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Applied spectroscopy Reviews, 47:233-243, 2012. Author: Saeed Farrokhpay a a Julius Kruttschnitt Mineral Research Centre (jkmrc), the university of. Queensland, indooroopilly, Queensland, australia. Article may be used for research, teaching, and private study purposes. Publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date.
Applied spectroscopy Reviews, 47:233-243, 2012. Author: Saeed Farrokhpay a a Julius Kruttschnitt Mineral Research Centre (jkmrc), the university of. Queensland, indooroopilly, Queensland, australia. Article may be used for research, teaching, and private study purposes. Publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date.
Applied spectroscopy Reviews, 47:233-243, 2012. Author: Saeed Farrokhpay a a Julius Kruttschnitt Mineral Research Centre (jkmrc), the university of. Queensland, indooroopilly, Queensland, australia. Article may be used for research, teaching, and private study purposes. Publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date.
Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Applied Spectroscopy Reviews Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/laps20 Application of Spectroscopy and Microscopy Techniques in Surface Coatings Evaluation: A Review Saeed Farrokhpay a a Julius Kruttschnitt Mineral Research Centre (JKMRC), The University of Queensland, Indooroopilly, Queensland, Australia Available online: 01 Dec 2011 To cite this article: Saeed Farrokhpay (2012): Application of Spectroscopy and Microscopy Techniques in Surface Coatings Evaluation: A Review, Applied Spectroscopy Reviews, 47:3, 233-243 To link to this article: http://dx.doi.org/10.1080/05704928.2011.639424 PLEASE SCROLL DOWN FOR ARTICLE Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims, proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material. Applied Spectroscopy Reviews, 47:233243, 2012 Copyright Taylor & Francis Group, LLC ISSN: 0570-4928 print / 1520-569X online DOI: 10.1080/05704928.2011.639424 Application of Spectroscopy and Microscopy Techniques in Surface Coatings Evaluation: A Review SAEED FARROKHPAY Julius Kruttschnitt Mineral Research Centre (JKMRC), The University of Queensland, Indooroopilly, Queensland, Australia Abstract: This article presents a review of the published articles related to the novel application of spectroscopy and microscopy methods in paint and coatings quality eval- uation. Traditional and simple techniques have been used in paint and coating industry for many years and proven to be effective. However, the paint and coating industry faces new formulations with nontraditional applications. Therefore, the industry needs to adjust itself with the current sophisticated production and testing methods. There are a number of modern microscopy and spectroscopy techniques that can be utilized in the paint and coating industry for a better understanding of the product quality and/or application performance. This, in particular, is highly applicable in modern and nontraditional applications such as nanotechnology and smart coatings. Though importance of spectroscopy and microscopy methods is being increasingly recognized in the industry, there is no current comprehensive review available to highlight the need for novel application of these techniques in surface coatings evaluations. Keywords: Surface coatings, paint, spectroscopy Introduction The paint manufacturing process involves many steps of quality evaluation. The rawmaterial and the production process undergo several tests, and the quality of the nal product (properties such as viscosity, neness, and density) is often checked. The product is then applied to a surface and parameters such as drying time, color and gloss, hardness, adhesion, and its resistance against different conditions is also evaluated. The paint and coatings industry is growing day by day around the globe. The current trends and challenges in paints and coatings technology have been recently reviewed (1). Traditional and simple techniques have been used in paint and coatings evaluation for many years. Although these techniques have been effective, today the surface coatings industry faces new and nontraditional applications. For example, using pigments as small as 2030 nm (nanotechnology), coatings that react to external stimuli in an intelligent way (smart coatings), and nontoxic protective pigments (environmentally friendly coatings). Therefore, the industry needs to adjust itself with the current sophisticated production and Address correspondence to Saeed Farrokhpay, Julius Kruttschnitt Mineral Research Centre (JKMRC), The University of Queensland, 40 Isles Road, Indooroopilly, QLD4068, Australia. E-mail: s.farrokhpay@uq.edu.au 233 D o w n l o a d e d
