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Design and develop a new generation of color PVD coatings for decorative applications

Final Report Summary - NANO4COLOR (Design and develop a new generation of color PVD coatings for decorative applications)

Executive Summary:
In Nano4Color project a new coating design was produced for the development of a new generation of color PVD coatings for decorative applications. Coating technology for the innovative coating design deposition was successfully developed enabling the production of a wide pallet of intrinsic colors.
The motivation being we all like aesthetical pleasant colors in our every day products: kitchen and bath accessories; domestic appliances; architectural, nautical or automotive fittings; electronics components; jewelry; medical devices. In fact color coatings are present in most everyday products.
PVD is one of the most promising coating processes offering brilliant and decorative finishes, superior hardness and wear resistance and lack of environmental concerns. But up until know only a limited number of intrinsic colors is produced and interference colors limit the application only to 2D objects.
In the Nano4Color project we developed a new strategy for the production of PVD hard decorative coatings based on an innovative coating design and hybrid technologies to produce nanocomposite coatings that yield tailored optical properties.
We used 3 approaches allowing overcoming the barriers associated to the use of PVD coatings with a restricted coating composition producing a color tailored solution resulting in greater freedom for color generation; including green and red tones. In addition we designed a new industrial coating process for the coating deposition.
New coating hardware, a cluster gun, and coating processes were developed and successfully used to deposit different colors, such as red, green, pink and orange in 3D objects with different substrate compositions (metal, glass and ceramic), surface finishing’s (polished, rough and textured) and sizes from small to large 500 mm parts. Coating consistency and reproducibility was achieved in tens of produced demonstrators.
Moreover a software predictive tool was developed allowing predicting the coating color and its mechanical properties, supporting the supply of coatings with tailored made colors on costumer request.
This way, Nano4Color it’s making affordable PVD coatings for the production of everyday appliances while providing an extended color palette, increased wear resistance and lower toxic emissions.
Creative industry has been identified as a key sector for future of European industry. In the transition from traditional manufacturing to new production based on creativity and innovation, design provides additional cultural value and experience. New technological solutions are required in order to unlock the full potential of this major growth sector. One application where new materials and solutions are critical is decorative coatings with a wide range of achievable wear and corrosion resistance. Greater flexibility in the color range is essential to provide freedom for creative industry professionals from different sectors where the decorative coatings are a demand and the application requires a high mechanical performance.
One of the 3 coating deposition approaches relies on a straight forward, already mature industrial deposition process enabling the immediate up scaling and offer of the color coatings to the market. The production of colored coated demonstrators at the SME job coaters demonstrated just that.
A business plan associated with a 5 year investment plan was developed for the marketing of the coatings, coating technology and software in a joint strategy among the SME partners positioned from beginning to end of the value chain, foreseeing a revenue of more than 6 million Euros in that five year period.
On the long run, the project results are expected to have a big impact on the 18,000 European SMEs working on decorative coatings with an estimated value of 11,350 M€. These innovations will benefit the overall surface treatment sector by reducing production costs, increasing commercial margins and addressing industrial legislations. Furthermore these advantages will also benefit the industrial manufacturers who will be able to offer more pleasant products with lower costs and environmental emissions.

