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MULTI-LEVEL PROTECTION OF MATERIALS FOR VEHICLES BY “SMART” NANOCONTAINERS

Final Report Summary - MUST (Multi-level protection of materials for vehicles by 'smart' nanocontainers)

Executive summary:

The advanced coatings and adhesives based on innovative combinations of nanotechnologies for improved safety, extended service life and aesthetic value, are today a worldwide topmost research area with an outstanding technical and industrial impact. The main objective of MUST project was the development of effective environmentally-friendly multi-level active protection systems for structural metallic materials used in future vehicles. The approach of MUST was based on a combination of advanced polymeric matrixes and active nanocontainers providing healing effects. A significant improvement of the durability and performance of a protective coating became evident after early stage degradation phenomena could be recovered and the barrier properties of the coating kept for a longer time.

Novel functional nanocontainers capable of storage of active agents and their controllable release triggered by specific conditions such as pH, temperature, mechanical impact, water and chlorides were developed in the project. These agents have healing properties and can therefore repair damages in coatings and protect underlying metallic substrate. The top facilities for nanocontainers fabrication and encapsulation of active species and the most modern characterization techniques were synergistically combined within MUST for achieving these edge research goals. The production technology of the most successful nanocontainers was scaled up during the project from gram-scale in the lab to several hundred liters batches in the pilot scale.

New experimental techniques and analytical methodologies were specifically developed to fulfill the needs of the project since the topic of self-healing coatings is relatively new and the existing experimental protocols for investigation of the self-healing effects are very limited. In addition, an algorithm and computational code for the multilevel protection was developed for systems consisting of multilayer coatings with water traps and containers with corrosion inhibitor that can be released upon internal trigger (salt concentration, pH), providing control on water and corrosive ions transport throughout the coating.

Novel technologies for active corrosion protection of cars and aircrafts were developed in MUST. Specifically, the addition of functional nanocontainers and nanotraps to automotive pre-treatments and primers led to significant improvement of the performance in terms of long-term corrosion protection and coating adhesion properties. The corresponding technologies are patented and are on the way to commercialization in the form of new products within the coming years.

The most successful products originating from MUST are:
- automotive self-healing pre-treatments with nanocontainers of corrosion inhibitors;
- active anti-corrosion primer with nanotraps for automotive applications;
- multi-functional aeronautical primer with nanocontainers;
- structural adhesives with inhibiting nanocontainers for cars;
- maritime coatings with organic inhibitor loaded nanocontainers.

The protective solutions developed in MUST provide sustainable components and offer the chance for decreasing cost by reducing process steps during pre-treatment and in paint shop, regardless of the specific type of transport industry. The performance in terms of corrosion protection still has to be optimized on the upscaled industrial level during the post-project phase in order to meet the good coupon level properties. An important effect on competitiveness is obtained not only by meeting but even surpassing the current environmental regulations.

MUST has produced some of the latest advances in the topic and has become worldwide recognized. Above 50 scientific publications in international journals of high impact, dissemination activities within the general public (including 4 open international workshops, videos and news) and transfer of technology via filing 5 patents and the creating 1 spin-off company are among the major impacts of MUST.

Project Context and Objectives:

The destructive effect of environment and the corrosion induced degradation are the important factors which determine the economical service life of a vehicle or its components. The application of organic coatings is the most common and cost effective method of improving protection and durability of metallic structures.

The long term performance of organic coatings is by nature subject to chemical and physical aging processes. One strategy to improve the in-service life of protective coatings is to respond to these conditions with healing reactions. This ability is expected to be most effective if it is reacting at certain stages of degradation with different healing processes. A significant improvement of the durability of protective coating is evident if early stage degradation phenomena are recovered and e.g. the decrease of the barrier properties of the coating is postponed to longer exposure times.

The main vision of the project MUST was to develop new active multi-level protective self-healing coatings and adhesives for future vehicle materials. These materials were based on "smart" release nanocontainers incorporated into the polymer matrix of current commercial products. A nanocontainer (or nanoreservoir) is a nanosized volume filled with an active substance confined in a porous core and/or a shell which prevents direct contact of the active agent with the adjacent environment.

The main objective of the MUST project were the design, development, upscaling and application of novel multi-level protection systems like coatings and adhesives for future vehicles and their components to improve radically the long-term performance of metallic substrates and structures. A multi-level self-healing approach combined - within one system - several damage prevention and reparation mechanisms, which were activated depending on type and intensity of the environmental impact.

The main novel idea suggested in MUST was the multi-level protection approach based on functional nanocontainers. Several self-healing protection mechanisms were suggested before but were never combined together in the same polymer system. The innovative idea of this project was a gradually active protection response of the coating depending on the nature and the degree of impacts from external environment.

The multi-level self-healing concept was based on gradual active feed-back of the protective systems to the environmental conditions. Different active components in the protective system were able to respond to four different types and levels of impacts imposed to the coating:

- The first level of protection was provided by the incorporation of nanotraps (nanoparticles able to absorb aggressive/corrosive species if their level in the coating or adhesive exceeds a critical value).

- The second level was based on the use of water displacing compounds, which were released from nanocontainers as soon as the first microdefects appeared in the polymer matrix.

- Further growth of the defects triggered the release of polymerizable precursors entrapped in other nanocapsules. Then a new thin polymer film was formed, covered the damaged area and repaired the layer, preventing crack propagation.

- The highest level of protection was based on encapsulation of organic and inorganic corrosion inhibitors in different types of nanocontainers (10 – 100 nm in size) acting on demand and suppressing corrosion and delamination processes occurring in open defects or at cut edges.

Project Results:
The MUST project consisted of 6 core sub-projects grouped in one work-package (WP2) devoted to development and testing of new nanocontainer-based solutions for different transport industries. The upscaling and demonstration of the developed technologies was performed in a separate workpackage (WP3).

WP2-SP1
The main target of SP1 - Development of nanocontainers involves design, development and testing of the nanocontainers, following both the multi-level active protection and the self-healing ability of the containers. To improve protection and functional (response) characteristics of nanocontainers, their shell can be functionalized using active compounds (e.g. metal and magnetic nanoparticles, polyelectrolytes) by either chemical binding or LbL electrostatic adsorption. The nanocontainers encapsulating various active agents are embedded as additives in model coating systems for further investigations on the different levels of corrosion protection in sub-project 2.

