RADTECH RADTECH RADTECH EUROPE
Promoting & Developing UV & EB Technology in European Industry
RTE plans 2014 Reporting
RTE Conference 2013 Innovation Award winner News from the Industry Update
Update on REACH
December 2013, Issue No. 2
RADTECH NEWS www.radtech-europe.com
Calendar of Events Q1-Q2 2014 February 2014 4 – 5 European Coatings Conference: Parquet and furniture coatings
March 2014 2 – 4 6 – 8
Print UV 2014 Paintindia 2014
Las Vegas, USA Mumbai, India
April 2014 7 – 9 8 – 10 8 – 11
American Coatings Conference 2014 American Coatings Show 2014 Paintexpo 2014
Atlanta, Georgia, USA Atlanta, Georgia, USA Karlsruhe, Germany
RTE Advertisement: Low priced deals for high exposure in industry Advertising in RTE RadFlash (e-newsletter) Place a static banner (630 x 150 pixels) in the monthly online e-newsletter of RadTech Europe. Only € 100,- for placement in one issue and € 1.000,- for one whole year (12 editions)! Online advertising on RTE website The RadTech Europe website (www.radtech-europe.com) is the go-to source for the European UV and EB industry. On average, the site attracts 5,000 pageviews on average divided over 1,400 visitor sessions on average per month. In the months surrounding the RadTech Europe Conference & Exhibition or other leading projects, the RTE site attracted nearly 2,500 visitors per month. A lot of this traffic is generated by registered visitors, potential RTE members that remain updated on RTE’s activities through regular newsflashes. Your company’s digital advertising reaches all those directly involved in, associated with, and even just interested in, the UV/EB Technology. NEW: Business Case With the new and improved RTE website launched in October 2011, RTE offers a whole new way of advertising. If you are a RTE member and you are interested in more exposure for your company’s latest developments/products, make use of the Business Case on our website! You get a full page on the RTE website, together with short summary which will be featured prominently on the home page and related industry pages, giving you maximum exposure on the relevant parts of the website. Ask the Secretariat for more information. Advertising in RTE News RadTech Europe offers members and non members the possibility to place an advertisement in the RadTech News. Prices per issue: € 1.500,- for 1 full colour page and € 750,- for a ½ full colour page. All advertisers taking up an advertisement in one or more issues of RadTech News will get the opportunity to add one page editorial space in the magazine. The article should be of general interest to our readership.
Media Rates RTE e-zine 1 page per issue (full colour) ½ page per issue(full colour)
Members € 1.500,- € 750,-
Non-Member € 3.000,€ 1.500,-
Business case online Banner in RadFlash One newsletter Per Quarter One year
- members only -
€ 250,- € 500,- € 1.000,-
- members only - members only - members only -
For agencies 15% discount on rates will apply. All prices excl. VAT
If you are interested please contact the Secretariat at firstname.lastname@example.org or find more detailed information in the Advertisement & Media Rates 2014 brochure on http://www.radtech-europe.com
Word of the President
Calendar of events
Word of the President
RTE Conference & Exhibition 2013
2014 RTE announcements
Winner Innovation Awards
Paper: UV-cured hybrid sol-gel coatings for
aeronautical and Direct-To-Metal
How to become a member of RadTech Europe?
Visit us at www.radtech-europe.com for more information and to download the registration form 2013 or contact the RadTech Europe Secretariat at email@example.com
Welcome to the 3rd RadTech News of 2013. As the year comes to a close, it is time to reflect on our activities, the UV and EB industry as a whole and to look forward to 2014. Although the affected by the current economic tide, our 25th anniversary conference and exhibition in Basel once again gathered a good audience for the cutting edge advances in the UV and EB domain. With an elaborate report later in this issue, let me state that it was a pleasure to see so many of you, including some who have been around since the dawn of the association. Looking forward, we will discuss the future format of the conference in the beginning of 2014. Over the years, the event has developed into what it has been in recent years: a leading technical conference, coupled with an exhibition on UV and EB technology. While the conference - the foundation of our association – continues to be a highly respected and appreciated event throughout the industry, we will review whether the format can be improved to even better serve the industry. Looking at the industry, visibility of UV and EB technology and RadTech Europe itself have increased over 2013. Certainly the PR programme has made a significant contribution here, providing access to end-user media and spreading the word on UV and EB. Likewise, the series of discussions between RadTech Europe and related associations such as CEFIC, EuPIA, ECMA and Intergraf are treading new ground, breaking down old walls and provide positive energy going into 2014. UV and EB are not a standalone industry –acceptance by endusers is key to our success, and we are opening up new venues. The next step here will be to continue our successful run of seminars in 2014, with an EB and food packaging seminar scheduled for the second half of the year. As a member, take advantage of these and spread the word to your customers – the events provide an excellent opportunity to learn about our technology and meet the experts! Another area of closer cooperation has been between the RadTech associations themselves. We were
pleased to welcome RadTech North America to speak in our plenary session this year, giving an overview of developments in the American market. Likewise, it was my honor to be invited to participate in the opening ceremony of RadTech Asia and to have our management committee present at the discussion panel in RadTech South America. Exchange of information between the associations, particularly in the area of health, safety and environment is increasing, and goes to strengthen the RadTech community as a whole. And that brings me to the close of this Word of the President: the community is what gives RadTech Europe its strength. Your active input and participation help us shape the industry and clear paths for wider use of UV and EB technology in the future. Best wishes for the New Year and to a successful 2014! Yours sincerely,
David Helsby President of RadTech Europe
RADTECH NEWS www.radtech-europe.com
GROWING THROUGH INNOVATION: RadTech Europe celebrates 25 years of its members’ achievements in UV/EB curing ‘The RadTech Europe event fully represents the wide-ranging chemistries, hardware, and enduse applications today for UV and EB curing technologies’, says RadTech Europe’s President, David Helsby
The two-yearly RadTech Europe Conference and Exhibition has become a major event on the radiation curing industry’s calendar, across a wide range of downstream markets -- from printing and packaging to flooring, automotive, electronics, and consumer goods. 2013 was no exception. Around 400 delegates from the world of radiation curing converged on Basel’s Congress Centre, 15-17 October 2013, to explore the event’s headline theme: ‘UV/EB – growing through innovation’. The event was an unmatched opportunity to learn about what is new in the scientific arena, in regulatory and health and safety concerns, and in innovation across a broad spectrum of applications. An exhibition that hosted 34 major industry suppliers from around the world – and also provided a convenient location for networking in conference breaks -complemented the intensive conference programme, which featured parallel sessions that enabled delegates to follow their own specific interests. RadTech Europe 13 was not only the thirteenth such annual event, but also the opportunity to celebrate RadTech Europe’s 25 years as the professional pan-European association promoting the use of UV/EB curing technology for inks, coatings, and adhesives. ‘Curing’, says RadTech Europe President David Helsby, ’is a process in the manufacture of many products, and a key factor in finishing that makes fit-forpurpose goods’. The association’s high visibility within the industries it serves is, he adds, ‘a reflection of our exceptionally strong, expert membership, and of the committed volunteer teams that constitute our board, and the conference programme committee which puts together such an inspiring event.’ Conference proceedings opened with the association’s annual general meeting, followed by a plenary introductory session chaired by Dawn Skinner, Heraeus Noblelight Fusion UV (UK), who welcomed participants, and set the scene for the following days. Reminding delegates of the event theme – growing through innovation -- she introduced the event’s keynote speaker, Dr James Bellini,
who delivered a thought-provoking and stimulating series of perspectives on tomorrow’s world, underlining the many ways in which innovation is driving the future. The market profile
included such tasks as marble repair on and offsite; cosmetic fingernail decoration; repairs to car windscreens; dental curing tasks; textiles and clothing; inkjetted solar panels; membrane panels; and the production of contact lenses.
It was then the turn of Paul Kelly, Perstorp (SE), on behalf of the RadTech Europe Marketing Committee, to deliver a wideranging overview of the market for energy curing. With supply and demand of crude acrylic acid now very close, he said, new capacity needs to be identified to keep the industry on track. In 2010, it represented 1.9% of the global coatings market, projected to grow by the end of 2013 to 3% and 3.9% in 2014. The AsiaPacific region commands the major market share – 5.4%. Worldwide, usage is mostly in industrial coatings (44%), with OP lacquers a 21% share, electronics applications 19%, and printing inks 12%.
In Europe, it is the German-speaking countries – Germany, Austria, and Switzerland – that command by far the largest market share overall, 40%. In terms of end-use markets, wood coating is by far the most important, representing 38% of usage, with OP lacquers and printing inks in joint second place with 22% of the market.
Mr Kelly went on to look at current market trends, quoting from the The Global Radiation Cured Products Industry market report, produced by Kusumgar, Nerlfi & Growney, Inc. in the spring of 2013: ‘new applications such as inkjet, field applied floor coatings, and waterbased UV could stimulate growth beyond modest growth prospects.’ He examined the current incursion of UV LED into traditional UV lamp territory – expected to grow at a CAGR of 43% through 2017, and highlighted developments in 3D technology – ‘once’, he said, ‘seen as prototyping, now often seen as OEM manufacture’.
