10^th Coatings Science International 2014

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Speakers COSI 2006

Dr. Ingo Alig

Deutsches Kunststoff-Institut, Darmstadt, Germany

Title Lecture

Monitoring of film formation, cure and ageing of coatings by an ultrasonic reflection method

Authors

I. Alig, D. Lellinger, S. Tadjbach and H. Oehler

Abstract

During film formation, cure and/or ageing of coatings changes in physical properties and chemistry of the material occurs. For this processes one have to consider a complex interplay of different factors. In order to get a more detailed insight in the mechanisms of film formation, cure or aging, it is desired to be able to monitor the changes of the mechanical properties in real time. In this work different modifications of an ultrasonic reflection technique [1] enabling such an analysis are described [2-5]. The ultrasonic method measures the complex acoustic reflection coefficient (changes in amplitude and phase) between a substrate and the coating for transversal and/or shear waves at ultrasonic frequencies.  From the complex acoustic reflection coefficient and the density of the sample the corresponding mechanical moduli and Poisson’s ratio can be calculated [3]. Different ultrasonic setups have been developed for monitoring of film formation from aqueous dispersions and solvent-based coatings [2,3], for curing of epoxies [3] or acrylates (including UV-curing [4]) and simulated weathering. The method can be considered as a real time dynamic mechanical analysis at high frequencies. Physical changes like vitrification, swelling and drying, crack initiation or delamination can be well monitored by this method. Recently, the ultrasonic reflection technique has been combined with near-infrared analysis [5] for monitoring of UV curing.  Moreover, the method was used to detect material changes while the samples are exposed to simulated weathering. Furthermore, setups for high throughput experimentation have been developed.

References:

1. W.P. Mason, W.O. Baker, H.J. McSkimin, J.H. Heiss, Phys.Rev., 1949, 75, p. 936-946.
2. I. Alig, D. Lellinger, J. Sulimma, S. Tadjbakhsch, Rev. Sci. Instr., 1997, 68, p. 1536.
3. D.Lellinger, S. Tadjbach, I. Alig, Macromol. Symp. 2002, 184, p. 203–213.
4. I. Alig, D. Lellinger, H. Oehler, Adhäsion, 2005, 49 (5),p. 36-39.
5. P.A.M. Steeman, A. A. Dias, D. Wiencke, I. Alig, D. Lellinger, Progress Organic Coatings, 2005 (in press).

Curriculum vitae:

• Ingo Alig (Ph.D., D.Sc.)
• Head of Department of Physics at Deutsches Kunststoff-Institut in Darmstadt, Germany lecturer at Technical University Darmstadt

Education

• Ph.D. 1983 in Physics, Technical University Merseburg
• Habilitation (D.Sc.)1988 in Experimental Physics

Positions

• 1978-1991 Senior scientist at Department of Physics at Technical University Merseburg 1989-91 visiting scientist at Research Center of Crete/Greece, McMasters University Hamilton/Canada, Max Planck Institute for Polymer Science
• 1991-1993 senior scientist at the Institute for Physical Chemistry of University Köln 1993-now Head of department of Physics at the Deutsche Kunststoff-Institut and lecturer at Technical University Darmstadt

Dante Battocchi

North Dakota State University, Department of Coatings & Polymeric Materials and Department of Chemistry, Fargo, ND USA

Title Lecture

The use of multiple electrochemical techniques to characterize Mg-rich primers for Al alloys

Authors

Gordon Bierwagen, Dante Battocchi, Aldo Simoes, Anthony Stamness and Dennis Tallman

Abstract

To insure that the corrosion protective behavior of Mg-rich primers over Al aircraft alloys is properly understood, multiple electrochemical techniques have been utilized to characterize the behavior of this class of Cr-free coatings. The electrochemical testing was done in conjunction with the subjective “qualification” testing of the primer materials for US Air Force and Navy specifications so that as this new class of primers did not encounter any unexpected corrosion protection-related deficiencies. To confirm that the Mg-rich primer did indeed provide cathodic, sacrificial protection to these alloys, the mixed corrosion potential of the mixed Al-Mg system the Open Circuit Potential (OCP),can be used to show when the potential of the alloy substrate is modified by contact with the Mg to yield a potential cathodic to the Al Alloy
This was done by a steady state measurement of the total system OCP in immersion and also by the measuring the potential of the minimum/free corrosion current (icorr) in a potentiodynamic scan of the mixed system.  Both methods yielded values in excellent agreement, but initial studies with a system top-coated with a high quality topcoat gave problems in OCP measurement due to an exceedingly high impedance causing steady-state measurement difficulties. Electrochemical Impedance Spectroscopy (EIS) and Electrochemical Noise Methods (ENM) were also used to characterize the system in immersion. Further, the Scanning Vibrating Electrode Technique (SVET) was used to examine local damage protection by the Mg-rich primer about a deliberately induced scratch in the coatings system. These results for the Mg-rich primer system yield a very interesting self-consistent set of data showing cathodic protection of one reactive metal (Al) by another more reactive metal (Mg).

Biography

Dante Battocchi,earned a degree of Doctor in Materials Engineering at Trento University (trento, Italy) and  Master degree in Coating Science at NDSU (Fargo, USA). Currently he is a Research Associate in the department of Coatings and Polymeric Materials in the North Dakota State University, Fargo (USA).He is leading the development of the Mg-rich primer, a totally chrome free system conducting electrochemical studies on other types of coatings supervising and training students.

Prof.dr. Gordon Bierwagen

North Dakota State University, Department of Coatings and Polymerix Materials, Fargo, ND, USA

Title Lecture

Lifetime prediction for corrosion protective coatings form electrochemical measurements - A new perspective

Authors

G.P. Bierwagen, B.R. Hinderliter, S.G. Croll, D.E. Tallmann and Q. Su

Abstract

Electrochemical resistance measurements on the accelerated weathering of corrosion protective coatings systems in this laboratory have yielded time series data that can be fit by a simple exponential decay function in time. A description of how this can be empirically used for lifetime prediction for coatings has already been presented[1][2][3][4]
In this paper we will present a simple model that can be used to interpret these results. This simple model which considers only loss of coating thickness by UV-induced ablation is applied to the interpretation of EIS time series results from coatings systems undergoing accelerated weathering.  Next, more complete models which description of electrolyte transport in coating films are applied to the same problem.  Incorporating these models for degradation as a simple RC equivalent circuit representation of a coating gives predictions of EIS performance that have reasonable agreement with experimental data.  Using a two layer representation of coating together with the application of known effective medium theories for dielectric and resistivity changes due to water intrusion allow prediction of the changes in EIS spectra seen in accelerated testing of coating films. These results illustrate the power of modeling physical processes in interpreting electrochemical data from coating films and predicting coating protective lifetimes

1. G. Bierwagen, J. Li, Lingyun He, and D. Tallman “Fundamentals of the Measurement of Corrosion Protection and the Prediction of Its Lifetime in Coatings”, Chapter 14 in Proceedings of the 2nd International Symposium on Service Life Prediction Methodology and Metrologies, Monterey, CA, Nov. 14-17, 1999, ACS Symposium Series # 805, J. Martin and D Bauer, ed., ACS Books, Washing ton, DC (2001) 316-350
2. C. Schiller & W. Strunz, “The evaluation of experimental dielectric data of barrier coatings by means of different models,” Electrochimica Acta, 46 2001 3619-25
3. S. Duval, M. Keddam, M. Sfaira, A. Srhiri, H. Takenouti, “Electrochemical impedance spectroscopy of epoxy-vinyl coating in aqueous medium analyzed by dipolar relaxation of polymer,” J. Electrochem. Soc., 149 (2002) B520-9
4. J.M. Hu, J.Q. Zhang, C.N. Cao, ”Determination of water uptake and diffusion of Cl- ion in epoxy primer on aluminum alloys in NaCl solution by electrochemical impedance spectroscopy,” Prog. Organic Coatings 46 (2003) 273-279

Francesco Ciardelli

Dept.Chemistry and Industrial Chemistry,University of Pisa and PolyLab-INFM,Pisa,Italy

Title Lecture

Conferring Dichroic Properties and Optical Responsiveness to Polyolefins Through Organic Chromophores and Metal Nanoparticles

Authors

Andrea Pucci,Giacomo Ruggeri,Simona Bronco,Monica Bertoldo,Chiara Cappelli,Francesco Ciardelli

Abstract

Organic Chromophores nanoaggegates and Gold nanoparticles coated with chromophoric thiols can be dispersed into  polyolefins functionalized with polar groups to various extent either by casting from solvents or by melt mixing. Also polymer/gold nanocomposites are prepared by photoreduction of gold chlorides in the presence of hydroxyl containing ethylene copolymers .The characterization of the morphology of the resulting composites containing less than 3% w of optical additive shows the presence of nanodispersed particles  .The resulting thin films can be oriented by mechanical stretching of the polymer thus providing films with high absorption and emission dichroism, the dichroic ratio being higher than 30 and than suitable for commercially used linear polarizers . The optical response can be modulated to high extent by varying the degree of  dispersion and the amount and dimensions of the dispersed phase by modulation of the interface nature. In particular by selecting appropriate stilbene containing chromophores thin polyolefin films were obtained showing optical response in the visible to mechanical stimuli.Also a combination of the experimental data and quantum mechanical investigations allowed to correlate the optical response to the molecular structure complexity of the chromophores and to the molecular and sovramolecular organization in the polymer matrix.

