2012 UV & EB Technical Conference Proceedings
Table of Contents
Monday, April 30, 2012
Weathering & Exterior Applications
Momentive Performance Material Radiation Curable Hardcoats with Improved Weathering Performance
New UV curable transparent coatings for plastics exhibited potentially significant improvements in weatherability compared to previous coatings. These new coatings have been shown to last for 14,000 kJ/m2 in Xenon weathering, which, based on UV radiation, is equivalent to five years of Florida exposure at a 45-degree angle. Also compared to previous coatings, the new coatings showed reductions in haze, yellowness, cracking, and delamination.
Suited For: End Users of Formulated Products & Curing Equipment
UV Curable Polysiloxane-acrylic Hybrid Resins
We have established a new synthesis approach to UV curable polysiloxane-acrylic hybrid resins, which enable to control the siloxane content between 25 wt% and 90 wt%. And we evaluated fundamental properties of the films made of this resins. The films have good appearance and remarkable weathering resistance, which is comparable to weather resistance of fluoro-olefin resins. Currently, the development of waterborne resin using this technology is also in progress from an environmental standpoint.
Suited For: Industry Suppliers (Formulators, etc)
Scratch and Abrasion Resistant UV Coatings: Various Approaches
Organic oligomers provide adhesion strength that enables many coating applications in UV curable systems. However, they have limitations in their mechanical properties as well as other performances, e.g. optical, magnetic, electrical, biological performances, some of which are essential for specific targeted applications. Often, end product manufacturers hold high interests in controlling coatings against scratching and abrasion. We prepared UV-cured nanocomposite coatings of different appearances and properties. Furthermore, we investigated various other methods to increase abrasion and scratch resistance. Benefits and drawbacks of each approach will be discussed.
Suited For: End Users of Formulated Products & Curing Equipment
Corrosion Resistant Coatings
UV Technology for High Performance Industrial Applications
UV Technology is suitable for high performance industrial applications requiring corrosion resistance. When compared to commercial epoxy and urethane paints on steel surfaces, high performance solvent-free UV curable coatings provide improved protection with dramatically faster cure and much lower material usage. In addition, excellent cure is obtained with UV technology at temperatures too low for standard paint to be used. UV Technology also provides corrosion resistance for high strength aluminum alloys used in aerospace applications.
Suited For: End Users of Formulated Products & Curing Equipment
Mitigating Biofouling and Biocorrosion via UV-Curable Coatings
Biofouling and biocorrosion are serious and significant problems for many industrial and consumer products and processes alike often resulting in expensive, laborious, and time-consuming remediation and can result in necessary equipment repair/replacement. Included herein is a potential means by which such remediation and the cost thereof could be reduced or eliminated by introducing a UV curable monomer into a commercial coatings formulation with little to no deleterious effects to the formulation’s designed performance or the environment. Corroborating experimental and “real world” evidence is provided within the paper and presentation.
Suited For: Both
"Radiation Curable Components and Their Use In Corrosion Resistant Applications"
This study will investigate the effects of the chemical structure of acrylated monomers and oligomers as it relates to their ability to reduce to effects of corrosion of metal surfaces. Testing will be conducted in accordance with ASTM B 117 Salt/Fog Testing. This method is an accelerated corrosion test that produces a corrosive attack to the coated samples in order to predict its suitability in use as a protective finish. Acrylated components will be tested and rated as to their effectiveness to reduce corrosion and correlated to their chemical structure.
Suited For: Both
Sustainability
Electron Beam Curing: An Important Option for Sustainable Packaging
High energy costs, climate change, and carbon emissions have forced various industries to evaluate the way they do their manufacturing. Due to this, the packaging industries are focused on sustainable packaging, and low carbon foot print as some of the terminologies being discussed globally and being mandated by consumer companies. This presentation will address what sustainable packaging is; and how energy curing, and in particular electron beam curing, is now recognized as a critical option in providing sustainable packaging.
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Physical Vapor Deposition and UV Curable Coatings
Due to growing environmental concerns with chrome plating, finishers have been requesting a “greener” alternative. Coatings for multi-purpose decorative and automotive lighting PVD applications have been used in the UV curable coating industry for over twenty years. However, these coatings do not have the required durability to replace chrome plating. As development of UV curable coatings for PVD has progressed, so has the understanding of the PVD process and its unique capabilities and applications. This paper will address the current chrome plating process, advantages of PVD, challenges associated with the various steps and layers of PVD applications, and suggestions for successful implementation of UV/PVD systems.
Suited For: End Users of Formulated Products & Curing Equipment
Study of Accelerated Natural Degradation on Pigmented UV/EB-Cured Print Inks
Print inks have assumed an important role on finished materials, such as plastic packages, which can have a long lifetime when disposed as municipal waste. By this way, it is important to evaluate the influence of physical parameters on the degradation of shot lifetime substrates covered by pigmented print inks cured under different doses of UV/EB radiation.
Suited For: Both
UV Curable Coatings, Another Option for Decorating Glass
With growing concerns over the effects of BPAs in plastics as well as consumer preference tending toward natural sustainable packaging, glass is becoming an increasing popular choice in many markets. Currently glass is being decorated with a variety of methods that, while durable, can be hazardous, time consuming, or limited in options. There are many formulation and processing challenges involved in coating glass. However, with the correct formulation choices and pretreatment knowledge, UV curable coatings can offer a safe, efficient way to offer aesthetic and functional value to glass in a multitude of different looks and finishes. *Note: There could be a possible co-author or changes to the abstract. We have a development partner on some new applications in this area and they are unsure of the level of involvement they want to have on this as of right now. Thank you!
Suited For: End Users of Formulated Products & Curing Equipment
Nanomaterials
UV/EB Curing of Nanocomposites for Enhancing the Functionality and Utility in Coatings Industry
Composite materials combine properties of the individual components in a synergetic manner to produce a variety of materials in an efficient and cost effective manner. Thus, composite materials are being used in various applications from automotive to furniture industries. Materials reinforced with nanoscale components are adding new dimensions to composite materials and enable further major improvements in functional and structural properties. The incorporation of only a few percent of nano-sized particles can make dramatic property changes that may result in enhancing physical and mechanical properties of the resulting composite. Several major issues need to be addressed to utilize the full potential of such nanofillers i.e. incompatibility or weak interfacial bonding between the matrix and the nanoscale component, and agglomeration of nanosized component during processing resulting in inhomogeneous distribution. UV/EB technology offers a way of overcoming these challenges by grafting of monomers/polymers including natural polymer onto the nanofiller surface thereby fixing their morphology and at the same time making them compatible with the host polymer.