Regulations and compliance
As well as these trends, Mr Kelly delivered an exciting list of applications for radiation curing taken from RadTech Europe’s innovation sessions – which
In the graphic arts markets, there are differences in predicted growth rates. Between 2011 and 2016, mainstream packaging use will grow at an estimated 24%, but UV inkjet print for labels and flexible packaging will see an estimated 250% growth over the same period. Environmental considerations are as strong in the market for printing inks as elsewhere, and of all the environmentallyfriendly ink technologies, UV inks are the fastest growing. UV inkjet inks are a major global growth opportunity, accelerating to an estimated 38% of the total market by 2017. In Europe, industrial coatings, Mr Kelly said, geographical growth to the east of Europe is evidenced, alongside significant technology shifts reflecting increased emphasis on energy costs, weatherability and corrosion resistance, among other factors, and increased interest in waterbased UV and EB systems. Regulatory and compliance requirements, from REACH and the Swiss and German ordinances to brand owner compliances and restrictions on components such as solvents and BPA create challenges for all curing systems – but radiation curing is well placed to meet them. ‘The Unpredictables’
Mr Kelly ended by defining the real threats to the industry, today and tomorrow, which he described as ‘The Unpredictables’: volatility in crude oil and raw materials prices and availability, as well as in freight and interest rates, and fluctuations in currency and stock markets. David Harbourne, Fusion UV Systems (US), and President of RadTech International North America, provided an
RADTECH NEWS interesting view of the parallel UV/EB markets on the opposite side of the Atlantic. Awards presentations
The agenda moved on to the important duty of announcing the winners of RadTech Europe’s Innovation Award and the Paul Dufour Award for the best-written conference paper -- named after one of the founding fathers of RadTech Europe, Paul Dufour, in recognition of his contribution to UV/EB technology. Both awards went to France this year: the company VisioTechnic received the innovation award for their NUMERICOAT® process. And Dr Nadia Moreau from Socomore was honoured with the Paul Dufour Award for her research paper on coatings for aeronautical and direct-to-metal applications. Specialist parallel conference sessions After lunch and networking in the exhibition area, the conference programme began in earnest with the first three (of twelve) specialist parallel sessions organised to give delegates the optimal choice of content for their personal needs and interests. Advances in photochemistry and polymerisation
Under the joint chairmanship of Prof Xavier Allonas, University of HauteAlsace (FR) and Prof Masamitsu Shirai, Osaka Prefecture University (JP), experts from academe, joined speakers from the commercial world to discuss and document scientific advances in photochemistry and polymerisation.
UV-reduced graphene oxide nanocomposites as a sustainable solution for the production of conductive graphene or conductive inks were proposed by the Politecnico di Torino (IT). Storage-stable thiol-Ene formulations, and their advanced applications in 3D printing were introduced by Vienna University of Technology (AT); and the University of Haute-Alsace (FR) described their study of the use of holographic recording and RTFTIR to optimise a photocyclic initiating systems for visible light.
A new UV-triggered tin-free catalyst offering improved processing times for 2K-PUR coatings and other practical benefits was introduced by BASF (DE), and Solutia (US) presented their timeresolved EPR study of singlet oxygen in the gas phase of coatings – which may affect their properties. Adhesion and adhesives
The key topic of adhesive curing was the subject of a second parallel conference session, chaired by Dr Dietmar Dengler of Delo Industrie Klebstoffe (DE). SolutiaEastman (US) looked at control release additives (CRA) and the peel release values of silicone release liners. Poly-Chem (DE) explained how polymeric hydrogels synthesised by the use of photopolymerisation and photocrosslinking deliver unique advantages across a number of end uses. Rahn (US) examined the basic energycurable laminating adhesive formulations for specific low-viscosity applications, and identified the differences between them. Esstech (USA) looked at ways to improve adhesion on metals such as stainless and tin-free steel and plastics such as PET, polycarbonate, and polyethylene. Metal, plastic, and automotive coatings
Metal, plastic, and automotive applications were the subject of the third parallel session, under the chairmanship of Dr Susanne Piontek, BASF Coatings (DE). High-throughput experimentation for coating new UV-curable paints for metal, based on a novel workflow, was detailed by Ocas (BE), while Socomore (FR) introduced UV-cured hybrid sol-gel coatings for aeronautical and direct-tometal applications – a project undertaken with financial support from the French government, Airbus, and others. The latest developments in energy-curable resins for state-of-the-art hardcoat applications, offering lower shrinkage and improved durability and abrasion resistance, were profiled by Allnex (BE), while DIC (JP) presented UV-curable polysiloxane-acrylic hybrid resins for the high-durability coating of plastic substrates. Allyl-functionalised triazines, used as crosslinking additives in UNcurable clearcoats have, as Fraunhofer IPA (DE) showed, evidence a positive effect on properties such as acid resistance, adhesion, and scratch resistance. The session concluded with a study of the rheological effects of novel thermal radical initiator used as an alternative crosslinker for dual-curable automotive clearcoats, researched by Korea University (KR).
The first day ended with a ‘poster session’ enabling manufacturers to deliver short commercial presentations on new product introductions, which preceded an evening of live music, food and drink in the exhibition area – RadTech Europe’s celebratory Silver Jubilee party, which saw Mr Helsby honour founders of, and key contributors to the association. He also announced a list of honorary members, granting retired former Presidents entry to future conferences. More on photochemistry and polymerisation
Next morning, the core topics of photochemical and polymerisation advances were once again the subject of a major conference session spanning the whole morning, and co-chaired by Prof Xavier Allonas, University of HauteAlsace (FR) and Prof Christopher Bowman, University of Colorado Boulder (US), featuring reports from academic authorities around the globe. Vienna University of Technology (AT) reported on investigating the reaction mechanisms of photoinitiators using magnetic resonance techniques. The University of HauteAlsace (FR) described how they have synthesized new linked dye-coinitiator molecules for highly-efficient red photoinitiating systems in free radical polymerisation. The University of Colorado Boulder (US) pointed the way to possible advances in materials research in such fields as photolithography, coatings, and adhesives through their research into a new approach to photopolymerisation reactions using the photoinitiated copper CuAAC reaction. The synthesis and characterisation of a novel fluotinated photoinitiator with benefits for decreased oxygen inhibition were presented by the Beijing University of Chemical Technology (CN), while Vienna University of Technology (AT) looked at the properties and commercial promise of highly-efficient novel initiators for twophoton induced polymerisation; and the advantages of new, highly-sensitive nonionic photoacid generators for i- and g-lines were examined in a paper from Osaka Prefecture University (JP). EB processing
Running parallel with this session was a
RADTECH NEWS www.radtech-europe.com programme on EB processing, chaired by Urs Läuppi of Comet (CH), which addressed small EB accelerators in a paper from Electronic Crosslinking (SE); a versatile, low-cost EB lab unit, presented by Comet (CH); low-voltage EB curing for high product throughput applications, explained by Energy Sciences (US); sustainability advantages of EB curing, and the effect of amine synergists on the EB curing properties of acrylate-based coatings from PCT Engineered Systems, (US); a comparison of UV and EB technologies for web-offset printing in short-run packaging applications from Müller Martini (DE).
downstream users, and Rahn (CH) discussed the notification of substances in the Swiss and German ordinances of materials. Food contact – a key issue in today’s marketplace – can be an opportunity, or a challenge, for radiation curing, according to BASF SE (DE), and the official authority for chemical and veterinary investigations, CVUA Stuttgart (DE) provided its ‘viewpoint and flashlight’ on migration and food contact print. OpSyTec (DE) provided a safety and risk assessment for UV curing systems, while Solatell UV Services (UK) discussed practical measurements for the safety assurance of the UV curing process.
