Articles

Indian Journal of Chemical Techno logy

Vol. 10, May 2003 , pp. 257-264

Modification of epoxy system for industrial applications: Preparation and

characterization
M Suguna Lakshmi & B S R Reddy
Industrial Chemi stry Laboratory , Central Leather Research Institute, Chennai 600 020, India
Received II Janua ry 2002; revised received 5 December 2002: accepted 6 January 2003

Modified DGEBA epoxy resin system was prepared using epoxy phenolic novolac (EPN), bisphenoi A cyanate
ester prepolymer and polyether sulphone (PES). DGEBA epoxy resin modified with cyanate ester prepolymer offers
process advantage in making prepregs for the preparation of structural composite materials. Further, the DGEBA
epoxy resin modified with EPN and PES along with cyanate ester prepolymer was fully polymerised by curing at
200C for 4 h. The cured resin was characterised by FT-IR, thermogravimetric analysis and differential scanning
calorimetric methods. The moisture resistance properties were studied for the cured resins. The morphology studies
were done for cyanate ester monomer, cyanate ester-epoxy polymer and PES-modified cyanate ester-epoxy polymers.
Carbon fibre laminates were made based on PES-modified cyanate ester and epoxy polymer. Mechanical properties
of the laminates were evaluated.

Epoxy resin is one of the most important increase the degree of crosslinking, it is intended to
thermosetting resins employed for high performance introduce epoxy phenolic novolac (EPN) component
industrial applications 1-6 . However, epoxy networks (scheme 2) into the epoxy system, which may result
are typically rather brittle and di splay low fracture in a more crosslinked network structure in the region.
toughness in contrast to high toughness, high modulus
characteristics required for high performance
applications. Moreover, the nature and amount of the
crosslinking agent used for making epoxy networks
also induces relatively high moisture absorption
characteristics. ln addition to this , lack of toughness
has limited the application characteristics of these n
systems. In order to improve these above-mentioned
drawbacks in properties, the DGEBA was chosen as Sche me 2-Structure of epoxy phenolic novolac (EPN)
model epoxy system for modification (scheme 1).
To reduce the water absorption of the cured resin 7-9 ,
bi sphenol A cyanate ester (scheme 3) was selected as
a curing agent to the epoxy resin.

Scheme !- Structure of diglycidyl ether of bisphenol A

(DG EBA )

Though DGEBA is known to produce highly

crosslinked thermosets upon curing, the degree of
actual crosslinking is limited. More tightly
crosslinked resins are required in high performance
composites for use at elevated temperatures. To
*For con-espondence (E- mail: incluLhc m:'OOO @yah ou.co m;
Fax: +91-44-491 1589).
Scheme 3-Structure of bi sphenol A cyanate ester
Several workers 10- 15 have investigated the
modification of epoxy resins with polyether sulphone
(PES) (scheme 4) . PES is introduced into the system
to act as a thermopl asticizer to lower the brittleness
and thereby improve the toughness of the system.
Articles
Scheme 4--Structure of polyether su iphone (PES)
The objective of the present work involved the
preparation of modified epoxy resin system by
incorporating multi-components and evaluation of its
spectroscopic, thermal and morphological studies.
Further, preparation of carbon fiber laminates from
modified epoxy resin system and evaluation of their
mechanical properties have also been reported.
Experimental Procedure
Materials
The epoxy resins DGEBA, EPN (L Y556 and EPN-
1138 of Ciba-Geigy Ltd., India), PES (Victrex 3600
p, ICI Ltd. USA) and cobalt naphthenate and nonyl
phenol (Aldrich) were used as received . Bisphenol A,
cyanogen bromide, nonyl phenol, triethylamine,
acetone and dichloromethane were procured from
S.D. Fine Chemicals, India. Bisphenol A was purified
by recrystallisation. Cyanogen bromide was used as
received . Triethylamine and acetone were dried over
anhydrous calcium chloride and distilled.
Synthesis of cyanate ester-monome/ 6
A batch scale of 100 g cyanate ester was
synthesized by reacting 74 .6 g (0.7 mole) cyanogen
bromide with 81 g (0.35 mole) of bisphenol A in the
presence of 90 g (0.89 moles) triethylamine as a
catalyst at ooc (scheme 5).
l-<0)--oo
C H1
t H + 2 CNB r
2( I.1N
Cz H.I
I
CH3
Q oC
Scheme 5- Synthesis of bisphenol A cyanate ester
Table !-Formulations (% WIW) , Tg and % moi sture absorption data of epoxy-cyanate ester
System DGEBA EPN TGDDM CYANATE
A ]()()
B 60 40
c 30 30 40
D 60 40
E 65
258
Indian J. Chern. Techno!. , May 2003
The reaction mixture was filtered under vacuum
and the filtered liquid was poured into cold distilled
water to isolate the product. The obtained product was
fu rther purified by recrystallization in methanol :water
(l: 1 VIV) at 5C to get white crystalline product. The
yield was 80% (78 g) and the melting point was 75-
780C. The sy nthesized cyanate ester mono mer was
1 13
characterised by Ff-IR, H/ C-NM R spectroscopic
methods.
Preparation of cyanate ester prepolymer
To I g of cyanate ester 18 mg of 2% cobalt
naphthenate solution in ethylmethyl ketone and 10 mg
no nyl phenol were added. This mixture was heated at
95C for 3 h and quenched to obtain a liquid cyanate
ester.
Curing and co-curing of cyanate ester resin
The curing and the co-curing of cyanate ester with
epoxy resin s were made by employing the
compositions as given in Table 1. The formulations
were heated to 90C and stirred fo r 0.5 h to obtain
homogenous liquid. In formulation C, the PES was
di ssolved in dichloromethane and added to the epoxy
and cyanate ester blend . All the formulations were
heated to 90C and kept under vacuum for 0.5 h and
further subjected to the high temperature by slowly
ratsmg the temperature to obtain void free
homogeneous samples. Thus, the samples were cured
at 180C for 2 h and cooled. The appearance of the
cured samples of formulations A, B and D were
transparent, hard and brown in colour, while the
formulations C and E were opaque. The formulations
A, B and C were characterised by Ff-IR, DSC and
TGA methods , while the formulations D and E was
analysed exclusively by DSC studies .
DDS PES Tg (OC) %Moisture
abso rption
250 1.1
225 1.6
25 210 1.6
260 2.7
35 262 4.5
Suguna Lakshmi & Reddy: Modification of epoxy system for industrial application Articles

