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Progress in Organic Coatings 71 (2011) 173–180

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Progress in Organic Coatings


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Effect of nano-sized calcium carbonate on cure kinetics and properties


of polyester/epoxy blend powder coatings
Mohammadreza Kalaee a,∗ , Shahin Akhlaghi a , Ali Nouri b , Saeedeh Mazinani c , Mehrzad Mortezaei a ,
Mehdi Afshari d , Dariush Mostafanezhad a,e , Ahmad Allahbakhsh a , Hamidreza Aliasgari Dehaghi a ,
Ali Amirsadri a , Donya Pakdaman Gohari a
a
Department of Polymer Engineering, Islamic Azad University, Tehran South Branch, Tehran, Iran
b
Department of Polymer Engineering, Islamic Azad University, Science & Research Branch, Tehran, Iran
c
Amirkabir Nanotechnology Research Institute (ANTRI), Amirkabir University of Technology, Tehran, Iran
d
Fiber and Polymer Science, College of Textiles, North Carolina State University, Raleigh, NC, USA
e
Ranguin Industrial and Chemical Company, Tehran, Iran

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

Article history: Today’s strict environmental laws pose significant challenges for coating’s formulators to look for eco-
Received 5 November 2010 friendly products. Powder coatings, particularly polyester/epoxy blends have demonstrated their ability
Received in revised form 7 February 2011 as alternatives to traditional solvent-borne coatings. Recently, the use of nanoparticles such as nano-
Accepted 15 February 2011
CaCO3 (nCaCO3 ) has been suggested as a beneficial strategy towards powder coating application with
improved properties. Here, we study the effect of nCaCO3 on morphology, cure behavior, adhesion and
Keywords:
hardness of polyester/epoxy systems. The nanoparticles shape, size and dispersion state were investi-
Powder coating
gated through X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron
Polyester/epoxy
Cure kinetics
microscopy (SEM) methods. Furthermore, isothermal cure characterization of the neat and filled systems
Adhesion was performed using a torque rheometer. The most important finding based on the rheological studies
Hardness was the catalytic effect of nCaCO3 on cure reaction of polyester/epoxy, leading to the shorter curing time.
Moreover, the kinetic analyses of rheograms revealed a marked decrease in the activation energy of the
cure process upon raising nCaCO3 content. Interestingly, pull-off adhesion and hardness tests showed
that the hardness and adhesion strength were dramatically increased by the addition of nCaCO3 into the
polyester/epoxy system compared to pure blend resin. Therefore, considering the strong competition in
powder coating market, the use of nCaCO3 as a commercial and inexpensive nanofiller is necessary not
only to reduce the dwell time which has benefits in terms of the energy consumption and economics,
but also to improve the performance of final polyester/epoxy coating.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction few rejection rate and less costly maintenance are taken into
account, the total operating cost of a powder application plant is
Recently stringent environmental regulations within the fin- lower than that of traditional liquid coatings [4]. Consequently, a
ishing industry have led to the development of technologies that wide variety of finishes such as structured, wrinkled, metallic and
should meet the requirement of both the environmental compli- antique finishes are available with powder coatings which emu-
ance and high performance. Powder thermoset coatings are solvent late the texture and hammer finishes achieved by solvent-based
free and unlike the conventional liquid coatings have zero-volatile coatings [5].
organic content (VOC) [1]. Thus they could offer the coating for- Nevertheless, the major drawbacks of the powder coatings were
mulators a highly promising approach to produce eco-friendly their poor yellowing in addition to their over bake resistance [6].
coatings. In addition, powder coatings are not only far easier to Therefore, in order to overcome these shortcomings, much more
apply than solvent-borne coatings but they also provide a thicker exploratory research was conducted to develop improved powder
and more uniform coating [2,3]. Meanwhile, when the economical systems. Accordingly, the output from these efforts resulted into
advantages of powder coatings like low costs of waste disposal, the introduction of polyester/epoxy blends as a new cutting-edge
technology. These systems are outstanding by their high coating
efficiency and excellent film smoothness, appropriate mechanical
∗ Corresponding author. Tel.: +98 2133722831. properties and adherence characteristics [7].
E-mail addresses: mr kalaei@azad.ac.ir, mohammad.kalaee@gmail.com Recently, some information has been developed dealing with
(M. Kalaee). various characteristics of polyester/epoxy powder coatings. For

0300-9440/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2011.02.006
174 M. R. Kalaee et al. / Progress in Organic Coatings 71 (2011) 173–180

Table 1
Samples specifications.

