High Performance Polymers

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Synthesis and characterization of epoxy modified cyanate ester POSS nanocomposites

Ayyavu Chandramohan, Kanniyan Dinkaran, Achimuthu Ashok Kumar and Muthukaruppan Alagar
High Performance Polymers 2012 24: 405 originally published online 3 June 2012
DOI: 10.1177/0954008312441640

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Article

High Performance Polymers

24(5) 405–417
Synthesis and characterization of ª The Author(s) 2012
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epoxy modified cyanate ester POSS sagepub.co.uk/journalsPermissions.nav

DOI: 10.1177/0954008312441640
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nanocomposites

Ayyavu Chandramohan1, Kanniyan Dinkaran2,

Achimuthu Ashok Kumar3 and Muthukaruppan Alagar1

Abstract
Polyhedral oligomeric silsesquioxane (POSS) viz; namely, Octa functional silsesquioxanes [octa amino (OAPS) and octa
glycidyl (OG)] reinforced epoxy modified cyanate ester nanocomposites were prepared through intercrosslinked net-
work. The intercrosslinking formation between cyanate ester and POSS was confirmed by Fourier transform infrared
spectroscopy. The morphology of nanocomposites was studied using X-ray diffraction, scanning electron microscopy,
transmission electron microscopy and atomic force microscopy techniques. The electrical properties of the nanocompo-
sites were evaluated by impedance analyzer. The influences of POSS macromer on the thermal and mechanical properties
of epoxy modified cyanate ester nanocomposites were also addressed. The thermogravimetric analysis indicates that the
thermal stability of the nanocomposites increases with increasing percentage of both types of POSS macromer. The
dielectric constant and dielectric loss are decreased with increasing POSS concentration in the epoxy modified cyanate
ester nanocomposites.

Keywords
cyanate ester, polyhedral oligomeric silsesquioxane, hardness, flame retardancy, dielectric properties, atomic force
microscopy

Introduction toughening of epoxy resins is one of the most promising

Development of materials with light weight and superior
mechanical and thermal properties are essential for high
performance aerospace engineering applications. Cyanate
ester resins (CEs) are one of the most important thermoset-
ting resins developed in the last few decades. CEs monomers
undergo conventional thermal or catalytic polycyclotrimeri-
zation to form the very stable polycyanurate. Cyanate esters
are currently in widespread use because of their many attrac-
tive physical properties such as low water absorption, better
mechanical properties, low shrinkage on cure, excellent
dielectric properties along with good chemical resistance,
flame resistant and radiation resistant properties.1–6
Unfortunately, highly crosslinked thermosets, such as
cyanate ester, tend to be brittle and have reduced impact resis-
tance. To improve the toughness of a cured cyanate ester, a
number of different modifiers such as hydroxyl-terminated
polybutadiene (HTPB) rubber, carboxyl-terminated
butadiene-acrylonitrile (CTBN) rubber, polysulfone, poly
(ether imide), polyarylate and poly(ether ketone ketone) have
been used.7–12 Among the various modifiers used for
candidates, owing to its outstanding adhesion to various sub-
strates, excellent solvent, chemical resistance and weathering
resistance.13–16
Polyhedral oligomeric silsesquioxanes (POSS) are
attracting increased attention in nanostructured organic–
inorganic hybrid materials. POSS attracts much attention
as one of the most important nano structured materials
owing to its excellent mechanical properties, thermal
1
Polymer Nanocomposites Laboratory, Department of Chemical
Engineering, Alagappa College of Technology, Anna University, Chennai,
India
2
Department of Chemistry, MIT Campus, Anna University, Chennai, India
3
Department of Chemistry, Arulmigu Palaniandavar College of Arts and
Culture, Palani, India
Corresponding author:
Muthukaruppan Alagar, Polymer Nanocomposites Laboratory,
Department of Chemical Engineering, Alagappa College of Technology,
Anna University, Chennai - 600 025, India
Email: mkalagar@yahoo.com

