal conductivity and wear resistance can also be improved in the future. Applications include coatings for aeronautics, automotive, energy, medical implants, construction, machine tools, catalysts and foams. Description of material properties which have been improved:

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Mainly dielectric properties has been improved at the moment; the thermal expansion coefficient can be changed. Advantages: "A metal ceramic coating sticks better to metal than normal ceramics. Incorporating nanoparticles as lubricants in implants give lower wear. The above mentioned properties are improved Fracture toughness is expected to be improved (Peter Hatto, 20-405)" Disadvantages: It is difficult to distribute the nanoparticles properly over the surface. The material is still hard to handle, the particles tend to cluster together. Possible application: Solar absorbing material Time Scale: Middle term (3-5 years) Description: Cermet (ceramic metal) coatings with metal nanoparticles can be applied as solar absorbing material in solar cells. (Shuxi Zhao et al, 2005) 5. Nickel (carbon coated) [Ni-C] powders Amorphous small sized, well-defined and regular shape nanopowders with good electrical, magnetic and thermal properties. They can be used for the fabrication of automotive parts as well as coatings, electrodes and filters. Description of material properties which have been improved: The reflectance in the infrared falls off more rapidly than in the noble metals. Advantages: The shape of the nanoparticles can be well defined through the fabrication process. Disadvantages: The morphologie of the nanoparticles can be very different. Possible application: Conductors Time Scale: Short term (0-2 years) Description: Its good conductivity and thermal properties makes it suitable for conductors in integrated circuits, batteries, fuel cells (in the anode and the catode) and solar cells. 6. Poly(9,9-dioctylfluorene-co-bithiophene) (F8T2) nanolayers High stability copolymer nanolayer, surface treated with a metal oxide with good electrical and optical properties, used for a reasonably efficient solar energy conversion and transitors. Description of material properties which have been improved: Promising material combinations for reasonably efficient solar energy conversion. Advantages: High stabiltity Reasonable electronic conductivity and control of the nanostructured morphology

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Disadvantages: The power conversion efficiency is limited by a poor fill factor, wich is attributed to an energy barrier at the polymer/metal interface (the best cell is made with reduced layer thickness and increased surface and offers an external quantum efficiency of 11.5%) Possible application: Solar energy conversion Time Scale: Middle term (3-5 years) Description: Structures based on a fluorene-bithiophene copolymer and TiO2 substrates of different morphology that is solar light sensitive. 7. Poly(octadecylsiloxane) (PODS) nanolayers Polymer nanolayers or nanostructures formed by nanoparticles of a controlled size around 100 nm with good optical, electrical and thermal properties, used for energy storage and energy generation, electronical devices and displays. Description of material properties which have been improved: They provide a viable approach for the fabrication of electron transfer and charge storage devices, also applicable obtaining a better control over the construction of composite and core/shell type nanoparticles. Advantages: Better control of the nanoparticle growth is achieved in nanostructured polymeric matrices. Viable approach for the fabrication of electron transfer and charge storage devices. Precise and versatile electrodepositions. Better control over the construction of composite and core/shell type nanoparticles. Disadvantages: The lack of functional groups in this polymer limits the degree of metallation. Possible application: Batteries and photovoltaics. Time Scale: Middle term (3-5 years) Description: It can store energy and be used as light sensitive part for photovoltaics or sensors. 8. Polyacrylonitrile (PAN) nanostructures Nanostructured polymers and polymer nanomembranes with a controlled band gap and good diffussion and electrical properties. They can be used for the design of semiconductors, photovoltaics, sensors, and filters. Description of material properties which have been improved: Its band gap can be modified with its nanostructure and it is possible to make nanostructured membranes for the diffusion of same substances. Advantages: Good control of the conductivitys band gap for photovoltaics applications, nanoelectronic, nanochips, super capacitors etc.

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It is possible to design membranes for specific applications and special filters for separation process across the nanostructured surfaces.

Disadvantages: High cost of the membranes and no industrial fabrication for the nanosurfaces (can only be fabricated manually). Possible application: Photovoltaic devices Time Scale: Short term (0-2 years) Description: This nanomaterial could be used as circuitry for solar cells and LEDs.

9. Polyaniline-SnO2 (PANI-SnO2) and Polyaniline-TiO2 (PANI-TiO2) nanostructured films Nanostructured polymer films which includes metal oxide nanoparticles with good electrical conductivity and chemical reactivity, used for CO gas sensors and solar cells. Description of material properties which have been improved: Conducting polymers have shown very promising results for application in gas sensors. The sensing, ageing and mechanical characteristics of the conducting polymer films have been improved by composite fabrication. PANI-SnO2 has shown a significantly increase sensitivity. Advantages: Polyanilines electrical properties can reversibly be controlled by changing the oxidation state of main chain and by the protonation of amine nitrogen chain. They have good reproducibility in sensing characteristics. Disadvantages: Such gas sensor lack selectivity and sensitivity at ambient humidity, which increase its conductivity. Possible application: TiO2 solid-state solar cells Time Scale: Middle term (3-5 years) Description: An organic solvent free heterojunction of n-TiO2/p-PANI with enhanced photovoltaic properties used as the sensing cells. 10. Polyfluorene / Polyaniline (PF / PANI) nanostructures Nanostructured polymer in which the electron aceptor and the electron donator can be controlled through the nanoimprint lithography. It has interesting electrical and optical properties and is suitable for low fabrication cost photovoltaic applications. Description of material properties which have been improved: Interface area between the electron aceptor and the electron donator can be controlled through the nanoimprint lithography (NIL) fabrication method. Advantages: Low fabrication cost.

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Disadvantages: Spin coating technique generates arbitrarily oriented domains. Possible application: Photoelectrical Devices Time Scale: Middle term (3-5 years) Description: Organic semiconductors have a bicontinuous bipartition that allows effective charge separation and transport of the electrons, thus making them suitable for photovoltaic applications. 11. Silicon [Si] nanopowders and nanowires Silicon nanopowders and nanowires are highly amorphous with high refractive index and typical semiconductor properties. They can be used for solar cells, light emitters and various high refractive-index applications. Description of material properties which have been improved: Silicon and its many compounds have some of the most useful optical properties. The growth of thin Si nanowires is attributed to the low reaction temperature. Advantages: Low heat of vaporization and smooth, silky feel make them especially attractive for use in personal care products. Amorphous silicon based solar cells are much cheaper to manufacture compared to the monocrystalline and multicrystalline silicon. Disadvantages: Low radiation resistance decreasing its efficiency. Possible application: Solar cells Time Scale: Short term (0-2 years) Description: Can absorb the incident light with only a few microns of material, reducing materials usage and hence cost. (3) Companies and institutes Institutes Fraunhofer ISE, University of Constance Germany EPFL, Switzerland - Prof. Michael Grtzel Technical University of Delft, Netherlands - Prof. Joop Schoonman Uppsala University, Sweden Prof. Anders Hagfeldt Polytechnic University of Madrid, Spain Prof. Javier Uceda Linz Institute for Organic Solar Cells, Austria Dr. Niyazi Serdar Sariftci SMEs Company Greatcell, Switzerland (www.greatcell.com) Company Mansolar, Netherland (www.mansolar.nl) Isofoton, Malaga Spain (www.isofoton.com) Free Energy Europe (www.free-energy.net) Solarion GmbH, Germany (www.solarion-gmbh.de)

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Wrth Solar GmbH, Germany (www.wuerth-solar.de) Sunways AG, Germany (www.sunways.de) ErSol, (www.ersol.de) Photowatt (www.photowatt.com) Eurosolare, Italy (www.eurosolare.it) Deutsche Solar, Germany (www.solarworld.de) Big companies BP Solar, Germany (http://www.bsolar.com/) Kaneka (http://www.kaneka.com/) Kyocera (http://www.kyocerasolar.de/) Sanyo (http://www.sanyo.com/home.cfm) Sharp (http://www.sharp-usa.com/SharpHome/) Shell Solar (www.shellsolar.com) Uni-Solar (http://www.unisolar.com/) WorldWide PV Solar Cell Companies (http://energy.sourceguide.com/)

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II.1.2. Hydrogen Conversion (1) Barriers to overcome High manufacturing costs due to expensive materials used for the fabrication of electrodes (bipolar plates), electrolytes, membranes and catalysts (especially because of the platinum price) (2) Possible solution through nanomaterials: Nanoscale hydrophilic (high affinity to water) inorganic materials in the electrolyte (salts, which work in the right temperature range) to improve hydrogen ion conductivity of the membrane at elevated temperatures. The functioning of the cell is related to the hydrogen ion conductivity of the membrane, which decreases strongly if water content is not sufficient. Perowskites, here most important are the different properties like for example the oxygen conductivity as a reactor at the hydrogen conversion (hydrocarbon, hydrogen) Capillar fuel cells in contrast to the flat cell membranes Saving of the bipolar plates of the electrodes. Flat cell membranes are much more expensive than capillar fuel cells because of the stacks and the capillary geometry. Therefore, with respect to the compact construction, a higher power density (3 to 6 times) with the capillary fuel cell is achievable. Miniaturisation of the capillar fuel cell is an additional advantage for portable applications Production technique of the capillary fuel cells is completely automated (a) Level of development of the nanomaterials

Figure 7: Expeted time frame for the development of nanomaterials in the Hydrogen Conversion segment.

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(b) Time frame of possible industrial applications

Table 2: Possible application: of nanomaterials in the Hydrogen Conversion segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

(c) Cost comparison Market size:

Figure 8: Expected costs of nanomaterials within the Hydrogen Conversion category (20062015).

Material costs:

Figure 9: Expected market size of nanomaterials belonging to the Hydrogen Conversion category (2006-2015).

(d) List of the nanomaterials in the Hydrogen Conversion sector 1. Ceria (CeO2) - nanoparticles, coatings Thin layers of nanosized ceria show an increased oxygen conductivity and an enhanced catalytic behaviour. Nanosized ceria offers highly improved performance in comparison to conventional cerium oxides. Description of material properties which have been improved: higher oxygen conductivity lower sintering temperatures. Advantages:

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Lower operating temperatures of SOFC's (Solid Oxide Fuel Cells) Ceria opens a broad field for outdoor applications. UV-protection can significantly enhance products durability.

Possible application: Solid Oxide Fuel Cells Time Scale: Middle term (3-5 years) Description: Nanosized ceria offers lower operating temperatures of SOFC's (Solid Oxide Fuel Cells), because of an increased ionic conductivity.

2. Metal ceramic nano nanocomposite (coating) This type of nanocomposite coating consists of highly dispersed metal and ceramic nanoparticles. Metal and Ceramic both make up a considerable share of the material volume. Dielectric properties are mainly improved at the moment. Biocompatibility, Piezoelectricity, Fracture Toughness, thermal conductivity and wear resistance can also be improved in the future. Applications include coatings for aeronautics, automotive, energy, medical implants, construction, machine tools, catalysts and foams. Description of material properties which have been improved: Dielectrical properties resistance to heat treatment. Advantages: "A metal ceramic coating sticks better to metal than normal ceramics. Incorporating nanoparticles as lubricants in implants give lower wear. The abovementioned properties are improved Fracture toughness is expected to be improved (Peter Hatto, 20-405)" Disadvantages: It is difficult to distribute the nanoparticles properly over the surface. The material is still hard to handle, the particles tend to cluster together. Possible application: Hydrogen production Time Scale: Middle term (3-5 years) Description: Ceramic metal nanocomposites (cermet based on nanocrystalline materials) can be applied in solid electrolytes for several applications including fuel cells. Patent US6387560 and family.

3. Nickel (carbon coated) [Ni-C] powders These nanopowders are amorphous small sized, well-defined and have a regular shape with good electrical, magnetic and thermal properties. They can be used for the fabrication of automotive parts as well as coatings, electrodes and filters. Description of material properties which have been improved: Reflectance in the infrared, falls off more rapidly than in the noble metals. Advantages:

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The shape of the nanoparticles can be well defined through the fabrication process.

Disadvantages: The morphologie of the nanoparticles can be very different. Possible application: Conductors Time Scale: Short term (0-2 years) Description: Its good conductivity and thermal properties makes it suitable for conductors in integrated circuits, batteries, fuel cells (in the anode and the catode) and solar cells.

4. Platinum (Pt) - Nanoparticles These platinium nanoparticles have paricle sizes with a diameter less than 100 nm. The particles are mainly used in catalysis e.g. hydrogenation reactions or as a catalyst of oxidation (methanol, monoxide). Description of material properties which have been improved: Catalyst activity Hydrogenation reactions Catalyst of oxidation (methanol, monoxide) Anti-microbial/anti-inflammatory/anti-fungal/ anti-proliferative properties biocompatibility Advantages: Due to the high catalytic activity of nano-sized particles it is possible to reduce the quantity of noble metal. Disadvantages: Tendency to aggregate, so that advantages of nano-size are lost. Difficulty in storage, and transport. Limited resources Platinum nanoparticles are deposited on the roads and so are not easily recoverable. Recycling is not cost effective. Possible application: Catalyst Time Scale: Short term (0-2 years) Description: Oxidation i.e for monoxide oxidation. Platinum catalysed gas diffusion electrodes Electrocatalyst for cathode of fuel cell (3) Companies and institutes SMEs o Altair (http://www.altairinc.com/) o QineriQ (www.nano.qinetiq.com) Companies o P 21 - 23

o Smart fuel cell o Master flex o Heliocentris, H-Tec o Brennstoffzellen Manufacture o Vailant, Viessmann, Buderus o Sulzer Hexis (CH) o Voller Energy (Great Britain) Institutes o Forschungszentrum Jlich II.1.3. Thermoelectricity Thermoelectric devices consist of two materials with different thermal conductivity. When exposed to a thermal gradient, an electrical current flows. Conversely, passing a current through the junction can result in cooling. Thermoelectric devices can achieve precise temperature control and also convert heat into electricity. Thermoelectricity illustrates a variant of photovoltaic which can directly convert thermoelectric radiation of a certain wave length with the aid of solar cells into electricity. The important component is the selective emitter, which emits the thermal radiation adapted on the spectral sensitivity of the solar cell and can achieve the desired selectivity, e.g. through nano-structuring of metallic surfaces. (1) Barriers to overcome: Efficiency / lifetime stability of surfaces at high temperatures loadings Low ZT (T as operating temperature and Z is proportional to the Seebeck coefficient, the electrical conductivity and reciprocal to the thermal conductivity) (2) Possible solution through nanomaterials: Nanowires: nanometer-wide wires for use in nano heating and cooling (a) Level of development of the nanomaterials

Figure 10: Expeted time frame for the development of nanomaterials in the Thermoelectricity segment.

