Mica pigments in solvent free coatings systems

Mica pigments are nowadays extensively used in different solvent containing paint systems, e.g. in automotive paints. Although water-borne coatings are gaining more and more importance, the need for even more environmentally safe to use coatings calls for coatings with less or even no solvents. To achieve this goal—no solvents—basically two technologies are used: one is powder coating, the other is radiation curing like UV- and electron beam-curable systems. Together with the need for more environmentally safe paint systems the consumer also requests highly esthetic coatings, especially concerning colour and effect. This paper describes how mica pigments, which are themselves environmentally safe and are used for high esthetic requirements, work in solvent free paint systems like powder coating and radiation-curable systems. Special attention is given to how mica pigments can be incorporated into powder coatings and what measures have to be taken to achieve an optimised effect. Concerning radiation, especially UV-curable systems, the advantages of mica pigments compared to other effect pigments are discussed.     

Organic vs inorganic light stabilizers for waterborne clear coats: a fair comparison

As a consequence of regulatory pressure to reduce solvent emissions, there is high growth rate of ??compliant technologies?? such as waterborne (WB) coatings. However, a change from conventional solventborne (SB) to WB technologies should not compromise the protective function of the coatings and the used raw materials. The use of light stabilizers, such as UV absorbers (UVA) and hindered amine light stabilizers (HALS) are state-of-the-art and largely improve the coating durability and service lifetime. Today in the case of UVA one has to differentiate between inorganic and organic products: the most widely used organic UVA for coating applications are 2-(2-hydroxyphenyl)-benzotriazole (BTZ) and 2-hydroxyphenyl-s-triazine (HPT) derivatives. Inorganic products are ideally nano particulate materials??so-called mineral screeners (MS)??comprised of titanium dioxide (TiO₂), zinc oxide (ZnO), or cerium oxide (CeO₂). The challenge here is to convert existing products which are in general hydrophobic substances into product forms that enable easy incorporation and unproblematic dispersion into WB systems. This article describes UV absorbers which are commercially available for waterborne coatings. Different classes are tested with regard to their protective function in joinery coatings as well as with regard to their influence on coatings color and transparency. The findings of this study showed clearly that the 2-hydroxyphenyl-s-triazine class outperforms all other UVA in terms of long-term performance without influencing initial coating properties.     

Confocal Raman microscopy study of the melamine distribution in polyester–melamine coil coating

Hexamethoxymethylmelamine, a common crosslinker used in combination with polyester resins to prepare thermosetting coatings, can self-condense during curing and in theory build up regions with high crosslink density (melamine enrichment). This distribution may affect such properties as the “local” glass transition temperature and structural heterogeneity and thereby modify formability, stain resistance, and weatherability. The self-condensation regions have not previously been observed in detail so their distribution in the film is unclear. Confocal Raman microscopy (CRM) has been used to characterize the melamine distribution in three polyester–melamine paint systems: one clear and two pigmented coil coatings. Both the surface mapping and depth profiling features of CRM were used to perform a 3D analysis. The depth profiling of the clear coating was performed in a nondestructive way, but due to the opaque nature of the pigments, cross sections of the pigmented coatings were prepared in order to facilitate the analysis of the melamine distribution through the film thickness. Melamine-enriched zones were found on the surfaces of all three samples. They appeared to be approximately spherical with diameters of around 5 μm. It was also observed from the cross sections that the melamine-enriched zones appeared as “particles” distributed randomly through the coating. The Raman spectra collected at these regions show significantly higher triazine ring band intensity. All of these findings confirm the hypotheses constructed over the past 20–30 years. This paper was awarded Second Place in the 2008 FSCT Roon Awards competition held as part of the FutureCoat! conference sponsored by the Federation of Societies for Coatings Technology, in Chicago, IL, on October 14–16, 2008.     