The following procedures were evaluated to get maximal encapsulation yield:

1. Capturing by reversible opening the pores of the container shell by different external factors (e.g. pH, solvent variation).
2. Precipitation followed by shell formation and modification.
3. Embedding (adsorbing) in a porous (empty) host also followed by shell assembly.
4. Impregnation from inhibitor-containing solution under vacuum pumping.
5. Ultrasonic or mechanic formation of oil-in-water emulsions accompanied by shell assembly with the active agent dissolved in the oil phase
6. Immobilization of inhibiting ions in ion-exchange pigments

The mechanism for the controlled release of active materials depends on the kind of nano container. Depending on the type of the nanocontainers, we envisaged 3 triggering mechanisms for the release of active materials:
- pH-triggering for containers with polyelectrolyte shell, shell containing weak polyacids/polybases, shell assembled by H-bonding;
- triggering by electromagnetic irradiation: for containers with the shell loaded with light-sensitive metal nanoparticles (Ag, Au) and azo-polymers;
- triggering by mechanic damage (opening) of the containers.

The main achievements according to the SP1 tasks are as following.
1st level of protection – nanotraps for water molecules and corrosion ions
Layered double hydroxides (LDHs) were taken as main material for this protection level. During the project execution, structural and morphological characterization and corrosion performance with anionic inhibitors has been discussed in detail. The structure of LDHs can be considered as versatile from the corrosion standpoint: being anion-exchangers, the LDHs can release the intercalated active material by exchange with aggressive ions from the surroundings (including chlorides, sulphates and carbonates). On the other hand, these structures may respond indirectly to pH: in high pH conditions the inhibitor can be exchanged with hydroxyl anions whereas in low pH conditions the LDHs start to dissolve and the inhibiting anions are released in the solution. In the release studies, two different types of LDHs were studied: Zn(2)-Al-MBT LDHs prepared by ion-exchange and Mg(3)-Al-MBT prepared by calcination-rehydration method.

2nd level of protection – micro-/nanocontainers with water displacing/repelling agents
The best examples of the nanocontainers with water displacing/repelling activity developed in MUST project are water nanotraps and polyurethane capsules with water-repelling agent.

Polymetacrylic water nanotraps were prepared by distillation precipitation polymerization. The ability of PMAA nano-microspheres to absorb water was succeeded by conversion of carboxylic groups to the corresponding sodium salts adding sodium hydroxide solution. The water nanotraps could be regenerated from the hydrogel by washing with an organic solvent, such as ethanol.

3rd level of protection – microcontainers with healing agents and catalyst
The preparation of PU containers with healing agents followed the procedure of membrane polymerization, at which MTEOS was mixed with monomer DVL in toluene. Membrane with pore size of 200nm was used. TOPCOAT films containing 10 wt % of capsules in benzyl alcohol were prepared on both Mylar and metallic substrates. Containers showed a wide range of particle size distribution. Two different washing processes were used to wash the PU capsules containing prepolymer; (1) filtration; (2) centrifuge (2000 rpm/10min). The samples seemed to be completely collapse after centrifugation while filtration seems to impose less damage to the capsules.

4th level of protection – nanocontainers with corrosion inhibitor
The optimization of method for encapsulation of the corrosion inhibitor, methylbenzothiazole (MBT), by layer-by-layer adsorption of polyelectrolytes was demonstrated. The oil phase for capsules' liquid cores was prepared by dissolution of AOT in 10ml of chloroform solution containing corrosion inhibitor. Final concentration of MBT in oil phase was 6%. Emulsion droplets were formed by addition of AOT/chloroform to polycation (PDADMAC) solution during mixing with a magnetic stirrer. After adsorption of the first layer of PDADMAC and formation of suspension of liquid cores stabilized by AOT/PDADMAC interfacial complexes, the consecutive layers of polyelectrolytes were formed by layer-by-layer technique using the saturation method. Therefore, the multilayer shells (PDADMAC/PSS/PDADMAC) were constructed.

WP2-SP2
Subproject 2 (SP2) mainly considered fundamental investigations of the dispersion, reactivity and self-healing properties of nanocontainers and their combinations in polymeric and inorganic layers. Functional nanocontainers with various host structures and encapsulated additives as developed in SP 1 were embedded in model coatings and adhesive systems, in order to study the mechanisms and kinetics of nanocontainer based processes on the respective protection levels. The structure and the elemental composition of the nanocontainer-impregnated coatings were investigated by means of microscopic (SEM, TEM, AFM) and spectroscopy techniques (FTIR, Raman, XPS).

Design and evaluation of model coatings
Suitable matrices compatible with the stimuli responsive nanocontainers as additives were designed and evaluated. Pretreatments, primer systems, polyelectrolytes, epoxy and PU- based coatings are some examples for the used model coatings.

Understanding of the interaction between the nanocontainers and the polymeric matrix
The interaction between the nanocontainers and the polymeric matrix was studied in order to improve the understanding of the compatibility of the nanocontainers and the respective coating matrix as well as to be able to predict the mechanical and barrier properties of the functional composite coating. Laboratory tests on the compatibility of nanocontainers in the paints were done on liquid coating materials as well as on cured coatings by SEM characterizations. Different containers were analysed with regard to the different corrosion protection level. For example, LDH and TiO2 nanocontainers (loaded with inhibitor), developed for the 4th level of corrosion protection, PU microcontainer (loaded with MTES, prepolymer, MBT) for the 2nd, 3rd and 4th level of corrosion protection.

Preparation of model defects and patterned coating systems
Defined small defects of varying size and geometry were prepared by the Focused Ion Beam Technique (FIB) or stretch forming and were analysed by a combination of integral and localized electrochemical techniques to extract information for a better understanding of the corrosion processes and corresponding repair of active microscopic defects formed on thin coatings containing inhibitor filled containers [1].

