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InnovativE anti-graFFiti product for Application in the Cultural Heritage of EURope

Final Report Summary - EFFACEUR (InnovativE anti-graFFiti product for Application in the Cultural Heritage of EURope)

Executive Summary:
Graffiti attacks and associated cleaning procedures cost Europe ca. 90 million € / year. Cultural Heritage (CH) is a typical market for SMEs because they provide specific case-by-case solutions; however at present these SMEs cannot offer suitable protection measures against graffiti on CH buildings and monuments, as anti-graffiti coatings are hard to find on the market for the type of materials found in CH. Furthermore the products used in CH must follow the strict guidelines of conservation practice. The development of specific CH anti-graffiti products has been delayed due to the conflicting requirements, high financial risk and lack of R&D infrastructures of the SMEs.

In this context, EFFACEUR is a clear opportunity for them to increase their competitiveness and economic benefit. Previously, the GRAFFITAGE project attracted much attention worldwide because of the innovative approach proposed to solve this problem, which consisted in the development of a polymeric charge complex with proven anti-graffiti behaviour suitable CH materials. The SME partners of EFFACEUR propose to use this novel formulation as the basis for a new anti-graffiti product that will satisfy this market. Thus, EFFACEUR aims at further developing, uspcaling and transferring into the market this novel protective anti-graffiti formulation.

The work and results obtained throughout the two project years are summarized here:
• Both latex and hydrophobised polycation further went through a comprehensive optimisation process. As scale-up proceeded feedback from formulation experiments performed by project partner CMPiW PAN became increasingly important for further adaptations. In the final phase, both main components of the EFFACEUR anti-graffiti formulation, the basic film-forming latex and the hydrophobized polycation, were successfully scaled up to 400 l reactor scale and the industrial viability of the production processes was demonstrated in the Fraunhofer pilot plant centre at Schkopau. Materials obtained in the pilot-scale polymerization runs exhibited low viscosity. Also, the physical parameters, such as solid content and particle size, were in the targeted range.

• The formulation of the new anti-graffiti paint based on modified polyanion and polycation was developed. The production technology and equipment to be used were defined. A large 100 kg charge of a new product for field tests was produced. The Technical Data Sheet, guidelines for paint application and Material Safety Data Sheet were developed.

• Reversibility tests were performed on substrates treated with anti-graffiti samples AP604-40 and the method for “reversing” the system was defined. Cleaning tests were performed with 2 anti-graffiti samples (AP604-40 and AP628-60). In the case of AP604-40, cleaning efficiency after 4 months was also tested. According to these experiments, functionality is better for AP604-40 overall but improvements are still needed. The compatibility of the anti-graffiti product with common conservation products such as water repellents, biocides and consolidants was also studied and in general, it can be said that it is good for all products except for the water repellent selected.

• Prior to applying the product on real case studies pre-tests with anti-graffiti samples AP604-40 and AP628-60 were performed on small samples of different types of substrates to get information on the drying and cleaning behaviour of the product. After, the product was applied in 4 different case studies in Germany, Belgium and UK and aspects the like application method, adherence, gloss, colour and weather resistance were studied. In general, the results were satisfying but it must be mentioned that the product cannot be regarded as permanent but sacrificial.

Project Context and Objectives:
European historic sites and cities are the pride of Europe and what makes them so attractive to hundreds of millions of visitors (around 450 million arrivals in Europe according to EUROSTAT) from all over the world. The built Cultural Heritage contributes to a great extent to Europe being the Nº 1 tourist destination in the world. Therefore, the protection and conservation of Cultural Heritage buildings is a major European aim and is laid down in article 151 of the European treaty. However, heritage buildings and monuments are still damaged by many factors - one of them is graffiti which is seen more and more often in almost any bigger European city. Graffiti is not only an aesthetic problem but can also cause damage to the historical material and it is also related to security aspects (areas in which buildings are vandalised by graffiti are often insecure and economic turnover in these sectors is going down). The graffiti attack and graffiti cleaning costs Europe nearly 90 million €/year. Suitable protection measures against graffiti on historic buildings and monuments, so called anti-graffiti coatings, are hard to find on the market because products must follow the strict guidelines and ethics of conservation practice. The numerous products available on the market are made for other purposes and do not fulfil the conservation/restoration requirements. However, the use of inadequate commercial protection products and cleaning methods are used resulting in irreversible damages of invaluable cost. Additionally, the economic costs to repair the effect of these harmful interventions are very high.