1. N. Tirelli, S. Amabile, C. Cellai, A. Pucci, L. Regoli, G. Ruggeri, F. Ciardelli" New terthiophene derivatives for ultrahigh molecular weight polyethylene-based absorption polarizers"Macromolecules, 34, 2129 (2001)
2. A. Pucci, N. Tirelli, G. Ruggeri, F. Ciardelli "Absorption and emission dichroism of polyethylene films with molecularly dispersed push-pull terthiophenes,Macromol. Chem. Phys., 206, 102-111 (2005)
3. F. Ciardelli, A. Pucci, G. Ruggeri, V. Liuzzo"Conferring smart behaviour to polyolefins through compatible blending with organic dyes and metal derivatives"ACS Symposium Series,916,18( 2005)

Biography

Professional career

• Doctor degree 1960 University of Pisa
• PhD 1968 Rome
• Research Associate, University of Pisa 1960-1965, University College, London 1965;
• Postdoctoral Fellow, Max Planck Institute, Mülheim/Ruhr (FRG) 1966-67;
• Assistant Professor, University of Pisa, 1968-1975;
• Visiting  Professor, University of California, Berkeley (USA) 1973 and 1985; Kyoto University (JAPAN) 1983; Polytechnic
• Zurich (ETH) 1986;
• University P.M.Curie, Paris (France) 1999.
• Professor of Polymer Chemistry, University of Pisa, since 1975.

Professional activity

• Member of the Scientific Board of three CNR Centers
• Member of the Scientific Board,CNRS Lab.,Lyon(France) (1986-1989)
• Chairman of the Italian Macromolecular Association (AIM) (1983-85)
• Chairman of 10 (eight) International Conferences
• Full Member of IUPAC-MACROMOLECULAR Division (1986-88)
• Invited Speaker to: three Gordon Research Conferences, 25 IUPAC Symposia, and more than 80 International Meetings
• Member of the European Polymer Federation Steering Committee (1988-1996)
• Director of the Departement of Chemistry and Industrial Chemistry of the University of Pisa (1996-1999)
• Chairman of the Division of Industrial Chemistry of the SCI (1997-2000)

Membership of Journals Advisory Boards

• Polymer Int., since 1983
• J. Polymer Science, 1983-1989
• New Polymeric Materials,  1989-99
• Polymers, since 1989
• Polymers for Advanced Technologies, since 1990
• J. Molecular Catalysis, 1995-2003
• Macromolecular Chemistry & Physics, since 1996-2002
• Polymer Bulletin, since 2004

Research Interests

• Transition Metal Catalysts for Olefin Polymerization
• Stereochemistry and Chirality in Macromolecules
• Clean Industrial Processes
• Polymer Functionalization ,Reactive  Blending and Composites
• Photoresponsive and Electroconducting Polymeric Materials
• Polymers for Coatings and Packaging

Publications
320 papers in refereed journals, 250 presentations to scientific meetings, 11 patents, 8 books.

Dr. Jacques Devaux

Université Catholique de Louvain, Département des Sciences des Matériaux et des Procédés, Unité de Chimie et de Physique des Hauts Polyméres, Louvain-La-Neuve, Belgium

Title Lecture

Polymer-based nanocomposites: overview, applications and perspectives

Authors

J.J.D.G. Devaux

Abstract

Nowadays "Composite" is an usual name given to a material to which (at least) two solid constituents provide not only average but "higher than additive" ( so-called "synergistic" ) properties. In the most usual acception such properties are mechanical, but they could be of  electric, optic, even biologic nature."Nanocomposite" means a composite into which the filler exhibits (at least) one dimension in the "nanometer" (10-9 m ) scale. In this case the prefix nano- was not added (only) for fashion, or because the nanometer became an "observable" dimension in the late 1980's, but decreasing the dimension(s) of the filler down to such a small scale allows to enhance the contribution of the contact zone (the so-called "interface zone" or, more precisely the "interphase") to the overall properties of the (nano-)composite. This "interphase" is the volume of the matrix what is "modified" by the presence of the neighbour solid filler.
For instance, for a spherical glass-like filler, going from I micron down to I nanometer diameter increases the contact surface from about 2,5 to 2500 m2/g. If the interphase is only I micron thick, in the latter case, less than 0.1% by weight of such a "nano"filler is enough to "modify" all the material !
Among nanocomposites which appears by now close to wide range applications, polymer-clay nanocomposites attracted most of the efforts. Owing to the growing interest for polymer-clay nanocomposites, the amount of research in this field exploded from the first Toyota's team report in 1990.
Applications are now looked for in the automotive industry where lightweigth, gloss, fire resistance are a few of the desirable properties for a material. But outside this most popular domain, medical, as well as food, coatings, etc. applications are arising.
So far, the price of the final materials, partly linked to the cost of the wet treatment needed for the pristine clay, remains a major factor hindering the commercial development of nanocomposites. But perspectives exist by now allowing the direct use of untreated cheap clay as starting material.

Kurt Dietliker

Ciba Specialty Chemicals Inc., Basel, Switzerland

Title Lecture

Advancements in Photoinitiators – opening up new Applications for Radiation Curing

Abstract

Over the past decades, radiation curing has found widespread use in an increasing number of industrial applications. Photoinitiators are key components in all photopolymerizable formulations, which allow the efficient transformation of the energy of light into chemical energy in the form of initiating species. A variety of efficient photoinitiators for different applications is today commercially available and used in coatings, printing inks or electronic materials.
However, several challenges for radiation curing still remain. These include for example the curing of thick or highly pigmented coatings or of coatings applied on three dimensional objects. Odor and extractables in the cured coatings are another issue of concern. Newly emerging applications eventually create novel requirements for the curing process and the properties of the cured material. Further improvements of photoinitiators and the development of new compounds are therefore essential for the further expansion of the UV curing technology. Modern photoinitiators are in fact more than just catalysts for the polymerization process: they are an integral part of sophisticated formulations, providing excellent properties in the manufacturing process and during the service time of the cured article.
This will be illustrated by some recent developments in photoinitiators. Well-approved initiator classes for radical photopolymerization have been significantly improved and optimized for use in coatings for outdoor applications and in printing inks. The new compounds allow fast cure and provide excellent properties to the cured coating, including no yellowing after cure and upon long-term weathering and low odor and extractables in printing inks. A new type of photoinitiator has recently been introduced for use in color filter fabrication. The compound can meet the challenging requirements regarding light transmission in the resist material, thereby guaranteeing the purity of the color in the display.
The development of photolatent amines, a completely new class of photoinitiators, has eventually made new resin types accessible for radiation curing. Either conventional coating formulations or newly designed formulations can be used with these photoinitiators. The alternative base catalyzed curing mechanism allows to overcome some of the limits of radically curing formulations. Coatings of excellent performance are obtained, and the scope of radiation curing is considerably expanded by this new technology.

Biography

Kurt Dietliker studied organic chemistry at the University of Zurich and received his PhD for a thesis on the photochemistry of aminoazirine and isoxazole heterocyles. After a postdoctoral year at the University of Fribourg focusing on the elucidation of the di-p-methane rearrangement, he joined the research department of the Additives Division of the former Ciba-Geigy AG in Marly.
After a short time dedicated to other topics, he became involved in photoinitiator research. Over the years, his work focused on the development of several new photoinitiators for radical and cationic curing. In addition to numerous patents and scientific papers in this field, he is the author or co-author of three books on photoinitiators.
Currently he holds the position of a Senior Research Fellow and is responsible for the development of new photolatent acids and bases for the Coating Effect Segment of Ciba Specialty Chemicals Inc. in Basel.

Bart Erich

Eindhoven University of Technology, Department of Physics, The Netherlands

Title Lecture

Drying of alkyd coatings on porous substrates measured with high resolution MRI

Authors

S.J.F. Erich, O. Adan, H.P. Huinink, L. Pel, K. Kopinga

Abstract

Many coatings are applied on porous substrates, e.g., wood, stone, or gypsum layers. The porosity of the substrate largely influences the drying behavior of the coating. Three phases can be distinguished. First, the solvent and/or the resins penetrate the substrate. In the second stage, the solvent evaporates from the coating and substrate. In the third stage, the coating starts to solidify by the formation of cross-links (curing). The depth of penetration is one of the important variables that determine the adhesive properties of the final fully cured coating. For the different types of alkyd coating (solvent borne, high-solid, and waterborne) applied on wood it is known that the penetration depth varies. The penetration can be altered by changing the viscosity of the coating. Monitoring the penetration and its effect on the drying of the coating as a function of depth is of major importance for the development and improvement of products. Until recently, no techniques were available to follow this process in-depth as a function of time with a high resolution (about 5 µm). In our studies, we found that with high resolution MRI the penetration of the substrate (wood and gypsum) can be observed. Not only the penetration depth and the evaporation process can be monitored, but also the chemical curing inside the substrate. We monitored the drying of a commercial available solvent borne alkyd coating. The results showed that the coating completely penetrated the wooden substrate and started curing inside the wood. We also investigated a waterborne alkyd emulsion on a gypsum substrate. Direct after application of this waterborne alkyd emulsion, the water is absorbed into the gypsum. Our data indicate that curing not only takes place at the surface of the coating, but also on the coating/substrate interface. The results clearly demonstrate the added value of high resolution MRI for research on the interaction of a coating with its substrate.