1st level of protection – nanotraps
The first level of protection was provided by the incorporation of nanotraps for corrosive chloride ions and water. To receive information about the trapping mechanism permeability tests of free standing films were performed amongst others. Zn–Al layered double hydroxides (LDHs) intercalated with nitrate anions are suggested as chloride nanotraps for organic polymeric coatings. The addition of such nanotraps to a polymer layer drastically reduces the permeability of corrosive chloride anions through the protective coatings. A coating modified with LDH–NO3 was found to exhibit significantly lower permeability to chlorides when compared to an unmodified coating, which proves the applicability of LDHs in delaying coating degradation and corrosion initiation [2].

2nd level of protection – micro-/nanocontainers with water displacing/repelling agents
The second level based on the use of water displacing compounds, which are released from nanocontainers as soon as the first microdefects appear in the polymer matrix. Water repellence was studied by the microscopic analysis of water accumulation within defects. The nanocontainers lead to the release of hydrophobic additives, the local contact angle increases and water repels from the defect areas in small droplets. To analyse this behaviour, a new apparatus was introduced, allowing the study of advancing and receding contact angles during the simultaneous stretch forming of the coated substrate. The incorporation of alkoxysilane loaded polymer capsules into a coating system led to a pronounced hydrophobization of cracks that were formed during the stretching of the sample. The local hydrophobization is assigned to the conversion of alkoxysilanes to polysiloxanes via hydrolysis and condensation which are initiated by the contact of those alkoxysilanes with the aqueous electrolyte during water attack [4].

3rd level of protection – microcontainers with healing agents and catalyst
For the analysis of self-sealing systems localized methods like local impedance spectroscopy (LEIS) were used to characterize the samples. LEIS measurements of scratched samples containing PU capsules with prepolymer displayed a reduced corrosion activity compared to the unmodified sample. By means of water contact angles measurements during stretch forming the release of prepolymer was shown.

4th level of protection – nanocontainers with corrosion inhibitor
The fourth level of protection is based on encapsulation of organic and inorganic corrosion inhibitors in different types of nanocontainers acting on demand and suppressing corrosion and delamination processes occurring in open defects or at cut edges. Coatings with single nanocontainers were analysed in addition to combinations of nanocontainers and multi-layer coatings. Besides the research of nanocontainers and mechanism of self-healing new experimental methods for testing of the self repair properties were introduced. A multi-electrode was shown to permit the assessment of the corrosion susceptibility and corrosion inhibition of different metals and alloys simultaneously [5]. Ion-selective microelectrodes offer the measurement of the scanning vibrating electrode technique (SVET) with the quasi-simultaneous measurements of pH. These measurements correlate electrochemical oxidation–reduction processes with acid–base chemical equilibriums [6].

Overall Conclusions:
The work in SP2 enabled to build a bridge between the nanocontainer design and the resulting properties of coatings and adhesives which were modified by these nanocontainers. Moreover, the fundamental results allowed the advanced simulation of coating properties.
It can be generally be concluded that repair processes and trapping are limited to confined dimensions of several ten micrometres due to the limited amount of functional additives that can be incorporated in the coatings and adhesives.

WP2-SP3
The main aim of SP3 – "Modelling and simulation" has involved development of effective simulation algorithms, which application allows quantitative description of processes occurring in the multifunctional anticorrosion coatings. Therefore, they can be used to optimise of composition of the coating with respect to contents of the capsules, their distribution in the coating, their surface properties, wetting properties of inhibitors and healing agents, etc. The algorithms were developed basing on the understanding of fundamental processes of formation of containers/particles used at every level of protection as well as their interactions with various layers of coatings or adhesives and mechanisms and rates of release and transport of inhibitor or healing agent.
The following processes were considered:

1. Modelling of the membrane emulsification process to produce cores for encapsulation of hydrophobic anticorrosion agents.
2. Transport of water or corrosive ions (e.g. chlorides) through the multilayer coating that contain water and ion traps and inhibitor pool with built-in various triggering mechanisms.
3. Release of active agent from the core-shell structure (nano- or microcapsule) – diffusion controlled release with permeability controlled by internal trigger (e.g. pH level).
4. Simple and complex simulations of the release of inhibitor or healing agent from capsules in the cracked/scratched coating – i.e. triggering by mechanic damage of the containers;
5. Release of inhibitor or healing agent to the scratch and evaluation of healing effect probability – risk of failure analysis.

The main achievements of the SP3 subproject are as following.
1. Membrane emulsification - The model of membrane emulsification based on the balance of forces acting on the drop of the dispersed phase formed at the mouth of the membrane pores were elaborated. The model takes into account process parameters as: viscosity of both dispersed and continuous phase, dynamic interfacial tension, average pore diameter and pore size distribution, membrane structure and wetting properties, temperature trans-membrane pressure and wall shear stress. The effect of hydrodynamic instability during droplet formation and necking was also considered in the model.

2. Molecular modelling of surface activity of amphiphilic silica sources - Molecular structure of surface active species provides information concerning the ratio of the hydrophobic and hydrophilic part of molecules, which allows to predict – using thermodynamic arguments - their surface activity, critical micelle concentration, shape of surface/interfacial tension isotherms. For the modelling, a two stage approach was applied. Quantum mechanics ab-initio calculation and optimization of molecular structure was used to find properties of single surfactants without taking into account explicitly solvent effects. Then the molecular mechanics calculations were used to determine interaction of surfactants with the solvent and to study the conformational effects at interfaces.

3. Kinetics of release of corrosion inhibitor from capsules – Model based on the two step process, transfer of the inhibitor through the oil/water interface (for hydrophobic cores) or dissolution of solid core and diffusion through the shell was developed and the software code based on the final differences integration scheme was prepared. The model was verified with the experimental results concerning the release of fluorescent dye from the hydrophobic core and used to describe the release of corrosion inhibitor.

4. Model of transport of water and ions through the multifunctional coating containing water and ion traps and inhibitor pools - The numerical model of multifunctional coating containing water/ion traps and embedded capsules with inhibitor was developed. The alternative algorithms for the solution of diffusion equation in inhomogeneous media, based on the lattice gas model and finite differences were elaborated. Finally the one dimensional diffusion equation describing water (or ions transport) in the effective medium was derived. In the model various triggering mechanisms of the release of inhibitor from containers as concentration thresholds of corrosive ions or corrosion products were considered. Single and multilayer coatings can be simulated with the arbitrary distribution of water, ion traps and inhibitor containers. The model was verified with experimental data obtained in SP2 for:

- diffusion of water through the epoxy film (EU3) containing polymer water traps (SP1);
- diffusion of chloride through the epoxy film containing LDH chloride traps (SP1);
- results for the salt spray test at the EG steel panels painted with a primer layer containing (calcined LDH).