Therefore, the overall aim of this project is to further develop, upscale and transfer into the market a novel protective anti-graffiti coating respecting the Cultural Heritage requirements.
As an outcome of a previous EC research project (GRAFFITAGE ), a highly innovative nanostructured formulation based on an aqueous silica emulsion with polyampholytes seems to be a promising candidate for a suitable anti-graffiti coating overcoming the restrictions of the existing products. At the moment 2 traditional groups of anti-graffiti systems are in use applications (suitable for other than Cultural Heritage): a permanent and a sacrificial. The first type is constituted of a durable, permanent coating with low surface energy, impeding the entrance of colouring agents into the substrate lasting several cleaning processes without being deteriorated. But they hinder critically free water exchange between the exterior and the inner structure of the substrate. Besides, most of these coatings are irreversible, so their use in Cultural Heritage has been prohibited in some European countries. The second type refers to temporary (sacrificial) coatings which are easily removed during the graffiti elimination process and must be reapplied after every cleaning process. Consequently, the use of sacrificial anti-graffiti is costly and not sustainable. Furthermore, subsequent cleaning operations can damage significantly the historic substrate.
Thus, none of the coatings currently available on the market presents the necessary characteristics to be applied on Cultural Heritage objects, namely: effective against graffiti removal, reversible; permeable to water vapour and impermeable to liquid water; minimal aesthetic alterations of the substrate after application; good adhesion to porous substrates; resistant to outdoor conditions (UV light, rain, etc.); compatible with other treatments (consolidants, water repellents, etc.); an environmentally friendly formulation; cost efficient.

In this scenario, the request from building protectors, owners of monuments, restorers and graffiti cleaners is obvious: efficient anti-graffiti products for their application in Cultural Heritage must urgently be developed.
At the moment there is a clear gap between the existing technology in protecting monuments against graffiti aggressions and the existing products and technologies used for this purpose. This gap could be transformed into a promising opportunity to significantly increase the competitiveness of the European SMEs involved in protection and conservation of ancient goods from graffiti if a solution to this important problem is found. The EFFACEUR project proposes to develop a novel industrial anti-graffiti formulation and its associated production process and graffiti cleaning procedure.
The Consortium behind this project wish to address a major market opportunity in this area. All SMEs involved in the mostly SME dominated Cultural Heritage market will be most benefited by this new production technology as they lack the highly specialized know-how and R&D infrastructures needed to perform such developments. This innovative process will increase the competitiveness of these SMEs as it will enable them to provide a differentiating solution for a promising and increasing market, not only at the European level but also at the international level. It will also have a positive impact on the environment as the ingredients of this new anti-graffiti product include an environmentally benign aqueous emulsion, avoiding the use of harmful climate killers like fluorocarbons which are part of most current permanent anti-graffiti coatings.

Description of the new anti-graffiti product: the FP6-2003-SSP3-513718 STREP (Specific Targeted Research Projects) European project “Development of a new anti-graffiti system, based on traditional concepts, preventing damage of Architectural Heritage materials, GRAFFITAGE” was a three-year-project aimed at “developing a modern reversible semi-permanent anti-graffiti and waterproofing treatment of Architectural Heritage” . Within the project, a totally new and original approach was proposed for the basis of the new anti-graffiti formulation: some recent studies on the basic chemical behaviour on polyampholyte complexes and fluorocarbon residues have led to the idea to use them as starting point for the development of anti-graffiti coatings. Polyampholytes are mixed with polymeric amines, modified by silicon-based residues instead of fluorocarbon residues. Similar structures based on charged polymers and complementary fluorocarbon surfactants have been applied before as protecting coatings, including anti-graffiti. However, it proved that their use was unsatisfactory for anti-graffiti due to their low mechanical stability and poor ageing behaviour. The approach for the new formulation was based on the replacement of the low molar mass surfactants by high molar mass amphiphiles which should strongly improve the performance. Furthermore, the replacement of the hitherto used polyelectrolytes by a polyampholyte, and the choice of protonated polyamines instead of quaternized polyammonium salts will allow the facile removal of the coating under basic conditions. Historical stone, bricks and mortar materials are considered to be inert to the latter. This strategy goes beyond the present variation of two standard approaches that are not able to cope successfully with the problem of graffiti on porous building materials of Cultural Heritage.
The project resulted in the development of a pH-sensitive charge complex formed by two polymeric components. This complex is formed by a polyampholytic or amphoteric building block (Component 1) and a temporary polycation (Component 2) which are bound by electrostatic interactions , , .

Figure 2. Schematic representation of the hydrophobically modified-based polymeric charge complex.

This promising anti-graffiti formulation showed the following behaviour: hydrophobicity and good adhesion to substrates of different porosity; low colour and gloss variations after application; improved water vapour permeability and drying behaviour in comparison to current commercial products; resistance to natural weathering; reversible but resistant to cleaning agents, thus considered as semi-permanent; acceptable cleaning efficiency; environmental friendly as it is based on aqueous emulsions.
The results obtained led to a European patent request for the new anti-graffiti formulation which is at present under evaluation.
The SME partners of the EFFACEUR project proposed to use this novel formulation as the basis for a new anti-graffiti product that will satisfy the Cultural Heritage market. However, the synthesis of this formulation is up to now a multi-step, highly complex synthesis, which means that the upscaling to larger production amounts requires further research to design and develop a specific upscaling route for its components which is acceptable for the SMEs. Besides, the final formulation is not yet achieved, as improvements related to durability and compatibility with other treatments need to be undertaken.

Project objectives:

As already mentioned, the overall objective of this project is to develop a new route for the upscaling of a new anti-graffiti marketable prototype product, based on an environmentally-friendly anti-graffiti formulation which has been tailor-made for Cultural Heritage applications.

