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Anti-microbial, self-cleaning copper composite coatings applied in metallic objects against infections transmission

Final Report Summary - AMSCOPPER (Anti-microbial, self-cleaning copper composite coatings applied in metallic objects against infections transmission)

Executive Summary:
AMSCopper is a successful project within the the EU Seventh Research Framework Programme (FP7) and specifically under the Research for the Benefit of SMEs funding scheme. 8 partners from five different countries participated in this 2 year project that has as a primary target to develop sefl-cleaning, anti-bacterial metallic coatings applied in everyday touched objects (e.g. doorknobs or handles) by utilization of electrodeposition technique. Objects coated with the AMSCopper coatings could cover an important social need for enhanced public hygiene.
The partners of AMSCopper have successfully combined the photocatalytic effect of the titanium dioxide nanoparticles with the anti-microbial activity of copper ions. The result of this combination was the production of composite coatings of copper based matrix that can be applied by electrodeposition to metallic surfaces, reinforced with doped titanium dioxide nanoparticles. The latter were obtained by developing an innovative sol gel method able to produce nanoparticles exhibiting photocatalytic activity by visible light irradiation. The immobilization (incorporation) of these doped-TiO2 nanoparticles in the Copper based matrix -typically exhibiting high esthetics coatings- was made by utilization the pulse plating electrodeposition method.
The resulted coatings were able to exhibit self-cleaning and antibacterial properties. These coatings have been applied to common touched objects and handles and were able to reduce the risk of getting infected by communicable diseases by a factor of 100% since the anti-bacterial measurements and validation tests showed the elimination of bacterial colonies in the surface of the coated samples.
The project was implemented in a period of 24 month and the partners have decided to continue this research job after the finalization of the project.

Project Context and Objectives:
According to healthcare experts and bacterial infections are one of the major causes of death worldwide. Especially, Health Care Acquired Infections (HCAIs) cause approximately 37.000 deaths annually, while they might severely affect an additional 110.000 across the EU in which around 4.100.000 patients is estimated to acquire them. The estimated annual cost of medical care for treating contagious diseases in Europe is about 120 €billion. Moreover HCAIs have become an immense financial burden on healthcare systems, given the fact that they cause 16 million hospital stays per year while the total annual healthcare cost for the EU is roughly estimated at 5,5 € billion .

Preventing and controlling infections is associated with hygiene in every aspect of our lives. Bacteria can be found in common places such as handrails, trolleys, door knobs or other metallic surfaces and that's why the hazard of infection is more than evident since everyone comes in contact with them several times on a daily basis. And even though hand washing and sterilisation are the best possible conventional practices, still they are not sufficient to address the problem as it shown from the above numbers.

In order to overcome this important social problem, the consortium participants propose a novel solution to be used against diseases transmission: The application of new coatings in metallic objects with photo-catalytic imposed self cleaning and anti-microbial activity. These novel composite coatings will consist of a copper alloy matrix (anti-bacterial agents) and chemically modified TiO2 nano-particles (NP) as reinforcing mean (self-cleaning agents), and will present enhanced photo-catalytic activity under visible light irradiation. These new coatings will be applied in various metallic objects - such as handles, door knobs or bedrails - that can potentially be reservoirs of communicable viruses and will lead to a decrease of the risk of getting infected by a factor of >80% .