Formulations and coatings
UV equipment and process control
A third parallel session on the second morning introduced another important topic – developments in formulations and coatings, chaired by Christopher Vergé, Sartomer Europe (FR), which highlighted high-performance building blocks for radiation-curing resins in a paper from Evonik Industries (DE); using silicones as a cross-linker in UV-cured systems, from Siltech (US); water-repellent acrylic photopolymers containing fluorinated monomers, from the University of HauteAlsace (FR); polyurethane itaconates – introduced as a new class of UV-curing binder by Fraunhofer WKI (DE); and minimising the impact of water on UVcured formulations, from Sartomer Europe (FR). New chemistries
After a break to enjoy lunch and tour the exhibition, delegates made their choice of three more parallel sessions. An innovation session dedicated to new chemistries, chaired by Barbara Fenzi of Lamberti (IT), focused on novel components, oligomers, and additives that are encouraging the growth of UV technology. Papers presented covered fluorosurfactants for UV coatings from Merck (DE); self-curing acrylate resin for UV inks and coatings for indirect product packaging, from Allnex (BE); new pigment-stabilising dendritic oligomers, from Dymax, USA; new multifunctional aromatic amine synergists from Citifluor (UK); and photopolymerisation using photolatent amine catalysts, from the University of Haute-Alsace (FR). HSE considerations
Health, safety, and the environment features are of considerable importance in the world of radiation curing, as elsewhere. In a parallel session focused on HSE legislation and issues, and on the safe use of UV/EB technology, chaired by Peter Rutishauser of Rahn (CH), speakers provided valuable updates on legislation and best practice. The ReachCentrum (BE) delivered an overview of REACH 20102018, and its impact for producers and
Dawn Skinner chaired the third parallel afternoon session on developments in UV curing equipment and process control, and her colleague from Germany opened the session with a review of an energyefficient colleagues UV solution for crosslinking hotmelt pressure-sensitive adhesives. Osram (DE) looked at VUVirradiation for additive-free matting, and Heraeus Noblelight Fusion UV (USA) examined the non-reciprocity of exposure of UV-curable materials, and the implications for system design. A presentation from IST METZ (DE) covered the modular MBS-3D system for threedimensional UV curing, while Heraeus Noblelight Fusion UV (USA) looked at advances in microwave-powered UV curing using solid-state, switch-mode power supply with a real-time diagnostic capability, and Fraunhofer IFAM (DE) talked about new UV detectors, offering high long-term stability, for the UV-A to UV-C wavelengths. New applications for UV/EB technology
On the final day of the conference, RadTech Europe President David Helsby of Rahn (CH) chaired an innovation session on new applications for UV and EB technology that are already taking market share or developing the future. Comet (CH) opened with a review of the world’s first compact, sealed 3000kv eBeam source. Energy Sciences (US) discussed in-line printing and lamination for packaging using EB curing; and Heraeus Noblelight Fusion UV (DE) introduced innovative solutions offering optimal curing quality using a combination of UV LED and UV-C lamps. Xenon flash sintering of aerosol and ink jet printed metal inks for the cost- and resource-efficient production of electronic devices was investigated by Fraunhofer IFAM (DE), and Vienna University of Technology (AT) introduced photo-curable P-AMPS-based proton exchange
membranes for low-temperature direct methanol fuel cells. The successful fabrication of microfluidic devices for chemical and life science applications using the photopolymerisation of acrylic oligomers and photolithographic processes was demonstrated by the Politecninco di Torino (IT). Conductive fibres, as the Swiss Federal Laboratories for Materials Science and Technology (CH) showed, can benefit from electrical insulation and protection against H2S corrosion through the use of plasma metallisation technology. The session concluded with a discussion of a UV varnish from Dumax (IT) that meets all ‘wish list’ criteria from the print sector. The graphic arts sector
Bernd Miller of Siegwerk (CH) chaired a parallel session looking at current progress in printed applications for UV curing. Inline monitoring of conversion on an offset press was introduced by the LeibnizInstitut für Oberflächenmodifizierung (DE), while Fraunhofer IVV (DE) introduced a new approach to evaluating the indirect transfer processes of printing ink compounds into foods from UV-printed packaging, and Lamberti (IT) detailed a new photoinitiator for clear and pigmented systems. Strong growth in UV flexo and UV inkjet have revived interest in amine-modified polyether acrylates, and BASF SE (DE) introduced their researches into the performance parameters of a new range of such products which can extend the reactivity level beyond that of known market standards. The implementation of UV LED curing in flexo printing – the subject of a paper from Phoseon Technology (USA) attracted high delegate attendance, proof of the keen interest in the technical, commercial, and environmental benefits in the technology today. The design for a UV-curable blocking primer that is compatible with digital printing (and additionally flexo) on low-barrier packaging films was explained by Agfa-Gevaert (BE), and Sartomer Europe (FR) introduced the safety of the safety of the current levels of BPA to which humans are exposed. Novel testing approaches have raised potential health concerns, and are driving authorities today to re-examine the prescribed limits. With the global trend in UV and EB moving towards ‘zero risk’ curing, the company has developed new products based on alternative, BPA-free chemistries which can be used to replace epoxy acrylates in most applications. Major UV inkjet market study
Market trends to 2018 in the UV inkjet
RADTECH NEWS print arena were set out in a paper from Smithers Pira (UK), based on findings from a major new market report published in conjunction with RadTech Europe -- The Future of UV Inkjet Printing to 2018 – which features quantitative market data for each region by print format and end-use market; key technology developments; and an analysis of key drivers. Formulations and coatings
Developments in formulations and coatings were once again the subject of a parallel session on the final day, chaired by Nils Erik Persson of Bona (SE) which focused on high-value solutions for end users. UK consultant Arthur Green looked at photoinitiator/sensitiser interactions and future possibilities for UV inks and coatings. Photoinitiator systems for use with LEDs and laser diodes in the visible light spectrum were the theme of a paper from the University of Haute-Alsace (FR), while Rahn (US) compared current UV LED curing technology with the traditional UV model, highlighting the single challenge presented by the
adoption of UV LED – effective choice and efficiency of photoinitiators. Huntsman Advanced Materials (CH) discussed new powerful and versatile stabilisers and stabilisation systems using photocurable polythiol-based (meth) acrylate resins which potentially represent versatile solutions for any polymers. The photopolymerisation of acrylate monomer mini-emulsions in a photochemical reactor using UV radiation has been explored by the University of HauteAlsace (FR), and their paper discussed not only the fundamentals but also implementation in the photoreactor. The formulation of resistant UV-curable coatings using nanosilica is proving to be the answer for many high-performance demands, as Evonik Hanse (DE) showed. They have explored the practicalities of successfully incorporating nanosilica at different particle sizes into traditional binders for UV-curable coatings to deliver a reliable solution. Participants in RadTech Europe 13 were
enthusiastic about the whole programme, and received a useful memento of the event in the form of a lively Anniversary Yearbook. The conference and exhibition combined outstanding networking opportunities across the whole supply chain and a formal conference agenda that unquestionably answered the chosen theme – growth through innovation. The President’s summary
Looking back on the event, RadTech Europe President David Helsby comments: ‘I was particularly happy that the theme of ‘growing through innovation’ was fully represented in the many exciting and new applications introduced in the various presentations; and, while every industry is still suffering from the after-effects of the global financial crisis, I was also delighted with the commitment shown by exhibitors, speakers, and delegates. The RadTech Europe conference and exhibition is a unique and broad forum and networking opportunity that is undoubtedly contributing significantly to driving the future profile of our industry.’ www.radtech-europe.com
RadTech Europe’s plans for 2014 RadTech Europe discusses with food packaging stakeholders, plans new food packaging seminar
Following the well-received seminars on safe use of radiation curing for food packaging, RadTech Europe has launched a series of discussions with associations throughout the value chain of the food packaging industry in order to identify the core questions, challenges and concerns in the value chain surrounding the use of radiation curing technology for food packaging and the role RadTech Europe can play in addressing these. Discussions with representatives of the European Chemical Industry Council (CEFIC), the European Carton Makers Association, the European Printing Ink Association (EuPIa) and the European Federation for Print and Digital Communication (Intergraf) have now taken place. While most discussion took place between the Graphic Arts Committee and representatives of the technical committees of the other bodies, RadTech Europe was invited to speak at a meeting of Intergraf with its national representatives. More discussions will be scheduled shortly, amongst others with FINAT, the European labeling association and brand owner associations. Establishing these connections is a crucial next step to ensure the acceptance and
safe use of UV and EB technology for food packaging. All stakeholders agreed on the importance of closer cooperation and exchange of information in the food packaging safety domain. For a start, presentations from RTE and the other associations at each other’s seminars could provide a helpful point of view to the audience. In addition, there was a lot of interest in the de-inking study done by RadTech Europe in cooperation with INGEDE. In the area of Public Affairs, EuPIA and CEFIC underlined the importance of the role of RadTech Europe in communication and marketing of the efforts of the industry, such as the on-going work on the REACH registration of substances, as well as the dossiers for submission under the Swiss Ordinance for food contact materials. Such efforts clearly demonstrate the commitment and pro-active approach of the industry. Given the request for more information from the end-user associations, the Graphic Arts working group will organize another food packaging seminar in the second half of 2014. Since the start in 2007, this series of seminars has become the go-to place for updates on food packaging safety in the UV and EB domain. Supported by the closer links with end-users, as well ass the new PR programme, we expect
attendance and publicity to exceed previous editions! Watch our newsletters for more information as it becomes available. EB seminar at end-user facilities scheduled for 2014
Meeting at RadTech Europe 2013, the EB committee has agreed to a follow up to its well-received EB seminar in 2012. Scheduled for September 2014, this event will again take place at an end-user of EB, this time in Norway. As such, it will offer participants a great chance to experience the practical implementation and benefits of EB-systems. It will also serve as a thorough introduction to the technology for companies new to EB. At the seminar you will: • learn about the benefits of modern EBtechnology in coating and printing technologies. • have the opportunity to visit an operating production plant. • learn about the strategic choice that was made to select Electron Beam Curing technologies as the heart of the production-line. • have the opportunity to talk to the people who designed, financed, built, operate and maintain an industrial EB plant. We will keep you posted as more news becomes available on this exciting event!
