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Plasma And Nano for New Age “soft” conservation

Final Report Summary - PANNA (Plasma And Nano for New Age “soft” conservation)

Executive Summary:
Cleaning and preservation of CH assets must take into account a variety of substrates. This includes stone, metal and mural paintings, and a variety of undesired 'dirt' layers such as soot, graffiti, corrosion products, oil paint, natural varnishes and finally aged polymers. Although a wide range of organic and inorganic protective coatings exist, most cannot be removed, without damaging, with sustainable methods such as dissolution with organic solvents or laser ablation. Thus, when they no longer serve their purpose, options for continued preservation are limited.

The EU project PANNA 'Plasma And Nano for New Age "soft" conservation' started on November 2011 and concluded in October 2014, addressed these issues and developed a technology facilitating surface cleaning, protective coatings deposition and their subsequent removal, introducing for the first time a fully reversible restoration “full-life” protocol.

The “full-life” protocol bases on a new technology, as the atmospheric plasma, and on novel hydrophobic coatings, self-diagnostic and easily removable by plasma.
The technology development has been constantly supported by Cultural Heritage applications testing in particular on stone and metal materials as well as mural paintings.

The project started with testing five different commercial plasma torches for cleaning applications in CH (WP3). The results highlighted that principal drawbacks can be the deposition of metal melted droplets coming from the electrodes, or high substrate temperatures reached during the treatments (even hundreds of degrees) or a too long treatment times. Thanks to this experimentation a new portable prototype plasma jet have been fulfilled (WP1) that allows the removal of organic substances or the reduction of metal corroded layers in a “green” and contactless way, without any thermal, mechanical or chemical harming of the artefacts. Moreover the new device can deposit protective coatings (WP4) and invisible tags for identification and prevention of counterfeiting with a fluorescent precursor (WP7). The device has been patented and is already available on the market. On the other side new hydrophobic coatings with solvent, water-based or UV-curing matrices have been developed guaranteeing their full and easy removal by atmospheric plasma (WP2). To the matrices fluorescent organic and inorganic dyes have been added (WP5) in order to achieve self-diagnostic properties with a twofold aim: monitor coating ageing with long lasting UV-responsive pigments and quality control just after application with short-life dyes. Also the coatings are now already available on the market. All the different developed solutions have been finally tested in Cultural Heritage applications, including case studies (WP8).

All the new technologies developed and their applications have been summarised in the “full-life” protocol demonstrator. Moreover the demonstrator has been equipped with manuals and operation protocols. The demonstrator has been used during the last year of the project to improve the awareness and knowledge of PANNA developments through the organisation of training workshop in all the partners’ countries (WP9). The LCA of the developed “full-life” protocol has shown an improvement to standard methodologies avoiding the use of solvents. Moreover it has been verified that the new plasma jet can be used in open air without any risk for the operator.
The good results obtained in the project prove the strong involvement of all the partners with a successful coordination (WP10). The results and activities of the project are also available on the website.

Project Context and Objectives:
In spite the wide range of technologies and materials available for Cultural Heritage restoration, restorers are always facing challenging case studies where it is difficult to preserve the original artefact, assuring it a long lasting protection in a compatible way. Causes of the need of artefacts restoration can be intrinsic due to the deterioration process of the materials itself or due to external factors as conservation environment or previous restoration processes or use or vandalism.

The modern restoration policy tries to reduce as much as possible the application of materials for protection and try to preserve the artefacts mainly by environment and exposure control and monitoring. Often these solutions are not sufficient and must be supported with intervention on the artefacts such cleaning processes or surface protection.

The PANNA project aimed to offer to restorers an innovative restoration protocol, named “FULL-LIFE” PROTOCOL, which allows cleaning and preserving the artefact with long-lasting and low-cost solutions assuring their full removability. The proposed “full-life” protocol therefore is fully reversible and guarantees the complete compatibility with the artefacts. The “full-life” protocol is formed by the following steps:

step 1. Surface cleaning
step 2. Surface protection
step 3. Protection coating removal

The “full-life” protocol bases on the introduction of a new technology and new materials, which enable its unique features:

• new technique → atmospheric plasma
• new materials → self-diagnostic coatings, identification markers

Step 1 – Surface cleaning
The atmospheric plasma allows a chemical action on surfaces in dry and contactless environment at room temperature. It is able to remove organic materials or reduce corrosion layers on metals. The operation can be done also in-situ.

Step 2 – Surface protection
Due to the implementation of a suitable atmospheric plasma device, different coating matrices become removable and therefore suitable for CH applications. Therefore new coatings solvent-based, water-based and UV-curing can be developed with improved hydrophobic and protection features. To these long-lasting matrices the self-diagnostic feature can be introduced enabling the long term easy monitoring of coating efficiency or the quality control of the coating application. The coating can be applied by brush or by the atmospheric plasma device itself.

Step 3 – Protection coating removal
The atmospheric plasma enables an easy removal of the applied coatings recovering the unprotected original surface of the artefacts. All the proposed technologies act only on surfaces with a nanometre range interaction, therefore allow the “full-life” protocol to be intrinsically “gentle”, easy to control and designed exclusively for surface treatments.

In addition to this whole reversible restoration process the “full-life” protocol offers also the possibility to invisibly mark the surface with a fluorescent ink by means of the atmospheric plasma device in order to allow artefacts identification.
In order to achieve these goals offered by the “full-life” protocol each technology and new material in the PANNA project had specific objectives.

The atmospheric plasma technology is spreading in different industrial sectors from the late nineties. Nowadays there are different commercial torches and every one has peculiar features. The project aimed to construct a portable plasma torch prototype with a specific design for Cultural Heritage artefacts treatments, avoiding any drawback that can be present in the commercial ones.
The atmospheric plasma device is expected to work contactless, involving exclusively chemical reactions at the surface. Therefore it was expected to respect the following requirements:

1. Applicable to any surface even temperature sensitive (T < 50°C);
2. No electrodes deposition on the substrate;
3. DBD RF-plasma design;
4. Removal rate or cleaning costs compatible but controllable by operator ;
5. Suitable for localised treatment by the restorer;
6. Suitable for in-situ operation (portability).

Moreover the new device must be able also to deposit coating for surface protection or the identification marker. Therefore the plasma device must include:

7. Vapour and aerosol precursors feeding;
8. Suitable to deposit organic and inorganic coatings;
9. Suitable for the deposition of nanocomposites;
10. Final cost compatible with the CH market.

The main objective of these new coatings is to allow instant checking of the presence and the functionality of a protective coating just by an on-site measurement (long-term) or the correct application of the coating itself (short-term). This improvement relative to standard protection coatings will allow firstly the a conservation cost reduction due to expensive preliminary assessment for maintenance work, and subsequently no impact on site touristic accessibility and increase in monitoring points.
The protective coatings must be designed in order to possess requisites such as:

• Features comparable with commercial protective coatings (transparent and hydrophobic, controlled or designed barrier properties
• Must be removable via plasma torch with no damage on substrate;
• Applicable via brushing;
• Easy application on artefacts of different size;
• Easy reading of the presence of the coating;
• Easy reading of the aging state of the coating.

The development of the coating was based on the development of new matrices solvent-based, water-based and UV-curing with improved hydrophobic and barrier features also by the addition of additives and nanoparticles. On the other side the self-diagnostic feature must be not responsive in the visible range and therefore photo-luminescent additives or pigments are considered for an easy inspection.
The different matrices and additives, also for the detection point of view, have been considered in order to offer customised solutions as a function of the artefacts substrate. The coatings can be deposited by brushing and some formulations also by atmospheric plasma.

The objective of this new material is to allow the possibility of marking directly the Cultural Heritage artefacts by means of an inorganic coating fully transparent in the visible range but visible under UV illumination. The reduced spot size of the plasma deposition allows also a “writing” capability. The inorganic nature of the coating assures its wear resistance and its unalterable behaviour.
In order to obtain such coatings by Plasma torch, a silica precursor with stably dispersed fluorophores nanoparticles or molecule will be used in the feeding for the deposition.
This particular identification marking coating allows:

• transparent labels in visible range;
• millimetre size labels;
• a first security level given by the specific spectral emission of the fluorophores mixing used;
• a second security level and label clarity given by the possibility to write a text or a picture;
• a easy and cheap reading of the label: just a UV lamp and a hand lens.

In order to develop new technologies and materials and to guide the development itself a continuous testing in Cultural Heritage is needed to have a leading feedback. This methodology was adopted through the whole process considering also ageing tests. The field of Cultural Heritage conservation is very complex due to the wide range of artefacts or buildings, their forming materials and deterioration states and kinetics, depending also from the environment and referring age. Therefore in the project the development and testing of the protocol is restricted on 2 categories of substrates of interest for Cultural Heritage conservation:

• Metals (Bronze and Silver)
• Stone and stone-like materials (Limestone, Marble, Sandstone and Wall paintings)

On selected samples and deterioration mechanisms of these 2 categories were therefore tested the long-term behaviour of the new materials and of the atmospheric plasma technique. Their performances compared to standard procedures were evaluated. The development was performed on laboratory mock-up samples and also on real cases, when available.
In particular for the atmospheric plasma, a careful testing of the performances of 5 commercial plasma torches was the bases for the new prototype device development.

