Progress in Organic Coatings xxx (xxxx) xxx–xxx

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Progress in Organic Coatings

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

Versatile protection of exterior coatings by the aid of graphene oxide nano-

sheets; comparison with conventional UV absorbers
⁎
M. Hasani, M. Mahdavian, H. Yari , B. Ramezanzadeh
Department of surface coating and corrosion, Institute for color science and technology, Tehran, 1668814811, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, graphene oxide nanoparticle was introduced as a versatile additive to enhance weathering and
Graphene oxide long-term corrosion performance of polyurethane (PU) coatings. For comparison purpose, the weathering per-
Weathering resistance formance of graphene oxide was compared with that of a typical organic UV absorber. The results demonstrated
Corrosion that graphene oxide could significantly improve the weathering and corrosion resistance of the coating. It was
UV absorber
also revealed that while organic UV absorber could stabilize the coating for a limited time of weathering
Polyurethane coatings
(temporary), graphene oxide stabilized the coating for a long time (permanent). The mechanisms of such per-
manent UV stabilization were also discussed.

1. Introduction In recent decades, various nano-structured inorganic particles like

Polymeric coating systems are designed for protective and aesthetic
demands. In a multi-layer coating system, topcoat as the final layer has
a crucial role because it is required to provide interesting appearance
and to protect the underneath layers and substrate against environ-
mental factors like sunlight, humidity, chemicals, etc. during service
life. If the topcoat remains intact during its service life; water, oxygen
and corrosive ions cannot easily reach to metal/coating interface and
thus adhesion loss and corrosion would not occur at early time of ser-
vice [1–3]. Therefore, the topcoat layer must be formulated not only
based on the most resistant polymeric binders but also should be
strengthened with some additives to enhance the long-term properties
of the topcoat.
Among several polymeric binders, polyurethane (PU) is considered
as the most common type of binders for topcoat applications thanks to
its outstanding properties especially weathering resistance. However,
further strategies like incorporating light stabilizing substances into PU
coating should also be utilized to guarantee the weathering resistance
of the coating for a relatively long time. Numerous studies, as reflected
by a great number of publications, have been performed to protect PU
systems against weathering conditions [4,5]. For such purpose, addition
of some light stabilizers like organic UV-absorbers (UVA) have been
extensively used [5,6]. These organic materials are effective in enhan-
cing the photostability, but their performance is restricted because of
their depletion in the coating during service life mainly due to photo-
decomposition, migration, evaporation and interaction with other
coating components [7].
Titania [8,9], Zinc oxide [10,11], Ceria [12] and Iron oxide [13] have
been introduced to improve the weathering performance of polymeric
coatings. The improvement mechanism of these nanoparticles is based
on their screening (both absorption and scattering) effect of incident
rays in the range of UV region. While these inorganics can significantly
stabilize the coatings against outdoor exposure, they have photo-
catalytic activity which can destruct the surrounding organic binder
[14,15]. Therefore, they usually have to be surface-modified to elim-
inate/quench their photocatalytic activity which is a time and money
consuming process [16].
Graphene-based materials have recently attracted very much at-
tention because of their especial electronical structure which create
unique electrical, mechanical, chemical properties [17–21]. These
novel materials are made of one to few layers of carbon which have
been conjugationally attached. Such electronic structure makes gra-
phene based materials capable of photon absorption in UV region which
have been extensively studied in many publications [22,23]. In these
studies, UV absorption has been investigated as a reliable criterion to
characterize different electronic transfer states occurring during
synthesis, modification and dispersion of graphene-based nano-struc-
tures [22,24,25]. Such absorption capability in UV region as well as no
photocatalytic activity of graphene based materials can be promising to
introduce them as novel candidates for polymeric coatings photo sta-
bilization. In addition, graphene based materials thanks to their high
surface area has been employed as barrier pigments in polymeric
coatings [26–28], but their corrosion performance during outdoor
weathering has not been considered yet. Graphene oxide, as a

⁎
Corresponding author.
E-mail address: yari-ho@icrc.ac.ir (H. Yari).

https://doi.org/10.1016/j.porgcoat.2017.11.020
Received 26 August 2017; Received in revised form 8 November 2017; Accepted 26 November 2017
0300-9440/ © 2017 Elsevier B.V. All rights reserved.