Project Context and Objectives:
In the Nano4Color project we developed a new strategy for the production of PVD hard decorative coatings based on an innovative coating design and hybrid technologies to produce nanocomposite coatings that yield tailored optical properties.
We used 3 approaches allowing overcoming the barriers associated to the use of PVD coatings with a restricted coating composition producing a color tailored solution resulting in greater freedom for color generation. In addition we designed a new industrial coating process for the coating deposition - the cluster gun and developed predictive software tools to support the cluster gun development and predicyion of the coatings optical properties and mechanical stress .
In work package 1, a selection of applications and product properties has been specified. Three types of applications have been identified:
1- In the first a drill (figure 1) and piston (figure 2) have been selected, the greater challenge of the color coating of these components being highly complex 3D geometries and large 3D objects respectively.
2- In the second multi faceted crystal 3D objects have been selected for jewelry and chandeliers
(figure 3), the greater challenge of the color coating of these components being highly complex 3D geometries and the use of transparent and opaque colors.
3- In the third porcelain tiles and stoneware pavement have been selected (figure 4), the greater challenge of the color coating of these components being high coating areas and coating uniformity in fine 3D details .
In table 1 there's a resume of the applications features and challenges.
Nanocluster production technology has been developed - several cluster gun prototypes as been produced (figure 5), supported by a predictive software. Several cluster gun hole designs were tested and in the end a slitter design proved to be the best model.
In work package 2, three coating techniques have been used to produce intrinsic colored coatings: the two foreseen: hybrid techniques Reactive Magnetron Sputtering (RMS)/Cluster Gun and RMS/HiPIMS and a third technique was used Co-RMS + annealing. This third technique hasn´t foreseen in the project, but in the discussion of the kick off meeting it was emphasized that the low cost of this technique, the potential to obtain the desired coating design and the strait foreword industrial scale up process (since this is a mature industrial PVD process) was the motivation to also make coating depositions using this technique (the large size demonstrators produced at the job coater partner, TEandM, premises proved using this approach was a good decision).
The proof of concept of the coating design was made early in month 9: a ceramic matrix with dispersion of nanoclusters, to produce tailored made colors. Not just different colors were obtain with different nanocluster sizes and dispersions, by all three techniques, but similar nanocluster sizes and distributions, using the three different techniques, gave origin to similar coating colors. The results obtain demonstrate without a doubt that the coating colors can be tailored, tailoring the nanoclusters sizes and distribution (figure 6).
Meaning milestone MS1 - Nanocomposite colored coatings deposited using cluster gun and HiPIMS, foreseen for month 12 early accomplished.
A wide palette of colors (blue, green, pink, yellow, brown, orange, red) of transparent and opaque colors were produced using the 3 deposition approaches. Coating optimization was performed concerning obtained color, coating deposition parameters, chemical compositional systems and costs. For the low cost objective other metals than noble were tested and dielectric nitrides instead of dielectric oxides were tested some colors like red, were obtained without the use of gold or oxides.
In work package 3 the complete characterization (HR-SEM, HR-TEM, GIXRD, transmission and absorbance/reflectance spectra using spectrophotometry and ellipsometry, plasmon resonance frequency of the nanoclusters, colorimeter for L*a*b color appearance, XRD, aspect ratio and diameter of the clusters, size effect parameter, volume fraction, layer thickness and chemical composition using EPMA ) of tens of coatings using TiO2 and Al2O3 ceramic matrix with nanoclusters of Ag, Au, Ni, Cu and Au + Ag.
Coating tests were performed under serve-like conditions to access the coatings suitability to the selected application in WP1 and also linking to the technology transfer demonstrators produced in WP5.
In work package 4 a simulation modeling of the nanoclusters formation process was developed and an unforeseen predictive model of the cluster gun was developed to support its development, in order to overcome some of the difficulties felt in its development namely the hole design and cluster gun parameters versus cluster size and distribution.
With the support of this model a slit cluster gun design proved to be the best to achieve large clusters impossible to obtain by the other 2 deposition approaches and new colors were produced.
A predictive model of the coatings optical properties was developed and successfully tested. Inputting the nanoclusters chemical nature, size and shape and also the chemical nature of the coating matrix, the software predicts the coating color. Moreover the software is also able to do the reverse meaning input a color and out put the range of nanoclusters chemical composition, size and shape and the chemical composition of the coating matrix.
Also a predictive model of the coatings mechanical properties was developed, modeling the coating stress distribution and focusing on the coatings adhesion failure prediction.
In work package 5 the developed coating technology in the previous work packages by the RTD partners was transferred to the SME partners. The predictive models were distributed to all SME partners (coating producers, job coaters and end user) and training on the models was performed during the consortium meetings from M18 to M24. A special training course was performed by RTD Inspiralia on partner SME, Alliance, premises to its development team.
The hardware coating technology was transferred to partners Alliance and KCS (the coating equipment producers SME partners. Moreover partner KCS is further developing the cluster gun using its expertise and a special coating unit on its facilities.
The process coating technology associated to the sequential deposition was transferred to PVDco and TEandM (the job coaters SME partners) and the process coating technology associated to the co deposition + annealing transferred to TEandM.
Tens of coated demonstrators were produced in both by PVDco and TEandM. The cutting tools demonstrators were selected for cutting trials because it is the most demanding operation from the mechanical performance point of view. Corrosion trials with saline environment were performed in glass coated components.
In work package 6, a plan for dissemination was established and dissemination actions were undertaken to the general public, (such as a website and the project video), the scientific community (conferences and posters) and the industry (trade fairs). Moreover training material was produced and disseminated to the SME’s.
A patent plan, 5 year investment plan and exploitation plan was developed including an exploitation agreement contract between the SME partners regulating the exploitation rules.