(b) Time frame of possible industrial applications

Table 3: Possible application: of nanomaterials in the Thermoelectricity segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

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Cost comparison Market size:

Figure 11: Expected costs of nanomaterials within the Thermoelectricity category (2006-2015).

Material costs:

Figure 12: Expected market size of nanomaterials belonging to the Thermoelectricity category (2006-2015).

(d) List of the nanomaterials in the Thermoelectricity sector 1. Boron [B] nanowires Entirely amorphous boron semiconductive nanowires can be doped to increase highly their conductivity in a specific direction and have also good mechanical properties. They can be used for nanoelectronics and for thermoelectric conversion. Description of material properties which have been improved: Can be dopped to achieve highly conductive nanowires. Advantages: No crystallization No outer layer of oxide Expected to be better conductor than carbon nanotubes Low density but high melting point Disadvantages: Not found Possible application: Thermoelectric energy conversion Time Scale: Middle term (3-5 years) Description: Amorphous Boron nanowires can work at high temperatures, and can be doped to achieve superconductors, making it useful for thermoelectric energy conversion and transport. 2. Carbides coatings and Related Materials Carbide coatings are layers of binary compounds containing carbon as ligant. Mixing sp2 and sp3 bindings open up the opportunity to adjust the property of the coating. Description of material properties which have been improved: Thermal stability The Melting point of carbidefilms and related materials covers a range from 2900 C up to 3060 C [Leiste1999] - 25

Absorption For same applications it is also used due to its black colour. [Interview Holleck 2004] Advantages: The huge advantage of these carbon based nanofilms is that it is possible to adjust independently the hardness and tribolocical characteristic of the coating by combining elements and building up nanolaminates. As it is appropriate for the application dry lubrication or wet lubrication with low friction coefficient can adjust [BMBF 2003]. A further benefit is that these layers have a very good adhesion. This good adhesion for example an a surgery knife can be realise because the underlying layer is different in composition than the top layer, which could dominated by sp3-carbon and shows diamond like properties. Carbidefilms and related materials (TiB2) are corrosion resistant [Ye 2003] Carbon based nanofilms can be sysnthesis by well known and widely established deposition techniques. These are physical vapour deposition (PVD) by radio frequency sputtering, or chemically enhanced PVD, or chemical vapour deposition (CVD), and physically enhanced CVD (PECVD). By variation of the ion bombardment during the sputter process, and other parameters of the process, the properties of the nanofilms can be defined. The deposition of the several layers for the nanolaminate can be done in one deposition process. These techniques can be performed at low temperatures. Therefore even substrates with low temperature resistance can be covered. Disadvantages: Not possible until now is the coating of hollow structures like drill holes, tubes from inside or caves. Possible application: High absorbing black coatings Time Scale: Short term (0-2 years) Description: Coatings of carbide and related material can be used as black coatings, which shows a high absorption in a in a wide range of wafe lengths. Due to their properties (Very hard, wear resistant, temperature resistant, corrosion resistant, biocompatibility good adhesion, adjustable tribological properties) theses coatings can be used for a huge variety of other applications.

II.1.4. Solar Thermal Energy Solar energy can be used to produce hot water, and heat homes and offices. Although nanotechnology is not a key technology for solar thermal energy, a Dutch research project running until 2005 is currently developing new aerogels as transparent and isolating material for applications in the cover material of solar collectors. The new aerogels include pores with the diameter of nanometers (Company Zonne Energie, Netherland) [Nanoforum]. Novel glasses that can change their properties in response to heat and light for a better insulation are also in development (Company Thermomax, Ireland - Association SOLAR-NAKLAR www.solar-na-klar.de) Anti-reflection coatings for the necessary glass coatings

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In thermophotovoltaic systems radiation emitted from an artificial light source is converted into electricity by photocells, nanostructuring wihin the source emitter can enable the spectrum of the emitted radiation to match that of the band gap of the photocell. (Nanotechnology Innovation for Tomorrows World, European Comission 2004) (a) Level of development of the nanomaterials

Figure 13: Expeted time frame for the development of nanomaterials in the Solar Thermal Energy segment.

(b) Time frame of possible industrial applications

Table 4: Possible application: of nanomaterials in the Solar Thermal Energy segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

(c) Cost comparison

Figure 14: Expected costs of nanomaterials within the Solar Thermal Energy category (20062015).

(d) List of the nanomaterials in the Solar thermal energy sector 1. Carbides coatings and Related Materials Carbide coatings are layers of binary compounds containing carbon as ligant. Mixing sp2 and sp3 bindings open up the opportunity to adjust the property of the coating. Description of material properties which have been improved: Thermal stability The Melting point of carbidefilms and related materials covers a range from 2900 C up to 3060 C [Leiste1999] Absorption For same applications it is also used due to its black colour. [Interview Holleck 2004] Advantages:

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The huge advantage of these carbon based nanofilms is that it is possible to adjust independently the hardness and tribolocical characteristic of the coating by combining elements and building up nanolaminates. As it is appropriate for the application dry lubrication or wet lubrication with low friction coefficient can adjust [BMBF 2003]. A further benefit is that these layers have a very good adhesion. This good adhesion for example an a surgery knife can be realise because the underlying layer is different in composition than the top layer, which could dominated by sp3-carbon and shows diamond like properties. Carbidefilms and related materials (TiB2) are corrosion resistant [Ye 2003] Carbon based nanofilms can be sysnthesis by well known and widely established deposition techniques. These are physical vapour deposition (PVD) by radio frequency sputtering, or chemically enhanced PVD, or chemical vapour deposition (CVD), and physically enhanced CVD (PECVD). By variation of the ion bombardment during the sputter process, and other parameters of the process, the properties of the nanofilms can be defined. The deposition of the several layers for the nanolaminate can be done in one deposition process. These techniques can be performed at low temperatures. Therefore even substrates with low temperature resistance can be covered. Disadvantages: Not possible until now is the coating of hollow structures like drill holes, tubes from inside or caves. Possible application: High absorbing black coatings Time Scale: Short term (0-2 years) Description: Coatings of carbide and related material can be used as black coatings, which shows a high absorption in a in a wide range of wafe lengths. Due to their properties (Very hard, wear resistant, temperature resistant, corrosion resistant, biocompatibility good adhesion, adjustable tribological properties) theses coatings can be used for a huge variety of other applications.

II.1.5. Bioenergetics The use of biological mechanisms of energy production and storage for technical applications is still a vision, which is quite far away from realisation. Fundamental research concentrates on understanding the biochemical processes of photosynthesis and there are only small steps towards a realisation in technical systems [Nanoforum]. The Grtzel cell is an example for a technical system, which uses at least biomimetic principles to generate electric energy. Unfortunately, no nanomaterials are entered for this domain into the database yet.

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II.2. Energy storage In the domain of energy storage the following applications and products can be identified (Figure 15).

Figure 15: Applications and products in the domain of energy storage

II.2.1. Rechargeable Batteries (1) Barriers to overcome: o Improve energy and power density (for example C-Anodes in Li batteries) o Lifetime: High Charge/Discharge rates o Safety o Costs o Toxicity (Nanoparticles can have an aggravated impact in lungs and other organs) o Flammability (for example metal hydrides nanoparticles) - As smaller the material, as bigger the danger of flammability. (2) Possible solution through nanomaterials: o Nanocrystalline composite materials and nanotubes are used to replace the normal Graphite of Lithium-Graphite-Electrodes. The nanostructure presents a high surface area which can lead to improved energy and power density as well as higher charge/discharge rates.

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o o o

Nano-structured anodes and cathodes with nanomaterials are more robust and are 100 times powerful than traditional one. They sustain an average of 500 charges and discharges before wearing out. Nano-scale metalalloy composites are investigated to increase the life cycle of actice/inactive composites nanomaterials can help to remove the problem of lifetime Nano-ceramic separators and polymer electrolytes can contribute to increase the power and the safety

(a) Level of development of the nanomaterials

Figure 16: Expeted time frame for the development of nanomaterials in the Rechargeable Batteries segment.

(b) Time frame of possible industrial applications

Table 5: Possible application: of nanomaterials in the Rechargeable Batteries segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

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(c) Cost comparison

Market size:

Figure 17: Expected costs of nanomaterials within the Rechargeable Batteries category (20062015).

Material costs:

Figure 18: Expected market size of nanomaterials belonging to the Rechargeable Batteries category (2006-2015).

(d) List of the nanomaterials in the Rechargeable batteries sector 1. Carbon Black Carbon Black refers to carbon nanoparticles but the vast majority of particles which are called Carbon Black are much grater than 100 nm. Carbon Blacks is actually a generic term for a family of products, which are usually referred according to the methods (or raw materials) used in their manufacture. Description of material properties which have been improved: Conductivity: Carbon black serves as conductive filler for organic composites. Advantages: Carbon black is cheap and can be (and is already) produced with low tech production facilities in high amounts.

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Disadvantages: Carbon black is already widely used. The potential for new applications is rather small. A problem is the fast aggregation of the particles during and after their production. The mostly used synthesis process, the partial combustion (99% of all carbon black is produced with that process) needs high temperatures and there for a lot of energy and achieves poor yields with high level of atmospheric emission. At 1450C the yield is 70% at 1680 C the is reduced to 50% and drop dramatically at higher temperatures [Fulcheri2002]. Possible application: Electrodes for batteries Time Scale: 2-5 years Description: Carbon black produced by self-decomposition (acetylene) (particle diameter 60-40nm) is used for Batteries [Fabry 2001]. 2. Carbon Nanotubes Carbon nanotubes are tubes consisting of a rolled up mesh like configuration of carbon atoms. The geometry of the rolled graphite sheets affects their properties. They can have an armchair configuration with metallic properties. The alternative zig-zag chiral configuration has semi-conducting properties. The tubes have diameters of 1-2 nm and lengths of up to several micrometers. Single walled carbon nanotubes consist of a single rolled graphite sheet. Multi-walled carbon nanotubes consist of several nanotubes rolled around each other. Description of material properties which have been improved: Conductivitiy The current carrying capacity is estimated to 1 billion amps per square centimetre [Collins 2000] Thermal stability Nanotubes resist temperatures up to 2800 C in vacuum and 750 C in air [Collins 2000]. Thermal conductivitiy The show a huge thermal conductivity, which is predicted to be high as 6000 watts per meter per Kelvin at roomtemperature[Collins 2000]. Advantages The high conductivity of metallic CNT make them interesting for the application for current transportation in mico-dimension for microchips or in macro-dimensions for low loss energy transportation through electronic wires [Smalley 2003]. Due to their huge thermal conductivity they are interesting for fillers for chip-packaging [Collins 2000]. Disadvantages: The main obstacle for a broader use of CNT is the extremely high cost. It is about 150 Euro per gram for SWCNT. [Luther 2004] It is difficult to produce pure Nanotubs of a specific constitution (length, metal-like, semiconducting, isolating, SWNT, MWNT), or to separate them from each other. [Krupke 2004, Haddon 2004] There is an ongoing need for a more thorough understanding of growth mechanisms for a

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selective and uniform production of carbon nanotubes with specific dimensions and physical properties. The toxicity in combination with their chemical inertness could be a problem [Lam 2004] Their strong fibrous nature may result in similar health risk to asbestos fibres. If elements such as iron from catalysts in the production process are present there is the possibility that the nanotubes may have free-radical releasing, pro-inflamatory properties. [Royal Academy 2004]. The extraordinary properties belong to the single nanotubes. Not solved until now is the question how to transform these properties like thermal conductivity, or strength to bulk material. Possible application: Medium for electrical energy storage Time Scale: Short term (0-2 years) Description: An application in the field energy storage is its use as anodes in batteries. In combination with Lithium, a twice as high capacity could allready realize in laboratory tests [Gans 2002]. 3. Carbon/metal/lithium_Fluoride Nanocomposite (CMFNC, nanostructure) These nanocomposites consist of a highly porous structure built up of carbon, metal, lithium and fluoride. The nanocomponent in the material is Iron Fluoride (FeF). The material has a high ionic and electronic activity and high specific capacity at high recharge rates. It is useful for reachargeable batteries. Description of material properties which have been improved: To achieve electrical energy-storage and delivery systems based on these cells, carbon metal fluoride nanocomposites are used in the positive electrode of the electrochemical cell of rechargeable batteries. Also, lithium fluoride compound nanocomposites are useful as the positive electrode material of rechargeable batteries. Advantages: The nanostructured metal fluoride behaves as active electrode component materials for fabrication of electrochemical cells, such as lithium battery cells. Enhancement of how much energy can be stored in the electrode materials of the storage technology for high-energy rechargeable energy (Li-ion battery). Possible application: Electrode material Time Scale: Long term (6-10 years) Description: This nanocomposite material could be used as electrode materials for rechargeable Li-ion batteries. The CMFNCs can be employed in the manner of prior rechargeable electrochemical cell fabrication compositions and as the electroactive material of positive cell electrodes. The negative electrode members of such cells may advantageously comprise any of the widely used lithium ion source materials, such as lithium metal, lithium alloys (LiAl, lithiated carbon) and lithiated metal nitrides. These nanocomposite electrode materials also function well with most other prior cell composition components, including polymeric matrices and adjunct compounds, as well as with commonly used separator and electrolyte solvents and solutes.