In order to make the “full-life” protocol accessible and ready for use at the end of the project and in order to allow PANNA results exploitation, all the needed tools to foster this process were inserted in the objective of the project.
All the new technologies and their application are included in the “full-life” protocol demonstrator. The demonstrator is provided with application protocols for at least 1 specific case for each substrate considered. The demonstrator was used through the organisation of training workshop in all the partners’ countries: Italy, Bulgaria, Belgium and Germany. Using this instrument, restorers and policy makers became aware of the new possibility offered by PANNA developments, making also trials on real cases that they carried to the workshop during the practical sessions.
Moreover case studies must be presented in order to show the “full-life” protocol performances in real cases. This activity aimed to improve also the connection and the involvement of the policy makers in the experimentation of these new technologies and materials.
In order to allow a prompt exploitation of the results after the project the demonstrator must be equipped with manuals and operation protocols for restorers in order to guide their use. Moreover the operational safety of the new technology had to be assessed also for the operators and for the environment with an LCA.

With the aim to fulfil all the project objectives the partnership was designed in order to cover all the aspects of the PANNA project. The partnership was formed by an important European consortium consisting of 9 partners coming from 4 different European countries, with a strong participation of the SMEs.

Veneto Nanotech ScpA Research center
IENI-CNR Research center
Rathgen Forschungslabor - Staatliche Museen zu Berlin Research center
University of Antwerp Research center
Nadir srl SME
Lorenzon Costruzioni srl SME
Center for Restoration of Art Works SME
Botega Z SME
Chemstream bvba SME

The partners represent very high skill experts from atmospheric plasma technology (NDR, VN), chemical coatings development (Chem, VN), CH materials characterization and new solutions development from a chemical point of view (IENI), leading experts from material science (VN, IENI), nanotechnologies (VN), CH conservation research public laboratories (AHA, RRL), conservation operators (CRA, LRZ, BTZ).
An added value of this project was also the strong participation of SME’s as Cultural Heritage operators and as technological R&D companies, which assure the possibility to scale the project to the market starting from the production point of view up to the end users.

Project Results:
The PANNA project successfully achieved all its objectives.
The ‘full-life’ protocol has been realised in all its technological aspects as the atmospheric plasma torch that fully fits the CH requirements, the self-diagnostic protective coatings and their full removal leaving the surface as it was before the protective treatment. The “full-life” protocol has been summarised physically in a demonstrator also with mock-up samples in order to show its operation and it has been widely used in the training workshops organised in the participating countries. The dissemination activity and the interest in the new technologies has been so relevant to increase the experimentation also outside the PANNA partnership, involving high level CH restoration centres as Laboratoires de Recherche des Monuments Historiques, Musei Vaticani and Central Laboratory for Restoration & Conservation in Istanbul. Moreover new events more than the planned ones have been asked to be organised as the one in Venice from the Soprintendenza Speciale per il Polo museale veneziano that demonstrates the successful involvement of the policy makers. The plasma cleaning has been also introduced in the new draft of the Italian stone cleaning standard.

One of the main results of the PANNA project is for sure the successful development of the atmospheric plasma jet by Nadir that has led also to its patent application. The particular design allows a good efficiency of the plasma keeping the temperature lower than 50°C and avoiding any metal deposition on the surface. These features allow a fully controllable operation by the restorers in complete safety conditions for the artefacts. The plasma cleaning has been tested to be successful in:

• Full removal of organic protective coatings also aged, i.e. acrylics (Paraloid®), epoxies, parylene, graffiti and animal glues;
• Fast surface activation and de-polymerisation of cross-linked aged polymers for a faster and easier removal with no toxic and less hard solvents;
• Controlled and compliant cleaning at the interface of organic coatings;
• Reduction of corrosion product on silver, silver alloys, brass, iron also on archaeological artefacts;
• Reduction of corrosion products on metal wires in textiles;
• Plastics yellowing removal;
• Removal of biological patinas including those produced by endolithic organisms;
• Removal of stains from paper.

The experimentation included also trials not foreseen in the project planning but performed thanks to the different collaborations developed during the project with several CH related institutions and SMEs. The substrates considered by the PANNA project have been stone, metals and mural paintings but the atmospheric plasma has shown interesting potentialities also on paper, leather and textiles although further experimentations are needed. The treatment in all the considered cases has shown to be no harmful for the artefacts, except for the lead-based pigments that have shown to be sensitive changing in colour as an effect of the plasma treatment.

Also the self-diagnostic protective coatings have been successfully developed using different matrices. In fact the use of the atmospheric plasma for coating removal allows the use of matrices at the moment not accepted in the CH field as the UV-curable. Three different matrices have been used: solvent based, water based and UV-curing. All the developed products show equal or better performance relative to the benchmark in contact angle (from 105° up to 130°) or in barrier performances (for metals), but at the same time they showed a guaranteed removability by atmospheric plasma. In particular the protective coating on silver can be removed by plasma without any oxidation of the surface. The choice on which coating have to be applied depends on the artefacts:

• Stone protection: solvent-based (CHEM1, CHEM3), water-based (Water2)
• Wall paintings: solvent-based (CHEM3), water-based (Water1, Water2)
• Metals: solvent-based (CHEM2), UV-curable (UV1, UV2)

To these high performance matrices the self-diagnostic feature has been added by the introduction of organic dyes and inorganic pigments without affecting the matrices properties. The best concentration of the fluorescent agent has been studied in order not to alter the colours but at the same time to be visible when needed. During the project several observations during the dissemination activities highlighted a difficulty for restorer to accept a fluorescent activity on the protective coating. Therefore the focus has been changed on selecting also short life dyes in order that the fluorescent activity can be used to check the correct application of the coating itself, as a quality control feature, but assuring a decay of the activity itself after few hours.
All these features integrated in the ‘full-life’ protocol are available as a demo-video on youtube (

Last technology development is the identification marker coating. As foreseen in the project the atmospheric plasma jet is able also to deposit coating and nano-composites by aerosol precursors feeding. This peculiar feature has allowed to successfully deposit the identification marker that is in fact an inorganic ceramic transparent coating with fluorescent features obtained by the deposition of silica embedding fluorescent dyes. It becomes therefore possible mark the surface in an invisible way by using the plasma torch at room temperature with an inorganic highly wear resistant ink. This cataloguing option seems to be interesting for restorers and museums as also confirmed by the Soprintendenza di Venezia restorers.

All these technological developments and the ‘full-life’ protocol implementation have been possible and have gained so much interest in the CH field also thanks to the continued testing of the developed solution in mock-up samples and case studies carried on by the restorers SME and research centres involved in the project. On different stone substrates, mural paintings as egg tempera and frescos and metals such as silver, silver alloys, brass and bronze the technologies have been widely tested giving also feedback to the developments. In some cases some deeper investigation has been also proposed with synchrotron radiation in order to better understand the mechanisms that are involved in the cleaning procedures. In order to investigate their application the following case studies have been faced:

• Removal of graffiti from vandalized statues in Prato della Valle in Padova (italy)
• Removal of aged protective coatings from wall paintings in S. Giorgio church in San Polo di Piave (Italy)
• Removal of black crust from Istria stone from Palazzo Ducale in Venice (Italy)
• Cleaning of aged varnishes from 18th century Russian icon (Bulgaria)
• Corrosion layers removal on silver plated waiters tray 1900 (Bulgaria)
• Soot removal in St. Alexander Nevsky Patriarchal Cathedral Stauropigial Memorial-Church in Sofia (Bulgaria)
• Cleaning of tarnishing on a Daguerreotype and the reduction of silver on glass negatives (Belgium)
• Removal of soot in St. Marina church in Veliko Tarnovo (Bulgaria)
• Removal of soot in Holy Assumption of the Virgin Mary monastrey church (17th century) in Arbanassi (Bulgaria)
• Removal of oil-overpaintings in St. George church in Golyamo Belovo (Bulgaria)
• Corrosion layers removal on “W. F. M.” Silver-plated cup – 1900 (Bulgaria)
• Corrosion layers removal on late 19th century French Gothic silver Paten (Ag 800 w%) (Bulgaria)
• Corrosion layers removal on 20th century (1950s) Bulgarian brass Lock (Cu/Zn 64/36 w%) (Bulgaria)
• Removable self-diagnostic coating application in Chiesa Madonna dei Broli a Farra di Soligo (Treviso) (Italy)
• Removable self-diagnostic coating application in Palazzo Costa in Venice (Italy)
• Removable self-diagnostic coating application in S. Giorgio Church in San Polo di Piave (Italy)

These briefly summarised foreground results have been achieved by a careful execution of all the planned activities of the PANNA project. In order to improve partners’ collaboration and keep the project schedule in time a meeting has been organised every 6 months and project management activities has been strictly followed (WP10). The workflow of the project is here below summarised.
The project started with testing five different commercial plasma torches for cleaning applications in CH (WP3). The results highlighted the following principal drawbacks: the deposition of metal melted droplets coming from the electrodes, the high substrate temperatures reached during the treatments (even hundreds of degrees) or a too long treatment time. Thanks to this experimentation a new portable prototype plasma jet have been developed (WP1) for surface cleaning. Moreover the new device can deposit protective coatings (WP4) and invisible tags for identification and prevention of counterfeiting with a fluorescent precursor (WP7). The device has been patented and is already available on the market. On the other side new hydrophobic coatings with solvent, water-based or UV-curing matrices have been developed guaranteeing their full and easy removal by atmospheric plasma (WP2). Fluorescent organic and inorganic dyes have been added to the matrices (WP5) in order to achieve self-diagnostic properties with a twofold aim: monitor coating ageing with long lasting pigments and quality control just after application with short-life dyes. Also the coatings are now already available in the market. The developed solutions have been finally tested in the end in Cultural Heritage applications also in case studies (WP8).
The last year of the project has been dedicated to disseminate the results, enhance the visibility of the project and the involvement of other research centres and policy makers, and to provide manuals, application protocol, risk analysis and safety datasheet of the ‘full-life’ protocol and of the developed technologies (WP9). These activities are essential to give a chance to the exploitation of the project results.
Here below we briefly summarise the activities of WP of the PANNA project highlighting their main results, which leaded to the final success of the project.