Project Results:
The project developed nanocomposite coating technology thru diferent coating processes, the design of nanocomposite coatings enabling tailored made colors and a simulation tool to support the relationship between the nanocomposite coating design and the obtained color and also a predictive software tools of the coatings mechanical properties, focusing on the stresses and coating adhesion.
The main project results involve the development of nanocomposite coating design, coating hardware, coating deposition processes, and predictive software:
- Industrial hybrid PVD/HIPMS equipment for nanocomposite coatings,
- Industrial hybrid PVD/Cluster Gun equipment for nanocomposite coatings,
- Tailored optical properties PVD nanocomposite coating based in HIPIMS technology,
- Tailored optical properties PVD nanocomposite coating based in Cluster Gun technology,
- Tailored optical properties tool,
- Coating Design, and
- Cluster Gun.

Potential Impact:
The project developed nanocomposite coating technology, the design of nanocomposite coatings enabling tailored made colors and a simulation tool to support the relationship between the nanocomposite coating design and the obtained color and also a predictive software tools of the coatings mechanical properties, focusing on the stresses and coating adhesion.
The impact of the Nano4color project will be tremendous. In the exploitation plan the established exploitation strategy will produce revenues over 6M€ in the first 5 years just taking into account the current client portfolio of the involved 5 SME´s.
Taking into consideration the overall potential market there are 18,000 European SMEs working on decorative coatings with an estimated value of 11,350 M€.
The PVD-based production technologies which are the backbone of the project are environmentally friendly. The proposed processes emit no VOCs and produce no toxic chemicals, either directly or indirectly. This will allow the end user SMEs of the project to develop new products suitable to replace chrome plating coatings and gain access to new markets.
The project results present a profitable and innovative solution that will contribute to raise the
competitiveness of a large group of European SMEs by offering them a new generation of coatings deposited by PVD technology, highly attractive to both surface treatment producers and end users (manufacturers of devices from different sectors: construction, automotive, medical, electronic, jewelry...).
The following market segments have been identified:
*Construction Segment
Although today, the present rate of construction for new building is below 2% in all major European countries construction sector still represents an opportunity for decorative PVD treatments due to the investments in retrofitting building which has led the production rate ranking of the 3.1 million of enterprises from the starting of economic recession. According to EU statistics, currently retrofit building market accounts for 30% of the complete building construction sector with a growing rate of 5% in 201018. Our forecast establish that the current demand of PVD technology in the potential construction market amounts to €33.21 million and it will grow to €51.51 million at the end of 2020.
* Automotive segment
The automotive coatings segment is an important component of the global coatings market. It comprises approximately 10.3 percent of the value of the total global coatings market, representing €5,478 million in sales for 2009. In spite of the decline by 14.7% in vehicle production in Europe due to economic recession, the automotive coating is projected to grow at a compound annual growth rate of 9.3 percent from 2009 to 2016. The reasons are the higher automotive production rates in Eastern Europe and the tremendous growth of this sector in Asia Pacific countries. In 2009, the European automotive OEM coatings market revenues were €1,672.5 million and in 2016 are expected to reach €2,475 million21. Therefore, PVD technology can find in the automotive sector a great potential market for decorative and anticorrosion purposes. We have estimated that the potential demand for PVD coatings has a value of €19.92 million, and it will reach the value of €35.12 million at the end of 2020.