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Barriers for the development: 1 - Technology 2 - Market The material can be available at practical processing and fabrication costs. These nanocomposites take advantage of the low cost and desirable environmental compatibility of metal fluoride-based systems. 3 - Regulatory 4 - Environmental impacts The nanocomposites can provide high specific capacity over wide cycling-speed ranges, voltages, and operating temperatures and are environmentally friendly. 4. Graphite Particles Graphite nanoparticles are particles of sp2-carbon in contrast to sp3-carbon (diamond). They could be producesd by Ball-Milling of graphite particles [Janet 2004] or by laser vaporization [Kokai 2003]. Description of material properties which have been improved: Exfoliated graphite oxide, which contains hydroxyl and carboxyl groups derived from oxidization of graphite, was applied to the assembly of composite thin films [Weng 2003] Disadvantages: Graphite nanoparticles cannot be dispersed in water and it forms micrometer-sized irregular aggregates in organic solvents. [Weng 2003] Possible application: Electrode material for batteries or supercapacitors Time Scale: Middle term (3-5 years) Description: The most promising application is the improvement of Li-ion batteries [Janot 2005] by replacing the layered graphite of the electrodes. For the same reason, why graphite particles are suitable for batteries, they are interesting as material for supercapacitors. 5. Magnesium-Nickel (Mg-Ni) Alloys - Nanocrystalline powders These powders have conventional size but possess a nanostructured interior. Efficient hydrogen absorption is reached without requiring long activation treatment. Also this is a lightweight, realtively low cost material. Description of material properties which have been improved: High hydrogen storage capacity and relativiely High hydrogen absorption/ desorption rate. Improved absorption and desorbtion rate comparing with non-nano structured materials. Advantages: High rate of absorbtion/desorbtion, High absorbtion capacity, Complete reversibility of the mechanism of hydride formation. Disadvantages: Still too high hydrogen desorption temperature and still insufficient kinetics of absorption/ desorption rate comparing to industry requirments.

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Possible application: Ni-MH batteries Time Scale: Long term (6-10 years) Description: This nanomaterial could be used as hydrogen absorption material in battery applications. Barriers for the development: 1 - Technology - Ability to reproduce the same high quality product on large scale consistency and reliability in volume production. In the case of reactive ball milling, the problem is contamination of the powders. The proper alloying and chemical composition for hydrogen absorption and release kinetics is not known yet 2 - Market No hydrogen fuel market exists yet. It is not clear if the so called hydrogen economy will be rally an alterative for future energy supply. 6. Metal ceramic nano nanocomposite (coating) This type of nanocomposite coating consists of highly dispersed metal and ceramic nanoparticles. Metal and ceramic both make up a considerable share of the material volume. Dielectric properties are mainly improved at the moment. Biocompatibility, Piezoelectricity, Fracture Toughness, thermal conductivity and wear resistance can also be improved in the future. Applications include coatings for aeronautics, automotive, energy, medical implants, construction, machine tools, catalysts and foams. Description of material properties which have been improved: - Dielectrical, wear, is resistant to heat treatment. - Conducting piezomaterials have a great promise in the future. Disadvantages: It is difficult to distribute the nanoparticles properly over the surface. The material is still hard to handle, the particles tend to cluster together. Applications: Solid electrolytes Time Scale: Middle term (3-5 years) Description: Ceramic metal nanocomposites (cermet based on nanocrystalline materials) can be applied in solid electrolytes for several applications including batteries. Patent US6387560 and family. Capacitors Time Scale: Middle term (3-5 years) Description: e.g. in mobile telephones Barriers for the development: 1 - Technology How to control the dispersion of the nanoparticles in the material. Now the composite is mainly used in bulk. We need to find a technique that keeps the nanoparticles in the cluster form in thin layers. This is a topic we are working on now. One solution may be spin coating to deposit the thin layer. We are looking for other techniques. These other techniques are in the technology invention phase.

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2 - Market Societal response to nanoparticles. People may be afraid of what they dont understand. 3 - Regulatory No problems expected. 4 - Environmental impacts No problems foreseen. 6. Nanoporous Carbon Nanoporous carbon is a three dimensional structure porous structure of carbon. The large surface area offered by the porous system recommends it for application as an electrical energy storage media. Bulk nanoporous carbon materials can be produced by selective etching redox reactions from metal (Ti, Mo), silicaon or boron carbides. The impregnation of the pores with guest molecules gives rise to nanocomposites. Description of material properties which have been improved: The increased surface area lead to predictions of excellent electrical energy storage capacity. The large surface area makes it suitable for use as an anode in Lithium ion batteries. Interesting magnetic and electrical properties are expected from such materials impregnated with metal ions, having Possible application: e.g. in Lithium ion batteries. Disadvantages: Unclear if the production can be scaled up to quantities sufficient for industrial processes. Possible application: Material for super capacitors and batteries Time Scale: Long term (6-10 years) Description: Du to its high surface area compared to its volume nanoporous carbon is an interesting material for the application in super capacitors and batteries. 7. Polymer with carbon nanoparticles/fillers (bulk) This nanocomposite consists of carbon fillers into a polymer matrix. The fillers can be carbon, carbon nanotubes or nanofibres. Electrical conductivity and mechanical properties are the main improved properties. Applications include aeronautics and automotive. Description of material properties which have been improved: Electrical conductivity and mechanical properties Advantages: Advantages of carbon nanofillers in polymer matrix include: growning of carbon fiber without any post production thermal processing, removal of polyaromatic hydrocarbons from surface (pyrolytically stripped carbon fiber), heat of carbon fiber at temperatures up to 3,000C, graphitize chemically vapor deposited carbon present on the surface of carbon nanofibres and create a highly electrically conductive carbon nanofiber. Disadvantages: Although the modulus of carbon nanotubes is very high, this has not yet been translated into big improvements in composite modulus. Possible application: - 36

Batteries Time Scale: Long term (6-10 years) Description: This nanomaterial could be used as conductive material in battery applications. Barriers for the development: 1 - Technology Problems that have to be solved are: improved dispersion of Carbon Nanotubes within the polymer matrix and improved interfacial coating. Understanding and optimisation of electrical charge movement in the nanotube composites to avoid strong localisation of charges which can lead to breaking. (Vasileos Koutsos, personal communication, August 2005) It is not clear how polymers filled with nanoparticles behave during processing in conventional processing equipment. The predictive models are inadequate to predict the thermal, mechanical and processing properties of nanocomposites. (Faraday roadmap 2005) 2 - Market Public perception of nanotechnology may become negative. This may not be a big problem if individual materials are not sold under a nano-label. User companies may not have enough trained personnel to work with the nanocomposites. User companies lack awareness of the potential of polymer matrix nanocomposites. (Faraday roadmap 2005) 3 - Regulatory IPR protection may inhibit knowledge transfer and take up of nano-composites. Legislation on toxicity testing will become more important, possibly leading to higher costs for toxicity testing of nanoparticles and the development of new handling and processing practices. Nanocomposite standards and innovative design concepts need to be developed. (Faraday roadmap 2005) 4 - Environmental impacts The long term service life behavior of nanocomposites is not clear. The risks of using nanoparticles in plastics have not been addressed, especially for medical applications. Nanocomposites can help to overcome problems related to recycling of materials and lead to reduced energy consumption especially in automotive and aerospace applications. (Faraday roadmap 2005) 8. Polypyrrole (PPY) nanotubes Polymer nanotubes and nanoparticles have the advantages of very high electrical conductivity, biocompatibility and degradability. Possible applications are drug delivery, rechargeable batteries, supercapacitors, sensors, anhydrous electrorheological fluids, microwave shielding and corrosion protection applications. Description of material properties which have been improved: The key property of PPY is the presence of conjugated double bond, which gives rise to the electrical conductivity as it allows the efficient transfer of electrons or positive charges along the polymer backbone. Advantages: -Facile synthesis -High conductivity -Good environmental stability -Inner-structure can be adjusted in the fabrication process. -Biodegradable composites - 37

Disadvantages: -Different templates are needed for its fabrication Possible application: Batteries and super-capacitors Time Scale: Middle term (3-5 years) Description: Thanks to the conjugated double bond which gives rise to the electrical conductivity and allows the efficient transfer of electrons or positive, it can be used as electrodes for supercapacitors and batteries. Barriers for the development: 1 - Technology Still little work has been carried out on the alternating current polymerization of PPY different templates. 2 - Market Many new materials in the energy field. 3 - Regulatory More biocompatibility studies necessary before use in drug delivery systems. 4 - Environmental impacts No toxic or environmental problems identified 9. Polystyrene-polyethylene oxide (PS-PEO) nanostructured films These nanostructured polymers have good biocompatibility, high ionic conductivity and mechanical strength properties and can be used for biomedical surfaces, electronic devices and energy storage. Description of material properties which have been improved: Ionic conductivity: it is a solution for the dendrite growth in Li Ion batteries and provides a good solution to combining high energy density with good cyclability. Advantages: -Stability, fluidity and intermembrane dynamics. -Good corrosion behaviour. -Enhanced conductivity. -Combine high ionic conductivity with a high elastic modulus. -Biocompatibility. Disadvantages: -High cost and difficult synthesis. Possible application: Polymer electrolyte material Time Scale: Middle term (3-5 years) Description: Nanostructured polymer electrolytes provide a solution for rechargeables Li ion batteries by combining high conductivity and elastic modulus Barriers for the development: - 38

1 - Technology High cost of the material and synthetization. 2 - Market No competitive price. 3 - Regulatory Many biocompatibility and toxicity studies necessary before using PS-PEO as cell culture material in humans. 4 - Environmental impacts Potentially toxic.

(3) Companies and institutes SMEs o AKKU Solar Technik, Germany (http://www.akkusolartechnik.com) o Emmerich Batterie AG, Germany (http://www.emmerich-batterie.de) o Fey-Elektronik GmbH, Germany (http://www.feyelektronik.de) o Jauch Quartz GmbH, Germany o Pohl Electronic GmbH, Germany (www.pohl-electronic.de) o VRI GmbH, Germany (http://www.vri-gmbh.de) o Omnitron Griese GmbH, Germany, o AccuCell, Germany, o BMZ Batterien Montage Zentrum GmbH, Germany o GP Battery Marketing GmbH, Germany o ITP Logistics GmbH, Germany o Olympia Batterien GmbH, Germany o Saft Batterien GmbH, Germany o Gaia, Nordhausen, Germany o Ionity, Kamens, Germany o Fortobat, Pfinstal, Germany Companies o Altair Nanotechnologies Inc. (http://www.altairnanotechnologies.com/) o Cabot Corporation (www.cabot-corp.com) o NanoLab (http://www.nano-lab.com/home.html) o VARTA Microbattery GmbH, Germany (www.varta-microbattery.com) o Sanyo Energy (Europe) Corporate GmbH, Germany o Panasonic Industrial Europe GmbH, Germany, (http://www.panasonicindustrial.com/batteries) o EMB GmbH Elektro-Montage-Bau, Germany, (www.emb-akku.com) o Creaves/Degussa, Germany (Batteries)

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II.2.2. Hydrogen Storage (1) Barriers to overcome: All of the presently available storage systems (DoE2003b) have some important drawbacks. No systems reach the goals of the DOE for a suitable storage system of at least 6.5 wt-% and 62 kg H2/m3. A good storage material should have a very high surface area, where the hydrogen atoms or molecule can be absorbed. So the focus of research is on materials with a large amount of pores of nanometer dimension. The binding of hydrogen should be strong enough to get a higher density of storage compared with normal gas storage without absorption material. On the other hand the binding must not be too high because then energy is needed for the hydrogen desorption [Nanoforum]. (2) Possible solution through nanomaterials: Nano-magnesium or nano-magnesium-alanate with nano-titanium as a catalyst are very promising candidates as storage material for automotive application. (a) Level of development of the nanomaterials

Figure 19: Expeted time frame for the development of nanomaterials in the Hydrogen Storage segment.

(b) Time frame of possible industrial applications

Table 6: Possible application: of nanomaterials in the Hydrogen Storage segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

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Cost comparison

Market size:

Figure 20: Expected costs of nanomaterials within the Hyrogen Storage category (2006-2015).

Material costs:

Figure 21: Expected market size of nanomaterials belonging to the Hydrogen Storage category (2006-2015).

(c) List of the nanomaterials in the Hydrogen storage sector 1. Aluminium (Al), Magnesium (Mg) and Al-Mg alloys - Bulk materials with nano-grains These materials show a specific texture on the nanoscale and are characterised by high strength comparing to the traditional counterpart. They may display high superplasticity and their main fields are: light weight structural applications. Description of material properties which have been improved: - High specific strength: light weight and high strength. - High diffusion rate of hydrogen along grain boundaries. Advantages: The known advantages of Aluminium and Magnesia alloys are further strengthened: high strength at low weight. Magnesia alloys are extensively researched for hydrogen storage. Relatively high solubility of hydrogen and fast diffusion rate of hydrogen along grain boundaries. Disadvantages: It is difficult to combine the nano- structure with ductility. This requires very well controlled processes.