Moisture absorption studies

The cured specimens were placed in water which
was maintained at 80C. The moisture absorption of
the specimens immersed in water was checked by
weighing them periodically for every 4 h. The
specimens were removed from water, neatly wiped
with a tissue paper, weighed immediately and placed
back into hot water. This procedure was repeated till
the samples attained the saturation of the moisture
absorption (no change in weight) .
4000 2000 1000 ~0
Wavenumber(cm- 1)
Fabrication of carbon fiber laminate (b)

For the formu lation C, an 8ply ( 12"x 6") carbon

cloth (T-300 plain weave, Toray Company) laminate
was fabricated. Each ply was impregnated with the
resin, allowed to stand for 25 days at RT and stacked
one on the other. Also a 1" width Teflon strip was
placed in the mid layer, along one side to act as a
crack initiator. The plies were placed in a laminating
press and heated under pressure. It was cured at
180C for 2 h and post-cured at 200C for 4 h. The
cured laminate was tested for flexural strength,
flexural modulus, tensile strength, tensile modulus
8 7 6 ~ 4 3 2 0
and Mode 1/Mode II fracture toughness properties. (c) PPM

Instruments
Nicolet Ff-IR spectrophotometer model 20 DXB
was used for studying the IR spectroscopy (400-4000
cm- 1) of monomers and cured samples . Analyses were
done using solid KBr pellets. 1H and 13C-NMR of the
compounds synthesized were run on a Bruker 320
MHz spectrometer at room temperature using CDCb
as a solvent and tetramethylsilane (TMS) as an
internal standard. Differential Scanning Calorimetric
(DSC) analysis was performed using a Du Pont 200 II l 1
instrument. The heating rate for DSC was I 0C per 160 120 80 40 0
min in the nitrogen atmosphere. Thermal stability of PPM
the formulations A, B and C (Table 1) were
Fig . I (a)- FT-IR spectra of cyanate ester monomer; (b) - 1H-
investigated on Mettler 3000 TG equipment. A S440 NMR spectra of cyanate ester monomer and (c)- 13C-NMR
model Scanning Electron Microscope was employed spectra of cyanate ester monomer.
to examine the morphol ogy of cured samples. The
surfaces of the samples were vacuum coated with Results and Discussion
gold . The universal testing machine model H T E-S- Characterization of cyanate ester monomer
Series, Hounsfield equipments Ltd , UK was used for FT-IR Spectr a
the following tests, employing ASTM specifications The cyanate ester monomer shows strong
(Tens ile test: ASTM-0 3479-76 and ASTM-D 790- absorption peak around 2236-2273 cm- 1 for the
84a). Mode I Fracture toughness (G 1c) was meas ured presence of - OCN and a doublet peak around 1351-
using Double Cantilever Beam (DCB) method . Mode 1383 cm- 1 for the presence of isopropyl group of
II Fracture toughness (G 1;c ) was measured using the bisphenol A cyanate ester. The peaks at 1169 and
End Notched Flexure (ENF) 17 method . 1198 em_, are due to C-0 stretchin g of phenol. The