Suited For: Both
Silica Nanoparticles with Functionalized Surface Chemistries for Improved UV Compatibility
Suited For: Both
EPOXY-GRAPHENE UV-CURED NANOCOMPOSITES
This work presents the preparation of functionalized graphene sheets (FGS)/epoxy coatings cured by cationic photopolymerization with enhanced mechanical properties. The kinetics of the photopolymerization process for formulations up to 1.5 wt% of graphene were evaluated by means of Real-Time FT-IR spectroscopy. The reinforcement of the cured coatings by the graphene was studied by measuring the dynamic mechanical properties and the surface hardness. An increase of almost 40 °C in the Tg was achieved by adding 1.5 wt% of graphene to the epoxy matrix. A good dispersion state and interaction of the graphene with the matrix were observed by TEM and FE-SEM analyses
Suited For: Both
Adhesives, Sealants & Release Coatings
Thermal & UV studies of the effects of HMPSA and UV silicone release based on compositional changes
Thermal and UV Studies of the Effects of HMPSA and UV Silicone Release based on compositional changes and degree of UV Cure. Recent experiments have shown that the certain processes and chemical compositions have a profound effect on the release performance of acrylate functional UV curable silicones. Various compositions of hot melt pressure sensitive adhesives (HMPSA), were applied to silicone coated BOPP which was cured under conditions of low UV dose, poor inerting and optimal conditions. Studies were made based upon thermal aging of adhesive and also on repeated subsequent exposure (8X) to UV light. This report will summarize the results of this study and what effects were observed.
Suited For: Both
Release films: Accomplishments and Problems
Films with a release coating are in strong demand for a wide range of applications from window films to flexible displays. We report progress on replacements for tin-based catalysts used to cure liquid siloxane coatings applied to film substrates such as PET, with the aim of preserving the essential characteristics of the tin-cured coatings.
Suited For: Both
Suitability of (Meth)acrylates for use in Sealant Applications
The use of (meth)acrylates in peroxide or amine cured sealant and potting compounds is a known and practiced art. By extension, using UV curing in these same applications is gaining interest versus current processes. A benchmarking of various monomer and oligomer structures was performed, with a focus on their performance in the areas of heat stability, moisture resistance, dielectric strength, and dimensional stability.
Suited For: Both
UV Curable Polysiloxane-acrylic Hybrid Resins
Plastics have been used in a wide range of products including architectural materials and exterior and/or interior automotive parts. Plastics can offer excellent impact resistance and clarity attractively, they allow for design freedom and thus allow for some very aesthetically appealing appearances that were once inconceivable. However, they have a major drawback in that they don’t always provide the desired degree of chemical, scratch and weather resistance. To overcome this problem, a new development work has been done in the coating area. We previously reported the inorganic-organic hybrid non UV curable resin which shows high weather resistance.
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Additives
Benefits of high-performance ultrafine polyamide powders in UV formulations
This talk will deal with ultra-fine polyamide powders, which are polymers and copolymers of lauryllactame and/or caprolactame obtained by direct polymerization. Those powders are micro-porous spherical beads with a very narrow particle size distribution. Those powders contrast from waxes due to their higher melting point, better chemical resistance and different migration process. We will address the benefits from using Polyamide powders in UV curing systems as it do not impact the viscosity of the UV/EB formulations even at a high level of addition. We will explain how it provides flexibility to the formulators providing low gloss, soft feel and textured coating without damaging the applicability and even improving the abrasion, scratch and anti-blocking performances.
Suited For: Both
Enhanced Wear Protection of UV-Cured Clearcoats using Sub-Micron Aluminum Oxide Additives
Alumina, because of its high hardness, has long been used as an additive for coatings and laminates to improve the wear resistance of these materials. However, because of the significant light scattering imparted by conventional micron-size alumina particles, it is not possible to use such additives in coatings applications requiring high gloss and/or clarity. Recently a series of nano- and sub-micron particle size alumina additives has been developed specifically for use in high transparency UV-cured coatings applications. These additives span the range of 20 – 800 nm in average particle size and are pre-dispersed in acrylate monomers at high concentration to allow for easy incorporation into 100% solids UV-cured formulations. Depending on the specific application criteria (coating thickness, clarity requirement, wear resistance need, and resin type) the optimum alumina additive particle size and loading level can be readily determined. Data will be presented showing the performance of the different particle size additives in a variety of resin types, and will compared to the performance of conventional scratch-resistant additives.
Suited For: Both
Novel Matting Agent for Low Gloss UV Coatings
While many technical advances have been made to produce low gloss, radiation curable clear coatings, they still present a challenge for most UV coatings manufacturers. Matting agents have been developed where particle size, treatment and structure have been modified to achieve low gloss. In this development, the combination of specific amorphous, synthetic silica combined with a specific Polydimethylsiloxane surface treatment was found to improve efficacy. Based on this experience, a new product especially designed for low gloss, high transparency and low viscosity was developed for UV-Coatings. This presentation will feature results comparing this new generation of matting agent to the matting technology considered “state of the art” in UV application. The focus will be on gloss vs. viscosity behavior. Photomicroscopy based on REM and TEM-Thin-Cut will be used to demonstrate the performance of this unique new technology.
Suited For: Industry Suppliers (Formulators, etc)
Cutting Edge Applications
Keynote Address Architecting Materials Through a New UV Photopolymerization Technique
Recently, a new UV photopolymerization technique has been developed to create microlattice materials with features ranging from tens of microns to millimeters. These materials are formed by interconnecting a three-dimensional array of self-propagating photopolymer waveguides, where each waveguide represents a single lattice member. Because the waveguides propagate from a single exposure plane and can be formed simultaneously, thick (> 1 in. possible) three-dimensional polymer microlattice materials can be formed in less than one minute. The inherent flexibility of this new approach enables precise control the microlattice material architecture, which ultimately enables the design of a material to achieve a particular property or function. In this talk, I will give a brief overview on the current state of development and highlight some of our on-going research efforts, including how this technology led to the creation of the world’s lightest material.