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Possible applications: Hydrogen storage tanks Time Scale: Unspecified Description: As far as hydrogen sorage in nanostructured magnesia, the expectations of industry are not met. Research is carried out to find proper alloying method. Another idea is using Al-Mg nanostrucutred aloys as hydrogen tanks. Barriers for the development: 1 - Technology High cost of powders and of method to induce the nanostructure by means of heavy plastic deformation. The nanostructure of the material is sensitive dependent on processing conditions. The uniformity and thermal stability of the structure is an issue. Ability to supply materials in a form or shape suitable for production of the final product. Thermal stability of the nanostructured Al and Al alloys may be an issue, what may limit the application temperature to about 200oC. Corrosion resistance of Mg alloys is an issue. 2 - Market Cost/performance relationship must be accepted by market. Science orientation of researchers instead of customer and production orientation. New product/new market barrier. Appropriate choice of new applications. 3 - Regulatory As for application of new materials in structures obtaining certificates, etc 4 - Environmental impacts Not different than all other aluminium and magnesium industry. 2. Aluminium (Al), Magnesium (Mg) and Al-Mg alloys - Nanocrystalline powders Powders to make of them light-weight, high-strength bulk materials with following properties: Superplasticity at very high strain rates, increased hardness, ductility. Making light weight structures or make coatings by thermal spray. Description of material properties which have been improved: From the powders it is possible to make by various powder metallurgy methods structure elements of light-weight and high-strength. It is also possible to make by thermal spraying coatings of high wear resistance. Advantages: Good mechanical properties at light weight. All advantages of aluminium alloys, but higher strenght and wear or corrosion resistance Disadvantages: Need to carefully control processing parameters. Low recrystalisation temperature limits the temperature of application. An oxide layer form on the powders. During sintering this leads to formation of oxide inclusions that may enhance brittleness. Possible applications: hydrogen storage Time Scale: Long term (6-10 years) Description: - 42

Mg alloys are intensively researched as a potential material for hydrogen storage. In nanostructured powders diffusion of hydrogen into the material or out of it is much faster than in conventional Mg. However, still the criteria set by industry are not reached. Barriers for the development: 1 - Technology High cost ofequipment for high volume production. The nanostructure of the material is sensitive dependent on processing conditions. Thermal stability of the nanostructured Al and Al alloys may be an issue, what may limit the application temperature to about 200oC. Not much work has been done in the field of fatigue properties of nanostructured materials produced by plastic deformation or mechanical alloying. Corrosion resistance of Mg alloys is an issue. Non sufficient hyrdrogen solubility. 2 - Market Production cost/price level must be acceptable. Science orientation of researchers instead of customer orientation. New product/new market barrier, appropriate choice of new applications. No hydrogen fuel market exists yet. 3 - Regulatory As for application of new materials in structures obtaining certificates, fatigue tests, etc. 4 - Environmental impacts not different from conventional materials 3. Carbon Nanotubes Carbon nanotubes are tubes consisting of a rolled up mesh like configuration of carbon atoms. The geometry of the rolled graphite sheets affects their properties. They can have an armchair configuration with metallic properties. The alternative zig-zag chiral configuration has semi-conducting properties. The tubes have diameters of 1-2 nm and lengths of up to several micrometers. Single walled carbon nanotubes consist of a single rolled graphite sheet. Multi-walled carbon nanotubes consist of several nanotubes rolled around each other. Description of material properties which have been improved: Conductivitiy The current carrying capacity is estimated to 1 billion amps per square centimetre [Collins 2000] Thermal stability Nanotubes resist temperatures up to 2800 C in vacuum and 750 C in air [Collins 2000] Thermal conductivitiy The show a huge thermal conductivity, which is predicted to be high as 6000 watts per meter per Kelvin at roomtemperature [Collins 2000]. Inertness The surfaces of nanotubes are inert. Chemical reactions for example for functionalisation could perform at the edges. Advantages: The combination of the high aspect ration together with their conductivity and their thermal stability make them a good candidate for new display technologies and cold cathode for SEM could be realized with Carbon Nanotubes. Cathodoluminescence could be achieved at low Voltages of 1 to 3 V [Bonard 2002, Collins 2000].

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The high conductivity of metallic CNT make them interesting for the application for current transportation in mico-dimension for microchips or in macro-dimensions for low loss energy transportation through electronic wires [Smalley 2003]. Due to their huge thermal conductivity they are interesting for fillers for chippackaging [Collins 2000].

Disadvantages: The main obstacle for a broader use of CNT is the extremely high cost. It is about 150 Euro per gram for SWCNT. [Luther 2004] It is difficult to produce pure Nanotubs of a specific constitution (length, metal-like, semiconducting, isolating, SWNT, MWNT), or to separate them from each other. [Krupke 2004, Haddon 2004] There is an ongoing need for a more thorough understanding of growth mechanisms for a selective and uniform production of carbon nanotubes with specific dimensions and physical properties. The toxicity in combination with their chemical inertness could be a problem [Lam 2004] Their strong fibrous nature may result in similar health risk to asbestos fibres. If elements such as iron from catalysts in the production process are present there is the possibility that the nanotubes may have free-radical releasing, pro-inflamatory properties. [Royal Academy 2004]. The extraordinary properties belong to the single nanotubes. Not solved until now is the question how to transform these properties like thermal conductivity, or strength to bulk material. Possible application: Material for hydrogen storage Time Scale: Unspecified Description: Hydrogen storage using carbon materials is of interest because of expected high gravimetric storage capacities [Dzenis 2004]. 4. Graphite Particles Graphite nanoparticles are particles of sp2-carbon in contrast to sp3-carbon (diamond). They could be producesd by Ball-Milling of graphite particles [Janet 2004] or by laser vaporization [Kokai 2003]. Description of material properties which have been improved: Exfoliated graphite oxide, which contains hydroxyl and carboxyl groups derived from oxidization of graphite, was applied to the assembly of composite thin films [Weng 2003] Advantages: Disadvantages: Graphite nanoparticles cannot be dispersed in water and it forms micrometer-sized irregular aggregates in organic solvents. [Weng 2003] Possible application: Material for hydrogen storage Time Scale: Long term (6-10 years) Description: An application, which is under discussion, is the use of graphite particles as hydrogen storage [Kiobayashi 2004].

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5. Magnesium-Nickel (Mg-Ni) Alloys - Nanocrystalline powders These powders have conventional size but a nanostructured interior. Efficient hydrogen absorption without requiring long activation treatment is reached. It is also a lightweight, realtively low cost material. Description of material properties which have been improved: High hydrogen storage capacity and relativiely High hydrogen absorption/ desorption rate. Improved absorption and desorbtion rate comparing with non-nano structured materials. Advantages: High rate of absorbtion/desorbtion. High absorbtion capacity Complete reversibility of the mechanism of hydride formation Disadvantages: Still too high hydrogen desorption temperature and still insufficient kinetics of absorption/ desorption rate comparing to industry requirments. Possible application: Material for hydrogen storage Time Scale: Long term (6-10 years) Description: Storing and transporting hydrogen in order to subsequently use it as a combustible High temperature hydride heat pumps, car fuel Barriers for the development: 1 - Technology Ability to reproduce the same high quality product on large scale consistency and reliability in volume production. In the case of reactive ball milling, the problem is contamination of the powders. The proper alloying and chemical composition for hydrogen absorption and release kinetics is not known yet 2 - Market No hydrogen fuel market exists yet. It is not clear if the so called hydrogen economy will be rally an alterative for future energy supply. 6. Titanium [Ti] nanoparticles Titanium nanoparticles with a great strength to weight ratio, resistance to radiation, high temperature and wear, and good biocompatibility. Can be used in the aerospace industry, for implants and for hydrogen storage. Description of material properties which have been improved: Amorphous titanium is a light material with high resistance to temperature and refractive index. Advantages: - Exceptionally high strength to weight ratio. - Very good resistance to corrosion and oxidation. - Advantage of the material for exposed applications is its resistance to discoloration under UV light. - It is easily fabricated

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Disadvantages: Not found Possible application: Material for hydrogen storage Time Scale: Middle term (3-5 years) Description: Hydrogen-storage capacity and hydrogenation rate of sodium aluminium hydrides (NaAlH4) improved by doping them with titanium nanoparticles. Barriers for the development: 1 - Technology 2 - Market The market for titanium nanoparticles is not yet significant in size; therefore, major companies dont invest in larger scale production, and the cost is yet elevated. 3 - Regulatory 4 - Environmental impacts Low order of toxicity. No environmental effects have been reported.

(3) Companies o Carbon Nanotechnologies Inc. (http://www.cnanotech.com/) o Hera Hydrogen Storage Systems (http://www.herahydrogen.com/)

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II.2.3. Supercapacitors Supercapacitors offer a unique combination of high power and high energy performance parameters. The energy density of supercapacitors is 100 times higher than in dielectric foil capacitors and the power density is 10 times higher than in normal batteries. (1) Barriers to overcome o The challenge is to produce a quality material that combines high surface area with a low resistivity o costs of the high performance electrodes due to miniaturisation o large requirements for long cycle life, around 100000 cycles (2) Possible solution through nanomaterials: o Nanotubes: mesopores allow an easy access of the solvated ions to the electrode/electrolyte interface for charging of the electrical double layer o Fullerene-like carbon nanoparticles o Nanoporous oxides like Iron oxide, Nickel oxide or Molybdenum oxide have the potential to give a large capacitance than carbon electrodes (a) Level of development of the nanomaterials

Figure 22: Expeted time frame for the development of nanomaterials in the Supercapacitors segment.

(b) Time frame of possible industrial applications

Table 7: Possible application: of nanomaterials in the Supercapacitors segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

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(c) Cost comparison Market size:

Figure 23: Expected costs of nanomaterials within the Supercapacitors category (2006-2015).

Material costs:

Figure 24: Expected market size of nanomaterials belonging to the Supecapacitors category (2006-2015).

(d) List of the nanomaterials in the Supercapacitors sector 1. Graphite Particles Graphite nanoparticles are particles of sp2-carbon in contrast to sp3-carbon (diamond). They could be produced by Ball-Milling of graphite particles [Janet 2004] or by laser vaporization [Kokai 2003]. Description of material properties which have been improved: Exfoliated graphite oxide, which contains hydroxyl and carboxyl groups derived from oxidization of graphite, was applied to the assembly of composite thin films [Weng 2003] Disadvantages: Graphite nanoparticles cannot be dispersed in water and it forms micrometer-sized irregular aggregates in organic solvents. [Weng 2003] Possible application: Electrode material for batteries or supercapacitors Time Scale: Middle term (3-5 years) Description: The most promising application is the improvement of Li-ion batteries [Janot 2005] by replacing the layered graphite of the electrodes. For the same reason, why graphite particles are suitable for batteries, they are interesting as material for supercapacitors. 2. Metal ceramic nano nanocomposite (coating) This type of nanocomposite coating consists of highly dispersed metal and ceramic nanoparticles. Metal and Ceramic both make up a considerable share of the material volume. Dielectric properties are mainly improved at the moment. Biocompatibility, Piezoelectricity, - 48

Fracture Toughness, thermal conductivity and wear resistance can also be improved in the future. Applications include coatings for aeronautics, automotive, energy, medical implants, construction, machine tools, catalysts and foams. Description of material properties which have been improved: Mainly Dielectric properties at the moment; Advantages: "A metal ceramic coating sticks better to metal than normal ceramics. Incorporating nanoparticles as lubricants in implants give lower wear. The abovementioned properties are improved Fracture toughness is expected to be improved (Peter Hatto, 20-405)" Disadvantages: It is difficult to distribute the nanoparticles properly over the surface. The material is still hard to handle, the particles tend to cluster together. Possible application: Capacitor material Time Scale: Middle term (3-5 years) Description: e.g. in mobile telephones Barriers for the development: 1 - Technology How to control the dispersion of the nanoparticles in the material. Now the composite is mainly used in bulk. We need to find a technique that keeps the nanoparticles in the cluster form in thin layers. This is a topic we are working on now. One solution may be spin coating to deposit the thin layer. We are looking for other techniques. These other techniques are in the technology invention phase. 2 - Market Societal response to nanoparticles. People may be afraid of what they dont understand. 3 - Regulatory No problems expected. 4 - Environmental impacts No problems foreseen. 3. Nanoporous Carbon Nanoporous carbon is a three dimensional structure porous structure of carbon. The large surface area offered by the porous system recommends it for application as an electrical energy storage media. Bulk nanoporous carbon materials can be produced by selective etching redox reactions from metal (Ti, Mo), silicaon or boron carbides. The impregnation of the pores with guest molecules gives rise to nanocomposites. Description of material properties which have been improved: Increased surface area lead to predictions of excellent electrical energy storage capacity. The large surface area makes it suitable for use as an anode in Lithium ion batteries. Interesting magnetic and electrical properties are expected from such materials impregnated with metal ions, having Possible application: e.g. in Lithium ion batteries.