259
Articles
broad peak around 1593-1631 em' implies the C=C
stretch in the benzene ring. The stretches at 811 and
831 cm- 1 show the 1,4-substitution in the aromatic
compound (Fig. 1a).
1
H and 13
C-NMR Spectra
1 a co-catalyst. This catalytic system was employed
In the H NMR spectrum, aromatic protons of the
benzene ring appear around 7.0-7.2 ppm. The protons
of the isopropyl group were observed at 1.5-1.6 ppm
13
(Fig lb). In the C-NMR spectrum, the OCN group
was observed at 151 ppm, which confirms the
formation of OCN group. The carbons present in the
phenyl rings were seen between 108-128 ppm while
the quaternary carbon present in the isopropyl group
was observed at 42.6 ppm. The methylene group
present in the isopropyl group was observed at 31.3
ppm (Fig lc). The 1H and 13 C-NMR spectra confirm
the absence of phenolic proton and the formation of
OCN group.
Characterization of cyanate ester prepolymer
Though epoxy-cyanate system is known for good
adhesion, high temperature resistance, and low
moisture absorption properties, the physical state
(solid) of the cyanate ester possess difficulty in the
preparation of its prepregs (the impregnated fibers
which are in the ready form for making composite
materials). Prepregs made by impregnating in the
solution of epoxy-cyanate mixture becomes dry once
the solvent get evaporated . On the other hand ,
prepregs made by impregnating in the melt liquid of
epoxy-cyanate mixture also becomes brittle after the
prepregs gets cooled. Since prepregs made by solution
and/or melt impregnation methods are dry, it is
difficult to stick them together. In the present studies,
cyanate ester prepolymer is in the liquid form for
making better prepregs. Both the epoxy-cyanate
systems prepared were found to be in the semi-solid
or liquid form which forecasts that the prepergs made
with them will have required tack properties.
Therefore, attempts were made to gel the cyanate
ester monomer so as to prepare the homogenous
epoxy-cyanate liquid system for application in
making tacky prepregs. The gelation was carried out
by the partial polymerisation of the cyanate ester
monomer. The polymerisation reaction proceeds via
polycyclotrimerisation by non-catalytic (thermally)
and catalytic methods . Non-catalysed thermal
pol ymerisation reaction is possible and the reaction is
supposed to be catalysed by impurities including
moisture and residual phenol from synthesis. Thermal
260
Indian J. Chern . Techno!. , May 2003
polymerisation requires high temperatures around
150C and above. Here the reaction proceeds faster
and results in highly crosslinked solid resin.
The cobalt naphthenate, manganous octoate and
copper acetyl acetonate catalysts were employed 18 19
for polycyclotrimerisation. Nonyl phenol was used as
because of its miscibility in neat resins , low
temperature curing and good latency at room
temperature. These catalysts perhaps help bringing
cyanate groups together into the ring forming
proximity while the hydroxyl group donates protons
20 2 1
for imido carbonate formation and step transfer .
To obtain low crosslinked cyanate ester, it was
necessary to optimize the quantity of the catalyst and
the temperature at which it was to be trimerised. After
conducting a number of trial experiments varying the
catalyst/co-catalyst concentration, the curing
conditions were optimized. The co-catalyst (nonyl
phenol) also acts as a solvent for the metal catalysts,
which is sparingly soluble in neat resins. When the
nonyl phenol concentration was increased, it
. .
pIastiCizes the cyanate ester22 . Hence, the liquid
cyanate obtained in the present investigation may be
due to the plasticizing effect of nonyl phenol present
in the mixtures . The cyanate ester prepolymer
prepared under present experimental conditions was
found to be in the liquid form at room temperature
which is advantageous for making tacky prepregs .
The pot life of the liquid resin was also observed and
was found to be 25 days.
Characterization of cyanate ester prepolymer-epoxy
prepregs
The prepreg plies made wi th cyanate ester
prepolymer were placed one above the other and
stacked well. On the physical observation, the plies
were in stack with each other for a minimum period
of 25 clays. Also, the liquid cyanate ester prepolymer
can be easily formulated with other liquid epoxy
resins to impregnate the fiber for making various
composite materials. The prepregs made out of liquid
cyanate prepolymer-epoxy system need not have to be
heated to melt the cyanate so as to stick the prepregs
together for making composites .
FT-IR Spectra
The cyanate ester prepolymer (Fig. 2a) shows
ab orption peak at 1598 cm- 1 which represents the
tri azine ring formation. The strong absorption at
2236-2273 cm- 1 shows the presence of - OCN. The
Suguna Lakshmi & Reddy : Modification of epoxy system for industrial application Articles