Biography

Ir. Erich received his master degree in physics at the Eindhoven University of Technology in 2002, in the group Transport in Permeable Media. During his study he designed and built a low field 3D Magnetic Resonance Imaging (MRI) setup for different kinds of drying experiment in permeable media. Afterwards he continued his work in this group as a Ph.D. student. His research is focused on the drying behavior of coating systems, in particular alkyd coatings. To study the physical and chemical processes in these coatings he constructed a specialized high resolution NMR setup.

Alexander Fedorov

Department of Applied Physics, Materials Science Centre and the Netherlands Institute for Metals Research, University of Groningen, Groningen, The Netherlands

Title Lecture

Degradation and recovery of adhesion properties of deformed metal-polymer interfaces studied by laser induced delamination

Authors

A.Fedorov, R. van Tijum, W.-P. Vellinga, J. Th. M. De Hosson

Abstract

Adhesion properties of polymer coatings on metals are of great interest in various industrial applications, including packaging of food and drinks. Particular interest is focused on metal-polymer interfaces that are subjected to significant deformations during manufacturing process. In this work beverage cans are examined which are manufactured by deep drawing processes from polyethylene terephthalate pre-coated steel sheets.
The experimental technique used in this study is a laser induced delamination method. In this technique a coating is subjected to a series of infrared  laser pulses with a stepwise increase of intensity. Upon increasing the laser pulse intensity, the pressure which is formed inside the blisters reaches a critical value, resulting in further delamination of the coating. From the experimental results the critical stresses required for the delamination and the practical work of adhesion are derived. The processing of the experimental data is based on a linear elastic description supported by finite element modeling.
The measurements have demonstrated a strong correlation between the adhesion strength of the metal-polymer interface and the strain introduced by the deformation. After applying a thermal treatment restoration of the adhesion properties has been observed. The thermal treatment parameters (temperature, duration) were varied in order to optimize the effect of recovery.

Maurizio Fermeglia

Molecular Simulation Engineering Laboratory, Department of Chemical Engineering, University of Trieste, Piazzale Europa 1, 34127 Trieste, Italy

Title Lecture

Multiscale modeling for polymer systems of industrial interest

Authors

Maurizio Fermeglia and Sabrina Pricl

Abstract

Atomistic –based simulations such as molecular mechanics (MM), molecular dynamics (MD), and Monte Carlo-based methods (MC) have come into wide use for materials design.
Using these atomistic simulation tools, we can analyze molecular structure on the scale of 0.1-10 nm. However, difficulty arises concerning limitations of the time- and length-scale involved in the simulation. Although a possible molecular structure can be simulated by the atom-based simulations, its is less realistic to predict the mesoscopic structure defined on the scale of 100-1000 nm, for example the morphology of polymer blends and composites, which often dominates actual material properties. For the morphology on these scales, mesoscopic simulations such as the dynamic mean field density functional theory (Mesodyn) and dissipative particle dynamics (DPD) are available as alternatives to atomistic simulations. It is therefore inevitable to adopt a mesoscopic simulation technique and bridge the gap between atomistic and mesoscopic simulations for an effective material design. Furthermore, it is possible to transfer the simulated mesoscopic structure to finite elements modeling tools (FEM) for calculating macroscopic properties for the systems of interest.
In this paper, we present a hierarchical procedure for bridging the gap between atomistic and macroscopic (FEM) modeling passing through mesoscopic simulations. In particular, we will discuss the concept of multiscale (or many scale) modeling, and present examples of applications of multiscale procedures for polymer-organoclay nanocomposites for the estimation of the binding energy and basal spacing of a montmorillonite – polymer – surface modifier system. Examples of application of multiscale modeling to immiscible polymer blends and polymer – carbon nanotubes systems will also be presented.

Biography

Maurizio Fermeglia was born in Trieste, October 9th 1955. Maurizio Fermeglia graduated in Chemical Engineering at the Engineering Faculty of the University of Trieste in 1980. He got his habilitation for chemical engineer in 1985. In 1981 and 82 he worked as visiting scientist at the Denmark Technical University (DTH). His current position is full professor at the Engineering Faculty of the University of Trieste, where he holds the course in ‘Chemical Reaction Engineering’, ‘Process Simulation’ and ‘Data base’. He is member of the PHD Council of the University of Padova and Trieste. He has been involved in teaching for the following courses: Physics, Physical Chemistry, Computer calculation, Unit operations, Transport and thermodynamic properties measurements, Transfer processes and units, Object Oriented Programming, Net Economy at University of Trieste.
He has been teaching courses and seminars for industries and academia on the following topics: phase equilibrium and thermodynamics, equilibrium properties calculation, process simulation, applied thermodynamics, molecular simulation, multiscale modeling for polymers. He held seminars on Programming, Operating Systems, Data Base, Networking, Internetworking, multimedia.
The main research activities are focused on transport and thermodynamic properties, their experimental determination, correlation and prediction, chemical process analysis and synthesis and molecular modeling. In computer science his main research activity is in the Data Base and Internet – Intranet. He is scientific consultant of ICS - UNIDO within the Subprogram 'Process Simulation' from 1999. He is IUPC fellows from 2003. He is reviewer of the following journals: AIChE Journal, Industrial Engineering Chemistry, Fluid Phase Equilibria, J. Chem. Eng. Data, Chemical Engineering Science, J. Supercritical Fluids, Polymers and Polymer Composites, Fuel Cells, Industrial and Engineering Chemistry, Chemical Engineering and Processing.
He is author of more than 200 publications in national and international journals and conference proceedings on thermodynamics, molecular modeling, process simulation and computer science.

Santiago Juan Garcia

Área de Ciencia de los Materiales, Departament d’Enginyeria de Sistemes Industrials i Disseny, Universitat Jaume I, Avda. Vicent Sos Baynat s/n, 12071 Castellón, Spain.

Title Lecture

Anticorrosive evaluation of organic powder coatings by means of electrochemical techniques (EIS and AC/DC/AC)

Authors

S.J. Garcíaa,*, A. Serrab, J.J. Suayc

Abstract

In the field of the organic coatings, one of the most actual researching interests is to develop a new technique able to evaluate the primers in very short times. The actual evaluation methods, like salt fog spray, are very subjective and acquire long times of exposure, being difficult to give a quick idea of the anticorrosive properties. Various electrochemical techniques have been used to evaluate the performance of organic coating/metal systems. The application of electrochemical impedance spectroscopy (EIS) to coated metals has been proved to be a useful technique in the study of the corrosion performance of anticorrosive primers [1, 2], although it takes days, weeks and sometimes months to obtain good results. During last years a rapid method for testing coated metals consisting in a combination of DC and AC measurements (AC/DC/AC procedure) has been developed [3-5] in our group.
EIS and AC/DC/AC techniques have been used in this work in order to evaluate the anticorrosive properties of different organic powder coatings, showing good accordance between the two techniques and with the salt fog spray, traditionally used in the industry. The different techniques have been applied to a traditional epoxy powder coating system (bisphenol-A cured with o-tolyl-biguanide) and to different new low curing temperature epoxy powder coatings using trifluromethanesulfonates of Erbium and Ytterbium (III) as catalysts. A full characterization of the different systems has also been carried out showing that catalysts improve the curing meaningfully, lowering the curing time for a given temperature and conversion degree and at the same time showing good mechanical and anticorrosive performance.

1. Bierwagen G.P., J. Coat. Tech., 64 (1992) 71-75
2. Hernández L.S., del Amo B., Romagnoli R., Anti-Corrosion Methods and Materials, 46 (1999) 198-204
3. Hollaender J., Schiller C.A., Strunz W., Proceedings of the EIS 2001, Marilleva (Italy), (2001)
4. Rodríguez, M.T., Gracenea, J.J., García, S.J., Saura, J.J. and Suay, J.J., Prog. Org. Coat., 50 (2004) 123-131
5. Rodríguez, M.T., García, S.J., Gracenea, J.J., Cabello, R., Suay, J.J., J. Coat. Tech., 2 (7) (2005) 557-564

Keywords: epoxy resin, catalyst, AC/DC/AC, EIS, triflate.

Biography

Santiago Garcia studied chemistry at the Jaume I University at Castello, Spain. He graduated in 2001. Afterwards het joined the Valencia Polytechnic Univeristy in Valencia, Spain were he currently is working on his PhD thesis.
Fields of Interest:

• Thermosetting materials
• Polymer characterization (mechanical, thermal…)
• Anticorrosive properties of organic coatings
• Curing kinetics

Prof. dr. Alex van Herk

Eindhoven University of Technology, laboratory of polymer chemistry.

