Progress in Organic Coatings 135 (2019) 574–581

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Progress in Organic Coatings

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Degradation of scratch resistance of clear coatings by outdoor weathering T

a,⁎ a a b
Naomi Kumano , Kanji Mori , Makoto Kato , Masahiko Ishii
a
Toyota Central R&D Labs., Inc. Nagakute, Aichi, 480-1192, Japan
b
Toyota Motor Corporation, Toyota, Aichi, 471-8572, Japan

ARTICLE INFO ABSTRACT

Keywords: Scratch resistance is important for maintaining car appearance. It is thus important to understand how scratch
Automotive characteristics change over time. Although accelerated weathering tests are commonly used, there is no specific
Coatings test optimized for estimating scratch resistance degradation. The present study investigates the relationship
Outdoor weathering between chemical changes and scratch resistance in the outdoor weathering test. To estimate the similarity in
Durability
degradation process between outdoor and artificial weathering, three kinds of automotive clear coating (two
Scratch
Accelerated weathering
isocyanate and one epoxy acid curing types) were subjected to outdoor weathering and xenon lamp accelerated
weathering tests. The scratch properties and chemical changes were examined using Fourier transform infrared
spectroscopy (FT-IR). Scratch resistance was measured in terms of the critical fracture force, which is defined
based on the microscope observation of cracks in a scratch trail after a scratch test with increasing normal load
applied to the scratch tip. For all coatings, the critical fracture force decreased after one month of outdoor
exposure. The FT-IR spectra showed that crosslink scission occurred in the coating surface layer due to oxidation
and hydrolysis during exposure. Scratch resistance degradation was found to be caused by chemical changes
over a short time in the surface layer. Although the xenon test also lowered scratch resistance and led to the same
kinds of chemical changes observed for outdoor weathering for all coatings, the extent of each reaction was not
proportional to outdoor reactions.

1. Introduction mechanisms of this degradation include crosslink scission, which is

caused by chemical reactions such as hydrolysis and leads to poor
Car owners want their cars to have a long-lasting scratch-free ap- strength, and crosslink formation, which is caused by the recombina-
pearance. Scratch resistance is thus one of the most important proper- tion of free radicals from photo-oxidation and leads to a hard and brittle
ties of automotive coatings [1–4]. Even superficial scratches or marring coating. Another possibility is that some residual crosslinking occurs
can deteriorate the high-gloss appearance of automotive coatings. Since during the early stage of exposure, making the coating hard and brittle.
the scratch resistance of automotive coatings is important for main- Fourier transform infrared spectroscopy (FT-IR) is the most pow-
taining appearance, it is necessary to understand the changes in scratch erful tool for understanding changes in the chemical properties of
resistance over time [4]. coating surfaces [12,13]. Other forms of spectroscopy and sample
To evaluate coating service life, degradation evaluation methods preparation techniques have been reviewed [14,15]. Changes in the
have been combined with chemical and physical characterization chemical and physical properties of polyester-urethane coatings ex-
techniques [5–8]. Typical degradation evaluation methods for coatings posed to accelerated weathering have been reported [8]. It was found
are outdoor weathering and accelerated weathering tests. Accelerated that crosslink density diminished during exposure, making the coatings
weathering tests are designed to simulate degradation under usage brittle. However, the tensile modulus of the coatings increased with
conditions in a short time. Commonly used scratch resistance tests in- exposure. These results suggested that in addition to diminished
clude simulated car wash tests, scratch tests, rubbing tests, and micro- crosslink density, polymer physical aging during accelerated weath-
hardness tests [9]. Scratch tests are the preferred quantitative me- ering contributes to the changes in mechanical properties. The de-
chanical measurement method because they can sensitively detect the gradation and physical aging processes are not yet fully understood,
degradation of a coating surface [6,10,11]. and thus further studies are required.
Several studies have reported that the scratch resistance of coatings Accelerated weathering is commonly used to simulate normal usage
degrades after exposure to accelerated weathering [5,6]. Possible conditions. In contrast, the outdoor weathering test is rarely used.