RADTECH NEWS www.radtech-europe.com
RadTech Europe honours award winners at biennial conference Celebrating innovation for the construction industry and research in coatings for aeronautical applications
innovation award for their NUMERICOAT® process. And Dr. Nadia Moreau from Socomore was honoured with the Paul Dufour award for her research paper on coatings for aeronautical and Direct-toMetal (DTM) applications. Innovation award: serving today’s architecture and construction industry
Arena-VT: Park & Suites Arena in Montpellier, France - Amethyst gemstone design on steel cladding. Architect: A+ Architecture.
RadTech Europe announced the award winners of its 13th conference edition that took place in Basel, Switzerland, last month. The association works consistently on identifying, comparing and communicating the numerous advantages of radiation cure technology. In addition, RadTech Europe strives to stimulate and reward research and development in the industry by distributing the biennial RadTech Awards for Innovation and the Paul Dufour Award for the best research/ paper. Both awards went to France this year: the company VisioTechnic received the
Sthyppolite-VT: Water treatment facility in St. Hyppolite, France - Local landscapes design on steel cladding.
“The RadTech award is open to all companies utilising UV/EB technology innovations. The award recognises and encourages innovative companies which manufacture products using radiation curing technology, while promoting the future development of UV & EB technology by highlighting its many benefits and new possibilities,” says David Helsby, President at RadTech Europe. “That is exactly what the winning NUMERICOAT® process from Visio Technic reflects - it is a combination of sustainable surface treatment and creative digital printing.” “Over the last decade, architects have been showing tremendous creativity by making the buildings they design as original as possible,” says Martin SaunierPlumaz, Sales and Marketing director at VisioTechnic. “The NUMERICOAT® process is a coating technique that allows users to transfer any digital image into the middle of a high resistant thermohar dening primar. This enables architects and construction builders to bring a unique design and effect to facades that is both durable and artistic. Moreover it is graffiti, UV and fire resistant.”
of ‘UV cured hybrid sol-gel coatings for aeronautical and Direct-To-Metal (DTM) applications.’ UV-curing technology and hybrid sol-gel chemistry have been combined to develop a single-step route toward chromate-free coatings. These novel UVcured hybrid sol-gel coatings have been found efficient to protect aeronautical substrates against corrosion. Moreover, this innovative out-of-bath technology can be applied on a vast array of substrates including metal and composites. “The research done on this topic has been part of my PhD,” says Ms. Moreau. “It has been a very rewarding and fun process so far, and I wish to gratefully acknowledge my colleagues and co-authors for their support. For researchers, receiving an award and recognition from the industry brings additional encouragements in our future scientific endeavors.” “Given the fact that papers at the conference typically number well over a hundred, winning one is no small feat,” comments Dawn Skinner from Heraeus Noblelight Fusion UV Inc. and Chair of the Conference Programme Committee at RadTech Europe. “The Programme Committee agreed that this paper combined academic research in a demanding application area and communicated the results in a clear and informative manner.”
Paul Dufour award: pioneering research and best conference paper
In 2003 the traditional award for the best conference paper was named after one of the founding fathers of RadTech Europe, Paul Dufour, in recognition of his contribution to UV/EB technology. The award, now in its tenth year, has become the UV/EB curing industry standard of excellence and is bestowed upon the most innovative paper presented at the conference. This year, Nadia Moreau, product manager at Socomore presented her winning paper on the opening day of the conference in the session called ‘Developments in metal, plastic and automotive.’ The paper covered the topic
Nadia Moreau: Product Manager Socomore
Public Relations 2.1 – communication befitting the future of the curing industry With the theme for this year’s RadTech Conference being ‘Growing through Innovation’, it seems fitting to share with you duomedia’s far-sighted ‘innovative’ approach in communication. Or as the agency calls it, Public Relations 2.1.
RadTech Europe’s activities. We want nonmember companies to join the organization, so that RadTech Europe grows even stronger and more representative of the radiation curing community.
Managing Partner Anja D’Hondt shares duomedia’s eight principles for ensuring RadTech Europe continues to influence the media agenda.
Remember, if you conduct your business in an honest and genuine way, you’ll eventually build a loyal following of people who want to support what you’re trying to achieve.
Principle 1 - Community building
In the business world, a community is a group of organizations and companies that share the same values, and one of their main goals should be to contribute to the prosperity and growth of their community. Being part of a community doesn’t mean ticking off set ‘community tasks’. You can contribute just by working hard, doing a good job, and doing the right thing by people. In return, your community members will recognize your efforts. One of the overarching goals of the PR programme is to ensure RadTech Europe makes a positive contribution to the UV/ EB curing community. In addition to the media outreach work, we are striving to integrate the social media channels to help RadTech Europe interact with the radiation curing community, as well as other related communities. Principle 2 - Value-based communication
Every company needs clear values and should live by them in their daily operations. It’s also really important that values are embraced by everyone in the organization. We are helping RadTech Europe to express the organization’s values – and those of the membership – through thought leadership pieces on how to improve the radiation curing industry. Principle 3 - Spiritual motivation
Adverts, direct mailers and even articles aren’t enough on their own to mobilize stakeholders. You have to engage with them and move them – motivate them to join your community. Essentially, it’s about generating an emotion to spur involvement – and this is what we’re trying to achieve in promoting
Principle 4 – Horizontal relations
interested in editors’ local markets. And from a commercial perspective, translated communications save editors’ time and money, and ultimately are more likely to be published. Principle 7 – Corporate social responsibility
For any organization, it’s very important to show how that it makes the effort to look beyond its own interests and support organizations, charities or people directly. This should be a genuine activity, and not used as PR stunt.
When it comes to respecting opinions, people believe their peers more than any anyone else in the supply chain, especially the organization or company selling the product / service.
Principle 8 – Ongoing innovation and creativity
This is why we’re so keen that RadTech Europe’s members promote the organization to non-member companies. If they hear first-hand from a like-minded member company how they’re benefitting from their involvement with RadTech Europe, they’re far more likely to join. And when they do, the community gets bigger and stronger, and all the member companies benefit.
In today’s digital era, consumers’ and businesses’ needs change quickly. Also, technology is evolving at a rapid pace. So it’s really important that companies constantly innovate and explore new technologies and creative ways of working.
Principle 5 - Authenticity and integrity
This is all about your image reflecting your true values and identity, and adopting an ethical code of conduct. And, crucially, all staff conducting themselves in the same way. So from RadTech Europe’s perspective, it means all members acting appropriately and responsibly to protect and enhance the reputation of the organization. In turn, member companies benefit from being part of a trusted and respected organization. Principle 6 – glocalization
From a commercial perspective, the world is getting smaller – which means you need to think global but act local. From RadTech Europe’s point of view, we want to reach out to as many companies and related organizations across the globe as possible. This is why when we draft a news release or feature article etc., we often translate and re-purpose them for local markets. We’ve believe that this investment pays big dividends. From a long-term, relationship-building perspective, translated documents show we’re
A company or organization that sticks to the same products and principles for too long will eventually fail.
This is one reason why RadTech Europe could embrace social media output. We have to move with the times. We appreciate that not everyone is a fan of LinkedIn, Facebook or Twitter. But from a communications perspective they’re crucial, cost-effective platforms for publicizing RadTech Europe’s activities. In summary, if we all adhere to the above principles we’ll continue to generate goodwill and credibility for RadTech Europe, internally and externally. It’s a lot of effort but well worth it – a strong, positive reputation is one of the most valuable and powerful assets RadTech Europe can have.
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RadTech Europe’s PR programme – telling the story of radiation curing Our PR campaign in collaboration with Duomedia has launched early 2013 to tell the strong story of radiation curing and increase the awareness and market share of UV and EB technology. For an association who has long been focused primarily on supporting its members, catering to end-user markets has been the next logical step, but one with its own specific challenges. By showing the benefits of UV and EB curing in various market segments and promoting RadTech Europe as a whole, we are in the process of establishing a much stronger media presence outside of the traditional radcure industry. Looking at the first half year of the programme, we’ve issued three press releases and three feature articles: • The Perfect Cure? • The Future of Electron Beam Curing • Today’s Best Practice in Achieving Functional and Decorative Coatings The first articles were of a rather general nature by necessity, in order to introduce end-user markets to the concept of radiation curing. As we move forward, we will issue more and more end-market specific articles, which should considerably increase pick up by the press. Looking at the results
From March till August 2013, we’ve generated 86 online clippings of our releases. In the printed media, 40 clippings were published, with more than 25 printed articles over 1 page in length.
