Progress in Organic Coatings 69 (2010) 241246

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Progress in Organic Coatings

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

Effect of nano TiO2 particle size on mechanical properties of cured epoxy resin
Hamad A. Al-Turaif
Chemical and Materials Eng. Dept., King Abdulaziz University, P.O. Box 80204, 21589 Jeddah, Saudi Arabia

a r t i c l e

i n f o

Article history:
Received 14 May 2010
Accepted 20 May 2010
Keywords:
Epoxy resin
TiO2 nano particles
Tensile stress
Flexural stress

a b s t r a c t
Mechanical properties of toughened epoxy resin with two nano particles sizes of TiO2 (17 nm and 50 nm)
at different weight fractions (1%, 3%, 5% and 10%) were investigated and compared to that of submicron
particles at 220 nm. The composites were characterized by tensile, exural, pull-off and abrasion tests,
followed by X-ray photoelectron spectroscopy and scanning electron microscopy of the fracture surfaces.
The investigated epoxy depicted high performance epoxy systems formulated with low molecular weight
epoxy resin and diethyltoluenediamine as a curing agent.
Results indicate an enhancement in the epoxy composite mechanical properties due to the addition of
small fraction of TiO2 particles. Highest tensile stress values were found at 3 wt.% for 17 nm and 50 nm
particles and at 5 wt.% for 220 nm particles. The maximum exural properties were found at lower TiO2
fraction of 1 wt.% only. The exural behavior of the epoxy composite was not improved by further addition
of the ller. The enhancement of modied epoxy with the smaller nano particles size showed a better
resistance to weight loss. It is suggested that the amount of particles present and its size affect the matrix
deformation and as a result, the quality of interface in the composite. A relation between tensile and
exural stress as function of the toughened particle size was found.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Since 1947 the epoxy resin has been extensively used in a variety
of wide industrial applications, such as surface coatings, adhesives,
painting materials as well as electronic devices. Like other thermosetting materials, epoxy resins are also extremely brittle, which
limits their application in products that require high impact and
fracture strength.
Various researchers attempt to overcome this problem by
introducing an intermediary phase through blending or chemical
reactions. Generally, the dispersed phase can be classied into four
types: reactive liquid rubbers, functionally terminated engineering thermoplastics, reactive ductile diluents, and inorganic/hybrid
particles. Their main objective is to enforce the crack resistance and
toughness without signicantly decreasing other inherent properties, such as thermo mechanical properties [1].
In recent years, nano particles are being used as advanced ller
to improve the mechanical properties of the epoxy resin. Different
types of nano particles like TiO2 [24], Al2 O3 [3], Silica [5], carbon
black [6], clay [6,7] and SiO2 [8] are used to improve the toughness
of the epoxy resins.
Several mechanisms leading to improve mechanical performance in nano lled epoxy have been introduced. The mechanisms

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doi:10.1016/j.porgcoat.2010.05.011

are crack deection, crack pinning and plastic deformation

(debonding) [3,9]. Small particles size in the epoxy matrix inuences the deformation mechanism. This mechanism of toughening
epoxy resins is believed to be a combination of the aforementioned
mechanisms.
In general, factors such as the extent of adhesion of the ller to
the epoxy matrix and the dispersion state of the ller in the epoxy
matrix as well as the shape and size of the particulate llers have
been found to affect mechanical properties of the epoxy composite.
In recent years, a considerable amount of research has been carried out to improve the performance of the toughened epoxy resins
using nano particles and new mechanisms and relationships have
been suggested. However, a lot of questions are yet to be answered.
In this paper, an attempt has been made to investigate the effect of
nano particle size and ller content on the mechanical properties
of the cured epoxy resin. Further, properties of tensile and exural
stress as well as pull-off strength and abrasion resistance have also
been investigated. Furthermore, relationship between particle size
and the different mechanical properties are reported.
2. Experimental procedure
2.1. Materials
Three types of rutile TiO2 , manufactured by KEMIRA, Finland,
were selected for this study. The grade, KEMIRA 660, is a multipurpose grade with 220 nm crystal diameter and surface treated