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406
stability and low dielectric constant. Reactive functional
groups can also bond POSS to resin molecules, which sub-
sequently cure into thermoset matrixes. Functionalized
POSS can be incorporated into polymer chains to modify
the structure and chain mobility in polymeric materials and
eventually improve the mechanical, thermal and other
physical properties. These enhancements have been shown
to apply to wide range thermoset systems such as epoxy,
polyimide and polybenzoxazine.17–23
Furthermore, in order to maintain the balance of proper-
ties suitable for high performance applications the incor-
poration of nano crosslinker OAPS and OG into the
epoxy modified cyanate ester system will enhance the ther-
mal, thermomechanical and dielectric properties. In the
present study epoxy modified cyanate ester POSS nano-
composites were prepared through intercrosslinked net-
work. The influence of octa functionalized POSS on the
thermal, mechanical, dielectric and morphological proper-
ties of DGEBA epoxy modified cyanate ester was studied.
The formation of nanocomposite was confirmed by Fourier
transform infrared (FT-IR) spectroscopy, X-ray diffraction,
transmission electron microscopy and atomic force
microscopy.
Materials
The diglycidyl ether of bisphenol-A, DGEBA (LY556
equivalent [E] weight 180) are received from Ciba-Geigy
Ltd India. Cyanogen bromide (98%), cyclohexanone
(99.5%) and o-cresol (99%) were received from Sigma
Aldrich (USA). Phenyltrichlorosilane (97%), tetraethoxysi-
lane (98%), tetramethyl ammonium hydroxide 25% in
methanol (25%), chlorodimethylsilane (98%), platinum
(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex sol-
ution in xylene (Pt *2%), allylglycidylether (97%), benzyl
trimethyl ammonium hydroxide 40% in methanol solution
(40%) and 5% Pd/C were purchased from Aldrich, USA.
Formic acid, triethylamine, tetrahydrofuran (THF), ethyl
acetate and hexane were purchased from SD Fine Chemi-
cals, India. Triethylamine was distilled with KOH and THF
was distilled under a nitrogen atmosphere from Na/benzo-
phenone prior to use. Octaaminophenylsilsesquioxane
(OAPS), octakis (dimethylsiloxypropylglycidylether) sil-
sesquioxane (OG) and 1,1-bis(3-methyl-4-cyanatophenyl)-
cyclohexane was synthesized and characterized as per the
reported procedure.24–29
Preparation of nanocomposites
Neat Cy-OCN/DGEBA epoxy systems were prepared by
melt-mixing of DGEBA epoxy with cyanate ester
(Cy-OCN) in 1 : 1 wt/wt ratio. The Cy–OCN dissolved in
molten epoxy at 120  C with constant stirring until forming
homogeneous solution. This blend was poured into a mould
without degassing to avoid premature curing and it was
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High Performance Polymers 24(5)
cured in an oven. The curing for neat DGEBA epoxy/
Cy–OCN systems was carried out successively at 120  C
for 3 h, 180  C for 2 h, 210  C for 2 h and post cured at
240  C for 1 h and finally removed from the mould and
characterized.
Epoxy/Cy–OCN/OAPS-based nanocomposites were
prepared by a solution blending process. First, OAPS (1,
3, 5 and 10 wt.% corresponding to weight of epoxy/cyanate
ester) was dissolved in a minimum amount of THF and the
resulting solution was transferred completely to the desired
amount of DGEBA epoxy resin while mixed at 30  C for
5 min. Then the THF solvent was removed completely
under vacuum at 30  C. After the complete evaporation
of solvent, Cy–OCN was mixed with liquid DGEBA/OAPS
(Cy–OCN/DGEBA is 1 : 1 wt. ratio) at 120  C with contin-
uous stirring until a homogeneous transparent blend was
obtained. The mixture was then poured into a preheated
mould without degassing to avoid premature curing. It was
cured in an oven at 120  C for 3 h, 180  C for 2 h, and
210  C for 2 h and post cured at 240  C for 1 h and finally
removed from the mould and characterized.
Epoxy/Cy–OCN/OG systems were prepared by a direct
blending. Cy–OCN was mixed with liquid DGEBA epoxy
(1 : 1 wt. ratio) at 120  C and stirred for 10 min until it
became a transparent liquid. Then OG (1, 3, 5 and 10 wt.%
corresponding to weight of epoxy/cyanate ester) was mixed
completely with the desired amount of DGEBA/Cy–OCN
(1 : 1 wt. ratio) at 120  C with continuous stirring until the
formation of a homogeneous transparent solution and the
mixture was poured into a mould without degassing and
cured in an oven by similar conditions adopted for
DGEBA/Cy–OCN/OAPS systems. The schematic repre-
sentation for the preparation of DGEBA/Cy–OCN/POSS
nanocomposites is presented in Scheme 1.
Characterization
FT-IR
FTIR spectra were recorded on a Perkin-Elmer 6X FTIR
spectrometer. Optical-grade KBr (ca. 100 mg) was ground
in a mortar with a pestle, and enough solid sample was
ground with KBr to make a 1 wt.% mixture for making KBr
pellets. After the sample was loaded, a minimum of
16 scans were collected for each sample at a resolution
of + 4 cm1.
Thermal properties
The glass transition temperature (Tg) of the samples was
determined using a DSC 200 PC differential scanning
calorimeter (Netzsch Gerateban GmbH) in the temperature
range between 50 to 350  C at a heating rate of
283 K min1 in flowing nitrogen. Thermo gravimetric anal-
ysis (TGA) was carried out using a DSTA 409 PC analyzer
Chandramohan et al. 407

R R
R
R Si Si
O CH3 CH3 O
O C O O C O Si Si
CH3 OH CH3 Si Si
n
Si Si R
R
DGEBA R R
+ +
NCO OCN octa-POSS

R= NH2 or O Si O
O

1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane

Si Si
Si Si Si Si
Si Si
Si Si
Si Si Si Si
Si Si
Si Si
Si Si
Si Si
Si Si
Si Si
Si Si
Si Si
Si Si
Si Si
Si Si
Si Si
Si Si Si Si
Si Si
Si Si
Si Si Si Si
Si Si
Si Si
Si Si

Scheme 1. Schematic representation of POSS reinforced Cy–OCN/DGEBA epoxy nanocomposites.

(Netzsch Gerateban GmbH) at a heating rate of
283 K min1 in flowing nitrogen.
Thermomechanical properties
Determination of the heat distortion temperature (HDT)
was carried out as per ASTM D 648 using HDT apparatus.
The specimens of size 120 mm in length, 3 mm in thickness
and 5 mm in width were kept in an oil bath under a load of
1.82 MPa. The temperature was raised at a rate of 2  C
min1, and the temperature was noted when the specimen
deflected by 0.25 mm. Coefficient of thermal expansion
of the samples was determined using METTLER TMA
2940 in the temperature range between 30 and 400  C at
a heating rate of 10.0 K min1 with a force of 0.05 N. The
sample dimension was 5 mm  5 mm  1 mm.
Dielectric properties
The dielectric constant and dielectric loss measurements
were carried out with help of an impedance analyzer (Solar-
tron impedance/gain phase analyzer 1260) at room tem-
perature. The polymer powder samples were made in the
form of pellets (1 mm thickness  8 mm diameter) by