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Printing Chemical, Biochemical, and Biological Activities in Energy Curable Resins
Energy curable resins contain a variety of chemical functionalities which impart unique properties to a cured polymer. Virtually any degree of polarity and amount of crosslinking are possible. The broad versatility provided by available chemical functionalities allow for tailor coupling between active compounds (eg. antimicrobial, chemical, biochemical functionalities) and energy-curable resins. Inexpensive, high activity, surface activation results from curing activity embedded thin energy curable print application on packaging surfaces. The advantage to embedding active packaging functionalities in energy curable resins include: application speeds up to 100 meters per minute, activity-sparing near ambient cure temperatures, simultaneous application of multiple activities, and activation cost per package similar in cost to graphic printing. Active surfaces researched to date include oxygen scavenging packaging (2 types), antimicrobial packaging (3 types), lactose-removing packaging, progress-toward-end-of-shelf life indicators, and oxygen detecting coatings.
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UV/EB curing technologies for textile innovative applications
For the last decades, radiation curable coatings technologies have gained full acceptance in a number of industrial applications. The major driving forces behind these technologies, when compared to other conventional curing technologies, are high output and throughput enabled by the fast polymerization rates, excellent surface properties, and significant environmental benefits due to the energy-efficiency of the process and the use of solvent-free resins, complying with the stringent legislation. Therefore, radiation curing has been in use extensively in the graphic arts industry, ink industry, commercial and industrial printing sectors, lamination technologies, packaging, and electronic industries, among others. However, radiation curing has had little impact on the textile industry, despite the widespread use of polymer treatments on fabrics and garments. Furthermore, the use of radiation curing to modify the surface properties of fabrics offers an alternative application with high commercial and market potential, based on the attainable high outputs and yields for a given process. In this paper we intend to give an overview regarding the use of UV/EB radiation curing technologies for textile innovative applications. The advantages of UV curable textile finishing processes over thermal curing formulations are clear and include lower energy consumptions, increased processing speeds and smaller plant installation space. The achievement of side-specific, water and oil repellent functionality in textiles is highly desirable for applications such as sports clothing, apparel, home and technical textiles. In our recent work, UV curable formulations and respective application process were developed, yielding superhydrophobic and oleophobic cotton and other textile surfaces, while maintaining the other intrinsic properties of fabrics. Furthermore, the treatment may be side-specific and it is resistant to common washing processes. Additionally, UV curing finishing lacquers able to improve the printing quality of flexible substrates, were developed in order to prepare architectural textiles suitable for graphic arts, but also as a substrate for printing electronics and organic electronics applications. Recent research projects have demonstrated the viability of direct deposition/printing of organic electronic devices, such as organic solar cells, directly onto pre-treated textile substrates having previously coated leveling layers. Theses leveling layers may be coated using novel UV and e-beam curing technologies, enabling the subsequent coating of the metal and organic layers of the device while maintaining the mechanical behavior of a conventional textile. Consequently, recent developments on organic photovoltaic technology have yielded new flexible solar cells with a wider range of possibilities, mainly in wearable applications that need autonomous systems. An alternative approach of the present work based its research on last developments and the target is to go beyond them by developing flexible and textile cells to obtain photovoltaic (PV) textiles with the properties inherent to fabrics: flexibility, weight, durability and water/dust resistance. These photovoltaic textiles will offer a range of useful applications in a variety of sectors like home and outdoor textiles, sports, leisure, clothing, automotive industry, since any PV textile surface exposed to solar radiations can be used for converting it into an energy generator. The standard PV structure is composed by different layers: substrate, active materials, transparent conductive layer and protective transparent layer. The target of the last layer is to protect the organic film stack from environmental conditions. We are developing the transparent high barrier films using Polymer Multilayer (PML) technique, which enables the deposition of nano-thick and nano-thin film polymer layers by the vacuum flash evaporation, (and subsequent electron-beam curing in line) and interlayering the polymer film with metal-oxide thin films coated by reactive sputtering. In other developments, we are developing polymeric materials with high ionic conductivities to incorporate in flexible electrochromic devices as electrolyte layers, for textile decorative applications. Polymeric matrices with very polar groups able to stabilize ionic species have been prepared with and without plasticizers. When compared with other curing methods for electrolyte gels, photopolymerization has proved to be a fast and clean method.
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Measurement
Effective Use of UV Radiometers and Radiachromic Films
This paper examines questions of accuracy and repeatability several different types of UV radiometers and “dosimeters,” multi-band instruments, stationary sensors, the “NIST traceability” chain, and the difficulty in measuring and interpreting the complex convergent/divergent ray patterns of focused and non-focused UV lamps. For situations that preclude instrument radiometers, radiachromic films also have characteristics that must be understood to utilize them effectively.
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A Novel Approach to Low Energy Dosimetry
Determining the surface dose of low energy electron beams (<125KeV) with conventional film dosimetry is difficult due to the depth dose profile within the film. Monte Carlo simulation software has been shown to work well in determining dose in different layers of material. To obtain acceptable results the user needs to know the energy of the accelerated electrons, the electron flux, exit window thickness and the air gap. While the window thickness and air gap are easy to measure the electron energy and flux are not. We propose to use a combination of conventional dosimetry and Monte Carlo simulation to determine the surface dose of low energy electron beams.
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Measuring Volatiles from 1) Radiation-Curable Monomers, Oligomers and Blends and 2) Thin Coatings
RadTech International NA has endorsed a new test method developed at 3M for measuring volatiles from the acrylate monomers, oligomers and blends used in UV-curable coatings. This method also provides a means to measure volatiles from thin UV-curable coatings, including inks, in the absence of those known interferences such as pigments that preclude the use of existing test methods. This talk will explain the test method and its relevance through examples.
Suited For: Both
Chemistry
Three-component Dye Sensitized Systems- Extending the Initiation Wavelenght Limit
Three-component photo-initiator (3C) systems: photo-sensitizer (PS), electron-donor (ED), electron-acceptor (EA) can cure acrylic monomers more efficiently than their two-component counterparts. However, in many cases they display a limited stability at room temperature, i.e. initiation efficiency decreases over dark storage time, or spontaneous “dark” polymerization is promoted. The source of the instability can be correlated to basic chemical parameters such as the basicity of the ED and the ionization potential of both ED and EA. In many cases thermal stability is inversely proportional to photoinitiation efficiency, as dictated by photo-induced (PET) and ground state (ET) electron transfer mechanisms. In this work, thermal stability and photoinitiation efficiency are examined based on choice and concentration of the initiator components, as well as monomer/ solvent properties. Thus, correlating thermodynamic and kinetic parameters of the PET and ET pathways with chemical structure and composition. Trends identified will aid in the design and development of improved photoinitiators. Systematically designed 3C systems for visible light activated free radical (and potentially cationic) curing could be very valuable in a wide range of applications from biomaterials to laser imaging technologies.
