Progress in Organic Coatings 64 (2009) 387–391

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Evaluation of mar/scratch resistance of a two component automotive

clear coat via nano-indenter
Z. Ranjbar a,∗ , S. Rastegar b
a
Department of Surface Coatings & Corrosion, Institute for Colorants, Paint and Coatings, Tehran, Iran
b
Farayand Rang Khodro Co., Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Nano-indenter as a technique for characterization and evaluation of mar/scratch resistance of a two
Received 18 June 2007 component automotive clear coat is used. Different responses of the coatings to the marring stress and
Received in revised form 28 July 2008 critical forces are discussed. The plastic deformation compared to the elastic part and the damage width
Accepted 1 August 2008
is decreased by adding nano-silica in the coatings formulation.
© 2008 Elsevier B.V. All rights reserved.
Keywords:
Automotive coatings
Clear coat
Nano
Mar resistance
Nano-indentation

1. Introduction ing after being subjected to a traversing tangential load of known

Beside corrosion protection consumers expect to have a high
gloss, good looking car even after many years of service. Durability
of appearance is given by clear coat, which has to have good mar
and scratch resistance even after long-term weathering.
Mar/scratch resistance of the automotive clear coatings is one of
the most important criteria for many customers [1] and is crucial for
coatings/materials in many applications, e.g. the polymer topcoats
used in the automotive industry [2–9].
Mar/marring refers to the light surface damages encountered
in the real field that are usually shallow and narrow while
scratch/scratching refers to the medium to severe damages.
A single mar may not be readily noticeable; however, the exis-
tence of a group of mars does degrade the appearance of coatings.
The term “mar resistance” is recommended in preference to other
terminology existent in the current literature, such as “scratch”
or “abrasion” resistance, since the latter terms have historically
referred to far more severe damage that is associated with serious
consequences such as allowing corrosion of the substrate to begin
(scratching) or complete loss of the protective coating (abrasion)
[10].
Conventional methods utilized to quantify the scratch resistance
of a coating are such measurements as reduction in gloss of a coat-
∗ Corresponding author.
E-mail address: ranjbar@icrc.ac.ir (Z. Ranjbar).
particle size abrasive (crockmeter test); measurement of damage
depth and recovery of damage depth of a coating after exposure to
a single point indentor (nano-indentor) [11]; or quantitative mea-
surement of the fraction of elastic, viscoelastic creep, and fracture
response of a coating after exposure to a single point indentor (scan-
ning probe microscope) [12].
Scratch resistance is rated using multi-scratch testing equip-
ment like the Amtec-Kistler laboratory car wash simulation, the
Rota-Hub Scratch-Tester or the crockmeter, which are designed to
simulate the damage occurring in practical use of a car. The ranking
is done by measuring the gloss loss of the coating with a reflec-
tometer. A high gloss loss means low scratch resistance. On the
other hand, the nano-scratch technique offers a scientific method
to reveal the mechanisms of scratch damage [13–15].
The results of both multi-scratch and nano-scratch experiments
are related to physical materials properties and chemical structure.
In the present study, nano-indenter and a scanning probe micro-
scope are used.
2. Experimental
2.1. Materials
A two-component solventborne clear coat based on acrylic
polyol resin (viscosity 3.5 Pa s, solids content 70%, clear, Cytec Co.)
and hexamethylene di-isocyanate (HDI, Bayer Co.) was used in the
experiments. Butyl acetate, xylene, and ethoxy propylacetate were

0300-9440/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2008.08.001
388 Z. Ranjbar, S. Rastegar / Progress in Organic Coatings 64 (2009) 387–391

Fig. 1. Two different mar configurations: (a) plastic deformation dominates and (b) abrasive wear (mass loss) dominates.

used to thin the samples for spray application. Nano-silica powder

was used to improve the mar and scratch resistance of the samples
(12 nm, NanoTech Co.) The dried film thickness of the samples was
20 ± 3 ␮m.

2.2. Instruments

A Nano-Scratch Tester (NST) from Hysitron Inc. was used for the
generation of a single scratch. In performing the scratch, the tip
first makes a pre-scan under a light load of about 10 mN or less to
measure the surface profile along the line to be tested. The surface
profile is stored and used to automatically correct subsequent data.
During the scratching procedure, lateral motion, applied load,
real-time penetration depth, and the frictional force encoun-
tered by the tip are recorded. Following the scratching, the tip
makes a post-scan to measure the residual depth of the scratch.
Curves of applied load, real-time penetration depth, residual depth,
and frictional force vs. the lateral movement of the tip can be Fig. 2. Illustration of how to calculate the micro-mar resistance (MMR) and three
plotted. different responses of coatings to marring stress [3].
 Z. Ranjbar, S. Rastegar / Progress in Organic Coatings 64 (2009) 387–391 389

Fig. 3. Representation of applied load vs. indenter displacement for blank (a) and nano-silica filled the clear coat (b).

