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