The S/T objectives of the EFFACEUR project will be the following:
-to develop the new upscaling route for the 2 components of the anti-graffiti formulation;
-to develop the production process for the anti-graffiti product;
-to optimise the properties of the final anti-graffiti product;
-to define the most adequate application and cleaning method for the new anti-graffiti product;
-to validate the behaviour and suitability of the new anti-graffiti in real case studies.

Project Results:

WP1: Exploitation:

In this WP, a market analysis was performed in order to develop a model to estimate the non-official documented efforts and budgets of public authorities to remove graffiti and to prevent it where irrevocable damage would occur by graffiti vandalism. It was concluded that it is not easy to accurately forecast the potential market of a new anti-graffiti product because no official data are collected. Two ready to use samples were produced as a result of the different approaches to produce upscaled polyanion-latex and hydropobized polycation components for the EFFACEUR product. These samples were mainly used to make pre-tests and the field tests. In spite of some very good performance peaks (handling, clearing up, water resistance) one main weak point exist for both samples: no solvent resistance. The coating was (nearly complete) washed away while cleaning with a solvent based cleaning agent. This was certified by different tests and was not a weather and substrate influence. So far these sample products have to be regarded as sacrificial systems. The text below examines the marketing impacts out of this classification as “sacrificial”.
Basic connection of decision influencing parameters of graffiti systems
The market for anti-graffiti products is characterized by the way of protection and out of this the behaviour of the protecting coatings when cleaned. The better the protection and removing characteristics and the less efforts needed for sustaining the ability to protect, the more expensive the anti-graffiti product will be. There is a direct correlation between the protection and the cleaning characteristics of the anti-graffiti products and the price. The highly potential two-component products with excellent cleaning characteristics are more expensive than simple wax-based products that are sacrificed when cleaned and must be recoated after cleaning.
The problem for heritage purposes is that protecting products with very good cleaning results are not reversible and in many cases not suitable to the historic substrates when used on them. The problems of vapour diffusion, salt transmission and water resistance are as important as the good cleaning results. Current commercial products are following this traditional structure of performance and price. The achieved performance of the new EFFACEUR anti-graffiti product to be permanent but as well sacrificial on demand leads to an outstanding portfolio position.
This outstanding performance may create a new market. Protecting heritage building against graffiti vandalism would lead to a complete new market, because the new EFFACEUR product should combine the following performance advantages:
-high substrate compatibility;
-high colour / ink / weather and solvent resistance;
-acceptable price;
-permanent with reversibility on demand.

These attributes have never been combined in one product or system before. And this would encourage heritage authorities and decision makers to invest more expenses than in the past into this new form of protection. In this sense, the EFFACEUR anti-graffiti product promises to be a good protection for heritage façades against environmental stress as well. This overall performance should be the main argument for the expected higher price of the achieve EFFACEUR anti-graffiti system.
The scaling up of the main two components of the anti-graffiti product was found to be very challenging. The results obtained so far indicate that this new anti-graffiti does not perform as a permanent anti-graffiti system, as expected, but as sacrificial. The main “k.o.” criteria was that the first ready-to-use EFFACEUR product AP604-40 shows very less resistance against cleaning. The cleaning results were good, but the product ripped off when cleaned and so it could only be regarded as a sacrificial system.

At the end of the project (in the last project month), the EFFACEUR anti-graffiti product was re-launched by the AP328-60 sample. The formulation was improved but it is not stable enough yet to be a permanent and cleaned-on-demand product. We have to continue working.
Considering the product is regarded as sacrificial so far, the position in the portfolio of substrate compatibility and solvent resistance significantly is changed. Not an outstanding position and clustered close to sacrificial and semi-permanent systems.
In this situation, it was decided to develop a more detailed market analysis once the durability of the product is improved and when the product can be regarded as permanent.
In this WP individual exploitation plans for SMEs participating in EFFACEUR were also developed. 3 different levels of exploitation were defined as shown in the figure below:
RTD and initiating SME level; Producer level; Consumer level.

WP2: Upscaling of material’s production:

In an initial phase, the shortcomings and potential weaknesses of the base materials from the predecessor project GRAFFITAGE, an amphoteric latex and a hydrophobised polycation, were identified and analysed. Based on this analysis, starting points for improvements were determined. This concerned both chemistry of the compounds and factors related to general problems in upscaling. Based on these analyses of the shortcomings and potential weaknesses of the chemistry and of the procedures, systematic variations of starting materials, stoichiometry and reaction and workup conditions were performed in the next phase. To monitor the influence of the varied parameters on-line, reactions were performed in a multi-sensor reactor. Conclusions drawn from these experiments permitted first scaling up steps. For the basic, film-forming latex, a strategy change was realised by recipe modifications. In spite of these modifications, latex performance and application properties could be kept constant in the pH interval of interest. For the hydrophobised polycation, variations in chemistry and procedures permitted an initial scale up by a factor of 25.
In the next phases, both latex and hydrophobised polycation further went through a comprehensive optimisation process. This was driven by process monitoring during synthesis and physical characterisation of the products. As scale-up proceed feedback from formulation experiments performed by project partner CMPiW PAN became increasingly important for further adaptations. In the final phase, both main components of the EFFACEUR anti-graffiti formulation, the basic film-forming latex and the hydrophobized polycation, were successfully scaled up to 400 l reactor scale and the industrial viability of the production processes was demonstrated in the IAP pilot plant centre at Schkopau.
For the latex synthesis, heat removal proved to be not critical and could be realised by wall cooling up to production scale. For larger scale reactors, a mixing system with axial flow component was required, which avoids phase separation between the lighter organic and the heavier aqueous phase. A multi-stage stirrer system was successfully applied at both 40 l and 400 l scale. Constant volume specific power input was used as scaling criterion for the mixing system.