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234 S. Farrokhpay testing methods. In this article, such techniques will be reviewed, and their applications in the surface coatings industry will be highlighted. The importance of the application of microscopy and spectroscopy methods in paint and coatings evaluation is being increasingly recognized. A comprehensive review of the application of spectroscopy in the coatings industry was published in 1975 (2). Although the science and technology has been rapidly growing since then, there is no current review available. It should be noted that the order in which the various techniques are discussed in this article is a matter of convenience and does not necessarily relate to their importance. Microscopy Techniques Microscopy is a technical term for using a microscope to view objects that cannot be seen with the naked eye. There are three well-known branches of microscopy: optical, electron, and scanning microscopy. In general, paint lms are opaque; therefore, microscopy methods can only be used for surface characterization. However, there are some microscopy techniques that can be used for paint lm depth analysis, as will be explained. Atomic force microscope (AFM) is a technique for measuring surface topography, and it is an important tool in colloid and interface analysis (3, 4). The vertical deection of the cantilever is measured by a detection apparatus indicating the local sample height and produces a surface topographic image. The phase shift between the driving force for the cantilever vibration and the optically detected motion of the cantilever is recorded in phase imaging (5). Two basic imaging techniques are tapping (noncontact) and contact mode (Figure 1 (6)). In the former, the surfacetip interactions are attractive, and in the latter, topographic images are derived from repulsive forces. Both methods have been used to image dry paint lms (7, 8). Although Biggs and his coworkers (8) have found a clearer representation of the pigmentbinder composite structure in exterior paints using the tapping mode, it is generally agreed that the same detail of surface topography can be obtained by both methods. The photooxidation of polystyrene and the changes in surface morphology of coating systems have also been investigated using AFM (9, 10). Figure 1. Two basic AFM imaging techniques: tapping mode (left) and contact mode (right). D o w n l o a d e d
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Surface Coatings Evaluation 235 AFM in combination with laser confocal scanning microscopy (LSCM) can cover a wide length-scale range, from micrometers to millimeters. This combination is a powerful technique for quantifying topographic changes of polymeric coatings resulting fromsurface roughening, pitting, and cracking (1114). AFM and LSCM have also been used to analyze surface topography changes during outdoor exposure (15, 16). AFM and LSCM have been used to measure morphological changes of the surface of pigmented coatings during UV exposure and it has been shown that both pigment dispersion and thickness of the clear layer played a role in the resulting topography. The increase in surface roughness measured by AFMresulted in a signicant decrease in gloss (7, 17). LSCMhas shown that gloss changes in pigmented coatings formulated with dispersants is mainly dominated by an increase in surface roughness (15). Scanning electron microscopy (SEM) can be used to examine paint surface defects, such as pits and cracks, and loss of adhesion. For example, SEM with energy-dispersive X-ray spectroscopy (EDX) has been used to identify the reasons for paint adhesion failures from a steel structure caused by welding splatter (18, 19). Chalking, which is a common problem with exterior paints, has also been investigated using SEM (2022). Chalking occurs as a result of oxidation of the surface layer of polymers containing white pigments such as anatase TiO 2 . SEM has been also used to obtain high-resolution images to show the extent of latex deformation resulting from particlesubstrate adhesion (23). Pigment dispersion characterization in coatings has been performed using SEM (15). SEM images of a typical paint lm are presented in Figure 2 (24). Transmission electron microscopy (TEM) is a microscopy technique in which a beam of electrons is transmitted through an ultra-thin specimen and interact with the specimen. An image is formed from the interaction of the electrons transmitted through the specimen and can be detected by a sensor. TEM is a popular analysis method in a range of scientic elds, including surface science, providing information on the particle shape, size, and Figure 2. SEM image of a paint lm (dimensions 12.8 8.9 m). D o w n l o a d e d