The leading partners of the AMSCopper project were the 4 participating SMEs:
1. Cerpotech that is a company producing nano-powders and has in the market a wide range of products utilizing innovative methods.
2. Tecnochimica that is a company in the field of finishing industry and more specifically produces and trades electrolytic baths for various plating applications
3. Lofran that is a company applying a various range of coatings both for decorative and functional applications.
4. Axon Engineering that is a metal manufacturing company producing various metal articles and metal components.
Additionally to the four SMEs, a large enterprise (a Private Hospital) participated in the project as an end user for validation of the new technology.
Finally, 1 university (Brunel University) and 2 research institutes (CERTH and Tecnalia) supported the SMEs in the research and development activities.
The main objectives of the project were:
1. Develop a method for producing doped TiO2 nano-structured particles in a sufficient and efficient way, able to deliver up to 20 kg per day of doped nano-powders. The TiO2 powder should exhibit low band gap (<2.3eV) in order to be activated under visible light irradiation.
2. Deliver an appropriate copper alloy electrolytic bath containing TiO2 nano-structured -particles with a maximum load of 50g/lt and also suitable organic additives. Also deliver the operation ranges for pH and temperature of the bath.
3. Set up a direct current process for applying copper alloy composite coatings.
4. Set up a pulse electroplating production line to apply copper alloy composite coatings able to operate at various values of Ton and Toff times with a lower limit of 5 ms.
5. Develop o direct current plating method for applying copper alloy composite coating. Provide the ranges of current density and hydrodynamic conditions of the system.
6. Develop a pulse current plating method for applying copper based composite coatings exhibiting anti-microbial activity, self-cleaning character and adequate mechanical and chemical properties (e.g. corrosion resistance) in metallic objects. (e.g. handrails, cart handles etc).
7. Obtain copper alloy composite coatings with doped-TiO2 nano-structured particles co-deposition rate higher than 10 wt.%.

Project Results:
In order to successfully achieve the objectives set in the project and to manage to bring up to a TRL-5 the technologies described in the DoW the RTDs performance have accomplished the following work in order to surpass the technical barriers:

At WP1 the main objectives were to generate data on the overall specifications and requirements of the anti-microbial/self-cleaning coatings as well as on the methods for production of titania powder and electrolytic coatings. For that purpose all partners have worked together in order to:
- Define the desired properties or TiO2 powder and the production methods
- Specify the chemicals, additives and other constituents and parameters of the electrolytes
- Define equipments for plating process focusing on pulse plating method
- Define the reliability test methods

At WP2 the most important target was to develop a method for production of doped-TiO2 nanoparticles exhibiting low band gap and photocatalytic ability under visible light irradiation. The achievements of WP2 were:
- Significant reduction of energy band gap (lower than 2.0eV) of TiO2 nanoparticles produced by HEBM by using doping elements such as C, Nb, Cu, Ze, Ag. However, the photocatalytic activity was not sufficient.
- Interested results were the reversible thermochromic and photochromic effect that Cu-doped TiO2 and Ag-doped TiO2 presented, respectively produced by HEBM
- By utilizing the wet method of sol gel (contingency plan) doped-TiO2 nanoparticles (doping elements were S, N and Ag) it was able to produce nano-structured powder with reduced band gap (<2.3 eV) and also efficient photocatalytic activity. The corresponding degradation percentage of methyl orange pollutant after 6 hours of visible light irradiation was more than 50%.

At WP3 the main objectives were to set up the plating equipment with emphasis in the pulse plating method and to deliver a suitable formulation of copper based electrotyte containing the TiO2 nanoparticles. The output of this WP was:
- Delivery of bench scale plating line
- Formulation of a free cyanides copper-nickel bath with appropriate additive containing 50g/L TiO2 nanoparticles operating in pH range 2,2-2.6 and temperature 27-33oC with current efficiency >95%.

The objectives of WP4 was to develop direct and pulse current electroplating techniques for the bath prepared at WP3 as well as to optimize the plating parameters for succeeding maximization of the TiO2 codeposition in the copper based matrix and consequently enhancement of photocatalytic activity. The results of WP4 were:
- Optimization of DC regime succeeding co-deposition rate of TiO2 nanoparticles up to ~9%wt
- Optimization of PC regime succeeding co-deposition rate of TiO2 nanoparticles up to ~11%wt by applying two different parameters.
- Characterization of samples with SEM-EDS, XRD, Salt Spray, verifying the high quality of the

At WP5 the main objectives were to accomplish the micro-biological, photocatalytic and contact-angle (self-cleaning ability) tests. The results showed:
- Reduction up to 50% of pollutant in photocatalytic tests by visible light irradiation.
- Reduction of bacterial coatings up to 99.9% for test conducted for Staphylococcus aureus and Pseudomona aeruginosa. This result confirmed that the main antibacterial effect was provided the copper metallic matrix.
- Significant reduction of the contact angle (up to 35o) of water droplets on the surface of composite coatings under visible light irradiation compared to pure copper coatings.