Title Lecture

From emulsion polymerization to nanotechnology

Authors

prof. Alex M. van Herk

Abstract

The Eindhoven group on emulsion polymerization has contributed to the field of encapsulation of many types of particles like pigments, fillers and clay particles, preparation of hollow multicompartment particles, encapsulation of nanotubes with latex particles and to the control of molecular microstructure and morphology through on-line techniques like Raman spectroscopy. Added to this is the introduction of controlled radical polymerization techniques as an additional means to control molecular microstructure and morphology in latex systems.
All these developments are very relevant for the next generation of coatings in which, more than in the past, improved properties are related to nanostructuring of the components in the coatings.
In this presentation an overview will be given on the many ways nanotechnology can be performed in the field of emulsion polymerization.

Biography

Alex van Herk is full professor in polymer chemistry in Eindhoven and visiting professor at the University of Göttingen (Germany). He graduated from the Free University of Amsterdam on the kinetics of ligand substitution reactions in vitamin B12 and joined the Eindhoven University of Technology in 1986 where he is active in the area of emulsion polymerization, polymerization kinetics, nanocomposites and alternative sources of initiation in polymerization processes. He is a member of the IUPAC working party on modelling of polymerization kinetics and a member of the international polymer colloids group. Since june 2001 he is director of the educational program in the faculty of chemical engineering and chemistry in Eindhoven. Furthermore he is chairman of the industrial liaison program emulsion polymerization.

Jos Huybrechts

DuPont Performance Coatings, Mechelen – Belgium

Title Lecture

2.1 VOC solvent borne 2K clear coats based on star oligoethers

Authors

Jos Huybrechts, Leen Tanghe

Abstract

The new European legislation for 2K car repair topcoats and clear coats forces the customers to use 3.5 VOC products by 2007. As of 2007, new VOC limits will be discussed depending on the state of the technology. The next step may be 2.1 VOC   and this limit can only be obtained with solvent borne products having a solids content of minimum 75%. It was believed that such high solids content could only be obtained with oligomers in which the reactive functional groups are blocked in order to get a sufficient long potlife. The crosslinking with the polyisocyanates can only take place when there is sufficient air humidity, water present in order to hydrolyze the oligomers during the film formation stage and become reactive with the isocyanates. Such systems will always lack robustness of application.
In this paper we will discuss a new class of hydroxyl functional star polyethers that allow formulating regular 2K clear and top coats at 2.1 VOC with an acceptable overall balance of potlife, appearance and drying properties.

Biography

Jos Huybrechts finalized his PhD from the University of Leuven in 1978 - Department Macromolecular and Organic chemistry with specialization in photochemistry and photophysics.
In 1978 he started with Dupont de Nemours Mechelen Belgium  in R@D Fluoroproducts.
In 1980 he moved to R@D resin development for OEM,Car repair,Trade and Industrial paints as well as specialty adhesives. (Dupont Fabrics and Finishes)
End 80 ties he got additional assignment for  several years  in resin development  for UV cure ( Dupont Electronics) and bead resins. (Dupont Specialty resins)
Since 1992 he is focusing only on resin development for OEM and Car repair. (Now Dupont Performance Coatings)
He is holding 40-50 patents mostly in the field of resins for OEM and Car repair and have several publications in this area of expertise.

Dr. Christine Jérôme

Center for Education and Research on Macromolecules (CERM)

University of Liège, B6 Sart-Tilman, B 4000 Liège, Belgium

Title Lecture

New developments in electrografting of thin polymer films

Authors

C. Jérôme, S. Gabriel, M. Cécius, R. Jérôme

Abstract

Electrografting is a one-step technique for tethering polymer chains onto conductive surfaces. In this process, polymerization of (meth)acrylic monomers is initiated at a well-controlled cathodic potential, whereas the chain propagation results from the chemical addition of the monomer to activated grafted species independently of the potential. This process has been successfully applied to a variety of acrylic monomers with the purpose to modify extensively the surfaces properties.
In a first example, an acrylate bearing a polymerization initiator in the ester group, thus an inimer, has been electrografted. Then polymerization of a second monomer (vinyl aromatic, lactone, cycloolefin…) has been initiated from the electrografted film ("grafting from" process), which allows for the film thickness to be increased in a controlled manner, for block copolymers to be synthesized and for nanostructures to be formed on the surface.
In a second example, N-succinimidyl acrylate has been electrografted, followed by the chemical grafting of a variety of nucleophiles, e.g., proteins, aminopolymers, aminoferrocene, by reaction with the succinimidyl substituents of the chemisorbed polyacrylate chains.
Finally, the electrografting of macromonomers, e.g., end-functional poly(ethylene glycol), poly(dimethylsiloxane) and poly(vinyl methyl ether) has been carried out. Surfaces with very specific properties such as protein repellency, high hydrophobicity and temperature responsivity, have accordingly been made available.Developments in the field of biosensors will be emphasized.

Sonny Jonsson*

Fusion UV-Curing Systems, Gaithersburg, MD 20878, USA

Title Lecture

Free radical induced photopolymerization of thio-ether vinyl esters

Authors

E. Sonny Jönsson Tai Y. Lee, Todd M Roper, C A. Guymon and C E. Hoyle

1. Fusion UV-Curing Systems, Gaithersburg, MD 20878
2. University of Southern Mississippi, Department of Polymer Science, Hattiesburg, MS 39406:
3. University of Iowa, Department of Chemical and Biochemical Engineering, Iowa City, IA 52242-2527

Abstract

The photopolymerization of vinyl acrylate/multifunctional thiol (trimethylol propane tris (3-mercaptopropionate)) mixtures as a function of thiol content in the presence and absence of photoinitiators has been investigated using real-time FTIR, thin-film calorimetry, and 2D-COSY NMR. The addition of a multifunctional thiol to vinyl acrylate significantly enhances the conversion of the vinyl double bonds of vinyl acrylate due to the preferential addition of the thiyl radical to the vinyl group. It was observed that two separate free-radical polymerization processes, acrylate homopolymerization and thiol/vinyl ester copolymerization, occur simultaneously in thiol/vinyl acrylate mixtures. Thin-film calorimetry and 2D-COSY NMR results are consistent with real-time FTIR results and give strong evidence for two separate free-radical processes.
One particularly interesting aspect of photopolymerization deals photoinitiator free photocuring processes by using monomers that self-initiate free-radical polymerization upon irradiation. In photoinitiator-free systems, various deleterious effects inherent to traditional photocuring including low initiation efficiency, residual extractable photoinitiator species, yellowing, and degradation resulting from unwanted byproducts can be eliminated. Recently, Hult et al.[4] reported photopolymerization results for a difunctional monomer with a reactive maleimide grou and an acrylate. Interestingly, since maleimides have been used as photoinitiators, [5-7] the difunctional maleimide/acrylate reported by Hult et al. [4] polymerized when exposed to light in the absence of an added photoinitiator. In this case, the maleimide not only initiates, but also participated in the free-radical polymerization process Another difunctional monomer with two reactive groups (acrylate and vinylester) that can participate in free-radical polymerization is vinyl acrylate.
Research on vinyl acrylate polymerization was reported by Fukuda et al in the early 1970s. [8-9] This research focused primarily on polymerization behavior of the two different functional groups and cyclic polymerization in solution. Recently, Kudyakov et al. [10-11] reported real-time infrared (RTIR) results showing that in bulk, the acrylate group homopolymerizes to about 70 percent conversion before the vinyl ester group begins to react. It was reported that the vinyl acrylate, like maleimide/acrylate monomer, can also self-initiates its own free-radical polymerization. Many photocuring techniques have been developed to enhance overall performance and provide specific properties of photopolymers. Studies have focused on such varied topics as the effects of polymerization kinetics on polymer morphology, [12-14] cationic hybrid curing systems, [15-16] and development of new monomers. [17] One particularly robust effort deals with photopolymerizable thiol-enes. [18-25] Thiol-ene additions were first discovered by Posner in 1905 and the basic chemistry, polymerization mechanism, and photoinduced reactivity of thiols with various enes have been extensively investigated. [18-21]
These studies have clearly demonstrated that thiol-ene mixtures exhibit significant polymerization advantages including rapid reactions, little or no oxygen inhibition,  selfinitiation, and formulation latitude due to the large number of enes that copolymerized with thiols. The final cured films also exhibit excellent physical properties such as low shrinkage and good adhesion to substrates. Herein, we report on the free-radical polymerization of thiol/vinyl acrylate mixtures which have three types of reactive species; acrylates, vinyls, and thiols. On such a multicomponent system, it is essential to understand how each component contributes to the polymerization kinetics. The effects of multifunctional thiol on both acrylate and vinyl group conversion of vinyl acrylate have been investigated as a function of thiol content in the presence and absence of external photoinitiators.