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408
applying a pressure of 3.5 tonnes for impedance measure-
ments using platinum (Pt) electrode in the frequency range
1 MHz. The dielectric constant and dielectric loss of the
samples were determined using e0 and e00 as the standard
relations. The dielectric constant was calculated from
impedance spectral data using the following equation
e0 ¼ Cp =Co ½Co ¼ eo =d .
Water absorption
Water absorption properties weres determined by swelling
the samples in distilled water for 48 h at 30  C. The sample
dimension was 10 mm  10 mm  3 mm. The percentage
of water absorbed by the specimen is calculated using equa-
tion. Percentage of water absorption ¼ ðw2  w1 Þ 100=w1
where w1 is the initial weight of the sample and w2 is the
weight of the sample after immersion in water for 48 h at
30  C.
Mechanical properties
The tensile (stress–strain) properties were determined
using Hounsfield-UTM as per ASTM D 3039 at
2 mm min1cross-head speed using specimen having a
width of 25 mm, length of 200 mm, and thickness of
3 mm. The flexural strength was measured (HTE-series-
H50 K-S Model, Hounsfield test equipment Ltd, UK) as
per ASTM D 790 using specimen with dimensions 3 mm
in depth, 10 mm in width, and 90 mm in length at
5 mm min1 cross-head speed. The Izod unnotched impact
strength of each sample was studied as per ASTM D 256-
88. Five specimens were tested for each sample. Hardness
was measured using a Durometer-Type D as per ASTM D
2240 and specimens with 3 mm thickness. Hardness was
determined at three different positions on the specimen at
least 6 mm apart and the arithmetic mean was taken.
Morphology
X-ray diffraction (XRD) patterns were recorded at room
temperature by monitoring the diffraction angle 2y from
0.5 to 70 as the low angle on a Rich Seifert (Model
3000) X-ray powder diffractometer. The diffractometer
was equipped with a Cu target (k ¼ 0.154 nm) radiation and
a Guinier-type camera employed as a focusing geometry
and a solid-state detector. A curved Ni crystal was used
as a monochromator. The step width (scanning speed) used
was 2y ¼ 0.04 min1. Bragg’s law (nl ¼ 2dsiny) was used
to compute the spacing. To study the morphological beha-
vior, the fractured surfaces were obtained from plain strain
fracture toughness tested specimens. Excess material was
removed from the other faces of the specimens by razor
blade. The fractured surfaces of the specimens were coated
with gold and examined under a scanning electron micro-
scope (SEM; JEOL JSM 6360). A JEOL JEM-3010
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High Performance Polymers 24(5)
Figure 1. FT-IR spectra of (a) DGEBA epoxy and (b) OG.
analytical transmission electron microscope, operating at
300 kV with a measured point-to-point resolution of
0.23 nm, was used to characterize the phase morphology
in the polymers. TEM samples were prepared by dissolving
polymers in dimethylformamide mounted on carbon-coated
Cu TEM grids and dried for 24 h at room temperature to
form a film of < 50 nm size. Atomic force microscopy
(AFM) measurements were carried out with the AFM Park
Instruments, XE-70 (South Korea). The mode was non-
contact with the set point ranging from 1–10 nm.
Results and discussion
FT-IR spectral analysis
FT-IR spectra of neat OG, DGEBA, Cy-OCN/DGEBA/
OAPS and Cy-OCN/DGEBA/OG nanocomposites are
shown in Figures 1–3. The crosslinking reaction between
the epoxy modified cyanate ester and OAPS was confirmed
by the disappearance of peak at 2263 cm1 corresponding
to Cy–OCN (Figure 2(a)) and the appearance of new peak
at 1640 cm1 corresponding to N–H bending of imino car-
bonate (–C¼NH) (Figure 2(b)–(d)). In the case of OG
reinforced Cy–OCN/DGEBA epoxy nanocomposites the
disappearance peaks at 2263 cm1 (Cy–OCN), 908 cm1
(Figure 1) and appearance of peaks at 1370 and 1560 cm1
due to sym-triazine rings confirmed the occurrence of
crosslinking reaction between OG and Cy–OCN/DGEBA
resin system.30
In all these cases the epoxy peak 913 cm1 (Figure 1)
was absent which confirms that the epoxy group was fully
involved in the reaction. In the Cy–OCN/DGEBA/OAPS
and Cy–OCN/DGEBA/OG nanocomposites the symmetric
and asymmetric stretching frequencies of cyclohexyl group
appeared at 2924 and 2868 cm1 respectively. O–H stretch-
ing of DGEBA epoxy was observed at 3385 cm1. It is
noted that the peak appeared for Si–O–Si linkage at
1101 cm1 confirmed the presence of both OAPS and
OG-POSS in the resulting hybrid nanocomposites.
Chandramohan et al.
Figure 2. FT-IR spectra of OAPS reinforced Cy–OCN/DGEBA
epoxy nanocomposites: (a) neat Cy–OCN; (b) 1 wt.% OAPS/
Cy–OCN/DGEBA; (c) 3 wt.% OAPS/Cy–OCN/DGEBA; (d)
5 wt.% OAPS/Cy–OCN/DGEBA and (e) 10 wt.% OAPS/Cy–OCN/
DGEBA.
Figure 3. FT-IR spectra of OG reinforced Cy–OCN/DGEBA epoxy
nanocomposites: (a) neat Cy-OCN; (b) 1 wt.% OG/Cy–OCN/
DGEBA; (c) 3 wt.% OG/Cy–OCN/DGEBA; (d) 5 wt.% OG/Cy–
OCN/DGEBA and (e) 10 wt.% OG/Cy–OCN/DGEBA.
Thermal properties
Differential scanning calorimetry. The results of DSC analysis
of nanocomposites are shown in Figures 4-5 and Table 1.
DSC measurements indicate that all the DSC thermogram
displayed a single Tg in the experimental temperature range
from 30 to 350  C.
The Tg value of unmodified Cy–OCN/DGEBA system
is 234  C. The incorporation of OAPS and OG into
Cy–OCN/DGEBA systems increased the value of Tg up
to 5 wt.% loading and further addition of OAPS and OG
decreased the value of Tg of the nanocomposites this may
be explained due to higher percentage loading of POSS
may result some of the groups becomes not available for
complete reaction and hence crosslinking density
decreases. The Tg of 3 wt.% of OAPS incorporated
Cy–OCN/DGEBA system was higher (251  C) than that
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409
Figure 4. DSC thermogram of OAPS reinforced Cy–OCN/
DGEBA epoxy nanocomposites.
Figure 5. DSC thermogram of OG reinforced Cy–OCN/DGEBA
epoxy nanocomposites.
of the same weight percentage OG incorporated
Cy–OCN/DGEBA system (245  C), this may be due to the
presence of flexible oxazolidone in OG-POSS and hence
molecular mobility occurs at little lower temperature than
that of the OAPS incorporated Cy–OCN/DGEBA system.
Thermogravimetric analysis. Thermogravimetric analysis was
carried out to evaluate the thermal stability of the
Cy–OCN/DGEBA and their POSS nanocomposites. The
results of TGA analysis of the unmodified system,
Cy–OCN/DGEBA/OAPS and Cy–OCN/DGEBA/OG sys-
tems are shown in Figures 6-7 and Table 1. The TGA
curves are presented in the temperature range from 30 to
800  C. The initial decomposition temperature showed a
decreasing tendency but char yield increased with an
increase of POSS content.31 Furthermore, when POSS
degraded, it left an inert silica layer which could form a
protective layer on the surface of the material preventing
further decomposition of the inner part of the matrix.32
410 High Performance Polymers 24(5)

Table 1. Thermal properties of POSS reinforced Cy-OCN/DGEBA nanocomposites.