Sample Polyester (60 wt%)/epoxy(40 wt%) nCaCO3 Benzoin Flow modifier

Neat 100 0 0.5 0.5


1%nC-HPC 100 1 0.5 0.5
3%nC-HPC 100 3 0.5 0.5
5%nC-HPC 100 5 0.5 0.5

instance, the degradation kinetics of polyester/epoxy powder coat- mixer with a rotor speed of 60 rpm at 95 ◦ C for 10 min. This proce-
ings was extensively investigated by Morancho and co-workers [8]. dure was performed in order to achieve a homogeneous dispersion
Interestingly, blend coatings exhibit a broader degradation tem- of nanoparticles. The resultant master-batch with epoxy content
perature interval and they volatilize to substantially less extent and other additives was then extruded on a Brabender twin screw
over pure epoxy and polyester powder resins. Moreover, Mirabe- extruder at 300 rpm and 105 ◦ C. The extruded compounds were
dini et al. [9] precisely studied the corrosion performance of various pulverized on a Retsch ZM-1 hammer mill and sieved to obtain a
pretreated polyester/epoxy powder coatings. The authors found powder with a particle size below 150 ␮m. The ground powder was
that zirconium-based treatments can improve the protection of then sprayed using a Gemma PG-1, Corona type spray gun with the
polyester/epoxy surface against corrosive environment. Further- output voltage of 60 kV on steel planes with the film thickness of
more, since the chemical reactions involving cure procedure were 75–85 ␮m. Finally, the samples were cured at 180 ◦ C for 10 min in
found to radically affect the physical, mechanical and chemical a gas fired oven. The formulation of the samples is given in Table 1.
behavior of the cured systems [10]; several researches have also
followed the cure kinetics of powder coatings. In this particular 2.3. Characterization methods
case, the work of Mafi et al. [11] to evaluate the curing behav-
ior of polyester/epoxy powder coatings is interesting. They found X-ray diffraction (XRD) studies were conducted on a Philips
that a decrease in carboxyl groups in the formulation leads to a X’Pert Pro X-ray diffractometer using Cu K␣ radiation ( = 1.542 Å)
higher degree of crosslinking. In addition, the characteristic points at a scan rate of 0.05◦ s−1 to determine the identity of crystalline
of the exothermal curing shift to higher temperature upon raising phase. The X-ray source was operated at an accelerating voltage
the heating rate. and applied current of 40 kV and 30 mA, respectively.
Recently, the application of the nano-materials in the field of The steady rheological measurements were carried out using
organic coatings has occupied a large area in the scientific litera- a Haake Torque Rheometer, System 90, coupled with a mixing
ture. Consequently, the use of nanoparticles like nanoclay and nano Rheomix 600 chamber under isothermal conditions at 170, 180 and
CaCO3 (nCaCO3 ) in coating application could enhance different 190 ◦ C and rotor speed of 60 rpm. Also, tangential banbury-type
properties such as hardness, scratch-resistance and also corrosion rotors were used with the mixing volume chamber of 300 cm3 . In
resistance [12–14]. However, the use of nanosized CaCO3 as one order to compensate the lag time for the temperature equilibration,
of the least expensive commercially available inorganic nanoparti- the time for loading the sample was kept to a minimum value.