WP3 regarded the experimentation and evaluation of commercial atmospheric pressure plasma torches for cleaning purposes on stone and metal materials, as well as mural paintings substrates. For each kind of substrate the most representative undesired “dirt” layers have been identified as production procedures for the mock-up samples and common characterisation techniques. In particular different “dirt” materials have been chosen for the different substrates:

• Serena Sandstone:Black crust, Acrylic polymer (Primal AC33)
• Carrara Marble: Siloxane (Silres BS 280), Graffiti (Deco Matt, Dupli color – Acrylic binder)
• Istria limestone: Epoxy polymer (Araldite), Graffiti (Deco Matt, Dupli color – Acrylic binder), black crust
• Egg tempera & Fresco: Soot, Oil-paint, Whitewash
• Silver and alloys: Oxides, Sulphides, Acrylic polymer (Paraloid ® B72)
• Copper alloys: Oxides, Sulphides, Chlorides, Wax (Cosmoloid H80), Acrylic polymer (Paraloid® B72)

Five different commercial plasma torches with different features have been chosen in order to verify advantages and drawback of each atmospheric plasma technology in the cleaning tests. In particular the following plasma torches have been selected:

• Kinpen from Neoplas, DBD configuration, 1.1 MHz, 8W, Ar/H2 (95/5), Ar/O2 (98/2), compressed air
• PlasmaSpot from Vito, DBD configuration, 70 kHz, 250W, He/H2, N2/H2, Ar/O2, compressed air
• PlasmaPen from PVATePla, Arc discharge configuration, 100W, compressed air, O2
• MEF-plasma from Tigres, Arc discharge configuration, 250W, compressed air
• Openair® from Plasmatreat, Arc discharge configuration, 700-1700W, compressed air, N2, or N2/H2

Major differences between these commercial devices are the power and the electrodes configuration in the device: dielectric barrier discharge (DBD) or arc discharge. Both parameters play an important role on the obtained results.

Removal of organic layers
Organic layers can be removed from the substrate through their complete oxidation with oxygen containing atmosphere by all the plasma devices with satisfactory results.
- Soot can be removed from wall paintings. Even if the technique is less efficient as traditional ones (e.g. Akapad), the thin plasma plume and handable equipment enables a contactless and accurate cleaning, where pores can be reached. A particular attention has to be given in the knowledge of the underneath paint layer, as some pigments are sensitive to oxidation: depending on the exposure conditions, yellow ochre can turn red, due to the dehydroxylation of Goethite [α-FeOOH] into Hematite [α-Fe2O3]. The change in colour of the yellow ochre can be observed only with arc discharge torches that induce a temperature increase higher than 100°C on the treated surfaces. As quality of the cleaning results:
o the Akapad mechanical cleaning show a partial removal also of the pictorial layer and soot remains in the pores;
o the solvent cleaning partially solubilise the soot layer leaving the cleaned surface a little bit greyish final colour
o the atmospheric plasma leaves the surfaces with brighter colours and fully remove the soot also in the pores without affecting the morphology, but the cleaning procedure needs minutes relative to seconds of the other techniques.
- Organic polymers used as coatings on stone objects as well as graffiti paint are removable using oxidative plasma. By plasma epoxy resin, several acrylic polymers and a microcrystalline wax have been removed also after ageing. General characteristic is that plasma torches using an arc discharge ignition system are much more powerful and allow insofar a viable cleaning. Nevertheless, this type of equipment presents an important drawback: the erosion of the central electrode leads to a deposition of metal particles on the treated surfaces. Another drawback of the arc discharges is the increase of the surface temperature that leads to the melting of the polymer layer. The melted polymer can therefore penetrate in the material or can be spread on the surface. On the other side commercial DBD torches show in some cases very low removal rate and therefore are not suitable for the application due to the long treatment times and therefore high costs. However, a combination of plasma with solvent treatment could enhance the removal of graffiti from stone, as well as the removal of naturally aged oil over-paint on wall paintings.
- Arc discharge treatments have shown to facilitate the removal of whitewash. After the treatment of the aged whitewash layer on mural painting, the whitewash was easily removable mechanically.
- The removal of polymers from the metal has been shown to be successful using oxidative atmosphere but oxidation of the substrate can arise in particular with arc discharge device. The removal without substrate oxidation can be obtained in reducing atmosphere.
- The treatment of black crust has shown to be ineffective if not harmful as the thermal effect prevails over the chemical one. In fact as a consequence of the plasma action, gypsum turns to gypsum emihydrate, that is highly sensitive to water and can be easily hydrated back to gypsum with possible deleterious effects on the surface. To overcome this problem, interesting result has been obtained by the combination of the application of cyclododecane and a following plasma treatment. The plasma treatment enhances the evaporation of the cyclododecane allowing a mechanical action effective for the removal of the gypsum itself.

Treatments of inorganic layers
- The Si-O-Si linkage of the silicon-based organic polymers (siloxane) is chemically too strong to be breakable with plasma. A removal of these materials is insofar not possible. The action of the plasma has only an effect on the side chain of the polymers (oxidation), which are responsible for the hydrophobic properties of the coating. Therefore the final effect of the plasma action turns out in a hydrophilic surface and therefore allows further treatments with compatible conservation materials but does not remove the siloxane backbone itself.
- Using plasma in a reductive atmosphere, silver sulphides, silver oxides, copper sulphides and copper oxides can be reduced. The efficiency of the reduction in particular on copper is strongly affected by the temperature. A threshold of about 100°C for copper reduction is identified therefore arc discharge plasma seems to be more effective in alloys cleaning. In fact the silver is the only metal that has an exothermic reaction for its reduction. For all the other metals as can be found also in literature the reduction process is endothermic therefore energy threshold for their activation arise. Moreover the reduction process, if the corroded layer is thick, leaves a rough surface due to the corrosion process itself. The reduction of the corroded layers is guided therefore Plasma can also be used for the treatment of gelatine glass negative or daguerreotypes. The reduction process and morphology changes have been studied also by synchrotron radiation XPS at ELETTRA and EXAFS analysis at ESRF.
- Titan dioxide (TiO2) is present is most of graffiti paints as a filler. If the binder and colorant can be oxidised by plasma, a dry tissue can be easily use to wipe the remnant TiO2 on the surface. This effect is present in all the organic coatings with filler, as are also the inorganic pigments. Therefore in pictorial layer treatment even if it doesn’t change in colour since the pigments are not affected by the treatment, it affects the binder that is removed. Therefore the restorers have to control when to stop the cleaning process.

General conclusion
- Atmospheric plasma has shown to be effective in the cleaning of the surfaces both in oxidation and in reduction mode.
- Arc discharge devices are faster and more effective in their chemical action but enhance the surface temperature of the artefacts during the treatment to more than 100°C. Moreover the electrode erosion provokes a deposition of metallic particles on the treated surface. Even if the deposition is not always visible at naked eye, this aspect prevents the use of plasma as cleaning device for CH assets.
- DBD plasma devices do not damage the artefacts but show very low rate processes. On metal surfaces where plasma action is faster their rate can be more compatible with restoration times.
- Some cleaning processes are also temperature activated.
- In some cases, the performance of traditional restoration techniques are enhanced by the plasma action. Therefore plasma treatment has to be seen only as restoration step and not as all-in-one process.
- WP3 activities gave interesting feedbacks for the development of the prototype plasma torch in the frame of WP1. Continuous improvement of the prototype was achieved taking into accounts the advantages and drawbacks of different commercial equipment shown during the tests. It likely does not exist only one plasma device suitable for all CH application since for example temperature provided by arc discharge devices has demonstrated to be synergic with plasma action. In any case in the project it has been decided to focus for the prototype in a real room temperature device as basic requirement, with no material deposition, trying to find the best compromise between these requirements and a sufficient efficiency and efficacy to be cost compatible to artefacts restoration.

The plasma torch construction started moving through five different designs, following the indication of CH partners. Different problems have been overcome during the development trying to fulfil the requirements. The partners have also updated these requirements as a result of the commercial plasma device experimentation in WP3 and of the results of the device development itself. The final requirements can be summarised:

1. Applicable to any surface even temperature sensitive (T < 50°C);
2. No electrodes deposition on the substrate;
3. Working set-up both in oxidation and reduction modes;
4. Removal rate or cleaning costs compatible but controllable by operator;
5. Suitable for localised treatment by the restorer;
6. Suitable for in-situ operation (hand-usable).
7. Vapour and aerosol precursors feeding;
8. Suitable to deposit organic and inorganic coatings;
9. Suitable for the deposition of nanocomposites;
10. Final cost compatible with the CH market.

