10^th Coatings Science International 2014

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Posters COSI 2010

Amira Abou-Hamdan

Chemspeed Technologies AG, Augst, Switserland

Title lecture

Faster & Better Synthesis, Formulation, Application and Testing of Paints & Coatings by Automated High-Output Solutions

Authors

Olaf Köhler

Abstract

Starting in the area of pharmaceutical industry, automation technologies have changed scientists´ daily laboratory routine in a variety of research areas. Nowadays emphasis is placed on high-output solutions in order to generate results of scientific value faster and more reliable (Fig. 1).

Fig. 1: Chemspeed´s vision on High-Output Product Development

Prominent progress got implemented in automated materials synthesis and formulation. For example Chemspeed´s fully automated formulation workstation FORMAX provides faster & better investigation of both the raw material and the process space. Essential for unrestricted automated formulation research is overhead gravimetric dispensing of liquids, viscous liquids, pastes, and waxes while stirring, scraping, heating, refluxing, and cooling.
This presentation will share a selection of case studies in paints & coatings research. Case studies from polymer synthesis, paint formulation, paint application, and testing (Fig. 2 & Fig. 3).

Fig. 2: Master workflow in paints & coatings research

Fig. 3: Detailed workflows in paints & coatings research

Indu Babu

Eindhoven University of Technology, Departement of Chemical Engineering and Chemitry, Laboratory of Materials and Interface Chemistry, Eindhoven, The Netherlands

Title lecture

Highly flexible 0-3 PZT/PDMS composite films

Authors

I. Babu and G. de With

Abstract

Highly flexible piezoelectric PZT/PDMS composites of 0-3 connectivity were fabricated by dispersing the piezo-ceramic lead zirconate titanate (PZT) in a poly dimethyl siloxane (PDMS) matrix. Solution casting technique is utilized for the fabrication procedure. The dielectric constant (ε_r) and the electrical conductivities of the composites were measured as a function of frequency range. The piezoelectric charge constant (d₃₃) of these composites was measured on a d₃₃ meter at a fixed frequency at 110 Hz. The mechanical properties of the composites were tested by dynamic mechanical analysis (DMA) in order to evaluate the flexibility of these composites.

Prof.Dr. Massimiliano Barletta

Università degli Studi di Roma Tor Vergata, Dipartimento di Ingegneria Meccanica,Roma, Italy

Title lecture

Manufacture and characterization of free-standing epoxy-polyester films

Authors

M. Barletta and D. Bellisario

Abstract

The present investigation analyzes the deformation behavior under static and dynamic loading conditions of electrostatically sprayed epoxy-polyester powder coatings by local and uniaxial tests, trying to account for the separate contribution of the raw polymeric material alone and of the adhesion to the underlying metal substrate. First, thermo-rheological properties of the basic material were characterized. Secondly, free-standing films were manufactured by electrostatic spraying of the thermosetting powders onto stainless steel substrates pre-coated with an intermediate layer of silicon-based heat curable release coating. The resulting free standing-films were macroscopically characterized by uniaxial tests. Finally, local mechanical characterization of the epoxy-polyester films was carried out by micro-scale depth sensing scratch and indentation on coatings "free-standing" and "rigidly-adhering" onto the metal. The experimental findings show the different mechanical behavior of the coatings when deposited on untreated or pre-treated substrates as well as on intermediate layers of release coating, thus contributing to understand how much of the coating properties is ascribable to the material or to the interfacial adhesion between coating and substrate.

Denise Bellisario

Università degli Studi di Roma La Sapienza, Dipartimento di Meccanica ed Aeronautica, Roma, Italy

Title lecture

Effects of IR pre-curing conditions on wear resistance of metal flakes powder coatings

Authors

D. Bellisario and M. Barletta

Abstract

Hybrid IR/convective oven baking of high quality industrial powder coatings is one of the most attractive method to achieve significant economic and process time savings. The optimization of the IR pre-curing and the correlation between the effect of polymerization degree of the basecoat and the wear resistance of the whole coating system are investigated. In particular, an experimental study in which the degree of chemical conversion of the pigmented basecoat, the overall coating morphology and its thermal, mechanical and tribological properties are analyzed in the light of IR-radiation time and power, has been performed. Experimental results show that the intermediate range of curing time and IR power investigated leads to properly cured basecoats and subsequently to better morphological, mechanical and tribological behavior of the whole coating system. These results were also validated by comparison to the coatings cross-linked by the traditional two-step oven baking process. Finally, a first approximation model which correlates the degree of conversion of the polymeric material and the mechanical and tribological behavior of the coatings has also been built on.

Camille Carcouët

Eindhoven University of Technology, Department of Chemical Engineerig and Chemistry, Laboraroty of Materials and Interface Chemistry, Eindhoven, The Netherlands

Title lecture

Nature-inspired superhydrophobic surfaces from raspberry-like particles

Authors

C. Carcouët, A.C.C. Esteves, R.A.T.M. van Benthem, G. de With

Abstract

Superhydrophobic surfaces have attracted much interest in the last decades for both fundamental research and practical applications. The development of such surfaces is mostly driven by the promise of self-cleaning properties of these coatings [1].
Superhydrophobic and self-cleaning surfaces already exist widely in nature, such as butterfly wings, legs of a water strider or leaves of some plants. Amongst them, the most famous example of self-cleaning is of course the lotus leaf, symbol of purity in several Asian religions. Despite growing in muddy water, the leaves remain clean; when rainwater hits the leaves of the lotus plant, the droplets roll off the surface, washing off any contaminations and dust (Figure 1).

Figure 1: Lotus leaf with water droplets on top (left) and nanostructure of the surface of a leaf (right).

Previous studies revealed that self-cleaning property of lotus leaves originates from the combination of micrometer-scale hills and valleys and nanometer-scale waxy bumps, together with the reduced adhesion between surfaces and particles. Their surface is usually labeled as, hydrophobic. [2]. Generally, a surface is called superhydrophobic if it exhibits a water contact angle larger than 150° and a low sliding angle. The dual-size roughness combined with the proper chemistry appears to be essential to reach superhydrophobicity.
In a previous cooperation between DSM and TU/e, a nature-inspired approach, christened the "raspberry" approach, has been developed, leading to superhydrophobic surfaces [3]. In this method, the key to introduce well-controlled dual-size roughness involved the synthesis of raspberry-like inorganic silica particles. In a first step, large epoxy-modified silica particles (700 nm) were reacted with small amino-modified silica particles (70 nm). The surface with a dual-size hierarchical structure was then developed by depositing these raspberry-like particles on an epoxy based coating. Finally, a layer of PDMS was grafted on the top of the rough surface to render the film surface superhydrophobic (Figure 2) [4].

Figure 2: Preparation of superhydrophobic films based on raspberry-like particles [3].

However, due to the large particle size, this superhydrophobic coating is not optically transparent. The "raspberry" approach typically uses particle sizes in the order of the wavelength of visible light and therefore scattering occurs. But for many applications, in particular for displays, transparency is of the utmost importance.
Hence, the first aim of this project is to develop a structure with sufficient hydrophobicity as well as transparency directly on a glass surface during tempering of the glass. To this end, it is necessary to realize a dual-sized surface topology as obtained with the raspberry approach on a much smaller scale, i.e. down to 10/80 nanometer scale. Thereafter, the aim is to further improve the scratch-resistance of the material, demonstrated in a previous work [4].
Herein, we present the successful synthesis of inorganic silica nanoparticles within the targeted range. The modification of the particles was investigated, leading to the amino- and epoxy-functionalization of the silica particles. The synthesis of the raspberry-like nanoparticles was further investigated, and the first superhydrophobic transparent coatings were prepared. The synthesized particles were characterized by DLS and IR Spectroscopy and their morphology was evaluated by SEM and TEM.

References

1. Bhushan, B.; Jung, Y.C.; Koch, K., 25, 3240, (2009)
2. Neinhuis, C.; Barthlott, W., Annals of Botany, 79, 667, (1997)
3. Ming, W.; Wu, D.; van Benthem, R.; de With, G., Nano Lett., 5, 2298, (2005?
4. Wu, Di - Nature-inspired superlyophobic surfaces - Eindhoven University of Technology, (2007)

Belén Díaz Benito

Materials Science and Engineering Department, Universidad Carlos III de Madrid, Madrid, Spain

Title lecture

Deposition of g-methacryloxypropyltrimethoxysilane coatings on 6063 aluminium alloy treated with atmospheric plasma: characterization by FTIR and contact angle measurements

Authors

Belén Díaz Benito, Francisco Velasco

Abstract

This study is based in the use of γ-methacryloxypropyltrimethoxysilane (MPS) as an environmentally friendly solution to remove chromium (VI) from the pre-treatment of lacquered aluminium. In this research, the hydrolysis process of MPS at 1% in aqueous solution by means of Fourier transform infrared spectroscopy (FTIR) was studied, determining the hydrolysis time for which a greater number of Si-OH groups has been obtained. Different times at pH 4 were studied to establish the most optimal application conditions for bonding to the substrate. It was possible to observe how the bands corresponding to the Si–O–C groups present in the pure silane spectrum continued to appear after short periods of hydrolysis. However these bands practically disappeared upon increasing of this hydrolysis time, with other new ones appearing corresponding to the Si–OH vibration.

The silanization of 6063 aluminium alloy samples was also carried out. Analysis of the silane layers by means of FTIR indicated that the immersion time may be important according to the hydrolysis conditions, and it also allowed optimizing the drying time. Silane distribution is not uniform generating defects in lacquered samples. Different ways of deposition have been studied. The commonly used way to silanize, immersion of the bare sample in the silane solution, is compared to the treatment of the bare samples with atmospheric plasma, which improve samples surface energy and it is expected to improve the distribution of the silane. The effect of the plasma in the bare samples was studied by contact angle measurements.

Dr Christine Dumas

Groupe des Procédés de Séparation (GPS), IPHC-DSA, UMR CNRS 7178, Université de Strasbourg, Strasbourg Cedex 2, France

Title lecture

Hydrogen permeation as an indicator to evaluate the porous/dense character of multiple nickel autocatalytic deposits

Authors

Jamal AMER, Christine DUMAS, Barbara ERNST

Abstract

In order to increase the knowledge of the coating process and to predict the quality of nickel layers versus the operating conditions, the growth of nickel deposits with high purity (99.3%) on ceramic supports, different in chemical nature (Al₂O₃, ZrO₂) and porosity (pore diameter from 5nm to 0.8mm) was investigated after several treatments in terms of texture by SEM observations and adherence (depth of penetration of the metal).
A preliminary study of the plating bath containing hydrazine as reducing agent by UV-visible spectrometry coupled with the FT-IR spectroscopy measurements allowing to identify the metastable complex, reduced during the electroless plating treatment, as the Ni-hydrazine complex ([Ni(N₂H₄)n(CH₃COO)₂ with n=2,3), pointing out the double role of hydrazine: complexing and reducing.
Obtaining nickel metal films in a reproducible manner with a thickness ranging from 2 mm to 40 mm depending on the number of treatments allows to conclude that the pore size of the support is a key parameter on the Ni film thickness and its adhesion on the support, induced by the diffusion or not of nickel particles (35 nm) through the support and by the autocatalytic activity of the nickel occluded in the pores. The texture of the deposits was star-shaped and seems to be dense after a thermal treatment at 900 °C under H₂/He. Differentiating finely the parameter of porosity or the presence of defects on each layer of very low specific surface area becomes a real challenge.
The selective permeation of hydrogen (kinetic diameter: 0.289 nm) towards molecules like nitrogen could be a technology of choice to detect the nanometric pores/defects by analyzing the mode of transport (Knudsen, surface diffusion, activated Knudsen). The results showed that more than the thickness and texture of the nickel layer, the efficient covering of the external porosity of the support by the metal could have a beneficial impact on the selectivity of these materials working in some cases as molecular sieve.

Roland Emmerich

Robert Bosch GmbH, Packaging Technology, Bosch Lab Systems, Waiblingen, Germany

Title lecture

Experience with Automated Development and Spray Application of Coatings

Authors

Roland Emmerich, Tobias Burk, Thomas Brinz. Robert Bosch GmbH, Waiblingen, Germany
Jürgen Ortmeier, Karl Wörwag Lack- und Farbenfabrik GmbH & Co. KG, Stuttgart, Germany

Abstract

In the pharmaceutical industry or for development of catalysts High Throughput Experimentation (HTE) has been used for more than 20 years. Meanwhile this technology has also found its way into other industries. Two years after the first implementation of an automated system for development of coating materials we are able to report about the benefits of this method. The High Throughput system was developed with a number of goals in mind: shorter duration of development, increased effectiveness, decreased time-to-market, higher quality of experimental results, reduced sample and waste quantity, close-to-reality spray application. Our poster shows that these challenging goals could be fulfilled by utilizing modern formulation technologies, conventional robotics and a modified standard spray head.
Design of Experiment (DoE) was used for selecting the parameter space when developing a new recipe for a water-based clear coat. The automated system produced the individual formulations and applied them to test panels by spray coating. Characterisation was carried out off-line after automated flash-off and curing at elevated temperature. The influence of two different additives, two solvents and two binders on the coating properties such as DOI was investigated. A matrix of over 200 samples was tested within a few days. We found that there is a non-linear relationship between the effects of the two additives. In a second set of experiments the effect of varying the rheology module and its concentration in an existing formulation was investigated.
The results of the experiments clearly showed that systematic optimisation of a coating can be carried out much faster and easier by utilizing DoE and lab automation. Interaction between the components of a formulation is not always linear. Automating the lab work flow can help to find such non-linear behaviours and enable the scientist to use this knowledge when developing new formulations.

Dr. Bart Erich

TNO Built environment and Geosciences, Delft, The Netherlands
Eindhoven University of Technology, Department of Physics, Group Transport in Permeable Media, Eindhoven, The Netherlands

Title lecture

Water transport through coatings into wood

Authors

S.J.F. Erich, P.A. v. Meel, H.P. Huinink, O.C.G. Adan, J. de Jong

Abstract

Coatings are applied on wood mainly for protective and aesthetic reasons. A coating should reduce and slow down moisture uptake by wood and thereby its degradation. The goal of the presented research was to investigate the influence of different coatings (waterborne acrylic and solventborne alkyd) on the moisture transport into wood (meranti, spruce and pine) by Magnetic Resonance Imaging. Moisture transport through coated wood is largely determined by the interaction between coating and the wood. Many factors determine the final moisture barrier properties, such as the type of binder, the viscosity and the degree of pigmentation of the coating as well as structure of the wood surface. Consequently, studying the barrier properties of coatings applied on different wood samples reveals the parameters that determine the barrier properties. In this study, the influence of several coatings on the moisture transport in wood was studied for meranti, spruce, and pine. These wood types were chosen because they largely differ with respect to their structure in general and the presence of porous channels in contact with the wood surface in particular. MRI monitors the moisture content in the wood non-destructively over time. In contrast to gravimetry, MRI measures the water absorption and desorption of coated and uncoated wood with high spatial and temporal resolution. In addition, water in lumina and cell walls can be distinguished with MRI relaxometry, which allows identifying the physical nature of the sorption processes in wood. A 4.7 T MRI scanner was used to measure the spatial moisture distribution during wetting and drying processes with a resolution of 33 μm, which made it possible to simultaneously visualize the moisture in the wood and the coating itself. It was shown that the sorption behavior of coated wood largely depends on the specific combination of wood and coating. The barrier properties of the waterborne acrylic and solventborne alkyd coating differed completely. The samples which were coated with the alkyd system showed almost no water uptake. The used acrylic paint did not reduce the water uptake in meranti, i.e. the water ingressed as fast in coated and uncoated meranti. For the pine the acrylic coating prevents water from entering the tracheids and resin canals. Further, a correlation is observed between the wetting and drying behavior of the wood-coating system. Additionally, results indicate that increased layer thickness (which was also investigated) might pose problems with respect to water retention.