⁎
Corresponding author.
E-mail address: [email protected] (N. Kumano).

https://doi.org/10.1016/j.porgcoat.2019.06.034
Received 15 March 2019; Received in revised form 19 June 2019; Accepted 19 June 2019
Available online 05 July 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.
N. Kumano, et al. Progress in Organic Coatings 135 (2019) 574–581

Table 1 isophthalate degradation, which does not occur in outdoor weathering

Weather conditions of outdoor exposure test sites in Naha, Okinawa, Japan. tests, was observed using photoacoustic infrared spectroscopy [17].
Exposure Sum of Temperature Relative Sum of Daily global However most clear coats today are based on acrylic resin backbones
precipitation humidity sunshine solar radiant because of their good balance of cost, durability, and scratch perfor-
duration exposure mance [19]. Clear coat materials based on acrylic resin today need
suitable verification to be applied accelerated weathering tests. More-
month mm °C % h MJ/m2
1 139.5 29.0 73 243.3 21.3
over, the effects of exposure conditions on scratch properties are not yet
2 267.5 28.2 74 150.5 16.1 fully understood.
3 214.5 26.4 72 208.1 15.9 The present study investigates the relationship between scratch re-
4 119.0 22.5 72 114.5 10.3 sistance and the chemical changes in acrylic clear coats in an outdoor
5 19.5 18.7 64 130.5 9.8
weathering test. Differences in degradation between outdoor exposure
6 32.5 16.7 64 103.9 9.7
7 37.0 19.9 73 134.9 13.2 and accelerated exposure are also discussed.
8 165.5 19.6 75 87.5 12.4
9 132.5 20.5 70 133.0 16.1 2. Experiment
10 185.0 23.7 73 219.4 21.6
11 402.0 26.4 81 159.9 18.5
12 62.0 29.2 77 253.8 22.8
Three types of coating were exposed to outdoor weathering and
investigated using a scratch test and FT-IR. The results were compared
with those for coatings exposed to accelerated weathering tests.

2.1. Sample preparation

Three types of coating with two types of crosslinking commonly

used in automotive coatings were examined in this study. The two
isocyanate coatings based on acrylic resins (2K polyurethane coatings)
are denoted Coating A (Tg = 70.0 °C, as determined by tan δ curve from
a dynamic mechanical analysis (DVA-220 dynamic mechanical ana-
lyzer, ITK Co., Ltd.) performed at a frequency of 1 Hz and a strain of
1%) and Coating B (Tg = 79.2 °C), respectively. A 1K epoxy acid coating
based on acrylic resins is denoted Coating C (Tg = 72.7 °C). To simulate
a typical automotive coating, the samples were prepared by succes-
sively applying an electrodeposited coating, a primer surfacer, a black
finishing coat, and clear coat over a steel substrate. Coating films were
prepared by spraying on the samples with a dry thickness of 30–40 μm
and subsequently curing them at 140 °C for 30 min.

2.2. Outdoor weathering test

Outdoor exposure was performed for 1, 3, 6, and 12 months in

Okinawa, Japan. After the outdoor weathering test, the samples were
stored at room temperature and humidity in the dark place. Table 1
shows the weather conditions for the outdoor exposure test sites in
Naha, Okinawa, from August 2008 to July 2009. These data were
provided by the Japan Meteorological Agency. One month in this study
means a unit of time equal to 365/12 days.

2.3. Accelerated weathering tests

Fig. 1. Photograph of xenon weathering test and xenon weathering test without
water spraying in the accelerated weathering chamber.
Three types of accelerated weathering test were performed on the
coatings.

However the effects of accelerated weathering may be different from

those caused by usage conditions [16]. Gerlock et al. [17] and Bauer
• Xenon weathering test. Accelerated weathering of the samples was
carried out in an accelerated weathering chamber (ATRAS Ci4000)
et al. [18] reported the weathering chemistry of polyester urethane according to ISO11341:2004 for 240 h. The xenon weathering test
clear coats subjected to outdoor weathering tests in Florida or Arizona protocol provides continuous exposure to xenon arc ultraviolet (UV)
and various accelerated weathering tests. They found that none of the radiation (60 W/m2 @ 300–400 nm irradiance), and 18 min of
accelerated weathering tests was acceptable for their samples because deionized water spray every 2 h with a black panel temperature of

Fig. 2. Definitions of scratch resistance parameters. (a)

Optical micrograph of scratch fracture. Critical fracture force
is defined as the force at which 10 cracks with a length of
more than 50 μm are observed in a microscope view area
(900 μm × 900 μm). (b) Cross-sectional profile. The depth of
scratch deformation was measured from the coating surface
plane.

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Fig. 3. Optical micrographs of Coating A after scratch test. Each micrograph shows the typical position. Dents indicate scratch ends.

63 °C and a chamber temperature of 40 ± 1 °C. Borosilicate glass

inner and outer filters were used with the xenon arc lump to si-
mulate the spectral distribution under usage conditions.
• Xenon weathering test without water spraying. The xenon test
without water was carried out on samples covered by borosilicate
glass container, which had a rectangular envelope shape and was
open at the bottom. This experiment was conducted under the same
temperature and humidity as those in the xenon test but there was
neither water droplet contact nor dew on the coating surface.
Samples used in the accelerated weathering chamber are shown in
Fig. 1.
• Water immersion test. A water immersion test was conducted on
Coating A and Coating B. The samples were immersed in deionized
water at 40 °C for 240 h. A constant-temperature water bath
(Yamato Scientific Co., Ltd., BA500) was used.