cles can be motivated since they exist in a broad range of particle Scanning electron microscopy (SEM) was performed by a Tescan
sizes and with a wide variety of surface treatments. Furthermore, VEGA-II apparatus equipped with an energy beam of 20 kV. The
nCaCO3 have been used as filler in various industrial applications prepared samples were cryogenically fractured in liquid nitrogen
for many years. Nevertheless, to the best of our knowledge, no ref- and then coated with gold by vapor deposition using a vacuum
erence is so far available regarding the effect of nano particles on sputter before SEM observation. Therefore, the SEM images were
the polyester/epoxy powder coating properties in open literature. all obtained through the inspection on cryogenic fractured surfaces
The objective of present work is to evaluate the effect of of the samples.
stearic acid treated nCaCO3 on the cure kinetics of polyester/epoxy Pull-off adhesion experiment for the polyester/epoxy/nCaCO3
blend powder coatings using rheological methods. In addition, the ternary systems was carried out with a Qualitest Positest adhesion
mechanical and adhesion properties of prepared samples are inves- tester according to ASTM D4541-95e1 standard. Coated samples
tigated in terms of tensile, hardness and pull-off tests. were pressed in an aligned jig between 12.5 mm diameter stud with
a thermally curable epoxy adhesive. Before application, the studs
2. Experimental were grounded with silicon carbide (180 grit) paper and washed
with a mixture of ethanol and acetone. The results reported here
2.1. Material are the average values of 16 repeated tests on each sample.
The hardness tests were conducted on BYK-Gardner Pendulum
The polyester powder coating used in this study was a commer- Hardness Tester Model HB-5855 in accordance with ASTM D4366
cial carboxylated resin, Crylcoat 1627-0 supplied from Cytex Co., based on Persoz and Konig methods. The tests preformed using a
USA. Solid epoxy resin based on bisphenol-A, Araldite GT 7014, used 500 g weight ball with 8 mm diameter. Also, the starting deflection
as hardener was purchased from Jana Co. The stearic acid coated was respectively 12◦ and 6◦ for the Persoz and Konig methods.
nCaCO3 , HAKUENKA CC-R, with bulk density of 0.4 g/cm3 and pH
9.2 was supplied from Omya Co., Austria. Moreover, the substrates 3. Results and discussion
utilized for mechanical and adhesion experiments were steel 304
grade panels with the dimension of 3 mm × 70 mm × 150 mm. All 3.1. Morphological characterization
the test substrates were initially degreased with pure acetone and
then polished with 180 grit sandpaper prior to coating application. Fig. 1 shows the diffraction spectra obtained from pure nCaCO3
comparing to those obtained from polyester/epoxy samples con-
2.2. Processing and preparation taining 1, 3 and 5 wt% nCaCO3 . To get more insight into the details
of the nanoparticles structure, the interplanar distances (d) of dif-
At the beginning, the polyester powder coating together with ferent crystal forms of nCaCO3 were calculated through Bragg’s
different nCaCO3 loadings (1–5 wt%) were mixed in an internal equation [15]:
M. R. Kalaee et al. / Progress in Organic Coatings 71 (2011) 173–180 175