Dr. Catarina Esteves

Eindhoven University of Technology, Departement of Chemical Engineering and Chemitry, Laboratory of Materials and Interface Chemistry, Eindhoven, The Netherlands

Title lecture

Superhydrophobic self-replenishing coatings through the design of surface topology and chemistry

Authors

A.C.C. Esteves*, M.W.P. van de Put, G. de With

Abstract

Nature has created materials with striking features, like the superhydrophobic rose petals or butterfly wings with iridescent colors1. In many cases this remarkable properties rely on the combination of a well-defined chemistry and surface topology (Figure 1).
Taking an inspiration from Nature, several functional coatings have been developed with advanced properties, such as self-cleaning, anti-fouling, stain resistant or water-repellency. In these coatings the combination of surface roughness and specific chemical composition is also the key for success.
Apart from a few exceptions2, most of the chemically synthesized superhydrophobic surfaces reported, are easily damaged (even by simple handling) resulting in the loss of: surface-structure, chemical functionalities and related chemical/physical properties. This irreversible damage reduces the materials service-life time and increases the maintenance efforts and costs. Hence, the investigation of robust structured-surfaces, which are able to withstand daily usage for a long period of time, is critical for the sustainable development of coatings with advanced properties, e.g. easy-to-clean/self-cleaning ability3. Since the damage of coatings can never be fully avoided, introducing self-repairing mechanisms which can (partially) recover the chemical/physical properties of the material can be one way to reduce it.
We are currently combining a self-replenishing polymer system4 and the incorporation of inorganic nanoparticles to design robust superhydrophobic self-replenishing coatings. The rough surfaces of these materials have low-surface-energy groups which can be reoriented towards new surfaces, created upon damage. Herein, we report our developments on the synthesis and characterisation of superhydrophobic coatings with a single and double-scale surface roughness and low-surface-energy groups segregated at the air/coating interface, which contain simultaneously a self-replenishing polymer system.

Figure 1: a) SEM image of red rose´s petals; AFM and SEM (inset) image of one of the self-replenishing coatings prepared with dual-scale roughness.

References

1. Xia, F.; Jiang, L. Adv. Mater. 2008, 20, 2842-2858.
2. Ming, W.; Wu, D.; van Benthem, R.; de With, G. Nano Letters 2005, 5, 2298-2301.
3. Solga, A.; Cerman, Z.; Striffler, B. F.; Spaeth, M.; Barthlott, W. Bioinspir. Biomim. 2007, 2, S126-S134.
4. Dikic, T.; Ming, W.; Thüne, P.; Tian, M.; Van Benthem, R.; de With, G. Polymer Preprints, Amer. Chem. Soc. 2008, 49, 972-973.

Dr. M. Farshchi-Tabrizi

Physics Department, Bu- Ali Sina University, Hamedan-Iran /
Max-Plank Institute for polymer Research, Maniz-Germany

Title lecture

Surface modification of chitosan membrane treated by N₂ and Ar Plasma

Authors

B. Jaleh, M. Farshchi-Tabrizi, P. Wanichapichart, N.gholamia, R.Mashayekhid,A. Pourakbar Saffare

Abstract

Dense chitosan membrane were prepared and investigated for surface modification using argon and nitrogen plasma produced at low pressures with Radio frequency (RF) at power ranging from10-50 W. RF plasma offers a unique route for surface modification of polymers. The influence of the plasma treatment conditions on the basic properties of the membranes, namely pore size and flow rate has been studied. The action of plasma on porous membranes results in polymer ablation leading to the increase of the mean pore diameter confirmed by increasing water flux for plasma treated pp membrane and decreasing constant dielectric. In determining the flux, the hydrophilicity of the surface played a role as important as that of the micropore size. Changes of membrane characteristics after the N2 and Ar plasma treatment were examined. The contact angle with water decreases and wettabilities have increases with the increase of plasma treatment time.

Emilie Faure

Center for Education and Research on Macromolecules (CERM), University of Liège, BelgiumK

Title Lecture

A green and refillable antibacterial coating for stainless steel

Authors

Emilie Faure, Aurélia Charlot, Valérie Sciannaméa, Sandrine Lenoir, Robert Jérôme, Christine Jérôme, Cécile Van De Weerdt, Joseph Martial, Catherine Archambeau, Nicolas Willet, Anne-Sophie Duwez, and Christophe Detrembleur

Abstract

Because of its resistance to corrosion and chemicals, relevant mechanical and esthetical properties, stainless steel (SS) is widely used in the daily life (food industry, household appliances, surgery …). However, SS is unable to prevent bacteria from adhering, proliferating and forming a resistant biofilm when ageing. Therefore, surface modification is needed for providing durable antibacterial properties.
We report here on an all-in-one approach to prepare refillable antimicrobial films [1] using the layer-by-layer deposition of polyelectrolytes. Specifically designed biocidal multilayered polyelectrolyte films that bear 3,4-dihydroxyphenylalanine (DOPA), known as a promoter of adhesion to inorganic surfaces, were deposited onto SS. DOPA was incorporated in the polycationic chains by radical copolymerisation of N-methacrylated DOPA with the quaternary ammonium salt of 2-(dimethylamino)ethyl methacrylate (DMAEMA⁺). In order to boost the antibacterial activity of the polycationic layer, AgNO₃ was added to the aqueous solution of P(DOPA)-co-P(DMAEMA⁺), which resulted in the in-situ formation of silver based nanoparticles, sources of biocial Ag⁺. The layer-by-layer deposition of aqueous P(DOPA)-co-P(DMAEMA⁺/AgCl/Ag⁰ suspension and aqueous solution of poly(styrene sulfonate) provides high antibacterial activity against Gram-negative E. Coli bacteria. Moreover, after silver depletion, films retain some antimicrobial activity, thanks to ammonium groups of the copolymer. We also show that the antibacterial activity of the films can then be easily re-boosted.[1]

Acknowlegments

The research was partly supported by BELSPO in the frame of IUAP VI/27 and Région Wallonne, ArcelorMittal and ULg through the PPP program BIOCOAT. C.D. is “Maître de Recherche” of the F.N.R.S. (Belgium), and thanks the F.R.S.-F.N.R.S. for financial support.

References

[1] A. Charlot, V. Sciannamea, S. Lenoir, E. Faure, R. Jerome, C. Jerome, C. Van De Weerdt, J. Martial, C. Archambeau, N. Willet, A.-S. Duwez, C.-A. Fustin, C. Detrembleur, Journal of Materials Chemistry 19, 4117-4125(2009)

Michele Fedel

Department of Materials Engineering and Industrial Technologies, University of Trento, Trento, Italy

Title Lecture

Silicon alkoxides sol-gel hybrid coatings containing clay nanoparticles for corrosion protection of galvanized steel

Authors

M. Fedel, F. Deflorian, S.Rossi,

Abstract

Silane sol-gel coatings are widely used as adhesion promoters between inorganic substrate, such as metals, and an organic coating. The aim of these pretreatments is to enhance the corrosion protection performances of the organic coating improving the adhesion with the substrate and acting as a barrier against water and oxygen diffusion. It is a matter of fact that the silane sol-gel coatings do not provide an active protection against corrosion processes, although they ensure a partial inhibition of the cathodic reactions occurring on the metal surface. The barrier properties of the silane sol-gel coatings can be further enhanced adding inorganic nanoparticles into the hybrid film. In principle, clay nanoparticles can be embedded inside a silane sol-gel solution due to the proved chemical interaction between the clay and the silicon alkoxides molecules. In this study sodium montmorillonite nanoparticles were used as nanofiller for the development of sol-gel hybrid coatings with improved corrosion protection properties. The sol-gel matrix consists in the combination of three different silicon alkoxides molecules, such as γGlycidil-oxypropil-triethoxy-silane (γGPS), Tetraethoxy-silane (TEOS) and Methyl-triethoxy-silane (MTES). Different amounts of the nanofiller (200 to 2000ppm of montmorillonite particles) were dispersed in water and mixed with the silicon alkoxide molecules. Hot dip galvanized steel sheets were coated with the silane solution containing the nanoparticles. After a heat treatment the film the properties of the sol-gel coatings containing different amounts of nanofillers were investigated. The effect of the montmorillonite nanoparticles on the barrier properties of the sol-gel coatings was investigated by means of electrochemical impedance spectroscopy (EIS) and polarization measurement. The experimental evidences highlighted the amount of nanofillers to obtain the highest corrosion protection performances. The films were also characterized using both scanning electron microscope (SEM) and transmission electron microscope (TEM). Electron diffraction patterns of the sol-gel films were also collected to determine the effect of the montmorillonite nanoparticles on the structure of the sol-gel films. The microscopy analysis seems to indicate that the nanofillers promote the formation of crystalline silica domains into the sol-gel matrix. Some attempts to correlate this experimental evidence with the different barrier properties of the produced sol-gel coatings were performed.

Dr. Adolphe Foyet

Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Laboratory of Materials and Interface Chemistry, Eindhoven, The Netherlands

Title Lecture

Barrier properties of a chromate free primer on Al-2024

Authors

A. Foyet, T. H. Wu, C. Hänsch, A. Kodentsov, L. G. J. van der Ven, G. de With, R. A. T. M. van Benthem

Abstract

The Al-2024 alloy widely used in Aircraft Company is a heterogeneous material containing galvanic couples between the intermetallic inclusions. Intermetallic compounds increase the strength but decrease the corrosion resistance of this alloy. The objective of paint and coatings companies is to provide efficient and environmental friendly coatings to protect this alloy against corrosion.
The aim of this work is to determine the diffusion coefficient, the permeability of water and the corrosion performance of a chromate free coating applied on Al-2024. The capacitance of two coatings of similar composition which are applied respectively on Al-2024 and platinum substrates is compared. The impedance of Al-2024 substrate coated with this primer was recorded after several hours of immersion in a 0.5 M NaCl aqueous solution.
Water and oxygen molecules diffuse into the coating. The water volume fraction in the coating increases with the immersion time and reaches a plateau after saturation. No saturation plateau was found in the case of coating applied on Al-2024 since the interfacial oxide layer also absorbs water. The solubility of water can be determined only when the coating is applied on inert substrate such as platinum. The permeability of water was estimate to be 7.6 x 10^-12 kg m^-1s^-1. After several days of immersion in sodium chloride, the impedance magnitude at low frequency remains higher than 10⁸ Ohm.cm². The coating maintains its barrier properties, no delamination was observed. The good performance is probably due to the combination of coating (with fillers particles) and the columnar oxide layer on Al-2024, both of which act as a passive film.

Santiago Garcia Espallargas

Delft University of Technology, Department of Aerospace Materials and Manufacturing, Kluyverweg 1, 2629 HS, Delft, The Netherlands

Title Lecture

Self-healing anticorrosive organic coating based on the release of a reactive Silyl Ester

Authors

S.J. Garcia, H.R. Fischer, P.A. White, J. Mardel, A.E. Hughes, J.M.C. Mol

Abstract

The easiest and mostly applied method to protect and to reduce corrosion rates of metals is the use of organic coatings which offer protection by active pigment release and passive barrier mechanisms. However, when these systems suffer any kind of damage the passive protection is no longer there and the metal substrate is directly exposed to the corrosive environment. Under these conditions, corrosion inhibitors, of which the most used and efficient ones are chromate-based pigments, are leached out from the coating and act at the metallic substrate. This mechanism is known as self-healing (SH) mechanism by inhibitor release. Intrinsic to this approach is that the pigment in the coating is released without control until there is no more pigment left in the coating. This leaves a depletion zone in the coating that does not allow further protection.
During the last decade, a different active SH mechanism based on the sealing of the crack-damage has been described and implemented to anticorrosive organic coatings. This second approach proposes the recovery of the barrier protection by the reaction of chemical species that are released from the coating or by the use of expandable phases which will close the crack. One of the problems of this approach is that the sealing of the crack can entrap water and corrosive agents between the newly created barrier system and the metal thus impelling undercoating corrosion processes.
A possible solution to these problems would be the use of a system that protects the metallic surface by reaction with water at the metallic surface creating a passive layer on top of the metal. In this work a new organic-based healing agent based on a silyl ester is presented and its synthesis and performance is described. The silyl ester was first tested as a repairing agent (assisted healing) and secondly encapsulated and incorporated into an organic matrix to study the autonomic self-healing properties of the complete system. A new high-throughput technique for healing agents´ evaluation named multiwell was employed to determine the minimum amount of agent to heal a crack. In order to evaluate the healing ability of the silyl ester, Electrochemical Impedance Spectroscopy (EIS) is used and identified to be a key technique for the development and performance evaluation of self-healing anticorrosive organic coatings.

Argyrios Georgiadis

University of Surrey, Department of Physics, Faculty of Engineering and Physical Sciences, Guildford, UK

Title Lecture

A new method for making hard, No-VOC waterborne coatings

Authors

A.Georgiadis, J.L. Keddie, M. Murray, J. Jennings, S. Emmett, P. Beharrell

Abstract

In the coatings industry, there is a need for hard and clear waterborne coatings. A polymer with a high glass transition temperature, Tg, must be used to make a hard polymer coating. When a latex film made from a hard polymer dries at room temperature, it is subject to cracking [1]. One method to avoid cracking is to add plasticizers to aid film formation, but the use of this type of additive is coming under scrutiny for environmental reasons. Another method is to heat the latex film to a temperature well above the Tg of the polymer. In the past, convection ovens have been used for heating, but this process consumes a relatively high amount of energy. We have developed an alternative technique for making hard latex films in which latex films are heated above the polymer´s Tg through radiative heating from an infrared (IR) lamp [2]. This technique has the advantages of not using VOCs and having low energy consumption.

This poster will demonstrate the film formation of an acrylic copolymer with a Tg of 38 °C using IR radiation. The sintering of the latex particles as a function of time of exposure under IR radiation has been studied with the aid of atomic force microscopy [3]. The flattening of the particles at the film surface, which is indicative of sintering, is faster under IR radiation than when the films are heated in a convection oven at 60 °C. Furthermore, the hardness of the IR-sintered films has been measured with indentation experiments [4] and found to be comparable to films formed in a convection oven.

Poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS), which is strongly IR absorbing, was added at low concentrations, and its effects on the sintering process were studied. The addition of PEDOT:PSS results in a higher temperature increase under IR exposure. Also, the sintering of the particles is faster under IR radiation for latex containing small quantities of PEDOT:PSS, compared to the plain acrylic latex.