References

1. Fouassier JP. Photoinitiation Photopolymerization and Photocuring; Fundamentals and Applications; Munich Vienna New York: Hanser Publishers, 1995.
2. Roffery C. G. Photopolymerization of Surface Coatings; Wiley Interscience: New York, 1982.
3. Pappav P. Radiation curing, Science and Technology; Plenum Press: New York, 1992.
4. Andersson, H.; Hult, A. J. Coat. Technol., 1997, 59(865), 91.
5. Hoyle, C. E.; Clark, S. C.; Jonsson, S.; Shimose, M. Polymer 1997, 38(22), 5695.
6. Decker, C.; Jonsson, S.; Clark, S. C.; Hoyle, C. E. Polymer 1999, 40, 2447.
7. Jonsson, S.; Sundell, P.; Shimose, M.; Owens, J.; Miller, C.; Clark, S.; Hoyle, C. E. Polym. Mat. Sci. and Eng. 1996, 74, 319.
8. Fukuda W.; Nakao, M.; Okumura, K.; Kakiuchi, H. J. Polym. Sci. : Part A-I, 1972, 10, 237.
9. Fukuda W.; Yamano, Y.; Tsuriya, M.; Kakiuchi, H. Polym. J. 1982; 14, 127.
10. Kudyakov, I. V.; Fos, W. S.; Purvis, M. B. Ind. Eng. Chem. Res. 2001, 40, 3092.
11. Lee, T. Y.; Roper, T. M.; Jonsson, E. S.; Kudyakovc, I.; Viswanathan, K.; Nason, C. Guymon, C. A,; Hoyle, C. E. Polymer 2003, 44, 2859.
12. Elliott, J. E.; Bowman, C. N. Macromolecules 2001, 34, 4642.
13. Young, J. S.; Bowman, C. N. Macromolecules, 1999, 32, 6073.
14. Kannurpatti, A. R.; Anderson, K. J.; Anseth, J. W.; Bowman, C. N. Polym. Sci., Part B Polym. Phys. 1997, 35, 2297.
15. Moussa, K.; Decker, C. J. Polym.Sci., Part A: Polym. Chem. 1993, 31, 2633.
16. Decker, C.; Veit, T. N. T.; Decker, D.; Weber-Koehl, E. Polymer 2001, 42, 5531.
17. Decker, C.; Moussa, K. Eur.Polym. J. 1991, 27, 403.
18. Morgan, C. R.; Kettl, A. D. J. Polym. Sci. Polym. Lett. Ed 1978, 16, 75.
19. Morgan, C. R.; Magnotta, F.; Ketley, A. D. J. Polym. Sci., Polym. Chem. Ed, 1977, 15, 627.
20. Gush, D. P.; Ketley, A. D. Modern Paint and Coatings 1978, 68, 58.
21. Jacobine, A. F. In Radiation Curing in Polymer Science and Technology III, Polymerisation Mechanisms; Fouassier, J.D., Rabek, J.F., Eds.; Elsevier Applied Science: London, 1993; Vol. 3, p 219.
22. Bor-Sen, C.; Saad, A. K. Macromolecules 1997, 30, 7322.
23. Hoyle, C. E.; Hensel, R. D.; Grubb, M. B. Polymer Photochemistry 1984, 4, 69.
24. Hoyle, C. E.; Hensel, R. D.; Grubb, M. B. J. Polym. Sci. Polym. Chem. Ed 1984, 22, 1865.
25. Hoyle, C.; Cole, M.; Bachemin, M.; Yoder, B.; Nguyen, C.; Kuang, W.; Bowman, C.; Cramer, N.; Jonsson, S.; Viswanathan, K. Radrech Japan 2000 Technical Proceedings, Tokyo, Japan, Dec 2000, p 211.

* During the conference this lecture was given by professor Mats Johanssen from KTH, Sweden.

Dr. ing. Ger Koper

Delft University of Technology, Department of Chemical Technology (DCT-PCMT), The Netherlands

Title Lecture

UV-protective coatings: what to learn from nature

Authors

J.F. Jacobs, G.J.M. Koper and W.N.J. Ursem

Abstract

Biosystems use a variety of mechanisms to protect themselves against the harmful effects of UV-irradiation. These include pigmentation, radical scavenging, and damage repair mechanisms. We present the interesting example of the Pinus mugo subs mugo where a natural coating with very special properties is used. This natural coating formed by the cuticalar wax layer, has the interesting property that it not only contains chromophores that absorb the most harmful UV-components of the solar radiation reaching the leaves, but that in addition the absorbed energy is converted into useful light for the photosynthesis in lower-lying cells. We discuss some potential coating technologies where this same principle of turning useless, or even harmful, radiation into useful energy is used.

Dr. Yoshinori Kushi

Nippon Paint Co. Ltd, Corporate Research Laboratory, Osaka, Japan

Title Lecture

Molecular Design of Novel Grafting Polymer for Aqueous Pigment Dispersants

Authors

Yoshinori KUSHI

Abstract

Novel grafting copolymers containing nonionic and/or ionic hydrophilic branches have been synthesized and tested as dispersants of various organic and inorganic pigments for waterborne pigment concentrates.
The influence of the types and quantities of functional groups providing water-soluble and anchoring properties onto dispersant upon the particle size and viscosity of pigment dispersions was studied using dynamic light scattering (DLS) and viscometer. In particular, introduction of hydrophobic moieties, like aromatic rings as the anchoring groups, resulted in making highly stabilized dispersions for a long period of time.
Moreover, to facilitate the selection of suitable hydrophilic branches for a superior aqueous dispersant, the interaction between the hydrophilic moieties of dispersants and ambient water molecules was examined.
In this presentation, an appropriate structure for aqueous pigment dispersants will be proposed.

Dr. Sviatlana Lamaka

Department of Ceramics and Glass Engineering, University of Aveiro, Aveiro, Portugal

Title Lecture

TiOx nanostructured sublayer as reservoir of corrosion inhibitors for pre-treatments with self-healing ability

Authors

Sviatlana V. Lamakaa, Mikhail L. Zheludkevicha, Kiril A. Yasakaua, M. Fatima Montemorb, Patricia Cecílio , Mário G.S. Ferreiraa

Abstract

The development of new coating systems with active corrosion protection instead of the carcinogenic chromates is an issue of prime importance for the wide range of industrial applications.
In this work we propose a novel approach that aims at developing a nanostructured porous reservoir that supports the corrosion inhibitor on the metal/hybrid sol-gel film interface.
The nanostructured porous TiO_x layer was obtained on the 2024 aluminium alloy surface by controllable hydrolysis of the titanium alkoxide in presence of a templating agent leading to formation of TiO_x self-assembled networks, replicating the structure of the etched alloy. Titanium oxide films loaded with organic inhibitors and coated with a sol-gel based thin hybrid film were used as effective environmental-friendly corrosion protective pre-treatments for metallic substrates. In contrast to direct embedding of the inhibitors in sol-gel matrix, the use of the porous reservoir eliminates the negative effect of the inhibitor on the stability of the hybrid sol-gel matrix.
TiOx – inhibitor – sol-gel systems show enhanced long-term corrosion protection and well-defined self-healing effects confirmed by EIS and SVET (Scanning Vibrating Electrode Technique) measurements. The morphology and the structure of the TiO_x film were characterized with SEM, EDS, TEM and AFM techniques.

Dr. Daniel Maetens

Cytec Surface Specialties, Anderlechtstraat 33, B-1620 Drogenbos, Belgium

Title Lecture

Weathering degradation mechanism in polyester powder coatings

Authors

Dr Daniel Maetens

Abstract

The replacement of terephthalic acid (TPA) by isophthalic acid (IPA), an isomer of TPA, in the polyester backbone produces a huge increase in the weathering resistance of powder coatings exposed to tropical climate. Super durable powders containing IPA-based polyesters achieve more than 10 years of exposure in Florida a significant improvement over the 2 to 4 years recorded with coatings containing TPA-based polyesters.
The study of weathering of IPA- and TPA-based powder coatings in accelerated weathering chamber has shown with support of FTIR spectroscopy, the formation of photo-byproducts that are proposed to be generated by a photo-induced oxidation converting -CH₂- in β position to CO of esters into anhydride groups. Subsequent hydrolysis of these anhydrides is responsible of polymeric chain cleavage generating acidic groups and coating bleaching which in turn appear as poor weatherability. 
FTIR analysis of exposed panels in Florida has demonstrated presence of same photo-byproducts but a contribution of hydrolysis of ester groups and/or oxidation of -CH- sites have to be integrated in this mechanism.

Biography

Daniel Maetens got his PhD in Organic Synthesis in 1980 from the University of Brussels, ULB. He started his career at the Central Research Lab of Solvay – Belgium located in Neder – Over – Hembeek, near Brussels. He worked on the structure identification of PVDF by using NMR techniques. In 1983, he joined UCB Chemicals in the R&D facility on the site of Drogenbos, also near Brussels. After 5 years working in the Powder Coating Resins Department as chemist, he became Group Leader Powder Coating Resins, a position that he is currently filling in the R&D Department of the newly created Cytec Specialty Chemicals (Drogenbos site).

Marshall Ming

Eindhoven University of Technology, The Netherlands

Title lecture

Surface wettability control inspired by Nature

Authors

W. Ming,* D. Wu, R. van Benthem, G. de With

Abstract

Millions of years of evolution in Mother Nature have perfected the design of the films of desired surface wettability. For instance, the leaves of the sacred lotus flower, known as “rising out of muddy water, untainted”, demonstrate self-cleaning property, which is due to a combination of low surface-energy species and a peculiar topographic feature based on dual-size roughness: the coarse-scale rough structure is about 10-20 µm whereas the finer structure on top of the coarse structure is in the range of a few hundred nanometers. Inspired by the lotus leaf structure, we prepared superhydrophobic epoxy-based, PDMS-surface-modified films from raspberry-like silica particles, on which the advancing contact angle for water is about 165° and the roll-off angle of a 10-µL water droplet is < 3°. The surface wettability (superhydrophobic vs superhydrophilic) can be tuned by introducing a thermally responsive polymer layer. It is envisaged that the robustness and simplicity of this procedure may enable widespread applications of so-prepared films.