In all studied cases the quantitative description of experimental results was obtained.

5. Model of the release of inhibitor or healing agent from capsules in the cracked/scratched coating – The model based on the geometrical arguments taking into account random distribution of capsules in the film and propagation of the inhibitor either by spreading or diffusion. Two limiting boundary conditions concerning the release mechanism induced by mechanical damage were considered. Either inhibitor is released only from capsules at the edge of the scratch and the material in the scratch volume is lost, or the inhibitor is released from all capsules in the crack/scratch. That simple model was applied to the description of:

- the propagation of hydrophobizing agent, alkoxysilane, from the polyurethane-epoxy capsules in the epoxy coating on aluminium surface;
- release of corrosion inhibitor (MBT) from capsules with polyelectrolyte shells embedded in the epoxy coating (EU3) on the aluminium surface;
- release of prepolymer and healing of the scratch;

In all cases qualitative agreement between the available amount of inhibitor/healing agent and efficiency of coating was observed. That simple model was the starting point to the more elaborate modelling of the active agent propagation in the scratch by the DPD method and finite differences algorithm for the large scale modelling. The latter enables to construct maps of probability of healing the scratch for a given amount of active agent in capsules and volume fraction of capsules in the coating.

WP2-SP4
The objectives for using nanocontainers in coatings and adhesives for automotive applications were mainly to improve corrosion protection in critical areas of the car body. Therefore pre-treatment, primer, e-coat and adhesive were chosen for the development of protective coatings. Novel automotive substrates like pre-coated coil steel were also in focus.

Additionally there was the idea that a new process could lead to a reduction of the complexity and thus to a reduction of cost compared to the current processes. Of course one of the important aspects was compliance with future environmental and legal requirements.

WP2-SP5
Due to the lack of suitable alternative inhibiting pigments for the replacement of chromates new inhibition concepts are required for aerospace coatings. The encapsulation of inhibiting substances is one approach to achieve sufficient effectiveness of inhibition also for long term protection purposes. The advantages are e.g.:
- Bigger choice of inhibitor candidates and combination thereof can be used because of better compatibility with matrix
- Smart and triggered release is enabled by encapsulation and controls inhibition process
- Increased inhibitor concentration can be obtained

The following systems could be integrated in the model film and the model primer and corrosion performance could be carried out:
- Polyelectrolyte shell
- Mesoporous silica
- Layered double hydroxide LDH
- Halloysites
- TiO2 nanoparticles

Several approaches were investigated for dispersing the nanocontainers properly and producing satisfying films. Finally a valid procedure could be specified to produce the coating system. Approximately 200 different combinations of film/container/inhibitor/pretreatment systems have been selected and applied for testing.

The following aerospace relevant tests were performed with the coatings:
- Paint adhesion test before and after water exposure
- Scratch resistance before and after water exposure and after exposure to hydraulic fluid
- Flexibility testing
- Drop Test for evaluation of corrosion protection of mechanical defects according to a test developed within MUST
- Salt spray test according to EN ISO 9227 for evaluation of scratch corrosion protection, protection against paint creepage and barrier properties
- Filiform corrosion test (for selected systems) according to EN ISO 3665 for evaluation of filiform corrosion resistance
- Alternate Immersion and Emersion test (for selected systems) for evaluation of leaching behaviour, corrosion protection of mechanical defects, protection against paint creepage and barrier properties. Some of the promising systems were also analysed in SP2 for basic understanding of the performance and mechanistic investigation (inhibition effect, barrier properties)

Corrosion on coupon level
In general it can be stated that the corrosion inhibition of exposed surfaces as tested by the drop test is not achieved by any inhibitor loaded system. This can be attributed either to the concentration, to the efficiency or the leaching behavior of the corrosion inhibitors.

Often the coating barrier is lowered by the integration of the containers. Low adhesion after water exposure or blistering in salt spray test is often the consequence. Nevertheless during the development work in the project it was possible to optimise the systems and to accomplish these problems.

Corrosion testing on demonstrator level
Specific design elements were to be selected which are representative for the certain areas of the aircraft structure. The demonstrator was to be defined with respect to the respective manufacturing process of the structure and the potential application process of the coating. The design of the demonstrator should reflect realistic but also challenging condition for the protection system and must also consider the existing requirements of the different testing and evaluation methods. With regard to availability, quality, reproducibility, performance and mechanistic understanding several encapsulations systems were prepared based on LDH-Inhib1, LDH-Inhib2, Halloysite-Inhib3, Polyelectrolyte-Inhib2 and compared with CrVI-free and CrVI-loaded reference systems.

Corrosion tests with demonstrators revealed the relevant corrosion hot spots: Paint creepages at defects, blistering on surfaces, galvanic corrosion, crevice corrosion. The chromate loaded reference systems inhibit these corrosion hot spots successfully over the test time. The MUST systems and the CrVI free reference primer allow these hot spots nearly to a similar degree to occur. A clear benefit of one of the MUST systems is not observed

WP2-SP6
The main objective of SP6 is the development of new multi-level protective coatings based on active nanocontainers for maritime applications. The currently used maritime coating formulations are modified by doping them with appropriate nano-/micro containers developed by SP1-partners in the MUST project. The objective as well as results of this particular work package is described in the following.

The substrate to be coated is defined, and the main candidate is mild steel which still is a main structural material for maritime applications. The coating formulations are selected from epoxy based systems currently employed for ships. The requirements for potential micro-/nano-containers are formulated from standpoint of compatibility with paint formulations in order to be used by SP1-partners during design of new active nanoreservoirs.