Suited For: Industry Suppliers (Formulators, etc)
Plasticizing Effect of Acrylates in Hydroxyl-containing Acrylate Hybrid Photopolymerization
Epoxide-acrylate hybrid systems promise to reduce sensitivity of the photopolymerization to oxygen and moisture. An hydroxyl-containing acrylate, acting as a plasticizer, was paired with a diepoxide to promote the faster Activated Monomer mechanism and increase epoxide conversion. Conversion profiles were obtained using real-time Raman spectroscopy. As the acrylate concentration was increased from 50 to 80%, the epoxide conversion increased from about 55 to 85%, indicating that the hydroxyl-containing acrylate facilitated the Activated Monomer mechanism.
Suited For: Both
Structure-Property Investigation of Functional Resins for UV-Curable Gaskets
Living radical polymerization was used to prepare (meth)acrylate functional telechelic polymers with controlled variations in molecular weight, functionality, and backbone composition. Each resin that was synthesized was formulated into a model UV-curable composition, and these formulations were characterized in terms of key performance parameters for UV gaskets, including compression set, tensile properties, and glass transition temperature.
Suited For: Industry Suppliers (Formulators, etc)
Nanogels Formation on Theta Solution Using EB Radiation
Nano-hydrogels made of bio-compatible hydrophilic polymers can be used in various medical applications such as drug delivery, imaging, etc. Preliminary results on the synthesis of poly(vinyl pyrrolidone) (PVP) nanogels in dilute theta solutions using electron beam, will be presented here. Radiation-induced synthesis of polymer nanogels, based on intra-molecular crosslinking process, was studied using dynamic light scattering. It was observed polymeric size reduction with radiation dose increase, indicating nanogel formation.
Suited For: Industry Suppliers (Formulators, etc)
Thiol-ene
Photopolymerization in Lyotropic Liquid Crystal Templates for Improved Polymer Properties
A developing method of synthesizing polymers with useful properties utilizes self-assembling lyotropic liquid crystals (LLCs) as photopolymerization templates to direct polymer structure on the nanometer scale. This work describes the synthesis of nanostructured polymers using LLCs as structure directing photopolymerization platforms and the impact of polymer nanostructure on physical and transport properties. Useful property relationships are observed for nanostructured of hydrogels and thiol-ene systems including increases in transport and mechanical properties relative to isotropic controls.
Suited For: Both
Two-Stage Reactive Polymer Systems
Polymer systems At a later point in time, a free radical polymerization of the excess acrylic functional groups is photoinitiated resulting in a high modulus, robust material. We have formulated and characterized two stage reactive thiol-acrylate networks that have intermediate stage rubbery moduli and glass transition temperatures that range from 0.5 - 100 MPa and -10 to 31 ºC. The same polymer networks can then attain glass transition temperatures that range from 5 to 195 ºC and rubbery moduli of up to 3500 MPa after the subsequent photocuring stage. The two stage reactive networks formed by varying the stoichiometeric ratios of the thiol and acrylate monomers were shown to perform as substrates for three specific applications- shape memory polymers, impression materials and as optical materials for writing refractive index patterns.
Suited For: Industry Suppliers (Formulators, etc)
THE EFFECTS OF POLYMERIZABLE ORGANOCLAYS ON PHOTOPOLTMERIZATION BEHABIOR AND ULTIMATE PROPERTIES
The effects of photopolymerizable organoclays on both the clay-nanocomposite processes and ultimate nanocomposites properties have bee investigated utilizing various thiol-acrylate mixtures. The incorporation of appropriate functional groups in clay structure enhances polymerization rate as well as changes polymerization mechanism, resulting in significant effects on nanocomposite characteristics. The functional group types in clays play a critical role in these behaviors. In addition, oxygen inhibition and polymerization shrinkage were remarkably reduced by adding polymerizable organoclays.
Suited For: End Users of Formulated Products & Curing Equipment
Electron Beam
Treatment of industrial wastewater from paint industry by electron beam irradiation
The segment of polymeric coatings for automotive and repainting is an important market, however produces effluent with organic pollutants. The goal of this study is to use ionizing radiation to destroy the pollutants and allowing the use of part of this effluent as reuse water. Samples were irradiated at electron beam accelerator applying absorbed doses of 10 kGy, 30 kGy and 50 kGy. The results, in this preliminary stage, showed a reduction of organic compounds and suspended solids.
Suited For: End Users of Formulated Products & Curing Equipment
Imparting Dimensional Stability on Cellulosic Material Utilizing Electron Beam
With any cellulose based material comes the tendency for the cell walls to take up or release moisture in relation to the atmospheric conditions surrounding it. By considering this affinity for water and the physical processes involved, this research looks to affect this tendency with the use of low molecular weight monomers polymerized by electron beam ionizing radiation. The focus is restricted to controlling the dimensional stability of 5 species of natural fibers. A number of specimens in individual fiber format from the various species were put through an experimental process that looked to test the moisture uptake characteristics of the specimens before and after treatment. Partial results from individual fiber tests and the interpretation of the data will be presented. Plans to create dimensionally stable composites from the treated fibers, and the benefits to various industries will be discussed.
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Advances in Low Energy Electron Beam Equipment Technology
Advances in low energy electron beam equipment are continuing. The energy spectrum for the new generation of compact equipment has been expanded to cover a range from 15 to 175 kV. The low end of this spectrum (15 kV) is useful for curing/treating materials within a vacuum chamber. The higher end of the spectrum (>80 kV) allow processing at atmospheric pressure. The highest energy in this range (175 kV) allows effective penetration of materials up to 150 microns thick in a single pass. Another EB equipment advancement involves the integration of compact sealed tube EB emitters for new material curing/treating applications. The units may be custom designed to handle materials ranging from webs to 3-dimesional parts. A third advancement in EB equipment involves integrated shield roll technology. These systems use a roll which supports the web during irradiation and is also a functional part of the shielding. The shield roll technology is being used in a full range of systems from compact sealed tube emitters to 300 kV industrial processors.