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Advantages: Not identified. Disadvantages: Unclear if the production can be scaled up to quantities sufficient for industrial processes. Possible application: Material for super capacitors and batteries Time Scale: Long term (6-10 years) Description: Du to its high surface area compared to its volume nanoporous carbon is an interesting material for the application in super capacitors and batteries. 4. Polypyrrole (PPY) nanotubes Polymer nanotubes and nanoparticles with very high electrical conductivity and biocompatibility and degradability. Possible application:s are drug delivery, rechargeable batteries, supercapacitors, sensors, anhydrous electrorheological fluids, microwave shielding and corrosion protection applications. Description of material properties which have been improved: The key property of PPY is the presence of conjugated double bond, which gives rise to the electrical conductivity as it allows the efficient transfer of electrons or positive charges along the polymer backbone. Advantages: -Facile synthesis -High conductivity -Good environmental stability -Inner-structure can be adjusted in the fabrication process. -Biodegradable composites Disadvantages: -Different templates are needed for its fabrication Possible applcation Batteries and super-capacitors Time Scale: Middle term (3-5 years) Description: Thanks to the conjugated double bond which gives rise to the electrical conductivity and allows the efficient transfer of electrons or positive, it can be used as electrodes for supercapacitors and batteries. Barriers for the development: 1 - Technology Still little work has been carried out on the alternating current polymerization of PPY different templates. 2 - Market Many new materials in the energy field. 3 - Regulatory More biocompatibility studies necessary before use in drug delivery systems.

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4 - Environmental impacts No toxic or environmental problems identified

(3) Companies and institutes Bullith, Munich, Germany

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II.3. Energy Saving In the domain of energy storage the following applications and products can be identified

Figure 25: Applications and products in the domain of energy saving

II.3.1. Insulation (1) Barriers to overcome o wasted energy in industry and home poor insulation heat loss o daily costs in industry and home (2) Possible solution through nanomaterials: o Aerogels have low conductivity, low solid density, high porosity high surface area and high dielectric constant making them one of the best available insulating materials, i.e. nanocomposite silica-aerogels (for example Airglass) o Carbon aerogel: first type of electrically conducting aerogel, the large infrared optical absorption coefficient makes it a promising material for high temperature thermal insulation o Reflective surface via ultra thin layers PDLC (Polymer-Dispersed Liquid Crystal) system better insulation, gain in heat (a) Level of development of the nanomaterials

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Figure 26: Expected time frame for the development of nanomaterials in the Insulation segment.

(b) Time frame of possible industrial applications

Table 8: Possible application: of nanomaterials in the Insulation segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

(c) Cost comparison Market size:

Figure 27: Expected costs of nanomaterials within the Insulation category (2006-2015).

Material costs:

Figure 28: Expected market size of nanomaterials belonging to the Insulation category (20062015).

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(d) List of the nanomaterials in the Insulation sector 1. Ceramic matrix nanocarbon Ceramic matrix nanocarbon is a ceramic matrix material filled with carbon nanotubes, fullerenes (football shaped cage of 60 carbon atoms) or carbon nanofibers. Several properties are improved. The material is more thermally insulating, electrically conducting and mechanically robust. The structural and thermal barrier properties are enhanced and fracture toughness increased. Main applications include automotive, aerospace, medical implants, energy saving, coatings and fire insulation in construction and bearings and cutting tools and stronger, stiffer textiles. Description of material properties which have been improved: thermally insulating electrically conducting Advantages: It is very strong, and the heat conductivity is easy to influence. The material is cheap and there is enough of it available. Since the fabrication is under control the material is made in large quantities. It is easy to produce. Disadvantages: Electrical conductivity, resistance and bandgap are still in a very early phase of development. Possible application: Energy saving Time Scale: Long term (6-10 years) Description: The material is useful in combustion and insulation as thermally insulating material. Barriers for the development: 1 - Technology There are no real technological barriers to development. The advantage of nanocarbon is that clustering of the particles does not occur. The particles are better dispersed inside the material. The development can continue normally. 2 - Market No problems foreseen. The material has known properties and is well described. It will be less suspicious for the public. 3 - Regulatory No change in regulation foreseen. 4 - Environmental impacts No information available. 2. Indium Tin Oxide (ITO) - thin films Indium Tin Oxide offers high transparency with several advantageous electromagnetic properties Description of material properties which have been improved: high transparency combined with several advantageous electromagnetic properties;

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Disadvantages: very expensive raw materials Possible application: IR-absorber Time Scale: Short term (0-2 years) Description: ITO increases the heat shield performance of transparent material. With ITO as IR-absorber a product can provide intrinsic heat protection resulting in reduced energy consumption and costs and less need for air conditioning. Barriers for the development: 1 - Technology limited indium resources worldwide 2 - Market expensive raw materials 3. Montmorillonite nanoclays (platelet) The montmorillonite is a smectite clay which has a sheet-like structure of nanometre dimensions. The structure is called platelet. Montmorillonite nanoclay is included in a polymer matrix to improve the mechanical and barrier to gas and liquid properties of such a matrix material. Properties of fluids and thermal properties are also improved. It can be applied in aeronautics, automotive, food packaging and other domains. Description of material properties which have been improved: - Barrier to gas and water in composites. - The mechanical properties of the polymers. Increase of the modulus of a polymer. The improvement in modulus tends to be higher above the glass transition temperature than below it. - The thermal stability of polymers. - The flammability of montmorillonite/polymer nanocomposites. Advantages: The nanoclay-modified polymers can have weight reductions, strength of their structural dimensions and increase barrier performance for material thickness. Disadvantages: The production cost of these nanofillers is high compared to the plastic materials in use: 5 10 / Kg. Possible application:s : Thermal insulators Time Scale: Middle term (3-5 years) Description: The thermal properties which are improved contribute to this application. Barriers for the development: 1 - Technology 'The industrial realisation of these nanocomposites is limited due to lack of production process. But there is scientific activity to reduce this limitation. For example, there is development of compatibilizer chemistry to ensure effective penetration of the polymer into the interlayer spacing of the montmorillonite clay. Future goals include production of PVC- 55

based systems is still some way off and challenges remain to be solved in PET nanocomposites. Additional reinforcement of clay nanocomposites by glass fibre is currently being investigated. There is also interest in the development of electrically conducting clay nanocomposites. The processing temperatures of polymers are 170-400oC and of commercial nano-clays below 170 oC. (Faraday roadmap 2005) 2 - Market High production costs. Public perception of nanotechnology may become negative. This may not be a big problem if individual materials are not sold under a nano-label. User companies may not have enough trained personnel to work with the nanocomposites. User companies lack awareness of the potential of polymer matrix nanocomposites. (Faraday roadmap 2005) 3 - Regulatory IPR protection may inhibit knowledge transfer and take up of nano-composites. Legislation on toxicity testing will become more important, possibly leading to higher costs for toxicity testing of nanoparticles and the development of new handling and processing practices. Nanocomposite standards and innovative design concepts need to be developed. (Faraday roadmap 2005) 4 - Environmental impacts The long term service life behavior of nanocomposites is not clear. The risks of using nanoparticles in plastics have not been addressed, especially for medical applications. Nanocomposites can help to overcome problems related to recycling of materials and lead to reduced energy consumption especially in automotive and aerospace applications. (Faraday roadmap 2005) 4. Polyhedral oligomeric silsesquioxanes (POSS) in polymers (bulk) This nanocomposite is a material in which POSS (Polyhedral oligomeric silsesquioxanes) structures are linked to polymer chains. The material can take the form of liquids, waxes and crystalline solids. POSS is the smallest form of silica. The fillers behave like modified clays. Improved properties include: reduced flammability, lower density, oxygen throughput, mechanical and thermal properties. Applications include fire retardant materials, aeronautics and medical applications. Description of material properties which have been improved: Property Enhancements via POSS observed in POSS-copolymers and blends are increased Tdec (decomposition temperature), increased Tg (glass transition temperature), reduced flammability, reduced heat evolution, lower density, disposal as silica, extended temperature range, increased Oxygen permeability, lower thermal conductivity, thermoplastic or curable feature, enhanced blend miscibility, oxidation resistance, altered mechanicals and reduced viscosity. For example, a major effect of POSS incorporation, in polypropylene, is retention of modulus above the glass transition temperature (Tg) of the unreinforced polymer. Increasing the concentration of the POSS structures in copolymers can have a dramatic effect in increasing the Tg of the polymer. Advantages: POSS segments in plastics enhance the physical properties of the compositions. Polymers containing POSS show delayed combustion and reductions in heat evolution.

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Usage temperature enhancement of nearly all types of thermoplastics and thermoset polymers. The glass transition can be increased by 100-200C or up to the decomposition temperature of the polymer. POSS additives can replace existing fillers. Bulk density reductions of up to 10% with viscosity reductions of up to 24% relative to silica may occur. POSS incorporation increases modulus and hardness while maintaining the stress and strain characteristics of the base resin. Additionally since POSS is a chemical nanotechnology, processing and moldability is maintained. Because of its chemical nature POSS technology can be tailored to meet resin and consumer compatibility needs. POSS can be used to upgrade the properties of existing patented compositions while enabling the patentability of the new material composition. Disadvantages: The POSS fillers and compounds made with them are expensive compared to materials without nanofillers. Possible application:s: Thermal insulator material Time Scale: Middle term (3-5 years) Description: The thermal and thermodynamic properties make it suitable for thermal insulators. Barriers for the development: 1 - Technology It is not clear how polymers filled with nanoparticles behave during processing in conventional processing equipment. The processing temperatures of polymers are 170-400oC and of commercial nano-clays below 170 oC. The predictive models are inadequate to predict the thermal, mechanical and processing properties of nanocomposites. The structure-property relations of nanocomposites are not completely clear. (Faraday, 2005) 2 - Market Public perception of nanotechnology may become negative. This may not be a big problem if individual materials are not sold under a nano-label. User companies may not have enough trained personnel to work with the nanocomposites. User companies lack awareness of the potential of polymer matrix nanocomposites. (Faraday, 2005) 3 - Regulatory IPR protection may inhibit knowledge transfer and take up of nano-composites. Legislation on toxicity testing will become more important, possibly leading to higher costs for toxicity testing of nanoparticles and the development of new handling and processing practices. Nanocomposite standards and innovative design concepts need to be developed. (Faraday, 2005) 4 - Environmental impacts The long term service life behavior of nanocomposites is not clear. The risks of using nanoparticles in plastics have not been addressed, especially for medical applications. Nanocomposites can help to overcome problems related to recycling of materials and lead to reduced energy consumption especially in automotive and aerospace applications. (Faraday, 2005)

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5. Polymer with carbon nanoparticles/fillers (bulk) This nanocomposite consists of carbon fillers into a polymer matrix. The fillers can be carbon, carbon nanotubes or nanofibres. Electrical conductivity and mechanical properties are the main improved properties. Applications include aeronautics and automotive. Description of material properties which have been improved: Electrical conductivity and mechanical properties Advantages: Advantages of carbon nanofillers in polymer matrix include: growing of carbon fiber without any post production thermal processing, removal of polyaromatic hydrocarbons from surface (pyrolytically stripped carbon fiber), heating of carbon fiber to temperatures up to 3,000C, graphitizing chemically vapor deposited carbon present on the surface of carbon nanofibres and creating a highly electrically conductive carbon nanofiber. Disadvantages: Although the modulus of carbon nanotubes is very high, this has not yet been translated into big improvements in composite modulus. Possible application:s: Thermal insulator material Time Scale: Long term (6-10 years) Description: The thermal properties make it sutable for thermal management systems in aeronautics. Barriers for the development: 1 - Technology Problems that have to be solved are: improved dispersion of Carbon Nanotubes within the polymer matrix and improved interfacial coating. Understanding and optimisation of electrical charge movement in the nanotube composites to avoid strong localisation of charges which can lead to breaking. (Vasileos Koutsos, personal communication, August 2005) It is not clear how polymers filled with nanoparticles behave during processing in conventional processing equipment. The predictive models are inadequate to predict the thermal, mechanical and processing properties of nanocomposites. (Faraday roadmap 2005) 2 - Market Public perception of nanotechnology may become negative. This may not be a big problem if individual materials are not sold under a nano-label. User companies may not have enough trained personnel to work with the nanocomposites. User companies lack awareness of the potential of polymer matrix nanocomposites. (Faraday roadmap 2005) 3 - Regulatory IPR protection may inhibit knowledge transfer and take up of nano-composites. Legislation on toxicity testing will become more important, possibly leading to higher costs for toxicity testing of nanoparticles and the development of new handling and processing practices. Nanocomposite standards and innovative design concepts need to be developed. (Faraday roadmap 2005) 4 - Environmental impacts The long term service life behavior of nanocomposites is not clear. The risks of using nanoparticles in plastics have not been addressed, especially for medical applications. Nanocomposites can help to overcome problems related to recycling of materials and lead to - 58

reduced energy consumption especially in automotive and aerospace applications. (Faraday roadmap 2005) 6. Synthetic Hectorite (clay platelets) Synthetic Hectorites are clay materials of the Hectorite type, which behave as colloids (small particles in suspension). They are water attracting (hydrophilic) swelling clays composed of silicate sheets which delaminate in water to provide an open three dimensional structure. Hectorite clays can be dispensed at the nanoscale into polymers. The platelets are 1 nm thick and 25-30 nm wide. Optical transparency, and properties of fluids are improved. Applications include paints and binder in many household products and potentially aeronautics, automotive, energy saving, medical implants and construction. Description of material properties which have been improved: Swelling in water and tixotropic agents Advantages: "The hectorite clays are much purer and cleaner than natural hectorites The processing of these nanoparticles is easy and well known They can be produced in large quantities Disadvantages: They have high prices compared to natural clay fillers, approximately 10-20 / Kg. Possible application:s: Binder material for Insulation Time Scale: Short term (0-2 years) Description: This nanomaterial can be used as a binder for thermal insulation applications. Barriers for the development: 2 - Market High production costs (3) Companies and institutes Institutes o Fraunhofer ISE Freiburg, Germany, Dr. Georg o Center of Energy Studies of LEcole des Mines de Paris, France o University of Wrzburg, Germany Prof. A.G. Fricke o Technical University of Delft, Netherland Joost Beckers o Technical University of Denmark, Denmark o LBNL o University of Lund Companies INTERPANE GmbH, Germany Metallbau Ralf Boetker GmbH FLABEG GmbH & Co. KG Gesimat GmbH Big Companies o ChromaFision (www.cesarcolor.com) o Polyvision (www.polytronix.com) o SageGlass (http://www.sage-ec.com/) o Thermosee (www.pleotint.com)

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II.3.2. More Efficient Lighting Point Sources (1) Barriers to overcome o Efficiency and colour of the light are more or less temperature dependent1 o Degree of efficiency o High production costs (pieces/blanks) o Lifetime (for example of the high-brightness LEDs) o Colour, brightness and form of the light of the LEDs o Colour reproduction of the white light LEDs (2) Possible solution through nanomaterials: Carbon nanotubes and band-gap engineering using nanostructured materials optimise the emission spectrum of the LEDs QCAs (quantum caged atoms, i.e. confining a single atom inside a nanocrystal) work by absorbing photons of ultraviolet (UV) light and re-emitting that same light at lower frequency, or colour. As the size of the nanocrystal cage approaches two nanometers, the conversion of light energy approaches 100 %. Quantum dots based solid-state lighting (SSL) runs so cool and will work under the most demanding condition, lasting hundreds of times longer than conventional lighting (a) Level of development of the nanomaterials

Figure 29: Expeted time frame for the development of nanomaterials in the More Efficient Lighting Point Sources segment.