TGA

Tg from Initial degradation Char yield at

System OAPS (wt.%) OG (wt.%) DSC ( C) (Td at 5%) ( C) 800  C (wt.%) LOI (wt.%)

Cy–OCN/DGEBA 0 0 234 420 19.7 25.38

1 – 246 411 21.5 26.11
3 – 251 405 23.1 26.74
5 – 255 398 26.3 28.02
10 – 238 390 30.5 29.73
– 1 238 408 24.2 27.18
– 3 245 396 26.9 28.26
– 5 233 386 29.5 29.31
– 10 227 379 33.6 30.94

Figure 7. TGA of OG reinforced Cy–OCN/DGEBA epoxy

Figure 6. TGA of OAPS reinforced Cy–OCN/DGEBA epoxy
nanocomposites.
On comparing OAPS and OG modified nanocompo-
sites, OAPS modified nanocomposites showed lower
weight loss rate due to the formation of strong iminocarbo-
nate linkage. For example, 10 wt.% of OAPS incorporated
Cy–OCN/DGEBA system the 5% weight loss occurred at
390  C whereas the same percentage weight loss occurred
at 379  C for OG incorporated Cy–OCN/DGEBA system
and this may be attributed to the thermally weak oxazoli-
done present in the OG incorporated system.
Flame retardancy. The flame-retardant behavior of Cy–
OCN/DGEBA system and POSS reinforced Cy–OCN/
DGEBA systems was calculated in terms of limiting oxy-
gen index (LOI) from the char yield resulting from TGA
analysis. Table 1 shows the value of LOI for unmodified
Cy–OCN/DGEBA system and POSS reinforced Cy–
OCN/DGEBA systems. The values of LOI increased with
the increase in the values of char yield. The flame resis-
tance can be represented by the LOI and were calculated
as per the reported procedure.33–34
The LOI values of POSS reinforced Cy–OCN/DGEBA
hybrid materials were increased with increased weight
nanocomposites.
percentage of POSS content. The inorganic nanosilica
segments were expected to improve the thermal stability.
This inorganic silica char formation could improve the
flame-retardant properties.31,35,36 The LOI values of
the OG-reinforced Cy–OCN/DGEBA hybrid materials
were higher than those of OAPS reinforced Cy–OCN/
DGEBA hybrid materials. These performances were ana-
lyzed based on the concept that silsesquioxane produces
silica (SiO2) char and interferes with the combustion pro-
cess during heating, pyrolysis, ignition and flame spread-
ing. Thick char forms a better thermal insulating layer; it
undergoes slow oxidative degradation and prevents heat
from reaching the remaining polymer, which eventually
leads to significant improvements in the overall flame
retardancy of POSS reinforced Cy–OCN/DGEBA hybrid
composites.
Thermomechanical properties
Heat distortion temperature . Heat distortion temperature
was determined to assess the thermomechanical behavior
of matrix systems. HDT values for neat system and
POSS reinforced systems (Cy–OCN/DGEBA/OAPS and

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Chandramohan et al. 411

Table 2. Thermomechanical and dielectric behavior of POSS reinforced Cy–OCN/DGEBA nanocomposites.

OAPS OG HDT CTE Dielectric constant Dielectric loss Water

System (wt%) (wt%) ( C) (ppm K1) (e0 ) (1 MHz) (e00 ) (1 MHz) uptake (%)

Cy-OCN/DGEBA 0 0 228 68.4 2.43 0.0054 1.86

1 – 237 67.1 2.38 0.0045 1.69
3 – 243 65.9 2.33 0.0039 1.61
5 – 246 64.2 2.27 0.0033 1.54
10 – 230 61.8 2.19 0.0029 1.46
– 1 232 69.6 2.42 0.0051 1.81
– 3 239 71.2 2.40 0.0045 1.75
– 5 231 72.9 2.36 0.0040 1.61
– 10 222 74.2 2.30 0.0033 1.55

76 of longer tether length between OG and polymer matrix.

Cy-OCN/DGEBA/OAPS
For example, the values of the coefficient of thermal expan-
74 Cy-OCN/DGEBA/OG
sion for the 10 wt.% OG loaded system was 74.2 ppm K1,
72 whereas for the 10 wt.% OAPS incorporated system it was
61.8 ppm K1.
CTE (ppm/K)