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Sealed Electron Beam Emitter for Use in Narrow Web Curing, Sterilisation and Laboratory Applications
A new generation of highly compact e-beam emitters with an accelerating voltage of 80 to 200 kV and treatment widths of up to 60cm is described. The new e-beam equipment features a sealed accelerator tube making vacuum pumping unnecessary. First applications are in the areas of surface sterilisation, narrow web curing and laboratory test systems. The paper describes the new generation e-beam emitter. In addition a narrow web curing system and an e-beam laboratory unit are presented, which incorporate the new generation e-beam emitter. The laboratory test system allows the treatment of A4-sized samples with a height of up to 50mm. The operation of the lab unit is simplified by a powerful user interface.
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Waterborne
Water Reducible UV Cure Allophanate Urethane Acrylates
The introduction of UV-curing polyurethane dispersions (UV PUDs) several years ago has established themselves as a key waterborne resin raw materials for markets that are requiring ultra-low VOCs and VHAPS. One obvious issue with the UV PUDS is that there delivery from requires the transportation of 60-65% water in the base UV PUD as well as the removal of this water before UV curing. This paper will purpose an alternative concept of water-reducible resins that are supplied at a low viscosity and 100% solids that can be water reduced to the desired solids level via a simple stirring process at ambient temperature. We have developed UV-curing resins based on hydrophilic modified allophanates that can be directly emulsified into water leading to a stable emulsion and water reducible grades that can be easily diluted by any amount of water to yield a clear solution. Typical application property deficiencies associated with highly water compatible binders will be addressed and could be significantly reduced.
Suited For: Industry Suppliers (Formulators, etc)
Waterborne UV Cureable Resins – Chemistries and Applications
The use of waterborne (WB) UV chemistry is growing because the technology provides high performance capabilities while satisfying increasing environmental requirements. With the growth in WB UV markets and the expanding availability of UV building blocks, the immense versatility of this technology is becoming apparent. This paper will discuss information relating to features, performance and advantages of WB UV coatings as well as a description of the chemistries involved. Applications covered will include clear and pigmented wood coatings, plastic coatings, metal coatings and field applied floor coatings. Formulating concepts will be discussed.
Suited For: Both
WATER-BASED RADIATION CURABLE EMULSIONS OPEN NEW HORIZONS FOR HARD COATS
Water-based radiation curable products largely respond to the current environmental concerns and to the quest for high-end coating performances. New advances in the technology are placed in the perspective of the different stabilization mechanisms of waterborne colloids ranging from dispersions to emulsions. The synthesis of model radiation curable polyurethane dispersions is given as an example showing the dual existence of dispersion and emulsion nano-structures, evidenced by using diffusion 1H nuclear magnetic resonance. The market requirements for hard coats are provided and tentatively transposed into a molecular design considering both functionality and equivalent weight of a model urethane : acrylate. As a result, the emulsion of polyacrylate molecules is proposed as the best route for this challenging application. The main characteristics of these emulsions are then presented with an emphasis on the major parameters that govern the emulsification process and the colloidal stability of the final product. Finally, it is shown that stable high-solid emulsions with a low viscosity for spray application are delivering outstanding performances as hard coats on many substrates like plastics.
Suited For: Both
Water-borne UV-curable coatings based on renewable materials
In the recent years, Rad-cure coatings are fast expanding into myriads of end-use applications primarily due to their superior performance, cure speed and lower environmental impact. Use of bio-based materials in formulation of such coatings can significantly expand their applications areas. This paper presents development of water-borne UV-curable coatings with high-bio-renewable contents, through a novel synthetic route. Our results show that by customizing oligomer structure and functionalities, it is possible to derive high-performance coatings with reduced carbon footprint.
Suited For: Both
Photovoltaics & Electronics
Suitability of Energy Curable Oligomers and Monomers As Encapsulants in Photovoltaic Modules
Photovoltaic module encapsulants act as an adhesive and as a shock absorbing layer. The thermoplastic or thermosetting film is laminated into the PV structure using a time consuming process requiring heat and pressure. In this paper, we will demonstrate UV curable materials will also meet the PV encapsulant performance requirements including thermal cycling, high temperature/humidity exposure and weatherability. In addition, UV curable materials will reduce the time to assemble the photovoltaic modules due to the fast curing capability of the technology.
Suited For: Both
Developments in Flexible Cholesteric Liquid Crystal Displays Based on Polymerization Induced Phase Separation Technique
We present recent developments in flexible bistable reflective cholesteric liquid crystal displays (ChLCDs) based on polymerization induced phase separation (PIPS) technique. The designed mixtures of ChLC with radiation curable acrylate materials can be easily assembled between flexible substrates resulting in electrically addressable low power bistable ChLCDs. Both encapsulated pressure insensitive systems enabling Reflex™ Electronic Skin-type display applications and pressure sensitive systems enabling Reflex™ Writing Tablets, called Boogie Boards™, will be discussed. Tuning of radiation curable formulations can significantly affect the ChLC optical, electro-optical, temperature characteristics and environmental robustness of the displays. Displays based on PIPS technology were successfully developed and commercialized enabling low cost, low power, light weight and rugged display applications with desired optical and environmental properties. In addition, this technology has resulted in great market success of the Boogie Board™ writing tablet as it offers environmentally friendly digital note taking with a paper-like feel, allowing users to dramatically reduce paper consumption
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Photonic Curing Processing with Results for Nanoparticle and Flake-based Conductive Inks, for Silve
At this event in 2011, developments in processing equipment based on the photonic curing concept were presented. Now, this processing method is shown as applied to a variety of new and off-the-shelf materials including copper and silver inkjet and screen inks, on plastic and paper substrates. Differences in required process energy and exposure power are discussed. The processing is shown to improve through-put via the very fast processing times, and improve product cost via enabling non-silver material options.
Suited For: Both
Barrier Coatings & Conductive Films for Flexible Electronics
Influences on Barrier Performance of UV/EB Cured Polymers
UV/EB cured materials utilized as barriers against moisture vapor and/or oxygen gas has been an interesting area of study for many different markets. Depending on the final requirements and thickness of application, UV/EB materials can be a suitable solution. Backbone chemistry, molecular weight, functionality, concentration gradients of monomers and oligomers, hydrophobic/hydrophilic balance, density, and the presence of additives or fillers all play a vital role in predicting barrier performance. In this presentation, these variables will be explored as performance predictors supported by real barrier testing results and trends.