(b) Time frame of possible industrial applications

Table 9: Possible application: of nanomaterials in the More Efficient Lighting Point Sources segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

www.led-info.de

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(c) Cost comparison Market size:

Figure 30: Expected costs of nanomaterials within the More Efficient Lighting Point Sources category (2006-2015).

Material costs:

Figure 31: Expected market size of nanomaterials belonging to the More Efficient Lighting Point Sources category (2006-2015).

(d) List of the nanomaterials in the more efficient lighting point source sector 1. Carbon Nanotubes Carbon nanotubes are tubes consisting of a rolled up mesh like configuration of carbon atoms. Description of material properties which have been improved: Conductivitiy The current carrying capacity is estimated to 1 billion amps per square centimetre [Collins 2000] Thermal stability Nanotubes resist temperatures up to 2800 C in vacuum and 750 C in air [Collins 2000] Thermal conductivitiy The show a huge thermal conductivity, which is predicted to be high as 6000 watts per meter per Kelvin at roomtemperature[Collins 2000]. Advantages: The high conductivity of metallic CNT make them interesting for the application for current transportation in mico-dimension for microchips or in macro-dimensions for low loss energy transportation through electronic wires [Smalley 2003]. Due to their huge thermal conductivity they are interesting for fillers for chip-packaging [Collins 2000].

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Disadvantages: The main obstacle for a broader use of CNT is the extremely high cost. It is about 150 Euro per gram for SWCNT. [Luther 2004] It is difficult to produce pure Nanotubs of a specific constitution (length, metal-like, semiconducting, isolating, SWNT, MWNT), or to separate them from each other. [Krupke 2004, Haddon 2004] There is an ongoing need for a more thorough understanding of growth mechanisms for a selective and uniform production of carbon nanotubes with specific dimensions and physical properties. The toxicity in combination with their chemical inertness could be a problem [Lam 2004] Their strong fibrous nature may result in similar health risk to asbestos fibres. If elements such as iron from catalysts in the production process are present there is the possibility that the nanotubes may have free-radical releasing, pro-inflamatory properties. [Royal Academy 2004]. The extraordinary properties belong to the single nanotubes. Not solved until now is the question how to transform these properties like thermal conductivity, or strength to bulk material. Applications: Field Emission Display (FED) Time Scale: Short term (0-2 years) Description: Samsung demonstrated a working carbon nanotube display prototype in 1999, and has almost completed the development of a field emission display (FED) with a 30-inch diagonal screen, according to a Korea Times report. The report said that Japan's government-backed New Energy and Industrial Technology Development Organization (NEDO) is likely to spend more than $5 million on FED projects in 2004 in an attempt to wrest leadership of display technology back from South Korea. (www.physorg.com)

2. Polyacrylonitrile (PAN) nanostructures Nanostructured polymers and polymer nanomembranes with a controlled band gap and good diffussion and electrical properties. They can be used for the design of semiconductors, photovoltaics, sensors, and filters. Description of material properties which have been improved: Its band gap can be modified with its nanostructure and it is possible to make nanostructured membranes for the diffusion of same substances. Advantages: -Good control of the conductivitys band gap for photovoltaics applications, nanoelectronic, nanochips, super capacitors etc. -It is possible to design membranes for especific applications and special filters for separation process across the nanostructured surfaces.

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Disadvantages: -High cost of the membranes and no industrial fabrication for the nanosurfaces (can only be fabricated manually). Possible application: Photovoltaic devices Time Scale: Short term (0-2 years) Description: This nanomaterial could be used for circuitry for solar cells and LEDs. Barriers for the development: 1 - Technology High cost of the machinery necessary for the fabrication of the nanosurfaces for nanoelectronical applications and nanomembranes. 2 - Market High cost of membranes due to the lack of an industrial fabrication method (fabrication of PAN thin films using self-assembly, template polymerization and bulk polymerization are currently under investigation). 3 - Regulatory More biocompatibility studies necessary before use in drug delivery systems. 4 - Environmental impacts Toxic gases produced during pyrolysis. 3. Zinc oxide (ZnO) - nanostructures (nanowires, quantum dots) Zinc oxide nanowires with diameters in the range of 30-300 nm can be produced due to self assembling by new growth processes e.g. laser deposition or molecular beam epitaxy. Description of material properties which have been improved: - due to the reduced dimensionality of the nanostructures the conductivity (doping) and therfore the light emitting properties are improved compared to bulk material. Advantages: - zinc oxide nanostructures are an alternative material instead of GaN for the optoelectronics and the production of blue LEDs. - better technological handling than GaN. Disadvantages: - production process. Applications: Blue LED Time Scale: Middle term (3-5 years) Description: Blue LEDs (light emitting diodes) based on zinc oxide nanowires/nanostructures are more efficient light sources than conventional ones and therefore one could save energy. Barriers for the development: 1 - Technology - homogeneous, high and stable p-doping; - production process; - 63

(3) Companies o Kopin Corporation (http://www.kopin.com) o Cree (http://www.cree.com/products/led/index.htm) o Osram-Sylvania (http://www.sylvania.com/) o Agilent Technologies, Germany (http://semiconductor.agilent.com/cgibin/morpheus/home/home.jsp?pSection=LED) o Nichia, Japan (http://www.nichia.co.jp/product/led.html) o Nanocrystals Technology, Australia (http://www.nanocrystals.com/index1.htm)

II.3.3. More efficient Lighting for Large Areas (1) Barriers to overcome Lifetime (lower lifetime of the OLEDs as compared to LEDs) (2) Possible solution through nanomaterials and risks linked: Thin, nanostructured polymer films for OLEDs screens OLEDs promise brighter and cheaper alternatives to LCDs or liquid crystal displays, made of about 100 nm thick organic layers OLEDs emit their own light, while LCD require a light source (a) Level of development of the nanomaterials

Figure 32: Expected time frame for the development of nanomaterials in the More Efficient Lighting for Large Areas segment.

(b) Time frame of possible industrial applications

Table 10: Possible application: of nanomaterials in the More Efficient Lighting for Large Areas segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

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(c) Cost comparison Market size:

Figure 33: Expected market size of nanomaterials belonging to the More Efficient Lighting for Large Areas category (2006-2015).

Material costs:

Figure 34: Expected material costs of nanomaterials belonging to the More Efficient Lighting for Large Areas category (2006-2015).

(d) List of the nanomaterials in the More efficient lighting for large areas sector 1. Alumina (Al2O3) - bulk material Alpha-Al2O3 bulk material with a grain size less then 400 nm produced from powders with partical size less then 100nm Description of material properties which have been improved: transparent alumina combined with high mechanical strength, low friction and low wear Advantages: almost pore-free and defect-less ceramic structure mechanical strength unreachable with conventional alumina combination of transparency with high mechanical strength Deposition of calcium by osteoblasts on nanospherical alumina was over four times greater than on respective conventional ceramic formulations. It is believed that the novel surface properties of nanophase ceramics influence initial interactions with proteins to subsequently increase osteoblast response and new bone formation. Disadvantages: very costly processing, state of knowledge low

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Possible application: Transparent alumina ceramics for street lighting Time Scale: Middle term (3-5 years) Description: Completely dense alumina ceramics with small grain sizes are transparent and offer much lower energy consumption as conventional alumina parts applied in street lighting systems. Barriers for the development: 1 - Technology basic work on raw materials needed, resource for alpha alumina still needed, nano corundum, shaping and sintering technology needed, 2 - Market 3 - Regulatory There should be a need for continuous monitoring of potential effects of newly designed and fabricated nanomaterials, especially under in vivo situations. 4 - Environmental impacts The health effects of small nanoparticles entering the human body through pores and accumulating in the cells of the respiratory or other organ systems (for example, when also becoming dislodged through wear debris) are practically unknown. Methoxy-ethylhexyloxypoly-para-phenylen-vinylene / fullerene (MEH-PPV / C60) nanostructured films Polymer nanoparticles films which can be highly uniform with good optical and electrical properties. The film thickness and the light absorption and emision will depend strongly in the film formation process. They can be used in light-emitting devices and photocells. Description of material properties which have been improved : Its solubility makes possible to form uniform films on appropriate substrates through low-cost processes such as spin-coating, electrophoretic deposition and printing technology. The diameters of the nanoparticles in the films are in the range of 100-200 nm. Advantages : -The electroluminiscent devices from the nanostructured polymer. -They are free from macroscopic pinholes wich hinder the electronic applications such as electroluminiscent and photovoltaic devices. Disadvantages : -Device performance using conjugated polymers strongly depends on the microscopic structure of the polymer film.

Light-emitting device and photocells Time Scale : Middle term (3-5 years) Description : Nanostructured polymer film for electronic devices and photocells sensitive pods.
Barriers for the development : 1 - Technology Not completely stable colloidal suspension of C60 during the electrophoretic deposition.

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2 - Market Not yet fully developed. 3 - Regulatory Fullerene presents serious health and environmental hazards, regulations are in study. 4 - Environmental impacts Effects of small nanoparticles entering the human body and accumulating in the cells of the respiratory or other organ systems are yet unknown. Poly(3-octadecylthiophene) (PAT 18) nanostructured films Polymer thin films or coatings sensitive to light formed by nanoparticles of 100 nm with good optical and electrical properties. Can be used for light emitting devices, photocells and fieldeffect transistors. Description of material properties which have been improved : Polymer thin films consisting of particles with a diameter of ca. 100 nm. with a highly nanostructured surface. Advantages : -The solubility of conjugated polymers makes it possible to be processed into thin solid films through simple and cheap techniques such as spin-coating, ink-jet printing and electrophoretic deposition (the ink-jet printing technology is closed to achieving the industrial production of full-colour polymer light-emitting displays). Disadvantages : -A dilute solution has to be used when thin films with sub-micron thickness are required. -The spin-coating technique is incompatible with pattering.

Light-emitting devices Time Scale : Middle term (3-5 years) Description : A light-emitting device fabricated through electrophoretic deposition from colloidal suspension obtaining a nanostructured conjugated polymer film has emitted light, directly indicating that pin-hole free nanostructured film can be obtained. Photocells and field-effect transistors. Time Scale : Middle term (3-5 years) Description : For electronical applications and displays. It can fuction as electrical sensitive layer for the photocells.
Barriers for the development : 1 - Technology No optimal post-deposition process has been investigated. 2 - Market Nanoporosity of the polymer film prevents a uniform emission. 3 - Regulatory

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Safety regulation for new materials in electrical applications. 4 - Environmental impacts Effects of small nanoparticles entering the human body and accumulating in the cells of the respiratory or other organ systems are yet unknown.

Poly(alkylbenzene)-Poly(diene) (PAB-PDM) nanoparticles Polymer nanoparticles thermally stable, biocompatible and biodegradable with good chemical and mechanical properties. Can be used to form larger structures for aeronautic, automotive and drug delivery applications. Description of material properties which have been improved : Generate high moldability and tenacity rubbers. Advantages : -Discrete particles are thermally stable and can disperse evenly throughout the matrix providing a uniform composition. Disadvantages : -Production of nano-strings is not a totally reliable process.

Quantum computers and dots Time Scale : Middle term (3-5 years) Description : It can be used in the circuitry for computers.
Barriers for the development : 1 - Technology Difficult to make reliable process capable of producing acceptable nano-strings. 2 - Market Only medium market size. 3 - Regulatory More biocompatibility studies should be done before use in human medical systems. 4 - Environmental impacts Effects of small nanoparticles entering the human body and accumulating in the cells of the respiratory or other organ systems are yet unknown. Poly(octadecylsiloxane) (PODS) nanolayers Polymer nanolayers or nanostructures formed by nanoparticles of a controlled size around 100 nm with good optical, electrical and thermal properties, used for energy storage and energy generation, electronical devices and displays. Description of material properties which have been improved : They provide a viable approach for the fabrication of electron transfer and charge storage devices, also applicable obtaining a better control over the construction of composite and core/shell type nanoparticles. Advantages :

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-Better control of the nanoparticle growth is achieved in nanostructured polymeric matrices. -Viable approach for the fabrication of electron transfer and charge storage devices. -Precise and versatile electrodepositions. -Better control over the construction of composite and core/shell type nanoparticles. Disadvantages : -The lack of functional groups in this polymer limits the degree of metallation.