Synergistic effect of hindered amine light stabilizers/ultraviolet absorbers on the plasticized PVC during photo-irradiation

Two kinds of piperidine derivatives including a low-molecular weight (Wt. 481, T770) and a high-molecular weight (Wt. 2000–3100, C944) hindered amine light stabilizers (HALS) are added singly or with ultraviolet absorbers (UVA) in combination to plasticized poly(vinyl chloride) (PVC) samples. Digital photos, color changes, attenuated total refection-Fourier transform infrared spectra (ATR-FTIR), and mechanical properties are obtained to investigate the photostable effect of the light stabilizers on the plasticized PVC after artificial aging. PVC samples with HALS perform well at the first 400 h of irradiation in color change, FTIR, and mechanical properties, but at the last 400 h the photostability decreases. Besides, C944 performs better than T770, because C944 is a high-molecular weight UV stabilizer and has good extraction resistance. Plasticized PVC samples with UVA resist discoloring and photooxidation from the photo-irradiation. Excellent synergism is observed between the combination of HALS and UVA. PVC with HALS/UVA performs better than PVC with HALS and PVC with UVA in color differences, FTIR, and mechanical properties. The synergism is due to the different stages of functions between HALS and UVA. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study of the anticorrosive behaviour of epoxy binders containing non-toxic inorganic corrosion inhibitor pigments

The anticorrosive performance of epoxy coatings pigmented with non-toxic corrosion inhibitors pigments was investigated in this work. The coatings used contained the following pigments: zinc phosphate (ZP), zinc phosphomolybdate (ZPM) and zinc calcium phosphomolybdate (ZCPM). For comparative studies epoxy coatings with the following compositions were made up: one only with filler (CRG); one without pigments, varnish (VR) and other with zinc chromate (ZC) pigment. The corrosion inhibitor performance of the coatings was evaluated by immersion tests in 0.01 mol L⁻¹ NaCl aqueous solutions and accelerated tests in a salt spray chamber. The corrosion inhibitor performance of the samples was monitored using open-circuit potential (E_oc) measurements and electrochemical impedance spectroscopy (EIS) technique. Complementary tests were carried out using water vapour permeability of free-standing films and thermogravimetric (TG) analysis. The permeability test showed that the addition of the studied pigments did not modify the barrier properties of the free-films in comparison that pigmented with chromate. Thermal analysis indicated that the addition of the pigments improved the thermal stability of the coatings and it suggested a resin/pigment interaction. The total immersion tests and salt spray tests demonstrated that the barrier properties of the coatings pigmented with the inhibitors were not degrading as much as that pigmented with ZC. Therefore, all the three pigments could replace ZC as an anticorrosive pigment in similar conditions to those described here. The best corrosion inhibitor performance in the total immersion test was presented by the ZPM and ZCPM coatings while in the salt spray test the corrosion inhibitor performance of all the three pigmented coatings was similar, suggesting that only in the less aggressive test is possible to detect any difference between the coatings with the non-toxic pigments.     

Photopolymerisable formulations for enhanced properties of pigmented films

Abstract

Ultraviolet (UV) curing is an important and widely used surface technology for coatings. The curable formulations containing: monomer: epoxydiacrylate, photoinitiating system: 4-methoxybenzoyldiphenylphosphine oxide/2-hydroxy-2-methyl-1-phenyl-propan-1-one, additive reactive: tertiary amine, and inorganic thermoresistant pigments: white (TiO₂) and blue (Al₂O₃–Cr₂O₃), were cured like films by UV exposure. A series of experiments was carried out in order to optimise the photoinitiator ratios in photoinitiating system, and pigment content in the photocurable formulation. Films with enhanced mechanical properties (pendulum hardness, scratch resistance), high resistance at solvents and good appearance were developed. In order to provide adequate hiding power of the pigmented formulation, the pigment content has been chosen in the range 5–15%. Up to 15% pigment content may affect the efficiency of photoinitiator. The polymerisation efficiency (conversion and polymerisation rates) of photoinitiating systems in pigmented formulations was performed by differential scanning photocalorimetry (photo DSC) in comparison with the original systems without pigments.     

New approaches in wood coating stabilization

A major drawback in the use of wood materials for construction and decorative applications is its sensitivity to light. Numerous researchers have shown that the ultraviolet (UV) as well as fractions of the visible (VIS) spectrum of solar radiation cause most of the chemical modification and mechanical breakdown of exposed wood. To insure the long life of wood substrates, they are usually coated with various decorative and protective finishes. The protection effect depends strongly on the opacity, i.e., the degree of pigmentation of the coatings. However, the use of UV absorbers (UVA) and hindered amine light stabilizers (HALS) both in the coating system and also in a direct wood impregnation step can improve the light stability considerably. Here the knowledge of the light sensitivity of wood is crucial for an optimal photoprotection concept for coatings and the wood substrate. This paper highlights findings of a systematic investigation of the light sensitivity of pine wood (Pinus radiata). Furthermore, it describes the correlation between quantity and type of organic UVA and HALS as well as the lignin stabilizer concept and the degree of pigmentation of the coating. These findings are of great importance for an efficient and economic use of light stabilizers in film-forming wood coating systems for pale wood species and allow a cost-effective stabilization. Presented at the 5th International Woodcoatings Congress: Enhancing Service Life, organized by the Paint Research Association (PRA), in Prague, Czech Republic, October 17–18, 2006.     