70

68

66
64
62
60
0 2 4 6 8 10
Wt % of OAPS and OG
Figure 8. Coefficient of thermal expansion of POSS reinforced
Cy–OCN/DGEBA epoxy nanocomposites.
Cy–OCN/DEGEBA/OG) are presented in Table 2. The
value of HDT for unmodified Cy–OCN/DGEBA was
228  C. The values of Cy–OCN/DGEBA/OAPS and Cy–
OCN/DGEBA/OG systems with 1, 3, 5 and 10% (by
weight) OAPS and OG reinforced systems were 237, 243,
246 and 230  C and 232, 239, 231 and 222  C respectively.
The values obtained for Cy–OCN/DGEBA/OAPS systems
were higher than that of Cy–OCN/DEGEBA/OG system
due to the higher crosslink density.
Coefficient of thermal expansion. Figure 8 and Table 2 present
the data of coefficients of thermal expansion (CTE) of neat
Cy–OCN/DGEBA and POSS reinforced nanocomposites
in the temperature range between 30 and 400  C. The
increasing percentage loading of OAPS into Cy–OCN/
DGEBA systems decreased the values of CTE more than
those of the neat system which could be ascribed to the
presence of rigid and lower tether length between OAPS
and polymer matrix.
It was also observed that the OG modified Cy–OCN/
DGEBA nanocomposites exhibited higher values of CTE
than those of neat Cy–OCN/DGEBA systems because of
the soft segments present in OG molecules and the presence
Mechanical properties
Tensile properties. The behavior of tensile strength and
modulus of neat Cy–OCN/DGEBA system and POSS
reinforced Cy–OCN/DGEBA systems are shown. The val-
12 ues are presented in Table 3. The incorporation of POSS
into Cy–OCN/DGEBA systems enhanced the values of ten-
sile strength as well as tensile modulus. The introduction of
1, 3, and 5% (by weight) of POSS improved the tensile
properties. However, in the case of 10 wt.% of POSS, the
loading decreased the value of tensile strength. This may
be explained due to the enhanced free volume with conse-
quent reduction in crosslink density. On comparing OAPS
and OG modified epoxy systems the OAPS modified
Cy–OCN/DGEBA systems exhibited higher values of ten-
sile properties due to the existence of higher crosslinking
density. The values of tensile modulus exhibited a similar
trend as in the case of tensile strength.
Flexural properties. Flexural properties of neat cyanate ester
(Cy–OCN) copolymerized with DGEBA epoxy systems
and POSS-reinforced Cy–OCN/DGEBA epoxy systems are
presented in Table 3. The properties of flexural strength as
well as flexural modulus were improved by increasing the
concentration of OAPS/OG up to 5 wt.% and then
decreased later with an increase of OAPS and OG content.
On comparison of values of flexural strength of Cy–OCN/
DGEBA/OAPS and Cy–OCN/DGEBA/OG systems, the
Cy–OCN/DGEBA/OG system possessed lower values due
to the presence of the flexible tether group of OG in the
Cy–OCN/DGEBA epoxy system which induced a plasti-
cizing effect to the network system that was greater than
that of OAPS reinforced Cy–OCN/DGEBA nanocompo-
sites. Similar trends were observed in flexural modulus as

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412 High Performance Polymers 24(5)

Table 3. Mechanical behavior of POSS reinforced Cy–OCN/DGEBA nanocomposites.

OAPS OG Tensile Tensile Flexural Flexural Impact strength Hardness

System (wt.%) (wt.%) strength (MPa) modulus (MPa) strength (MPa) modulus (MPa) (J m2) shore D

Cy–OCN/ 0 0 69.5 +4 2801.1 + 15 120.4 + 4 3018.9 + 20 123.1 + 6 45

DGEBA 1 – 71.7 +1 2912.6 +8 129.3 + 5 3115.5 + 12 127.3 + 3 51
3 – 73.8 +5 3063.5 + 21 138.1 + 1 3193.2 + 14 133.6 + 2 56
5 – 78.4 +2 3176.3 + 19 145.5 + 7 3272.1 +8 138.8 + 4 59
10 – 69.2 +3 2792.2 + 10 136.7 + 2 3101.8 + 11 141.4 + 7 62
– 1 70.1 +3 2906.3 + 10 127.3 + 2 3079.2 + 18 130.3 + 9 49
– 3 72.9 +7 3032.8 + 21 135.1 + 4 3178.5 + 13 137.2 + 5 52
– 5 76.7 +5 3143.2 + 18 141.2 + 1 3231.1 + 19 142.8 + 2 56
– 10 68.2 +2 2683.5 + 15 131.3 + 3 3091.4 + 24 150.4 + 4 58

noticed in the case of the flexural strength of Cy–OCN/

DGEBA epoxy systems.
Impact strength. The behavior of impact strength of neat
Cy–OCN/DGEBA system, Cy–OCN/DGEBA/OAPS and
Cy–OCN/DGEBA/OG systems are presented in Table 3.
The incorporation of POSS (up to 10 wt.%) into Cy–
OCN/DGEBA systems enhanced the values of impact
strength, due to the presence of flexible tether group in the
OG molecules. However, the value of impact strength was
higher in the case of OG/Cy–OCN/DGEBA systems than
that of rigid OAPS reinforced systems. For example, 5 wt.%
of OAPS reinforced Cy–OCN/DGEBA system showed the
value of impact strength of 138.4 J m2 whereas the same
5 wt.% of OG incorporated system displayed the value of
impact strength of 145.2 J m2. The values of impact
strength of OG based nanocomposites were higher than that
Figure 9. XRD pattern of OAPS reinforced Cy–OCN/DGEBA
of OAPS based nanocomposites and can be explained due epoxy nanocomposites.
to the better flexibility imparted to the network structure by
the former than latter.
of appropriate dimension in deionized water at 30  C for
Hardness. The hardness values for neat Cy–OCN/DGEBA 48 h. Low water absorption is a very important property for
system, Cy–OCN/DGEBA/OAPS and Cy–OCN/DGEBA/ a material used for insulation applications, especially those
OG are presented in Table 3. The value of hardness for neat requiring stable high performance. In general, the absorbed
Cy–OCN/DGEBA system was 45. The incorporation of 1, water will affect the properties of the original material
3, 5 and 10% (by weight) of OAPS and OG into Cy–OCN/ including thermal, mechanical and dielectric properties,
DGEBA systems enhanced the hardness. The enhancement etc. Among the systems studied, Cy–OCN/DGEBA/OG
in the values of hardness for POSS reinforced Cy–OCN/ systems exhibited a higher percentage of water uptake
DGEBA systems was due to the formation of an intercros- when compared with that of Cy–OCN/DGEBA/OAPS sys-
slinking network between POSS and Cy–OCN/DGEBA. tems due to the presence of hydrophilic OH groups present
The introduction of the inorganic segments into the organic in tether after curing.37,38
polymer could improve the wear resistance and surface
hardness of the nanocomposites. This phenomenon sug-
gested the inseparable architecture of the nanocomposites Dielectric constant and dielectric loss
and nano reinforcement effect of the inorganic segments. The increased addition of less polar natured POSS mole-
cules into Cy–OCN/DGEBA systems decreased the values
of dielectric constant as well as dielectric loss of the nano-
Water absorption behavior composites as shown in Table 2. Among the systems stud-
Water absorption characteristics of the neat Cy–OCN/ ied, the Cy–OCN/DGEBA/OAPS systems exhibited lower
DGEBA system, Cy–OCN/DGEBA/OAPS and Cy–OCN/ values of dielectric constant and dielectric loss because of
DGEBA/OG systems are presented in Table 2. The water the creation of more free volume during the formation
absorption test was carried out by immersing a specimen of less polar nature of triazine ring between the epoxy