Relative to objective foreseen in the proposal it has been chosen to increase the plasma jet spot from 500 µm up to about 1 cm because for restoration is preferable a wider spot. The chosen design based on a DBD configuration RF driven in the MHz range in order to reduce the treatment temperature. Capacitive design instead of inductive design has been chosen in order to reduce jet size and reduce treatment temperature. In order to avoid any metal deposition on the treated surfaces, a dielectric barrier acts as insulator for the electrodes. The surfaces in view of the plasma have been nanostructured with ceria nanoparticles to improve the secondary electron emission with no evident advantages for the device. In order to reduce the temperature and improve the efficiency the prototype has been designed to work with noble gases with low percentage of reactive gas as oxygen or hydrogen in order to work in oxidative and reduction mode. These conditions reduce also the production of toxic compounds as NOx and ozone in order to improve the safety of its use by hand. The temperature of the treatment on insulating and conducting samples have been measured to be lower than 50°C event after 5 minutes of continuous operation on a spot. The device has been finally designed to be hand-able and transportable in order to allow its use also in situ.
An inner coaxial duct has been introduced for the precursors introduction that allows also aerosol feeding. The prototype has been tested therefore not only for cleaning purposes but also for deposition of organic and inorganic coatings and also nanocomposites with particles dispersed in the precursors supplied by aerosol. In order to obtain the coatings a supersonic precursors inlet was not needed.

All the developed designs have been tested on mock-up samples for CH application. The final design has been compared also to other commercial torches and has shown an improvement in the removal rate of more than 3 times with respect to DBD system fulfilling all the requirements previously defined for CH applications included the treatment temperature lower than 50°C and avoiding the metal particles deposition on the surfaces. The final design has been submitted to an Italian patent application now extended also to a PCT application.

The objective of WP2 is to provide the formulation protocols of protective coating matrices for different substrates with long lasting performances and with hydrophobic and super-hydrophobic properties (θ>105°). The new protective coatings must also be removable using an atmospheric plasma torch. As the first activity, the definition of the required properties of the coating has been performed gathering information from the partners and from a literature survey and by the definition of benchmarks. Paraloid acrylic resins showed a dominant position both in literature and by an evaluation by partners specialised in CH applications. As a consequence of that, Paraloid B72 should be used as a benchmark in the development of the new protection coating. For stone protection also siloxanes are often used and therefore are added as benchmark, even if they are not removable. On the other side, the most important characteristics of the new coating should be its plasma-removability, its hydrophobicity and its transparency. Other important properties such as water vapour permeability were determined in a later stage of the matrix development. In addition, the new coating should be applied and cured at room or slightly elevated temperature (<60°C). It should be chemically resistant and compatible with the substrate. For the stone substrates the coating should inhibit the water absorption and be permeable for water vapour, whilst for the metals samples it should provide a barrier to all gasses.
The protective coating development has been performed as planned with a two-fold approach: an organic matrix and an inorganic matrix were developed. In particular for the organic matrices 3 different matrix solutions have been identified: solvent-based, water-based and UV-curable. In these matrices particles and additives have been introduced in order to impart good hydrophobic properties. The removal of the protection coating has been studied for all the approaches. The patenting of the formulation is still under evaluation.

The solvent-based solution starts from a modified acrylic polymeric matrix. Following this approach, contact angle can be increased up to 150° by using nanoparticle of different size and hydrophobic agents. A good compromise having full transparency and a contact angle of 113° can be obtained. The coating removal has been tested with commercial plasma torches also after ageing and the coating can be easily removed within few second of plasma treatment with arc discharges.

The water-based solution starts from a modified acrylate latex emulsion, with about 75% of water. Improvement of hydrophobic properties agents was achieved by addition of wax and nanoparticles. The obtained coatings show a contact angle of about 130˚. These matrices have been finally tested to be easily removable by atmospheric plasma.

The UV-curable coatings start by an acrylate monomer and have shown contact angles of 105° with good transparency. After its application on the surfaces, the latter one appears very shin. As a consequence of that, i.e. its barrier properties and for its aspect, it turns out to be more suitable for metals protection rather than for stone/wall paintings treatments. The coatings were plasma removable.

Inorganic matrix
The inorganic matrix development by sol gel hybrid solutions have shown to be not removable by atmospheric plasma. The plasma does not affect the inorganic bonds since they are already oxidised and cannot be easily reduced. The addition of some organic components does not allow the complete removal of the coating: the inorganic part remains as a skeleton even if the organic part has been removed. A double layer coating was proposed to overcome this problem: first layer organic and second layer inorganic. The outer inorganic layer can be functionalized in order to obtain contact angles of 105°. This solution has shown to be removed by Tigres atmospheric plasma in particular on insulating substrates, but mainly by its thermal action, since the inorganic layer is a barrier to the plasma action on the organic coating below.

The inorganic matrix therefore has been abandoned for the continuation of the project, and the development has focused on the organic solutions. All the organic solutions developed fulfilled the identified requirements and are comparable or better performing than the benchmark products.

In WP4 the different settings of the prototype plasma torch for cleaning different samples of cultural heritage interest were tested. After a characterization of the effect of the main parameters involved (plasma power, ionization gases, and geometrical factors) in removal performances, the prototype has been tested in cleaning and removal of different unwanted layers from selected substrates:

• Soot from mural paint
• Graffiti from marble
• Paraloid B72 from bronze and brass
• Corrosion products from silver
• Epoxy resin from Istria limestone
• All the protective matrices developed in WP2

Removal tests were performed on mock-up samples in spot treatment mode and in manual mode, i.e. moving the plasma on the sample surface by hand.
All the organic coating can be removed without any increase of temperature to more than 50˚C and without any deposition of material on the treated surfaces. The removal rate has been measured by FT-IR and by quartz microbalance. For not aged Paraloid B72, the removal rate of 20 µm/min has been achieved. No changes in colour in red and yellow ochre or in azurite pigments were observed confirming the low temperature of the cleaning process. The removal rate has been confirmed to be at least three times higher than other DBD commercial plasma torches. Epoxy resin can be removed without any melting of the epoxy even if aged. The prototype as the commercial plasma torches has been tested also in combination with other techniques such as solvents. In particular for graffiti removal - even if the plasma removal rate has been improved - it takes too much time to remove the hundreds of microns thick layer, therefore solvents can do a first rough removal. Then, when the interface is reached, plasma can be used for finalizing the cleaning. This solution strongly enhanced the removal efficiency, although the coatings underneath the surface cannot be removed by plasma that is characterised just by a surface action.
All the matrices developed in WP2 have been shown to be easily removable by the prototype.
The prototype has been tested also in reduction mode. The device shows very fast cleaning results on silver in open air without any use of glove box or controlled atmosphere and at room temperature. On silver alloys it has been shown as a controlled increase in temperature heating the metal mock-up sample up to 80-100˚C evidently improves the cleaning results. The advantage of the prototype since it works at room temperature is that the heating can be controlled separately to the plasma treatment itself.
The portability of the device was well proved with success in in-situ tests, such as the following case-studies:

• Removal of graffiti from statues in Prato della Valle (Padova), where the plasma removal has been compared to laser and solvent treatments. The best results have been obtained by the combination of solvent and plasma removal with no changes in stone colour and morphology, no diffusion of the paint in the stone pore and a full removal of the paint.
• Removal of aged protective coatings from wall paintings in S. Giorgio church (San Polo di Piave), where aged protective coatings composed by a mixture of acrylic and epoxies have been removed without harming the secco integrations of a previous fresco restoration. Solvents that have been used for comparison cannot obtain the same result.
• Removal of black crust from Istria stone from Palazzo Ducale (Venezia), where the prototype has highlighted that only the organic part can be affected.
• In-situ cleaning tests on selected samples from Vatican Museums (Vatican City), where different natural aged varnishes has been removed and silver foils cleaned.
• Cleaning of aged varnishes from 18th century Russian icon (Sofia), where it has been highlighted how the plasma can depolymerise the surface layers of an aged varnish allowing after its removal just with ethanol, where before no results were obtained even with stronger solvents.

The multiple coaxial design of the prototype torch allows the introduction of chemical precursors directly in the plasma region. Through plasma polymerization the prototype can produce coatings on the treated surfaces. The following matrices have been successfully deposited:

• organic-inorganic hybrid silica coatings
• acrylic copolymers
• UV curable coatings

The coating can then be removed by the same prototype. The removal rate is about 2 times slower than the deposition rate.

The objective of WP5 was to impart self-diagnostic properties to the long-lasting protective coatings developed in WP3 and to provide a device which can detect the presence of the additive and correlate its concentration with the health status of the coating. Therefore, as a first step, commercially available fluorescent additives were screened in the solvent based protection coating formulations. The fluorescent response was found to be proportional to the additives concentration and coating thickness. The choice relied on UV-responsive additives as their detection is easier, more rapid and inexpensive compared to IR- responsive additives.
In order to link the response of the additives to the health status of the coating, coated laboratory samples were aged under UV illumination. UV ageing strongly affected the luminescence properties of the additives in coatings. Curves of luminescence intensity vs ageing time were obtained for the selected additives.
The procedure for coating diagnosis was also set-up. Two levels of diagnosis are available. Fast screening qualitative determination is possible with the use of a common Wood lamp. In situ quantitative response can also be measured using a small portable UV spectrofluorimeter.
At the end of WP5 it was possible to deliver matching diagrams linking self-diagnostic additives, coating matrices and substrates. The best performing self-diagnostic coating on each substrate was therefore selected. In particular 2 categories of fluorescent additives has been identified: a long-life category mainly based on inorganic pigments that allows to see if the coating is still on after years, and a short-life category which activity decay in few hours that allow just to monitor the correct application of the protective coating as coated area and thickness uniformity in order to have a quality control. The subdivision in these 2 categories have been asked by the restorers who are not all interested and convinced in using long-term fluorescent coating.

WP6 regarded the comparison of water repellent coatings being developed in WP2 with the most used commercial ones on stone, metal and paintings (wall and icon paintings). Effectiveness and harmfulness of the treatments were assessed by means of sample characterisation, before and after application of the different products. The following questions were of interest:

1. Does the treatment change the colour of the substrate? Does it improve the water repellence?
2. Particularly for stone substrate: How does the treatment affect the water absorption by capillarity? Does the coating act as a barrier for the water vapour? What is the effect of the ageing of the coating on the water absorption and water vapour permeability?
3. Especially for metals: How does the coating protect the surface from corrosion? Does ageing affect its effectiveness?