Fig. 2. TEM image of CaCO3 nanoparticles as received.

torque begins to rapidly increase as the onset of curing and also


the whole curing time. It is evident that, at a given nCaCO3 load-
Fig. 1. XRD patterns of nCaCO3 powder and polyester/epoxy systems containing 1,
3 and 5 wt% nCaCO3 . ing, an increase in the isothermal curing temperature drives the
curing reaction forward besides decreasing the curing time. The
reason for such observation could be correlated to the availability
(1)d = n/2sin␪ of more thermal energy in addition to lower viscosity of the com-
where  is the scattering angle and  is the wavelength (here pound which facilitates the formation of the crosslinking networks
 = 1.542 Å). Also, n is an integer determined by the order given [18]. A closer view to the experimental data showed that nCaCO3
which here equals to 1 (d values are indexed in Fig. 1). As indicated nanoparticles introduced to the system seem to act as accelerators
by XRD analyses, the characteristic diffraction peaks at 2 = 29◦ , 39◦ , regarding to the cure reaction times. This acceleration effect should
43◦ , 47◦ and 57◦ are corresponding to the calcite crystal form and be referred to the fact that the stearic acid layer on nCaCO3 surface
the peaks at 2 = 23◦ , 36◦ and 48◦ are attributed to the vaterite form possesses strong acid sites to activate electrophiles effectively at
[16,17]. Rietveld quantitative phase analysis of powder XRD pattern the curing temperature [19]. Moreover, according to Wang et al.
indicates that the inorganic phase is composed of 85% calcite and [20] acidic treated inorganic fillers can effectively absorb the hard-
15% vaterite. Therefore, it can be inferred that calcite was the pre- ener and act as a support to disperse the hardener during the curing
dominant form over the vaterite in nCaCO3 used for this study. Also, procedure of the resin system. Therefore, it can be inferred that
Fig. 1 shows a broad peak at 2 = 10–35◦ for all the coating systems there is relatively high concentration of curing agents on the sur-
which is related to the amorphous character of polyester/epoxy face of the nanofiller at the beginning which then they advance into
blends [16]. the unreacted zone in the nCaCO3 modified polyester/epoxy resin.
The majority of calcite crystal form which appears to be in lay- Interestingly, it can be observed that the higher the nCaCO3 loading,
ered and rhombohedral shape can be seen in TEM image of CaCO3 the shorter the cure time for the polyester/epoxy systems. In other
nanoparticles used in this work before processing as depicted in words, the addition of treated nCaCO3 increases the amount of the
Fig. 2. Moreover, the average primary particle size of the stearic acid stearic acid layer on the nanofiller surface which provides extra
coated CaCO3 nanofiller was measured around 65 nm. Moreover, regimes for the crosslinking reaction; and thus further catalyz-
most of the nCaCO3 particles were agglomerated; therefore the dis- ing effect occurs during the curing reaction. However, one cannot
persion processing step was essential in this work. On the other ignore the contribution of large surface area of nCaCO3 particles
hand, the SEM micrographs, as shown in Fig. 3, revealed that the which ensures the proper, sufficient and increased dispersion of
nanoparticles were reasonably well dispersed in polyester/epoxy the radical reactant.
systems at 1, 3 and 5 wt% nCaCO3 loadings after the processing and It is well known that the maximum torque of the rheometer
dispersion step. curves is the most relevant factor to the crosslink density of the
cured systems [21]. The retractive force to resist a deformation is
3.2. Rheological characterization proportional to the number of network-supporting polymer chain
per unit of thermoset and the higher number of junctures increases
3.2.1. Isothermal cure behavior the number of supporting chains [22]. In this regard, T∞ is expected
Fig. 4 illustrates the rheographic profile of neat polyester/epoxy to increase at higher value of the network chain density. However,
and polyester/epoxy blends containing 1, 3 and 5 wt% nCaCO3 at as it can be observed in Table 2, the variation of the minimum torque
170, 180 and 190 ◦ C. From each of the curves shown in Fig. 4, some concerning the curing temperature and composition of the sample
characteristic parameters were determined as listed in Table 2. is not so appreciably related to the maximum torque. Hence, the
These parameters included: T∞ and T0 as the maximum and min- difference T = T∞ − T0 is normally used to analyze the experimen-
imum torque during the curing process; the time at which the tal data in order to exclude the effect of T0 . As it is clear from the
176 M. R. Kalaee et al. / Progress in Organic Coatings 71 (2011) 173–180

Fig. 4. Torque (T) as a function of cure time for the neat and filled systems containing
1, 3 and 5 wt% nCaCO3 at analyzed temperatures.

obtained T values, a tendency is observed to increase this value


as the amount of nCaCO3 content increases up to 3 wt%. In contrary,
dissimilar behavior was observed for the effect of cure temperature
on the torque value. In this case, the availability of more thermal
energy helps to the segmental and diffusional chain motion which
leads to lower torque values.

Fig. 3. SEM images from fractured surfaces of polyester/epoxy blends containing 3.2.2. Isothermal cure kinetics
(A) 1 wt%, (B) 3 wt% and (C) 5 wt% nCaCO3 . The torquemeter test results under isothermal condition yielded
valuable information of the amount of torque versus time which
could be used to evaluate the kinetic parameters by using series of
mathematical expressions. In this concern, the degree of curing, ,
which was employed to indicate the extent of resin crosslinking,
M. R. Kalaee et al. / Progress in Organic Coatings 71 (2011) 173–180 177