WP6 had as target the successful plating of real metal articles (handles), the proper installation of the aforementioned coated articles and their testing to real environment conditions. Also the compariosof the results with pure copper coating and uncoated objects present in the same places. The results from these activities were extremely promising:
- The metal articles were successfully deposited by the developed plating baths by applying both direct and pulse current regime
- The handles were installed in various places of the Metropolitan Hospital
- The tests conducted in the samples and especially the swamp method showed significant reduction of the CFUs up to 3-4 times in comparison with the reference samples

Finally, at WP7 dissemination (e.g. participation in conferences, website launch and video) and exploitation (e.g. business plan, SWOT analysis etc) activities were undertaken by all partners.

The overall foreground of the AMSCopper is shown below:

Result 1: Method for production of doped-TiO2 nano-particles via sol-gel method
Type of result: Process/methodology
Description of result
This result concerns the methodology for production of doped-TiO2 powder. It includes, the starting materials and the steps of the process (preparation of starting materials, hydrolysis process, reaction, condensation, purification, heat treatment and milling).
The initial plan was for production of doped-TiO2 via High Energy Ball Milling process. However, during the first period it was found that although HEBM process can provide doped nano-particles with low energy band-gap (<2.3 eV), their photocatalytic activity was not enhanced in the visible light. This was attributed mainly in condamination reasons. Thus, the contingency plan written in the risk mitigation table was initiated and the sol-gel method process was followed. The resulted nano-particles exhibited both low band gap and excellent photocatalytic activity.

Result 2: Doped-TiO2 nanoparticles with such a low band gap that will be able to be activated indoors
Type of result: Product
Description of result
This result concerns the produced powder. The testing and validation of the produced powders was undertaken by the RTDs and the methodology for this testing is part of the result.

Result 3: Electrolytic bath used on copper salts, doped-TiO2 nanopowders and appropriate additives
Type of result: Product
Description of result
This result concerns the formulation of the electrolytic bath for the electroplating process including the proportions of chemical salts, acids, dispersants, additives and doped-TiO2 nanopowder. Also, the proper steps for preparation of the bath including the adjustment of bath parameters such as pH, temperature and hydrodynamic conditions are mentioned.
A deviation from the initial plan was made in the synthesis of the bath after the first review meeting. As it was discussed in that meeting, pure copper coatings might be vulnerable to oxidation and tarnishing effect. Thus, it was decided to proceed with an alloying system of Copper – Nickel for higher protection from oxidation.

Result 4: Method for electroplating Cu-TiO2 coatings exhibiting anti-microbial, self-cleaning properties indoors
Type of result: Process
Description of result
This result concerns the methodology for application of the Copper based composite coating on metal articles. It contains two methodologies:
- Direct current plating
- Pulse current plating
This result also contains the pre-treatment process of substrates, the optimum parameters for obtaining coating with enhanced photocatalytic and anti-microbial activity as well as the materials used for the electroplating process

Result 5: Coated metal articles with Cu-TiO2 coatings exhibiting anti-microbial, self cleaning properties indoors
Type of result: Product
Description of result
This result concerns the products obtained by the applying the methodology of result 4 and concerns the different coating obtained as well as analytical characterization of their structure and properties, focusing on the self-cleaning ability and anti-bacterial activity.