Interactions between light stabilizers and pigment particles in polymeric coatings

Adsorption experiments have been carried out to understand the interactions responsible for UV light stabilizer adsorption on pigments in coatings. Light stabilizer adsorption on various pigments was studied in xylene solutions to eliminate potential interference from the cure process. Adsorption isotherms were determined for UV absorbers and hindered amine light stabilizers (HALS) compounds. Infrared spectral analysis revealed that chemical interactions at the pigment surface are responsible for the observed effects. In some cases the chemical surface interactions are likely to prevent the adsorbed molecules from functioning as light stabilizers.     

Chemisorption and physical adsorption of light stabilizers on pigment and ultrafine particles in coatings

Hindered amine light stabilizers (HALS) and UV absorbers (UVA) added to pigmented coatings adsorb on certain pigment and ultrafine oxide particles. Analysis of adsorption isotherms taken in xylene solutions and spectroscopic data revealed that chemisorption is the dominant interaction mechanism between the light stabilizers and the pigment particles. In contrast, the stabilizer interactions with ultrafine oxide particles are based on van der Waals forces, i.e., physical adsorption. In thermoset coatings, the chemisorbed stabilizers remain bound to the pigment surface on cure. The physically adsorbed stabilizers desorb on cure and migrate within the coatings. The chemistries involved in chemisorption were investigated using Fourier transform infrared spectroscopy and time-of-flight secondary ion mass spectroscopy. Stabilizers containing ester linkages hydrolyze to varying degrees into carboxy-late salts and alcohols. Acetyl groups also hydrolyze. Some of the chemisorbed light stabilizers lose the ability to protect coatings from photodegradation. Presented at the 25th International Waterborne, High-Solids, and Powder Coatings Symposium, February 18–20, 1998, New Orleans, LA. 1937 West Main St., P.O. Box 60, Stamford, CT 06904-0060.     

Solution combustion of spinel CuMn2O4 ceramic pigments for thickness sensitive spectrally selective (TSSS) paint coatings

A series of spinel-type CuMn₂O₄ ceramic pigments were prepared by a facile and low-cost sol-gel solution combustion method and used as cost-effective materials to fabricate thickness sensitive spectrally selective (TSSS) paint coatings by a convenient spray-coating technique. The chemical component, crystalline morphology, and optical property of the copper manganese oxide ceramic pigment could be accurately controlled by altering the annealing temperature. X-ray diffraction (XRD) analysis confirmed that the ceramic pigments annealed at 500 °C for 1 h coincided well with the XRD patterns of crystalline CuMn₂O₄ in the JCPDS database, and there were segregated phases of CuO and Mn₂O₃. Furthermore, the pure spinel CuMn₂O₄ phase could be achieved at 900 °C for 1 h. The copper manganese oxide ceramic pigments could serve as an effective pigment for fabricating the TSSS paint coating, and the TSSS paint coatings based on ceramic pigments calcined at 900 °C showed solar absorptance of 0.895–0.905 and thermal emittance of 0.186–0.310. In addition, the accelerated thermal stability test revealed that the TSSS paint coating exhibited good thermal stability when it was exposed to air at a temperature of 300 °C for 300 h. Hence, the fabricated TSSS paint coating could be used as a solar absorber coating in the low-to-mid temperature domain.     

Characterization of waterborne acrylic based paint films and measurement of their water vapor permeabilities

Recently, production of waterborne coatings has increased significantly as a consequence of strict pollution regulations. Waterborne coatings are sensitive to humidity, thus, their barrier properties with respect to permeation of moisture needs to be determined. Among various coating constituents, binder represents the matrix structure and its amount relative to the amounts of pigments and fillers can significantly affect the structure, hence the barrier property of the coating. In this study, waterborne acrylic based paints applied as protective coating on interior and exterior wall of the buildings are studied. The paint samples formulated with four different binder contents by a commercial paint company are used in the experiments. We first determine unknown ingredients of the paint samples using different characterization tools and then investigate the effect of the binder content on the structure of the paint films. In addition, water vapor permeability of the paint films is measured using a permeation cell. Results show that the barrier property of the waterborne acrylic based paint films against humidity decreases with decreased binder content due to uneven distribution of the pigments, consequently, porous structure formation in the films.     