might be estimated from the time dependency of torque values


using the following equation [23]:
T (t) − T0
= (1)
T∞ − T0
where T(t) is the torque at a given time of curing process. There
are two primary mechanisms describing most thermoset curing
including nth-order and autocatalytic [24]. The nth-order model
assumes that the reaction rate is proportional to the concentration
of unreacted material (1 − ), as shown in Eq. (2), where n is the
reaction order [25]:
d n
= K(1 − ) (2)
dt
Nevertheless, the nth-order model seems to be incapable of
describing the progress of the entire reaction because several
simultaneous reactions may occur during the cure process [23]. For Fig. 5. Variation of conversion, , as a function of curing time for the entire samples
an isothermal reaction, nth-order mechanism predicts the max- at different test temperatures.
imum of reaction rate at time = 0. However, this is not the case
for autocatalytic cure processes, in which the final products of the
cure reaction can catalyze the subsequent reaction between the
resin and hardener. On the other hand, in an autocatalytic model,
the conversion rate is proportional to both of the concentration of
unreacted and reacted material:
d n
= K(1 − )  m (3)
dt
where m is also a reaction order. In both autocatalytic and nth-
order models, K represents the temperature-dependent reaction
rate constant obeying the well known Arrhenius equation as [23]:
 −E 
K = A exp (4)
RT
where A is a frequency factor corresponding to the incidence of
molecular collisions that should be obtained to produce a chemical
reaction. In addition, E, R and T are the activation energy, the gas
constant and the absolute temperature, respectively.
Commonly, isothermal cure of thermoset material may be the
result of more than one type of chemical reaction [25]. In the
present case, the dominant cure reaction between carboxylated
polyester and bisphenol-A epoxy is given in Scheme 1. As depicted,
such a reaction leads to the formation of pendant hydroxyl groups
that are available for crosslinking. It is known that the initial step
to produce these groups proceed uncatalyzed. Furthermore, the
resultant hydroxyl groups are able to catalyze subsequent reac-
tions. Consequently, the overall reactions could be considered as
an uncatalyzed initiation followed by autocatalysis [26]. This com-
bination of reactions can be represented by generalized expression
given by Kamal and Sourour:
d
 −E   −E 
n n
(1 − )  m
1 2
= A1 exp (1 − ) + A2 exp (5)
dt RT RT
The first term in this model corresponds to an nth-order reaction
and the second one attributes to an autocatalytic reaction occurring
during the cure reaction of the material under study [27].
Fig. 5 shows the plots of conversion against cure time for
neat and nanocomposite systems at various temperatures. More-
over, Fig. 6 represents the plots of cure rate, d/dt, versus  for Fig. 6. Variation of d/dt versus conversion, , for the entire samples at the analyzed
the entire samples at three different temperatures. Indeed, at a temperatures.
given cure temperature, the reaction rate rapidly increases with
the conversion to reach a practically constant value; however,
higher conversions could hinder the mobility and consequently the compounds at lower temperatures which could hinder the forma-
crosslinking stops. As shown in Fig. 6, the cure rate (d/dt) increases tion of crosslinks between the polymer chains.
upon increasing the nanoparticle contents which indicates a direct For further understanding the cure kinetics of polyester/epoxy
relationship between catalytic effects on cure reaction with nCaCO3 blends in the presence of nCaCO3 , the curves shown in Fig. 6 were
loading. It is interesting to note that (d/dt)max increases with the fitted using Eq. (5) through the non-linear regression method. The
increment of curing temperature due to the high viscosity of the obtained kinetic parameters (m, n, K1 and K2 ) are listed in Table 3.
178 M. R. Kalaee et al. / Progress in Organic Coatings 71 (2011) 173–180

Scheme 1. Reaction between an epoxy and carboxylic groups.

Table 2
T0 and T∞ obtained from the rheometer curves (Fig. 3), for the entire samples at the analyzed temperatures.

Sample Curing temperature (◦ C) T0 (N m) T∞ (N m) T Onset of cure (s) Curing time (s)

Neat 170 1.4 25.3 23.9 600 750


180 1.1 24.6 23.5 510 580
190 0.8 23.7 22.9 390 470

1%nC-HPC 170 1.3 39.5 38.2 560 660


180 1 37 36 480 450
190 0.7 35.2 34.5 410 360

3%nC-HPC 170 1.5 48.4 46.9 530 470


180 1.2 47.6 46.4 460 320
190 0.8 44 43.2 390 230

5%nC-HPC 170 2 42.3 40.3 510 340


180 1.5 40.7 39.2 450 250
190 1.1 36.4 35.3 380 150

Table 3
Combination of cure kinetic model parameters determined from the curve fits of d/dt versus  (Fig. 6) and the values of the nth-order and autocatalytic mechanism activation
energies for the entire samples at analyzed temperatures.