All the coatings developed in WP2 have been tested. The solvent-based formulations are based on a polymer matrix consisting in an acrylic polymer with hydrophobic agents, in which water repellent particles of different size were added. Moreover, two UV-curable coatings, based on different acrylate monomers and three water-based products (acrylate latex emulsion) were tested. For each substrate the best performing developed coatings has been evaluated and compared to the best commercial product as benchmark.

• Carrara marble has been tested with 2 solvent based coatings compared to Silres BS 280 (Wacker)
• Istria limestone has been tested with 1 solvent based and 1 water based coating compared to Fluoline P.E. (CTS)
• Serena sandstone has been tested with 1 solvent based coating compared to SILO 111 (CTS)
• Sterling silver has been tested with 1 solvent based coating compared to Paraloid B-72 (Rohm nad Haas)
• Brass and bronze has been tested with 3 solvent based and 2 UV-curable coatings compared to Paraloid B-72 (Rohm nad Haas) and Cosmoloid H 80 (Kremer Pigmente)
• Wall paintings has been tested with 1 solvent based and 2 water based coatings compared to Paraloid B-72 (Rohm nad Haas)
• Icon has been tested with 1 solvent based coating compared to Varnish Crytsal (Pebeo)

All the developed coatings show results comparable to the selected benchmarks. As added value of the variety of coatings developed it is the tailoring of the formulation as a function of the application finding the best customised compromise between contact angle, water absorption, corrosion resistance and aesthetic finishing. As general conclusions:

• The solvent based coatings show performances similar to Paraloid B72 but with improved contact angle
• Water based coatings can lead to a whitening appearance of the surfaces
• UV-curable coatings show a clearly enhancement in corrosion barrier properties relative to the benchmark
• All the developed coatings have guaranteed plasma removability

The developed solutions have been tested also with the deposition by the prototype device. The coating obtained show less performances than those applied by brush due to the deposition method that introduce more defect in the applied coatings.

In WP7, the possible use of plasma deposition for identification markers was assessed. The deposition brings to silica films, containing dispersed or dissolved materials with luminescent properties.
The chosen dyes and pigments had to dissolve in the same solvent used to dilute the siloxane monomer, or, in case they are insoluble, they must have a particle size in the order of nanometres suitable to be incorporated in a silica thin film. Furthermore, the photoluminescence emission intensity had to be high even for low concentrations of dye, in order to react to UV exposure making visible marker coatings of nanometric thickness. One inorganic pigment and three organic dyes were used in the preparation studies of an identification marker layer.
Results of this activity show that the used inorganic pigment presents a too large size for the embedding purpose; therefore the use of this pigment was discarded as a possible marker.
Better results were obtained by using the organic dyes: Tinopal has been successfully deposited and fixed on the substrate by mean of a two-step strategy (1 spray deposition of the organic dye solution, 2 plasma deposition of a silica layer). Experimental results show that the organic dye is not affected by the plasma action and preserves its luminescent characteristics. The only problem that has been observed is that the two-step strategy leads to a thick dye coating that results visible also in normal conditions.
In order to overcome these problems, a one step deposition has been implemented by the use of Europium-based metallorganic dyes dissolved directly in the HDMSO precursor, then introduced in the plasma jet by aerosol. This single step strategy here used showed the best results: thin and well-fixed luminescent layers were obtained.

The aim of this work package was to characterise self-diagnostic coatings developed within the PANNA Project.
Three additives were tested in different concentrations and combinations with the three CHEM coatings (1, 2 and 3) developed in WP6. The additives tested were one inorganic pigment (IP), one organic pigment (OP) and one organic dye (OD) and their properties were previously tested to help the partners choosing the most appropriate for their substrates.
None of the additives caused drastic changes to the hydrophobic features of the CHEM formulations. The thickness of the coating, the concentration of the additive, the morphology of the surface, are just a few examples of parameters that might influence the hydrophobicity. It is mainly important to remark that no additive caused drastic changes to the hydrophobicity of the coating.
The qualities and drawbacks of each fluorescent substance, tested in the above mentioned substrates can be resumed as follows:

IP – the fluorescence of this additive withstands artificial ageing very well. After laboratory tests described in detail in part 9 of this report, the fluorescence of this pigment did not decrease. Its drawbacks are related to its aesthetic properties: it causes a whitish coating on silver, bronze, white marble and Serena sandstone. Plus, since the particles are quite big (µm range), they require a thick coating otherwise the coating matrix is not able to hold on the surface the pigment particles, which can be easily wiped off. Nevertheless, if a thick coating can be applied and no aesthetical alterations on the surface of the substrate are observed, this additive might be suitable.

OP – the self-diagnostic coating prepared with this additive showed very fast fluorescence fading. It is therefore suitable for quality check control just after the application of the protective coating. On the other hand, the thicker the coating, the longest the fluorescence withstands and therefore, in some cases where a thick coating is applied, this additive might be used also for long-term diagnostics.

OD – this additive showed excellent qualities, its fluorescence withstands ageing better than OP (although not as good as IP), it is homogeneously spread on the surface not causing meaningful aesthetic changes and, for example in the case of the self-diagnostic coating applied on marble, it reduced its Künzel value, which means it has improved its hydrophobic qualities.
Regardless of all the results here presented, it is important to keep in mind that the use of a coating with a fluorescent additive should always be planned carefully.

At the end of the testing the best solutions have been identified and all the “full-life” protocol has been integrated in a demonstrator. The full-life protocol demonstrator is made up of:

1. Plasma Torch Prototype
2. Self-diagnostic coating formulations
3. Wood lamp
4. Mock-up samples for cleaning demonstration (wall painting with soot and silver with tarnish)
5. Mock-up samples for coating demonstration (wall painting and silver)

With this equipment the main features of the “full-life” protocol can be shown. In particular the following steps can be shown:

1. Cleaning of soot from an yellow ochre egg tempera wall painting operating the atmospheric plasma prototype by hand
2. Cleaning of tarnished silver
3. Application of water droplets on the surface to show the surface wetting of yellow ochre egg tempera wall painting
4. Application of the solvent based self-diagnostic protective coating on yellow ochre egg tempera wall painting
5. Application of water droplets on the surface to show the hydrophobic features of the coated surface
6. Illumination with Wood lamp to check the presence of the coating by fluorescence inspection via Wood lamp illumination
7. Removal of the protective coating operating the atmospheric plasma prototype by hand
8. Illumination with Wood lamp to show that the coating is no more present on the surface and no fluorescence signal can be observed
9. Application of water droplets on the surface showing that the surface wetting as come back as prior coating application
10. Application of a tarnishing solution as Na2S on silver surface showing the tarnishing of the unprotected surface
11. Application of the solvent based self-diagnostic protective coating on the not corroded silver surface
12. Illumination with Wood lamp to check the presence of the coating by fluorescence inspection via Wood lamp illumination
13. Application of the tarnishing solution as Na2S on the coated silver surface showing corrosion protection action of the coating
14. Removal of the protective coating operating the atmospheric plasma prototype by hand
15. Illumination with Wood lamp to check the presence of the coating by fluorescence inspection via Wood lamp illumination
16. Application of the tarnishing solution as Na2S on the silver surface where coating has been removed showing that the surface is again tarnished as in the beginning when the surface was unprotected

The demonstration, with the addition also of the graffiti cleaning from a marble surface by combination of solvent and plasma action, was also video recorded and is available on YouTube at the following site:
The demonstrator clear shows the technological successful development of the “full-life” protocol in all its steps.

The last year of the project has focused in particular on the dissemination activities in order to obtain the best exploitation of project results. In fact, this particular field is usually slowly implementing new technologies due to different factors:

• High and often unique value of the artefacts
• Complexity of treatments for multi-materials artefacts, often old and aged (so mainly unknown)
• Every artefact is different
• Damages cannot be recovered
• Restoration operations are controlled by policy makers
• Technologies and materials have to be widely experimented, even monitoring their behaviour for tens of years
• The owners market is fragmented
• The restorers companies are mainly SMEs
• The market depends mainly on public funds

In order to improve the time-to-market and therefore the exploitation of the PANNA results, WP9 was fully dedicated to dissemination through the organisation of workshops with theoretical and practical sessions. This activity was mainly carried on through the individual networks of the consortium members, which come from Italy, Germany, Belgium and Bulgaria. The workshops were addressed especially to restorers and policy makers in order to improve the awareness of the developed technologies by really making them practiced on mock-ups and real objects.
The dissemination to restorers and policy makers, who are the ‘end-users’, was improved also by the participation to fairs and to the NANOMECH Cluster, widening the dissemination audience. The realisation of case studies of the “full-life protocol” strongly improved the impact of these dissemination activities, which showed to be effective since new restorers, institutions and policy makers joined the experimentation asking also for additional workshops.
Moreover application protocols and manuals for the new technologies were drawn up as guidance and for simplifying their use by operators.
On the other side, not only the ‘end-users’ were addressed for the dissemination but also other target groups were considered: scientific community and general public.
The scientific community was reached by the participation to international conferences with oral and poster presentations, article publications in international journals, networking and collaborations.
The general public was reached via press releases, newspapers, TV, radio, websites and social media, accomplishing dissemination of the project results in a wide range of audiences.