Even after optimisation of the stirrer system, frequent coagulum formation was a challenge in synthesis of the base latex. Hence, the system needed intense optimisation at the 40 l scale.
In addition, a number of slight recipe adaptations were carried out in order to adjust product properties, mainly adjustment of TG and acidity. After taking these steps, the final latex recipe was successfully transferred to 400 l scale without particular problems. Product characteristics of these final batches on 40 l and 400 l scale are very similar and within the targeted specifications. The runs exhibited good operability and only very limited and acceptable fouling.
Starting point for the final scale-up of the hydrophobised polycation synthesis was the batch-wise recipe with temperature program developed in Fraunhofer IAP at Golm, which recipe was already successfully transferred to 40 l (filling level 25 l) scale.
However, calorimeter experiments showed a very significant peak in the reaction exothermy of about 100 kW per m³ reaction volume. Heat transfer calculations revealed that this high exothermy cannot be removed by wall cooling, if a scale of some 100 l is exceeded. Hence, recipe and experimental setups were adopted for heat removal by condensation cooling. This implied changing of the initiator system. Though the project was already in a quite advanced stage, the change was successfully accomplished.
Furthermore, the change to condensation cooling offers a convenient way of removing side products, which are formed due to partial hydrolysis of one of the constituting monomers of the hydrophobised polycation.
After switching to condensation cooling and development of the revised recipe, further scale up of the hydrophobized polycation synthesis to 40 l and to 400 l scale was fairly straightforward and thus successfully accomplished. For larger scale reactors, multi-stage stirrer systems were successfully applied; constant volume specific power input was the scaling criterion for the mixing system. Materials obtained in the pilot-scale polymerization runs exhibited low viscosity. Also, the physical parameters, such as solid content and particle size, were in the targeted range.
A number of product samples of pilot-scale latex and polycation runs were forwarded to project partner CMPiW-PAN for further formulation trials.

WP3: New formulation and final product characteristics:
during the first 9 months of the project, evaluation of modified version of polyanions and polycations were performed, the best version of polyanion and polycation were selected, and the main rules for the anti-graffiti paint formulation were developed.

In the second part of the project (months 10 to 24) a new formulation of anti-graffiti paint based on a modified version of polyanion and polycation made by Fraunhofer was developed.

In January 2012 a charge of 100 kg anti-graffiti paint AP 604-40 was produced. This charge was sent to SMEs and TECNALIA for testing in April 2012. The technology for the anti-graffiti paint production was developed based on this charge.
In December 2012 a new anti-graffiti paint based on the new modified version of polyanion and polycation was produced. This paint (AP 628-60) was sent to the SMEs and TECNALIA for testing. Experiences of preparation of large charge, led to the developing of the anti-graffiti paint production technology, choice of suitable equipment and method of testing. Physicochemical properties of this charge and properties of other compositions made in laboratory were the basis of Technical Data Sheet.

Based upon the tests performed with the developed anti-graffiti samples, the experience in use of anti-graffiti paints and application remarks from CMPW PAN, Nortech prepared the Guidelines for application of a new anti-graffiti product.
The Technical Data Sheet for the new anti-graffiti was developed containing the following information: shelf life of the product and stability during shelf life and the physicochemical parameters.

The Material Safety Data Sheet is based on the following aspects:
-chemical characteristics of polyanion and polycation from Fraunhofer IAP;
-MSDS of anti-graffiti paint components from their producers;
-final formulation of anti-graffiti paint.

A cost analysis for the new formulation has also been performed. The estimated cost of raw materials for 1 kg of anti-graffiti paint (10% solid matter content) is 2,9 euro. This calculation has been performed based on:

-raw material cost for polyanion and polycation developed by from Fraunhofer;
-cost of additives in the Polish market.

“Technical Data Sheet of the EFFACEUR anti-graffiti product”: the EFFACEUR anti-graffiti is a new ready to use one component polymer based protecting system especially designed for the protection of natural stones, as they are frequently found in heritage buildings (e.g. sandstone, limestone and bricks; ask for test references). It has been intensively tested for the most of natural mineral building substrates except substrates with higher alkalinity (pH > 8-9), such as fresh concrete and fresh mortar.