2.4. Scratch test

Scratch tests were carried out on a micro-scratch tester (CSM

Instruments, MST) using a diamond stylus with a 0.1-mm tip radius at
25 °C and 50–52% relative humidity. In the scratch tests, the load was
progressively increased from 0.05 to 0.98 N at a scratch speed of
300 mm/min and a scratch length of 50 mm. When no cracks were
observed in the scratch trail, the initial load was increased by 0.98 N
and another scratch test was conducted. This process was repeated until
cracks appeared. Scratch deformation and fracture were observed using
confocal microscopy (Lasertec, OPTELICS H1200). As the normal force
was increased from 0.05 to 4.98 N at a constant rate, the critical frac-
ture force, defined as the force at which 10 cracks with a length of more
than 50 μm were observed in the microscope view area
(900 μm × 900 μm), was determined (Fig. 2(a)). Although the critical
fracture force can be used to quantify scratch resistance, the load at
which the first crack forms is experimentally unstable. We thus chose
the load at which a contiguous crack is initiated as a quantitative
measure. The criterion we adopted (10 cracks with a length of more
than 50 microns in a 900 μm × 900 μm field of view ensures high re-
producibility and stability. The depth of the scratch deformation was
measured from the coating surface plane (Fig. 2(b)).
Fig. 4. Critical fracture force plotted against outdoor exposure and accelerated
exposure for (a) Coating A, (b) Coating B, and (c) Coating C.

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Fig. 5. Relation between load and depth of scratch deformation in scratch test for (a) Coating A, (b) Coating B, and (c) Coating C.

Fig. 6. FT-IR difference spectra before and after tests for Coating A.

2.5. Ft-ir telluride (MCT) detector with the attenuated total reflectance (ATR)
technique. The samples were washed with a sponge and mild detergent
The FT-IR spectra were obtained using an FT-IR spectrometer and wiped with alcohol before being analyzed. We selected a germa-
(Thermo Scientific, Nicolet iS50) equipped with a mercury-cadmium- nium prism with a contact area 100 μm in diameter as the internal

Fig. 7. FT-IR difference spectra before and after tests for Coating B.

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Fig. 8. FT-IR difference spectra before and after tests for Coating C.

weathering after 1 month for all sample types. As scratch deformation is

related to viscoelastic properties, the results suggest that the viscoe-
lastic properties of the coatings remained unchanged after 1 month of
outdoor weathering. Thus, it is assumed that coatings exposed to out-
Scheme 1. Degradation reaction for 2K polyurethane coatings. door weathering for 1 month had lower fracture resistance than that of
unexposed coatings even though their viscoelastic properties were un-
changed.

Scheme 2. Degradation reaction for epoxy acid coatings.

reflection element, which permitted the infrared beam to a depth of

between 0.3 μm (4000 cm−1) and 1.2 μm (1000 cm−1), to detect only
the degradation of the topmost surface of the coatings. The spectra were
recorded from 4000 to 400 cm-l at a resolution of 8 cm−1. A total of 64
scans were accumulated. The contact load was controlled to be a con-
stant value to ensure high quantitative accuracy [20]. The difference
spectra were obtained by subtracting the spectrum of the unexposed
coating from that of the exposed coating without normalizing the
spectra. The accuracy of difference spectra was checked by comparing
spectra taken at two different locations in a same sample. The re-
producibility of the difference spectra was estimated to be 2% in ab-
sorbance by comparing the results obtained at different locations.

3. Results and discussion

3.1. Scratch properties of coatings subjected to various weathering tests

Fig. 3 shows a typical micrograph of Coating A after the scratch test.

Scratch deformation was observed on the coating surface, and fracture
occurred with cracks at forces above the critical fracture force. This
crack morphology was observed for all samples. Fig. 4 shows the critical
fracture force for coatings subjected to various weathering tests.
The critical fracture force for unexposed coatings was found to be
greater than that for coatings exposed to outdoor weathering for all
sample types. No cracks were observed at 4.9 N in unexposed samples
for Coating B. The critical fracture force of coatings exposed to outdoor
weathering declined abruptly within 3 months, and then changed
slightly from 3 to 12 months. It was found that the coatings become
brittle after a short exposure (1 month) to outdoor weathering.
Fig. 5 shows the relation between the load and depth of scratch
deformation of the coatings in the scratch test. The progress curves of
scratch deformation have a linear relationship with the normal load. Fig. 9. Relation between critical fracture force and absorbance for each group
There were no significant differences in the depth of scratch deforma- in Coating A. (a) Chain scission, (b) Degradation products, and (c) Desorption
tion between unexposed coatings and coatings exposed to outdoor products. ●■▲: Outdoor weathering test, ○□△: 240-h xenon test.