Please cite this article as: Hasani, M., Progress in Organic Coatings (2017), https://doi.org/10.1016/j.porgcoat.2017.11.020
M. Hasani et al.
Fig. 2. The total color change (ΔE) versus exposure time for different samples during
weathering.
frequently-used graphene-based material in composites, has the gra-
phene basal plane which contains several oxygenated functional groups
(hydroxyl, epoxide and carboxylic) on the basal plane and the edges
[29]. While, these functional groups disarrange the hybridized sp2
carbon continuity, they facilitate sheet exfoliation and better dispersion
in organic solvents and matrices. Graphene oxide is excellent filler for
the polymer reinforcement. From a physical point of view, graphene
oxide has much higher transmittance in visible region compared to
graphene which is more favorable to be used as UV screener in top-
coatings.
The objective of this research is to study the influence of graphene
oxide addition on the weathering performance of a PU coating. In order
to evaluate the protection efficiency, PU coating loaded with graphene
oxide was compared with two control PU coatings (a neat PU coating
and a PU coating containing a typical organic UV absorber). All
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Progress in Organic Coatings xxx (xxxx) xxx–xxx
Fig. 1. b*variations during exposure to ac-
celerated weathering condition.
coatings were exposed to accelerated weathering condition and after
various weathering time, different techniques were employed to phy-
sically, chemically and structurally evaluate the degradation occurred
on each coating. In addition, the weathered coatings were further ex-
posed to salt spray test to study the corrosion performance of different
coatings during weathering.
2. Experimental
2.1. Materials
Natural graphite flake (supplied by Kropfmuehl Graphite Co,
Germany) was utilized for the synthesis of graphene oxide. An Organic
UV absorber (2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol, Tinuvin
328) were purchased from Ciba Company. The molecular weight and
melting point of UV absorber were respectively 351.5 gr/mol and 88∘C.
PU coating was based on a hydroxyl functional acrylic resin (Tacryl
1210N provided from Taak Resin Chemical Co, hydroxyl percentage:
4.5%, solid content: 60%) and a typical aliphatic polyisocyanate
hardener (Desmodure N75, purchased from Bayer Company, NCO
content: 12.5%, solid content: 75%).
2.2. Samples preparation
Graphene oxide was synthesized via modified Hummer’s method
[30–32]. The aqueous graphene oxide suspension was subjected to a
solvent-exchange process to achieve fine graphene oxide dispersion in
Dimethylformamide (DMF). The organic UV absorber was a yellow
powder form which also dissolved in DMF.
The coating system used in this study was a bilayer coating system
applied over a pre-treated steel panel; an epoxy-polyamide based
coating filled with various barrier pigments as primer and the PU-based
coating as topcoat. To prepare primer coating, a Bisphenol A- based
Fig. 3. Variations in gloss of different coatings at various exposure
time.
M. Hasani et al.
epoxy resin was formulated with some barrier fillers (i.e. iron oxide,
TiO2 and talc mineral) and conventional additives (i.e. leveling agent,
defoamer and dispersing agent) and toluene as solvent. The mixture
was mixed for 3 h by a pearl-mill in order to obtain an average particle
size up to 15 μm. Then, the polyamide curing agent (Cray amide 115,
solid content 50 wt.%) was added to the epoxy resin at weight ratio of
4:1 (epoxy: polyamide) and mixed for 10 min. The resulting coatings
were applied on the bare steel by an air spray. Samples were then kept
at room temperature for 24 h.
In order to evaluate the weathering performance of graphene oxide
and compare its efficiency with a commonly used UV absorber, three
topcoat formulations were prepared. The PU coating without any ad-
ditive coded as “Blank” was considered as the control coating. 0.1 wt.%
(based on binder content) of synthesized graphene oxide and UV ab-
sorber (Tinuvin 328) were separately added to the PU formulations
which are respectively coded as “GO” and “Tin” hereafter. The PU
composites (Blank, Tin and GO) were applied on the epoxy primer
coatings using a film applicator. Finally, samples were cured in an oven
at 120 °C for 30 min. The dry thicknesses of primer and topcoat layers
were 45–55 μm and 50–60 μm, respectively.
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Progress in Organic Coatings xxx (xxxx) xxx–xxx
Fig. 4. Variations of water contact angle against exposure time for
different coatings.
