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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
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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
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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).
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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).
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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
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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
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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
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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.
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