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Fig. 10. Relation between critical fracture force and absorbance for each group Fig. 11. Relation between critical fracture force and absorbance for each group
in Coating B. (a) Chain scission, (b) Degradation products, and (c) Desorption in Coating C. (a) Chain scission, (b) Degradation products, and (c) Desorption
products. ●■▲: Outdoor weathering test, ○□△: 240-h xenon test. products. ●■▲: Outdoor weathering test, ○□△: 240-h xenon test.

The critical fracture force of coatings exposed to the xenon test radicals formed in the photo-oxidation reaction are responsible for the
without water or water immersion was almost the same as that of un- observed degradation. The photo-oxidation reaction leads to the scis-
exposed coatings. Coatings exposed to the xenon test exhibited cracks in sion of the polymer network or chain, resulting in decomposition at the
the scratch trail, and their critical fracture force was as low as that of coating surface.
coatings exposed to outdoor weathering for 1 month. Scratch resistance For the epoxy acid coatings, there were decreases with outdoor
degradation after 1 month of outdoor exposure could thus be re- exposure time in the C]O stretching absorption (1727 cm−1), C–H
produced by 240 h of the xenon test. Moreover, it was found that both stretching (2927 cm−1) and C–O stretching (1161 cm−1), and increases
water and ultraviolet light are necessary to reproduce the degradation. in OeH stretching (3462 cm−1) and COeOH stretching (1700 cm−1).
Epoxy acid coatings consist of ester bonds formed in acrylic resin and in
crosslinking; therefore, either one of the polymer network or chain
3.2. Chemical changes of coating surfaces subjected to various types of
scission occurs as a function of outdoor exposure time due to hydrolysis
exposure
or photo-oxidation reactions (Scheme 2). An absorption peak at
1755 cm-1 appeared. Therefore, the polymer network or chain is as-
Figs. 6–8 show FT-IR difference spectra for various exposed and
sumed to be diminished by the photo-oxidation reaction for epoxy acid
unexposed samples. Peaks rising and falling from the baseline indicate
coatings.
increases and decreases in the absorption of functional groups, re-
It was found that degradation on the surface is consistent with main
spectively.
chain scission for all samples. Possible mechanisms for this degradation
For the 2K polyurethane coatings, there were decreases with out-
on the surface, even after a short exposure time, are as follows. The
door exposure time in COeNH (amide II) bending absorption (peak
attenuation of UV light that passes through the clear coat depends on
area centered at 1510 cm−1), C]O stretching (1741 and 1691 cm−1),
pass length due to the effect of the UV light absorber additive. However,
C–O stretching (1240 cm−1), C–H stretching (2931 cm−1), and C–H
the UV light absorber cannot effectively shield the topmost surface of
bending (1480 cm−1), and increases in OeH stretching (3462 cm−1)
coatings due to the Lambert-Beer law. Therefore, UV light leads to the
and NeH stretching (3280 cm−1). This indicates that main chain scis-
chemical degradation of the coating surface even after a short exposure.
sion occurs as a function of outdoor exposure time due to hydrolysis
The UV light absorber is effective for deeper regions of the coatings,
reactions (Scheme 1). The absorption peak at 1755 cm-1 indicates that
which thus retain their bulk properties.
peroxides were generated. These results indicate that the peroxides and

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Table 3
Estimation of outdoor exposure time (months) that corresponds to 240 h of
accelerated exposure for Coating B.
ν(C-H) ν(N-H) ν(O-H) ν(COO) ν(C-O) ν(NH-CO)

Xenon test 0.7 0.3 0.6 1.2 2.3 1.6

Xenon test 0.7 0.2 0.4 0.2 1.4 0.3
without water

Table 4
Fig. 12. Estimation of outdoor exposure time that corresponds to the ac- Estimation of outdoor exposure time (months) that corresponds to 240 h of
celerated exposure from FT-IR absorption. (The difference in the absorbance of accelerated exposure for Coating C.
the alkyl bond was 0.0024, indicating that the degree of degradation in the
ν(C-H) ν(COC = O) ν(COO) ν(O-H) ν(C = O)
xenon test after 240 h corresponds to that after 0.94 months of outdoor ex-
posure for Coating A. The estimation line is the linear interpolant between Xenon test 2.0 0.95 1.7 0.35 0.0
experimental points.). Xenon test 1.3 0.0 0.17 0.0 0.0
without water