Besides the technical development and the application effectiveness of the ‘full-life’ protocol, the project included the evaluation of the impact of the innovative techniques on the environment and human health, and the identification of the safe uses mode for operators. The activity is included in WP9, and the impact and safety assessment is limited to the application phase of both methods. In particular for the evaluation of the atmospheric plasma cleaning with the prototype it has been chosen to restrict to the case of the removal of a Paraloid B72 coating on mural painting; while for the self-diagnostic coating the analysis is limited to the comparison of Paraloid B72 and UV-curing coatings application for silver protection. The aim of the study has been twofold:

- A simplified LCIA, carried out according to ISO 14040 standard;
- An exposure scenario assessment, according to REACH approach, to identify safe use conditions.

As main results it can be stated that the impact of plasma technology is in general lower than the solvent technology for cleaning purposes. Plasma technique is eventually fully VOC free. On the other side plasma emissions have to be considered. The prototype has been verified to not produce toxic NOx, as far as FT-IR measurement in gas phase. At the same time it produces only when used in oxidation mode ozone that can be in any case captured or chemically reduced with appropriate means, still reducing its health and environmental impacts.
For the protective coating application the UV curing technique seems to be advantageous because it avoids the use of organic solvents, and the amount of energy used for the resin curing is very low. Therefore, the impact on human health in situ is greatly reduced.
The safe use of the innovative techniques concerning the emission of toxic substances and other stressors has been also evaluated. The approach followed a risk assessment procedure, comparing the exposure scenario with regulatory limits (if available). The main aspect is the ozone generation by the atmospheric plasma in oxidation mode. As measured at a distance between 40 and 50 cm in open-air environment the level are in any case below the regulatory limits for 8h of continuous work. In indoor applications, the use of the plasma torch needs a suction fan due to the use also of argon as carrier gas that can saturate the closed atmosphere in a room.
For UV coating application no risk is foreseen since the only stressors of relevance is the UV lamp use that can be controlled by the use of Personal Protection Equipment.

In order to introduce the plasma technology for cleaning purposes it is important that it is included in standards for cleaning. The design of a new Italian Standard UNI for the cleaning of stone material has been the case for the first introduction of this technique. CNR-IENI was part of the UNI-Normal Commission preparing the standard and plasma has been introduced at that moment as one of the techniques available. The Standard is still not approved but it is in its “Final Public Enquiry” state.

A careful project management has allowed an efficient coordination of the different activities with no relevant delays respect to the working plan and involving all the partners in the project. In order to achieve these results technical meetings have been organised every 6 months. Moreover in order to support the dissemination activities factsheets and brochures have been prepared in occasion of the most important events and particular attention has been devoted on keeping updated the website.
The PANNA website has reached from 1/10/2012 up to 31/10/2014 more than 4100 users highlighting the growing interest in the PANNA project. After the midterm and in the last year with the organisation of the different workshops it has been observed a smooth increase in the connections in particular in coincidence with the different events. Obviously the higher number of users comes in order from Italy, Belgium, Germany and Bulgaria that are the participating countries, but a relevant number of users come also by other European countries as Poland, UK, Netherlands and France and by other extra-European countries as USA with about 400 users and Brazil with about 170 users.

The PANNA project successfully achieved its objective in realizing the “full-life” protocol in all its steps, developing all the technologies needed for its use such as the only market available atmospheric plasma device suitably designed for cultural heritage applications, that shows the best performances for the field, a new selection of protective coating with tuneable self-diagnostic properties with guaranteed removability features and the identification markers. The “full-life” protocol has been tested in all its steps in the CH field on mock-up samples and in case studies. Moreover a strong dissemination action has led to the increase of testing network, the involvement of policy makers, the introduction of plasma technology in standards cleaning procedures preparing the bases for the final products exploitation.
In order to see the “full-life” protocol as a whole or in single steps used in the cultural heritage field it will take probably some time and the dissemination, testing and developing activities must continue. In any case the PANNA project has allowed to drawn the following general conclusions:

• Atmospheric plasma cleaning is now more than a research idea for Cultural Heritage. The results are promising and a dedicated instrument is now available on the market. Even other atmospheric plasma torch producers are looking to implement other devices suitable for CH applications. The wide testing has allowed to highlight how the atmospheric plasma is not competing with other CH cleaning technologies as solvents, poultices or hydrogels and lasers but offer new features due to its purely chemical, dry, room temperature, controllable and contactless action on the surface.
• Due to its features and its slow operation it is probably not the all-in-one technique for wide area surfaces, but it allows to achieve in combination with other techniques the best cleaning results. On metals its action is compatible with restoration times. Its features in any case probably allow its use to a wider range of substrates other than just metals, wall paintings and stones, such as textiles paper, plastics, multi-materials artefacts and modern art materials where standard techniques have more drawbacks. In particular it can be used not only for organic layers removal or corroded metals reduction but also for sterilisation or pesticides destruction.
• The atmospheric plasma coatings on the other side have the peculiar feature of deposit only on the surface not filling pores, even if they don’t achieve the protective performances of coatings applied by brush. This feature can be useful for example in some temporary consolidation treatments or UV protection.
• The use of atmospheric plasma for organic removal allows the use of protective coatings based on resins such as the UV-curable or epoxies nowadays not used in the CH field. The use of these matrices can allow a widening of the products usable for CH on the different substrates, enhancing the use of green technologies and the reduction of use of organic solvents.

Potential Impact:
The main product of the PANNA project is the “full-life” protocol, which consists of mainly 3 technological innovations: the atmospheric plasma jet, the self-diagnostic and removable protective coating and the identification marker.

• As a whole the protocol is innovative for cultural heritage since it present a fully reversible restoration process.
• As singles technologies are innovative: the atmospheric plasma offer new unique restoration alternative and the coatings are self-diagnostic and their removal is guaranteed.

Evaluating the market, the potential impact of these technologies has different strength points:

• it does not currently exist in the cultural heritage market an equivalent product as the “full-life protocol” that considers how to clean, coat and re-clean offering the complete removal of the treatment in an integrated way.
• it does not currently exist in the cultural heritage market an atmospheric plasma torch with similar performances as the one developed by Nadir.
• there aren’t any protective coatings certified as removable in the cultural heritage market

Moreover results of the PANNA project has allowed to drawn some general conclusions that in view of the potential impact from the socio-economic point of view can be summarised in:

• The plasma technology is a new tool, does not overlap with other technologies but can be used in combination, therefore does not compete with the other technologies.
• The plasma technology, greener products and guaranteed removability can only have growth trends.
• Applications of the ‘full-life’ protocol elements are wider than only on the substrates and cases tested during the PANNA project.

All these aspects lead to an interesting potential impact of the technologies proposed by PANNA in the Cultural Heritage restoration field. Unfortunately this particular field is usually slowly implementing new technologies due to different factors:

• High and often unique value of the artefacts
• Complexity of treatments for multi-materials artefacts, often old and aged (so mainly unknown)
• Every artefact is different
• Damages cannot be recovered
• Restoration operations are controlled by policy makers
• Technologies and materials have to be widely experimented, even monitoring their behaviour for decades
• The owners market is fragmented
• The restorers companies are mainly SMEs
• The market depends mainly on national or federal-state public funds

For this reason the activity of WP9 has been focused on the dissemination activities trying to involve restorers, museum and policy makers outside the PANNA partnership. It has already been taken different actions to involve policy makers as Soprintendenza di Venezia (I) and Verona (I) and Museums (Deutsches Museums in Munich (D), Vatican Museums (Vatican City) and research centres in Cultural Heritage as the Directorate of Central Laboratory for Restoration & Conservation in Istanbul (TR) or the Laboratoire de Recherche des Monuments Historiques de Champs-sur-Marne (F). This activity has to be improved since it is the only way to overcome the market barriers:

• Testing in different case studies in collaboration with the institutions in charge for CH preservation
• Only museums and big centres can be the first customers, private restorers at the beginning will only rent the plasma equipment
• The market is very fragmented so it is important to take action in different countries

Moreover Moreover a structured dissemination plan has been planned in order to allow a fast exploitation of the results in order to overcome the death valley between the end of the project and the first products sold by the commercialising SMEs.

Some of the target audiences, which have been already identified by the partners, can be categorised in the following groups:

• End users including:
o Companies, principally restorers SMEs, which are interested in new technologies in order to widen their business offering something new, for example restorers already using laser technique, so more used to technical improvements.
o Museums with the restorers’ workshops, which can also improve the uptake of the new technologies since they can easily experiment on a wide range of artefacts. Moreover they can multiply the dissemination effects since are in contact with a lot of restorers and institutions.
o Policy makers as Government departments that control and preserve the Cultural Heritage in the different countries, including national and international standardisation committees.
o Small and Medium sized Enterprises that produce or distribute materials and technologies for the Cultural Heritage market, that can be interested in commercialise the PANNA products.

• Scientific community:
o Research and academic groups, working in relevant areas addressed by PANNA technologies that are interested in the methods/techniques to be applied on Cultural Heritage.
o Research and academic groups, working in relevant areas addressed by PANNA technologies, that are interested in the methods/techniques to be applied not in the Cultural Heritage fields but for other topics that can open other markets.
o Research laboratories for conservation, both governmental and related to museums that can improve the uptake of the new technologies since they can easily experiment on a wide range of problems.

• General audience:
o Private owners of Cultural Heritage artefacts, resellers of Cultural Heritage artefacts or people generally involved in the Cultural Heritage market.
o Wide community interested to be aware of technological development or of how EU is supporting research and development. Common people can also be seen as final end-users of Cultural Heritage as tourist that always more often appreciate not only the artefacts and their history but also the restoration process.