As expected, the majority of articles have been published in Germany (48%), but surprisingly high interest was generated in Italy (16%) and in Spain (13%). The translation and issue of our articles in multiple languages might have played an important role here. Overall, given the early stage of the PR campaign, the results so far are very encouraging. Beyond the published material, contacts by the press and endusers with the association have increased notably. Our story in 2014
With the basic story now established, we will continue to strengthen RadTech Europe’s position in the media. RadTech Europe’s marketing committee is now in the process of deciding the topics of choice to ensure the needs of the members are best served. We have much to shout about: technologies that provide a host of advantages for a variety of applications in terms of VOC reduction and curing speed, as well as print/coating quality. The EB and food-packaging seminars scheduled for later 2014 will provide ideal platforms for showing our expertise and addressing the press. As we go forward, keep a look out for us in the press and be sure to share any ideas you may have for articles with us. After all, radiation curing is a story worth telling for all of us!
Health, Safety and Environment update REACH Draft update of substance evaluation planning for 2014-2016
ECHA has prepared a proposal to update the Community rolling action plan (CoRAP) for 2014-2016. The draft update contains 125 substances that are proposed for review by 22 Member States under the substance evaluation process of REACH. It contains 56 newly selected substances and 69 substances that come from the update published on 20 March 2013. New factsheet explaining the follow-up to dossier evaluation decisions
Dossier evaluation covers compliance checks and testing proposal examinations. Both processes may lead to ECHA decisions requesting further information from registrants. In the follow-up to these decisions ECHA assesses whether the registrants provided the requested information by the deadline set in the decision and whether this new information should lead to further actions. A new factsheet has been published clarifying this follow-up stage. New note for guidance available on treated articles
The European Commission has finalised support material related to treated articles under the Biocidal Products Regulation. The document is structured in the form of questions and answers, addressing the most frequently asked questions, and a link is available from ECHA’s treated articles web page. ECHA publishes updated Guidance on the Application of the CLP Criteria
The European Chemicals Agency (ECHA) has published an update to the Guidance on the Application of the CLP Criteria following the conclusion of a full consultation process. The Guidance is now available in the ‘Guidance on CLP’ section of the ECHA website.
food safety Council of Europe Food Contact Material Database Belgium has received a mandate from the Council of Europe (CoE) to maintain and enrich a database containing all substances known and used in food
contact materials (FCM) in the Member States after 2013 and will be supervised by an advisory group at the CoE.
human health aspects of its risk assessment prior to finalising its scientific opinion.
The database consists of a compilation of lists of known substances which can be used in FCM. It is based on national legislation, EU regulations and directives and, resolutions of the Council of Europe. The database will contain approximately 10 000 substances including their CAS number and their presence in the FCM existing lists at national and European level. It will include the output obtained with existing QSAR prediction software (i.e. Toxtree and Derek). The ultimate goal is to establish an exhaustive database containing all the listed substances and the references to the existing regulations linked to their toxicity data.
RadTech members to start work on Swiss & German Ordinance Dossiers for photoinitiators
A co-funding from the private sector in addition to the public funding is expected. EFSA public consultation for assessment of BPA
EFSA has launched a public consultation on an updated and extended assessment of exposure in Europe to bisphenol A (BPA), a substance used in food contact materials and in other products. The Authority’s last exposure assessment of BPA was in 2006 and this new assessment will mark a major update, encompassing both dietary and non-dietary sources (including paper, inhalation and dust). With the first phase now finished, the second stage is to start in early 2014, when EFSA will publicly consult on the
PRA Supplement For each RTE News edition, PRA World Coatings supplied us with a RADnews industrial and technical supplement. Unfortunately due to a shift in priorities at PRA, it has decided to cease its journals, publications, abstracting and library activities with immediate effect. RadTech Europe and PRA are now looking for possible replacement services for the future. RTE would like to thank PRA for their great input over the years and apologizes to the members for the lack of a RADnews supplement in this issue. In this edition, to replace the PRA supplement, we have included the best paper winner of the 2013 RTE conference; UV-cured hybrid sol-gel coatings for aeronautical and Direct-To-Metal (DTM) applications, presented by N. Moreau of SOCOMORE (page 11 and 12).
A number of RadTech Europe members are participating in a joint initiative together with EuPIA to prepare food contact dossiers for a number of commodity photoinitiators such as EPD, 369 and TPO-L. In these dossiers, toxicity data as well as real-life migration data will be presented to the Swiss authorities to achieve a listing on the Swiss positive list and attain the highest acceptable migration limits. In addition, the data is to be presented to the German authorities. EuPIA members will provide migration data and any other information relating to their areas of expertise to allow the authorities to determine the highest levels of acceptable migration. Clearly, it is in the best interests of the industry to cooperate on all of these issues in order to maintain an innovative and customer safety focused industry. All RadTech Europe members and other companies are invited to join this initiative – should your company be interested, please contact the RadTech Europe secretariat for more details. For an up-to-date overview of the project and the involved companies, please see the RadTech Europe website.
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Winner of Paul Dufour award RTE Conference 2013 UV-cured hybrid sol-gel coatings for aeronautical and Direct-To-Metal (DTM) applications N.Moreau1, L. Ni2, C. CroutxĂŠ-Barghorn2, A. Chemtob2, T. Bouder1, G. HervĂŠ1 1
SOCOMORE, ZI du Prat, CS 23707, 56037 Vannes Cedex, France firstname.lastname@example.org 2 Laboratory of Macromolecular Photochemistry and Engineering (LPIM), University of Haute-Alsace, ENSCMu 3 rue Alfred Werner, 68093 Mulhouse Cedex, France email@example.com Introduction Corrosion protection in the aeronautic industry is a key issue. Nowadays, multilayer coatings are used to protect aeronautical metallic substrates. A typical system contains hexavalent chromium, or chromate, to provide high active corrosion protection, and is made up of three layers applied on a previously prepared surface. However, hexavalent chromium is an extremely toxic, carcinogenic, mutagenic and environmentally hazardous compound. From 2017, the use of chromate will be subjected to authorization under the REACH directive. Hence, the replacement of chromate compounds is an urgent and major issue for the aeronautic industry. Up to now, EADS Businesses Units including Airbus have succeeded in replacing chromate in anodizing and etching (chemical acid treatment to deoxidize and prepare metallic surfaces) steps. In addition, different alternatives based on inorganic and organic inhibitors, low temperature plasma deposition or sol-gel coatings1 have been investigated so far and reported. To date, none of these approaches has been found to be as efficient as chromate-based coatings. In the framework of MHYRCEA project belonging to ANR research program, we have combined a UV-curing technology and hybrid sol-gel chemistry to develop a single-step route toward chromate-free coatings. Our UV-driven procedure is compliant with novel environmental regulations and the reduction of manufacturing cycle time in the aeronautic industry. In addition, the hybrid sol-gel materials have demonstrated good passive corrosion resistance for metal substrates because of their good adhesion on metals and their ability to form dense barriers to the penetration of corrosion initiators2-4. This single-step process combines a photoinduced sol-gel process and a cationic (or free-radical) organic photopolymerization5,6. Through the catalysis of a phototoacid generator, the organic groups carried by the organoalkoxysilanes can photopolymerize with an organic resin while an inorganic network is formed simultaneously by inorganic polymerization of the alkoxysilyl groups7,8. The organic resin affords more flexible and thicker coatings than pure inorganic sol-gel layers. The present study focuses on the characterization of these novel UV-cured hybrid sol-gel coatings, and the understanding of the protective mechanism. The first part presents a range of characterizations of hybrid coatings prepared with an epoxy resin and n-alkyltrimethoxysilane precursors exhibiting different chain lengths. The second part discusses the performances of UV-cured hybrid sol-gel coatings in terms of corrosion protection on various substrates including aeronautical substrates and composites, solvent resistance, UV stability and adhesion. Experimental part Materials and coating preparation The different n-alkyltrimethoxysilane precursors used to synthesize hybrid sol-gel coatings were n-butyltrimethoxysilane (C4TMS), n-dodecyltrimethoxysilane (C10TMS), n-
octyltrimethoxysilane (C8TMS), n-hexadecyltrimethoxysilane (C16TMS). Irgacure 250 , denoted I250, ((4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate at 75 % in propylene carbonate), was used as a photoacid generator (PAG). Darocur 1173, denoted D1173; (2-hydro-2-methyl-1-phenyl-propan-1-one) was used as radical source. The cationic resin used was an epoxy resin (denoted ER) and the radical resin was a dimethacrylate resin. Two UV-cured hybrid sol-gel coatings were compared to three DTM coatings cured at room temperature. The Table 1 gives the main characteristics of these formulations. Table 1: Composition of the UV-curable and DTM formulations.