Biography

W.(Marshall) Ming is an Assistant Professor (UD) in Polymer Chemistry & Coatings Technology since November 2000. He received his B.S. in Materials Chemistry at Fudan University in Shanghai in 1993, and a Ph.D. in Polymer Chemistry and Physics in 1998 from the same university with Prof. S. Fu, Prof. F. N. Jones, and Prof. T. Yu as supervisors. From January 1996 to June 1997 he was a research associate with Prof. F. N. Jones in Coatings Research Institute at Eastern Michigan University. From November 1998 to October 2000 he was a post-doc fellow at Prof. van der Linde's group of Coatings Technology. His current research interests include nature-inspired functional polymers, nanostructured materials and applications, and environmentally benign polymer systems.

Tijs Nabuurs

DSM NeoResins, The Netherlands

Title Lecture

Nanomorphology control in aqueous coatings

Authors

T. Nabuurs, S. van der Slot, F. Bückmann, A. Overbeek

Abstract

In the last decade the performance of poly(meth)acrylic dispersions as binders for aqueous coatings has improved dramatically by optimisation of particle morphology. By having two or more polymer phases present in one particle, average domain sizes can be decreased and compatibility between the polymer phases increased over simple blends yielding higher performance final coatings.
In this paper we will demonstrate that morphology control can be taken right down to the individual polymer chain level to achieve so called nanomorphology control.
Nanomorphology control is achieved by copolymerising functional macromonomers in emulsion polymerisation. In this way comb like polymer chains are prepared. By varying composition of the various phases and molecular weights of the macromonomers coating properties can be optimised. The benefits of nanomorphology control in the final coatings will be described

Biography

Tijs Nabuurs graduated in 1991 from the University of Nijmegen in the group of prof. Nolte. He obtained his PhD in 1997 from the University of Eindhoven in the group of prof. German. His PhD thesis was on alkyd-acrylic hybrids prepared by emulsion polymerisation.
In the same year he started to work for Zeneca Resins, in the acrylic emulsions team.
His main interests over the years have been particle morphology control of aqueous polymer emulsions, crosslinking in coatings and controlled radical polymerisation.

Louise Nobel

Delft University of Technology, Department of Chemical Engineering, Section Nano Structured Materials, NSM, The Netherlands

Title Lecture

Waterborne nanocomposite coatings

Authors

M.L. Nobel, Prof.dr. S.J. Picken, Dr. E. Mendes

Abstract

Organic acrylic polymers in aqueous dispersed form are binders that can be used for the production of environmentally friendly coatings. The film properties have been improved by adding small amounts of fully dispersed inorganic hard phases in the form of needle shaped Boehmite, disc shaped Laponite and Montmorrilonite sheets. Depending on the location and structure of the nanoparticles in the emulsion after application and curing of the nanocomposite binder various morphologies are found in the transparent and flexible films. Hydrophilic nanoparticles located at the interfaces of the polymer droplets and hydrophobic nanoparticles completely or partially located inside the polymer droplets yield dramatically increased strength of the cured film as well as an adjustable rheology of the binder. Improved blocking and scratch resistance, higher elasticity and improved indentation hardness are thought to result from the high aspect ratio of the filler particles.

Bart Noordover

Laboratory of Polymer Chemistry - Eindhoven University of Technology, The Netherlands

Title Lecture

Renewable polyester resins for powder coating applications

Authors

B.A.J. Noordover, R. Duchateau, C.E. Koning, R.A.T.M. van Benthem, W. Ming, J. van Haveren, A.E. Frissen

Abstract

Monomers from renewable sources are attractive starting materials for polymer synthesis, since building blocks with great functional diversity are available from a wide range of resources. Thermosetting coating systems often contain low molecular weight polyesters as binder resins. Conventional coating resins contain terephthalic moieties, obtained from fossil feedstock, to increase Tg.
In this study, we synthesized renewable polyesters through polycondensation of diol and diacid monomers. Aliphatic polyesters were synthesized using monomers such as succinic acid, 2,3-butanediol, 1,3-propanediol and isosorbide. The latter, a rigid bicyclic molecule with two hydroxyl functionalities, was introduced to increase Tg. Glassy polyesters with Mn > 2000 g/mol and T–g > 45 °C were obtained, having either hydroxyl or carboxylic acid end-groups for curing purposes. The materials are thermally stable up to 250 °C. Reacting linear OH-functional resins with citric acid moieties significantly increased polyester functionality.
The resins were cured using conventional cross-linkers: poly-isocyanates for OH-functional materials and triglycidyl isocyanurate or primid for COOH-functional resins. Using branched polyesters instead of linear polymers significantly improved coating performance. The resulting colorless to pale yellow coatings show good resistance to solvent (> 100 acetone double rubs) and rapid deformation (impact testing). In addition, they have König hardnesses exceeding 200 seconds.
The work described here is financed by the Dutch Polymer Institute.

Dr. Willem Posthumus

Stahl International BV, Waalwijk, The Netherlands

Title Lecture

Reactions of carbodiimides with free and bonded carboxylic acids

Authors

W. Posthumus, A.J. Derksen, L.C.J. Hesselmans

Abstract

The reactions of carbodiimides with carboxylic acids are well-described for liquid systems. If the carbodiimide-carboxylic acid reaction is used for crosslinking of polymers, the reactive groups have a limited mobility which may affect the course of the reactions. In this paper we discuss the reactions of polycarbodiimides with both free and bonded carboxylic acids. The reaction of carbodiimides with carboxylic acids can result in different groups like acyl-urea, dicarboxylic acid anhydride, amide, and isocyanate. When comparing the reactions of polycarbodiimides with carboxylic acid monomers and with polymers with attached carboxylic acid groups major differences can be found. Not only are the rate of the reactions and the maximum conversion affected, but also the type of the newly formed groups. The effects of polycarbodiimide concentration and functionality are described and the kinetics of the crosslinking of carbodiimides is compared with the kinetics of polyaziridine crosslinking.

Biography

Willem Posthumus was born on the 5th of December in Wijnjeterp, the Netherlands. He studied chemistry at the University of Groningen with a specialization in Organic Chemistry. After working for one year at Philips CFT he went to the Technical University of Eindhoven to obtain a PhD. With Professor van der Linde as promoter he successfully defended his thesis on UV-curable acrylate metal oxide nanocomposite coatings. Since 2004 he is working as chemist in the research and technology laboratory of Stahl International bv in Waalwijk, the Netherlands.

Dr. Paula Puomi

University of Cincinnati, Department of Chemical and Materials Engineering,  Cincinnati, OH USA

Title Lecture

Novel, one-step, chromate-free coatings containing anticorrosion pigments for metals

Authors

W.J. van Ooij, P. Puomi, A. Ashirgade, S. Bafna, A.Seth, C. Shivane and Z. Yin

Abstract

The concept of superprimers, i.e., primers for metals with the conversion coating built in, has proven to be feasible. Such primers do not require a chromate (or other) conversion treatment of the metal and can be applied on any bare metal. The VOC content in the primer is kept low by using water-dispersed organic resins. Because of the high concentration of organofunctional silanes contained in the superprimer, its adhesion, both to the substrate and to overcoats, is excellent. The corrosion resistance of the primer can further be improved by adding corrosion inhibiting pigments such as micronized phosphate into the formulation. In this presentation we will discuss epoxy-silane, acrylate-epoxy and novolac-polyurethane based systems for aluminum alloys, HDG steel and CRS. The corrosion protection performance of these coatings is evaluated using electrochemical methods and performance tests. The reactions occurring in the superprimer dispersion have been analyzed by NMR and the resulting coatings with SEM/EDX, TOF-SIMS and FT-RAIR. The characterization methods have provided information on the formation of the coatings and the mechanism by which the coatings protect the metal substrates. It will also be shown that 2000 hours of salt spray resistance has been obtained with the primers both on AA2024-T3 and HDG steel.

Keywords: silane, superprimer, pigment, chromate, aluminum alloy

Biography

Paula Puomi is a post-doc fellow in Materials Science at the University of Cincinnati. She helds a D.Sc. in physical chemistry from Åbo Akademi University, Turku, Finland. She did her D.Sc. Thesis “Pretreatment of galvanized steel in relation to paint adhesion and corrosion resistance” in collaboration with Rautaruukki Steel to whom she also developed a chromate-free coil coating process in 2001. Her research interests are in corrosion, silane paint chemistry and surface characterization. She has authored and co-authored about 15 papers and worked as a teacher on all levels from university to upper secondary school.

Alexander Routh

Department of Chemical and Process Engineering, University of Sheffield, Mappin Street, Sheffield S1 3JD UK

Title Lecture

Surfactant distributions in latex films

Authors

Venkat Gundabala and Alexander Routh

Abstract

Surfactants are added to latex dispersions during particle synthesis to aid particle stability. The location of this surfactant in the final film can have dramatic effects on the film performance. For example, accumulation at the substrate will affect adhesion, whilst accumulation at the air interface affects feel and gloss.
A transport model for surfactant distributions through the film reveals the surfactant adsorption isotherm to control the distribution and Rutherford Back Scattering has been used to examine the distribution for four different surfactants. These experiments also reveal the large lateral inhomogeneity in surfactant concentration
Marangoni flows, which result from surface tension gradients cause thinning in liquid films. Such flows are caused by surfactant concentration gradients and the lateral flow, film thinning and even rupture of latex films has been observed. In this work thin film fluid mechanics is linked with profilometry experiments of the final latex film profile.