References

1. K. B. Singh and M. S. Tirumkudulu (2007) Physical Review Letters, 98, 218302.
2. J.L. Keddie and A. Georgiadis (2009) British Patent application GB0903297.0.
3. M. Cynthia Goh, D. Juhue, On Man Leung, Y. Wang, and M.A. Winnik (1993) Langmuir, 9, 1319-1322
4. K.W. Xu, G. L. Hou, B.C. Hendrix, J.W. He, Y. Sun, S. Zheng, A. Bloyce, T. Bell (1998) Journal of Materials Research, 13, 3519-3526

Dr.ir. Nathalie De Geyter

Department of Applied Physics Faculty of Engineering - Ghent University (UGent), Belgium

Title lecture

Plasma-assisted deposition of polymethyl methacrylate onto TiO₂ substrates

Authors

N. De Geyter, R. Morent, M. Frère-Trentesaux, P. Dubruel, C. Leys1 and E. Payen

Abstract

Plasma polymerization is a unique technique to fabricate thin polymer films from a wide variety of organic and organometallic precursors. Plasma polymerized films are pinhole-free and highly cross-linked and therefore insoluble, thermally stable, chemically inert and mechanically tough. Furthermore, such films are often highly adherent to a variety of substrates including conventional polymer, glass and metal surfaces. Due to these excellent characteristics, plasma-polymerized films have been used in a wide variety of applications including barrier coatings, protective coatings, selective permeation membranes and dielectric layers in microelectronics. Besides these well-known examples, state-of-the-art applications are continuously being developed, especially in the biomedical domain.

Generally, a large part of research related to plasma-assisted thin film deposition has involved low pressure non-thermal plasma technologies. Although vacuum treatment processes afford good control over gas chemistry and provide the possibility of using high energetic species (in the range of several eV to hundreds of eV) in the deposition process, atmospheric pressure processing techniques are offering specific advantages, such as the elimination of expensive vacuum equipment, easier handling of the samples and scalability for industrial on-line processing. Therefore, in recent years, a lot of effort has been put into the development of non-thermal plasma reactors for thin film deposition working at or near atmospheric pressure.

This paper will focus on the formation of coatings in an atmospheric pressure dielectric barrier discharge (DBD) using methyl methacrylate (MMA) as gaseous precursor. Plasma polymerized films will be deposited onto TiO2 samples, which is a common material used for artificial hips. Depositing a polymethyl methacrylate (PMMA)-like coating onto TiO2 can improve the fixation of artificial hips, since the bone cement used to fixate the hip into the human body normally consists of MMA or PMMA. In this work, the chemical and physical properties of the obtained PMMA-like coatings will be discussed in detail using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM).

Prof.Dr. Mahmood Ghoranneviss

Islamic azad University, Plasma Physics Research Center, Science and Research Branch, Tehran, Iran

Title lecture

Investigation on Dye ability and Antibacterial activity of nano- Layer Platinum Coated Polyester fabric Using DC Magnetron Sputtering

Authors

M.Ghoranneviss, S.Shahidi, J.Wiener, H.Shahbakhti, A.Hatmi

Abstract

Low temperature plasma treatment has been conducted in textile industry and has some success in the dyeing and finishing processes. PET fibers have been increasingly used in textile industries for a variety of applications ranging from filtration, composites, and tissue engineering and electronic textiles. The surface properties of these polymer fibers are of importance in various applications. The surface properties of PET fibers can be modified by different techniques. The affinity of Polyester fibers to natural dyes is too weak, so many research have done to improve the dyeability of this fiber. In this research work, one side of PET fabrics was coated by Platinum using DC magnetron sputtering. The textile properties of Pt-coated polyester fabrics were evaluated by different standard testing methods in terms of both physical and chemical performances. The dye ability of coated and uncoated samples to different natural and synthetic dyes was evaluated. The antibacterial counting test was used for determination of antibacterial efficiency of both treated and untreated samples, and durability of antibacterial properties was compared. The results show that, the existence of platinum nanolayer on the surface of PET fabrics causes improve the dyeability of fabrics. However, this improvement for natural dyes is more significant. Also the antibacterial activity of natural dyed samples is notable.

Ismail Dogan Gunbas

Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Polymer Chemistry, Eindhoven, The Netherlands

Title Lecture

Maleic Anhydride Based Copolymer Dispersions for Surface Modification of Polar Substrates

Autors

I.D. Gunbas, M. Wouters, R.A.T.M. van Benthem, C.E. Koning

Abstract

Chemical modifications of polymer surfaces can be applied to control adhesion, wettability, and biocompatibility as important surface properties of polymers that are of interest for a variety of applications. Flame treatment, corona discharge treatment, plasma modification, and surface graft polymerization are the practical approaches to polymer surface modification. Unfortunately, these techniques do not result in chemically well defined surfaces which in view of their demanding properties should be carefully designed and prepared. Our approach is that surface functionalities are introduced by a modification of polymer surfaces with water-based, alternating maleic anhydride copolymers, chemically modified with primary amines. Electrostatic stabilization of styrene maleic anhydride (PSMA) based particles can be obtained by partial ammonolysis of the anhydride groups with ammonia. The remaining anhydride groups can be used for crosslinking with diamines [1-3], as is schematically represented in Scheme 1, and/or for interaction with the polar polymer substrate.

Scheme 1. Schematic representation of the different possible reactions with cyclic anhydride units in the PSMA polymer

In this work, we report the preparation of surfactant-free artificial latexes on the basis of PSMA copolymer which was then modified using n-heptylamine and mono amino functional polydimethyl siloxane (PDMS-NH2). Self-emulsifying latexes with an average particle diameter of 150-190 nm and a zeta-potential of -65 mV have been successfully obtained from modified anhydride-containing polymers with various Tgs. It was found that the latexes are stable in the pH range of 2-9. Furthermore, the film formation of these latexes was studied; for the differently modified copolymer latexes, curing at temperatures above the Tg of the respective copolymers led to homogeneous film formation. Different latexes were coated on aluminum substrate. The wetting of the substrates could be optimized by etching the metal substrate. An alkaline pretreatment improved the adhesion with the polymer films for aluminum substrates. For future coating applications, these systems based on surfactant-free latexes have displayed promising properties.

References

1. W.J. Soer, W. Ming, B. Klumperman, C.E. Koning, R.A.T.M. van Benthem, Polymer 47,2006, 7621-7627.
2. B. Schlarb, M. Gyopar Rau, S. Haremza, Progress in Organic Coatings 26 1995;207-215.
3. D.C. Blackley, H.F. Mark, N.M. Bikales, C.G. Overberger, G. Menges and J.I. Kroschwitz, Encyclopedia of Polymer Science and Engineering, Vol. 8, Wiley, New York 1987;pp. 66.

Dr. Claudia Haensch

Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Laboratory of Materials and Interface Chemistry, Eindhoven, The Netherlands

Title Lecture

Screening of different epoxide/ amine combinations for the preparation of coating materials onto aluminum alloy 2024 substrates

Autors

C. Haensch, T. H. Wu, A. Foyet, A. Kodentsov, L.G.J. van der Ven, R.A.T.M. van Benthem, G. de With

Abstract

Aluminum alloy 2024 represents a high strength aluminum screw machine stock alloy, [1,2] which is known for its optimal weight to strength ratio.This makes the alloy an ideal candidate for applications requiring high strength, such as aircraft fittings and structures, computer parts, gears, shafts, hinge pins, valve blocks and valve parts, bolts, nuts, [1] fasteners, truck parts and brake components.However, it contains also many different intermetallic inclusions. Therefore, this alloy is one of the most susceptible to localized [3] corrosion due to segregation of intermetallic particles at the grain boundaries. One possibility to still take advantage of the mechanical properties is to cover the substrate [2] with a layer of an organic material, which works as a protection layer. An interesting candidate for coating the aluminum alloy is a polymer network consisting of epoxide and amine due to their low water permeation coefficient and their strong adhesion to the substrate. However, the permeability of these epoxy/ amine coatings is strongly depending on the mixing ratio, the curing conditions and the application of the material onto the substrate.
The aim of the presented study is to design extremely resistant interphases between the Al alloys 2024 and the organic coating as well as to control of the mobility of water, hydrate ions and to improve the long-term stability of the polymer on the aluminum alloy.
Therefore, a screening of different combinations of epoxides and amines is presented to study the properties of these coatings. A selection of two epoxides and four different amines is shown to enlarge the variety of different combinations. The polymer network is varied concerning hydrophobic/ hydrophilic properties, different crosslink-densities and the influence of aromatic vs. aliphatic moieties. Moreover, various curing conditions were applied to optimize the coatings. Additionally, the properties of these coatings are analyzed by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA).

References

1. http://www.alcoa.com/gcfp/catalog/pdf/alcoa_alloy_2024.pdf.
2. A. Foyet, T.H.Wu, A. Kodentsov, L. van der Ven, G. deWith, R. van Benthem, Progress in Organic Coatings 2009, 65, 257-262.
3. S.V. Lamaka, M.L. Zheludkevich, K.A. Yasakau, M.F. Montermor, M.G.S. Ferreira, Electrochim. Acta 2007, 52, 7231.

Dr. Mijeong Han

Advanced Materials Division Korea Research Institute of Chemical Technology, Yuseong-gu, Daejeon, South Korea

Title Lecture

Corrosion and wear resistance of multi-functional organic-inorganic hybrid coatings

Autors

Mijeong Han, Ji Yeon Seo, and Jiyoung Mang

Abstract

Organic-inorganic hybrid coatings containing both corrosion and wear resistance were prepared via each photo-curing and sol-gel process. Photo-curable formulations were prepared by using functional acrylates which have anti-corrosion groups and organically modified silica nanoparticles with acrylate for the better dispersion. Modified silica was added to methylene chloride and the solution was ultrasonificated. At this point, functional acrylate monomer was added and it was possible to prepare each coating solution containing tetramethyl tetra(ethoxyacrylate)cyclo tetrasiloxane(D4A) and photo initiator. Coating solution was dip-coated on iron plate and photo-curing was conducted with mercury lamp (80W/cm) for 5min. The corrosion protection properties of hybrid coatings on iron were studied by salt spray chamber test and electrochemical impedance spectroscopy (EIS), and wear resistance was measured by pencil hardness test. The corrosion and wear resistance of coating containing functional acrylate and D4A were superior to those of coatings with conventional acrylates. For thermal curing formulations via sol-gel process, sol-gel precursors containing anti-corrosion properties were synthesized by sequential Michael addition of methylaminoethanol to 1,4-benzoquinone, followed by the reaction with 3-isocyanatopropyltriethoxysilane. Epoxy was modified by 3-isocyanatopropyltriethoxysilane and the completion of the reaction was confirmed by the disappearance of NCO group in FT-IR. Sol-gel precursors, modified epoxy, HCl, H₂.O, and diaminodiphenylmethane in tetrahydrofuran were stirred at room temperature for 1h and the solvent was removed under the reduced pressure. The resulting mixture was coated on iron substrates by dip-coating and heated to 80 ℃ for 12h and 160 ℃ 12h. The coatings on substrates were clean and transparent and showed very high pencil hardness up to 8H. The anti-corrosion properties of hybrid coatings were studied by salt spray chamber test and EIS. It was observed that the hybrid coatings with sol-gel precursors containing anti-corrosion ability exhibited much better corrosion protection on iron than those without them. This could be explained by the good adhesion and high affinity of anti-corrosion functional group to iron surface. Effects of the weight ratio of acrylate monomer and sol-gel components on the corrosion properties of hybrid coatings will be further discussed.

Dr. Marc Herold

Bühler PARTEC GmbH, CTO Business Unit PARTEC- Bühler AG, Saarbrücken, Germany

Title lecture

Superior eco friendly waterborne coatings due to nanoparticle technology

Authors

Dr. M. Herold and Dr. K. Steingröver

Abstract

Eco-friendly waterborne paints and coatings already gained considerable interest and market shares compared to traditional solvent borne systems. This ongoing development is not only driven by stricter legislation but also due to the general increasing environmental awareness. Even on the rise, waterbornes have well known limitation in overall performance compared to classical solvent born systems preventing their general use in several field of application.

An innovative performance additive, potentially closing the gap in performance deficiency of waterborne paints and coatings, will be presented. The exceptionally effective additive is based on nanoparticle technology containing tailor-made nanoparticles which improve the overall coating performance due to direct resin interaction. We assume that the nanoparticles interfere in the drying process resulting in a polymer network of higher density. This effect closely depends on the high degree of dispersion as well as by the high surface area of the nanoscaled particles. In addition, due to the neglectable light scattering, the technology is widely applicable also in transparent clear coats.

The general chemomechanical process to produce nanoscaled dispersions of inorganic oxides from agglomerated nano powders will be present including the chemical surface modification reaction under well-defined mechanical stress conditions for customization of nanoparticles with respect to industrial formulation.

Paramount advantages in performance enhancement on water-based acrylic emulsion systems for wood and metal substrates by utilizing this new additive will be presented. It positively improves several coating properties at the same time without negative consequences on others. In particular the considerable improvements regarding MEK rub stability, drying time, blocking resistance and stability against humidity will be highlighted.
In conclusion a novel and innovative approach by making use of nanoscaled particles will be presented having the potential to alter the landscape of eco friendly waterborne coatings.

Eliana Ieva

Solvay Solexis, Spinetta Marengo, Italy

Title lecture

Dirt pickup resistant PVDF coatings for architectural applications

Authors

Eliana Ieva, Shiow Lin, Valery Kapeliouchko, Bradley Kent

Abstract

Polyvinylidene fluoride (PVDF) coatings have been successfully used as long-lasting architectural coating[1] thanks to their superior performances than other competitive coatings . Architectural coatings are subjected to prolonged weather exposure that leads to photo-oxidative aging, gloss reduction, color change, chalking, and film erosion. Coatings based on Hylar® 5000 PVDF have outstanding properties such as high weatherability, excellent resistance to chemicals and corrosive atmospheres, resistance to oxidative degradation, exceptional color and gloss retention and a low level of chalking over a service life of >40 years. Dirt pickup is the deposit of foreign matter consisting of dirt, soot or stain that darkens the surface of a coated panel after exterior exposure [2] . The dirt pickup phenomenon is a complex issue and is determined by many factors. Dirt pickup of an exterior paint affects its long term appearance and corrosion protection to substrate. For certain applications, such as architecture coatings, the appearance after a long term service is essential. Therefore, the ability for a coating to resist dirt pickup becomes part of performance consideration. In the communication results that show the excellent dirt retention resistance of PVDF coatings will be presented.

Reference

[1] S-C. Lin and K. Argasinski, Chapter 7, Fluoropolymers 2: Properties, 1999, edited by Hougham et al. Plenum Press, New York.
[2] ASTM D3719-00 Standard Test Method for Quantifying Dirt Collection on Coated Exterior Panels

Dr. Byung-Koog Jang

Fine Particle Processing Group, Nano Ceramics Center National Institute for Materials Science (NIMS), Tsukuba, Ibaraki, Japan

Title lecture

Microstructure of Nanoporous Zirconia Coatings Fabricated by EB-PVD

Authors

B.K. Jang, Y. Sakka, K. Matsumoto, H. Matsubara and H.T.Kim

Abstract

Electron beam-physical vapor deposition (EB-PVD) is a widely used technique for depositing thermal barrier coatings (TBCs) on metal substrates for high temperature applications, such as gas turbines, in order to improve the thermal efficiency. Low thermal conductivity is one of the most important properties for obtaining superior TBCs. To optimize TBCs for integration into gas turbines, characterization of the relationship between microstructure and thermal properties of the coatings is necessary. This work describes the microstructure of ZrO2-4mol% Y2O3 (YSZ) coatings as a function of the substrate rotation speed.