UV-curable hybrid sol-gel formulations Formulation Photoinduced sol-gel Corrosion and… inhibitor UV HSG 1 Cationic no photopolymerization UV HSG 2 Radical no photopolymerization
DTM Formulations Resin
Corrosion inhibitor yes
Coatings were applied on the substrates (AA2024-T3 or steel panels or BaF2 pellets) using an automatic film applicator equipped with a wire wound bar. Aluminium panels were specifically treated before application with an alkaline degreasing solution and an acid etching. The photopolymerization of UV-curable hybrid sol-gel formulations was performed using an UV-conveyor system equipped with a belt speed of 10 m/min and a Fusion lamp (H bulb). Each film was polymerized in 5 successive passes (total light dose : 7.3 J/cm 2). The DTM formulations were polymerized at room temperature during 7 days without UV exposition. After curing, the average thickness of each coating was measured by eddy current instrument. Characterization techniques Salt Spray Test (SST) Salt Spray Test (SST) was used for assessment of the corrosion resistance of metallic materials. This test is performed according to the ISO 9227 standard and compares the actions of different coatings on corrosion protection in an artificial atmosphere. The coated panels were placed into the cabinet at 35 °C ± 2°C on racks with an angle of 20° ± 5° from vertical. They were exposed to an artificial fog produced from a sodium chloride solution at 50 g/L ± 5 g/L. Its pH shall be 6.5 to 7.2 at 25C°C±5°C. The appearance of corrosion on panels was examined regularly and any sign of corrosion (i.e. uniform corrosion, pits,…) was reported. Real-Time Fourier Transformed Infrared Spectroscopy (RT-FTIR) The epoxy consumption and methoxysilyl hydrolysis were monitored by using RT-FTIR in transmission. For these measurements, the formulations were applied onto a BaF2 crystal, and then exposed simultaneously to an UV light and also to an IR analytical beam at room temperature. The IR spectra were recorded by a Bruker Vertex 70 Spectrophotometer equipped with a MCT detector. The resolution of the infrared spectra was 4 cm-1. The irradiation device was a Hamamastu L8252 He-Xe equipped with a reflector at 365 nm and coupled with a flexible light guide. The light intensity was 200 mW/cm2. During UV irradiation, the evolution of the band at 3050 cm-1 (epoxy C-H stretching) was selected to determine epoxy function consumption. The disappearance of the vibration band at 2840 cm-1 (CH3symmetric stretching) enables to assess the kinetic of hydrolysis of methoxy functions. Nuclear Magnetic Resonance spectroscopy (NMR)
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The 29Si cross polarization Magic Angle Spinning (CP MAS) solid state NMR experiments were performed on a Bruker Avance II 400 spectrometer with a Bruker double channel 7 mm probe. In this case, zirconium rotors were employed at 79.48 MHz using a recycling delay of 5 s, a spinning frequency of 4 kHz and a contact time of 4 ms. Contact angle Water contact angle measurements were performed with a KRUSS DSA 100 material equipped with a video camera. The measurements were made at room temperature by means of the sessile drop technique. Ten measurements were performed for each sample and averaged out. UV and chemical resistance The QUV accelerated weathering tester enabled to simulate outdoor weathering and reproduce the damage caused by sunlight and rain. The UV resistance was evaluated conform to the cycle 1 of the ASTM G154 standard. Gloss retention was measured according to the ISO 2813 standard at 60°. The chemical resistance is conformed to the ISO 2812 standard. The coated panels were exposed to chemicals at room temperature by drop contact or by full immersion. Adhesion evaluation To assess the resistance of coatings to separation from substrates, cross-cut tests were performed according to the ISO 2409 standard. A measurement of the adhesion of coatings was done before (t=0) and after 14 days immersion in water (t=14) at room temperature. Results and discussion Understanding protective mechanism of UV-cured hybrid sol-gel coatings The starting point of this study was to use a completely new UV-driven sol-gel process to synthetize a corrosion protective coating on AA2024 T-39. A photolatent photoacid generator (PAG) was used to cure a film based on from n-alkyltrimethoxysilanes and epoxy resin10. Hydrolysis and condensation of the inorganic moieties of a hybrid organoalkoxysilane precursor could be achieved by the photogeneration of Brönsted superacids following PAG decomposition. The cationic photopolymerization of the epoxy functions takes place at the same time. The combination of both organic and inorganic photopolymerization through a one-step UV-curing process led to the formation of innovative coatings having interesting corrosion protection performance since, as shown Figure 1, only few corrosion pits were observed after 400 hours exposure to SST. When increasing the alkyl chain length from C4 to C8, corrosion protection was significantly enhanced. However, moving from C8 to C16 decreased the corrosion protection performance.
Figure 1: SST results after 400h exposure for CnTMS/ER in 50/50 weight ratio (dry film thickness (dft) 20 ± 5µm).
During this study, other characterization tests were performed to understand the protective mechanisms of theses coatings and determine which parameters or combination of parameters could lead to high corrosion protection performance. Concomitancy of organic-inorganic photopolymerization RT-FTIR was used to monitor both methoxysilyl hydrolysis and epoxy function consumption. Figure 2 shows that both reactions are concomitant and occur at the same time scale. The simultaneous organic and inorganic polymerizations can contribute advantageously to the formation of homogeneous hybrid materials with minimal or no phase separation. Both networks can be interpenetrated at the molecular scale. The epoxy function consumption was only slightly influenced by the length of the alkyl chain while hydrolysis was slower with longer alkyl chains. Such results are clearly consistent with a dominant steric effect on the hydrolysis kinetics, reported in sol-gel chemistry11.
Figure 2: Influence of alkyl chain length on methoxy hydrolysis (a) and on epoxy function consumption (b) during concomitant organic-inorganic photopolymerization of CnTMS/ER 50/50 wt.% coatings. RT FTIR 2 experiments (light intensity: 200 mW/cm )
Inorganic network density Information on the inorganic siloxane network was obtained from 29Si solid state NMR. The silicon atom environment was determined for different alkyltrimethoxysilane precursors (Figure 3). The weight ratio of the inorganic precursor was fixed at 50 wt.%. The absence of resonances corresponding to T0 sites means that all of the Si atoms were involved in some degree of Si-O-Si crosslinking proving the efficiency of sol-gel reactions. The length of alkyl chain affected the density of the inorganic network since the proportion of T 1 species increased with the alkyl chain length. OX
OX Si O Si OX R
Si O Si O Si R
Si O Si O Si O Si R
C16TMS C12TMS C8TMS C4TMS
Figure 3: H- Si CP-MAS NMR spectra of UV-cured coatings for formulation CnTMS/ER 50/50 wt.%.
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Surface hydrophobicity Water contact angle measurements enabled to assess the hydrophobicity of the film surface. Figure 4 shows that the longest alkyl chain length leads to the most hydrophobic surface. Moreover, the addition of only 5 wt.% alkyltrimethoxysilane precursor has increased the water contact angle from 76째 to 101째. Thus, the hydrophobicity is thought to hinder water and corrosion initiator penetration, thereby retarding the hydrolysis of Si-O-Al bonds and the appearance of corrosion phenomenon.
Figure 4: Alkyl chain length effect of alkyltrimethoxysilanes on the surface properties of CnTMS/ER 50/50 wt.% coatings.
Performance of UV-cured hybrid sol-gels versus DTM formulations Corrosion protection performance The main required property of coatings which are directly applied on metallic substrates is the corrosion protection. The performance of corrosion protection was evaluated on the AA2024-T3 (reference aluminium alloy substrate in the aeronautic industry) and on steel panels. Depending on the substrates, two UV-curable hybrid sol-gel formulations could be chosen. In fact, the composition is adapted to the substrates to give the best corrosion protection performance. As seen in Table 2, UV-cured hybrid sol-gel coating (UV HSG2) was the most efficient coating to achieve very high corrosion protection on AA2024-T3. On steel, the corrosion protection are lower but the UV-cured hybrid sol-gel coating (UV HSG1) was still the most efficient coating compared to other DTM coatings.
Table 2: SST performance on AA2024-T3 panels of UV-cured hybrid sol-gel coating versus DTM coatings.
Chemical resistance Coatings are frequently exposed to different chemicals: base, acid, solvent, etc. Solvent resistance is a key point for their practical application. Table 3 presents chemical resistances of UV-cured hybrid sol-gel coating versus DTM coatings. UV-cured hybrid sol-gel coating is the only coating resistant to all chemicals and more particularly to Skydrol (i.e. aeronautical hydraulic fluid). Table 3: Chemical resistances of UV-cured hybrid sol-gel coating versus DTM coatings (NOK = Not OK).