The milky homogenous liquid with light amine odour can be applied by brush or roll, and it can be sprayed. Its low viscosity permits penetration into the surface and its components will form a thin, special combined layer, which is resistant towards neutral water, acid rain and various organic solvents.

If the product is applied in two layers wet in wet it matts. Applied twice or more often with drying between each layer, the appearance will improve to silky gloss. To avoid a shiny appearance, dilute the anti-graffiti product with demineralized water between 5-7%.

SCOPE OF APPLICATION

This new anti-graffiti is easy to use and provides protection against the penetration of spray colours or marker inks, which are typically used by graffiti attackers. It also offers protection against typical environmental fall out, which pollutes natural stone construction. This product has the functional protection effects of permanent graffiti prophylaxes systems but can be removed easily on demand. Therefore, it is especially suited for all purposes in heritage building protection. Colours can be removed by using the tested system cleaner or if necessary by removing a layer. The EFFACEUR product is pervious to vapour and even transported salt and mineral in solution can be transported through the protection layer.

TECHNICAL FIGURES AND DATA

Base Special polymer emulsion, ready to use
Thinner Demineralized water
Density 1,06 – 1,10 g/ml (20°C)
Viscosity 10-12 s (20-21°C, DIN cup 53211)
Content of solid matter 9.0 – 11.0% (120°C, 1 h)
pH 10 ± 0,5 (20°C)
Color Milky, white
Storage 12 months in not opened, original cans at temperature > 5°C. After opening product should be stirred. After prolonged storage (more than 6 months) product should be filtered through the filter 125 µm.
Table 1. Technical figures and data for the new anti-graffiti product.

BASIC APPLICATION REMARKS

Preparing the surface: The surface must be dry, solid and clean and there may not be sanding or loose parts of the material.

Working condition: Temperature: > + 10 °C (best 150C) and < 40 - 45°C, 30C over dew point.
Relative humidity: max. 70 %

Application: Brushing, rolling and spraying.

Standard efficiency: 200 g/m2 depends on the porosity of stones (test before applying).

Drying: Minimum 60 minutes (20°C, 65%RH). Depending on humidity and temperature, drying time may be longer or shorter.

Number of coats: Minimum 2 coats, depending on porosity of substrate; tests must be performed on the substrate.
Recoatability: 30 minutes after drying of previous coats.

Shelter against rain: 6 -24 hours depends on humidity and temperature. Application should not be planned during rainy weather and before expected rain.

Cleaning tools: Directly after used with clear water.

Disposal: Rest of coating should be treated as regulated by environmental procedures.
WP4: Product lab-scale performance

In this WP we aimed at:
-finding the most appropriate cleaning method for the anti-graffiti coating; finding the most adequate product to make the anti-graffiti coating reversible;
-determining the number of graffiti cleanings that the new anti-graffiti can withstand;
-analysing the compatibility of the new anti-graffiti with other treatments;
-establishing the durability of the anti-graffiti coating.

Selection of cleaning method

In this task, a selection of the most common cleaning methods was made, and the pros and cons of each individual methods was evaluated, as well as which one reached the best cleaning results. Different types of methods were tested with the same anti-graffiti product on different substrates including granite, shell limestone, Carrara marble, greywacke, brick wall, white sandstone and a limestone. Different kinds of natural stones, with different physical properties, especially of their surface, as well as a brick wall-imitate were used, to cover a wide span of different characteristics. Also, different types of colours were used, with diverse chemical compositions and their different behaviour at the application process. The results were evaluated following the TP-AGS procedure. The tested methods were the BAM cleaning machine and hot water high pressure cleaning.
The BAM cleaning machine produces good cleaning results with excellent reproducibility. It is especially adequate for soft surfaces. However, hot water high pressure cleaning is the standard method for cleaning in reality. Different conditions of hot water high pressure cleaning were tested, up to 80 bars and 80°C. It was observed that soft substrates were sensitive to pressures above 20 bars. The AGS seems to be removed at temperatures above 40 °C and high pressures, too.
According to the results obtained, the cleaning conditions were set to 20 bars and 40 °C, to avoid damages of the material and the anti-graffiti product.

Results of cleaning tests:
The next step was to perform the cleaning tests on the selected substrates. Samples were coated with the 2 formulations available: AP604-40 and AP328-60.
All substrates passed the tests, according to the rules of TP-AGS procedure, but great differences were observed between the substrates. Granite showed an excellent cleaning behaviour; nearly all graffiti was removed. Very good results were reached on marble, greywacke and shell-limestone, too. But the cleaning efficiency on limestone and sandstone was clearly worse, compared to the other substrates. The analysis of the gloss conditions showed, that the application of the AGS leads to an increasing degree of gloss for all substrates. After cleaning, the degree of gloss drops down, back to the degree before coating the substrates. It is obvious, that at least at the direct surface, the AGS is removed by the cleaning process. The colour change analysis showed that there are significant changes of the colour after applying the AGS, as well as after the cleaning procedure, so the differences have to be connected to the anti-graffiti product itself. The limits, given by TP-AGS, are exceeded only in individual cases.