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236 S. Farrokhpay Figure 3. TEM images showing pigment particle size and morphology (left) and dried paint lm layer thickness (right). surface topography. Farrokhpay (6, 25), Morris et al. (26), and Farrokhpay et al. (27) have used TEM to identify TiO 2 pigment particle size and morphology and have successfully shown a very thin inorganic coating (alumina type) layer present on the pigment surface (Figure 3). TEM is an ideal method to study pigment dispersion in dry paint lms, because it allows viewing inside the lm (7). The thickness of paint lm has also been measured using TEM (Figure 3) (7). TEM and SEM both have been used to determine the contact diameters of various sizes of latex (28, 29) and dispersion of nano alumina and silica particles in automotive polyurethane coatings (30). In conventional SEM, a high vacuum is required; therefore, it is not capable of analyz- ing a wet sample. Furthermore, in order to obtain clear images of nonconducting samples, the sample must be coated in carbon, gold, or platinum. Environmental or universal scan- ning electron microscopy can be now used to avoid these disadvantages. This allows the observation of wet samples without the need for dehydration and coating. These instruments have been used to study emulsion as well as drying paint lms (31). It should be noted that the microscopy techniques are, in fact, complementary to each other. For example, AFM provides a picture of the surface only, and TEM provides thin depth (cross-section) details. Therefore, one can hardly expect complete results using a single technique. It is also worth mentioning that though the microscopy techniques described thus far are useful because they provide a direct picture of the actual lm, they can only target a very small area of the paint lm (32). Image Analysis for Quantitative Data Although microscopy techniques provide comparative and qualitative results, a quantitative understanding of, for example, the degree of pigment dispersion, cannot be made through visual observations of electron micrographs. This is partially due to the tendency of human eye to see nonexisting patterns and the inability to intuitively judge whether a distribution of objects is truly random, ordered, or articially disordered (24). A technique for quan- tifying the degree of TiO 2 dispersion in paint lms has been developed based on electron microscopy and image analysis (24). Results obtained using this technique also provide an upper limit for improvement of pigment dispersion. This technique includes imaging the paint lm with an electron microscope (such as SEM), determining the coordinates of the particle centers, and analyzing the resulting coordinates using algorithms that divide the image into a large number of subareas (Figure 4). The particle attributes in each subarea are D o w n l o a d e d
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Surface Coatings Evaluation 237 Figure 4. Dispersion analysis via comparison of image subareas using SEM images of paint lm. The degree of variability between subareas increases from left to right (Color gure available online). then compared to those in other subareas. A high degree of variability between subareas indicates poor dispersion and a low degree of variability shows that the particles are well dispersed. Farrokhpay et al. (7, 17) have analyzed TEMand AFMimages using analySIS (a commercially available software from Olympus Company, Hamburg), to show the degree of pigment dispersion and the presence of pigment aggregates in paint lms. Image analysis can also be used as a straightforward and reliable method for characterization of porosity (33). It should be noted that the main concern in applying image analysis technique is that they depend heavily on the quality of images. Therefore, sufcient contrast between the matrix and particles is often required to obtain meaningful data (34). Spectroscopy Techniques There is a key difference between spectroscopy and microscopy techniques. In spectroscopy, the data are usually in the formof a spectrum, which contains a series of points plotted along two axes. On the other hand, in microscopy analysis, the information is assimilated by a computer into a comprehensive image of the sample, as discussed in the previous section. X-ray is being used widely for material structural analysis due to its strong transmission capability (35). Small-angle X-ray scattering (SAXS) is a nondestructive method that can be applied to soft materials, such as liquids and suspensions (3638). SAXS complements microscopic techniques by providing statistically averaged information on the sample morphology. Although SAXS is a powerful tool for structural analysis, it has rarely been applied in paint and coatings. The maximum measurable range of SAXS is usually in the range of hundreds of