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Chandramohan et al.
Figure 10. SEM morphology of POSS reinforced Cy–OCN/DGEBA epoxy nanocomposites: (a) neat Cy–OCN/DGEBA; (b) 5 wt.% of
OAPS in Cy–OCN/DGEBA and (c) 5 wt.% of OG in Cy–OCN/DGEBA.
Figure 11. TEM morphology of POSS reinforced Cy–OCN/
DGEBA epoxy nanocomposites: (a) 5 wt.% of OAPS in Cy–
OCN/DGEBA and (b) 5 wt.% of OG in Cy–OCN/DGEBA.
and –OCN.36,39 In the case of Cy–OCN/DGEBA/OG
systems, the values of dielectric constant and dielectric
loss were higher due to the presence of the polar nature
of hydroxyl group. The values of dielectric constant of
10 wt.% POSS-reinforced systems of Cy–OCN/DGEBA/
OAPS and Cy–OCN/DGEBA/OG were 2.19 and 2.30,
respectively. These values were the lowest values reported
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413
so far. For example, the dielectric constant of the DDS-
cured DGEBA system was reported to be 3.56 at 1 MHz,
the dielectric constant reported for 10% OAPS blended
epoxy was 2.87.24 A similar trend was also observed in the
case of values of dielectric loss.
Morphological properties
X-ray diffraction analysis. The X-ray diffraction patterns for
the neat OAPS and OAPS-reinforced Cy–OCN/DGEBA
systems are shown in Figure 9. From Figure 9, it was
observed that a strong peak at 2y ¼ 7.7 (d-spacing
1.11 nm represents the inter-cubic distance of OAPS). The
diffraction pattern of OAPS reinforced Cy–OCN/DGEBA
system showed a broad amorphous peak at 2y ¼ 18.31 ,
which suggested that the OAPS molecules are completely
dispersed in the Cy–OCN/DGEBA matrix systems. The
XRD pattern of all the Cy–OCN/DGEBA/OAPS based
nanocomposites were similar and implied that OAPS
was homogeneously dispersed in Cy–OCN/DGEBA
networks.19,40
414 High Performance Polymers 24(5)

Figure 12. AFM microphotographs of POSS reinforced Cy–OCN/DGEBA epoxy nanocomposites: (a-1) the phase image of neat
Cy–OCN/DGEBA; (a-2) the topography 3D image of neat Cy–OCN/DGEBA; (b-1) the phase image of 5 wt.% of OAPS in Cy–OCN/
DGEBA; (b-2) the topography 3D image of OAPS in Cy–OCN/DGEBA; (c-1) the phase image 5 wt.% of OG in Cy–OCN/DGEBA and
(c-2) the topography 3D image of OG in Cy–OCN/DGEBA.

Scanning electron microscopy. The morphology of the frac-
tured surfaces of various hybrid systems after impact break
was studied by SEM to analyze the effect of POSS on the
mechanical properties of Cy–OCN, as shown in Figure 10.
The morphology of the neat Cy–OCN/DGEBA systems
and OAPS and OG-reinforced hybrids were investigated
by SEM. Figure 10(a) shows the fractured surface was
smooth without any microphase separation. Figure 10(b)
and (c) shows the appearance of a lot of ‘filar’ shape for the
cured systems after the cured samples was impacted, which