Determination of the cleaning cycles that the anti-graffiti product can withstand without reapplication: resistance against graffiti cleaning means the number of cleaning cycles that the product can withstand with the selected cleaning method and what is the resistance against graffiti cleaning. The efficiency of removing graffiti from natural substrates depends on the substrate itself, the anti-graffiti product and the method of cleaning. The cleaning cycles tests were performed on AP604-40 and on AP328-60, on the 7 mineral substrates mentioned previously and according to the TP-AGS procedure. Additionally, a selection of substrates coated with AP604-40 was weathered for 3 months.
The results of cleaning tests show in general a better functionality for the AP604-40, but in both cases some substrates did not pass the test. So sandstone and lime stone seems to be critical substrates for this kind of anti-graffiti formulation, because they failed the test for both anti-graffiti system after the first cleaning and also for the weathered samples of AP604-40. The tests of gloss and colour measurement showed clearly that in both cases the durability of the systems is low, which manifests in a loss of the coating after cleaning. In case of the AP328-60 the durability seems to be improved a little bit.

Reversibility testing
Reversibility refers to how the anti-graffiti product can be made reversible.
Reversibility tests were performed with the first anti-graffiti samples produced and identified as AP604-40. Samples were prepared by applying the both generations of the new anti-graffiti product on the selected EFFACEUR substrates.
In collaboration with the Fraunhofer Institute, the following products were selected for performing the reversibility tests:
-sodium carbonate salt (soda);
-a fatty acid emulsifier: sodium palmitate salt.

Aqueous solutions of different concentrations were prepared as follows: for sodium carbonate (Na2CO3 salt): 0.05M 0.5M and 1M; for sodium palmitate (Na palmitate salt): 0.05M concentration, the lowest molarity because of its high price.

In addition to this, two others products/methods were used for reversibility tests: hot water and ethanol. These two products were selected for being considered as “soft cleaning agents”. The effectiveness of reversibility treatments was assessed by SEM image analysis that allowed calculating the percentage of anti-graffiti removed for each substrate and treatment (%clean surface).
From the results obtained, 2 treatments were selected as the most effective methods for reversing the new anti-graffiti product.
1st method: the Na2CO3 salt of 1M concentration was usually the most efficient for removing the applied anti-graffiti for most of the substrates (overall %clean surface ≥ 80%). It was also considered the rubbing with scotch as a complementary effect in the case of Flossenbürg granite and Lindlar greywacke substrates.
2nd method: hot water in the case of Carrara marble and ethanol in the case of Crailshaim grey substrate.
Compatibility with other treatments. The compatibility of the new anti-graffiti product with respect to other common conservation treatment such as water repellents, consolidants or biocides was also studied. For this study, handmade brick tiles were chosen as test substrate, because in previous tests it was observed that this material was the most sensitive. The pre-treatments were done with the three mentioned conservation agents and for the evaluation of the compatibility the parameters measured were gloss, colour and functionality. The cleaning tests were done according the procedure already mentioned but only for sample AP328-60. The functionally test only failed for the sample with pre-treatment with water repellent agent. But for all combinations in general the functionality seems to be improved in comparison to the single system tests. A loss of the anti-graffiti system is observable in this case. As a conclusion of cleaning and compatibility test, there is an improvement of the stability and durability for the system between the evolution steps remarkable, but there is some work to do with a view to the cleaning efficiency. The compatibility of the new anti-graffiti with regard to conservation agents was proven and an improvement of cleaning ability was detected.

WP5: Product performance in real case studies:

The main objective of this WP was to test the new EFFACEUR anti-graffiti system in real case studies. The focus of the WP was to prove that by these field tests:
-different substrates;
-different textures;
-during different weather conditions;
-applied by different persons;
-if possible applied using different methods (brushing, rolling, spraying);
-can reliably be protected by the system.

In this WP, we learnt how to prepare, to handle and to clean substrates coated with the new anti-graffiti product. Real test applications and behaviour tests on real substrates were made. Additionally, pre-tests were performed prior to performing the tests in the case studies in order to give feedback to RTDs producing the anti-graffiti. The evaluation of the anti-graffiti product was centered in the following aspects:
-cleaning behaviour on different natural stones;
-behaviour under and influence of salt penetration;
-gloss and colour change on natural stones;
-optical and physical restoration of destroyed bricks.

Regarding the pre-tests, the work was concentrated on developing pre-test and application advice to make sure that real case studies were applied and handled in the same, comparable way.
By performing the pre-test the following aspects could be defined:
-gloss and cleaning stability;
-application test for substrates with salt penetration;
-cleaning procedure for real case studies (preparing the substrate e.g. on bricks);
-application procedure for test colours for real case studies;
-cleaning procedure for test colours for real case studies;
-application information (video, photos…) for real case studies and to be used also as dissemination material;
-monitoring the appearance after application of the EFFACEUR anti-graffiti product;
-developing data sheet for users (updated to the actual EFFACEUR anti-graffiti product);
-testing different application methods to improve stability by alternative primering.