In order to reach the different target groups different instrument have been implemented during the project.

In order to make the project recognizable a logo has been expressly designed in order to be easy to read and identify.

A website for the PANNA project was set up at the address within the 31st of December 2011. The website has all the functionalities needed for the internal coordination between partners’ activities, for the EU project officer monitoring and for dissemination purposes. The content of the website has been continuously updated during the project.
In the upper banner of all the website pages the PANNA logo appears together with the symbol of the 7th Framework programme and the EU flag. The home page is designed in order to show the featured articles published on the website as a function of time, preferentially news. On the left side the “Latest News” and the “Most read articles” are always shown on the homepage. Different menu entries have been reserved for:

• Project description
• Partnership
• Work Packages structure
• Deliverables
• Downloads
• News
• Contacts

Since October 2012 the free Google analytics instrument has been used to monitor the visits of the PANNA website and more than 4100 users visited the PANNA website. It was observed that the midterm events had a strong impact probably due to the different actions taken, from newspapers to workshops, and for sure also the event organized by the EU commission with all the projects of the same call. On the other side also the organization of the dissemination workshops held in all participating countries in the last six months gave results. Moreover also from autumn 2013 it can be observed there was an increase, probably due to the participation at scientific conferences. As good point from autumn 2013 also the uploading of results and case studies on the website that allowed to improve the average time per session.
The most “connected” country was Italy followed by the other countries participating in the project, in order: Belgium, Germany, Bulgaria, but also other European and extra-European countries showed an interesting number of users. Indeed the results of the first 50 sessions that spent more time connected to the website are not relative to the partners but come from all over the world.

In occasion of the MidTerm (June 2013) of the project, when the experimentation and the technology developments had already shown their results, a brochure/leaflet presenting the PANNA project was prepared. The brochure was printed in 2000 copies with A4 format and has been provided in all the events organised during PANNA (Workshops, Training workshops, Conferences or fairs) and was also downloadable from the website.
The brochure describes in different sections:

• Project administrative details
• The consortium
• The objectives of the project
• The different results on technological developments (plasma jet and coatings) and on their Cultural Heritage testing

Moreover the project has been also the opportunity for some partners to improve their visibility. The Centre for Restoration of Artworks (CRA) for example realized its own brochure more linked to the company in order to use the project also as a marketing opportunity and present the PANNA technologies as already available in Bulgaria.
A factsheet was prepared within March 2012 describing the project following the template given by the project officer. The factsheet has been printed in 2000 copies. Then the factsheet has been updated during the project.

Three different press releases have been prepared during the project: the first at the beginning after the kick-off meeting, the second for the midterm evaluation and then the third for the end of the project. The press releases have been diffused in the media network highlighting the outcomes of the project for a general public.

As dissemination material widely accessible from everywhere and to everyone, the instruments closest to social media were chosen, easy to share, as You Tube. This has been done by the creation of a PANNA Project official channel and by using the channels of the partners as the one of the Centre for Restoration of Artworks (CRA). On You Tube can be found the following videos:

• Panna Project: The Full Life Protocol Explained in Few Steps
• Botega' Z - Icon Plasma Cleaning
• Soot removal using atmospheric plasma - a case study
• Water repellency commercial coating on marble
• Water repellency ChemStream coating on marble
• Plasma cleaning

Moreover in order to improve the dissemination of the results in particular making people aware of the events organised, not only contact lists have been used but also social media. In particular LinkedIn, with publication of the event in “Cultural Heritage Conservation Science. Research and practice” Group, was used.
Also other instruments as the e-mail forum ‘ConsDistList’ ( have been used for example to announce the workshops held in Antwerp and Berlin.

In order to improve the visibility, also the websites of the different project partners have been used with direct publishing of the results and links to the events and to the PANNA project website. In particular Centre for Restoration of Artworks (CRA), Chemstream (Chem) and Nadir (NDR) websites always integrate the news on the events, results and meetings. The University of Antwerp website hosted the subscriptions and the results of the Antwerp workshop, September 2014.

In order to start the dissemination to the target end-users and scientific community, workshops illustrating the PANNA objectives and results have been performed during the project also before the planned final training events scheduled in WP9. The workshops have been performed in conjunction with the internal meetings around Europe and were organised with oral presentations.

• 7/2/2013 Public presentation of results achieved in the first year of PANNA Project at CNR-ICIS venue in Padua (Italy)
• 17/6/2013 Public presentation of results achieved in the first 18 months of PANNA Project at University of Antwerp venue in Antwerp (Belgium)
• 5/11/2013 Public presentation of results achieved in the 24 months of PANNA Project at Star Hotel venue in Plovdiv (Bulgaria)

PANNA training events with practical sessions on the “full-life” protocol have been organised in the different participating countries. The training workshops have been organised with a 2-days structure, the first day on plasma cleaning and the second on coatings and their removal, with oral presentations in the morning and practical sessions in the afternoon.
These activities have been the most effective in the dissemination of the results to the end-users. The events have been calibrated for about 30-60 people attending. Here below in the table we summarise the different events organised:

• 26, 27 May 2014 Vatican Museums Vatican City
• 9, 10 June 2014 National Academy of Arts, Sofia Bulgaria
• 2, 3 September 2014 Sammlung-Scharf Gerstenberg, Staatliche Museen zu Berlin Germany
• 8, 9 September 2014 Conservation Studies, University of Antwerp Belgium

The events had a so high number of applications for participation that an additional 1-day workshop has been organized:

• 30 October 2014 Ca’ d’Oro, Soprintendenza Speciale di Venezia Italy

To this event 60 people participated coming from Veneto, Lombardia and Emilia Romagna, including restorers coming from different National offices dealing with CH conservation. This result indicates that also policy makers have been reached by the dissemination actions.
A Final Event has been organized September 4th 2014 in Berlin at the National Museums of Berlin with around 60 people that booked their participation and with external invited speakers from the scientific community. The participation of external speakers has been the occasion to improve the collaboration network. Invited speakers, experts on plasma techniques, allowed a better assessment of the project results and the future of plasma technology through a fruitful discussion, also involving them in future developments and project proposals.

As planned the dissemination activity to the scientific community has started as soon as possible with the dissemination of the first results in particular of Cultural Heritage plasma cleaning tests with the different commercial torches. The activity has continued through the whole project involving all the other topics of the projects development. The PANNA topics have gained always more interest up to the presentation of a keynote lecture at Plasma Surface Engineering International Conference (PSE 2014), that is the most important biannual conference on industrial plasma applications in Europe.

• Oral presentation at European Workshop on Cultural Heritage Preservation EWCHP 2012 workshop held in Oslo (Norway)
• Oral presentation at EUROMED 2012 congress in Limassol (Cyprus)
• Poster presentation Metal 2013, the triennial conference of the International Council of Museums Committee for Conservation Metal Working Group, in Edinburgh (Great-Britain)
• Oral presentation at European Workshop on Cultural Heritage Preservation (EWCHP 13), held in Bolzano (Italy)
• Poster presentation at XII European Meeting on Ancient Ceramics, EMAC, Padova (Italy)
• 2 oral presentations at 6th International Congress “Science and Technology for the Safeguard of Cultural Heritage in the Mediterranean Basin” at the National Technical University of Athens (NTUA)(Greece)
• Poster presentation at "Voorbij het kijken" colloquium, Gent, FARO organisation (Belgium)
• Oral presentation at Lustre et brillance en conservation-restauration, Auditorium Hadewych, Brussels (Belgium)
• Oral presentation at AIAr 2014 Congresso Nazionale di Archeometria, Bologna (Italy)
• Poster presentation at the WoodMusICK Opening Conference is being held in Paris (France)
• Oral presentation at the “Preserving the Thracian Cultural Heritage” discussion at Credo Bonum gallery in Sofia (Bulgaria)
• Keynote lecture at the Plasma Surface Engineering International Conference (PSE 2014) in Garmisch (Germany)
• Oral presentation at the Convegno APLAR 5 at the Vatican Museums (Italy)

Participation to fairs was sought in order to reach end-users target. In the first period aim of the participation was mainly the increase of interest on the project and the improvement of the awareness of the technologies. In the last period aim of the participation was to show the results and make clear with case studies presentations where the “full-life” protocol can be used and how it works.
• Workshop Nanotecnologie per l’architettura contemporanea. At XV Salone dei Beni Culturali – Venezia (Italy)
• Workshop “Nuove tecnologie per la tutela e la valorizzazione dei beni culturali e per lo smart building”. At VEGA Parco Scientifico e Tecnologico di Venezia – Venezia (Italy)
• Participation to 8th AR&PA fair – biennial of heritage, restoration and management in Valladolid (Spain)
• Presentation of PANNA Project at KMO-Kennisbeurs fair in Leuven (Belgium)
• Oral presentation and workshop organisation at the XXI Salone del Restauro in Ferrara within the workshop organised by PANNA and NanoMatch projects (Italy)
• Presentation of PANNA Project at KMO-Kennisbeurs fair in Antwerpen (Belgium)

Thanks to the EU clustering efforts other opportunities have been added to the dissemination planned. The cluster events in particular allowed to improve PANNA technologies awareness among the partners of other projects of the same EU funding call. This has been clearly seen by the website visitors sessions after the clustering meeting of the 21st June 2013. These events have been particular fruitful for the audience itself, since the audience was mainly of end-users that are already involved in new technologies testing and therefore more sensitive to projects results and in collaborations.
• Clustering meeting 'Nano and advanced materials for cultural heritage' dedicated to FP7 projects HEROMAT, IMAT, NANOFORART, NANOMATCH, PANNA and ROCARE at the Madou Auditorium in Brussels
• 2 oral presentations at the workshop organized by the NanomeCH cluster during the EWCHP 13
• Oral presentation at the HEROMAT meeting in Novi Sad
• Oral presentation at NANOMATCH project final event
• Oral presentation at IMAT project final event

In order to reach a wider and more general audience other instruments have been used such as radio, TV, digital media and newspapers.
• Radio Interview on Radio Rai (National Italian Radio)
• Article on “Horizon – The EU Research & Innovation Magazine
• Digital Article on ECOWEB
• Article in newspaper “De Nieuwe Gazet”
• Digital Article on “” and “”
• Digital Article on “”
• Digital Article on issue 61 of “Bulgarian science” online magazine
• Radio Interview on BNR (Bulgarian National Radio)
• TV news on bTV (private national Bulgarian television)
• Monthly Magazine “Formiche”
In order to facilitate the dissemination to a general audience, press releases have been diffused after the kick-off meeting, at the Mid Term and at the end of the project.