YSZ coatings were deposited by EB-PVD onto zirconia substrates. Coated specimens formed at different rotation speeds namely stationary, 1, 5 and 20 rpm. The average coating thickness was about 300 μm. X-ray diffraction (XRD) and Raman spectroscopy were used to determine the crystal structures of the phases present and to determine if any preferred orientation developed in the coatings. The YSZ coatings consist of porous-columnar grains containing nano pores. Nano sized pores could be observed around feather-like grains as well as inside of columnar grains. The total porosity and numbers of nano pores of YSZ coatings increased with increasing substrate rotation speed during deposition.

Prof.Dr. Yeon-Gil Jung

School of Nano & Advanced Materials Engineering, Changwon National University, Changwon, Republic of Korea

Title lecture

Dual Coating Process of High Functional Reinforcement Phase in Metal Matrix Composite

Authors

Eun-Hee Kim, Je-Hyun Lee, Yeon-Gil Jung

Abstract

Metal matrix composites (MMCs) have been researched to improve the poor wear resistance of pure metals and to reduce the high friction coefficient of alloys, for possible applications in engineering materials with high performance in energy technology and automobile industry. Therefore, the reinforcement phase, especially ceramic phase, has been incorporated into the metal matrix, which should be well dispersed in the matrix to maximize effects of reinforcement phase. In this work, inoculant, that is ferrosilicon, was used as a core particle for fabrication of reinforcement phase, which has been generally used in foundry industry to improve crystal growth and to restrict formation of cementite. The reinforcement phase has been formed by a dual coating process; (1) first process is the coating of TiC particles on the surface of inoculant to increase mechanical properties of the matrix, and (2) second process is the coating of Ni particles on the TiC-coated inoculant to enhance dispersibility of the TiC-coated one in the matrix. TiC particles were coated onto the surface of inoculant using an inorganic binder converted into glassification phase by the heat treatment following hydrolysis reaction, inducing the enhancement of coating efficiency. The TiC-coated inoculant was coated again by Ni particles. Nickel nitrate (Ni(NO3)2), existing as Ni cation (Ni2+) in aqueous solution under optimum pH value, was used as a precursor of Ni particle. The coating efficiency and morphology have been investigated with contents of inorganic binder and Ni precursor. As the content of inorganic binder is decreased, TiC particles are well coated on the surface of inoculant without any aggregation and localization of TiC particles. The content of Ni2+ on the TiC-coated inoculant is increased with increasing the content of Ni precursor. The reinforcement phase by the dual coating process has been successfully fabricated, expecting the increase in mechanical properties of the matrix owing to the improvement of dispersibility.

Dr. Eun-Hee Kim

School of Nano & Advanced Materials Engineering, Changwon National University, Changwon, Republic of Korea

Title lecture

Preparation of Ni-Coated TiC Particles using Potential Hydrogen (pH) for Dispersion into a Molten Metal

Authors

Eun-Hee Kim, Je-Hyun Lee, Yeon-Gil Jung, Sang-Hoon Lee, Jin-Ju Park, Chang-Kyu Rhee

Abstract

Metal matrix needs to improve mechanical properties such as wear resistance, elastic modulus, and strength, for possible applications in extreme environments and rapid technological advances. One of possible ways is to reinforce ceramic particle into the matrix. In order to achieve these properties, the reinforcement phase must be well dispersed in the matrix. In this work, titanium carbide (TiC) particles coated with nickel (Ni) particles have been prepared using potential hydrogen (pH) for enhancing the dispersion of TiC particles into a molten metal. The coating behavior and morphology have been investigated as functions of the pH in TiC suspension and the heat treatment condition. TiC particles were dispersed in an aqueous solutions of various pH levels, and then nickel nitrate (Ni(NO₃)₂) as a Ni precursor was added. The concentration of Ni ion (Ni²⁺) on the surface of TiC particle is affected by the pH of TiC suspension; as the pH increases the concentration of Ni²⁺ increases, owing to an increase in the attractive force between TiC particle and Ni²⁺, arising from the negative charge density of TiC particle. Heat treatment was conducted at 500 °C and 1000 °C under both inert (Ar) and reducing (H₂) atmospheres. The Ni-coated TiC particles heat-treated at 500 °C under H₂ atmosphere indicate the TiC and Ni phases only, whereas those heat-treated at 1000 °C under Ar atmosphere show a titanium oxide (TiO₂) with the TiC and Ni phases, which is resulted from the oxidation of TiC particle by oxygen contained in Ar gas. The Ni-coated TiC particles with a face-centered cubic structure show a magnetic property, independent of the heat treatment condition. The dispersibility of TiC particle into a molten metal would be improved through the coating of Ni particle (or phase), due to the enhanced compatibility of TiC particle with a molten metal, resulting in the improvement and reliability of mechanical properties. For the better adhesion and homogeneous coating of Ni particles onto TiC particles without oxidation reaction, it is essential to control the pH of TiC suspension and to determine the most favorable heat treatment condition.

Jae-Hyun Kim

School of Nano & Advanced Materials Engineering, Changwon National University, Changwon, Republic of Korea

Title lecture

Microstructural evolution and thermal stability of layered thermal barrier coatings in cyclic thermal exposure

Authors

Sang-Won Myoung, Jae-Hyun Kim, Sang-Yup Lee, Tae-Woong Kang, Yeon-Gil Jung, Kee-Sung Lee, Ungyu Paik

Abstract

Thermal barrier coatings (TBCs) have been modified with a layered structure in both bond and top coats using different feedstock powders for the top coat (204 C-NS and 204 NS) and the bond coat (METCO 461 NS and AMDRY 9625) in the specialized coating system of TriplexPro-200. The microstructural evolution of the top coat has been investigated under cyclic thermal exposure, including the thermally grown oxide (TGO) layer and the thermal stability at the interface of the bond and top coats, in order to understand the effects of the microstructural design on the thermal durability and damage tolerance of TBCs. Cyclic thermal exposure tests were performed at a surface temperature of 1100 °C with a temperature difference of 150 °C between the surface and bottom of sample, with a dwell time of 1 h for 800 cycles. Three layers in both coats were prepared with different microstructures in the top coat and compositional change in the bond coat. Each layer thickness deposited in both bond and top coats is about 100 and 200 μm, respectively. After 800 cycles, the TBCs with the layered structure show a sound condition without an evidence for delamination at the interface. The mechanical properties of the TBCs with the layered structure are not much degraded with the thermal exposure, compared with the TBCs with the single structure. The TBC with a relatively porous microstructure (204 C-NS) at the base layer indicate better thermal stability at the interface than that with a relatively dense microstructure (204 NS), showing higher damage tolerance in the case of TBC with the relatively dense microstructure at the surface layer. Both layered TBCs become soft and hard with the thermal exposure, and show thin and thick TGO thicknesses, compared with the TBCs of the single structure with 204 NS and 204 C-NS, respectively. AMDRY 9625 and METCO 461 NS as the bond coat indicate better thermal stability with the top coat and the substrate, respectively, in the thermal exposure. The results indicate that the layered TBC with the relatively dense and porous microstructures at the surface and the interface, respectively, is more efficient in protecting the substrate from the thermal exposure and contact environments, with less degradation of mechanical properties.

Dr. Hans Kranenburg

Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Laboratory of Materials and Interface Chemistry, Eindhoven, The Netherlands

Title lecture

Self-healing adhesion of coating networks

Authors

J.M. Kranenburg, R. M. Kops, R. P. Sijbesma, R.A.T.M. van Benthem, G. de With

Abstract

Adhesion of coatings to the substrate is of utmost importance to their performance. Adhesion normally relies strongly on ionic and covalent bonds across the interface. These bonds, once broken in a delamination process, cannot be restored. Alternatively, the use of reversible supramolecular bonds across the coating / substrate interface offers the potential of restoring (much of) the original adhesion. In this project, we aim to demonstrate self-healing adhesion. The (re-) adhesion is investigated using the JKR technique.

Alicja Krella

The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences, Gdansk, Poland

Title lecture

Degradation model of hard coatings under cavitation action

Authors

Alicja Krella

Abstract

Nowadays the most machining tools are coated with hard coatings to prolong their lifetime and to improve the working efficiency. They are used for high wear applications, where they are regularly subject to cyclic impact loading. Their main benefits are based on the combination of high hardness and toughness, properties which are especially important in the conditions of dynamic impact wear when high cyclic local loading is the main cause of coating degradation. Cavitation test can be useful tool for studies of plastic deformation, crack initiation and propagation in thin hard coatings. Cavitation damage is caused by repeating action of imploding cavitation bubbles in the vicinity of solid surface. The collapse of the cavitation bubbles implies that an impulse is applied, typically by an impacting microjet or by a pressure wave impact.

Analyse of degradation mechanism of thin nanocrystalline coatings under the impact degradation results in the achievement of the new parameter to assess their resistance of hard coating against cavitation. Because materials undergo plastic deformation in the incipience erosion, plastic properties and adhesion play the main role in coatings resistance. Experimental investigations show that all defects in coatings influence on erosion race, so the number of phases and coating´s thickness are also the key factor in cavitation resistance of the coating. Cavitation pulses hit material with high velocity during few μs emitting temperature of thousands degrees; this indicate that thermal properties cannot be omitted in the parameter of coatings resistance against cavitation. The new parameter joins mechanical properties of a coating as well as its thermal and structural properties.

Because TiN and Cr-N coatings are the most popular coatings for commercial applications, they were chosen to prove the new parameter. TiN and Cr-N coatings with various thickness were deposited on stainless steel, by means of the cathodic arc evaporation method at various temperatures and bias voltage. All tests were performed in the same cavitation condition in the cavitation chamber with a system of barricade. Obtained results have showed very good correlation between the mass loss and the new parameter.

Patricia Lammel

EADS Innovation Works, Dept. Metallic Technologies and Surface Engineering, D-81663 Munich, Germany

Title lecture

Solid particle erosion behaviour of nickel- and chromium based coatings

Authors

Patricia Lammel^1,2, Helena Simunkova², Adam Whitehead², Bernhard Gollas^3
1: EADS Innovation Works, Dept. Metallic Technologies and Surface Engineering, unich, Germany
²: CEST, Viktor-Kaplan-Str. 2, A-2700 Wiener Neustadt, Austria
³: Technical University of Graz, Institute for Chemistry and Technology of Materials, Stremayrgasse 16, A-8010 Graz, Austria

Abstract

Composite materials are widely used in aircraft because of their low density, high strength and stiffness. However, the impact of sand or dust particles during flight may cause serious degradation of the surface. Therefore a suitable functional coating is necessary to enhance the wear and erosion resistance.
Different electrodeposited nickel-based alloys and dispersion coatings, namely: nickel, nickel tungsten (NiW), nickel/silicon carbide (Ni/SiC), nickel/diamond, and hard chromium layers on copper-coated glass fibre reinforced polymer (GFRP) substrate have been prepared and characterized. The coatings were investigated under solid particle erosion conditions using a TE 68 Gas Jet Erosion Rig at 55 m s^-1 with rounded silica particles having an average diameter of 220 μm. Due to the influence of impingement angles to the erosion process, impacts at 20° and 90° were tested. The erosion behaviour has been studied by optical microscopy, scanning electron microscope (SEM) and profilometry measurements. Moreover, the mechanisms of solid particle erosion will be discussed.

Sang-Yaop Lee

School of Nano & Advanced Materials Engineering, Changwon National University, Changwon, Republic of Korea

Title lecture

Microstructural evolution and oxidation behavior of thermal barrier coating system with buffer layer in thermal exposure

Authors

Sang-Yup Lee, Jae-Hyun Kim, Kwang-Su Song, Jae-Young Kwon, Je-Hyun Lee, Yeon-Gil Jung, Ungyu Paik

Abstract

Effects of buffer layer on microstructural evolution and oxidation behavior of thermal barrier coating (TBC) systems have been investigated under thermal exposure. The buffer layer was prepared with blended powders of 65% magnesium zirconate (MgZrO₃) and 35% nickel–chromium alloy (Ni–Cr) by an air-plasma sprayed (APS) process, which was introduced between the bond and top coats in zirconia (ZrO₂)-based TBCs to improve the interfacial stability of TBCs. The thermal exposure tests were conducted at T = 950 ℃ in the one-side exposed condition and the fully impeded condition in a furnace, with dwell times of 1 and 24 h, respectively. After thermal exposure, the TBC with the buffer layer sustains a relatively continuous microstructure, showing a step like distribution of Zr element between the top and bond coats. The oxidation of bond coat is severely progressed in the TBC without the buffer layer in both tests, showing an evidence for delamination in the case of fully impeded condition. Especially, in the case of TBC without the buffer layer, the diffusion layer (or reaction region) onto the substrate side in the range 50–80 mm is observed in both thermal exposure conditions, with a broad range in the case of fully impeded condition. However, the TBC with the buffer layer does not show any diffusion layer onto the substrate side in the one-side exposed condition, and does indicate the diffusion layer within a few micro ranges in the fully impeded condition. The TBC system with the buffer layer is more efficient in improving the oxidation resistance than that without the buffer layer. With increasing the exposure time, the hardness values are slightly increased due to the re-sintering effect, and then decreased by formation of cracks due to the thermal fatigue, independent of the buffer layer. The buffer layer can be promising for use in TBC application, resulting in improving the reliability and lifetime performance of components with TBCs in gas turbines. The influences of thermal exposure condition at same equivalent operating hour (EOH) on microstructural evolution and mechanical properties of TBCs with and without the buffer layer are discussed.

Yingyuan Li

Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Laboratory of Polymer Chemistry, Eindhoven, The Netherlands

Title lecture

Waterborne polyurethane dispersions based on dimer fatty acid-based diisocyanate and isosorbide

Authors

Yingyuan Li, Rolf A.T.M. van Benthem, Cor E. Koning

Abstract

Introduction

Polyurethane dispersions (PUDs) have been developed since the late 1960s in the coating industry. Since then, solventborne and waterborne dispersions have been widely used in making polyurethane coatings. With respect to solventborne systems, waterborne polyurethane dispersions have many advantages. [1-3] The formulated coatings are non-toxic, non-flammable, low in VOC content, and consequently are environmentally friendly. Therefore, in spite of their relatively low solid content, waterborne PUDs have been receiving much more attention in the recent decades.
Fossil fuel-based chemicals and chemical derivatives are not any longer optimal for the long-term development, which require replacement by corresponding alternatives from renewable-based resources. [4,5] Fortunately, nowadays there are many natural resources-based monomers available. Suitable renewable monomers for polyurethane synthesis are already available on the market. Examples are dimer fatty acid-based diisocyanate, isosorbide, 1, 3-propanediol and lysine-based diisocyanate. Those renewable resources provide us with the opportunity to prepare waterborne PUDs based on renewable resources.
The objective of this project is to develop fully biomass-based waterborne polyurethane dispersions using an industrialized ionic water dispersion process. The application of these dispersions should result in durable and sustainable coating systems suitable for the protection of surfaces such as floors, textile, leather and automotive parts. The resulting PUs and PUDs are characterized with SEC, ¹H NMR, ¹³C NMR, IR, DSC, titration, DLS and Zeta-Potential measurements.