光固化光纤彩色涂料的研制

采用环氧丙烯酸酯和脂肪族聚氨酯丙烯酸酯共混的方法研制了一种新型光固化光纤彩色涂料。研究了基料树脂、活性稀释剂、光引发剂、颜料、助剂等对涂料综合性能的影响。结果表明，环氧丙烯酸树脂与脂肪族聚氨酯丙烯酸酯配比为40：20，单、双、多官能团稀释单体配比为3：20：10，复合光引发剂用量10％，有机颜料用量1．5％，所配制的光固化光纤涂料性能优良。     

Long-term weathering behavior of UV-curable clearcoats: Depth profiling of photooxidation,UVA, and HALS distributions

The long-term weathering performance of two UV-curable clearcoat systems was studied using in-plane microtomy in combination with infrared spectroscopy, UV spectroscopy, and ESR spectroscopy. Oxygen transport characteristics were also studied using the half-time method. The photooxidation versus depth profile was highly dependant on the presence of hindered amine light stabilizers (HALS) for both coating systems. Ultraviolet light absorbers (UVA) had little effect on the photooxidation profile. A photooxidation gradient was formed in both clearcoats due to a reduction in oxygen solubility when compared to standard thermoset clearcoats. This gradient was only seen in formulations not containing HALS. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Use of reactable light stabilizers to prevent migration and to improve durability of coatings on plastic substrates

One of the challenges of coating plastic substrates for exterior automotive applications involves the tendency for light stabilizers, which inhibit UV degradation of the coating, to migrate out of the topcoat and into the underlying plastic substrate. The consequent depletion of the stabilizer from the topcoat could account for significantly poorer durability for coatings applied on plastic than on a nonpermeable substrate such as steel. These studies investigate the migration of both nonreactable and reactable UV absorbers (UVAs) and hindered amine light stabilizers (HALS) in fully formulated 2K urethane coatings applied on thermoplastic olefin (TPO) and steel substrates. Extensive migration of the nonreactable stabilizers occurs during accelerated exposure of the cured coating, and this migration correlates with poorer performance on TPO. Functionalization of the stabilizer with a group which covalently reacts into the coating will prevent much of this migration, and the improved degree of retention of the reactable light stabilizers in the topcoat correlates with improved performance on TPO substrates. In addition, stabilizer variables, such as the type and extent of functionalization as well as their chemical structure, have an effect on both the migration and performance of the stabilizers.     

The role of chromate in filiform corrosion inhibition

This paper is part of a study on filiform corrosion (FFC) on aluminum alloy 2024-T3 and focuses on the surface characterization of corroded samples. Untreated samples were used as well as samples which had undergone pretreatments including polishing, surface etching and chromated conversion coatings (CCC). These samples were coated with both pigmented and non-pigmented epoxy-based coatings. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS) analysis was used to investigate the nature of the surface as well as optical images to gauge the rate of FFC advancement. FFC corrosion rates decreased on samples which had received a surface etching pretreatment and a chromate conversion coating. Pigmented coatings reduced the rate of FFC further and led to two different types of corrosion surface morphology. On pretreated samples, the corrosion appeared deeper and pit-like, possibly due to an enhanced polymer-substrate bond. On untreated samples, widespread FFC developed. SEM and EDX analysis of various intermetallic particles (IMPs) on all samples, inside and outside of corroded regions, revealed that Cr from pigments was found deposited on Cu-containing intermetallics in corroded areas while Fe/Mn-containing particles were free from all pigment traces. These results suggest that the Cr deposition on Cu particles hinders the cathodic reduction of oxygen necessary for FFC advancement. For this reason, the coating pigments proved, under FFC conditions, to be a more effective inhibitor than the Cr originating from a chromate conversion coating.     