Potential Impact:
The products and services that resulted from the AMSCopper, may find applications in six major market segments as follow:
Six market segments have been identified up to now to concern to photocatalytic materials: construction, consumers, environment, automotive, medical and energy. The ‘consumer’ sector is mainly interested in building envelope air cleaning devices, components with anti-bacterial properties and other photocatalytic household appliances. Photocatalytic products in the construction sector account for the largest share of the market, with 2009 revenues of $740.3 million (or 87.4% of the total). The agents (applications) for cleaning water or air, for the removal of mold, and for indoor and outdoor coatings are available for domestic use and the industry. In 2014, the worldwide market for photocatalytic products was ca. €1.6 billion. The expected compound annual growth rate (CAGR) will be 14.3% for the next five years. The sales volume of construction materials representing the largest sector was approximately €3.9 billion by 2014. The CAGR for consumer products is predicted to rise by 13.2%over the next five years (the market volume was ca. €148 million in 2014).
However, the fraction of nano-enabled products has been increasing during recent years, and this trend is likely to continue in future. Moreover, cleaning of the environment is not the only aspect of photocatalysis, as the positive results are also visible in applications that are related to energy, namely extraction of fuels by water (hydrogen) fission or by reduction of carbon dioxide in the artificial process of photosynthesis which leads to the very much desired re-use of the CO2 emissions. Japan is the global leader in photocatalytic applications with respect to both production and consumption of photocatalitic products. Asian market of photocatalytic products was estimated to be near 500 M USD in 2010 and forecasted to grow to near 900 M USD in 2015. The market is projected tocontinue increasing driven by demand in Asian and developing countries. The Chinese market is growing rapidly and photocatalytic TiO2 nanoparticles for self-cleaning and deodorizing effect are in strong demand in the rest of Asia. EU takes second position with near 175 M USD in 2010 and expected to grow to almost 450 M USD by 2015.
The surface finishing technology sector is part of mechanical engineering and metal working and focuses on the treatment and coating of metals in specialized industrial manufacturing SMEs. According to Eurostat, in 2010 a turnover of €30 billion was generated involving 22,000 companies operating in EU27 with 330,000 employees. Germany, France, Italy, Spain and the UK are leading the industry in Europe with more than 10,000 surface engineering companies. Statistics in Germany highlight the sector’s high segmentation, as 800 electroplating companies are recorded employing 44,000 people (55 on average) and 2.100 small companies employing 49.000 people (23 on average). However, thanks to wide range of applications and the significant added value generated to most fabricated products, the surface finishing sector’s contribution to the European economy is remarkable. The surface finishing industry’s production accounts for the 0,9% of the European GDP, however indirect value is considerably higher, taking into account for example savings achieved through the prolonged lifetime of surface protected products which otherwise would be exposed to increased corrosion, wear, melt or abrasion (reaching 10-20% of GDP) [ ].The produced by MMCs exhibiting photocatalytic and anti-bacterial activities targets the following markets:
There are around 15.000 hospitals operating in Europe with approximately 3.000.000 beds [ ]. With an average of 6 beds per room we have 500.000 rooms, which with the addition of 500.000 other rooms (administrative, storage rooms and toilets) reach the number of 1.000.000. Given that a patients’ room contains usually 2 doors (=4 doorknobs), 6 cabinets / dressers / bedside tables (24 handles), 2 taps, 2 windows (=2 handles), an average number of 20 items per all kind of rooms can define the potential quantity of coated objects that can be sold per room (=20.000.000 items).
According to Otus Analytics [ ] there are more than 14.700 hotels in Europe operated by the major international chains, which are more eager to invest to our product’s functionality. With an average of 190 rooms per hotel and 20 items per room, the SelfClean potential sales could reach the 55.860.000 objects.
Electroplating Companies
The consortium plans to start licensing the product’s electroplating process in 2019, given that the consortium SMEs cannot satisfy the market’s needs at this time. The procedure will target the 22,000 electroplating companies operating in the EU27.
Other Technological applications
TiO2 nanopowder can be also used in other technological applications such as photocatalytic paints, sprays for buildings, solar cells and cars. The manufacture of Titanium Dioxide (TiO2) nanoparticles is a significant niche industry and demand for these materials is strong. 50,400 tons of nanoparticle TiO2 was produced in 2010, representing 0.7% of the overall TiO2 market. By 2015, production is projected to increase to 201,500 tons.
Secondary potential markets
Apart from the above mentioned markets, there are some secondary potential markets that will be investigated at a later stage in order for the SelfClean products to be promoted.
The school buildings sector consists a really big market with enormous sales potential. Indicatively, according to Eyridice, [ ] in France there are 6.748 public pre-primary schools, 194 private pre-primary schools, 37.075 public elementary schools, 5.336 private elementary and 11.413 collèges and lycées, which in total makes a number of 60.766 school buildings. In the UK there are 33.892 school buildings (3.326 nursery, 21.968 primary, 4.176 secondary, 2.542 private mainstream, 1391 special schools and 489 pupil referral units). In Greece there are 14.030 school buildings (5883 public pre-primary, 312 private pre-primary, 5.443 public primary, 370 private primary, 1892 public secondary, 130 private secondary). In Denmark there are 2.777 school buildings (1.600 Folkeskole, 760 private elementary, 148 gymnasiums and HF-courses, 117 vocational colleges, 152 higher education institutions). In Spain there are 21.227 school buildings (5.810 private and 15.417 public). Only these 5 countries consist a market of 132.692 school buildings. With an average estimation of 100 items sold per school, there is a capacity of 13.269.200 items only for these 5 countries. Extending the market to the other counties of E27 and the rest of Europe will give obviously great results.
Finally, the public transportation market has great sales potential as well. Only in Great Britain [3 ] the total number of public service buses is 84.500 (46.300 buses, 23.000 coaches, 15.200 mini buses). Coating the plenty of handles and handle bars will create real profit for the SMEs .The sales expansion of sales to trains and underground wagons as well and the penetration of the whole European market will boost the profits to enormous numbers.