The following real field case studies were selected:

1. Knight´s Mansion wall, Völksen (Germany);
2. Local Residence Community, Völksen (Germany);
3. Church made of typical marl stone, outside Brussels (Belgium);
4. Ss Great Britain Trust complex wall (UK).
The work done showed the strengths and the weaknesses of the two samples tested by the SMEs in different situations and on different substrates (samples AP604-40 and AP328-60). The tendencies of performances found were very similar. Therefore, the following can be stated:
-relatively good handling ;
-good water repellence;
-good weather stability;
-good cleaning results;
-good substrate acceptance on most of the substrates;
-relatively little colour and gloss changes in real field testing;
but no significant solvent resistance.

One of the greatest problems for the SME partners was not of technical nature but of “psychological”. The problem was to win the confidence of the owner of heritage buildings or heritage authorities to allow the application of the EFFACEUR anti-graffiti product. The low solvent resistance was a real problem, because traditional cleaning methods use solvents in different forms. This may be the main reason why the SMEs, in a certain way, hold themselves back in coating on large field test areas. Shaken confidence in professional work and lost reputation for SME is a central problem and it is one of their most important efforts to avoid this. No professional SME will risk this. NORTECH was able to work in the field test project Old Malt Factory. For the owner the trust in professional anti-graffiti service was nearly destroyed by bad services done before. This had created following problems like damages caused by freezing of water contained inside the substrates and destroying brick surfaces. The appearance of some small test areas convinced the owner at least to try the system. He liked the light glossy appearance that was very similar to the original gloss of not destroyed bricks. He was fully informed that up to that point of time the system was regarded as a sacrificial system. Because a permanent system was the reason for the walls damages, he accepted the sacrificial performance of the protection.

In this case study it was possible to compare the results obtained with the EFFACEUR product and a traditional wax product. The appearance of the EFFACEUR product was better, no grayish film and no weather related washing away of the product till the end of the project period. The wax product turned to a light greyish shining after 2 and half months under rain influence. Though a strong interest in getting a good protecting product for private owners of heritage buildings and heritage authorities to recommend is to be found, the tests will go on with new samples produced out of improved products components (also after the official end date of the project).

Potential Impact:

The main project outcome is a new anti-graffiti product specially designed for its application in Cultural Heritage materials (porous stones, mortars and bricks) and the associated manufacturing process to produce it at industrial scale. Considering this, the overall impacts of EFFACEUR are multiple. Firstly, the successful market transfer of the anti-graffiti product stimulates and enhances the whole Cultural Heritage sector: it is the first time that after 20 years of EC research funding that research results really enter the Cultural Heritage market. This is a great success and it will motivate other SMEs from the Cultural Heritage field to use previous research results to develop a marketable product;
secondly, this project contributes to the requests from the European Parliament that money for research needs to be converted into money generated by markets;thirdly, this project is also important for the European Commission to increase visibility for successful Cultural Heritage research and to reach the Lisbon goals of a knowledge-based society. It helps Europe to stay the Nº 1 in Cultural Heritage research and can offer high-tech products and services to the rest of the world.

The societal implications of the project are mostly addressed by the following aspects:
-improving quality of life of the citizens living in historic cities. The visual effect that graffiti aggressions causes in monuments, and the social meaning of these expressive actions (mostly related to social protests and vandalism), produces stronger societal impact than any other type of monument decay. Graffiti and subsequent inadequate graffiti cleaning originates heritage damage, causes insecurity to people living/visiting the affected cities and increases social degradation of cities. EFFACEUR faces a solution to these problems, thus highly contributing to increase quality of life;
-creation of new direct high level jobs in the field of anti-graffiti production and high added value service of graffiti cleaning, mostly highly qualified attractive jobs;
-creation of indirect jobs mostly linked to cultural tourism, by promoting social dynamisation and conservation of historic urban areas. It is difficult to estimate the exact number.

The main environmental impact of EFFACEUR relates to the design of an environmentally-friendly product because:
an environmentally benign emulsion and dispersion polymerization technology of monomer mixtures has been used;
the substitution of climate damaging fluorocarbon hydrophobes (which are used so far) has been implemented by completely avoiding the use of fluorocarbons;
there has been a decrease in the cost of the environmental management of fluorinated wastes.

Dissemination activities:
Several dissemination activities have been carried out throughout the project. At the beginning of the project, the project website was launched. This served as a means of publication of all the project information and results to the general public and to the expert public. All information published there has the publication agreement of all SMEs participating in EFFACEUR. The website contains 2 different sites: a public site and a private site. The private site provides access only to project participants and was created to share deliverables, reports, dissemination documentation and other relevant documentation of the project.
A project presentation leaflet was also designed and translated into the 7 languages: German, Spanish, Polish, Italian, French, Italian and Dutch. The leaflet has been used as a dissemination tool in events such as fairs, project presentations, conferences, workshops, etc.
Besides, presentations of the project were done at the ECTP Conference of 2011 in Warsaw (4-5 October 2011) and in the Functional Coatings Conference in Berlin (5-6 June 2012).
A poster was prepared for the Advances in Coatings Technology - ACT ’12 Conference in Sosnowiec, Poland (9-11 October 2012) and a stand was organized in the Spanish fair AR&PA (24-27 May 2012). This fair was inaugurated by the Queen Sofía of Spain.