Anti-corrosion
In order to test how nano/micro containers doped with anti-corrosion inhibitors can be dispersed into the selected maritime epoxy coating, complete samples of the coating systems is send to six SP1 partners for them to test and describe how this successfully can be done. Each of the partners has received both a water borne epoxy system and a solvent free epoxy system complete with hardener. Each SP1 partner has doped the nano/micro containers with their best working anti-corrosion inhibitors and dispersed them into the epoxy system. The complete system is tested for anti-corrosion properties in salt spray chamber where after the best candidate is chosen for large scale testing and demonstration in the WP3 project phase. Testing of panels for anti-corrosion properties is done both according to 'ASTM B-117/ISO 9227 – Corrosion testing in salt spray' and 'ISO 2812 - Determination of resistance to liquids'. All together it is prepared 280 test specimens to test 18 different systems in various environments. The selected candidate from these tests is halloysite-based nano containers from Max Plank loaded with the corrosion inhibitor 1H-benzotriazole in two different ways.

Anti-fouling
To test and select the most promising coating system with nanocontainers doped with biocides for anti-fouling properties test specimens are submerged in seawater for prolonged periods at test stations in Norway and in Singapore. Preliminary results from testing maritime coating system with CuO nano containers doped with biocides are showing promising development. But as the samples being tested only has been immersed in sea water for a few months it is too early to judge whether they will continue to develop in a positive manner, and if they will show better results than traditional epoxy systems with copper and biocides. As there is no way to accelerate anti-fouling tests to get quick results the tests will continue for a prolonged period to see if the nano-system outperforms service-life of standard system which is five years.

WP4

Objectives
The dissemination strategy of MUST envisaged at reaching a broad range of audiences, including the scientific and industrial communities, the general public and the key decision makers. All the partners have been encouraged to be involved in the dissemination activities. Specifically, the partners were committed to present the project results in conferences, info-days and other dissemination events; to participate in workshops, to prepare scientific papers for conference presentations or journals, to contribute for the web-site contents, to be involved in training and formation of researchers and to highlight the project results.

Key activities developed:

Electronic dissemination
The MUST web portal (see http://www.sintef.no/Projectweb/MUST online) highlights the project objectives, achievements and relevant events that were organized. In addition to this portal, several partners have created advertisements in the web pages of their institutions, thus creating additional branches for the project dissemination. Targeted to a large array of audiences, with a high visual impact and a clear and concise language, the MUST video, will increase the awareness of the project.

Education and training
Mobility of researchers, at the doctoral and post-doctoral level has been implemented in MUST. This strategy contributed for educating and training high-level researchers, more capable of contributing effectively for the implementation of the R&D and technical activities developed in MUST, supporting the EU research effort.

Six training courses were organized within MUST, both by the R&D and industrial partners:

1. Electrochemical Impedance Spectroscopy, Lisbon , November 6-7 (MUST AND MULTIPROTECT) – IST + UAVR
2. Cleaning and Pre-treatment technology , March 9-10 – IST + CHEMETALL
3. Risk analysis – IST + STEINBEIS R-TECH , March 11, 2009
4. LbL of nanocontainers – IST + MPI, October 15-16
5. Adhesion and related characterization techniques, University of Paderborn, September 2010.
6. Adhesives and its testing - SIKA AG Zurich March 16-17 2011.

Recommendations and guidelines
EADS and Chemetall created datapools for collecting all the data gathered in the various tests performed on aeronautic and automotive materials, respectively.

R-Tech created a database repository for SDSes (safety data sheets) in ENM. Currently, there are 157 SDS stored in the database. SDSes of the nanocontainers were requested from the project partners. In addition, MUST WP3 meeting in Leverkusen identified the nanocontainers required for the database. SDSes in the database are classified into 5 categories: Nanocontainers from the MUST project partners (9), Primary nanomaterials from the external sources, Functionalized nanomaterials from the external sources, Products contained nanomaterials and other.

Patents
The MUST exploitation strategy was successfully represented in 5 patent applications: Preliminary patent application (Nr. 106256): "Process for coating metallic surfaces with coating compositions containing particles of a layered double hydroxide", M.G.S. Ferreira, M. Zheludkevich, J. Tedim, V. Gandubert, T. Schmidt-Hansberg, T. Hack, S. Nixon, D. Raps, D. Becker, S. Schröder, Universidade de Aveiro, Chemetall GmbH, EADS Deutschland GmbH and Mankiewicz Gebr. & Co. GmbH & Co. KG.

Business creation and new jobs
A small and medium-sized entreprises (SME) – SMALLMATEK (see http://www.smt.pt online) was created during MUST and its business activities are very much focused on nanomaterials production for improved durability of coated materials. This small and medium-sized entreprise (SME) created two full time equivalent jobs.

In addition MUST has created new jobs (at least two), by hiring 2 researchers to work at full time in the project development.

Exploitation plan
Preliminary exploitation plan was developed and delivered (18M). Basis for the development of the preliminary exploitation plan were implementation plan according to CORDIS guidelines and the Exploitation Strategy Seminar by Mauro Caocci, CIMATEC, ESS Coordinator. The preliminary exploitation plan identified the results with exploitation potential of the MUST project. The plan was continuously updated. R-TECH launched 2 surveys to collect and analyse interests, data and ideas concerning the possibilities for further deployment and exploitation of the MUST project outcomes.

1. From 37 exploitable results as most desired for exploitation indicated:
- Testing equipment and methods: Surface and electrochemical characterization (13 p)
- Nanocontainers with inhibitors (13 p)
- Nanotraps (13 p)
- Nanocontainers with water displacing /repelling agents (12 p)
- Pre-treatment and primer formulations Automotive applications (11)
- Self-healing anticorrosion coating systems for automotive application (10 p)
- Formulation for nanocontainer - based coating systems Aerospace application (10 p)

2. Tame to market
Despite the fact that in some cases additional development and validation work will still have to be done, some of the new technologies may already be implemented within 12-18 months after the termination of the project. Expected time frame for commercial exploitation - Average: 3 years

3. Foreseeable markets and estimation of competitors
- NC production and applications have small markets (mostly 1-5 competitors)
- For formulation for nanocontainer – based adhesive systems: competitors Dow Automotive, Henkel, EFTEC, Lord
- Application markets often have no competitors with nanocontainer technology
- Market size is generally "medium" for production and applications
- Methods and testing have competitors in top EU universities

4. Intended exploitation (exploitation claims)
- Production and commercialization: 59.5% exploitable results
- Internal use: 78.3% exploitable results
- License to 3rd parties: 35.1% exploitable results
- Provide services: 35.1% exploitable results