Sample Curing temperature (◦ C) K1 (×10−4 s−1 ) K2 (×10−2 s−1 ) m n R2 E1 (KJ/mol) E2 (KJ/mol)

Neat 170 1.03 1.33 1.15 1.05 0.98


180 4.90 2.81 1.49 1.63 0.98 19.57 78.81
190 10.17 3.34 1.47 1.29 0.99

1%nC-HPC 170 1.80 2.19 1.35 0.90 0.99


180 6.24 3.57 1.22 1.13 0.98 16.28 70.03
190 12.09 4.97 0.96 1.37 0.99

3%nC-HPC 170 2.89 3.84 1.33 1.31 0.99


180 8.13 5.90 1.61 1.16 0.98 14.05 66.82
190 14.96 8.41 1.72 1.64 0.99

5%nC-HPC 170 3.15 4.24 1.52 1.33 0.98


180 8.26 6.27 1.20 1.08 0.99 13.70 55.64
190 15.69 8.13 0.83 0.92 0.98

All the values were rounded to two decimal places according to the parameters are represented in Table 3 for the entire samples. Inter-
error bands associated with 95% confidence limits. Careful inspec- estingly, both E1 and E2 are sharply decreased with the increment
tion of the calculated m and n values reveals that there is no trend of nCaCO3 content. This observation is consistence with the discus-
for the systematic variation of either m or n with temperature in sion previously mentioned that the cure rate of polyester/epoxy
the isothermal cure of samples with nCaCO3 loading. As already systems increases upon raising the nCaCO3 content. Consequently,
reported by many authors, this conclusion is expected to be reached lower amount of energy for curing together with shorter cure time
theoretically, since m and n are not depend on curing tempera- of nCaCO3 containing polyester/epoxy samples over the neat blends
ture and nanofiller content [23–27]. In addition, the cure kinetic could offer the coating’s formulators an excellent approach to meet-
characterizations show a direct proportionality between both the ing the requirements of today’s challenging in coating market.
nth-order and autocatalytic reaction rate constants and also the
curing temperature. However, for all the samples, K2 value were 3.3. Adhesion characteristics
higher than K1 that suggests autocatalytic mechanism was more
favorable than the other one. A variety of reasons might be given Polymer’s adhesion to surfaces is a crucial property for coat-
for the large K2 value including the fact that the reaction mix- ing’s applications which strongly depends on a wide variety of
ture is very viscous. Indeed, because of the high viscosity, upon different parameters such as surface chemistry, the viscoelastic
completing the initial uncatalyzed reaction, the reactants cannot properties of the bulk materials, temperature and also the film
move away but they would rather sequester together. As a result, thickness [28]. Hence, adhesion of coatings to a given substrate is
they are more prepared for subsequent catalyzed reactions [27]. generally determined empirically. Among the various techniques
It is interesting to note that the increment of the nCaCO3 content available to measure the adhesion of coatings, pull-off test is an
increases the rate constant obtained for the systems which seems inexpensive and easy-to-use technique which is commonly used
to be connected with the higher polyester/epoxy chains absorbed to evaluate the adherence of coatings to obtain direct informa-
on the stearic treated nanofiller surface rather than catalytic effect tion on the performance characteristic and also the adhesion loss
of nCaCO3 . for in-service conditions [29]. The results obtained for the pull-off
In addition, the value of nth-order and autocatalytic activation strength of the entire samples are listed in Table 4. Interestingly, the
energies (E1 and E2 ) can be determined from the slope of linear maximum tension applied to the coating is considerably increased
relationship between ln(K1 ) and ln(K2 ) versus 1/T (plots not shown for the filled samples over the neat polyester/epoxy blend. It can
here). The numerical values calculated for the above-mentioned be suggested that the improvement in the pull-off strength of the
M. R. Kalaee et al. / Progress in Organic Coatings 71 (2011) 173–180 179

Table 4
Pull-off strength and hardness (Persoz and Konig) values.