3.3. Relationship between chemical degradation and scratch properties

A. Therefore, the degradation reactions in the xenon test were more
The relationship between the critical fracture force and FT-IR ab- promoted than those in the xenon test without water. The degree of
sorption associated with main chain scission, degradation products, and degradation after 240 h of the xenon test without water corresponds to
desorption products was examined (Fig. 9 and 10). After outdoor ex- that after 0–4.4 months of water immersion for Coating A. The amount
posure for 3 months, the critical fracture force decreased and absor- of peroxide equivalent to 3.5 months was generated by photo-oxida-
bance changed, indicating degradation of the coatings. This implies that tion, and those of OH bonds and NH bonds equivalent to 0 and 0.63
there is a good correlation between the critical fracture force and the months, respectively, were generated by the hydrolysis of crosslinks in
degradation reaction. This interpretation can also be applied to the water immersion. The ratio of each reaction in the water immersion test
epoxy acid coatings (Fig. 11). However, the critical fracture force be- was different from that in the outdoor weathering test. The degradation
came almost constant from 3 to 12 months, even though degradation is reactions in various accelerated weathering tests were different from
assumed to have continued after 3 months. The critical fracture force is that in the outdoor weathering test for Coating B (Table 3) and Coating
only weakly related to the degree of degradation after 3 months for all C (Table 4).
sample types. Therefore, scratch resistance degrades as a function of The degradation reactions with accelerated exposure were the same
main chain scission in the early exposure period. kinds as that with outdoor exposure, but the balance between the ex-
tents of reactions was not reproduced. The photo-oxidation reaction in
3.4. Comparison of degree of degradation with outdoor exposure and the xenon test was more promoted than that in the outdoor weathering
accelerated exposure test. This may be due to the difference in exposure conditions between
the outdoor weathering test and the accelerated weathering test in
To investigate the difference in the effects of outdoor exposure and terms of UV radiation, temperature, and moisture, and the changes of
accelerated exposure on these coatings, the degree of degradation de- these parameters or other substances derived from the environment.
termined from the FT-IR spectrum of each functional group was com-
pared. Fig. 12 shows the method used to estimate the equivalent ex-
posure time for the alkyl bond. The difference in absorbance by the 4. Conclusions
alkyl bond between outdoor exposure and accelerated exposure was
0.0024, indicating that the degree of degradation after 240 h of the This study revealed that the physical and chemical changes of
xenon test corresponds to that after 0.94 months of outdoor exposure coatings exposed to outdoor weathering are related to scratch re-
for Coating A. Tables 2–4 show outdoor exposure time that corresponds sistance. These changes were compared to those in accelerated weath-
to accelerated exposure time for each functional group for Coating A, ering tests.
Coating B, and Coating C, respectively. After only 1 month of outdoor exposure, the scratch resistance of
The degree of degradation after 240 h of the xenon test corresponds both isocyanate and epoxy acid coatings remarkably decreased even
to that after 0.49–2.3 months of outdoor exposure for Coating A though there was almost no change in the bulk properties. This decrease
(Table 2). The amount of peroxide equivalent to 2.3 months was gen- in scratch resistance is likely due to crosslink scission in the coating
erated by photo-oxidation, and those of OH bonds and NH bonds surface layer by oxidation and hydrolysis during exposure.
equivalent to 0.49 and 0.62 months, respectively, were generated by Although the xenon test also lowered the scratch resistance and
the hydrolysis of crosslinks in the xenon test. The ratio of each reaction caused the same kinds of chemical changes as those found with outdoor
in the xenon test was different from that in the outdoor weathering test. weathering, the proportions of each reaction were different between the
The degree of degradation after 240 h of the xenon test without water two types of weathering. Neither the xenon test without water spraying
corresponds to that after 0-0.84 months of outdoor exposure for Coating nor the water immersion test could reproduce the scratch resistance

Table 2
Estimation of outdoor exposure time (months) that corresponds to 240 h of accelerated exposure for Coating A.
ν(C-H) ν(N-H) ν(O-H) ν(COO) δ(C-H) ν(C-O) ν(NH-CO)

Xenon test 0.94 0.49 0.62 2.3 1.2 1.9 1.8

Xenon test 0.1 0.3 0.71 0.84 0.68 0.19 0.0
without water
Water immersion 0.59 0.0 0.63 3.5 4.4 2.8 0.13

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