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Chandramohan et al.
Figure 13. Visual observation of POSS reinforced Cy–OCN/DGEBA epoxy nanocomposites: (a) neat Cy–OCN/DGEBA; (b) 5 wt.% of
OAPS in Cy–OCN/DGEBA and (c) 5 wt.% of OG in Cy–OCN/DGEBA.
looked like bamboo when they were pulled out. Addition-
ally, the inorganic segments (POSS) were dispersed homo-
geneously throughout the epoxy matrix. All the reactants
(DGEBA, Cy–OCN and POSS) were well mixed on the
nanometer scale.29,41,42
Transmission electron microscopy. Transmission electron
micrographs of the POSS-reinforced systems are shown
in Figure 11(a) and (b). The TEM pictures show the uni-
form nano level dispersion of POSS macromer into the
Cy–OCN/DGEBA matrix. The POSS segments cluster
could be observed directly in the TEM microphotograph.
The organic and inorganic segments of the Cy–OCN/
DGEBA hybrid materials were distributed uniformly on the
nanoscale.43,44
Atomic force microscopy. The topology of the neat Cy–OCN/
DGEBA systems and OAPS and OG reinforced hybrids
were investigated by AFM. Figure 12(a) and (c) present the
topographic 3D image and phase image of the POSS
reinforced Cy–OCN/DGEBA hybrid nanocomposites.
From Figure 12(a), the phase separation was not clearly
observed; however, from Figure 12(b) and (c), it was
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415
observed that the POSS reinforced matrices showed a
rougher surface than that of neat hybrid matrices. The
phase images also indicate that the POSS domains were
uniformly dispersed throughout the matrix.
The morphology of neat Cy–OCN/DGEBA system and
Cy–OCN/DGEBA/POSS nanocomposites was further
examined by visual observation studies and are shown in
Figure 13(a) to (c). The neat Cy–OCN/DGEBA system,
10 wt.% of OAPS reinforced Cy–OCN/DGEBA and OG
reinforced Cy–OCN/DGEBA systems showed homoge-
neous morphology. This was confirmed by the reaction of
POSS (OAPS and OG) with Cy–OCN and epoxy resin.
Conclusion
In this study, the varying weight percentages of octafunc-
tionalized OAPS and OG were reinforced separately with
Cy–OCN modified DGEBA epoxy resin (1 : 1 wt/wt). The
hybrid nanocomposites containing POSS up to 10 wt.%
were obtained via in-situ polymerization of cyanate ester
(Cy–OCN) and DGEBA epoxy in the presence of POSS.
FT-IR results confirmed the intercrosslinking reaction
416
between DGEBA-modified cyanate ester (Cy–OCN) and
POSS macromer in the Cy–OCN/DGEBA nanocompo-
sites. The POSS reinforcement increased the both glass
transition temperature (Tg) and thermal degradation tem-
perature of the nanocomposites.
The limiting oxygen index also increased with increas-
ing loading of POSS up to 10 wt.%. The increasing weight
percentage of POSS in the epoxy-modified Cy–OCN
nanocomposites improved the mechanical properties
such as tensile strength, flexural strength, impact strength
and hardness. The values of dielectric constant and dielec-
tric losses were decreased with increased loading of
POSS. XRD analysis indicated the molecular level disper-
sion of POSS molecules. Furthermore, the nano level
dispersion of POSS molecules within the polymer matrix
was confirmed by SEM, TEM and AFM. The uniform
dispersion of POSS was also confirmed by visual observa-
tion studies.
Acknowledgements
The authors acknowledge the financial support for this work by
University Grants Commission (UGC), New Delhi. The authors
also acknowledge Dr S. Nagendiran, Dr S. Jothibasu, Dr V.
Selvaraj, Dr K.V. Thiruvengadaravi, Dr P. Baskarlingam, M. R.
Vengatesan, S. Devaraju, R. Kumaran, Miss M. Mandhakini, Miss
M. Selvi and Mrs K. Kanimozhi, Polymer Nanocomposite Lab,
Department of Chemical Engineering, A.C. Tech, Anna Univer-
sity, Chennai for their support.
References
1. Hamerton I (ed.) Chemistry and technology of cyanate ester
resins. Glasgow: Blackie Academic and Professional, 1994.
2. Gu AJ. High performance bismaleimide/cyanate ester hybrid
polymer networks with excellent dielectric properties. Comp
Sci Tech 2006; 66: 1749–1755.
3. Zhang F, Wang ZG and Zhang X. Synthesis and properties of
a series of cyanate resins based on phenolphthalein and its
derivatives. Polymer 2009; 50: 817–824.
4. Huang Y, Ma XY, Wang X, et al. Modification of dicyanate
ester resin by liquid carboxyl-terminated butadiene acryloni-
trile copolymer. Mater Chem Phy 2010; 121: 241–248.
5. Han CF, Gu AJ, Liang GZ, et al. Carbon nanotubes/cyanate
ester composites with low percolation threshold high dielec-
tric constant and outstanding thermal property. Comp Part A
2010: 41: 1321–1328.
6. Sheng X, Akinc M and Kessler MR. Cure kinetics of thermo-
setting bisphenol E cyanate ester. J Therm Anal Calori 2008;
93: 77–85.
7. Iijima T, Kunimi T, Oyama T, et al. Modification of cyanate
ester resin by soluble polyarylates. Polym Inter 2003; 52:
773–782.
8. Hwang JW, Park SD, Cho K, et al. Toughening of cyanate
ester resins with cyanated polysulfones. Polymer 1997; 38:
1835–1843.
Downloaded from hip.sagepub.com at BEN GURION UNIV NEGEV on July 24, 2012
High Performance Polymers 24(5)
9. Kim YS, Min HS, Choi WJ, et al. Dynamic mechanical
modeling of PEI/dicyanate semi-IPNs. Polym Eng Sci 2000;
40: 665–675.
10. Harismendy I, Rio MD, Marieta C, et al. Dicyanate ester-
polyetherimide semi-interpenetrating polymer networks. II.
Effects of morphology on the fracture toughness and mechan-
ical properties. J Appl Polym Sci 2001; 80: 2759–2767.
11. Liu J, Ding N, Xu R, et al. Cyanate ester resin modified by
hydroxyl-terminated polybutadiene: morphology, thermal,
and mechanical properties. Polym Eng Sci 2011; 51:
1404–1408.
12. Zeng MF, Sun XD, Wang Y, et al. A positron annihilation
study on the microstructure of cyanate ester resin toughened
by carboxyl-terminated butadiene-acrylonitrile rubber
system. Polym Adv Tech 2008; 19:1664–1671.
13. Alagar M, Thanikaivelan TV, Ashok Kumar A, et al. Synth-
esis and characterization of high performance polymer hybrid
siliconized epoxy composites for aerospace applications.