nanometers and does not cover the larger size region that is desirable in the surface coatings industry. Therefore, ultra-small-angle X-ray scattering (USAXS) has been specially designed for such micrometer-size applications. USAXS can measure up to several micrometers using monochromatized and parallel X-ray (32, 3841) and can be used to analyze paint and coating lms. Previous ultra-small-angle neutron scattering (USANS) experiments have been performed on wet paint systems under varying shear rates (42). The result of this study (42) has shown that the degree of occulation is shear rate dependent. USANS measurements cannot be used in real-time experiments due to its low signal, whereas USAXS has high scattering signals and is suitable for real-time measurements. Raman spectroscopy (43) is a spectroscopic technique based on inelastic scattering of monochromatic light. Raman spectroscopy has been widely used to study the pigments present in both prehistoric and historic items (44). It has been used to characterize pigments used on prehistoric rock art (45, 46), Greek and Roman murals (4750), medieval frescos (51), and painted pottery (52). Raman spectroscopy has been used to investigate blue and green pigments used on the wall paintings at the Maya site of EkBalam(53). Micro-Raman D o w n l o a d e d
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238 S. Farrokhpay spectroscopy is an ideal nondestructive technique for studying the ne paint layers of these historic samples. The individual particles within each paint layer can also be identied due to the high spatial resolution of this technique (44). Laser-induced breakdown spectroscopy (LIBS) has also been used in combination with Raman microscopy to identify the pigments applied in different types of painted art. This combination has led to a detailed characteriza- tion of the pigments used in old paintings (54). Raman spectroscopy is a suitable technique for in situ identication of synthetic organic pigments in complex binding media (55). Electrochemical impedance spectroscopy (EIS) is a nondestructive method used to evaluate the performance of organic coating/metal systems (56, 57). EIS has been widely used to investigate the corrosion performances of protective coatings, including nano coat- ings, applied onto mild steel substrates (5863). EIS has also used to understand the degra- dation mechanism by studying defective areas in coating, as well as the electrochemical performance of zinc-rich paints in articial seawater (64, 65). It should be noted that EIS data are usually difcult to interpret, due to the fact that the results actually represent an average response for the entire surface, though coating degradation (such as blistering) generally occurs locally. Therefore, the reproducibility of the impedance data is usually low and statistical data analysis is often necessary (66, 67). Moreover, EIS does not provide any information about the failure site location or the degradation mechanism. To overcome such limitations, new techniques that perform local measurements have been developed such as scanning vibrating electrode technique (SVET) (6870), scanning Kelvin-probe (SKP) (7173), localized electrochemical impedance spec- troscopy (LEIS) (74, 75), and scanning acoustic microscopy (SAM) (7678). SAM has been used to characterize delamination processes at the water-borne epoxy coatingsteel interface (76) as well as coating adhesion (7982). Another microelectrochemical technique that can be used to study corrosion of coated metals is scanning electrochemical microscopy (SECM) (83), which combines scanning probe techniques with electrochemistry. This technique is applicable for both insulating and conducting surfaces (84, 85) and can be used to quantitatively detect the reactants and products involved in corrosion reactions (84, 86, 87). SECM has been used to observed damage to paint and coatings resulting from immersion in aqueous brine solutions (88). Indications of coating failure cannot be observed by conventional electrochemical techniques or visual observation. It has been reported that chloride increases coating degradation at a very early stage (85). X-ray photo spectroscopy (XPS) and Fourier transform infrared spectroscopy in atten- uated total reectance mode (FTIR-ATR) have been used to showthat latex lms containing different surfactants behave differently during lm maturation (89, 90). According to these studies, some surfactants do not migrate to the interfaces probably due to greater com- patibility with the copolymer system. Probe microscopy methods, in particular scanning electrical potential microscopy (SEPM), have been also successfully used to produce the rst electrical maps of polymer lms and particles (9193). It has been demonstrated that transparent lms from