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with Al2 O3 SiO2 . The other two grades, UV-TITAN L830 and UVTITAN L181, are ultra-ne with 50 nm and 17 nm crystal diameter,
respectively.
The matrix was selected as it is commercially known formulation which is used as a binder in oor coating industry [10]. The
epoxy resin chosen was DER 331TM . It is an undiluted DGEBA-based
liquid epoxy resin manufactured by DOW Chemical Company.
Low molecular weight grades of epoxy resin, such as these, have
become standard due to their versatility in various applications.
Typical properties for the resin include: epoxy equivalent weight
of 182192 g/mol, a viscosity of 110140 poise at 25 C and density
of 1160 kg/m3 at 25 C [11].
Isophorone diamine (IPDA) is also used as a curing agent in
conjunction with salicylic acid, to act as a catalyst. The IPDA is manufactured by Huntsman under the name of Aradur 42 with an amine
value of 645665 mg KOH/g, a viscosity of 6.2 cP at 25 C and a density of 920 kg/m3 at 25 C. ANTIFOAM C100 of Basildon Chemical
Company Limited was used in the mix as an air release agent with
the supplier recommended dose.

The length between supports span was equal to 50 mm as

recommended by the standard.
The bars were loaded to failure and the exural strength ( f )
was calculated from the following standard relation: [13]
f =

3PL
2bd2

where P is the load to break, b and d are the width and the thickness
of the specimen, respectively, L is the length between supports. Five
samples were used for each test.
2.5. Abrasion test
Abrasion test for all the samples investigated was performed
using the Taber Rotary Abraser 5135 according to (ASTM D 406007) [14]. The measurement of abrasion resistance was done by
weighing of the material sample before and after subjecting it to
a known abrasive stress throughout a known time period. The load
was 500 g on each side, the number of cycles was 75 rounds using
H-22 wear. The samples shape was square 20 cm 20 cm.

2.2. Sample preparation

2.6. Pull-off test
TiO2 particles were mixed with epoxy in different weight ratios,
1%, 3%, 5% and 10%. The mixing process of the epoxy resin with
TiO2 was carried out in batches of about 500 g using a moderate speed paddle mixer for about 30 min after which the mixed
material was de-gassed for 6 h at 80 C and 700 mbar. This is a
common mixing procedure prevailing in industry as well as theory
[11].
Mixing the formulated epoxy resin with the curing agent was
done on the basis of stoichiometric ratio and performed on batches
of about 100 g using the mix ratio provided by the material supplier.
Mechanical paddle stirrer was used and each batch was mixed for
approximately 3 min. After the completion of the mixing process,
the mix was allowed to stand for 5 min before casting.
For the tensile and exural tests, the mixed material was casted
in silicon rubber molds which were specically designed to fabricate the samples required for testing. The molds were internally
coated with debonding agent in order to avoid the adhesion of the
epoxy material to the mold during the curing process. The molds
were left for an initial cure at room temperature for 24 h in desiccators at zero % RH, then de-molded and moved to the post curing
stage for 2 weeks under the same conditions. In the meanwhile, the
mixed material was applied on a concrete block as one coat for the
abrasion and pull-off tests. The concrete block was at and with
40 cm 20 cm dimensions.
2.3. Tensile test
Tensile testing was carried out on dumbbell-shaped samples
(ASTM D-638-91, Type I) [12] using a universal testing machine
Instron 5568. The measurements were carried out at 23 1 C
using an extension rate of 0.5 mm min1 . The tensile stress-strain
curve is a tool to provide data on toughness (area under the curve),
ultimate tensile strength, ultimate elongation at break and Youngs
modulus.
2.4. Flexural test
Flexural properties of the materials were obtained according to (ASTM D-790) [13]. Samples length to depth ratio kept
in range 1:16. Flexural tests were carried out at room temperature (23 1 C) in Instron 3367 machine at crosshead
rate of 2.5 mm min1 . Flexural strength were measured in
three-point bending using specimen dimensions equal to
3 0.5 mm 14 0.5 mm cross-section and 80 1 mm in length.