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Non-Active Materials for Tomorrow's Solar Modules
While today's solar market is dominates by conventional crystalline silicon technologies, a number of innovative thin-film modules - like flexible CIGS - and improvements to conventional x-Si - like selective emitter or back contact cells - open a door for new barrier coatings, encapsulants, and other non-active materials. Ideal non-actives enable broad adoption of new technologies, and could provide a segway into new applications like building-integrated photovoltaics (BIPV). In this presentation, we'll examine the materials opportunities of tomorrow's solar modules, and their potential in a volatile yet growing solar demand market.
Suited For: Both
UV Based Conductive Inks for Flexible Printed Electronics
The demand for printed flexible electronics has been rapidly increasing for several applications including flat panel displays and touch-screen devices. This has stimulated a rapid growth in the development of different types of inks and use of various printing methods. Printing technologies and methods employed must be able to print metal traces with resistances much lower than that possible using current ITO technology, with comparable optical transparency. Bulk of the present efforts on printed conductors is based on thermal sintering of nano-particles of silver and copper. This paper illustrates our progress in printed conductor development using UV cure technology approach to achieve low resistance features without a thermal sintering requirement. Two-sided printed conductors are required in many touch applications. UV ink printing has been scaled to batch and roll to roll films to develop fine line conductors on one or both sides of very thin flexible substrates.
Suited For: Both
Stereolithography
Photofixation of Diels–Alder Networks
3D printing devices utilize a diverse array of techniques including laser sintering, fused deposition modeling, and stereolithography. While stereolithography provides the greatest resolution, it suffers from the liquid nature of the media, which cannot support overhanging and high aspect features. Thus complicated support structures must often be designed and then later removed. This problem can be avoided by the use of a solid resist, where a reversibly crosslinked polymeric material provides a continuous scaffold to support the desired shape. The support material can then removed by depolymerization. Using Diels–Alder based polymer networks, we developed a photoresist based on the selective elimination of bond reversibility. Thiol and photoinitiating species are readily incorporated into the initial mixture, and upon irradiation the Diels–Alder adduct undergoes a thiol-ene reaction, rendering the bond irreversible and the network structure permanent, or fixed, like any other thermoset. The unexposed regions retain their reversible behavior, and are later removed upon heating that achieves reversion of the remaining reversible crosslinks to monomer via the retro- Diels–Alder reaction. This allows complex shapes, such as sets of interlocked rings to be readily fabricated. This approach provides several key advantages over current techniques including solventless preparation, the ability to pattern arbitrary three dimensional shapes, and reduced complexity.
Suited For: Industry Suppliers (Formulators, etc)
Development of Antimony Free Stereolithography Resin for Investment Casting
Stereolithography (SL) is the most widely used rapid prototyping technology. This process creates complex 3D models from digital data by successively curing a liquid resin layer by layer using a UV-laser. SL materials have long been applied for investment casting. During the investment casting process, ash from burnout of typical SL resin investment cast patterns could negatively affect the surface of metal castings by leaving surface defects. Analytical result showed that the ash content was largely antimony oxide which came from the cationic photoinitiator used in almost all SL materials on the market today. As a solution, an antimony free SL resin was invented by using an iodonium borate photoinitiator in combination with a photosensitizer. The addition of antioxidants could contribute to the reduction of the potential run-away reaction when the compositions were exposed in bulk to actinic radiation. The absence of antimony in SL resins reduced the residual ash to be less than 0.01%, verse 0.3% for a conventional SL resin, gave this new resin a significant advantage for investment casting.
Suited For: Industry Suppliers (Formulators, etc)
Photoinitiator
Polymeric Photoinitiators – Low migration, low odor, favorable toxicology
UV/EB-curing printing inks and coatings are widely used in a variety of packaging applications. When it comes to food packaging for indirect contact, odor and the potential migration of mobile components are a concern for every formulator, independent of the curing mechanism. In UV-curing inks and coatings, the main focus is on photoinitiators that usually are of low molecular weight and which have a tendency to migrate, either through the substrate or via reverse-side migration (set-off). In response to existing and pending legislation on permissible migration levels for inks used in food packaging, a product range of polymeric, high molecular weight photoinitiators, that meet the demands for low migration and odor and have favorable toxicology has been developed. In this paper, updated information for polymeric photoinitiators regarding performance, formulation guidelines, and toxicological findings are presented.
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High performance photoinitiators with low emission properties
High curing performance alone is not always sufficient for sensitive UV applications. Health safety concerns and regulations play an increasingly large role. These legitimate concerns must be addressed. The presentation will show how progress can be achieved in cationic initiators. It will introduce triarylsulfonium photoinitiators that reach highest reactivity without heavy metals and volatile photocleavage products. The paper will include migration results in critical applications, such as printing inks for food packaging.
Suited For: Both
A fluorinated photoinitiator for surface oxygen inhibition resistance
This paper reported a fluorinated photoinitiator to solve the surface oxygen inhibition and improve the surface properties of UV-curable materials. The 2-methyl-2-benzoylethanol-pentadecafluorooctanote (1173-F) was synthesized by the esterification of 2-Hydroxy-2-methylpropio phenone (1173) and Pentadecafluorooctanoyl chloride (PFOC). The chemical structure of this fluoro-based photoinitiator was confirmed by 1H NMR, 19F NMR and IR. The activity of 1173-F as a photoinitiator was studied by UV absorption spectroscopy, real-time infrared spectroscopy (RTIR). The migration characteristic was detected by UV Spectrophotometer (UVS), X-ray photoelectron spectroscopy (XPS), gel permeation chromatography (GPC) and line mapping energy dispersive spectrometer (LM-EDS).
Suited For: Both
Brasil
Electron beam application on production of bioethanol from sugarcane bagasse: status and perspectives
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Mechanism of electron beam radiation damage on carbon nanofiber surface
This study explored the use of a high energy electron beam as the only available technique for selective area surface modification of carbon nanofibers through controlled parameters such as radiation dose, sample temperature, and environment. The application of this variable space led to the production of unique morphological features on the nanofiber surfaces. Transmission Electron Microscopy was used to allow direct observation of carbon structures undergoing electron beam irradiation and establish the mechanism for these surface modifications. Depending on the exposure parameters, a nanofiber surface rich with some or all of the following was created: i) free radicals, ii) chemisorbed or physisorbed functional groups, iii) surface roughness from peeling and recombination of graphene layers, and iv) activated carbon surface with nano to meso porosity. To further understand the structural changes of irradiated carbon nanofibers, WAXD analysis was performed on non irradiated and irradiated samples. There is a considerable expansion of the lattice in the irradiated samples leading to an increase of interplanar spacing (d spacing). The free radicals created during electron radiation process were investigated by Electron Paramagnetic Resonance.