Fraunhofer produced 2 internal articles about EFFACEUR in their annual report of 2011 and promotion was also done with Museo Vaticano, and with ASSORESTAURO (Italian association for the architecture, art and urban restoration).
Eura, Nortech and Fraunhofer, as representatives of EFFACEUR visited DENKMAL (“European Trade Fair for Conservation Restoration and Old Building Renovation”) in Leipzig in November 2012. Exploitation of EFFACEUR results
The main exploitable result of the EFFACEUR project is the procedures for large-scale production of main anti-graffiti formulation components. The purpose of the procedures is to enable production of the main anti-graffiti components on an industrial scale. They may be exploited by the SMEs involved in the project for commercialisation of the anti-graffiti formulation developed in the project. IP exists in form of the background. At present, no further IPR measures are planned. As of now, lab and field testing of the anti-graffiti formulations is continued.
If commercialisation is successful, the impact will be an improved graffiti protection of European cultural heritage and a new source of revenues for European SMEs via a new product and the offer new, qualified services.
The scale up of the anti-graffiti formulation was an iterative process. The laboratory recipes were iteratively transformed and further developed, taking into account the outcome of scale up experiments regarding process observations as well as consistency and physical parameters of the products, the feedback from the formulation tests of CMPiW PAN, and the feedback from performance tests of the anti-graffiti formulation, as illustrated in the scheme below.
The adaptations, which were made in different stages of the scale up process, and their rationale, are detailed in the table below. Starting point for formulation and performance tests were recipes for the basic film-forming latex and for the hydrophobised polycation, which were adapted for large scale production and were put into practice at lab scale in an initial stage. Test formulations prepared with these materials were compared to those from the predecessor project GRAFFITAGE, showing comparable results.

In the course of the scale up experiments, the polyanion latex development required time for intense optimisation at the 40 l scale, mainly because of coagulum formation and sub-optimal physical parameters in intermediate stages, which in turn gave rise to sub-optimal performance characteristics of the anti-graffiti formulation generated with this material.

Likewise, the formulation tests and the various performance tests inevitably required a finite amount of time. Hence, to date, the vast majority of performance tests have been made with the formulation AP 604-40, which is now outdated from the point of view of materials development.

The physical parameters (viscosity, particle size, Tg) of the final WP 2 materials closely resemble the ones of the materials, which were used for initial tests with very promising results. Therefore, all EFFACEUR project partners agreed to continue the testing after the formal end of the project with the formulation generated by CMPiW PAN using the final materials of WP 2 prepared by IAP.

List of Websites:
EFFACEUR project website: www.effaceur.eu. Contact details:
Partner 1 (coordinator):TECNALIA; address: Parque Tecnológico de San Sebastián
Mikeletegi Pasealekua, 2 E-20009 DONOSTIA (Spain); contact: Dr. Oihana García
Tel.: +34 667 178 860;
Fax: +34 94 607 3349;
E-mail: oihana.garcia@tecnalia.com. Partner 2:
Fraunhofer; address: Hansastrasse 27C
80686 MÜNCHEN (Germany); contact: Prof. André Laschewsky;
Tel.: +49 31 5681327;
Fax: +49 331 5683000;
E-mail: andre.laschewsky@iap.fraunhofer.de. Partner 3: CMPWi PAN; address: M. Curie-Skłodowskiej 34, 41-819 ZABRZE (Poland) ; contacto: Dr. Krzysztof Manczyk;
Tel.: +48 322 716 077;
Fax: +48 322 312 831;
E-mail: krzysztof.manczyk@cmpw-pan.edu.pl. Partner 4: Eura; address:
Halesfield 19, Unit H10,
TF7 4QT, Telford (United Kingdom); contact: Mr. Robert Turner;
Tel.: +44 1952 680218;
Fax: +44 1952 585044;
E-mail: Robert.turner@eura.co.uk. Partner 5: Nortech; address:
Ziegeleiweg 44,
31832 Springe (Germany); contact: Mr. Hartmuth Boron;
Tel.: +49 5041 989037;
Fax: +49 5041 989038;
E-mail: office@info-nortech.de.
Partner 6: RESTAURACIONES SIGLO; address:
Licenciado Poza, 51
48011 Bilbao (Spain); contact: Mss. Maripaz Revilla;
Tel.: +34 94 442 3222;
Fax: +34 94 442 3222;
E-mail: restauracionessigloxxi@restauracionessigloxxi.es. Partner 7: COO.BE.C.; address: Zona industriale Santo Chiodo SNC
06049 Spoleto (Italy); contact: Mr. Bernardino Sperandio; Tel.: +39 0743 220966;
Fax: +39 3355 880561;
E-mail: info@coobec.it.Partner 8: TCI; address:
Via Sorte 2/4,
24030 Barzana BG (Italy); contact: Mr. Roland Vaes;
Tel.: +32 4 73970061;
Fax: +32 1 1434189;
E-mail: rolandvaes@tecnochem.eu.