Pull-off strength of the modied and unmodied epoxy resins

was obtained according to ASTM D-4541 [15]. Portable pull-off
adhesion tester (the electrometer 106) measures the force required
to pull a specied diameter of coating away from its substrate. The
pull-off test is a near-to-surface method in which a circular steel
disc (dolly) is attached to the surface of the concrete with an epoxy.
The force required to pull this from the surface, together with an
attached layer of concrete, is measured. For each particle size at different TiO2 contents ve samples were measured and the average
was reported.
2.7. X-ray photoelectron spectroscopy (XPS)
X-ray photoelectron spectroscopy (XPS) was used to check
whether the TiO2 particles were evenly distributed in the molded
epoxy resin matrix. XPS technique, used in this investigation, is a
part of MAX 200, a multi-technique surface analyzer manufactured
by Leybold, Germany. The test was carried out on different areas
on the sample surface and in the core of the specimen after being
mechanically split.
2.8. Scanning electron microscopy (SEM)
Tensile and fracture surfaces of samples with different toughening agent contents were coated with gold and then analyzed using
JEOL JSM-SEM 6360 scanning electron microscope, Model T300,
operated at 20 kV.
3. Results and discussions
3.1. Tensile test
Effects of TiO2 particle size and fraction content on the epoxy
composite tensile properties are shown in Figs.14. In general, it
is observed that inclusion of a small percentage of submicron and
nano particles (around 1%) improves all tensile properties of the
cured epoxy resin system under investigation. Further increase of
TiO2 content causes an additional improvement in the tensile properties up to an optimal concentration which, for the system under
investigation, is 35%. At this range, all tensile properties reach their
maximum value with all the particle sizes tested.
If nano particles (17 nm and 50 nm) are used as toughening
agent in the epoxy resin, its ultimate tensile strength (UTS) can be

H.A. Al-Turaif / Progress in Organic Coatings 69 (2010) 241246

243

Fig. 1. UTS of different TiO2 particles size at different weight fractions.

Fig. 4. Youngs modulus of different TiO2 particles size at different weight fractions.

Fig. 2. Elongation of different TiO2 particles size at different weight fractions.

improved, more than what could have been achieved by using submicron particles (220 nm) (Fig. 1). However, this is true for low TiO2
contents up to 3%. At 3% TiO2 content the improvement achieved in
UTS reached about 14%. Further increase in the TiO2 content above
3 wt.% leads to a gradual reduction in the values of UTS. On the
other hand, at submicron particles (220 nm), a maximum of 13%
increase in UTS is achieved but with higher TiO2 content of around
5%. Further, if we increase the TiO2 content above 5 wt.%, a gradual
reduction in the values of UTS is observed (Fig. 1).
The effects of the TiO2 fraction content on elongation at break,
toughness and the Youngs modulus of the epoxy resin composite
for the different particles sizes investigated are shown in Figs. 24,
respectively. A similar behavior as shown for UTS can be observed
here; at 17 nm and 50 nm the optimal values are at 3% while for
220 nm the optimal values are at 5%. This result corroborates with
the optimal fraction content of 4% found earlier for toughened
epoxy resin with 190 nm TiO2 particles size [16]. It seems that there
is a relation between the particle size and the fraction content producing the optimal values of the tensile properties, as one decreases
the particle size the optimum fraction content decreases. From an

economical point of view, the determination of the optimal fraction

content will help using only the precise quantity of the expensive
particulate toughening agent.
The improvement in the epoxy composite mechanical properties by using small amount of TiO2 nano toughening agent may
be attributed to the improvement of the interfacial interaction.
Characteristics of the small nano particles such as, higher rigidity
than epoxy, high specic surface area, and sufcient particle-matrix
adhesion should be credited for the interfacial interaction improvement. However, the interfacial region is complex, and when the
interfacial area is very large, the whole polymer matrix may essentially be the interfacial region. The traditional composite theory,
although very far advanced in describing properties that are relatively independent of the interface, is still in its infancy when it
comes to taking into account the role of the interfacial region. This
poses one of the major challenges in polymer nanocomposites [17].
As nano particles gets smaller, the interface area increases
resulting in cracks interacting with more particles. If a homogenous distribution of the particles is achieved in the epoxy matrix
through good particles dispersion, this can improve the mechanical properties. The best mechanical properties were found at 17 nm
followed by 50 nm then 220 nm particles.
It is generally known that the presence of more Van Der Waals
forces between the smaller size particles would limit its dispersion
capability and would result in production of agglomerates of particles in the matrix. Smaller particles size will agglomerate at lower
particles content than bigger particles. This may explain why the
mechanical properties of the toughened epoxy resin with 17 nm
and 50 nm decreases at 3% while with 220 nm decreases at 5%.
However, when the present particles exceed the optimal distribution, i.e. the optimal fraction content, the main interaction
becomes between particles and particles and not between particle
and matrix causing a change of the mechanical properties. Above
optimal fraction content the particles start to form clusters bigger in
size than the voids. These clusters act as surface defects responsible
for losing the high mechanical properties.
3.2. Flexural test