5. IPR Issues
IPR issues are regulated in MUST project in the following way:
- Joint ownership of foreground makes sense if the more beneficiaries have contributed to the foreground
- According to CA/GA of MUST the situation is quite flexible and simple at the moment:
Each of the joint owners can use foreground without obtaining consent of other owners as long as not otherwise agreed.
- Just:
Notification has to be made about licensing
Objection to licensing is possible within 4 week

6. Non-commercial Exploitation
- The promising results obtained during MUST will prompt further R&D activities in small, bilateral collaborations with some of MUST industrial partners towards development of systems for commercialization
- Further R&D in the field of systems/plants for surface pre-treatment and treatment
- Improvement of current coating systems and surface treatments to improve long term performance
- Further R&D test: transfer nanocontainers for other applications and systems
- Application of Nanocontainer Know -how to new formulation of coating systems
- Application of Nanocontainer Know-how to new functionalities of coating systems (Multifunctionalty)
- Further fundamental research on the functionality of additive filled nanocotainers in thin films
- By publishing high-quality papers about the MUST results, academic partners will obtain improved international visibility and improve their position
- Finally, it is foreseen that universities and research institutes will exploit the results by integrating them into their educational and training programmes, allowing more and better qualified engineers completing their master and PhD programmes
- Within MUST project 5 PhD Thesis and 5 Msc Thesis are completed 15 mobility tracks for students (Msc and PhD) betwen partners report

7. Patents and recommendations
- Part of the research and development work performed in MUST was incorporated directly in patents and recommendations.

8. New business opportunities
- University of Aveiro has created a spin-off company Smallmatek, Small Materials and Technologies, Lda (see http://www.smallmatek.pt online). This is a R&D Company that provides consultancy services and products in the field of coating technology, corrosion and nanocontainers. The main activity is monitoring, characterization and development of coatings for corrosion protection, using new and innovative nanotechnology solutions, including controlled release of active species from micro and nanocontainers. Some of the products may include LDH nanocontainers. This is probably a good vehicle to maximize the application of developed materials, processes and applications related to LDH systems.
- Contractually regulated collaboration between University of Aveiro and Chemetall GmbH

9. Possible new applications of MUST results
The Multi-level protection approach and MUST solutions will also open new opportunities for the application such as:
- Knowledge and contacts on incorporation of nanocontainers in adhesive formulations
- The topic of controlled release of active species from LDHs is promising for applications in other fields of coating technology and structural materials.
- Introduction on NC for other functionalities like erosion protection, self-cleaning, anti-icing.
- Application of MUST solutions for self-healing in damage protection of bulk materials.
- Further development in medicine, self-healing etc
- The coil coating lines, systems for temporary corrosion protection and primers are potential systems for the implementation of solutions boosted by the MUST achievements.
- Some partners involved in project proposals concerned with the application of Nanocapsules in the building field (cement production)

10. Exploitation Risks
Technological risks
- Lack of quality control of the NC production
- No reproducible results
- NC size is too high due to aggregates
- No stable dispersions
- Non homogeneous pre-treatment layer on the test panels
- Functionality for any commercial product is not proven yet for any system
- Outstanding demonstrator result
- Improvement of processing for up-scaling - Analysis of causes for scattering of performance - Reduction
- The scale up is still a limitation for some products
- Application process of self-healing products has still to be investigated and tested
- No obstacles are forecasted in the design and production of self-healing products applications systems.
Market risks
- Rapid drop of the coating market
- Existence of several worldwide suppliers of LDH materials for generic applications
- Potential costs associated with scale up of production of nanocontainers
- to find investors to support the exploitation at industrial scale
- to develop the market (the companies within MUST)

Partnership risks
- Protection of the technology
- Complex patent situation

Conclusion / remarks
Now that MUST project has ended, it can be concluded that MUST was very successful. Certain know-how, products, processes and tools developed in the MUST project have a high potential for future exploitation and usage in different applications for public (non-commercial) as well as commercial use.

For example, the promising results are:

- successful development of pre-treatments and primers
- e-coat and adhesives modified with smart additives for improved durability
- Nanocontainers and nanotraps for all four levels of protection are developed
- The concept of different healing mechanisms is proven in model coating systems
- Different level of technology readiness is achieved in the case various nanocontainers
- The synthesis of most promising nanocontainers are up scaled to 30 L batch without loss of performance
- Modelling
- Tools for risk assessment

The adequate exploitation activities will be carried out by the individual partners in such ways as they see fit and in accordance to the terms and conditions under which such activities may be performed

Relevant factors that set the basis for a good exploitation of MUST results are:

- Cooperation among strategic partners with complementary business role
- Experimental validation in lab trials, in order to get early feedback at the research stage
- Patent Applications in order to protect the innovative produced knowledge.

To maximize the exploitation high value was set on the following action points:

- Exploitation-oriented upgrade of the official MUST project website and partner web sites
http://www.sintef.no/Projectweb/MUST
http://must.risk-technologies.com
- Publishing of the MUST methodology and solutions in order to lay the foundation of potential commercial projects
- Participation at conferences, exhibitions, fairs and workshops, where the results of the project could be presented to business stakeholders and contacts for potential commercial projects could be built. 106 publications, 37 scientific publications, 55 conferences, 10 workshops
- It is foreseen that universities and research institutes will exploit the results by integrating them into their educational and training programs, allowing more and better qualified engineers completing their master and PhD programs
- Within MUST project 5 PhD Thesis and 5 Msc Thesis are completed
- 15 mobility tracks for students (Msc and PhD) between partners reported

Concluding statements
A network of industrial partners was created around MUST, leading to closer discussions between MUST consortium and those interested external companies.

Potential Impact:
1. Socio-economic impact and the wider societal implications of the project
The coating materials and materials systems that were developed in MUST are based on smart properties like controlled release on demand of inhibiting compounds and self-healing function reacting to different levels environmental excitation. These protection systems will provide for more sustainable components and give the chance for decreasing cost by reducing process steps during pre-treatment and in the paint shop independently of the specific type of transport industry. The results of the MUST project will directly enhance the economic success and competitiveness of industry. An additional indirect effect on competitiveness could be obtained through improvement of the environmental situation by saving energy consumption in the surface pre-treatment and painting processes and avoidance of hazardous compounds in the used materials and applied processes.