Fig. 5. Variations of coatings roughness against exposure time to
weathering.
Fig. 6. Variations of coatings roughness against exposure time.
2.3. Accelerated tests
2.3.1. Weathering condition
According to ASTM G154, a weathering chamber Model BGD856
was employed to accelerate the weathering condition on coating sam-
ples. The coated samples were cyclically exposed to UV-A radiation
(energy 0.71 W/m2) for 4 h followed by a humidity condensation for
4 h at 50 °C. This cyclic exposure continued up to 700 h while at dif-
ferent pre-determined durations (200, 400 and 700 h), samples were
removed to follow the changes in coating performance during weath-
ering.
2.3.2. Salt spray
In order to assess the corrosion resistance of different samples
during weathering, the weathered coatings were placed in a salt spray
cabin according to ASTM B117. The pH, NaCl concentration and tem-
perature in cabin were 7, 5 wt.% and 35 °C respectively.
M. Hasani et al.
Fig. 7. UV–visible spectra of different coatings a) before and b) after 700 h exposure.
2.4. Characterization
2.4.1. Appearance
Color measurements were performed before and after weathering
with a portable spectrophotometer model sp-64 manufactured by X-rite
(d/8° measuring geometry, 10° standard observer, D65 standard illu-
mination source). The overall color change (ΔE) was calculated using
following equation in CIE L*a*b* color space system:
3 ΔE = (Δl*)2 + (Δb*)2 + (Δa*)2
Where L* is lightness, a* and b* describe the chromatic coordinates on
the green-red and blue-yellow axes, respectively.
Gloss of different coatings before and after various time of weath-
ering were measured at 60° using a Micro-TRI-Gloss instrument from
BYK Gardner.
2.4.2. Surface properties
In order to characterize the hydrophobic/hydrophilic character of
different coatings during weathering, water contact angles of the
samples were measured by Kruss G40 contact angle measuring system.
Optical photographs were taken from the water droplet using a CCD
camera and the contact angle was measured using software attached to
the instrument. Surface roughness of different coatings was measured
using a TR100 Surface roughness tester. Ra is reported as average
roughness of surface coating.
Micro indentation technique was used to evaluate coatings' hard-
ness. In this test, a predetermined force (F), which is equivalent to 1 kg
is applied on the coating surface for ten seconds and the hardness was
calculated according to below equation:
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Progress in Organic Coatings xxx (xxxx) xxx–xxx
α
F Sin F
HV = = 2F 2 2 = 1854.4 2
A d d
Where d is the residual impression diameter [33,34].
The morphology of the coatings surface after being exposed to
weathering condition was investigated using a LEO1455 VP scanning
electron microscope (SEM).
2.4.3. Bulk properties
UV–vis spectroscopy was used to study the absorption/transmission
capacities of free-standing films of different topcoats in the range of
200–700 nm before and after exposure to weathering. In order to in-
vestigate the structural attributes of Blank, GO and Tin coatings, dy-
namic mechanical thermal analysis (DMTA) was also carried out by
means of a Teritec 2000 instrument. The temperature range was
30–160 °C which was scanned with a heating rate 10 °C/min. A peri-
odical strain (up to 0.1%) with a frequency of 1 Hz was applied on the
sample during DMTA experiment. Thin free film of coatings were used
for UV–vis and DMTA. A FTIR spectrometer model SPECTRUM ONE
was employed to study the changes in chemical groups of various
coatings during exposure to weathering.
2.4.4. Electrochemical properties
Electrochemical impedance spectroscopy (EIS) was employed to
investigate the corrosion protection performance of variously weath-
ered coatings. EIS analysis was carried out in a conventional three-
electrode cell including saturated Ag/AgCl, Platinum and steel sample
as reference, counter and working electrodes, respectively. The mea-
surements were done in the frequency range of 10 kHz to 10 mHz at
10 mV amplitude sinusoidal voltage using the Ivium Compactstat at
open circuit potential. Measurements were performed on 1 cm2 of the
coating surface immersed in the 3.5 wt.% NaCl solutions. The EIS
measurements were performed 3 times for each sample to ensure the
repeatability of the measurements.