Mater Manu Proc 1999; 14: 67–83.
14. Ashok Kumar A, Alagar M and Rao RMVGK. Synthesis and
characterization of siliconized epoxy-1,3-bis(maleimido)-
benzene intercrossliked matrix materials. Polymer 2002; 43:
693–702.
15. Prem kumar S, Karikal Chozhan C and Alagar M, Studies on
thermal, mechanical and morphological behaviour of capro-
lactam blocked methylenediphenyl diisocyanate toughened
bismaleimide modified epoxy matrices. Eur Polym J 2008;
44: 2599–2607.
16. Rajasekaran R, Karikal Chozhan C and Alagar M. Effect of
polyethersulfone and N,N0 -bismaleimido-4,40 -diphenyl
methane on the mechanical and thermal properties of epoxy
systems. eX Polym Lett 2008; 2: 339–348.
17. Pittman CU, Li G and Ni H. Hybrid inorganic/organic cross-
linked resins containing polyhedral oligomeric silsesquiox-
anes. Macro Symp 2003; 196: 301–325.
18. Fina A, Tabuani D and Camino G. Polypropylene-
polysilsesquioxane blends. Eur Polym J 2010; 46: 14–23.
19. Ohno T, Tagawa S, Itoh H, et al. Size effect of TiO2–SiO2
nano-hybrid particle. Mater Chem Phy 2009; 113: 119–123.
20. Pellice SA, Fasce DP and Williams RJ. Properties of epoxy
networks derived from the reaction of diglycidyl ether of
bisphenol A with polyhedral oligomeric silsesquioxanes bear-
ing OH-functionalized organic substituents. J Polym Sci Part
B Polym Phy 2003; 41: 1451–1461.
21. Ni Y and Zheng S. Nanostructured thermosets from epoxy
resin and an organic-inorganic amphiphile. Macromolecules
2007; 40: 7009–7018.
22. Yani Y and Lamm MH. Molecular dynamics simulation of
mixed matrix nanocomposites containing polyimide and
polyhedral oligomeric silsesquioxane (POSS). Polymer
2009; 50: 1324–1332.
23. Lee YJ, Kuo SW, Su YC, et al. Syntheses, thermal properties,
and phase morphologies of novel benzoxazines functiona-
lized with polyhedral oligomeric silsesquioxane (POSS)
nanocomposites. Polymer 2004; 45: 6321–6331.
Chandramohan et al.
24. Nagendiran S, Alagar M and Hamerton I. Octasilsesquioxane-
reinforced DGEBA and TGDDM epoxy nanocomposites:
characterization of thermal, dielectric and morphological prop-
erties. Acta Materialia 2010; 58: 3345–3356.
25. Vengatesan MR, Devaraju S, Ashok Kumar A, et al. Studies
on thermal and dielectric properties of Octa (maleimido phe-
nyl) silsesquioxane (OMPS) polybenzoxazine (PBZ) hybrid
nanocomposites. High Perform Polym 2011; 23: 441–456.
26. Choi J, Yee AF and Laine RM. Organic/inorganic hybrid
composites from cubic silsesquioxanes epoxy resins of octa
(dimethylsiloxyethylcyclohexylepoxide) silsesquioxane.
Macromolecules 2003; 36: 5666–5682.
27. Filho NLD, Aquino HA, Pires G, et al. Relationship between
the dielectric and mechanical properties and the ratio of
epoxy resin to hardener of the hybrid thermosetting polymers.
J Braz Chem Soc 2006; 17: 533–541.
28. Dinakaran K and Alagar M. Preparation and characterization
of cyanate ester-epoxy interpenetrating matrices/organoclay
hybrid nanocomposites. Polym Adv Tech 2003; 14: 574–585.
29. Nagendiran S, Karikal Chozhan C, Alagar M, et al. Inorganic/
organic hybrid nanocomposites involving OMMT clay and
cyanate ester-siloxane modified epoxy resin: Thermal,
dielectric and morphological properties. High Perform Polym
2008; 20: 323–347.
30. Hu JT, Gu A, Liang G, et al. Preparation and properties of
high-performance polysilsesquioxanes/bismaleimide-triazine
hybrids. J Appl Polym Sci 2011; 120: 360–367.
31. Ma CM, Chiu YC, Chou IC, et al. Morphology, thermal and
mechanical properties of the polyhedral oligomeric silses-
quioxane side-chain epoxy hybrid material. J Appl Polym Sci
2010; 118: 3723–3732.
32. Tarrio SJ, Lopez BJ, Naya S, et al. Effect of silica content on
thermal stability of fumed silica/epoxy composites. Polym
Deg Stab 2008; 93: 2133–2137.
33. Van Krevelen DW. Some basic aspect of flame resistance of
polymeric materials. Polymer 1975; 16: 615–620.
34. Lin ST and Huang SK. Thermal degradation study of
siloxane-DGEBA epoxy copolymers. Eur Polym J 1997;
33: 365–373.
Downloaded from hip.sagepub.com at BEN GURION UNIV NEGEV on July 24, 2012
417
35. Liang K, Li G, Toghiani H, et al. Cyanate ester/polyhedral
oligomeric silsesquioxane (POSS) nanocomposites: synthesis
and characterization. Chem Mater 2006; 18: 301–312.
36. Zhou C, Gua A, Liang G, et al. Novel toughened cyanate ester
resin with good dielectric properties and thermal stability by
copolymerizing with hyperbranched polysiloxane and epoxy
resin. Polym Adv Tech 2011; 22: 710–717.
37. Li WF, Xin WL, Liang GZ, et al. Cure reaction of cyanate
ester resins and the catalyst. J Aero Mater 2003; 23:
56–62.
38. Dai S, Gu A, Liang G, et al. Preparation and properties of cya-
nate ester/ polyorganosiloxane blends with lower dielectric
loss and improved toughness. Polym Adv Tech 2011; 22:
262–269.
39. Schulze K, Schuldt U, Kahle O, et al. Novel low-k polycya-
nurates for integrated circuit (IC) metallization. Micro Eng
2005; 82: 356–361.
40. Fina A, Tabuani D, Frache A, et al. Polypropylene-polyhedral
oligomeric silsesquioxanes (POSS) nanocomposites. Polymer
2005; 46: 7855–7866.
41. Fu J, Shi L, Chen Y, et al. Epoxy nanocomposites containing
mercaptopropyl polyhedral oligomeric silsesquioxane: mor-
phology, thermal properties, and toughening mechanism.
J Appl Polym Sci 2008; 109: 340–349.
42. Xie XL, Tjong SC and Li RKY. Study on in situ reinforcing
and toughening of a semiflexible thermotropic copolyestera-
mide in PBT/PA66 blends. J Appl Polym Sci 2000; 77:
1975–1978.
43. Pu KY, Zhang B, Ma Z, et al. Synthesis, morphology and
photophysics of novel hybrid organic-inorganic polyhedral
oligomeric tethered poly(fluorenyleneethynylene)s. Polymer
2006; 47: 1970–1978.
44. Liu YR, Huang YD and Liu L. Effects of TriSilanolIsobutyl-
POSS on thermal stability of methylsilicone resin. Polym Deg
Stab 2006; 91: 2731–2738.
45. Xie K, Zhang Y and Yu Y. Preparation and characteriza-
tion of cellulose hybrids grafted with the polyhedral oligo-
meric silsesquioxanes (POSS). Carb Polym 2009; 77:
858–862.