Sample Pull-off (psi) Hardness (Persoz) (s) Hardness (Konig) (s)

Neat 210 ± 1.17% 413 ± 0.14% 49 ± 0.11%


1%nC-HPC 350 ± 3.32% 428 ± 0.18% 59 ± 0.09%
3%nC-HPC 827 ± 1.14% 435 ± 0.27% 67 ± 0.12%
5%nC-HPC 561 ± 2.88% 444 ± 0.13% 71 ± 0.15%

retarded elasticity, the pendulum hardness value is proportional


to the reciprocal of damping capacity or mechanical loss [34].
Therefore, the validity of this method is restricted to homologous
materials, but it might be reasonably used for measuring the vis-
coelastic properties of coating films [35]. The Persoz hardness of the
entire samples is listed in Table 4 as a function of nCaCO3 content.
Apparently, such high hardness values of filled systems (428–444 s)
indicate the formation of a hard and glassy material by the inclu-
sion of CaCO3 nanoparticles [36–39]. Moreover, the hardness values
obtained based on Konig method as well as Persoz method pointed
to the fact that the incorporation of a higher amount of nCaCO3
effectively increases the surface hardness. Since it seems as if stearic
treated CaCO3 nanoparticles include the capacitance to form extra
interaction points with polyester/epoxy resin [31,32]. This ability
can enhance the compactness of the coating and lead to the higher
surface hardness.

4. Conclusion
Scheme 2. Hydrogen bonding between nCaCO3 and polyester/epoxy resin.
This study set out to investigate the effect of stearic acid coated
filled polyester/epoxy system is due to the presence of nano-sized CaCO3 nanoparticles on the morphology, cure behavior, adhesion
and well-distributed calcium carbonate particles which can min- and hardness properties of the polyester/epoxy blend powder coat-
imized the porosity of the coated films and thus it depicts better ings. The morphological studies were performed by XRD, TEM and
adhesion performance compared to the neat system. In addition, SEM methods and the results clearly indicated suitable disper-
nCaCO3 could probably enlarge the interacting area or/and enhance sion of nCaCO3 in matrix. Also, the rheological characterizations
the adhesion strength which leads to the increment in adhe- of the blend systems were carried out at various nCaCO3 loadings
sion strength of the samples [30]. Moreover, acidic modification under isothermal condition. Moreover, the adhesion strength and
of nCaCO3 nanoparticles causes the hydrophilic surface structure hardness of the coated samples were evaluated by pull-off, Per-
which in turn results in enhancement of adhesion between the soz and Konig test methods. The most interesting finding of the
coating and metal substrate [31]. As could be inferred from Table 4, present work was the catalytic effect of nCaCO3 on the cure reac-
a maximum value of 827 psi (393% increment) is reached for the tion of polyester/epoxy powder coatings which in turn resulted
system containing 3 wt% nCaCO3 . It could be traced to the high in less energy consumption during the curing process. Simultane-
crosslinking density of 3%nC-HPC samples which will be explained ously, a noticeable increase was observed in the final performance
in the cure behavior section. However, followed by the increased of nCaCO3 filled coatings in terms of the adhesion and hardness
addition of samples containing over 3 wt% nCaCO3 , the surface properties.
wetting-ability of the coating is reduced due to the increased vis-
cosity, which is contrary to the adhesion strength [30]. It is worth Acknowledgement
mentioning here that a mixed failure mode (cohesive and inter-
facial) was observed for the incorporated samples. In contrast, The authors wish to thank the Research Council of “Islamic Azad
interfacial failure occurred for the samples without nCaCO3 . Based University Tehran South Branch” for the financial support of this
on the above results, it is possible to assume that the addition of work based on the grant no.: “B/16/611”.
nano-sized CaCO3 may reinforce both the interfacial and cohesive
forces. The main reason that leads to the superior cohesive forces References
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[3] P. Castell, M. Wouters, H. Fischer, G. de With, J. Coat. Technol. Res. 4 (2007) 411.
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