Suited For: Both
Radiolytic Degradation of Humic Acid: an alternative to complement the chemical test of water resou
The radiolytic degradation process is a new method of mineralization by advanced oxidation applied in chemical tests to remove humic compounds in any water systems. Their effects were investigated in a laboratory scale upon gamma-irradiation from 60 Co and electron beam source. The efficiency of this degradation process, which is still under development, can be observed by measurement of the total organic carbon (TOC) that is one of the degradation products by irradiation.
Suited For: Industry Suppliers (Formulators, etc)
China Session
Molecular design concepts and manufacturing feasibilities for new generations of photoinitiators
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Global Market Overview
Electron Beam Applications in Korea
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North American Market Overview
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Environmental, Health, & Safety
Proposition 65: How the Law Relates to UV/EB Coatings, Inks and Adhesives
California annually publishes a list of chemicals "known to the State to cause cancer or reproductive toxicity." The current list contains almost 900 substances and is constantly growing. It is more important than ever to understand the law and how it affects your products, including what UV/EB ingredients are listed and when appropriate warning labels are needed. If not compliant, the company could be fined up to $2,500 per violation per day, as well as face criminal penalties and citizens' suits. This presentation will provide an overview of Prop 65 and how the law affects chemicals found in UV/EB coatings, inks and adhesives. It will explore RadTech's products and the associated hazard analyses and safe harbor warnings that are affected by the law.
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Multifunctional acrylate toxicology - Results of New Studies Generated for REACH
In 2010, high production volume multifunctional acrylates such as hexanediol diacrylate and trimethylolpropane triacrylate were registered in Europe to meet the requirements of the EU REACH legislation. Few of these acrylates already had the full set of toxicology studies needed for such a registration. Therefore, a number of toxicology studies were conducted on these acrylates to fill existing data gaps. This presentation will review the results of the newly conducted studies and changes in the European hazard classification of the multifunctional acrylates based on these and other existing studies. In addition, a summary of NTP’s conclusions on the TMPTA 2-year cancer bioassay will also be discussed.
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The Impact of REACH on the Hazard Communications of US substances
Implementation of the European legislation called REACH is under full swing. The first phase of chemical registrations is complete, and the second phase of chemicals is undergoing the testing required. As new data come to light, changes in the hazards are identified leading to new labeling requirements in Europe. Those new hazards also trigger changes to the MSDS in the US. While companies may be global, hazard communication standards are not, and there is confusion regarding the differences seen in the European SDS and the US MSDS. Furthermore, the old classifications and labels used in Europe are modified under REACH. The Globally Harmonized System adopted by Europe is not yet global, adding to the confusion. This presentation will review those changes using the example of a well-known photoinitiator, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.
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Staying in Compliance and in Business with UV/EB
Regulations play a prominent role in shaping business decisions and spark end user interest in UV/EB technology. An end user is not only subject to Volatile Organic Compound (VOC) regulations but also toxics and greenhouse gas requirements. Find out regulatory trends that can give UV/EB technology an advantage. California usually leads the nation in setting emission standards. This presentation will highlight key California policies as well as upcoming national issues such as energy efficiency, which can be used as tools to make the case for conversion to UV/EB processes
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Raw Materials
Urethane Acrylate Oligomers with Hydrophilic Moieties
Hydrophilic polyurethane polymers are important materials in the optical and medical device industries due to their anti-fog properties and biocompatibility. The ability of some to be dispersible or even soluble in water has also led to their extensive use in other fields, such as wood coatings. This paper will explore the properties of several urethane acrylate oligomers with hydrophilic moieties. The effect of the structure and concentration of such moieties on various coating properties such as scratch and chemical resistance will be investigated.
Suited For: Industry Suppliers (Formulators, etc)
An Alternative To Bisphenol A Based Epoxy Acrylates
Epoxy acrylates have had a successful and long history in the coatings industry due to their cost and performance advantages. However, the safety of bisphenol A based epoxy resins has been questioned in various applications. Stepan has developed a new polyester polyol, when acrylated, that can be used as an alternative to epoxy based acrylates. The new product has coating properties that are similar to or exceed standard epoxy acrylate-based formulations including increased hardness, high gloss, great wear resistance and excellent chemical resistance.
Suited For: Industry Suppliers (Formulators, etc)
A Simple Process for Preparing Low Viscosity Diacrylate-Functional Epoxy Oligomers
An investigation was conducted to determine if an inexpensive, simple approach to significantly reducing the viscosity of acrylate-functional oligomers could be developed. This work began with an attempt to reproduce claims of U.S. Patent 4,687,806. This patent claims that small amounts of aqueous LiBr solution will significantly reduce the viscosity of an epoxy diacrylate oligomer. The claims were not corroborated in this study but even lower viscosities were obtained than were claimed. This paper summarizes the claims of the patent and presents data that show that the presence of LiBr is actually detrimental and that water alone is a surprisingly effective diluent.
Suited For: Both
Cationic
Chain Transfer Agents in Cationic Epoxide Polymerizations: Kinetic and Physical Effects
Cationic epoxide photo-polymerizations in the presence of different types of alcohols and water were monitored by real-time Raman spectroscopy. Epoxide conversions increased linearly with hydroxyl concentration. Photo-polymer films were prepared and physical/mechanical properties determined using dynamic mechanical analysis and gel fraction measurements. The molecular weight and functionality of the alcohol significantly impacted polymer properties. The addition of alcohols to epoxide resins results in high conversions, high curing speeds and facile property tuning capabilities.
Suited For: Both
Analyzing Consumption of BPh as a Function of Film Depth and UV light Intensity (I0)
Abstract The influence of UV lamp power or UV light intensity (I0) on Benzophenone (BPh) photo decomposition at different depths of UV cured films was studied. UV absorption of a UV curable formulation is a function of [PhI]. A depth profile of BPh consumption at different depths of module formulation was analyzed. This investigation was performed with a variety of film depth, different curing speeds and different I0 (mW/cm2) with different or equal UV Exposure.