Displays, diodes Time Scale : Middle term (3-5 years) Description : For electronical and electrical applications as lighting material.
Barriers for the development : 1 - Technology Manual production leads to a high cost of the technology, and there are no other processes solutions. 2 - Market No competitive prices. 3 - Regulatory Safety regulation for new materials used in electronic applications. 4 - Environmental impacts Polyacrylonitrile (PAN) nanostructures Nanostructured polymers and polymer nanomembranes with a controlled band gap and good diffussion and electrical properties. They can be used for the design of semiconductors, photovoltaics, sensors, and filters. Description of material properties which have been improved : Its band gap can be modified with its nanostructure and it is possible to make nanostructured membranes for the diffusion of same substances. Advantages : -Good control of the conductivitys band gap for photovoltaics applications, nanoelectronic, nanochips, super capacitors etc. -It is possible to design membranes for specific applications and special filters for separation process across the nanostructured surfaces. Disadvantages : -High cost of the membranes and no industrial fabrication for the nanosurfaces (can only be fabricated manually).

Field emission arrays Time Scale : Middle term (3-5 years) Description : It can cast electrons under an electric field and be used for field emission devices such flash memory or electronic microscopes.

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Barriers for the development : 1 - Technology High cost of the machinery necessary for the fabrication of the nanosurfaces for nanoelectronical applications and nanomembranes. 2 - Market High cost of membranes due to the lack of an industrial fabrication method (fabrication of PAN thin films using self-assembly, template polymerization and bulk polymerization are currently under investigation). 3 - Regulatory More biocompatibility studies necessary before use in drug delivery systems. 4 - Environmental impacts Toxic gases produced during pyrolysis. Polyfluorene / Polyaniline (PF / PANI) nanostructures Nanostructured polymer in which the electron aceptor and the electron donator can be controlled through the nanoimprint lithography. It has interesting electrical and optical properties and is suitable for low fabrication cost photovoltaic applications. Description of material properties which have been improved : Interface area between the electron aceptor and the electron donator can be controlled through the nanoimprint lithography (NIL) fabrication method. Advantages : -Low fabrication cost. Disadvantages : -Spin coating technique generates arbitrarily oriented domains.

Photoelectrical Devices Time Scale : Middle term (3-5 years) Description : Organic semiconductors have a bicontinuous bipartition that allows effective charge separation and transport of the electrons, thus making them suitable for photovoltaic applications.
Barriers for the development : 1 - Technology Multilayers of donor and acceptor polymers hasnt yet been studied, only monolayers can be generated. 2 - Market Not yet developed. 3 - Regulatory Safety regulation for new materials in electrical and energy applications. 4 - Environmental impacts -

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(3) Companies and institutes Big Companies o Cambridge Display Technology (http://www.cdtltd.co.uk/)

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II.3.4. Combustion (1) Barriers to overcome o efficiency o emission o industrial waste o high processing temperatures (2) Possible solution through nanomaterials and risks linked: Fuel additives o nanoparticles based on metal oxides promote combustion reactions decreased emissions by increasing combustion efficiency Catalysts o nanoporous catalyst based on nano-sized perovskite oxides and limited amount of Pd (CAT-NAT, automotive application) o nanoporous catalyst based on metal oxide ceramic coatings have an increased surface area to remove harmful gases nanoporous catalyst can be used to supply separate oxygen from air under pressure across thin film membranes (themselves products of the nanotechnology). This pure enriched oxygen supply reduces noxious emission and reduces the need for heat recovery systems (a) Level of development of the nanomaterials

Figure 35: Expected time frame for the development of nanomaterials in the Combustion segment.

(b) Time frame of possible industrial applications

Table 11: Possible application: of nanomaterials in the Combustion segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

(c) Cost comparison Market size: No information available.

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Material costs:

Figure 36: Expected market size of nanomaterials belonging to the Combustion category (2006-2015).

(d) List of the nanomaterials in the Combustion sector 1. Aluminium (Al) - Nanoparticles Aluminium particles with diameter in the range 100 nm or less which show high chemical activity. These particles are used e.g. as additive to rocket fuels or explosives. Description of material properties which have been improved: High chemical activity Advantages: Foster burning of fuels and increasing explosion force of explosives

Disadvantages: Explosive - requires special precautions. Nanopowders - difficult to handle, health impact not known yet Possible application: fuel/explosive additives Time Scale: Short term (0-2 years) Description: Propellants - Fuel additives for rocket proppulsion systems, military, space launch systems Barriers for the development: 1 - Technology Explosiveness , high reactivity 2 - Market Fuels, explosives; This is a special market of very demanding applications. 3 - Regulatory Regulations on handling explosives, fuels, military activities 4 - Environmental impacts As long as health impact of inhalation of nanoparticles or contact with skin is not known, special precautions necessary to avoid inhalation/skin contact.

2. Ceramic matrix nanocarbon (bulk) Ceramic matrix nanocarbon is a ceramic matrix material filled with carbon nanotubes, fullerenes (football shaped cage of 60 carbon atoms) or carbon nanofibers. Several properties are improved. The material is more thermally insulating, electrically conducting

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and mechanically robust. The structural and thermal barrier properties are enhanced and fracture toughness increased. Main applications include automotive, aerospace, medical implants, energy saving, coatings and fire insulation in construction and bearings and cutting tools and stronger, stiffer textiles. Description of material properties which have been improved: thermally insulating, electrically conducting, mechanically robust. Structural and thermal barrier enhancements. Fracture toughness. Advantages: It is very strong, and the heat conductivity is easy to influence. The material is cheap and there is enough of it available. Since the fabrication is under control the material is made in large quantities. It is easy to produce. Disadvantages: Electrical conductivity, resistance and bandgap are still in a very early phase of development. Possible application: energy saving Time Scale: Long term (6-10 years) Description: The material is useful in combustion and insulation as thermally insulating material.

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II.3.5. Lighter and Stronger Materials (1) Barriers to overcome Efficiency Harmful emission/waste recycling Costs of the manufacturing processes Weight fuel consumption (2) Possible solution through nanomaterials and risks linked: Nanocrystalline ceramics such as zirconia, silicon nitride and silicon carbide which all combine lightweight with excellent physical, mechanical and chemical properties Manipulating magnesium on the nanolevel (innovate of nanocomposite coatings) and the resultant alloy is more useful than aluminium for car manufacturing lighter relative to the equivalent load bearing potential much easier to recycle making this material a must a transport for both automotive and aeronautics needs

(a) Level of development of the nanomaterials

Figure 37: Expected time frame for the development of nanomaterials in the Lighter and Stronger Materials segment.

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(b) Time frame of possible industrial applications

Table 12: Possible application: of nanomaterials in the Lighter and Stronger Materials segment, with a time perspective of short (0-2 years), mid (3-5 years) and long term (5-10 years).

(c) Cost comparison Market size:

Figure 38: Expected costs of nanomaterials within the Lighter and Stronger Materials category (2006-2015).

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Material costs:

Figure 39: Expected market size of nanomaterials belonging to the Lighter and Stronger Materials category (2006-2015).

(d) List of the nanomaterials in the Lighter and stronger materials sector 1. Aluminium (Al) - transition metal alloys (Fe, Ni, Ti, Zr) - Nanocrystalline powders Powders of conventional size, but with nanocrystalline or amorphous structure and usually made my spray atomisation. These powders can be consolidated to obtain bulk nanostructured shapes which are used to produce structural materials of high specific strenght. Description of material properties which have been improved: The powders themselves: are suitable for consolidation using various techniques: sintering, forging etc. Powder metallurgy methods can be used to make any shape. They can be also used as starting material for various flame spray methods to produce coatings. The products made with the powders: Good mechanical properties, low density, elevated temperature strength and oxidation and corrosion resistance. Advantages: Lower sintering temperatures than conventional material. Uniform and fine structure of end products can be obtained. The final products: combination of light weight and strength as well as oxidation resistance Disadvantages: The sintered material can be brittle because during sintering impurities are absorbed. Possible application: Starting material to sinter near net shapes of light, structural materials Time Scale: Middle term (3-5 years) Description: The powders can be used as starting material to produce by various powder metallurgy methods near net shapes of structural parts of engines or other contructions. The final product: lighter and stronger materials, oxidation resistant. Al-Ti alloys are attractive candidate materials for automotive and aerospace structural and engine applications. Barriers for the development: 1 - Technology Expensive equipment for production of nanopowders and compaction. Scale up of production: costs of equipment. As far as final products after compaction of powders: not enough research in questions of fatigue, machinability, etc. - 77

2 - Market Cost/price level must be accepted by market. Advantages of the product must be convincing. It is likely such technology can be afforded in the first stage only by big companies working for aerospace or large automotive industry. Or by small companies working on contracts for such industry. 3 - Regulatory As for application of new materials in transport industry obtaining certificates, fatigue tests etc. 4 - Environmental impacts Not different than in standard powder metallurgy industry

2. Aluminium (Al), Magnesium (Mg) and Al-Mg alloys - Bulk materials with nano-grains These materials show a specific texture on the nanoscale and are characterised by high strength comparing to the traditional counterpart. They may display high superplasticity and their main fields are: light weight structural applications. Description of material properties which have been improved: High specific strength: light weight and high strength. High diffusion rate of hydrogen along grain boundaries. High wear resistance. Advantages: The known advantages of Aluminium and Magnesia alloys are further strengthened: high strength at low weight. Magnesia alloys are extensively researched for hydrogen storage. Relatively high solubility of hydrogen and fast diffusion rate of hydrogen along grain boundaries. Disadvantages: It is difficult to combine the nano- structure with ductility. This requires very well controlled processes. Possible application: Structural material Time Scale: Middle term (3-5 years) Description: Light weight structural applications for aerospace, and automotive industry - commercial and military. High specific strenght Complex form ocan be btained with superplastic forming Barriers for the development: 1 - Technology High cost of powders and of method to induce the nanostructure by means of heavy plastic deformation. The nanostructure of the material is sensitive dependent on processing conditions. The uniformity and thermal stability of the structure is an issue. Ability to supply materials in a form or shape suitable for production of the final product. Thermal stability of the

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nanostructured Al and Al alloys may be an issue, what may limit the application temperature to about 200oC. Corrosion resistance of Mg alloys is an issue. 2 - Market Cost/performance relationship must be accepted by market. Science orientation of researchers instead of customer and production orientation. New product/new market barrier. Appropriate choice of new applications. 3 - Regulatory As for application of new materials in structures obtaining certificates, etc 4 - Environmental impacts Not different than all other aluminium and magnesium industry. 3. Aluminium (Al), Magnesium (Mg) and Al-Mg alloys - Nanocrystalline powders Powders with particle size less than 100 nm. One can make of them light-weight, highstrength bulk materials with following properties: Superplasticity at very high strain rates, increased hardness, ductility making light weight structures or make coatings by thermal spray. Description of material properties which have been improved: From the powders it is possible to make by various powder metallurgy methods structure elements of light-weight and high-strength. It is also possible to make by thermal spraying coatings of high wear resistance. Advantages: Good mechanical properties at light weight. All advantages of aluminium alloys, but higher strenght and wear or corrosion resistance Disadvantages: Need to carefully control processing parameters. Low recrystalisation temperature limits the temperature of application. An oxide layer form on the powders. During sintering this leads to formation of oxide inclusions that may enhance brittleness. Possible application: Light weight structural applications Time Scale: Middle term (3-5 years) Description: Aerospace, construction, and automotive industry - commercial and military, details of complex form obtained with super plastic forming, joining elements, stringers, trimming elements of plane fuselage Barriers for the development: 1 - Technology High cost ofequipment for high volume production. The nanostructure of the material is sensitive dependent on processing conditions. Thermal stability of the nanostructured Al and Al alloys may be an issue, what may limit the application temperature to about 200oC. Not much work has been done in the field of fatigue properties of nanostructured materials produced by plastic deformation or mechanical alloying. Corrosion resistance of Mg alloys is an issue. Non sufficient hyrdrogen solubility.

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2 - Market Production cost/price level must be acceptable. Science orientation of researchers instead of customer orientation. New product/new market barrier, appropriate choice of new applications. No hydrogen fuel market exists yet. 3 - Regulatory As for application of new materials in structures obtaining certificates, fatigue tests, etc. 4 - Environmental impacts Not different from conventional materials 4. Carbon Nanofoam Carbon nanotubes and polymer composites can form foams. These materials are just beginning to be investigated and are hoped to produce lightweight foams with improved electrical, mechanical, and thermal properties. Electrically conductive carbon nanofoams are a new material with many of the properties of traditional aerogel material. These materials are available in the form of monoliths, granules, powders and papers. They are synthetic, lightweight foams in which the solid matrix and pore spaces have nanometer-scale dimensions. Prepared by sol-gel methods, nanofoams typically have low density, continuous porosity, high surface area, and fine cell/pore sizes. The foams are also electrically conductive and have a high capacitance. Carbon nanofoams are being used as lightweight, high temperature insulation, absorbents and coatings, specialty optics, and electrodes for water deionization cells, fuel cells, and other devices. Standard densities of carbon nanofoams range from 0.25 to 1.00 g/cm3. Description of material properties which have been improved: Nanocomposite foams will have usefully improved mechanical, electrical and thermal properties through the formation of nanofibre-reinforced struts, electrically conductive networks, and the modification of optical absorption properties. Possible application: Strong lightweight material Time Scale: Long term (6-10 years) Description: Such modified foams are likely to be used in lightweight components for transport applications, leading fuel savings, as well as in electronics packaging 5. Carbon Nanotubes Carbon nanotubes are tubes consisting of a rolled up mesh like configuration of carbon atoms. More: The geometry of the rolled graphite sheets affects their properties. They can have an armchair configuration with metallic properties. The alternative zig-zag chiral configuration has semi-conducting properties. The tubes have diameters of 1-2 nm and lengths of up to several micrometers. Single walled carbon nanotubes consist of a single rolled graphite sheet. Multi-walled carbon nanotubes consist of several nanotubes rolled around each other. Description of material properties which have been improved: Hardness Nanotubes show a strengthness up to 45 billion pascals [Collins 2000] and a hight resilience.