Results and discussions

The ionic waterborne PUDs have been successfully prepared from dimer fatty acid-based diisocyanates (DDI 1410) and isosorbide (IS), referring to Figure 1, as the main building blocks, dimethylolpropionic acid (DMPA) being an internal dispersing agent after neutralization of its pendent COOH group with triethylamine (TEA). These PU prepolymers ultimately were chain extended with ethylenediamine (EDA). The obtained dispersions are stable in the pH range from 1.5 to 12. Also they show colloidal stability for more than one year, referring to Figure 2. Coating films have been formulated which exhibit high contact angle and good impact resistance, but insufficient acetone resistance and low könig hardness (Table 1). The molecular weight of the chain extended PUDs appears to be too low and should be improved.

Figure 1. The structures of dimer fatty acid-based diisocyanate (a) and isosorbide (b).

Figure 2. The results of Zeta-potential/size measurement as a function of pH.

Table 1. Coating films properties formulated from the renewable based PUDs.

Conclusions

It can be concluded that waterborne PUDs can be prepared from renewable resources, such as fatty acid-based diisocyanate and isosorbide. PU coatings can be formulated based on the prepared PU dispersions and exhibit good impact resistance and high contact angles, but poor acetone resistance and low könig hardness. The molecular weight of the chain extended PUDs needs to be improved.

References

1. Kim, B. K., Colloid and Polymer Science 1996, 274, 599-611.
2. Jiang, L.; Xu, Q.; Hu, C. P., Journal of Nanomaterials 2006, 1-10.
3. Dieterich, D., Progress in Organic Coatings 1981, 9, 281-340.
4. van Haveren, J.; Oostveen, E. A.; Micciche, F.; Noordover, B. A. J.; Koning, C. E.; van Benthem, R.; Frissen, A. E.; Weijnen, J. G. J., Journal of Coatings Technology and Research 2007, 4, 177-186.
5. Noordover, B. A. J.; Heise, A.; Malanowski, P.; Senatore, D.; Mak, M.; Molhoek, L.; Duchateau, R.; Koning, C. E.; van Benthem, R., Progress in Organic Coatings 2009, 65, 187-196.

Prof.Dr. Ronaldo D. Mansano

Laboratory of Integrated Systems (LSI) - Polytechnic SchooL of University of São Paulo, São Paulo -SP Brazil

Title lecture

Micropatterning of single-walled carbon nanotubes forest

Authors

A. P. Mousinho, R. D. Mansanoo

Abstract

Carbon nanotubes (CNTs) have attracted increasing interest due to their excellent electrical, mechanical, thermal, and optical properties. The outstanding properties of CNTs have established CNTs films as a new class of optically transparent and electrically conduction materials that can be used in applications such as field emission displays, sensors, transparent electrodes for optoelectronic devices, and microelectronic devices. The high aligned single-walled carbon nanotubes forest have been grown using high density plasma chemical vapor deposition technique and patterned into micro-structures by means of photolithographic techniques that are commonly used for silicon integrated circuit fabrication.
The single-walled carbon nanotubes were deposited at room temperature by High Density Plasmas Chemical Vapor Deposition (HDPCVD) system. This deposition system uses a new concept of plasma generation, where a planar coil coupled to an RF system for plasma generation was used with an electrostatic shield for plasma densification. In this mode, high density plasmas are obtained. The carbon nanotubes films were obtained using pure methane plasmas and using iron as precursor material (seed). The iron layer was deposited on silicon wafers (75 mm diameter, 380 μm thick and orientation (100)) by Magnetron Sputtering using 250 W (power), 5 mTorr (process pressure), 15 minutes (time), argon plasmas and an iron target. For the carbon nanotubes forest growth, the process pressure was 15 mTorr, the RF power was 250 W, and the final time deposition was 3 hours.
The micropatterning process of CNTs forest includes conventional photolithography and oxygen plasma treatment. In this situation, the iron layer is patterned and the high aligned carbon nanotubes are grown in the regions with iron precursor and in the other regions (without iron), it occur the diamond-like carbon (DLC) formation. The results were proved by Scanning Electronic Microscopy and Raman Spectroscopy.
In conclusion, we have obtained the micropatterned deposition of high aligned single-walled carbon nanotubes by high density plasma chemical vapor deposition, using and patterned iron layer as precursor material. For this, we have used photolithography processes and plasma processing for patterning the materials. With this techniques is possible the fabrication of single-walled carbon nanotubes forest-based electronic and optoelectronic devices.

Prof.Dr. Marcos Massi

Technological Institute of Aeronautics, Plasma and Processes Laboratory, Physics Department, S. J. dos Campos, Brazil

Title lecture

Comparison between conventional and hollow cathode magnetron sputtering systems to deposition of photocatalytic anatase titanium dioxide thin films

Authors

D. A. Duarte, M. Massi, A. S. da Silva Sobrinho

Abstract

Hollow cathode magnetron sputtering is an efficient device used to improve some discharge parameters like plasma density and electron energy, whose effects contributes to the increase of the energy influx on the substrate surface. This work reports the growing of photocatalytic titanium dioxide thin films by two techniques namely, conventional magnetron sputtering (CMS) and cylindrical hollow cathode magnetron sputtering (HCMS). Titanium dioxide thin films were deposited on p-Si (100) substrates, varying some plasma parameters, such as, axial distance and oxygen concentration in the Ar+O₂ mixture. Samples were characterized by profilometry, XRD and AFM. Profilometry results shown that the deposition rate of HCMS system is higher than the deposition rate of CMS. XRD patterns shown that all films deposited by CMS system present predominantly the anatase phase, while the films deposited by HCMS system present a mixture of anatase and rutile phases. The rutile phase crystallization in films deposited by HCMS is probably attributed to the permanent conversion of the anatase phase to rutile phase, once all films deposited by HCMS reached a surface temperature of about 400 °C, that is approximately the temperature required to convert anatase phase into rutile phase. The Rrms values measured by AFM are lower for films deposited on the CMS system. This effect can be directly correlated with the energy influx on the substrate surface produced by the hollow cathode effect. The CMS is a versatile technique to grow titanium dioxide with anatase orientation that has good catalytic properties. However, the photocatalytic reactions on the titanium dioxide surface can also be optimized by increasing the surface area or the surface roughness of the film exposed to ultraviolet radiation. In this sense, the HCMS system is more appropriated to deposit photocatalytic films than the CMS system, because it predominantly deposits TiO2 films with anatase phase and higher surface roughness.

Prof.Dr. Marcos Massi

Technological Institute of Aeronautics, Plasma and Processes Laboratory, Physics Department, S. J. dos Campos, Brazil

Title lecture

Effects of Microwave Excited Plasma Treatment on Adhesion Properties of EPDM rub

Authors

Abstract

The purpose of this work was to investigate the surface treatment of EPDM (ethylene propylene diene monomer) rubber by microwave excited plasmas processes. EPDM rubber is a potential material for application in aeronautics industry mainly as thermal protection of rocket motors, due to its low specific mass, excellent mechanical properties and low cost, when compared to other elastomers used for similar application [1]. However, the EPDM exhibits low surface energy, which damages its adhesion properties to epoxy and urethane based adhesives. The use of plasma treatment is an interesting alternative to modify the rubber surface, from a few nanometers up to some micrometers, changing the surface without generating harmful byproducts, keeping unaltered the bulk properties of the material [2]. In the present work, microwave excited plasma (2.45GHz, 1kW) was used to modify the surface properties of the EPDM rubber. The samples were treated by a plasma comprised of a mixture of hydrogen, nitrogen and argon (4:1:1) in discharges with total gas flow rate of 50 sccm under pressure of 250 mTorr. The focus of this work was to verify the influence of the treatment time on the amount of superficial specimens of the samples, analyzed by X-ray photoelectrons spectroscopy (XPS) and their thermodynamics properties like surface energy and work of adhesion, calculated from goniometry data. Their mechanical properties were determined by tensile strength tests. The results showed that the plasma treatment can significantly change the contact angle, from 101° (untreated sample) to 34° (sample treated for 120 seconds), corresponding to an increase in the work of adhesion of the rubber from 59 mJ/m2 to 135 mJ/m2, and a considerable augment in the species amount present on the surface.

[1] J H Moraes et al J. Phys. D: Appl. Phys. v.40 (2007) 7747-7752.
[2] K F Grythe; F K Hansen; T Olsen J. Adhes. v.83 (2007) 223-254.

Daisaku Matsukawa

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

Title lecture

Chain Propagation in UV Curing of Difunctional Methacrylates

Authors

Daisaku Matsukawa, Haruyuki Okamura, and Masamitsu Shirai

Abstract

UV curable resins are significant materials in relation to applications for coatings, adhesives, photoresists, and printing plates. Multifunctional methacrylates are mainly used and the cured materials show excellent physical and/or thermal properties. To improve the performance of the UV curable resins, it is important to study the kinetics of photopolymerization and the chemical structures of the cured materials. However, it is not easy to investigate the network structure of the UV cured resins. Recently, reworkable resins, which are thermosets having thermally or chemically degradable properties, have been reported. These reworkable resins have attracted much attention in terms of environmental regulations and functional materials. From this point of view, we have synthesized thermally degradable difunctional methacrylates and used to elucidate the kinetic chain length of the UV cured resins. These methacrylates were photochemically cured and the cured resins were degraded to obtain linear polymers soluble in organic solvents. Size exclusion chromatography was used to measure the kinetic chain length of the UV cured resins. It was shown that the kinetic chain length of the UV cured resins was affected by the concentration of initiator, exposure dose intensity, and so on.

Christopher Mealy

Fire Protection Engineer, Hughes Associates, Inc. Baltimore, Maryland, USA

Title lecture

Intumescent coatings for application on Munition containers

Authors

Pauline Smith, Chris Mealy, Carol Wong, and William Ruppert

Abstract

Currently, the U.S. Army is evaluating the application of coatings applied to the exterior of ammunition containers to provide thermal protection to the stored munitions. Intumescent coatings are coatings that typically expand approximately 5 to 30 times the original thickness during a fire exposure. The char layer created during this expansion insulates the substrate from heat which slows the heating of the munition, thereby delaying any potential burning, deflagration, or detonation. Intumescent coatings have been successful in passive fire protection applications; however several physical tests related to the robustness of intumescent coating systems have shown poor results. This is mainly due to their limited flexibility and impact and moisture resistance. The intumescent coatings also do not fully meet sequential rough handling (SRH) requirements [1], especially at cold temperature extremes where the coatings tend to shatter off of the substrate. SRH tests are intended to be arduous to determine how long a system will endure extremes in the field before beginning to fail. The risks associated with the use of intumescent coatings are that they will not provide enough thermal insulation for the munitions, or that pockets of energetic material in the munitions may heat up during a slow cook-off scenario, causing premature detonation. Some coatings have also been observed to have durability issues when exposed to harsh environments as well as fire events.

Dale Molloy

School of Mechanical and Aerospace Engineering, Queen´s University of Belfast, Ashby Building, Belfast, UK

Title lecture

Thermal analysis of brush plated nickel sulfamate coatings

Authors

Molloy, D. A., Malinov, S., and Hill, P.

Abstract

Nickel sulfamate solution was applied to mild steel substrates by the process of selective plating. The coated samples where heated to temperatures in the range of 50 °C to 1000 °C. Thermal analysis and microscopy techniques where used to investigate the effect of secondary heating on the microstructure and composition of the surface coatings.

High temperature x-ray diffraction and thermogravimetry analysis where used to study the phase transformations occurring in the coatings during secondary heating, with optical and scanning electron microscopies being used to investigate the micro- and nanostructure changes of the heat treated coatings. In addition energy dispersive X-ray analysis was applied to investigate the local composition changes and phase transformations taking place during secondary heating. The surface hardness of the coatings as they underwent heat treatment was also investigated.

The microscopy analysis showed that the secondary heating caused diffusion within the coating itself and diffusion between the coating and the substrate. This diffusion redistribution caused a number of phase transformations and changes in the surface layers. Layer and grain growth at different conditions were investigated. The grains were also found to take their preferred orientation as they where heated. The surface hardness was found to initially rise until 200 °C before steadily decreasing.

Dr. Rino Morent

Department of Applied Physics Faculty of Engineering - Ghent University (UGent), Belgium

Title lecture

Allylamine plasma polymer films for biomedical applications

Authors

R. Morent, N. De Geyter, M. Frère-Trentesaux, P. Dubruel, C. Leys and E. Payen

Abstract

The importance of amino functionalization of polymers, for instance in biomedical applications, only starts to become apparent. In contrast to most other functional groups, the protonated amino group introduces a localized positive charge to the polymer and may, in aqueous solution at physiological pH values, primarily attract negatively charged biomolecules. In addition, due to their good chemical reactivity, amino groups are widely used in biochemistry for covalent coupling of proteins in aqueous environments. Amino groups are therefore efficient in immobilizing biomolecules and in promoting cell adhesion. In this work, allylamine will be plasma-polymerized onto polypropylene (PP) films in order to obtain PP surfaces with a high amount of amino groups. The chemical and physical properties of the obtained coatings will be discussed in detail using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM).

Dr. Ana Puala Mousinho

Laboratory of Integrated Systems (LSI) - Polytechnic SchooL of University of São Paulo, São Paulo -SP Brazil

Title lecture

Stress analyze of the diamond-like carbon films using raman spectroscopy

Authors

A. P. Mousinho, R. D. Mansano

Abstract

Carbon can exist in many forms, amorphous, glassy and crystalline. Carbon materials have been the objects of intense research in recent decades because of their unique properties and applications. Diamond-like carbon (DLC), also called amorphous diamond or amorphous carbon or tetrahedral bonded amorphous carbon, however, does not have a unique composition but consists of a mixture of amorphous and crystalline phases. Its properties vary considerably with the deposition conditions. In this work, were deposited Diamond-like Carbon (DLC) films by High Density Plasma Chemical Vapor Deposition system (HDPCVD). Recently developed high-density plasma chemical vapor deposition techniques have made it possible to produce DLC films with nano-structures formation with low surface roughness and high sp³/sp² hybridization ratio. The roughness and the sp³/sp² ratio from DLC films have been studied. The different substrates topography influences in the characteristics of the DLC films due the different surface energies obtained to the DLC films.
Five methods were used for the surface modification of the samples: with diamond powder dispersion; with graphite powder dispersion; roughness generated by plasma etching; roughness generated by wet chemical etching solution and Reference (only submitted to a chemical clean).
The Stress Analyses of the DLC films were made using the Raman Spectroscopy. In this work, we related the stress with the position of the G and D bands, creating a new method to analyze stress of the DLC films. Using this new method to analyze the DLC films stress, we have seen that DLC films with greater sp³ hybridization, show a greater displacement of the central position of the band G, in this case, these films show greater stress. The kind of the topography surfaces it also influence in the displacement of the central position of the band G and in stress of the films. Thus, using these techniques was possible analyzed the grain size and the structures of the DLC films, than are depend on the various surface topographies generated and the stress of these films using de Raman Spectroscopy

Dr. Ana Puala Mousinho

Laboratory of Integrated Systems (LSI) - Polytechnic SchooL of University of São Paulo, São Paulo -SP Brazil

Title lecture

Micro-raman spectroscopy used for analyzing the diameter distribution of high-aligned single-walled carbon nanotubes films

Authors

A. P. Mousinho, R. D. Mansanoo

Abstract

In this work, we have obtained high-aligned single-walled carbon nanotubes deposited at room temperature by High Density Plasmas Chemical Vapor Deposition (HDPCVD). The deposition system uses a new concept of plasma generation, where a planar coil coupled to an RF system for plasma generation was used with an electrostatic shield for plasma densification. In this mode, high density plasmas are obtained.
Single-walled carbon nanotubes were deposited using pure methane plasmas, the deposition process pressure was 15 mTorr and the RF power was 250 W and the final time of the deposition processes was 3 hours. We have used three kinds of substrates: metallic (steel), ceramic (alumina) and silicon wafer. To obtain high aligned carbon nanotubes, we used iron (obtained by Magnetron Sputtering 250W, 5 mTorr, 15 minutes and argon plasmas), as precursor material (seed). The carbon nanotubes were analyzed by Raman Spectroscopy, Infrared Spectroscopy and Scanning Electronic Microscopy.
Using the micro-Raman spectroscopy it was possible prove that the carbon nanotubes obtained by HDPCVD, showed different diameters. The relationship between the bands (intensities and positions) in the Raman spectrum is inversely proportional of the nanotubes diameter. Thus, we have obtained carbon nanotubes with big diameters and carbon nanotubes with diameter range of 1.2 to 1.8 nm. The Radial Breathing Mode (RBM) band in the spectra prove the presence of single–walled carbon nanotubes, and the presence of band in around 170-500 cm^-1, indicate the variation of nanotubes diameters. Using the scanning electronic microscope it was prove the results, because it was possible see the high aligned carbon nanotubes films and the variation of these diameters. Thus, we have proved that it is possible use micro-Raman spectroscopy for analyzing the high aligned carbon nanotubes diameters deposited at room temperature and these carbon nanotubes can be used for many applications.