3. Results and discussion
This paper aims at investigating the capabilities of graphene oxide
nanosheets to be used as a novel candidate for weathering and corro-
sion resistance enhancement of coatings. For this purpose, its perfor-
mance has been also compared with conventional organic UV absor-
bers.
3.1. Colorimetric analysis
Color change of coatings during weathering is an important para-
meter to visually evaluate the coating degradation. The color of dif-
ferent coatings before weathering was evaluated to compare their in-
itial color. The color components of different coatings are: Blank
(L*:80.88, a*: −0.64 b*: −0.7), Tin (L*:80.88, a*: −0.69 b*: −0.7)
and GO (L*:58.18, a*: −0.64 b*: 1.2). These data clearly demonstrate
while UV absorber does not change the color of the coating, GO causes a
reduction as much as 25% in lightness of the coating and makes it
slightly yellower. This level of color change might be critical where a
high level of transparency and clarity is required like automotive
clearcoats, but it is acceptable in most industrial coating applications
and dark-colored pigmented topcoats.
The main color components which are usually considered in
weathering performance are b* and total color change (ΔE). Fig. 1
shows the variations in b*. It is observed that b* value increases for all
samples as the weathering time elapses. This increase is the con-
sequence of polymeric chain scission and formation of chromophoric
groups which absorb short wavelengths of visible region, making the
samples yellowish [35]. While b* values for Blank and Tin samples are
lower than that of GO coating, they experience a sharp increase in b*
especially at early time of weathering so that their b* increases to values
M. Hasani et al. Progress in Organic Coatings xxx (xxxx) xxx–xxx

Fig. 8. The graphs of a) storage modulus b) Tan delta for all samples
during weathering.

Table 1 It is observed that for all coatings the gloss linearly declines during
Crosslink density, Tg and width of tan delta for different samples before and after 700 h weathering. The gloss retention after 700 h exposure time demonstrates
exposure to weathering. that while the Blank coating has the least gloss retention, the coating
Crosslink density (mmol/cm3) Tg(°C) peak width(°C)
containing graphene oxide nanosheets retains its gloss more efficiently
compared to Blank and Tin samples.
Before After Before After Before After The gloss of Blank and Tin samples at beginning is highest, because
it doesn’t have nanoparticles in their formulation but over weathering
Blank 0.69 0.41 37 46 16 19
Tin 4.72 2.62 48 43 15 20
period they lose their gloss with a steeper drop. Gloss retention in
GO 1.03 3.06 46 75 10 20 percentage was calculated as the difference between initial and final
(after 700 h exposure) gloss divided by initial gloss. As seen in Fig. 3,
GO sample experiences the least changes and maintains its gloss rela-
higher than that of GO. According to Fig. 1, GO experiences an increase tively.
in b* for first 200 h after which it remains unchanged. The lowest
variations in b* belongs to the GO which indicates the less intensive 3.3. Contact angle
formation of degradation products in presence of graphene oxide na-
nosheets. In order to study the surface properties of coatings during weath-
ΔE, as the most comprehensive criterion of the color changes which ering, water contact angle measurement technique was performed.
is the sum of changes in all color components, is shown in Fig. 2. Fig. 4 demonstrates water contact angle for different coatings exposed
As can be seen, the most color variations over the whole exposure to various time of weathering. The results show that before being ex-
time belong to Blank PU coating. The sample containing graphene oxide posed to weathering condition, the GO sample possesses the lowest
nanosheets at early exposure time has considerable color change and water contact angle value that may be attributed to the hydrophilic
after 400 h of exposure its color remains unchanged. For Tin sample, it character of graphene oxide nanoparticles and higher surface roughness
performs between Blank and GO, but its character is more similar to of this sample (which will be shown in next section). When the poly-
Blank which reveals a sharp rise in ΔE at first 400 h exposure followed meric coatings are exposed to weathering condition the photo-oxidation
by an alleviated increment rate for longer exposure. According to these products are formed. These products are hydrophilic and make surface
changes, it is shown that on contrary to Blank and Tin samples, GO coatings more hydrophilic as the weathering proceeds. It is seen that
experiences the least changes and keeps its stability during weathering. while the Blank sample experiences the highest variations, GO sample