low-T g latex contain electrically positive boundaries between par- ticles (94). ATR-FTIR is also commonly used to measure chemical changes of coatings during ultraviolet (UV) degradation (95, 96). Surface defects in dry paint lms are a major problem in the coatings industry. Although these defects are very small, they are detectable by the naked eye. Surface defects are often caused by substances in the rst few monolayers; therefore, a surface-sensitive technique is required to characterize them. Laser microprobe mass analysis (LAMMA) and time-of-ight secondary ion mass spectroscopy (ToF-SIMS) are often used for this purpose (97). These two methods similarly characterize and identify paint lm defects; however, whereas LAMMA mainly provides information on inorganic materials, ToF-SIMS is used to characterize organic materials. In particular, ToF-SIMS is used to distinguish between D o w n l o a d e d
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Surface Coatings Evaluation 239 different silicone oils based on the same monomers (97). Recently, a combination of Raman and XRF spectroscopy has been used in forensic examinations of different kinds of trace evidence (98). Combinations of electrochemical techniques (EIS) and surface analysis techniques (AFM, SEM, EDX) have been used to evaluate protective properties of paint lms (99). Another study has shown that LIBS is a suitable technique for detecting lead in paint at the hazard levels dened by federal agencies. Although, this technique offers a way to obtain unique information, its current costs limit its practical application (100). Conclusions There are a number of novel applications of spectroscopy and microscopy techniques in paint and coating industry to obtain a better understanding of the product quality and/or application performance. These methods are highly applicable in modern and nontradi- tional applications such as nanotechnology and smart coatings. These techniques often require special sampling methods, highly trained operators, and high capital cost invest- ment. However, the surface coatings industry needs to apply these new techniques due to the complexity of the current sophisticated production and testing methods. References 1. Farrokhpay, S. (2011) New developments in paint and coatings technology. In Paints: Types, Components and Applications, Sarrica, S.M., Ed. (pp. 141149). Nova Science Publishers: New York. 2. Grieser, R.H. (1975) Spectroscopy and the coatings industry: A review. Progr. Org. Coating., 3: 171. 3. Butt, H.J., Berger, R., Bonaccurso, E., Chen, Y., and Wang, J. (2007) Impact of atomic force microscopy on interface and colloid science. Adv. Colloid Interface Sci., 133: 91104. 4. Binning, G. and Quate, C.F. (1986) Atomic force microscope. Phys. Rev. Lett., 56: 930933. 5. Tiarks, F., Frechen, T., Kirsch, S., Leuninger, J., Melan, M., Pfau, A., Richter, F., Schuler, B., and Zhao, C.L. (2003) Formulation effects on the distribution of pigment particles in paints. Progr. Org. Coating., 48: 140152. 6. Farrokhpay, S. (2004) Interaction of Polymeric Dispersants with Titania Pigment Particles. Ph.D. Thesis, Ian Wark Research Institute, University of South Australia, Adelaide. 7. Farrokhpay, S., Morris, G.E., Fornasiero, D., and Self, P. (2006) Titania pigment particles dispersion in water-based paint lms. J. Coating. Tech. Res., 3: 275283. 8. Biggs, S., Lukey, C.A., Spinks, G.M., and Yau, S. (2001) An atomic force microscopy study of weathering of polyester/melamine paint surfaces. Progr. Org. Coating., 42: 4958. 9. Rudoi, V.M., Yaminskii, I.V., and Ogarev, V.A. (1999) Effect of photooxidation on the surface properties of polystyrene. Polymer Sci. Polymer Chem., 41: 16711674. 10. Bierwagen, G.P., Rebecca, T., Chen, G., and Tallman, D.E. (1997) Atomic force microscopy, scanning electron microscopy and electrochemical characterization of Al alloys, conversion coatings, and primers used for aircraft. Progr. Org. Coating., 32: 2530. 11. Van Landingham, M.R., Nguyen, T., Byrd, W.E., and Martin, J.W. (2001) On the use of the atomic force microscopy to monitor physical degradation of polymeric coating surfaces. J. Coating. Tech., 73: 4350. 12. Gu, X., Sung, L., Kidah, B., Oudina, M., Martin, D., Rezig, A., Stanley, D., Jean, J.Y.C., Nguyen, T., and Martin, J.W. (2009) Relating topographical change to gloss loss of polymer coatings during UV radiation. In ACS Symposium Series, Nanotechnology Applications in Coatings, R.H. Fernando and L. Sung, Eds., Washington: American Chemical Society. pp. 328348. 13. Gu, X., Nguyen, T., Oudina, M., Martin, D., Kidah, B., Jasmin, J., Rezig, A., Sung, L., Byrd, E., Martin, J.W., Ho, D.L., and Jean, Y.C. (2005) Microstructure and morphology of amine-cured D o w n l o a d e d
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