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Density Nanotubes have a low density of 1,3 to 1,4 g/cm3 [Collins 2000] Advantages: The combination of the high aspect ration together with their conductivity and their thermal stability make them a good candidate for new display technologies and cold cathode for SEM could be realized with Carbon Nanotubes. Cathodoluminescence could be achieved at low Voltages of 1 to 3 V [Bonard 2002, Collins 2000]. Their hardness in combination with their resilience they could enhance the strength of compound materials. The high conductivity of metallic CNT make them interesting for the application for current transportation in mico-dimension for microchips or in macro-dimensions for low loss energy transportation through electronic wires [Smalley 2003]. New textiles are conceivable with extraordinary durability. They could used to realize new biosensors. Due to their huge thermal conductivity they are interesting for fillers for chip-packaging [Collins 2000]. Disadvantages: The main obstacle for a broader use of CNT is the extremely high cost. It is about 150 Euro per gram for SWCNT. [Luther 2004] It is difficult to produce pure Nanotubs of a specific constitution (length, metal-like, semiconducting, isolating, SWNT, MWNT), or to separate them from each other. [Krupke 2004, Haddon 2004]. There is an ongoing need for a more thorough understanding of growth mechanisms for a selective and uniform production of carbon nanotubes with specific dimensions and physical properties. The toxicity in combination with their chemical inertness could be a problem [Lam 2004] Their strong fibrous nature may result in similar health risk to asbestos fibres. If elements such as iron from catalysts in the production process are present there is the possibility that the nanotubes may have free-radical releasing, pro-inflamatory properties. [Royal Academy 2004]. The extraordinary properties belong to the single nanotubes. Not solved until now is the question how to transform these properties like thermal conductivity, or strength to bulk material. Possible application: Formation of foams with carbon nanotubes Time Scale: Long term (6-10 years) Description: The formation of foams with carbon nanotubes in polymer composite materials for use in a range of polymer foam materials is being investigated. Such foams are expected to have improved mechanical, electrical and thermal properties. Expected applications are as lightweight components in automotive systems and in packaging materials, leading to lower transport costs. 6. Metal Matrix Composites (MMC) This type of materials consists of metals reinforced with ceramic fibres, including Silicon Carbide (SiC) or Aluminum Nitride (AlN) fibres. The thermal, mechanical and tribological properties can be improved. Applications may include aeronautics, automotive, energy saving and environmental technology. - 81

Description of material properties which have been improved: High heat resistance, firmness, thermal conductivity, controllable thermal expansion, low density. Strength increase up to 25% Advantages: High potential for aerospace applications. Disadvantages: Not clear. Possible application: light and strong material Time Scale: Middle term (3-5 years) Description: automotive, aerospace, energy saving, environmental technology. The materials low density and increased strength (up to 25%) make it light and strong. Barriers for the development: 1 - Technology Production must be scaled up. (kg/day in 2003) 2 - Market Cost saving in aerospace possible. 3 - Regulatory Not clear. 4 - Environmental impacts Not clear. 7. Polystyrene-block-poly(4-vinylpyridine) (PS-P4VP) nanowires Polymer liquid-like elastic nanowires with high ion conductivity and mechanical strength. They can be used in various nanoscale electronic devices, fabrics and "smart materials" which change its properties depending on the environment. Description of material properties which have been improved: Ionically conducting liquid-like polyelectrolyte with rigid mechanical properties. Also multifunctional "smart fibers" nanolayers can be grafted from hybrid polymer brushes. Advantages: -High ionic conductivity. -High elasticity. -Good mechanical properties. Disadvantages: -Multi-functional "smart fibers" are in a premature state of development Possible application: Nanowires and conductors Time Scale: Short term (0-2 years) Description:

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Its high ion conductivity makes it useful to manufacture transistors, sensors, motors and other nanoscale passive or active devices Barriers for the development: 1 - Technology "Smart fibers" need further development before entering the market. 2 - Market Only medium market size. 3 - Regulatory Regulation for application of new materials in electronics. 4 - Environmental impacts Effects of small nanoparticles entering the human body and accumulating in the cells of the respiratory or other organ systems are yet unknown.

8. Silicon Nitride (Si3N4) - bulk material Silicon nitride bulk ceramics with homogeneous nanosized structure showing improved tribological properties. Description of material properties which have been improved: homogeneous nanosized microstructure Advantages: improved tribological properties (friction, wear coefficient) under dry slip-rolling friction Disadvantages: Powder and ceramic technology are more expensive than for conventional powders Possible application: Machine tool industry Time Scale: Short term (0-2 years) Description: Ceramic bulk material made of nanosized silicon nitride offer the possibility to achieve very low friction coefficients without lubrication. Possible application:s can be friction bearings, thread guides or tools. Barriers for the development: 1 - Technology expensive nano powders and technological route 2 - Market market for nanosized non-oxide ceramics depends on the acceptance of structural non-oxide ceramics at all 3 - Regulatory 4 - Environmental impacts The health effects of small nanoparticles entering the human body through pores and accumulating in the cells of the respiratory or other organ systems (for example, when also becoming dislodged through wear debris) are practically unknown. - 83

9. Titanium (Ti) - Bulk material Bulk nasnostructured material made by heavy plastic deformation. Thermally stable at temperatures up to 300oc Light specific weight, good high temperature strength, good corrosion resistance, and biological compatibility. Used in construction of implants Description of material properties which have been improved: Fine grained Ti reveals considerable increase in strenght. Commercially pure titanium is chemically inert and biologically more compatible than the Ti-6Al-4V alloy, which is currently the material of choice for most medical implants High strength/ specific weight ratio, good corrosion resistance, improved strength and fatigue Advantages: Titanium biocompatible Light specific weight, yield strength >900MPa, Improved fatigue-limit, good corrosion resistance, Disadvantages: Titanium: need for high purity material, low technological plasticity at room temperature, difficult machinability. Reduced creep resistance: is thermally stable at temperatures up to 300C. High production costs Possible application: aeronautic/automotive structure elements Time Scale: Unspecified Description: Parts/components (structure elements) springs for automotive applications

of

airplanes,

vehicles,

spacecrafts

Barriers for the development: 1 - Technology For materials produced by severe plastic deformation: high cost of the equipment for high volume production. Technology for large scale production consistency and reliability in volume production. Ability to supply materials in a form or shape suitable for production of the final product. Not much work has been done in the field of fatigue properties of nanostructured materials produced by plastic deformation or mechanical alloying. 2 - Market Production cost/price level must fit into existing commercially prices. Scientific results orientation of research instead of customer orientation. New product/new market barrier, appropriate choice of new applications. This is rather a special market of very demanding applications. 3 - Regulatory As for application of new materials in structures obtaining certificates, fatigue tests etc. 10. Titanium-Aluminium (Ti-Al) alloys - Bulk materials Titanium-Aluminium alloys with a nanostructure produced by heavy plastic deformation. This material show superplasticity and an ultimate strength up to 1500 MPa. - 84

Description of material properties which have been improved: Ultimate tensile strength 1500 MPa High hardness (6 GPa) Superplasticity at elevated temperature Good corrosion resistance Relatively good ductility despite high strenght Strenght reamins even at elevated temperatures Advantages: High specific strenght. For proper production conditions may have relatively good ductility. Disadvantages: High superplastic deformation temperature Thermal instability at high temperatures Low room temperature ductility Needs very well controlled processing. Possible application: automotive/aeronautic body parts Time Scale: Middle term (3-5 years) Description: Body parts. Light weight plates. Motor parts Barriers for the development: 1 - Technology For materials produced by severe plastic deformation: high cost of the equipment for high volume production. Ability to reproduce the same high quality product on large scale consistency and reliability in volume production. In the case of mechanical alloying, the problem is contamination of the powders with oxides, and then consolidation of the powders into bulk materials. The oxides may cause brittleness and also porosity of the product. Ability to supply materials in a form or shape suitable for production of the final product. Not much work has been done in the filed of fatigue properties of nanostructured materials produced by plastic deformation or mechanical alloying. 2 - Market Production cost/price level must fit into existing commercially prices. Science orientation instead of customer orientation. New product/new market barrier, appropriate choice of new applications. This is rather a special market of very demanding applications. 3 - Regulatory As for application of new materials in structures obtaining certificates, fatigue tests etc.

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III.

Conclusions The main challenges for the application of nanomaterials in the energy sector are the improvement of the efficiency, the reliability, the safety and the lifetime as well as the reduction of costs. The most promising application fields for the energy conversion domain will be: photovoltaics (solar cells), hydrogen conversion (fuel cells) and thermoelectricity (themoelectronic devices). The solar cells will be interesting for the local energy supply, if the costs can be significantly reduced and the electric energy can be efficiently saved. The most promising cost reduction at the solar cells will be expected by the dye solar cells and the organic polymer solar cells. An important breakthroughs can be reached with the nanotechnology, however these types of solar cells are still in the research and development phase. The distribution of the fuel cells is limited nowadays due to the high prices. However, the improvements based on the nanotechnology, at membranes, catalysts and electrodes will lower the cost of the fuel cells as well as improve the efficiency. Thereby, a potential future market for the fuel cells could be the automotive industry, however, the fuel cells are nowadays in the research and development phase. Also, for thermoelectric devices nanostructured materials show future application possibilities, which will improve the efficiency. For the energy storage domain the most promising application fields will be the rechargeable batteries and the supercapacitors. In rechargeable batteries (for example in lithium batteries) nanocrystalline materials and C- nanotubes as electrode materials have been demonstrated to greatly improve both energy and power density, lifetime and charge/discharge rates. The miniaturisation of the electrodes plays here a quite important role. Like in the rechargeable batteries also for the supercapacitors advances through nano-porous electrode materials will be expected. Thereby, nanotechnology will open new potential markets for batteries and capacitors or the combination of both for mobil phones, laptop computers and semiconductors. For energy saving interesting will be the applications fields of insulation (aerogels, smart glazes) and more efficient lightning (LEDs, OLEDs). Advances in insulation via nanotechnology will help to reduce the energy demand as well as the daily costs in homes and industry. Thereby, nanotechnology contributes to this area in form of aerogels or smart glazes in form of ultra thin layers. In the field of more efficient lighting, LEDs and OLEDs, based on the nanotechnology , will improve the quality of the resolution of displays, which will be strong future market for cameras, cell phones, laptops and computer monitors.

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IV.

Sources and References Report from Nanoforum.com: Nanotechnology helps solve the worlds energy problems April 2004 Report from VDI Technologiezentrum: Industrial application of nanomaterials chances and risks, August 2004 Report from Deutschen Bundestag, 15. Wahlperiode, Technikfolgenabschtzung, TAProjekt Nanotechnologie, March 2004 Report from Bine: schaltbare und regelbare Verglasungen Report from VTT Technology studies, NanoRoadMap project, October 2004 Expert interview, Mrs. Wohlfahrt-Mehrens, ZSW Ulm Expert interview, Mr. Stroh, Fraunhofer IGB Stuttgart, Department fuel cells Expert interview, Mr. Springer, ZSW Stuttgart Expert interview, Mr. Gross, Fraunhofer ISE Freiburg, Department fuel cells Expert interview, Mr. Georg, Fraunhofer ISE Freiburg, Department glazing Expert interview, Mr. Kern, Fraunhofer ISE Freiburg, Department solar cells www.agilent.com www.led-info.de

Experts: Biomaterials: Carbon-based materials: Ceramic-based materials: Metal-based materials: Nanocomposites: Nanoglasses: Nanopolymers: Dr. Markus Linder, VTT, Finnland Dr. Regine Hedderich, FZK, Germany Dr. Tassilo Moritz, Fraunhofer IKTS, Germany Dr. Witold Lojkowski, Unipress, Poland Ineke Malsch, MTV, Netherlands Prof. Eusebio Bernabeu, UCM, Spain Prof. Alicia Larena, UPM, Spain

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V.

Impressum

This SWOT analysis was made in connection with the European project Development of Advanced Technology Roadmaps in Nanomaterial Sciences and Industrial Adaptation to Small and Medium sized Enterprizes (NanoroadSME). The project was funded by the European Community under the Sixth Framework Programme (Contract No NMP4-CT2004-505857). Authors: Dr. Ulrich Sutter, Dr. Jonathan Loeffler (Steinbeis-Europa-Zentrum, Karlsruhe, Germany)

Contact of project co-ordinator: Dr. Jonathan Loeffler e-mail: loeffler@steinbeis-europa.de Steinbeis-Europa-Zentrum Erbprinzenstrae 4-12, 76133 Karlsruhe Germany The authors are responsible for the content. All rights reserved except those agreed by contract. No part of this publication may be translated or reproduced in any form or bay any means without prior permission of the authors.

Version March 2006

Front page pictures: Source: BASF AG, Ludwigshafen

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