undergoes the least changes which can be an indication of high level of
3.2. Gloss retention protection in presence of graphene oxide particles.

The gloss variations of coatings during weathering are depicted in 3.4. Roughness
Fig. 3. Considering gloss values of different coatings before weathering
(exposure time = 0 h) reveals that addition of UVA and graphene oxide Surface roughness changes is a typical phenomenon in weathering
nanosheets into the coating reduces its gloss around 5–8 °. degradation that can spoil the aesthetic properties especially gloss of

5
M. Hasani et al.
the coatings. In Fig. 5, variations in coating roughness during exposure
are presented. The roughness values of different coatings indicate that
as the weathering proceeds, the coatings surface becomes rougher. This
can be assigned to release of some degradation products, short poly-
meric chains or some water soluble degradation species from coating
surface, leaving some unevenness on the coating surface. The roughness
results can also account for the reduction of contact angles and gloss. It
is well known that according to Wenzel equation, increase in roughness
for a hydrophilic surface promotes its hydrophilicity [36]. Thus, beside
formation of polar products, the roughness increment can be another
reason for water contact angle reduction during weathering. On the
other hand, increase in roughness decreases the gloss due to light
scattering caused by decreased smoothness of the coating surface. It is
observed in Fig. 5 that for Blank sample the roughness continuously
increases as the weathering time elapses. For Tin sample it relatively
maintains its roughness for first 400 h, after which it suddenly loses its
smoothness and become rougher which may be an indication of lost
efficiency of UVA molecules at later time of exposure. In case of GO
sample, it is seen that while its initial roughness is higher than Tin and
Blank (because of the nanoparticles), it retains its roughness more ef-
ficiently than other samples. Once more, it is demonstrated that the
coating loaded with graphene oxide nanosheets exhibits the highest
level of weathering stability compared to Blank and Tin coatings.
3.5. Hardness
Hardness is one of the most important mechanical characteristics of
top coating systems that should be considered to not be negatively af-
fected during weathering. Fig. 6 shows hardness of different coatings
during weathering. Hardness of different coatings before weathering
reveals that while addition of UVA slightly decreases the hardness,
graphene oxide significantly enhances the coating hardness.
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Progress in Organic Coatings xxx (xxxx) xxx–xxx
Fig. 9. FTIR spectra of different coatings before and after exposure to
weathering.
As depicted, for all coatings hardness decreases during weathering
exposure. Loss of hardness can be attributed to the chain break as a
result of degradation reactions which gradually destruct the polymeric
network and consequently the mechanical properties of the coatings.
The most hardness decline over exposure time is related to Blank
samples and addition of UVA slightly improves the performance espe-
cially for first 400 h of weathering exposure. It is also seen that GO
coating performs much well during weathering compared to Tin and
Blank coatings and experiences the least changes.
The results presented so far clearly demonstrate that both graphene
oxide and organic UV absorber could improve the weathering perfor-
mance of the PU coating, but the former outperforms considerably the
latter especially at later time of weathering exposure. The reason of
such improvement might be assigned to the different responses of
variously loaded coatings to the incident rays reaching the coating
surface. Thus, UV–vis spectra of different coatings were recorded for
such purpose.
3.6. UV–vis spectroscopy
Absorbance spectra of different PU coating before and after 700 h
exposure to weathering condition in the range of 200–500 nm are
shown in Fig. 7.
As can be seen in Fig. 7a, while Blank sample reveals the least ab-
sorption capability, Tin sample exhibits the highest level of absorption
in UV region (ranked based on the absorption: Tin > GO > Blank).
After 700 h exposure to weathering condition (Fig. 7b), GO sample has
the most absorption (ranked based on the absorption: GO > Tin >
Blank). These evidences clearly show that the absorption capabilities of
Tin coating decreases over weathering exposure. This can explain the
reduced weathering performance of Tin sample at longer time of
weathering. The reduction of protection efficiency of organic UV
M. Hasani et al.
Fig. 10. Variations in a) urethane b) carbonyl indices of coatings during weathering.