Chemical Ethanol HCl HNO3 NaOH Acetic acid Skydrol MEK/Toluene/methoxypropylacetate
UV SGH2 OK OK OK OK OK OK OK
Formulation DTM1 DTM2 OK OK NOK NOK NOK NOK OK OK OK OK NOK NOK OK NOK
DTM3 OK OK OK OK OK NOK NOK
UV resistance In case of exterior DTM applications, a UV stability evaluated by the gloss retention after UV exposure, is required. Panels were examined regularly and gloss retention was measured. 80 % gloss retention was expected. Figure 5 represents the gloss retention at 60째 measured for the UV-cured hybrid sol-gel coating and the three DTM coatings. None of these formulations contain UV stabilizers. After 400 h, two DTM coatings were under the requirement levels. The DTM coating formulated with the acrylate dispersion is the best coating as regards to UV resistance. The developed UV-cured hybrid sol-gel coating meets the requirements in terms of gloss retention.
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Figure 5: Gloss retention at 60Â° after QUV exposure for UV-cured hybrid sol-gel versus DTM coatings.
Adhesion on composites Composites are increasingly used in the aeronautical industry. In this case, corrosion protection performances are not useful but a very strong adhesion of the coating to the substrate is expected. To examine this property, the UV-curable hybrid sol-gels were applied on CFRP (carbon fiber reinforced plastic â€“ epoxy matrix) panels with the surface prepared by mechanical abrasion. The adhesion of the coating was evaluated after UV-curing and after 14 days immersion in water by cross-cut test. First of all, the wettability of UV-curable hybrid sol-gel formulations was excellent. Secondly, as it can be observed in the Table 4, adhesion of UV-cured hybrid coatings was very high since the edges of the cuts are smooth and no square of the lattice is detached. Table 4: Cross-cut results of UV-cured hybrid sol-gel coating on composite before (t=0) and after 14 days (t=14) of water immersion.
Conclusion A one-step photoinduced sol-gel and free-radical photopolymerization process was proved to be an efficient process to synthesize hybrid sol-gel coatings with interesting properties, in particular high corrosion protection performances. Indeed, AA2024-T3 substrate which is widely used in the aeronautical industry was efficiently protected since less than 5 corrosion pits could be observed after 3000 hours exposure in SST. A combination of key parameters
was identified to account for such a high corrosion protection: a relative concomitancy of both organic and inorganic polymerizations; a surface hydrophobicity and a high barrier effect provided by two organic and inorganic networks. It was found that our UV-cured hybrid sol-gel coatings are more efficient than DTM coatings in terms of corrosion protection, chemical and UV resistance. In particular, none solvent tested altered the hybrid coating. Another important feature of this innovative out-of-bath technology is its application on a variety of substrates, in particular on non-metallic composites. Acknowledgment French National Research Agency (ANR-08-MAPR-0003, research project MHYRCEA with EADS IW and Airbus S.A.S. as major industrial partners) is gratefully acknowledged for financial support. References 1 2 3 4 5 6 7
9 10 11
Zheludkevich, M. L.; Salvado, I. M.; Ferreira, M. G. S.: Sol-gel coatings for corrosion protection of metals. Journal of Materials Chemistry 2005, 15, 5099-5111. Boisier, G.; Portail, N.; Pébère, N.: Corrosion inhibition of 2024 aluminium alloy by sodium decanoate. Electrochimica Acta 2010, 55, 6182-6189. Campazzi, E.; Goletto, V.; Sanchez, C.: Use of a nanostructures material, as protective coating of metal surfaces. Patent WO/2007/119023 2007. Metroke, T. L.; Parkhill, R. L.; Knobbe, E. T.: Passivation of metal alloys using sol-gel-derived materials -- a review. Progress in Organic Coatings 2001, 41, 233-238. Croutxé-Barghorn, C.; Chemtob, A.; Ni, L.; Moreau, N.; Bouder, T.: Radiation radically and cationically curable composition, and method for preparing a hybrid sol-gel layer on a surface of a substrate using said composition. PCT/IB2013/001306 unpublished 2013. Croutxé-Barghorn, C.; Chemtob, A.; Ni, L.; Moreau, N.; Bouder, T.: Radiation curable composition, and method for preparing a hybrid sol-gel layer on a surface of a substrate using said composition. PCT/IB2013/001356 unpublished 2013. Belon, C.; Chemtob, A.; Croutxé-Barghorn, C.; Rigolet, S.; Le Houérou, V.; Gauthier, C.: Combination of radical and cationic photoprocesses for the single-step synthesis of organicinorganic hybrid films. Journal of Polymer Science Part A: Polymer Chemistry 2010, 48, 41504158. Belon, C.; Chemtob, A.; Croutxé-Barghorn, C.; Rigolet, S.; Schmitt, M.; Bistac, S.; Le Houérou, V.; Gauthier, C.: Nanocomposite coatings via simultaneous organic–inorganic photo-induced polymerization: synthesis, structural investigation and mechanical characterization. Polymer International 2010, 59, 1175-1186. Ni, L.; Moreau, N.; Chemtob, A.; Croutxé-Barghorn, C.: Organic–inorganic tandem route to polymer nanocomposites: kinetic products versus thermodynamic products. Journal of Sol-Gel Science and Technology 2012, 1-10. Chemtob, A.; Versace, D.-L.; Belon, C.; Croutxé-Barghorn, C.; Rigolet, S.: Concomitant Organic-Inorganic UV-Curing Catalyzed by Photoacids. Macromolecules 2008, 41, 73907398. Loy, D. A.; Baugher, B. M.; Baugher, C. R.; Schneider, D. A.; Rahimian, K.: Substituent Effects on the Sol-Gel Chemistry of Organotrialkoxysilanes. Chemistry of Materials 2000, 12, 3624-3632.
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News from RadTech North America
On this page relevant news from RTNA is posted. uv.eb EAST had highest attendance yet for the event. A UV LED “Summit” at EAST included presentations, a lively UV LED Road Mapping session, and a special evening gathering to gauge the potential of a RadTech UV LED measurement initiative. As discussed at the meeting, with the re-opening of the U.S. Government, RadTech will pursue measurement efforts with NIST, and explore grant opportunities for our road mapping efforts. The event also offered a wide ranging view of select UV/EB applications including metal finishing; achieving performance and design solutions with UV and PVD; the UV curing of biomaterials, including mushroom structural materials; 3D and additive manufacturing; and micro patterning. Special thanks to non-profit organizational sponsors: New York State Energy Research & Development Authority (NYSERDA); and the State University of New York Institute for Sustainable Materials and Manufacturing. Please find a review of the event by Coatings World at http://bit.ly/174AOzh. The State University of New York College of Environmental Science and Forestry (SUNY-ESF), along with RadTech, has launched a new educational opportunity for UV/EB, the Radiation Curing Program (RCP). Funded in part by a U.S. Department of Labor, Skills Training Grant, RadTech members are showing strong support for our participation in this vital educational effort. Please follow the link below to see a posting to the American Chemical Society’s (ACS) Green Chemistry Institute Blog about the initiative: https://communities.acs.org/ community/science/sustainability/greenchemistry-nexus-blog/blog/2013/10/09/ low-energy-radiation-curing-programoffered-at-suny. RadTech members receive a discount for participation. For complete information please visit www.esf.edu/ outreach/radcuring. Please mark your calendars for the RadTech Winter/Annual Meeting, February 27-28 in Miami; and RadTech 2014, May 12-14 in Chicago.
News from other RadTech associations Visit to RadTech Asia
By David Helsby, RTE President
In May of this year I was given the opportunity to represent Radtech European by presenting and participating in the Radtech Asia Conference held in Shanghai China. My first visit to China was in 1994 and my second in 2004, all trips where to Shanghai and all Radiation Curing related. How things have developed, the city always an active and progressive place has grown and modernised beyond belief but the most dramatic change has been with its People and their outward appearance and attitudes towards Business and Technology. This was demonstrated by the attendees of the Radtech Conference and Exhibition, open, friendly, professional and very lively. The Asian Radtech organisation is an Umbrella organisation representing the Radtech of China, Japan, Malaysia, Korea and Taiwan. This year China held its own Radtech conference conducted in Chinese and then hosted the Asia Radtech conference conducted in English followed with an Exhibition of suppliers. Opening of the Conference
Great Pomp and Ceremony accompanied all the events and exhibitions, with flower displays, speeches, ribbon cutting and hostesses dressed in traditional costumes. All were accompanied with many Photo and filming opportunities. The Conference was a three day event covering many diverse topics and dominated by many of the Academic Universities and Institutes of China. This differs somewhat from the European and US conference where there is a greater
commercial presence especially in the US. The Conference content had a predominate theme of novel, innovative and new, with the major application area being that of Electronics and opto-electronics. A number of papers were also given exploring the growing LED technology and Nano particle modifications. In the second session of the third day I presented a technical Paper, a session that I also had to Chair, a rather strange setup compared to Radtech Europe, where you cannot chair and present in the same Session. Exhibition opening Ceremony with Presidents of Radtech Europe, China and Asia.
In the Exhibition was the usual core of European Suppliers but of course outnumbered by the many more Asian. Glancing through the raw materials on offer one discovered many new and by European experience, exotic products, all focused to the expanding electronics markets of Asia. With my three trips to China spanning almost 20 years I have seen China develop from a basic copying of technology to active co-development and finally emerging as market leaders in some technologies with an active and energetic research and development core. With the establishment of closer links between Radtech Europe and China I believe we are well placed to take mutual advantage of this exciting new Market.