Biography

Education

• PhD, Princeton University, USA 2000
• BA, MA, MEng, Cambridge University, 1995

Employment

• January 2006 – present Lecturer, Department of Chemical Engineering, University of Cambridge
• January 2002 – December 2005 Lecturer (senior lecturer from Oct 2005), Dept of Chemical Engineering, Sheffield University
• December 1999 – December 2001 Post-Doctoral Research Associate, Bristol University
• September 1995 – December 1999 PhD (May, 2000), Dept of Chemical Engineering, Princeton University, USA

Research Interest
To understand macroscopic phenomena from the microscopic and nano-scale architecture of materials: I have achieved world-leading expertise in drying of dispersions and modeling of film formation.  My future research directions include morphological manipulation of encapsulating particles resulting in external control of chemical reactions. In addition I am currently moving into bio-related fields, including protein separation and enzymatic reactions, in collaboration with colleagues in Cambridge and elsewhere 

Dr. Hiroshi Sasaki

Taogosei Co. Ltd, Nagoya, Japan

Title Lecture

High Performance Cationically Curable Formulations

Authors

Hiroshi Sasaki

Abstract

Photo-cationic formulations are known to possess high performance such as good adhesion to substrates, low shrinkage cure and so on. At the same time, their curing speeds, however, are rather slow. In the cationic ring-opening polymerization of cyclic ethers, three major factors, i.e. ring strain, basicity and steric factor, are known to govern the reactivity. Using computational calculation method, we have already investigated those factors and correlated to the actual physical properties.
At present stage, oxetanes and cycloaliphatic epoxides seem to be the best candidate for the high performance formulations.
In this presentation, the latest investigation of the curing mechanism of above monomers together with performance of their formulations will be discussed.

Biography

Educational Background

• 1986 Master Degree at Hokkaido University
• 1996 Doctor Degree in Polymer Chemistry at Hokkaido University

Work Experience

• 1986-Present Researcher at Toagosei Co. Ltd.
• 1991-1992 Visiting scientist of Prof. Crivello's lab at Rensselaer Polytechnic Institute

Research Interests

• Design, Characterization and Evaluation of Photo- or Thermal-Curable Materials
• Cationic Ring Opening Polymerization of Cyclic Ethers
• Polymer Chemistry
• Computational Chemistry
• Rheology

Carsten Schellenberg

Ciba Specialty Chemicals Inc., Coatings Effects Segment, Basel, Switserland

Title Lecture

Polymer colloids by miniemulsion polymerization - new additives for waterborne coatings -

Authors

Delphine Kimpel, Wolfgang Peter, Carsten Schellenberg

Abstract

The number of waterborne applications is increasing in different coating areas. On the other hand many additives were developed for solvent-borne coatings only. These substances (e.g. light stabilizers) are hydrophobic in nature and can’t be used in waterborne systems directly.
Progress has been made with the development of waterborne product forms of hydrophobic, water-insoluble additives by using heterophase polymerization techniques. The interdisciplinary combination of colloid, macromolecular and organic chemistry lead to the availability of advanced additives for a broad range of waterborne paint formulations.
The wood photoprotection against discoloration and broad compatibility can be significantly improved by using the new additive - waterborne product form of a red-shifted UV-absorber based on triazine chemistry - in either film forming or penetrating wood coatings for example.
Based on this nanoencapsulation technology further high performance additives such as UV-absorbers or hindered amine light stabilizer (HALS) hitherto limited to the solvent borne coatings market are in the innovation pipeline for transformation into true stir-in additives for the growing and environmentally friendly waterborne coatings market.

Biography

Carsten Schellenberg studied chemistry at University of Marburg (Germany), where he graduated in 1997. Afterwards he joined Max Planck Institute of Colloids and Interfaces and obtained PhD degree in the field of polymer colloids. In April 2000 he joined Ciba Specialty Chemicals in Basel working as R&D project leader in Coating Effects Segment on different projects for BL Coatings. His main focus was on additives for waterborne coatings. Since 2005 he is at the R&D Center in Amagasaki (Japan) working as project leader in the area of flat panel displays for BL Electronic Materials.

Wolfgang Schrof

BASF Aktiengesellschaft, Ludwigshafen, Germany

Title Lecture

Combinatorial Materials Research of UV Coating Formulations

Authors

W. Schrof, S. Koltzenburg, N. Gruber, R. Schwalm, W. Paulus, E. Beck, H. Larbig

Abstract

Isocyanateacrylate molecules with both acrylate and isocyanate functionalities can act as starting materials for versatile toolboxes of radiation curable binders. UV Formulations of these binder libraries with commercial reactive acrylate thinners of different functionalities and concentrations will yield attractive coating properties. Combinatorial methods are intensively used to prepare, coat, cure, and characterize the coating films for hardness, elasticity, scratch and chemical resistance. The results are discussed using network simulation and measurements of UV conversion by Raman spectroscopy.

Biography

Wolfgang Schrof was educated in physics at the universities of Ulm and Stuttgart. After PhD he joint BASF Aktiengesellschaft in 1987. There he worked in the polymer physics department in the field of laser spectroscopy (nonlinear optics, two-photon microscopy, Raman microscopy, and real-time IR spectroscopy).
Today he is head of combinatorial materials research (CMR). This technology offers the perspective to accelerate industrial research for superior polymers, catalysts, formulations and coatings. He is taking care for the developing and implementing combinatorial tools (parallel reactors, formulation robots, automated application testing, data management and mining), for combinatorial projects in collaboration with internal and external customers and for the contacts to academia and start-ups active in CMR.
He heads the DECHEMA working group on high-throughput research.

Mohamad Shalati

Nuplex Resins LLC, Louisville, USA

Title Lecture

Controlled molecular structure polymers

Authors

E. Bzowej, R. Brinkhuis, M. Gessner, and M. Shalati

Abstract

Increasingly stringent environmental regulations continue to challenge the automotive coatings industry to reduce emissions while improving film properties at the same time.  Achieving performance requirements as the VOC is lowered can be met using Controlled Molecular Structure Polymers (CMSP).  CMSP polymers are polyols that possess controlled distribution of functionality, structure, lower molecular weight and narrow polydispersity.  1K and 2K prototype coating formulas have been developed for OEM and Vehicle Refinish clear coats having VOCs in the range of 350 – 400 g/l, good scratch resistance, durability, and environmental etch resistance equal to or better than commercial clear coats.  This presentation will focus on   structure-property relationships for polymers and coatings.

Biography

Mohamad Shalati received his:

• B.Sc. Chemistry – Damascus University – 1971
• M. Sc. Chemistry – Eastern Michigan University – 1974
• Ph.D. from the University of Michigan in 1979: Chemistry and Macromolecular Science & Engineering under the direction of Prof. Charles G. Overberger. 

25 Years of Industrial Experience in Polymers and Coatings at:

• Procter & Gamble
• Sherwin Williams
• PPG Industries
• Akzo Nobel Resins
• Nuplex Resins

He is the author / inventor of over 50 Patents and Publications in Polymer Synthesis, New Chemistry, and Coatings 
He assumed various Technical and Managerial responsibilities in R&D capacities .
He is currently the Director of R&D at Nuplex Resins for the Americas, and residing at the Louisville, Kentucky Lab.

Prof. Masamitsu Shirai

Osaka Prefecture University, Department of Applied Chemistry, Osaka, Japan

Title Lecture

Reworkable UV curing materials

Authors

M. Shirai

Abstract

UV curing materials are widely used as coating materials, printing inks, adhesives, photoresist, and solder masks, because the cured materials show excellent physical and/or thermal properties. In some cases, we need to remove the cured materials to repair or reuse the substrates. However, it is difficult to thoroughly remove the crosslinked materials from the substrate without damaging underlying materials. In this paper, we report the UV curing materials which become soluble in solvents by thermal degradation. We have newly synthesized multifunctional monomers which have epoxy, acrylate, or methacrylate units as a crosslinkable moiety.   Those monomers also have thermally degradable units such as tertiary ester linkages, acetal linkages or hemiacetal ester linkages in a molecule. Photo- and thermal curing of those monomers and thermal degradation of the cured materials are studied in detail. The onset temperature of degradation was strongly dependent on the structure of the monomers.

Biography

Masamitsu Shirai received his Ph.D. degree from Osaka Prefecture University (OPU) in 1978.    After working as an assistant professor and then an associate professor at OPU, he was promoted to a professor of applied chemistry at OPU in 1997.  He spent his early career as a postdoctoral fellow  (1978-1979) at State University of New York at Syracuse, USA.
His research interests include synthesis and applications of photosensitive polymeric materials, especially photoresists, photoacid generators, photobase generators, UV curing materials, and photodegradation and stabilization mechanisms of polymeric materials. He has published more than 250 research papers including reviews and books.