absorber has been previously illustrated in literature [7]. Migration,
photodecomposition and evaporation are the main factors in depletion
of organic UV absorbers during weathering [37,38]. On contrary to Tin
sample, GO sample maintains its absorption during weathering which
rationalizes the high protection efficiency of GO sample for the whole
range of weathering. Permanent absorption provided by graphene
oxide is not the only reason of better performance of GO compared to
Tin and Blank sample. It seems there should be other mechanisms in-
volved in extensive and efficient protection in presence of graphene
oxide. Other capabilities of graphene oxide like UV scattering and free
radical scavenging can also play a big role in achieving such level of
protection against degradation. Unlike organic UV absorbers which
protect the substrate via only UV absorption, Graphene oxide na-
nosheets thanks to its particulate nature can also scatter the incident
rays and partially deviate the harmful energies from their transmission
direction and reflect back them, resulting in less degradation in the
coating. Free radical scavenging function of carbon-based materials like
carbon nanotubes and graphene-based nanostructures has been thor-
oughly studied [39,40]. Since UV absorbers are not able to perfectly
block the incident rays, incorporating a combination of a UV absorber
and a free radical scavenger is highly recommended to achieve a high
level of weathering stability. Thus, the considerable improvement of
weathering protection of GO coating is beholden to the dual function
(UV blocking and free radical scavenging) of graphene oxide.
3.7. DMTA
DMTA is a powerful technique to evaluate some structural char-
acteristics (such as cross-linking density, Tg and homogeneity) of the
network formed during curing and weathering. The graphs of storage
modulus, tan delta (E”/E') versus temperature for all coatings before
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Progress in Organic Coatings xxx (xxxx) xxx–xxx
and after 700 h weathering are shown in Fig. 8. As the temperature
increases, the various physical interactions between polymeric chains
are diminished and therefore, their movement occurs more easily. Such
structural changes with temperature lead to gradual reduction in sto-
rage modulus (clearly shown in Fig. 8a) and simultaneously increase in
loss modulus of the coatings. Such variations in storage and loss mod-
ules cause a maximum in Tan delta diagram versus temperature (evi-
dently depicted in Fig. 8b). This maximum is a reliable criterion for
determination of Tg.
Crosslink density of each coating is calculated by the following
equation:
E′
ve =
3RT
Where νe is crosslink density. E' and T are storage modulus (MPa) and
temperature (°K) at beginning of rubbery plateau zone, respectively. R
as Gas world constant is equal to 8.314. The temperature at which the
tan delta is maximum is considered as Tg and the width at half height of
tan delta peak indicates the homogeneity of the system.
Crosslink density, Tg and width of tan delta results are presented in
Table 1. According to Table 1, before weathering Tin and GO samples
have higher crosslink density and Tg values compared to Blank and the
highest values belongs to Tin sample. All results before weathering
clearly demonstrate that different coatings have different behaviors
during curing.
It is observed that while crosslinking density and Tg decrease for
Blank and Tin during weathering, they increase for GO. The increased
crosslinking density of GO sample during weathering is probably as-
signed to the presence of graphene oxide nanoparticles which contains
several hydroxyl and carboxyl groups on its surface and can further
react with residual isocyanates [41]. Such functional surface can act
M. Hasani et al.
Fig. 11. SEM micrograph of surface after 700 h exposure to weathering condition.
like a crosslinker within the PU network, enhancing the crosslinking
density. In case of homogeneity, for all coatings it is seen that homo-
geneity decreases during weathering. Increased Crosslinking density of
GO by the aid of graphene oxide can decrease the homogeneity of the
system, as revealed by a significant increase in peak width for GO
sample during weathering.
In order to explain changes occurred in network structure before
and during weathering, more details about chemical structure of coat-
ings would be so useful. Thus, FTIR spectroscopy was utilized for this
purpose.
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Progress in Organic Coatings xxx (xxxx) xxx–xxx
3.8. FTIR
In order to study the variations in the chemical structure occurred
during weathering, FTIR spectra of different coatings before and after
400 and 700 h weathering are illustrated in Fig. 9. According to lit-
erature [42], changes in urethane bond and C]O urethane bonds
(corresponding peak around 1500–1550 cm−1 and 1720–1750 cm−1,
respectively) during a certain time of exposure can provide a reliable
criterion to compare weathering performance of PU coatings.
In order to quantify FTIR results, the intensity of these peaks were
M. Hasani et al.
normalized. For this purpose, the CeH peak at 2800–3000 cm−1 was
considered as a reference for each spectrum and other peaks were
normalized with this peak. The normalized values of urethane and
carbonyl for all weathered samples are shown in Fig. 10. The under
peak area of urethane (or carbonyl) was divided by that of reference
peak and the result was considered as urethane (or carbonyl) index.