Arturo Muñoz-Castro

Instituto Nacional de Investigaciones Nucleares, México DF

Title lecture

Surface PIII modification of CpTi for dental applications

Authors

R. López-Callejas, R. Valencia A., A. E. Muñoz-Castro, R. Peña-Eguiluz A. Mercado-Cabrera, S. R. Barocio, A. de la Piedad-Beneitez

Abstract

Specifically designed and built CpTi pieces in the shape of threaded root-form dental implants have been treated by means of plasma immersed ion implantation (PIII) in an optimised 80% nitrogen 20% oxygen mixture at 1*10^-2 Torr. The low surface wearing resistance of CpTi can thus be prevented while developing a highly biocompatible rutile phase titanium oxide layer for a better osseo-integration. Stratified TiO₂ (rutile) and TiN_x layers were identified from XRD and Raman spectroscopy. An upper rutile layer is found to be immediately followed by a nitride (TiN_x) one, which leads to a superior microhardness performance. The implant surface hardness was improved up to more than six times with respect to that of the untreated reference pieces. Most all these treatments of titanium are conducive to corrosion resistance parameters higher than those of the most usual metals used in prosthetics

Dr. K. S. Nagaraja

Department of Chemistry, Loyola Institute of Frontier Energy, Loyola College Chennai, India

Title lecture

Formation of SiC(O) by plasma assisted liquid injection chemical vapor deposition (PA-LICVD)

Authors

J. Selvakumara, D. Sathiyamoorthyb, K. S. Nagarajaa

Abstract

Low dielectric constant (low-k) materials become increasingly important for microelectronics as interconnect delays limit circuits performance. Many researchers have developed various kinds of organic, inorganic and hybrid materials as an alternative to the conventional SiO₂ film. They include various low-k materials such as SiOC, SiOF, a-C:F, SiLK, hydrogensilsesquioxane (HSQ), etc. The dielectric films formed from inorganic materials have good thermal, mechanical stability and adhesion. One of the promising methods of SiOC(–H) film deposition is plasma enhanced chemical vapor deposition (PECVD) using organosilane molecules as source materials. We hereby report the synthesis of SiC(O) material by plasma assisted liquid injection chemical vapor deposition (PA-LICVD) at 773 K in an Ar/H₂ plasma environment with methanol orn-pentane solution of organosilane as precursor. The activation energy for the evaporation of organosilane precursor was calculated as 29 kJ mol^-1 (323-337 K) using Arrhenius expression from the differential thermogravimetry analysis in high pure nitrogen atmosphere. The plasma assisted liquid injection CVD system was indigenously developed for the deposition of SiC(O). The SiC(O) deposition was carried out by using various plasma current and Ar/H₂ gas composition. The precursor solution (0.09 g mL^-1) was delivered continuously using a valveless metering pump (FMI “Q” Pump-QG 150) with a mean feed rate (0.5 mL min^-1) to the vaporizer. The films were characterized by SEM, EDX, FT-IR, TG and X-ray analysis. The surface morphology of the deposited thick films exhibit densely packed microstructures free from structural defects on various substrate materials such as Si, glass, alumina and graphite under a deposition pressure of 0.8-1 mbar. The synthesized films are SiC(O) with the thickness of ~10-15 mm. The film deposited using 0.27 A as plasma current exhibited a high oxygen incorporation and low carbon composition in the film, suggesting that the 0.18-0.25 A current range is more appropriate for depositing oxygen-free SiC thin films in the future for nuclear applications. The extensive film coverage on the surface suggests that the present CVD apparatus and process is more appropriate to industrial and technological applications.

Tatyana Nesterova

Technical University of Denmark, Department of Chemical and Biochemical Engineering, Lyngby, Denmark

Title lecture

Synthesis of durable microcapsules for self-healing anticorrosive coatings

Authors

Tatyana Nesterova, Kim Dam-Johansen, and Søren Kiil

Abstract

Self-healing materials have become a very intense field of research in the last decade. These materials have a built in capability to retain functionalities and restore structural integrity autonomically after material damage, giving advantage of a long service life and costs reductions to the objects they are used for.

In this work a self-healing concept is applied to development of epoxy-based anticorrosive coatings and utilizes incorporation of microcapsules, filled with reactive agents, into the coating matrix. Upon small damages to the coating the reagents are released from the capsules and react forming a cross-linked network which heals the crack. However, to make the concept work, microcapsules have to be strong enough to remain intact during storage, coating formulation, and application. Furthermore, the capsules must remain stable for many years in the dry coating.

Laboratory experiments, primarily conducted on encapsulation of bisphenol-A epoxidised resin into poly(urea-formaldehyde) shells, revealed a number of challenges associated with the synthesis of stable microcapsules. It was found that the nature of the core material strongly affects the microcapsule stability and performance. It also appeared that experimental procedures developed for certain core materials were not suitable for encapsulation of others without modifications. Results of experiments, aiming at finding optimal conditions for robust microcapsules production, will be presented.

Naofumi Ohtsu

Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido, Japan

Title lecture

Calcium titanate coating on titanium by simple chemical treatment using calcium-hydroxide slurry

Authors

Naofumi Ohtsu, Manabu Hayashi

Abstract

This presentation proposes a novel chemical treatment technique for calcium titanate coating on titanium. Calcium titanate film has gained considerable attention as a biomedical and photocatalytic material. Our chemical treatment technique for the formation of calcium titanate coating is as follows: the titanium substrate is buried in the calcium hydroxide-slurry prepared by mixing of calcium hydroxide powder and distilled water, and the slurry is heated in air. When using the heating temperature beyond 873 K, a stoichiometric calcium titanate coating crystallized in a pervskite-type structure could be prepared, and concomitantly, a titanium dioxide layer having rutile-type structure was formed between the calcium titanate layer and the substrate. The thickness of the calcium titanate and titanium dioxide layers was several ten and hundred nanometers, respectively, and the thickness increases with the increase of the temperature. When the substrate buried in a calcium-hydroxide powder not containing distilled water, the calcium titanate coating could not be formed. This result indicates that a slurry type reagent is effective for diffusing calcium into titanium substrate. For investigating a biocompatibility, surface modified titanium prepared through this process was immersed in a simulated body fluid. After the immersion, a hydroxyapatite layer of about several micrometers in thickness was precipitated on the plate, indicating that the modified titanium plated has sufficient biocompatibility.

Önnaz Özkanat

Materials Innovation Institute (M2i), Delft, The Netherlands & Delft University of Technology, Department of Materials Science and Engineering, Delft, The Netherlands

Title lecture

A combined FTIR-RAS and macroscopic adhesion study of the interfacial bonding of epoxy coatings on pretreated AA2024-T3

Authors

Önnaz Özkanat, S.J. Garcia, J.M.C. Mol, H. Terryn, J.H.W. de Wit

Abstract

The adhesion of organic coatings and corrosion resistance of polymer/(hydr)oxide/aluminum interfaces plays a pivotal role in the engineering of lightweight components especially for the aerospace industry. Interfacial bonds between the polymer and aluminum substrate have to withstand high mechanical forces and corrosive attack over long times to protect the functional properties of the composite. At this point, it is crucial to understand the molecular adhesion forces at these interfaces and to control the de-adhesion and delamination of organic coatings in humid and corrosive environments. This can be done by investigating and controlling the molecular bonding mechanism of the functional groups in the coating to the metal (hydr)oxide surface. Chemical pretreatments change the hydroxide fraction at the surface, the acid/base characteristics and the surface morphology and thus, the bonding of the functional groups.

In this work, the interaction of bisphenol-A based epoxy coatings on pretreated AA2024-T3 aerospace aluminum alloy surfaces is studied by means of FTIR-RAS and macroscopic adhesion tests. Besides the as-delivered state, various model pretreatments including alkaline, acid and pseudoboehmite treatments, as well as industrially relevant pretreatment were applied on the aluminum alloy surface to investigate the effect of modification of surface chemistry and morphology on the interfacial bonding. The influence of these surface pretreatments on micromolecular bonding mechanism was investigated by FTIR-RAS analysis of model compounds adsorbed on metal (hydr)oxide surface. Macroscopic adhesion of epoxy coatings was further investigated by shear and scratch tests. The results indicate a clear correlation of macroscopic adhesion and molecular bonding properties at the polymer/metal interface, with the surface chemistry and morphology of pretreated AA2024-T3 alloys.

Bahram Ramezanzadeh

Amirkabir Universiyy of Technology, Polymer and Color Engineering, Department of Polymer and Color Technology, Tehran, Iran

Title lecture

Comparison the corrosion performance of trivalent and hexavalent chromium based conversion coatings on steel

Authors

B.Ramezanzadeh, M.M.Attar, M.Farzam

Abstract

Hexavalent chromium and phosphate conversion coatings are the most important anticorrosive conventional conversion coatings for automotive surface bodies treatment. Due to the excellent corrosion performance of these treatments, they could be able to produce a conversion coating on metal substrates. However, the producing toxic and carcinogenic compounds and their irretrievable unacceptable effects on environment, they have been decreasing and replacing by the environmental friendly coatings. This study aims to investigate and compare the corrosion performance of an automotive substrate treated by an environmental friendly treatment of Cr(III) with the conventional conversion coatings of Cr(VI) and phosphate. To this end, chromium nitrate (Cr (NO3)3) was utilized as chromate bath. The Cr(III) conversion coatings were applied over the two steel metal substrates with and without mill scale. In order to obtain the optimum condition of chromium bath, samples were coated at various immersion time and pH's of chromate bath. The corrosion resistance of Cr(VI) and phosphate conversion coatings, and Cr(III) treatment were obtained using an electrochemical impedance spectroscopy (EIS) and anodic polarization in a 3.5 wt% of NaCl solution. In addition, a scanning electron microscope (SEM) was utilized to study the morphology of conversion coatings on two substrates. Results revealed that, Cr(III) treatment can produce an anticorrosion performance on steel substrate without mill scale layer. No appropriate anticorrosion performance was obtained on steel with mill scale. Comparing the results of the corrosion performance of two conversion coatings of Cr(III) and Cr(VI), it can be clearly found that although, Cr(VI) coating has had better performance than Cr(III) at shorter immersion times in corrosion environment, a comparable corrosion resistance of Cr(III) coatings can be observed at higher exposure times indicating an acceptable anticorrosion performance of this treatment on steel.

Dr. Zahra Ranjbar

Institute of Colorants, Paints and Coatings, Department of Surface Coatings and Corrosion, Tehran, Iran

Title lecture

Synthesis and Characterization of diethylene glycol monobutyl ether -Blocked Diisocyanate Crosslinkers

Authors

Z. Ranjbar, Sh. Montazeri, M. Mohammad Raei Nayini

Abstract

A solution to overcome to high reactivity and high toxicity of isocyanates that used in automotive paint and coatings is the use of blocked isocyanates. Typically blocked isocyanate systems are used to obtain the performance of two components thermally cured system. In this study 4 types of isocyanates , Hexamethylene Diisocyanate, Diphenylmethane Diisocyanate, Isophorone Diisocyanate and Toluene Diisocyanate (aliphatic, aromatic and cycloaliphatic) were blocked with one ether alcohol , diethylene glycol Monobutyl ether (butyl carbitol) and elimination of isocyanate group and creating of urethane bonds was studied by FTIR spectroscopy and titration methods. Thermal dissociation of blocked-diisocyanates was analyzed by DSC technique. Structure-property relationship of these aromatic and aliphatic blocked diisocyanates was compared by DSC and TGA technique. It was found that deblocking temperature of blocked aromatic isocyanates (MDI and TDI) are higher than aliphatic ones (IPDI and HDI) and presence of catalyst (DBTL) was important for synthesis of blocked diisocyanate and affects on deblocking temperature.

Celia Ribes

Instituto de Tecnología Cerámica. Asociación de Investigación de las Industrias Cerámicas. Universitat Jaume I. Castellón, Spain

Title lecture

Relation between the scratch resistance and the chemical structure of organic-inorganic hybrid coatings

Authors

Yolanda Bautista, Pilar Gómez, Celia Ribes, Vicente Sanz

Abstract

Organic inorganic hybrid materials can be defined as material combining organic an inorganic domains in a nanometric scale. The development of these organic inorganic hybrids has achieved together properties from both organic and inorganic realms, in the same material.
In this research we have study the scratch behaviour of coatings of organic inorganic hybrid materials prepared by sol-gel processing, using as precursors, trialkoxysilanes with organic functionalities (covalently bonded) capable of polymerize by free radical polymerization. We have also evaluated the influence of pure inorganic precursor as tetraalkoxysilanes or pure organic precursors on the scratch behaviour. The main goal of this research was to evaluate how the chemical structure of the organic inorganic hybrid influences the scratch behaviour of the coatings.

Vinicius Rizzo

Laboratory of Integrated Systems (LSI) - Polytechnic SchooL of University of São Paulo, São Paulo -SP Brazil

Title lecture

Electro-optical sensitive Diamond-Like Carbon (DLC) coatings deposited by reactive magnetron sputtering for electronic devices application

Authors

V. Z. Rizzo, R. D. Mansano

Abstract

DLC films were deposited by reactive magnetron sputtering on silicon and quartz substrates, The DLC films properties are consequences from the relation between sp³, sp² and sp¹ hybridizations, which is consequence from the deposition technique and conditions. The optical and electric properties of DLC films are crucial for the development of electro-optical devices as photo detectors.
It was produced eight samples of DLC films, varying the reactor pressure between 5 mTorr and 10 mTorr and the RF power was applied at 13.56 MHz and varied between 100, 150, 200 and 250 watts. The DLC films were analyzed by its electric resistivity, dielectric constant, Raman analysis, in order to determine the sp³/sp² ratio of the C-C bonds, and the photoluminescence of the films. Then, these characteristics were compared and the influence of the deposition parameters was studied. These characterizations allow relating the chemical bond structure to the electric and optical characteristics of the films.