Enhancing corrosion resistance of aluminum composites in 3.5% NaCl using pigmented epoxy fluoropolymer

The corrosion protection performance of AA6061 T6–10% Al₂O₃ composite, coated with four different fluoropolymer paint systems, were investigated in 3.5% NaCl aqueous solutions under uniform and scratched conditions. A comparison between epoxy-treated clear and pigmented fluoropolymer coatings with newly developed vanadate-based fluoropolymer coatings was performed from corrosion protection, adhesion and durability points of view. The corrosion rates of epoxy-treated clear FLBZ 1074 increased dramatically after less than one month of exposure in 3.5% NaCl aqueous solutions. The addition of iron oxide or titanium oxide as pigments to the fluoropolymer decreased the porosity of epoxy and hence, improved the corrosion resistance. The newly developed vanadate based-clear FLBZ 1074 system showed outstanding corrosion resistance even after two months of immersion in 3.5% NaCl aqueous solutions under scratched coating conditions. The durability of such new coating based on salt spray test results was very promising (>2000 h without any sign of corrosion). The vanadate-pigmented FLBZ 1074 showed a dramatic increase in the corrosion rates. Moreover, the presence of pigments affected negatively the adhesion performance as well as the durability of the coating. A general model has been used to analyze the impedance data in terms of reactions occurring during the interaction of the coated metal with the environment. It was found that the vanadate-treated specimens not only improve the protective power against filiform corrosion as a factor of time, but also maintain the adhesion performance within the acceptable ranges.     

各类稳定剂对聚乙烯薄膜光氧老化的稳定作用

研究了不同光稳定剂和抗氧剂及其配合使用、光稳定剂含量对聚乙烯薄膜耐光氧老化性的影响。结果表明：在各类光稳定剂中、受阻胺类稳定剂的效果最好;紫外线吸收剂与受阻胺配合使用可使膜的耐老化性有所提高;各类抗氧剂对聚乙烯膜的耐光氧老化性没有不利影响;光稳定剂含量增加,薄膜耐老化寿命提高。     

Effect of UV aging on electrochemical behavior of an anticorrosion paint

The effect of the photochemical artificial ageing (UVA) on the electrochemical behavior of an anticorrosion paint has been studied by electrochemical impedance spectroscopy (EIS). Two types of coatings have been tested: a formulated tri coat system (FS) formed by a primer (epoxy), an intermediate coat (epoxy) and a topcoat (alkyd) which presents a total film thickness of 240 μm and, on the other hand, a non-formulated varnish (NFV) which presents a total film thickness of 70 μm. Panels have been aged in a QUV chamber and the maximal exposure's time was about 1000 h. EIS testing were carried out with a naturally aerated 3% NaCl solution.     

On the combined use of UVA, HALS, photooxidation, and fracture energy measurements to anticipate the long-term weathering performance of clearcoat/basecoat automotive paint systems

Transmission UV spectroscopy measurements of clearcoat ul traviol et light absorber (UVA) disposition, electronspin resonance (ESR) spectroscopy measurements of clearcoat and basecoat Active hindered amine light stabilizer (HALS) disposition, and transmission Fourier transform infrared (FTIR) measurements of photooxidation have been carried out on 5 μm thickslioes of clearcoat/basecoat/primer/e-coatpaint systems on steel panels as a function of outdoor exposure. These analysis results are combined with clearcoat fracture energy measurements to assess the possibility that a clearcoat/basecoat paint system will resistcatastrophic cracking/peeling failure at long times. Taken together, all results indicate that these nontraditional paint weathering performance metrics should be added to the existing repertoire of paint weathering performancemetrics to ensure that inferior clearcoat/basecoat automotive paint systems are not introduced into service. Ford Research Laboratory, MD 3182SRL, P.O. Box 2053. Dearborn, MI 48124     

The use of new blockcopolymeric dispersing agents for waterborne paints — theoretical and practical aspects

Newly developed blockcopolymeric dispersing agents are evaluated in their performance with a number of pigments in order to obtain a deeper understanding of the dispersing process and of the factors that affect the stability of waterborne binder free pigment concentrates. Special attention is paid to the variation of the amphiphilic ionic/non-ionic and hydrophobic/hydrophilic properties of these new dispersants. By measuring particle surface charges and particle size distributions of pigment pastes and by determining relevant properties of the films obtained after application the effect of a number of binders and other paint components on the stability of dispersions is also evaluated. Guidelines for efficient and economically optimum preparation of pigmented waterborne paints are given.