The urethane linkages of different coatings before exposure reveal
that Tin has the greatest content of urethane linkage and Blank sample
has the lowest content of urethane groups. The urethane content is a
good criterion for the extent of curing reaction between hydroxyls of
polyol with isocyanates of hardener. The lower urethane content of
Blank is a good indicative of its immature network. This can be also
confirmed with the presence of free isocyanates peak at 2270 cm−1.
This peak is so weak for Tin and especially for GO which points out to
their relatively more mature cured network. These evidences are in
good agreement with crosslinking density data reported earlier that
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Progress in Organic Coatings xxx (xxxx) xxx–xxx
Fig. 12. Bode plots of different weathered a) 0 h b) 400 h c) 700 h
coatings before exposure to salt spray.
Blank and Tin revealed respectively the lowest and highest values of
crosslinking density. The high level of curing reaction in presence of
organic UV absorber may be attributed to the catalytic effect of several
tertiary amine groups available on the triazole moieties of UV absorber
which accelerate urethane formation [43,44].
In addition, polyurea linkage formation is another reaction which
occurs during PU network formation. Polyurea formation is a parallel
reaction in PU systems in which free isocyanates, via reaction with
water/humidity, are partially converted to amine groups. These amines
react with other free isocyanates, producing polyurea linkage. This
linkage can be recognized with a peak around 1680 cm−1 which is
assigned to polyurea carbonyl. The intensity of this peak for different
coatings before weathering reveals that GO has the strongest polyurea
carbonyl peak. The more extensive polyurea formation in GO may be
due to the hydrophilic nature of graphene oxide surface which uptakes
greater water/humidity and the higher probability of polyurea
M. Hasani et al.
formation.
As have been discussed in literature [42,45–47], the chemical
changes happening during weathering of PU systems are so complicated
because several counteracting reactions occur simultaneously during
weathering. While urethane bond scission, as the main weathering
degradation reaction of PU, decreases the urethane linkage content of
the coatings, post-curing reactions between residual functional groups
(free hydroxyl and isocyanates) increase the urethane content. Another
reaction occurring during weathering is the conversion of urea linkages
to urethane ones under UV exposure, [42,48]. The post curing reactions
and conversion of urea to urethane can be confirmed by a dis-
appearance of free isocyanate and urea carbonyl peaks respectively
located at 2230 and 1680 cm−1 as the weathering proceeds.
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Progress in Organic Coatings xxx (xxxx) xxx–xxx
Fig. 13. Bode plots of different weathered a) 0 h b) 400 h c) 700 h
samples after exposure to salt spray test condition.
As shown in Fig. 10, the urethane linkage decreases for all coatings
as the weathering time elapses. Urethane scission is a common reaction
which occurs during weathering degradation of PU coatings. It seems
that in spite of urethane formation via post curing and urea conversion,
urethane scission outweighs urethane formation, leading to diminish in
urethane. The higher rate of scission compared to that of formation is a
common phenomenon especially at later time of weathering [49]. Its
reason might be related to this fact that urethane formation is dominant
at initial times of weathering, while the weathering-induced urethane
scission reactions are dominant at longer times of weathering [46,47].
As seen, the rate of urethane depletion is higher for Blank sample
compared to Tin and GO samples.
Carbonyl formation is another product of photodegradation of
M. Hasani et al.
polymeric system during weathering [50]. The rate of carbonyl for-
mation is the most important indicator of photodegradation. As de-
picted, while the carbonyl formation rate is the highest for Blank
sample, GO sample presents the lowest rate of carbonyl formation. Both
urethane and carbonyl linkages clearly reveal that GO sample experi-
ences the least chemical changes during weathering. In good agree-
ments with all previous results, FTIR results could chemically illustrate
that graphene oxide nanosheets is an efficient nano-structured additive
to promote the weathering stability of coatings.
3.9. SEM
SEM technique was employed to study the degradation morphology
of different weathered coatings. Fig. 11 illustrates SEM images (with
two magnifications) for all samples after 700 h exposure to weathering
condition. As seen, Blank and Tin samples have been degraded in wide
area of coating surface (2000 x images). SEM image with higher mag-
nification of Blank sample (Fig. 11b) clearly shows the formation of
cracks on the coating surface. It is also observed that GO sample has
uniform degradation after being exposed to weathering condition and
with increase in magnification no cracks are visible on coating surface.