Dr. Petra Uhlmann

Leibniz Institute of Polymer Research Dresden, Dresden, Germany

Title Lecture

Research agenda surface technology: Future demand of research in the field of coatings materials

Authors

Petra Uhlmann, Ralf Frenzel and Brigitte Voit

Abstract

The acquisition of the future demand of research in the field of innovative coatings materials was one part of a project funded by the German Ministry of Education and Research and coordinated by the German Research Society of Surface Treatment (DFO, Düsseldorf) with the aim to identify the demand of research in the area of surface technology in the next 10 to 15 years [1]. In the project development several German research institutions and numerous representatives of companies acting in the field were involved.
The functions of coated materials that were identified to be the most innovative and to have the biggest driving force for research will be shown for certain industrial branches. The most promising coatings materials to fulfill the desired functions in the future will be discussed, visions will be mentioned and conclusions about general trends in the field of coating materials will be drawn.

Biography

Background:

• Graduated from Dresden University of Technology in Chemistry in 1992,
• PhD at Dresden University of Technology about waterborne coatings as primers for corrosion protection, 1992-1993,
• Post-doctoral stay at CNRS, Centre de Recherches sur la Physico-Chimie des Surfaces Solides, Mulhouse, France, group Dr. E. Papirer

Career:
Since 1993 at the Leibniz Institute of Polymer Research, Dresden, current position: group leader in the department of Nanostructured Materials (head: Prof. Manfred Stamm), field of work: functional, nanostructured and switchable polymer thin films and coatings.

Leo van der Ven

Akzo Nobel Coatings Research Arnhem, P.O. Box 9300, 6800 SB Arnhem, The Netherlands

Title Lecture

Interactions between basecoats and clearcoats in Car Refinish systems

Authors

Leo G.J. van der Ven, René T.M. Leijzer,Nico van Duijvenvoorde, Keimpe J. van den Berg

Abstract

The introduction of VOC compliant waterborne basecoats and solventborne basecoats on one hand and the introduction of VOC compliant clearcoats on the other hand forces to look to the interactions between the two systems. As well known from studies in the automotive OEM area small molecules like HALS and UV-absorbers additives diffuse from the clearcoat into the basecoat. This influences the durability performance of the system. The main question addressed in this paper is the interaction of the binder system of the basecoat and clearcoat. In general crosslinkers for e.g. poly-urethane coatings are rather low molecular weight materials which may diffuse between layers as well. Also the lower molecular weight functional resins of the binder may move throughout the system.
The interactions of several basecoat/clearcoat combinations were investigated by means of chemical and physical techniques. The effect of a medium solid clearcoat, a VOC compliant p-urethane clearcoat and UV-clearcoat on interpenetration, adhesion, physical and paint properties were studied.
Also some attention is paid to the diffusion of HALS and UV-absorbers from the clearcoat into the basecoat.

Biography

Leo van der Ven received his degree in chemical engineering in 1974. After his study he joint Akzo Nobel Central Research as a gas chomatographic specialist.
In the beginning of the eighties he shifted to the coating research group. First as research fellow dealing several projects as durability of coatings, PUR curing and mechanistic studies of isocyanate free systems.
Later on he focussed on the study of waterborne systems, film formation, cure mechanisms and durability prediction.
Currently he is responsible for the coatings resin and film characterization group of Akzo Nobel Coatings Research in Arnhem (the Netherlands).

Douglas Wicks

School of Polymers and High Performance Materials, The University of Southern Mississippi 118 College Drive  #10076, Hattiesburg, MS 39406, USA

Title Lecture

Impact of Waterborne Dispersants on Biocide Efficacy

Authors

Douglas A. Wicks and Alicyn M. Rhoades

Abstract

The issue of polymer microbial degradation is of vital importance to researchers, producers, and the end market consumer.  Waterbased polymeric formulations contain a myriad of components, consistently including dispersing groups and molecules. These may be ionic or non-ionic in nature, and fall into a wide range of chemical compositions. Biocide or preservative additives are also common components in the final formulation. Biocide molecules are added to effectively prevent and reduce microbial contamination within a formulation. These are traditionally tested under neutral conditions, but are expected to perform over time within the dynamic wet coatings environment with a wide range of chemical species and components not found in the base line studies. Work within our research group has shown the reality of interactions between surfactant and biocide molecules in solution, and that the chemical nature of the surfactant determines the resulting efficacy of the biocide molecules. The current study moves the research forward by looking at the effects of polymer bound dispersing groups and what the differences are between unbound versus bound functional groups.

Biography

Dr. Douglas A. Wicks is the Robert M. Hearin Support Foundation Professor of Polymer Science in the School of Polymers and High Performance Materials at the University of Southern Mississippi in Hattiesburg, MS. His current research interests focus on development of new resins for coatings applications, use of high throughput screening for studying formulations and the investigation of polymers in biomedical applications. At USM, Dr. Wicks heads a National Science Foundation (NSF) Partnership for Innovation project on the use of High Throughput methods for the investigation of polymeric formulations and NSF Integrative Graduate Education Research and Training
(IGERT) program on Entrepreneurship at the Interface of Medicinal and Polymer Sciences.
Prior to joining the University of Southern Mississippi in 2002, he was at Bayer Corporation for 13 years in a succession of research positions of increasing responsibility. His final position at Bayer Corp. was as Vice President for Research of the Coatings and Colorants Division with broad responsibilities in all aspects of polyurethane and coatingcoating technology. Dr. Wicks has 37 patents and 28 publications related to polyurethane technologies for coatings, adhesives and sealants.

Dr. Harm Wiese

BASF AG, Ludwigshafen, Germany

Title Lecture

Nanocomposite dispersions - An innovation in waterbased coatings

Authors

Harm Wiese, Joerg Leuninger, Franca Tiarks

Abstract

We describe the preparation of new silica/acrylate nanocomposite particles by emulsion polymerization. Film formation of these nanocomposite dispersions takes place at the same temperatures as for acrylate dispersions having the same polymer composition, whereas film hardness and strength are strongly improved. The films are highly transparent, provide an excellent hardness/elasticity compromise, do not swell in water and show very low water whitening. Further film properties are high heat resistance, water vapour permeability, solvent resistance, adhesion to mineral substrates and a favorable burning behavior. Silica/acrylate nanocomposite dispersions therefore are a highly promising approach for solvent-free coatings. Special application features for paints are low dirt pick-up and high blocking resistance.

Biography

Dr. Harm Wiese, BASF AG Ludwigshafen born 1958, studied Chemistry at the TU Darmstadt and got a PhD in Physical Chemistry in 1987 with an electrochemical study in the group of Prof. Konrad G. Weil. After spending a postdoctoral year at IBM Rueschlikon/Switzerland with Prof. Heinrich Rohrer he joined the Polymer Physics Department of BASF AG's Polymer Research Division in 1989. In the following five years he worked on the physicochemical characterization of highly concentrated colloidal dispersions. In 1994 he moved to Emulsion Polymers Research where he worked on the analytics of polymer dispersions, protective colloids and nanocomposite dispersions as well as on applications like adhesives and concrete roof tile coatings.
Since January 2004 he is managing BASF's research group 'Coatings and Construction Chemicals'.

Frederik de Wit

Delft University of Technology, Department of Mechanical Engineering, Marine Technology and Materials Science and Engineering, Netherlands Institute for Metals Research (NIMR), The Netherlands

Title Lecture

Bonding of organic molecules on aluminium and magnesium alloy

Authors

F.M. de Wit, J.J. Kleikers, J. van den Brand, H. Terryn, J.H.W. de Wit

Abstract

To protect products based on aluminium alloys from corrosion in aggressive environments, organic coatings are applied in industry. These coatings sometimes do not adhere well in aqueous environments, resulting in delamination. This lack of adhesion is not well understood. Van den Brand [1,2] studied the bonding of specifically selected molecules (representing polymers) to a relatively pure aluminium alloy, AA1050, by FTIR-RAS. His results showed that the bonding of these molecules to aluminium hydroxides could be influenced by changing the environment in which they were applied or afterwards exposed to (e.g. air, N₂ and water).
In industry, aluminium alloys with a higher amount of alloying elements are used because of their improved mechanical properties. The aim of this research is to understand the bonding on the pure alloying metals, i.e. pure aluminium (99,99%) and pure magnesium (99,99%) and industrial alloys of the two. The number of hydroxide groups at the interface depends on the pretreatment. For the Al/Mg alloys the surface layer can be Mg rich, which will probably influence the bonding strength considerably. The first results, which include the study of composition and morphology of the surfaces by AFM, SEM, XPS and FE-Auger and FTIR spectra showing details of the molecular bonds, will be presented.

1. J. van den Brand, O. Blajiev, P.C.J. Beentjes, H.Terryn, J.H.W. de Wit, Langmuir 20 (15): 6308-6317 (2004)
2. J. van den Brand, O. Blajiev, P.C.J. Beentjes, H.Terryn, J.H.W. de Wit, Langmuir 20 (15): 6318-6326 (2004)
3. J. Flores, PhD Thesis, TU Delft, 2006, to be published

Biography

Frederik de Wit studied Materials Science and Engineering at Delft University of Technology. After receiving his master’s degree from the Corrosion Technology and Electrochemistry group, he started working on a PhD project at the Netherlands Institute for Metals Research in November 2004.