The results from MUST will contribute to improve the competitiveness of the European transport industries as summarized below:
- Effective and environmental friendly protective coatings for transport industry are available in sufficient time to fulfil existing and projected European, US American environmental regulations, thereby increase the sales of the coating suppliers and enhance the global market attractiveness of the vehicles.

- Lower weight of the coating system and higher amount of implementation of light weight substrates will further reduce operational costs by fuel consumption savings and decrease CO2 emissions.

- The multi-level approach will decrease production costs by reducing process steps during pre-treatment and the paint shop. There is also the potential for simpler and faster processes, lower amount of waste and facilitation of multi material treatment. Depending on the complexity of the protection scheme to be replaced, the manufacturing cost for the coating application can be considerably reduced up utilizing micro- and nanocontainers with reasonable costs.

- The increased application of improved long term stable adhesives to the body in white will enhance the passive safety by increase the fatigue stability, stiffness and the crash performance.

- The application of self-healing and long-term sustainable protection system offers the chance to increase service life of the futures vehicles. Improved sustainability will reduce maintenance cost by fewer amounts of repair charges and extended inspection intervals in service. Reduction on maintenance costs of 20-30% per vehicle is achievable.

Environmental impact:
- Replacement of less environmental-friendly technologies with more intelligent systems with environmental friendliness. (Expected in less than 5 years).
- Reducing of material waste losses due to improved service lifetime and reduced corrosion activity. (Expected in 5-10 years).
- Safer working conditions (Expected in less than 5 years).
- CO2 emission reduction due to savings in materials for pre-treatments and paints (Expected in less than 5 years).

A social impact on improving the quality of life to European citizens is expected as well:
- Contribution to "quality of life" due to amending of current ecological situation and dissemination of green technologies. (Expected in 1-4 years).
- Contribution to the prevention of man-caused environmental disasters, improving safety. (Expected in 5-10 years.
- The novel technologies in perspective can create the new jobs in respective industries increasing employment. Expected in less than 5 years.

2. Main dissemination activities
The dissemination strategy of MUST envisaged at reaching a broad range of audiences, including the scientific and industrial communities, the general public and the key decision makers. All the partners have been encouraged to be involved in the dissemination activities. Specifically, the partners were committed to present the project results in conferences, info-days and other dissemination events; to participate in workshops, to prepare scientific papers for conference presentations or journals, to contribute for the web-site contents, to be involved in training and formation of researchers and to highlight the project results.

2.1 Electronic dissemination
The MUST web portal (see http://www.sintef.no/Projectweb/MUST online) highlights the project objectives, achievements and relevant events that were organized. In addition to this portal, several partners have created advertisements in the web pages of their institutions, thus creating additional branches for the project dissemination. Targeted to a large array of audiences, with a high visual impact and a clear and concise language, the MUST video, will increase the awareness of the project.

2.2 Education and training
Mobility of researchers, at the doctoral and post-doctoral level has been implemented in MUST. This strategy contributed for educating and training high-level researchers, more capable of contributing effectively for the implementation of the R&D and technical activities developed in MUST, supporting the EU research effort.

Six training courses were organized within MUST, both by the R&D and industrial partners:
1. Electrochemical Impedance Spectroscopy, Lisbon, November 6-7 (MUST AND MULTIPROTECT) – IST + UAVR
2. Cleaning and Pre-treatment technology, March 9-10 – IST + CHEMETALL
3. Risk analysis – IST + STEINBEIS R-TECH , March 11, 2009
4. LbL of nanocontainers – IST + MPI, October 15-16
5. Adhesion and related characterization techniques, University of Paderborn, September 2010.
6. Adhesives and its testing - SIKA AG Zurich March 16-17 2011.

2.3 Recommendation and guidelines
EADS and Chemetall created data pools for collecting all the data gathered in the various tests performed on aeronautic and automotive materials, respectively.

R-Tech created a database repository for SDSes (safety data sheets) in ENM. Currently, there are 157 SDS stored in the database. SDSes of the nanocontainers were requested from the project partners. In addition, MUST WP3 meeting in Leverkusen identified the nanocontainers required for the database. SDSes in the database are classified into 5 categories: Nanocontainers from the MUST project partners (9), Primary nanomaterials from the external sources, Functionalized nanomaterials from the external sources, Products contained nanomaterials and other.

2.4 Patents
The MUST exploitation strategy was successfully represented in 5 patent applications: Preliminary patent application (Nr. 106256): "Process for coating metallic surfaces with coating compositions containing particles of a layered double hydroxide", M.G.S. Ferreira, M. Zheludkevich, J. Tedim, V. Gandubert, T. Schmidt-Hansberg, T. Hack, S. Nixon, D. Raps, D. Becker, S. Schröder, Universidade de Aveiro, Chemetall GmbH, EADS Deutschland GmbH and Mankiewicz Gebr. & Co. GmbH & Co. KG.

2.5 Business creation and new jobs
A small and medium-sized entreprise (SME) – SMALLMATEK (see http://www.smallmatek.pt online) was created during MUST and its business activities are very much focused on nanomaterials production for improved durability of coated materials. This small and medium-sized entreprises (SME) created two full time equivalent jobs.

3. Exploitation of the results
Preliminary exploitation plan was developed and delivered (18M). Basis for the development of the preliminary exploitation plan were implementation plan according to CORDIS guidelines and the Exploitation Strategy Seminar by Mauro Caocci, CIMATEC, ESS Coordinator. The preliminary exploitation plan identified the results with exploitation potential of the MUST project.