*Electrical and optical equipment's segment
The electrical machinery and optical equipment sector is an important and strategic part of Europe’s manufacturing sector, producing a wide range of mostly high-technology products (for example, computers, switchgears or semiconductors). The microelectronics and optical equipment's encompassing semiconductors components and flat panel displays represent the largest market for PVD technology. The growth of materials in microelectronics and the fierce competition require new differentiated coatings adapting to the market requirements. The 202.6 thousand enterprises active in the electrical machinery and optical equipment manufacturing sector generates together a turnover of €710 thousand million in 2006, with an average growth rate of 4.5% per annum. Our estimations establish a current demand of €19.92 million and we have foreseen that this value will be €32.67 in 2020.
*Medical devices Segment
In 2010, revenues for the European orthopedic devices market was estimated reached €6,858 million. The market is expected to reach €9,612 million in 2016. The growth rate is likely to be 5.69% from 2009 to 2016. Although is not fully implemented in this sector, PVD process represents a promising technology with an estimated current demand of €33.21 million and forecast of €49.35 million in 2020.
*Decorative segment
This sector counts with 30 thousand enterprises which generated revenues with a value of €13 billion. Output grew each year thereafter, averaging 1.6 % per annum between 2003 and 2007.The application of PVD coatings is already a reality in this sector, but the limited number of colors available in job coaters has decelerated the demand by designers. We estimate an average growth rate of 10% for this special purpose. We have estimated a potential market of €66.41million at the end of present year reaching €75,93 million at the end of 2020.
*Other segments
Domestic electrical appliances and miscellaneous fabricated metal products, according with the growing rates of these subsectors, have a forecast demand of €10.89 million by 2020.
These figures, from all market segments show that the market opportunities for this technology exist and are significant, since the forecast of European potential markets for PVD coated products will be around €255 million by the end of 2020.
We have estimated a conservative market penetration of the 6% in the first five years over the potential market for PVD coated products. That means that in 2020, NANO4COLOR technology will achieve the 6% of market share within the surface treatment technologies taking into account the purchase of new equipments and replacement of the existing technologies.
These figures allow us to estimate the sound impact of NANO4COLOR technology in the European Coating Industry, can additionally achieve, to the project SME’s current costumer base €32.31 millions over the first five years.

List of Websites:
A project website can be found in http://www.inform.pt/nano4color/index.html
More about the partners can be found at the project website or in:
- TEandM, www.teandm.pt. Contact person Mr. Ricardo Alexandre [ricardo@teandm.pt].
- PVD-CO-SARL www.pvd-co.fr. Contact person Mr. Frédéric Perry [frederic.perry@pvdco.fr].
- KCS EUROPE www.kcs-europe.com.Contact person Mr.Peter Jaschinski [Jaschinski@kcs-europe.de].
- ALEA METAL EXPERIENCE www.aleaexperience.com. Contact person Mr.Nacho Calvo [ncalvo@aleaexperience.com].
- ALLIANCE–Concept www.alliance-concept.com. Contact person Mr. Raymond SIREILLES [contact@alliance-concept.com].
- IPN, www.ipn.pt.Contact person Mr.João Paulo Dias [jpdias@ipn.pt].
- Uppsala University, www.uu.se.Contact person Mr.Tomas Kubart [tomas.kubart@angstrom.uu.se].
- TECNOLOGIAS AVANZADAS INSPIRALIA S.L. www.itav.es.Contact person Mr.Pablo Gamallo [pablo.gamallo@inspiralia.com].