Matthias Rydzek

Bayerisches Zentrum fuer Angewandte Energieforschung e.V., Abteilung: Funktionsmaterialien der Energietechnik, Bavarian Center for Applied Energy Research, Division: Functional Materials for Energy Technology, ZAE Bayern, Wuerzburg, Germany

Title lecture

Comparative Study of Sol-Gel Derived Tin-doped Indium- and Aluminum-doped Zinc-Oxide Coatings for Electrical Conducting and Low-Emitting Surfaces

Authors

Matthias Rydzek, Matthias Reidinger, Maria-Carla Arduini-Schuster, Jochen Manara

Abstract

In addition to the well-established functional coatings of doped indium oxides (e.g. indium tin oxide - ITO), cost-efficient transparent conductive oxide (TCO) compounds based on doped zinc oxides (e.g. aluminum zinc oxide - AZO) have been investigated. The electrical, morphological and optical properties of both types of coatings are compared. Furthermore, the influence of sintering temperature and process-gases on the layer qualities is discussed.

At ambient temperature, the contribution of thermal radiative transfer to the total heat transfer is very significant in many applications. Here, the emittance of a surface is of mayor importance regarding its radiative exchange with its surroundings. Low-emitting surfaces can significantly decrease the radiative heat transfer by reducing the emission in the infrared spectral region or by reflecting the main part of the incident infrared radiation. For the deposition of transparent conductive oxides, such as tin-doped indium oxide and aluminum-doped zinc oxide on various substrates, improved sol-gel processes have been developed. Colloidal solutions consisting of inorganic precursors were applied via dip-coating or similar methods, crystallized on the substrate and subsequently annealed in order to enhance the number of free charge carriers and the electrical conductivity, respectively.

In addition to the conventional layer properties like high transparency in the visible spectral region, this work mainly focuses on the comparison of the infrared-optical characteristics in the mid and far infrared spectral region. The directional-hemispherical reflectance and transmittance of functional tin-doped indium oxide and aluminum-doped zinc oxide multilayer structures with thicknesses of 30 to 500 nm were measured in the wavelength range between 0.25 and 35 µm and the thermal emission was calculated and correlated with the electrical layer properties and the doping level of the coatings.

Important characteristics of the coatings such as thickness, smoothness, porosity, charge-carrier mobility and concentration, doping level, band gap as well as the position of the plasma wavelength were influenced by varying the preparation parameters. To gain further insights, the films were analyzed using SEM, EDX, XRD and 4-point conductivity measurements.
Both types of the functional coatings are highly transparent in the visible spectral region with over 80 % and their specific resistivity reaches values up to 3.0×10-4 W×cm. By applying multilayered coatings on a float glass substrate, the surface emittance was reduced from 89 % to less than 20 % in the infrared spectral range.

Sudeshna Saha

Université du Québec a Chicoutimi, Canada

Title lecture

Photo-stabilization of Acrylic Polyurethane Coatings for Exterior Application on Wood Using Bark Extract

Authors

Sudeshna Saha, Duygu Kocaefe, Yaman Boluk, Andre Pichette

Abstract

Heat-treated wood is a value added product which has many advantages compared to non-treated wood e.g., improved dimensional stability, biological resistance and thermal insulating capacity and moreover an attractive dark color. Saguenay-Lac-St-Jean region of Quebec in Canada is the leader of heat-treated wood in North America.Exposure of heat-treated wood to various environmental factors such as solar radiation, water, heat, pollutants etc. for long periods leads to photochemical reactions resulting in discoloration of wood surface. With the move towards added-value products and with higher quality product specifications discolorations have become an important, economic problem. Therefore, color defects are less tolerable and they ultimately lead to a reduction of some physical, chemical and biological properties of heat-treated wood. In order to increase the service life of this new non toxic product, development of environment friendly transparent coatings with minimal use of chemicals is very important for wood industries. For coating development, the main challenge lies in balancing between aesthetic and protection. From the aesthetic point of view the consumer´s trends favor the natural look of the wood whereas best protection is provided by the pigmented coatings which tend to cover the wood surface. For exterior exposure, clear coatings are not recommended since lignin present at the surface beneath the coatings can easily absorb UV radiation and photo degradation occur. This leads to delamination of coating, consequently, to catastrophic failure. Water based acrylic polyurethane coatings have wide applications and chosen for this study because of their high durability characteristics and environment friendliness. In this study, the acrylic polyurethane coating is further improved by adding natural antioxidant (bark extract) and lignin stabilizer in order to have a better resistance against different weathering factors. An accelerated aging test has been carried out for comparing performances of different coatings, thus, predicting their longevity when exposed to different environmental factors. The color changes of acrylic polyurethane coating prepared with different additives are measured before and after different weathering times. Also the gloss changes are studied as a function of aging time. The modifications in chemical structure of coatings are characterized by ATR-FTIR analysis. The color change data shows that coatings containing bark extract and lignin stabilizer are the most promising coatings for UV protection of heat treated wood. The results are compared with those of the best available industrial pigmented semitransparent solvent borne coating.

Alireza Salehi Movahed

Wallenberg Wood Science Centre (WWSC) and, Department of Fibre and Polymer Technology, School of Chemical Science and Engineering. KTH, Royal Institute of Technology. Stockholm, Sweden

Title lecture

Effect of phenolic lignin structures on the oxidation of unsaturated fatty acids

Authors

Alireza Salehi Movahed, Stacy Trey, Gunnar Henriksson1, and Mats Johansson

Abstract

One of the problematic issues in oil-wood drying processes is the complex auto-oxidation mechanism of the fatty acids during wood treatments. Numerous studies have been performed on the oxidation of unsaturated fatty acids, both catalyzed and un-catalyzed, to reveal more details on the different reaction routes. [1,2,3] Less has however been studied on the chemical interaction between the wood substrate itself and an air-drying oil. Previous result however indicates that wood can accelerate the oxidation of drying oils although the exact mechanism for this is unclear.[4] The present investigation has been focused on studying the autoxidation of methyl linoleate in combination with lignin model compounds to reveal more details on how the chemical interaction between wood and an air-drying system affect the drying. Lignin acts as a cementing and fixating structure between wood cells and is one of the more hydrophobic constituents of wood why a chemical interaction between lignin and an oil can be expected.[5] Methyl linoleate autoxidation process was analyzed alone and combined with 1wt% of phenolic and non-phenolic lignin model compounds at 70 °C. The effect of the lignin compounds on methyl linoleate autoxidation process was investigated with different analytical techniques. The process was studied using nuclear magnetic resonance (NMR), Size exclusion chromatography (SEC), and real-time infrared spectroscopy (RT-IR) as experimental techniques. The results show that phenolic groups and radical conjugation are the main contributors to an antioxidant effect of lignin compounds on the oxidation rate of the methyl linoleate. None of the model compounds increased the oxidation rate. Effects were seen even with heterogeneous systems due to a slight solubility or interface interactions. The degree of chemical interaction can be observed by the retarding effect on this oxidation process with greatest to least effect being: ferulic acid > syringaldehyde > 2-propen-1-ol, 3-(3,4-dimethoxyphenyl) > vanillin > 3.4.5-Trimethoxy-benzyl-alcohol. This is opposite to the previous findings that wood accelerates the drying of oxidative oils indicating that other wood constituents including extractives, trace metal ions, cellulose, and hemicelluloses along with external effect such as UV light and temperature also affect the oxidation.

References

1. Porter, N.; Wujek, J. Journal of Organic Chemistry, 52, (1987), 5058-5089.
2. Porter, N.; Wujek, J. Am. Chem. Soc. , 106, (1984), 2626-2629.
3. Okan Oyman, Z. "Towards Environmentally Friendly Catalysts For Alkyl Coatings", Doctoral thesis, Technische Universiteit Eindhoven, ISBN 90-386-2916-8, Eindhoven, The Netherlands, (2005).
4. Stenberg, C. "Influence of the fatty acid pattern on the drying of linseed oils", licentiate thesis, Fiber and Polymer department, ISBN 91-7283-811-6, KTH, Stockholm, Sweden (2004).
5. Lawoko M, Henriksson G and Gellerstedt G Holzforchung, V60, (2006), 156 - 161.

Mahdi Samadzadeh

Petroleum University of Technology, Abadan, Iran

Title lecture

Tung Oil: An Autonomous Healing Agent for Self Healing Coatings Based on Microcapsules as Core Material

Authors

M. Samadzadeh, S. Hatami Boura, M. Peikari, M. Kasiriha, A. Ashrafi

Abstract

The capability of the encapsulated Tung oil was investigated as a crack healing agent for self healing coatings. Encapsulation of Tung oil with urea-formaldehyde shell was carried out by in-situ polymerization. Before the mechanical agitation of microcapsules into epoxy resin (EPON-828), their characteristics were evaluated by optical microscopy, Scanning Electron Microscope (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). Released Tung oil from ruptured microcapsules healed the artificial crack in the coating matrix successfully. The self repairing process observed on optical microscopy; corrosion resistance of healed area was evaluated by Electrochemical Impedance Spectroscopy (EIS) and the results were compared with neat epoxy coating.

J. Selvakumar

Department of Chemistry, Loyola Institute of Frontier Energy, Loyola College Chennai, India

Title lecture

Evaluation of Vapor pressure measurements of M(tmhd)x [M= La(III), Sr(II) and Mn(III); tmhd - 2,2,6,6-tetramethyl-3,5-heptanedione] for Plasma-assisted LICVD process of metal oxide thin films

Authors

Abstract

The congruent vaporization of La(tmhd)3, Sr(tmhd)2 and Mn(tmhd)3 were verified from the molar mass of the vapor species obtained using FAB-mass spectra (MS), thermogravimetry (TG) and vacuum sublimation techniques. The sublimed product was found to have the same XRD and FT-IR as the initial product taken. The equilibrium vapor pressures over a temperature span of 395-542 K was determined by adapting a calibrated horizontal dual arm single furnace thermo-analyzer as a transpiration apparatus. The temperature dependence of pe/Pa could be represented as Clausius - Clapeyron equation by the least squares expression are:

La(tmhd)3: ln[pe/pa\ = -13695 ± 369 K/T + 36 ± 1 (446-509 K) r = 0.9964
Sr(tmhd)2: ln[pe/pa] = -10113 ± 441 K/T + 27 ± 1 (457-542 K) r = 0.9869
Mn(tmhd)3: ln[pe/pa] = -9465 ± 496 K/T + 29 ± 1 (395-437 K) r = 0.9918

The equilibrium vapor pressure data yielded a straight line when ln pe- was plotted against reciprocal temperature, leading to standard enthalpy of sublimation (ΔsubH°) values of 114±3, 84±3 and 79±4 kJ mol^-1 for La, Sr and Mn tmhd complexes, respectively. The activation energy of the complexes was calculated from non-isothermal TG studies using model fitting and isoconversional techniques. Thin films were grown at 773 K on alumina and Si substrates using a single solution source of La, Sr and Mn tmhd complexes dissolved in triglyme. These films were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray for their composition and morphology. The surface morphology analysis using scanning electron microscopy (SEM) revealed a grainy and densely packed agglomerates structure for films. Chemical analyses by energy dispersive X-ray (EDX) analysis showed the presence of lanthanum and strontium in the films, due to lower percentage of Mn added in the process, could not be identified from EDX analysis. Complete evaporation as single step at lower temperature of the synthesized precursors is identified themselves as an ideal precursor for CVD applications.

Sheila Shahidi

Technical University of Liberec, Department of Textile Chemistry, Faculty of Textile, Liberec, Czech Republic

Title lecture

Influence of plasma sputtering treatment on wool natural dyeing and their antibacterial activity

Authors

Sheila. Shahidi^1,2,*, Mahmood.Ghoranneviss³, Jakub.Wiener^1
1 Department of Textile Chemistry, Faculty of Textile, Technical University of Liberec, Liberec, Czech Republic
² Department of Textile Chemistry, Faculty of Engineering, Science and Research Branch, Islamic. Azad University, Tehran, Iran
³ Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, P.O.Box: 14665-678, Tehran, Iran

Abstract

In this paper, the effect of low temperature plasma treatment on the natural dyeing properties of wool and the possibility of substituted it for mordant treatment was studied. The Madder and Weld were used as a natural dyes and Copper sulphate (CuSO4) as a metal mordant. Moreover, Copper were used as an electrode, in DC Magnetron Plasma Sputtering System. For natural dyeing, first some of wool samples were treated with mentioned mordant, and some of them were sputtered with copper metal particles, using plasma sputtering treatment. Then all of wool samples were dyed with mentioned natural dyes. The color strength of plasma treated and untreated samples were analyzed using Reflective Spectrophotometer. Washing and light fastness were investigated and the results show that, the color strength and fastness of dyed wool samples are improved after plasma treatment. The antibacterial counting test was used for determination of antibacterial efficiency of both plasma treated and mordanted samples and durability of antibacterial properties was compared.
As a result, it can be concluded that the low temperature plasma treatment could improve the natural dyeing on wool in replace on mordant treatment. Also this treatment causes increase the efficiency of antibacterial activity.

Peyman Taheri

Materials Innovation Institute (M2i) and Delft University of Technology, Department of Materials Science and Engineering, Delft, The Netherlands

Title lecture

Evaluation of interfacial bonding of succinic acid on pure zinc by means of XPS and FTIR

Authors

P.Taheri, J.M.C. Mol, H. Terryn, J.H.W. de Wit

Abstract

The present paper investigates the correlation between the macroscopic adhesion properties of polymer coatings on galvanized steel and the nature of molecular interfacial bonds between the functional groups of the polymer and zinc-coated steels. Despite the extensive research done on the macroscopic adhesion properties of polymer coatings on metals, some questions still remain concerning how exactly the interfacial properties are influenced by the chemical composition and morphology of the metal surface versus the functionalities present in the organic coating. One approach is to investigate in detail how maleic anhydride grafted or copolymerised polyolefin polymer is bonded to the zinc surface. In order to mimic the interaction between the functional groups and zinc surfaces, succinic acid molecules were adsorbed on a variety of chemically pretreated zinc surfaces. Zinc surfaces mainly consist of Zn, ZnO, Zn(OH)₂ phases. However, variation of the chemical treatment of the zinc surfaces prior to succinic molecule adsorbance results in different composition ratios of the (hydr)oxides and carbonates. Any changes in the composition and morphology of metal surfaces can dramatically change the bonding characteristics of the polymer coating. For this reason, it is crucial to understand the molecular adhesion mechanisms and forces at these interfaces which control the (de)adhesion of polymer coatings in different environments. In this work, X-ray Photoelectron Spectroscopy (XPS) and Fourier Transform Infrared Reflection Absorption Spectroscopy (FTIR-RAS) are combined to evaluate the zinc surface composition, the amount of adsorbed molecules and the interaction mechanism between the succinic acid functionalities and the differently pretreated zinc surfaces. This study underlines the major importance of a detailed fundamental understanding of the metal surface chemistry with respect to interfacial bonding mechanisms.