Lab homogenizer (UP400S, 400 W, 24 kHz, Hielscher Co.) was
used to disperse the nano-silica in the clear coat.
2.3. Preparation of clear coat containing nano-silica
4 wt% of silica powder based on total weight of resin was dis-
persed in ethoxy propylacetate via an ultrasonic process (UP400S).
The resin was mixed with HDI based on the molar ratio of 1:1
for –OH/–NCO at room temperature.
3. Results and discussion
Most tested coatings showed a combination of the responses as
shown in Fig. 1.
The total cross-section area of the two shoulders is less than
the cross-section area of the ditch. In this case, the area of the two
shoulders reflects the plastic deformation, and the difference, con-
sidering the compressibility of the tested coatings is no more than
5%, between the total area of two shoulders and the area of the
390 Z. Ranjbar, S. Rastegar / Progress in Organic Coatings 64 (2009) 387–391

Fig. 4. Comparison between plastic and elastic deformation depth for blank and
nano-filled samples.

ditch reflects the abrasive wear, i.e. mass loss. Fig. 2 illustrates how
to calculate the micro-mar resistance (MMR) and three different
responses of coatings to marring stress, based on the dimensions of
the mar. The largest inverted triangle represents the cross-section
area of the tip that penetrated the surface during the marring, which
was calculated based on the real-time penetration depth during the
marring and the shape of the tip.
The difference between it and the cross-section area of the resid-
ual ditch reflects the immediate elastic recovery. The calculation of
plastic deformation and abrasive wear was mentioned above. In
the MMR calculation, the cross-section area of the ditch was used
first to divide the applied force. Later, it was replaced by the cross-
section area of the rough, which is the cross-section area of the
ditch plus the area between two shoulders, if any, based on the fol-
lowing consideration. Suppose two mars possess the same size of
ditch, but one has two shoulders and the other has none. Due to
the larger topographic fluctuation of the surface, the damage of the Fig. 5. Horizontal distance for the blank (a) and nano-filled samples (b).
first sample will be more visible. To make the MMR more consistent
with the visual judgment and other optical evaluations, the cross-
section area of the trough was used to replace the cross-section tic part decreases which results in improving mar and scratch
area of the ditch in the calculation of MMR. resistance.
Although the nano-indenter equipped with the diamond tips The other parameter which is very important for a mar to
can make artificial mars/scratches with dimensions similar to those be visible on the coatings surface is the horizontal distance of
encountered in the field, the scraping speed is much slower than the mar/scratch which has remained on the surface after mar-
most scrapings in the real field. The speeds used in the tests are lim- ring/scratching. As Fig. 5 shows the horizontal distance for the blank
ited by the data-taking rate of the indenter, which is five data points sample is equal to 1758 nm and is declined obviously by adding
per second. To acquire enough data points of the real-time pene- nano-silica to 498.05 nm which confirm that the mar resistance of
tration depth, encountered frictional force, etc. along the scratch the clear coat has improved.
for analysis, we keep the scraping speed slower than 20 mm/s in
the majority of tests, which is the main limitation of the micro- and
nano-scale measurements. 4. Conclusion
As Fig. 3 shows the elastic and plastic contact depth are equal
to 312 and 73 nm (385 (total deformation) − 310 (elastic deforma- A nano-indenter is used to characterize the mar/scratch resis-
tion) = 75 nm (plastic deformation)) for the blank sample while by tance of automotive clear coatings. The results showed that by
adding nano-silica to the clear coat the elastic and plastic contact adding nano-silica to the clear coat the plastic deformation is
depth decrease to 280 and 70 nm (350 (total deformation) − 280 decreased. Also the other parameter which is very important for
(elastic deformation) = 70 nm (plastic deformation)). So, it could a mar/scratch to be visible is the horizontal distance of the damage.
be concluded that increasing nano-silica has positive effect on the The latter is reduced dramatically by adding nano-silica.
plastic and total deformation of the clear coat. As Fig. 3 shows the
hardness of the sample containing nano-filler has increased con-
siderably (250 MPa for the blank sample compared to 300 MPa for Acknowledgements
the nano-filled sample).
Fig. 4 shows the comparison between plastic and elastic This work is supported by the National Science Founda-
part of deformation for blank and nano-filled samples. As could tion/Ministry of Science, Research and Technology. The authors are
be seen by adding nano-silica to the formulation the plas- grateful to Mrs. Kardar for her collaboration.
 Z. Ranjbar, S. Rastegar / Progress in Organic Coatings 64 (2009) 387–391
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