News from the Industry
ACTEGA wins ALTANA Innovation Award 2013 14 November - The specialty chemicals Group ALTANA focuses on and commits to research and innovation. Around 160 top researchers and developers of the ALTANA Group from all over the world came together at the 6th ALTANA Innovation Conference in Wesel to discuss technical as well as economic developments and future innovative trends. As a highlight of the international event, the group‘s best innovation is honored with the ALTANA Innovation Award. Coating innovation awarded This year, the coveted ALTANA Innovation Award went to the project team of Frank Kamphuis, Tim Kammer, Marcel Altenburg, and Timo Kondziela, from the ACTEGA division. The development of special coatings for in-mould labels (IML) for the labeling of plastic packaging was awarded. Any structured or printed foil is placed in a casting mould for the packaging and liquid plastic is extruded into the form. The individual steps are performed at high speed, and the technology used is one of the most complex procedures in the packaging industry. To ensure accurate processing at such speeds creates new challenges for printers and packaging manufacturers. It quickly became clear to the researchers of the ACTEGA team that standard coatings would not be able to meet the high requirements. Completely new development approaches were required. Joined together specifically for this purpose, a team of experts developed a solution by combining product and process innovations. As part of their research, the developers identified new raw materials and used innovative formulation strategies. Not least thanks to the positive interaction between technology and marketing, ACTEGA can now speak of a resounding success. Its subsidiary ACTEGA Terra today is the European market leader for IML coatings in a still dynamically growing market, which promises a bright future for this product group. Chief Technology Officer (CTO) Dr. Georg F.L. Wießmeier about the award: „Without doubt, ALTANA attaches high priority to innovation. Our innovation culture is clearly demonstrated and practiced through events like the ALTANA Innovation Conference.“ Wießmeier continued: „We owe our leading position in particular to our determination to perfect our products continuously, and to develop new ones to meet the needs of our customers and to exceed their expectations.“ He praised all the teams who competed with great dedication for the ALTANA Innovation Award 2013.
For ALTANA, innovation is the pivotal key to further growth. With research and development expenditure of more than 6% of its sales, which is clearly above the industry average, ALTANA secures its technological edge and provides its customers with unique, innovative products and services. New developments are investigated together with the customer, for the customer, and in close proximity to the customer. More than 50 laboratory and research sites worldwide offer customers innovative solutions in the area of surface protection and surface finishing. Every fifth ALTANA employee worldwide works in research or application technology. More information: http://www.actega.com/
IST METZ wins two Print Stars UV specialist from Nuertingen scores with multifunctional packaging Nürtingen, 17th October 2013: The innovative packaging that IST METZ presented in June at its inhouse trade fair UV DAYS in Nuertingen, won two awards at Print Stars 2013. A complimentary gift that has caused a sensation: At UV DAYS IST METZ presented the prize-winning packaging as an example for the printed product of the future. The packaging is decorated with highclass varnish effects that have been achieved via sheet-fed offset and inkjet printing. An inline embossing additionallly creates the special haptic. The printed product is complemented by an app with which you can see a 3D animation on a smartphone or tablet PC that shows how to transform the packaging into an ambient light. The packaging was developed at the Marketing Department of IST METZ. It was printed on the inhouse printing press of IST METZ, longstanding partners from the south of Germany supported the production in terms of finishing and the development of the IST METZ App.
At Print Stars 2013, the most renowned award in the German printing industry, the packaging has been nominated in two categories and won both: on the one hand the special award for “Print Gimmick of the Year”, on the other hand the Silver Award in the
category “Cross-media linkage print/online”. On October 16th, the award ceremony Print Night took place in Stuttgart. Dirk Jägers, Managing Director of IST METZ, is glad about the prizes: “With the UV DAYS packaging, we not only wanted to show the possibilities UV technology offers, but also an overall concept of print and online elements. Both awards are a wonderful feedback for us from the printing industry.” Prizes have been awarded in 25 categories in total. More than 900 brand owners, print shops, agencies, photographic studios, publishers, pre-press and print finishing companies took part in the competition. A jury of 22 experts from the printing industry chose the winners. More information: www.ist-uv.com
PCT marks ten years of Electron Beam innovation September 2, 2013 – This month PCT Engineered Systems celebrates its 10-year anniversary as the manufacturer of the BroadBeamTM line of electron beam (EB) systems. By 2003 PCT had been in business for nearly two decades, enjoying a successful and growing automation system integration practice. In the fall of that year, the company purchased the BroadBeam technology from one of their key clients, adding a fascinating and radically different facet to their portfolio of products and services. “We knew there was great potential in both EB technology and the BroadBeam line of products,” noted PCT Director of Sales and Marketing Karl Swanson. EB technology is used most often in manufacturing to cure inks and coatings or add strength to plastic films. An EB system operates by generating a cloud of electrons, and then propelling them onto a moving web surface, effectively altering the molecular composition of the inks, coatings or plastic films being treated. Inks and coatings dry instantly (called curing); and the plastic film physical properties are altered (called crosslinking) during this process. Ongoing enhancements in EB system technology, lower system costs, smaller-sized equipment, and the increased availability of EB-curable inks, coatings and adhesives have all contributed to growth in the use of the technology. These and other perceived benefits among potential EB users have not only allowed EB technology to evolve into a viable option for a wide range of industries like package converting and pressure sensitive adhesive (PSA) manufacturing, it has begun to elicit opportunities for EB introduction into new applications, like sterilization, metal coil coating and digital (inkjet) printing. The demand for a very green and environmentally friendly technology is also driving growth in EB technology.
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“Over the past ten years, PCT has led a charge to raise all levels of EB performance,” notes PCT’s president, Terry Thompson. “PCT’s obsession to improve EB system technologies has helped position BroadBeam as the premier EB system globally in quality, performance and reliability.” Specific PCT innovations over the past ten years include a patented integrated shield roll design, in which a temperature controlled roll supports material as it moves through the curing process while simultaneously providing necessary safety shielding. “We haven’t seen the end of EB technology evolution,” Thompson concludes. “Forward-thinking companies from a wide range of industries continue to discover benefits and efficiencies from EB technology that were unimagined when we started this journey ten years ago – and PCT intends to continue providing these organizations with the most high quality, efficient, powerful EB systems possible.”
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Located in Davenport, Iowa, PCT has provided engineering services, automation systems integration, and custom machine building worldwide since 1986. They continue to leverage themselves as a global leader in the design and implementation of industrial electron beam systems. Additionally, their
award-winning Innovation Team has extensive experience in empowering American manufacturers to improve their operations through increased productivity, higher quality and improved safety. More information: www.teampct.com
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New members of RadTech Europe in Q4 2013 New company members Decorad Systems B.V. UCS BVBA
Rob Muller Kurt Troch
New individual members Decorad Systems B.V.
Category 5 (Supplier of equipment) Category 5 (Formulator)
RadTech Europe welcomes all new members!
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Colophon RadTech News Issue 2, December 2013 RadTech News (e-zine) is published 2 times a year exclusively for members of RadTech Europe. In 2013, the hard copy yearbook was published in October as a conference/anniversary book for all involved in the UV/EB radiation curing industry. RadTech Europe is the European Association for the promotion of UV/EB curing technology for inks, coatings and adhesives. Edited and published by RadTech Europe Lejeune Association Management Mark Macaré Elke Verbaarschot P.O. Box 85612 NL-2508 CH The Hague, The Netherlands Tel.: +31 (0)70 3123920 Fax: +31 (0)70 3636348 Email: firstname.lastname@example.org Website: www.radtech-europe.com Management Committee President: Vice-President Treasurer:
David Helsby, RadLab/ RAHN Matteo Vasconi, Allnex Philippe Thepot, Sartomer Europe Barbara Fenzi, Lamberti SpA Nick Gruber, BASF Nick Ivory, Sun Chemical Urs Läuppi, COMET AG Arnd Riekenbrauck, IST METZ GmbH Dawn Skinner, Heraeus Noblelight Fusion UV Inc.
Chair Marketing Committee Audrey de Wulf, Allnex Chair HSE Committee: Mark Macaré (interim Chair) Chair Metal Coatings Group: vacancy Chair EB Project Group: Urs Läuppi, COMET AG Chair Printing & Packaging Group: Emilio Martin, DSM RTE Conference
Dawn Skinner, Heraeus Noblelight Fusion UV Inc
Association management for RadTech Europe Mark Macaré, Secretary General Elke Verbaarschot, Senior Management Assistant Cora Van der Lek, Financial Support Printing & Design de Swart, The Hague RadTech Europe News issue has been compiled with utmost care, RadTech Europe declines any responsibility for possible incompleteness of any information published in this issue.
RadTech Europe: Promoting & Developing UV & EB Technology in European Industry