In addition to the conferences participation, also the publication of scientific articles has been addressed. This activity has obviously some delay relative to the participation to conferences and will improve probably after the end of the project. In fact in the first 18 months the technologies has been developed and then were later tested, so the possibility to have a full view on the problems and characterisations needed for peer reviewed articles, came close to the end of the project. Moreover the developed technologies have Intellectual Properties Rights of the SMEs, since also a patent application on the plasma device has been presented in November 2013 by Nadir.

• Patelli et al.; PANNA Project – Plasma and Nano for New Age Soft Conservation. Development of a Full-Life Protocol for the Conservation of Cultural Heritage. Lecture Notes in Computer Science 7616 (2012) pp.793-800
• Aibéo et al.; EU-PANNA Project: Development of a portable plasma torch for cleaning multi surfaces and coating deposition. 2nd European Workshop on Cultural Heritage Preservation. Elin Dahlin (ed.) NILU - Norwegian Institute for Air Research. pp. 55-64
• Aibéo et al.; Preliminary assessment of atmospheric plasma torches for cleaning of architectural surfaces. 3rd European Workshop on Cultural Heritage Preservation. Institute for Renewable Energy, EURAC research. pp. 85-88
• M. Stefanova et al; Cleaning of varnish on 18th century Russian icon Saint Nicolas by means of Atmospheric pressure plasma. 6th International Congress on Science and Technology for the Safeguard of Cultural Heritage in the Mediterranean Basin. Session B: Diagnostics, Restoration and Conservation, (Vol. 2), 2014. pp.427-435. VALMAR-Roma. ISBN 978-88-97987-04-8
• V. Kamenova et al; Oil overpaintings removal using atmospheric plasma pressure plasma. 6th International Congress on Science and Technology for the Safeguard of Cultural Heritage in the Mediterranean Basin. Session B: Diagnostics, Restoration and Conservation, (Vol. 2), 2014. pp. - . VALMAR-Roma. ISBN 978-88-97987-04-8
• P. Storme; De zwarte glans van zilver. Colloquium Postprints: Glans in de conservatie-restauratie = Lustre et brilliance en conservation-restoration, ISSN 1782-0685, S.I. VIOE, 2014, p.134-143
• Aibéo et al., Cleaning graffiti and soot with atmospheric plasma, Berliner Beiträge zur Archäometrie, Kunsttechnologie und Konservierungswissenschaft, 22, 2014, pp. 69-76, in Press

In order to reach the end-users it is important to offer also some guidelines for the “full-life” protocol application. The guidelines drawn regard the use of the “full-life” protocol on the different substrates, i.e. stone, wall-paintings and metals. The guidelines include the operation manuals and best practice for the use of the atmospheric plasma prototype and the self-diagnostic coating.
The utilization protocols give a preliminary overview of the steps achieved in the development and assessment of the plasma device and the self-diagnostic coatings. Subsequently the guidelines report, through an answer&question scheme, all information about applications of plasma cleaning and coating protection with practical examples of treatment on different substrates. Also possible limitations or drawbacks in relation to the substrate to be treated and to the device and materials employed are given.
The guidelines include also a section related to health and environmental issues and risk management of the new developed plasma and the chemicals.

The dissemination activity has led to a multiplying effect allowing getting in contact with other research institutions working in Cultural Heritage conservation and policy makers such as the Istituto Centrale del Restauro in Rome (Italy) or the Directorate of Central Laboratory for Restoration & Conservation in Istanbul (Turkey).
In particular two collaborations have been fruitful for improving the project dissemination and visibility and are still going on, also after the project. These are the collaboration with the Gabinetto della Ricerca Scientifica of the Musei Vaticani in Rome direct by Prof. U. Santamaria and the Laboratoire de Recherche des Monuments Historique in Paris in the person of Dr. V. Detalle. With both of them there has been the possibility to investigate the atmospheric plasma jet prototype in different case studies, highlighting good and bad points.

The scientific dissemination in particular on the local scale has been the opportunity also to strengthen the connection with the closest universities. This improved connection has allowed to disseminate the PANNA results and activities also in the Academia network.
In particular the activity of the thesis on self-diagnostic coatings has been performed also with the collaboration of Chemstream (Chem) who hosted the student for about 6 months.

• Master Degree Thesis “Optical marker methods for Cultural Heritage based on rare-earth doped Yttria nanophosphors” – Università Ca’ Foscari di Venezia – Venezia (Italy)
• Master Degree Thesis “Removal of chewing gum from stone substrates by means of atmospheric plasma” – Università Ca’ Foscari di Venezia – Venezia (Italy)
• Master Degree “Atmospheric Plasma as tool for the removal of protective acryl coating on historical and/or artistic pottery” Università degli Studi di Padova – Padova (Italy)
• Master Degree “Self-diagnostic coatings for cultural heritage: fluorescent additives Characterization, Light-fastness and influence on a waterborne Coating yellowing and plasma removability of commercial pigments – Università Ca’ Foscari di Venezia – Venezia (Italy)

In order to improve the dissemination to the end-users different case studies have been performed.

• Removal of graffiti from statues in Prato della Valle in Padova (italy)
• Removal of aged protective coatings from wall paintings in S. Giorgio church in San Polo di Piave (Italy)
• Removal of black crust from Istria stone from Palazzo Ducale in Venice (Italy)
• Cleaning of aged varnishes from 18th century Russian icon (Bulgaria)
• Corrosion layers removal on silver plated waiters tray 1900 (Bulgaria)
• Soot removal in St. Alexander Nevsky Patriarchal Cathedral Stauropigial Memorial-Church in Sofia (Bulgaria)
• Cleaning of tarnishing on a Daguerreotype and the reduction on glass negatives (Belgium)
• Removal of soot in St. Marina church in Veliko Tarnovo (Bulgaria)
• Removal of soot in Holy Assumption of the Virgin Mary monastrey church (17th century) in Arbanassi (Bulgaria)
• Removal of oil-overpaintings in St. George church in Golyamo Belovo (Bulgaria)
• Corrosion layers removal on “W. F. M.” Silver-plated cup – 1900 (Bulgaria)
• Corrosion layers removal on late 19th century French Gothic Paten in silver (Ag 800 w%) (Bulgaria)
• Corrosion layers removal on 20th century (1950s) Bulgarian Lock in brass (Cu/Zn 64/36 w%) (Bulgaria)
• Removable self-diagnostic coating application in Chiesa Madonna dei Broli a Farra di Soligo (Treviso) (Italy)
• Removable self-diagnostic coating application in Palazzo Costa in Venice (Italy)
• Removable self-diagnostic coating application in S. Giorgio Church in San Polo di Piave (Italy)

The intense dissemination work carried on during the last year still has to be improved also after the project if a real exploitation of the PANNA results is desired. As the Cultural Heritage field is a particular market difficult to penetrate with innovations a strong networking is needed for the product exploitation between technological SMEs and Cultural Heritage actors as research centres and SMEs. Although the technological products are almost ready, there is still a strong need of experimentation and case studies to demonstrate its potentialities and guarantee the results and the return of the investment for the “full-life” protocol customers. Therefore a restoration experts network build during the project will be used to continue the experimentation and dissemination of the “full-life” protocol.
In fact the technological innovations can be sold also separately and not only as a whole as in the “full-life” protocol. The main products are 2:

• The atmospheric plasma device
• The protective self-diagnostic and removable coatings

Both the products are already available on the market. The plasma device is patent protected and it is commercialised by Nadir who own also the IP rights. The chemicals for the coatings application are at the moment confidential formulations of Chemstream who also commercialise the product.
Since the market still has to be created the first buyers that have to be addressed are museums, research centres and reference institutions that can validate the technology on a wider range of case studies and have a higher budget for equipment. Moreover since the price of the plasma technology can be high for CH applications some equipment for rental will be prepared.
In order to reduce the time-to-market focused applications of the ‘full-life’ protocol will be performed in modern and contemporary artworks that are the main market for art galleries and auction houses. Since this market is less controlled by the public institutions and more linked to finance can offer an interesting volume for the introduction of such new and soft technologies.

List of Websites:
The website has been realised following EU guidelines.


• Veneto Nanotech Alessandro Patelli
• IENI – CNR Monica Favaro
• Rathgen Forschungslabor Ina Reiche
• University of Antwerp Patrick Storme
• Nadir Paolo Scopece
• Lorenzon Costruzioni Andrea Lorenzon
• Center for Restoration of Art Works Veska Kamenova
• Botega Z Zdravko Kamenarov
• Chemstream Frank de Voeght