SEM micrographs reveal that graphene oxide nanosheets could protect
the coating more efficiently than organic UV absorber.
3.10. EIS measurement
Since the long-term durability of a coating applied over a substrate
includes both weathering resistance and corrosion resistance, in a
complementary series of experiments, the corrosion performance of
different coatings during weathering were also evaluated. The Bode
diagrams of different coatings before exposure to salt spray test for
different exposure times to weathering condition are given in
Fig. 12a–c.
From Fig. 12, it can be clearly seen that the impedance modulus at
low frequency (10 mHz) of all samples are greater than 109 ohm.cm2
and the phase angle is almost −90° at high frequency region, indicating
that all coatings are intact and no corrosive factors has penetrated.
The Bode diagrams of the variously weathered coatings after being
exposed to salt spray test are given in Fig. 13a–c.
It can be seen from Fig. 13a that the impedance modulus at low
frequency (10 mHz) for the un-weathered samples are equal to
1010 ohm.cm2 and the phase angle is almost −90° at high frequency
region. For the specimens with 400 and 700 h exposure to weathering
condition and salt spray, the impedance modulus at low frequency and
the phase angle decrease as illustrated in Fig. 13b,c.
The variations in impedance at low frequency versus exposure time
to weathering condition are shown in Fig. 14. As it can be seen, the
impedance at low frequency for all specimens before exposure to
11
Progress in Organic Coatings xxx (xxxx) xxx–xxx
Fig. 14. The values of impedance at 10 mHz (a) and impedance re-
tention (b) for the Blank, Tin and GO samples as a function of ex-
posure time to weathering condition.
weathering condition is greater than 1010 ohm.cm2. After exposure to
weathering condition, the impedance of the Blank sample decreases by
the increase of weathering exposure time. For Tin sample the im-
pedance decreases with a slow rate during first 400 h, after which it
endures a sharp drop in impedance modulus. As clearly seen in Fig. 14
the GO coating encounters with the least variations even after 700 h
exposure to weathering condition and maintains its high resistance to
corrosion.
These results indicate that degradation of outer layer has con-
siderable impact on the electrochemical behavior of the whole coating
system. Degradation of polymeric coating leads to the chain scission,
formation of polar groups and macro/microscopic cracks in the coating.
All of these changes together are the main reasons of drop in the barrier
properties of the Blank and somehow for Tin sample.
The stable barrier properties of GO coating are beholden to the
highest stability of this coating against weathering and intrinsic barrier
function of graphene oxide nanosheets. It has been demonstrated by
various techniques that GO sample outperformed much significantly
than Blank and Tin samples without any crack formation (Fig. 11)
during weathering. The much less extended occurrence of degradation
on GO coating guarantees the retention of barrier properties of the
coating during aggressive exposure to weathering condition. On the
other hand, it has been previously demonstrated that the high aspect
ratio of graphene oxide is a key structural parameter which slows down
the diffusion of water, oxygen and other corrosive species to the un-
derneath layer and metal/coating interface. This barrier function of
graphene oxide nanosheets is another key point which accounts for the
excellent stability of GO coating against corrosive environment.
4. Conclusion
Weathering performance of PU coating loaded with graphene oxide
nanosheets was compared with neat and UV absorber containing PU
coatings. It was found that addition of graphene oxide into PU sig-
nificantly improved its weathering performance so that the least
changes were observed after 700 h exposure to UV radiation. On con-
trary to such great UV stabilization, organic UV absorber had a limited
performance for only 400 h accelerated weathering after which it lost
its stabilization performance. It was also explained that UV blocking,
free radical scavenging and barrier (respect to water, oxygen and cor-
rosive species) capabilities are the main functions by which graphene
oxide considerably enhances the outdoor stability and corrosion re-
sistance of coatings during service life. Such promising findings are
quite enough to introduce graphene oxide as a novel multifunctional
additive for aggressive environmental condition. However, application
of graphene oxide as weathering stabilizer is in its germinal state and
further investigations focusing on all types of graphene based materials,
their modification and manipulations are required to reach its mature
M. Hasani et al.
state.
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