Fig. 3. Toughness at different TiO2 particles size at different weight fractions.

Flexural mechanical test was performed to evaluate the stiffness

of the material. Five samples of each type were tested for measuring
the exural properties of neat epoxy resin and toughened epoxy
composite samples using ASTM D790.
Modifying the epoxy with various sizes of nano TiO2 particles
did improve the exural strength (Fig. 5). Further, adding a small
percentage of 1% of the TiO2 particles caused a clear increase in the
exural stress. In the case of 17 nm, 50 nm and 220 nm particles the
TiO2 epoxy composite shows 22%, 17% and 14% increase in exural
strength, respectively. However, the exural behavior of the epoxy

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H.A. Al-Turaif / Progress in Organic Coatings 69 (2010) 241246

Fig. 5. Flexural stress of different TiO2 particles size at different weight fractions.

resin did not improved by additional amount of the TiO2 particles.

A similar behavior was found in the literature where the exural
behavior of the epoxy resin was not improved by the presence of
micro thermoplastic llers [18].
In general, there is a strong argument in the aforementioned
literature over the effect of ller content on the exural strength
of modied composite. Some researchers showed that the exural strength of micro particle lled composites is reduced with
rising ller content [19], while others argue that exural strength
increases with nano particles [4].
In order to explain this phenomenon, two factors should be considered: the dispersion state of the nano particles and the interface
in composites.
Regarding the rst factor, more agglomerates are likely to be
formed at higher ller contents which may cause embrittling
effects. Large agglomerates in the matrix will cause a propagation
crack and induce the initiation of the nal failure. In our study,
there wasnot much difference on the exural properties. According to this explanation no agglomerates should be present in the
matrix and this was conrmed with XPS. The XPS results indicate
that the chemical compositions were comparable at different areas
on the surfaces and in the core of the samples. This is an indication that TiO2 particles are evenly distributed and no agglomerates
are formed in the samples. This demonstrates the importance of
homogenous distribution of nano particles within the matrix.
As discussed earlier, the nano particles interface in composites
plays a major role in the improvement of the mechanical properties. Stresses transfer and elastic deformation from the matrix
to the llers are governed by the interface quality [20]. Due to
the higher rigidity of llers compared to epoxy, the deformation
comes from the polymer. Up to 1% by weight, the nano particles
are able to induce further mechanisms of failure without blocking
matrix deformation. According to the crack pining theory, particles may act as obstacles to crack growth by pinning [21]. Crack
pinning was veried by SEM examination to be present in the
epoxyTiO2 nanocomposite [3]. On the other hand, when llers
exceed 1% by weight, large number of llers now dominate, and
reduce the matrix deformation. This result indicates that there is
no signicance of increasing the ller content above 1%. This explanation was conrmed by looking to the results of the different TiO2
particles contents and sizes tested. No signicant changes on exural strength of TiO2 content after 1% were observed for different
sizes tested.
Fig. 6 illustrates the relation between tensile and exural
stresses as function of particle size. Using Table Curve 3D v4 software indicates the following simple relation:
exural stress =

Fig. 6. Relation between the tensile and exural stresses as function of particle size.

Fig. 7. Weight loss % of different TiO2 particles size at different weight fractions.