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Electron Beam Activated Cationic Curing
Electron beam (EB) irradiation was used to activate cationic polymerization in the presence of onium salt catalysts. These systems cured in air without nitrogen interting. The effect of the monomer and catalyst composition on the cure dose response was studied. The applied film thickness also had an effect on the cure dose. The cured material had excellent adhesion to difficult substrates including polyester film and metals without the need for primers.
Suited For: Industry Suppliers (Formulators, etc)
Formulation
UV Coatings for Automotive Interior Applications
With increased desire for higher quality, more durable appearances, OEMs are upgrading performance testing, especially for interior automotive coatings. With harsher requirements across properties such as chemical resistance, abrasion resistance, or some combination of the two, UV coatings are becoming more suited for these types of automotive interiors. This presentation will focus on the evaluation and comparison of thermal vs. UV and show how we arrived at the use of UV coatings for a cost effective option to achieve this appearance and performance.
Suited For: Both
Evolution of High Solids, High Performance UV Coatings for Spray Application
High solids coatings are nothing new to the UV industry, they have been around for quite some time in inks, wood coatings, and industrial markets. However, for coatings at or near 100% solids, application methods have generally been restricted to roll coat. When spray applied, performance properties of these coatings generally suffered due to the increased monomer content necessary for the required viscosity reduction. As focus has increased in lowering the environmental implications of higher VOC coatings, resin manufacturers have delivered in providing higher performance resins at lower viscosities. These developments have in turn allowed coating formulators the ability to design coatings that can meet sprayable criteria, with exterior durable performance standards.
Suited For: Both
Study on Polypropylene - Acrylic blocked copolymers for additives in UV curable coatings
Polypropylene - acrylic blocked copolymers have been developed for additives in UV curable coatings which give excellent adhesion to polypropylene substrates. In this study the factors affecting the coating performance properties have been investigated. The results show that the balance of the compatibility and the adhesion to polypropylene substrates is achieved through controlling the melting temperature, the molecular weight and the chemical structure of the blocked copolymers.
Suited For: Industry Suppliers (Formulators, etc)
UV/EB Thermoset Polymers Intended for Thermoforming Applications
This paper will investigate the use of new UV/EB curable polymers for thermoforming applications. Current growth in this area can be contributed to the added properties that UV coatings can provide such as pencil hardness, scratch and abrasion resistance, and chemical resistance. The effects of backbone structure, crosslink density, molecular weight, and percent conversion will be used to evaluate several new oligomers designed with varying ratios of hard and soft segments in the polymer backbone.
Suited For: Industry Suppliers (Formulators, etc)
Kinetics
Photo-enforced stratification is a method of photopolymerization designed to induce a compositional gradient in a polymer thin film upon co-photopolymerization in the presence of a light gradient by taking advantage of the temporal and spatial control that photopolymerization affords. The light gradient will establish a gradient in the reaction rate of polymerization. If one of the monomers in the copolymerization preferentially reacts, then photo-enforced stratification can result in a surface enrichment of that monomer.
Suited For: Both
Thermal and UV-curing Behavior of Inks,Adhesives, and Coatings by Photo-DSC and In-situ DEA
The use of Differential Scanning Calorimetry (DSC) with the extension of a UV (ultra violet) light source allows the investigation of the exothermal UV-curing reaction of adhesives, paints, and inks. The main advantage of light-curing systems is their fast reaction time. Monomer solutions which are mostly free of solvents can be cured within only a few seconds at low temperatures. A combination of thermal and light curing reactions is often applied to dual cure adhesives or paints. The advanced Photo-DSC 204 F1 Phoenix works in the temperature range from -100 to 200°C. UV light-reactive resins such as paints, coatings, and adhesives can be analyzed in a pure inert gas atmosphere by means of the gas-tight DSC measuring cell with purge gas control regulated by a mass flow controller (MFC). With Photo-DSC most standard industry or laboratory lamps for cationic or radically resins can be used.Using a modified automatic lid-lifting device, a defined distance between the two light guides and the sample and reference is assured. This achieves high reproducibility of measurement results. For normal DSC analyses above 200°C,a retrofit of the standard lid-lifting device is possible, or the manual lid can also be used without problems. For high sample throughput, an Automatic Sample Changer (ASC) for up to 64 samples is recommended Due to the fast data acquisition rate, the dielectric analyzer DEA 231/1 Epsilon with an inter-digitated comb sensor and a lamp connected via a light guide is ideal for studying the UV curing - even in-situ.
Suited For: Both
Control of Free Radical Reactivity in Photopolymerization of Acrylates
In practical use, it is the rate of gelation or rate of cross-linked network formation that is of most interest in the free radical curing of acrylates. One of the simplest indicators of the gel point is the sharp rise in MEKR that occurs as a function of radiation dose applied. It is well-known that oxygen inhibition and radical-radical recombination limit efficiency, delaying the onset of gel formation to higher dose or longer exposure time. This paper explores means to alter the reactivity of the intermediate free radicals, in one case by chain transfer to RSH species and in another by complexation with stable nitroxide radicals, thereby altering the population of chain-carrying species to favor longer-lived radicals or radical precursors which by their nature are less affected by the normal termination processes. By chain transfer formation of thiyl radicals, a simple titration of reactive radicals is possible as observed by detection of the point of maximum MEKR as a function of dose for different starting RSH concentrations. By this means, we can demonstrate that approximately 10X more radicals are created in a typical UV cure formula following 300 mJ/cm2 exposure than are created in an EB cure formula using the same monomer following 30 kGy exposure. At low concentrations of organic nitroxides, a surprising decrease in radiation dose at the gel point is observed, paired with an increase in ultimate rub resistance. This optimal concentration depends strongly on nitroxide structure, but in all cases it occurs at nitroxide concentrations much smaller than the estimated free radical concentration at the point of cure. Both observations are consistent with a colloidal model of gelation where first-formed cure domains are cemented together in a slower second step. Finally, we show that latent cure is accentuated by these longer lived radicals and oxidation products formed from them, allowing a post heat to significantly advance cure by re-initiation of free radicals.
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EHS for End Users
Field Applied
Global Marketing View of UV Curable Field Applied Floor Coatings
LED Session
Printing & Packaging: Print Challenges
Komori HUV – (R)Evolution in Curing