Prof.Dr. David I. Tetelbaum

Leading Researcher, Physico-Technical Research Institute, of University of Nizhny Novgorod, Nizhny Novgorod, Russia

Title lecture

Unusual influence of weak light irradiation on defect and defect-related properties of metal foils and semiconductor wafers covered with thin dielectric films

Authors

D.I. Tetelbaum, E.V. Kuril´chik, S.V. Tikhov, Yu.A. Mendeleva, G.P. Pokhil

Abstract

Recently we have discovered some unusual effect for metal foils and semiconductor wafers irradiated at certain conditions by the white light with rather weak (practically nonheating)intensities. The effect manifests itself in the change of defect-related properties revealed near the sample side that is opposite to the irradiated one. This phenomenon was investigated by means of several methods: microhardness, Rutherford back-scattering/channeling and photo-e.m.f. This effect only takes place for samples covered by thin dielectric films, e.g. native oxide. Most prominent features of the effect are as follows.

• The effect is observed for many kinds of materials: metal foils (Cu, Ni, Mo, Co, Al, permalloy, amorphous alloys, etc.) and semiconductor wafers (Si, GaAs).
• The effect is not revealed for the samples with low concentration of extended defects, such as "dislocation-free" silicon and perfect epitaxial layers.
• In the case of irradiation with unfiltered white light, changes only take place at the side, that is opposite to the irradiated one; however, the changes take place on each sides, if the filter cutting off the short-wave part of spectrum is used.
• Dependence of the change magnitude on irradiation duration has nonmonotonous shape.
• After stopping the irradiation, the effect magnitude falls down; the characteristic time of the magnitude vanishing is ~30 min at room temperature and decreases with elevation of temperature with the activation energy ~0.2 eV.

It is proposed that the effect is caused by the excitation of acoustic waves in the film-substrate system. These waves result in transformation of state of defects and change in the defect-related properties of solids. Role of photoemission of electrons from metal or semiconductor into dielectric layer is considered and conformed by influence of spectral composition of light.

Prof.dr. Funda Tihminlioglu

Izmir Institute of Technology, Chemical Engineering Department, Urla Izmir, Turkey

Title lecture

A Novel Biodegradable Polymer Nanocomposite Coating for the Protection of Stone Monuments

Authors

Ocak Yilmaz, Aysun Sofuoglu, Hasan Böke, Funda Tihminlioglu

Abstract

Degradation and deteoriation of stone based monuments mainly depends on water absorption and water vapor permeability in the presence of air pollutants. Therefore, to increase the water repellency from the stone surface is the most important issue on the protection of stone. This can be achieved by coating the surface which can repel the water. For the historical monuments the International Conservation Community of Historic Monuments and Building requires reversibility and repeatability properties on the coating agent when the surface is modified for the protection.

In this study, the effectiveness of the biodegradable polymer nanocomposite coatings on the marble surfaces was investigated. Two different types of nanofillers (clay, silica) were used for the preparation of polymer-nanocomposite coatings. Marble plates were coated by using a dip coating apparatus. The examination of uncoated and coated surfaces were compared by observing surface roughness and morphology, capillary water absorption, water permeability color alteration, and surface hydrophobicity depending upon the nanofiller type and concentration. The results indicated that the addition of nanofillers improved the surface hydrophobicity depending on the filler concentrations (1, 3, 5 and 7 wt %). The optimum filler concentration was obtained at 7 wt % for both fillers type. At this concentration, the water permeability and capillary water absorption values of biodegradable polymer coated marble surfaces were in agreement with the surface hydrophobicity results. The nanofiller addition on the color of the coated surfaces did not change significantly. Consequently, biodegradable polymer nanocomposites can be potential environmentally friendly candidate coating agent.

H. Vakili Tahami

Surface Coatings and Corrosion Department, Iran Color Research Center, Tehran, Iran

Title lecture

Colloid stability and electrokinetic characterization of waterborne epoxy amine adducts

Authors

H. Vakili Tahami, Z. Ranjbar and S. Bastani

Abstract

Restrictions on volatile organic compounds have forced the producers of solvent-based coatings to develop safer products. Water dispersions of epoxy resins are successfully replacing solvent-borne products in the coating industry. This study is focused on analyzing the colloidal stability of epoxy amine adducts. The epoxy amine adducts were prepared by modification of epoxy (DGEBA) resin with various amount of diethanol amine and characterized by FTIR. The resulted self-emulsifying epoxy resins were dispersed in a mixture of acetic acid and deionized water. The stability behavior of these colloidal dispersions was studied by the analysis of time-resolved Nephelometric measurements. The experimentally resulted stability ratios were compared to current models, relating the stability ratio to intermolecular forces between particles. The Hamaker constant and the diffuse potential obtained from the stability ratio plot by using the DLVO and Fuchs theory and used to calculate the total interaction energy at several electrolyte concentrations. A set of parameters were found that provide critical coagulation concentration values that were in accordance with the experimental one. Moreover, the analysis of the theoretical pair interaction energy suggests that better colloidal stability was observed for the specimens with higher amount of reacted amine, which has a higher surface charge value.

Jesus Manuel Vega

CENIM/CSIC, Departamento de Ingeniería de Materiales, Degradación y Durabilidad, Madrid Spain

Title lecture

Paint systems formulated with calcium-exchanged silica pigment. Effect of steel surface preparation in the anticorrosive behaviour

Authors

N. Granizo, J.M. Vega, D. de la Fuente, J. Simancas, B. Chico and M. Morcillo

Abstract

Until recent years many anticorrosive paint formulation technologies have relied on the use of chromates as inhibitor pigments of the metalic corrosion, especially in the case of steel, due to theirexcellent cost/efficiency ratio. However, the toxicity of hexavalent chromium compounds, both for human health, with carcinogenic effects, and the environment, is giving rise to severe restrictions on their use. One such alternative, which is very attractive from a scientific point of view, is the use of ion-exchangeable pigments.

Is well known that the primer paint coating is a critical element in the anticorrosive behaviour of the paint systems preserving the metallic state of the substrate, and anchoring the paint coating to the steel base. Therefore the surface preparation plays an important role to the success of protective paint systems.

In this research, following a previous study on alkyd paint primers formulated with Ca/Si pigment and applied over carbon steel [1], the effect of the sanded treatment of the base steel, prior to application of the primer paint, and the application of an enamel alkyd topcoat layer over the primer coating have been studied. A traditional zinc chromate pigment has also been included in the study for comparative purposes.

To study the anticorrosion behavior of organic coating systems various accelerated corrosion laboratory tests were carried out: Condensing Humidity, Salt Fog and Kesternich. The degree of coating deterioration has been monitored by recording the degree of blistering, underfilm corrosion, degree of oxidation in scribe and delamination from scribe. Electrochemical impedance spectroscopy (EIS) has also been applied to know in depth the mechanisms and the anticorrosive capacity of this ion exchange pigment when is incorporated in the paint coating system.

Perumal Venkatesan

Central Electrochemical Research Institute, Karaikudi,India

Title lecture

Corrosion Behavior of reinforcement with speciality coating embedded in concrete and Exposed At Atmospheric, High Tide Levels And Immersed In Seafloor For Four Years

Authors

P.Venkatesan, A.Madhava Mayandi

Abstract

Corrosion of reinforcement is a major problem in the concrete structures constructed in marine as well as in industrial areas. In this research paper corrosion of mild steel plain reinforced concrete exposed at atmospheric, high tide levels and immersed in seafloor for four years is presented. The reinforcements are coated with speciality coatings for corrosion protection namely cement polymer composite. The corrosion behavior of coated as well as uncoated reinforcement is monitored periodically using Open Circuit Potential (OCP) measurements. After completion of four years the reinforced concrete specimens were subjected to the following measurements linear polarisation resistance (LPR), a.c. impedance, electrochemical noise (ECN) and weight loss. Based on the above measurements using Stern-Geary equation the corrosion rate was calculated. Corrosion rate was greater for the specimens immersed in seafloor. The pH measurement, chloride analyses were also carried out. The results are presented and discussed. Biofouling was predominant on completion of three months immersion.

Reference

A. Stoica-Guzun et al., Nucl. Instr. And Meth. in Phys. Res. B. 265 (2007): 434-438.
A. Linggawati et al., European Polymer Journal. 45 (2009): 2797-2804.

Dr. Mariëlle Wouters

TNO Science and Industry, Eindhoven, The Netherlands

Title lecture

Digital Dyeing - towards a more environmental friendly functional fabric

Authors

Mariëlle Wouters, Frank Vercauteren, Ralph Stevens, Timme Lucassen, Aike Wypkema

Abstract

Digital printing, finishing and dyeing are the future for the textile industry. The functionalisation technology based on digital micro-disposal of functional compounds through arrays of programmable nozzles will allow on-demand production at high speed effective at ambient temperature under atmospheric conditions and will support a wide range of functionalities, thus offering a good balance between user acceptance and reduced environmental impact.
Within this contribution we will present a comparison between conventional and digital dyeing of fabrics. The characterisation of fabrics, as a complex porous substrate for the functional coatings, will be presented as a starting point as well as a model system that describes the interaction of the coating formulation with the porous substrate.
The effect of particle size and particle size distribution of functional components in the formulation as well as the porosity (pore size) and polarity of the substrate are important parameters in the model that will be demonstrated.

Te-Hui Wu

Technische Universiteit Eindhoven, Departement of Chemical Engineering and Chemistry, Laboratoyr of Materials and Interface Chemistry, Eindhoven, The Netherlands

Title lecture

A DSC isothermal study on the curing kinetics of epoxy/ amine/ carbon black system during the formation of nanocomposite

Authors

T H Wu, A. Foyet, A. Kodentsov, L. G. J. van der Ven, R. A. T. M. van Benthem, G. de With

Abstract

The effects of carbon black nanoparticles (CBN) on the reaction of a bisphenol-A based epoxy cured with polyetheramine have been studied by using a differential scanning calorimeter (DSC). Composites with CNB concentrations 0, 1.5, and 2.5 wt% were prepared and the curing reactions were performed at 50 °C, 70 °C, and 100 °C, respectively. The curing reaction for all curves can be described well with the autocatalytical model. The results first showed that the overall curing reaction was accelerated in the presence of CBN, and at composite with CBN concentration 2.5 wt% the highest reaction rate was observed. This might be attributed to the hydroxyl groups, which were located on the CBN surface and further enhanced the catalytic reaction. Moreover, it was found that the curing conversion was first increased in the presence of CBN till 1.5 wt%, and then was reduced with additional CBN concentration. Corresponding results were observed in the T_g measurements. The T_g reached a peak at 1.5 wt% CBN and then decreased with increasing CBN concentration. Further experiments and analysis are needed to confirm this observation.

Lee Ying-Chieh

Department of Materials Engineering National Pingtung University of Technology and science, Pingtung, Taiwan, R.O.C.

Title lecture

The Effect of Cu Doped on Microstructure and Phase Transformation of ZnTiO₃ Thin Films Prepared by RF Magnetron Sputtering

Authors

Ying-Chieh Lee, Po-Shun Chen, Yi-Bin Chen

Abstract

Cu doped zinc titanate (ZnTiO₃) films were prepared using RF magnetron sputtering. Subsequent annealing of the as-deposited films were performed at temperatures ranging from 600 to 900 °C. It was found that the as-deposited films was amorphous and contained 0.84 wt% Cu. This was further confirmed by the onset of crystallization that took place at annealing temperatures 600 °C. The phase transformation for the as-deposited films and annealed films were investigated in this study. The results showed that Zn₂Ti₃O₈, ZnTiO₃, and TiO₂ can exist at 600 °C annealing. When annealing is at 700 °C, the results revealed that ZnTiO₃ main phase with Zn₂Ti₃O₈ and TiO₂ minor phase can be existed. Unlike pure ZnTiO₃ films, this result shows that the hexagonal ZnTiO₃ phase stable at temperatures above 700 °C. It means that the Cu doped on ZnTiO₃ films leads to formation of ZnTiO₃ phase at lower temperature (600 °C). However, it was found that decomposition from hexagonal ZnTiO₃ to cubic Zn₂TiO₄ and rutile TiO₂ took place with a further increase in temperature to 900 °C. Unlike bulk ZnTiO₃ ceramics, the results exhibit that the hexagonal ZnTiO₃ phase remained stable at temperatures below 945 °C, followed by decomposition to cubic Zn₂TiO₄ and TiO₂ phases at 945 °C, as indicated in the phase diagram of ZnO-TiO₂.

Ju Young Yook

Hybrid Materials Research Center, Korea Institute of Science and Technology, Seoul, Korea

Title lecture

Epoxy Type Sol-Gel Coating on Poly(ethylene terephthalate) Surface Treated with Nitrogen-Containing Plasma

Authors

Ju Young Yook, Jaeho Jun, Soonjong Kwak

Abstract

Hybrid materials containing inorganic metal oxide (MO_x) layers on polymeric substrates are attracting increasing interests in many scientific and industrial areas. However, one of the problems in preparing these hybrid materials is an easy delamination of metal oxide layers from polymeric surfaces due to poor adhesion and large differences in thermal expansion coefficients between the two materials. Therefore in order to improve their adhesion properties, various surface treatment techniques have been developed for polymeric surfaces, including wet chemical methods treating with dichromate/sulfuric acid or hydrogen peroxide/sulfuric acid as well as dry methods including plasma or ozone treatment, where surface hydroxyl groups are commonly incorporated. Afterwards the surface hydroxyl groups take part in sol-gel reactions and form chemical bonds with metal oxide layers, leading to an improvement in adhesion properties. However, since C-O-M bonding formed at the interface is usually weak to moisture, a delamination with time commonly occurs.

In the present study, nitrogen-containing plasma treatment of poly(ethylene terephthalate) (PET) surfaces was performed with the purpose of incorporating amino groups on the surface of PET and the incorporated amino groups were utilized as anchoring sites for epoxy type sol-gel coating. For reliable determination of amino groups, we have employed a chemical derivatization of amino groups and then subsequently analyzed the surface with XPS. In conjunction with the derivatization method, optical emission spectroscopy (OES) analysis of the gas-phase plasma glow and FTIR analysis of the treated PET surface have also been used to understand the chemical processes occurring on the PET surface during the nitrogen-containing plasma treatment. The durability of the epoxy sol-gel coating was tested and compared with that of regular sol-gel coating using surface hydroxyl groups for interfacial bonding.

Dr. Jörg Ulrich Zilles

Quarzwerke GmbH, High Performance Fillers, Frechen, Germany

Title lecture

Highly transparent Micro Fillers for the Enhancement of UV-Curable Lacquers

Authors

J.U.Zilles

Abstract

The usage of micronized fillers in UV curing parquet lacquers is not common due to lack of transparency.Nevertheless there is the tendency, to use fillers more and more to increase scratch resistance and for cost reduction reasons. Nano additives are able to increase scratch resistance but the usage is limited due to lack of economic efficiency. Formulations for highly transparent, lacquers on the basis of different acrylat-binders have been developed with different micro-High-Performance-Fillers. A characterization regarding optical and applicable properties as well as different methods of scratch resistance tests were made.