1. From 37 exploitable results as most desired for exploitation indicated:
- Testing equipment and methods: Surface and electrochemical characterization (13 p)
- Nanocontainers with inhibitors (13 p)
- Nanotraps (13 p)
- Nanocontainers with water displacing /repelling agents (12 p)
- Pre-treatment and primer formulations Automotive applications (11)
- Self-healing anticorrosion coating systems for automotive application (10 p)
- Formulation for nanocontainer - based coating systems Aerospace application (10 p

2. Time to market
Despite the fact that in some cases additional development and validation work will still have to be done, some of the new technologies may already be implemented within 12-18 months after the termination of the project. Expected time frame for commercial exploitation - Average: 3 years

3. Foreseeable markets and estimation of competitors

- NC production and applications have small markets (mostly 1-5 competitors)
- For formulation of nanocontainer – based adhesive systems: competitors Dow Automotive, Henkel, EFTEC, Lord
- Application markets often have no competitors with nanocontainer technology
- Market size is generally "medium" for production and applications
- Methods and testing have competitors in top EU universities

4. Intended exploitation (exploitation claims)
- Production and commercialization: 59.5% exploitable results
- Internal use: 78.3% exploitable results
- License to 3rd parties: 35.1% exploitable results
- Provide services: 35.1% exploitable results

5. IPR Issues
IPR issues were regulated in MUST project in the following way:
- Joint ownership of foreground makes sense when several beneficiaries have contributed to the foreground
- According to CA/GA of MUST the situation is quite flexible and simple at the moment:
Each of the joint owners can use foreground without obtaining consent of other owners as long as not otherwise agreed.
- Just: Notification has to be made about licensing. Objection to licensing is possible within 4 weeks.

6. Non-commercial Exploitation
- The promising results obtained during MUST will prompt further R&D activities in small, bilateral collaborations with some of MUST industrial partners towards development of systems for commercialization
- Further R&D in the field of systems/plants for surface pre-treatment and treatment
- Improvement of current coating systems and surface treatments to improve long term performance
- Further R&D test: transfer nanocontainers for other applications and systems
- Application of Nanocontainer Know -how to new formulation of coating systems
- Application of Nanocontainer Know-how to new functionalities of coating systems (Multifunctionality)
- Further fundamental research on the functionality of additive filled nanocontainers in thin films
- By publishing high-quality papers about the MUST results, academic partners will obtain improved international visibility and improve their position
- Finally, it is foreseen that universities and research institutes will exploit the results by integrating them into their educational and training programmes, allowing more and better qualified engineers completing their master and PhD programmes
- Within MUST project 5 PhD Thesis and 5 Msc Thesis are completed 15 mobility tracks for students (Msc and PhD) between partners report

7. Patents and recommendations
- Part of the research and development work performed in MUST was incorporated directly in patents and recommendations.

8. New business opportunities
- University of Aveiro has created a spin-off company Smallmatek, Small Materials and Technologies, Lda (see http://www.smallmatek.pt online). This is a R&D Company that provides consultancy services and products in the field of coating technology, corrosion and nanocontainers. The main activity is monitoring, characterization and development of coatings for corrosion protection, using new and innovative nanotechnology solutions, including controlled release of active species from micro and nanocontainers. Some of the products may include LDH nanocontainers. This is probably a good vehicle to maximize the application of developed materials, processes and applications related to LDH systems.
- Contractually regulated collaboration between University of Aveiro and Chemetall GmbH

9. Possible new applications of MUST results
The Multi-level protection approach and MUST solutions will also open new opportunities for the application such as:
- Knowledge and contacts on incorporation of nanocontainers in adhesive formulations
- The topic of controlled release of active species from LDHs is promising for applications in other fields of coating technology and structural materials.
- Introduction on NC for other functionalities like erosion protection, self-cleaning, anti-icing.
- Application of MUST solutions for self-healing in damage protection of bulk materials.
- Further development in medicine, self-healing etc.
- The coil coating lines, systems for temporary corrosion protection and primers are potential systems for the implementation of solutions boosted by the MUST achievements.
- Some partners involved in project proposals concerned with the application of Nanocapsules in the building field (cement production)

10. Exploitation Risks
Technological risks
- Lack of quality control in NC production
- Non reproducible results
- NC size often is too high due to agglomeration
- Unstable dispersions
- Non homogeneous pre-treatment layers when applied on metallic substrates
- Functionality for commercial products not effectively proved the developed systems
- Outstanding demonstrator results
- Improvement of processing for up-scaling - Analysis of causes for scattering of performance - Reduction
- The scale up is still a limitation for some products
- Application process of self-healing products has still to be investigated and tested
- No obstacles are forecasted in the design and production of self-healing products applications systems.

Market risks
- Rapid drop of the coating market
- Existence of several worldwide suppliers of LDH materials for generic applications
- Potential costs associated with scale up of production of nanocontainers
- to find investors to support the exploitation at industrial scale
- to develop the market (the companies within MUST)

Partnership risks
- Protection of the technology
- Complex patent situation

4. Concluding remarks
Now that MUST project has ended, it can be concluded that MUST was a very successful project. Certain know-how, products, processes and tools developed in the MUST project have a high potential for future exploitation and usage in different applications for public (non-commercial) as well as commercial use.

For example, the promising results are:
- Successful development of pre-treatments and primers
- e-coat and adhesives modified with smart additives for improved durability
- Nanocontainers and nanotraps for all four levels of protection are developed
- The concept of different healing mechanisms is proven in model coating systems
- Different level of technology readiness is achieved in the case various nanocontainers
- The synthesis of most promising nanocontainers are up scaled to 30 L batch without loss of performance
- Modelling
- Tools for risk assessment
- An exceptional level in terms of scientific publications
The adequate exploitation activities will be carried out by the individual partners in such ways as they see fit and in accordance to the terms and conditions under which such activities may be performed

Relevant factors that set the basis for a good exploitation of MUST results are:
- Cooperation among strategic partners with complementary business role
- Experimental validation in lab trials, in order to get early feedback at the research stage
- Patent Applications in order to protect the innovative produced knowledge.

To maximize the exploitation high value was set on the following action points:
- Exploitation-oriented upgrade of the official MUST project website and partner web sites
http://www.sintef.no/Projectweb/MUST
http://must.risk-technologies.com
- Publishing of the MUST methodology and solutions in order to lay the foundation of potential commercial projects
- Participation at conferences, exhibitions, fairs and workshops, where the results of the project could be presented to business stakeholders and contacts for potential commercial projects could be built. 101 communications in conferences and workshops and41 scientific publications in peer reviewed journals.
- It is foreseen that universities and research institutes will exploit the results by integrating them into their educational and training programs, allowing more and better qualified engineers completing their master and PhD programs
- Within MUST project 5 PhD Thesis and 5 Msc Thesis are completed
- 15 mobility tracks for students (Msc and PhD) between partners reported

List of Websites:
http://www.must-eu.com

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