The correlation factor was R2 = 0.943. Other researchers found

a parabolic relation between the tensile and the exural stresses
for a particular particle size [4]. Further investigation will help to
conrm our correlation.
3.3. Abrasion test
As shown in Fig. 7, reinforcing the epoxy resin with 1% TiO2
resulted in a sharp decrease in the weight loss. Further increase
in the TiO2 content causes no further improvement in the weight
lost. It was found in the literature, that low wt.% of boron carbide
ller in epoxy resulted in a better performance to the three body
abrasive wear than higher wt.% [22].
The weight lost due to the abrasion test was affected by the
particle size. The weight loss after abrasion test was decreased by
69%, 55% and 38% for particles size of 17 nm, 50 nm and 220 nm,
respectively. Decreasing the reinforcement particle size improved

a+b
c ln(tensile stress)
+
ln(particle size)
(tensile stress)2

where the constants; a = 50.727753, b = 42.59891 and c = 190.58268

Flexural and tensile stresses in MPa and particle size in nm.

Fig. 8. Pull-off strength of different TiO2 particles size at different weight fractions.

H.A. Al-Turaif / Progress in Organic Coatings 69 (2010) 241246

245

the epoxy composite resistance to weight loss which means nano

particle gives much better results than micro particle.
Nano particles provide a very higher specic surface area than
the micro particles which generates a much larger interface area.
This allows the propagation cracks to interact with far more particles and prevent cracks. During abrasion test, nano particles would
require more energy to be removed and would leave smaller holes
than micro particles. As a result, the weight lost of the nano particles is less than that of micro particles. This indicates that the
particle size selection is a key factor for the reinforcement of the
polymer.
3.4. Pull-off test
In this test, the pull-off strength was gauged for ve samples of each type investigated (Fig. 8). The pull-off strength
was improved by the addition of the TiO2 particles. It was
observed that parts of the cement blocks were pulled out with
the reinforced samples. This indicates that the strength of the
reinforced samples increases. Either any further TiO2 content
increase or the TiO2 particle size decrease causes any signicant improvement in the pull-off strength. A small amount of 1%
weight of any nano particles is enough to increase the pull-off
strength.
3.5. Scanning electron microscopy (SEM)
SEM micrographs of fracture surfaces of un-toughened and
toughened epoxy resin are shown in Fig. 9. Fig. 9(a) shows the
unmodied epoxy after tensile testing in which a smooth fracture
surface as well as cracks in different planes can be seen. This is
an indication of a brittle fracture of the unmodied epoxy. It can
be observed that the fractures intersect each other in the top left
corner of the micrograph, indicating a brittle river fracture pattern
similar to that resulting from the cleavage fracture of a metal. This
indicates that a relatively small amount of energy was consumed
to fracture the specimens.
Fig. 9(b)(d) shows the modied epoxy after tensile testing for
17 nm at 3 wt.%, 5 wt.% and10 wt.% of TiO2 , respectively. As the TiO2
weight percentage increases the resulted cleavage decreases. The
highest cleavage is at 3 wt.% TiO2 . This result indicates the resistance of the material and emphasizes that the ultimate stress is at
3 wt.% of TiO2 for 17 nm particles.
They depict rougher features such as stress whitened zones and
out-of-plane aking markings which normally exploit additional
strain energy to be formed during the deformation process of the
specimens. This further corresponds to an increase in the fracture
toughness of the lled epoxy resin relative to the un-lled one.
4. Conclusion

Fig. 9. SEM micrographs of the tensile fracture surfaces of epoxy resin modied with
17 nm TiO2 particles at different weight fraction: (a) 0 wt.%, (b) 3 wt.%, (c) 5 wt.%, and
(d) 10 wt.%.

In this study the mechanical properties of toughened epoxy

composite were investigated using two nano size TiO2 particles
and one submicron particle at different TiO2 fractions. Adding small
amount of nano and submicron particles improved all mechanical properties investigated including tensile stress, elongation at
break, toughness, the Youngs modulus, exural stress, abrasion
rate and pull-off strength. Smaller particles produce better mechanical properties than bigger particles. However, additional amount of
TiO2 particles causes decrease in the mechanical properties. It was
concluded that the highest mechanical properties can be achieved
at an optimal TiO2 fraction that is related to the particle size. A correlation between tensile and exural stress as function of particle
size was reported.

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H.A. Al-Turaif / Progress in Organic Coatings 69 (2010) 241246

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