Thus, the participating SMEs have a wide market range where they can be active by adopting the new technologies in their production lines. Preliminary financial estimations have shown that the AMSCopper technology may have a significant impact in the business of the participating SMEs reaching a total increase of revenue of more than 7.000.000 after 5 years from the adoption of the technology. This will lead to the creation of at least 70 new employees position in the companies.

Concerning the wider impact in the European community.
Approximately 4 100 000 patients are estimated to acquire a healthcare-associated infection in the EU each year. The number of deaths occurring as a direct consequence of these infections is estimated to be at least 37 000 and these infections are thought to contribute to an additional 110 000 deaths each year.
The most frequent infections are urinary tract infections, followed by respiratory tract infections, infections after surgery, bloodstream infections, and others (including diarrhoea due to Clostridium difficile). Meticillin-resistant Staphylococcus aureus (MRSA) is isolated in approximately 5% of all healthcare-associated infections.

The technology of a self cleaning – antibacterial coating may provide an additional weapon on solving the problem of viruses and bacteria transmission through inanimate objects such as surfaces of common touched objects like knobs, handles etc, will be very easily accepted by the majority of the society. Dramatically reducing the main factor for hospital-acquired infections and spread of epidemics will not only offer a feeling of security to people, but will also give a relief to the national insurance systems both in terms of vacancies in hospitals as well as concerning the cost of health care treatment of such cases.

AMSCopper has extremely promising results since the technology that was tested in the Metropolitan Hospital has shown reduction of the bio-burden in the surfaces of doorknobs up to 100%. By proper application of the AMSCopper technology in various common touched objects and surfaces a reduction of more than 20% in HAI can be achieved.

AMSCopper consortium has proceed to the following promotional activities:
1. AMSCopper website. A project website where the project is presented to the general public Useful information about the project is presented including the objectives, the benefits and the workplan of the project. Additionally the partners of the project are presented, their role in the project and a link to partner’s website is provided.
2. AMSCopper printed material: Posters, leaflets and other printed materials have been used for the dissemination of the project
3. AMSCopper video: A video has been released showing the basic principles of the project as well as the main results. The video can be found in:
4. Participation in conferences.

List of Websites:
Public website address:
Contact details:
Dr. Alexandros Zoikis-Karathanasis
Center for Research and Technology, Hellas
email: -
tel: +30 6948724831