Table 3-Thermal data of epoxy-cyanate ester formul ati ons

(a) (A, 8 , and C)

Formu- lOT Decom- Temp. ( 0C) vs weight loss %

lation (0 C) position of polymer
range 40 60 80 90
(OC)
,....,
fl. A 410 410-670 425 514 564 593
........
(1)
u
c 8 421 421-592 410 428 518 550
.
.....0
~

E
Ill
c (b) c 376 376-592 400 526 583 609

..-e
Characterisation of epoxy-cyanate ester polymer
FT-IR Spectra

Homo- and blends of different compositions were

prepared (Table I) and characterised by Ff- IR (Fig.
2b). The characteristic infrared spectral absorptions
are listed in Table 2. The spectra confirm the presence
of the original constituents like methylene in the
novolac resin , sulphone in the PES resin and epoxy
4000 2000 1000 500
ether in the epoxy resins. The triazine and
Wavenumbers (cm-1) isocyanurate rings formed during the curing reaction
have also been confirmed.
Fig. 2 (a)-Ff-IR spectra of cyanate ester prepolymer and (b)-
Ff-IR spectra of cyanate ester ho mopolymer, T her mogravimetric analysis

Thermal properties of cyanate ester homopolymer

Table 2-Ff-IR spectral .ssignmen : . l ~ puxy-cyanate ester (A), epoxy-cyanate polymer blend (B) and the PES
polymers
modified epoxy-cyanate polymer blends (C) (Table 3)
were investigated by recording the thermograms of
Chemical class Absorbing Reference Wave number
these systems in air (Fig. 3). The cyanate ester homo
group compound (cm- 1)
polymer undergoes two-step degradation. The
Epcxy resin Epoxy ether DGEBA 1245, 1242 maximum decomposition of crosslinked cyanurate
EPN rings shows at 410C. The co-cured cyanate epoxy
polymer undergoes multiple degradations since the
Arylcyanurate Tri az ine Trimer 1599, 1598
initial decomposition temperature (IDT) of the
Novolac resin -C H2- EPN 2971 , 281 3 systems B and C coincide with the IDT of the cyanate
polymer. The cyanurate crosslinked structure that
Sui phone so2 PES 1150 . )J
decomposed around 400C was conftrmect- . It was
Oxazo1ine
noted that IDT of the system C was less than the IDT
- NCO Cyanate 2280
ol mer of the systems B and A. This may be due to the
flexible functional groups present in PES , which did
influence the cyanate-epoxy system to lower the
peaks for the presence of OCN as well as the triazine thermal stability . It can be concluded that the system
ring lead to assumption that the cyanate ester is (A) and (B) possess similar thermal stability . The
partially polymeri sed to yield a cyanate ester system (C) though shows slightly lower IDT, its
prepolymer. decomposition range was similar to the system B.

261
Articles Indian J. C hern. Tec h110I. , May 2003

- -- -0
---- b
-------- ----'C

M~- - 411 .
-- ... 1-4 ...... ......... . .
c
a (\
CTI

I"
I \

'
I

I
~
r1
\

.\
\. J
'
I \ !
\ \I
I
I
II I
0

I ~
I ,I
f1rv,.
~ l

100 200

Fig . 3 (a) - T hermog ram of cyanate ester homopolymer;

(b)- Thermogram of epoxy-cyanate ester polyme r blend and
(c)-Therm ogra m of PES modifi ed epo xy-cya nate es ter po lymer
blend .

Differential scanning calorimetric and moisture absorpti on

studies
The Tg and the % of moi sture absorpti o n properties
of e poxy-cyanate syste ms were co mpared w ith the
properties of conventional epoxy-am in e cured sys te m.
Cya nate ester ho mopolymer (A) gave hi gh Tg (250C)
and the lowest mo isture absorption ( 1.1 %). The Fig. 4--Scanning e lectro n microg raphs: I-S EM of cyanate ester
homopolymer; 11-SEM of epoxy-cyanate ester polymer blend ;
epoxy-cya nate systems (8 , C and D) were compared and III - SEM of PES modified epoxy-cyanate ester polymer
with epox y-amine (TGDDM-DDS ) sys te m (E). The blend.
Tgs observed were in the same ra nge for th e epoxy
res in c ured w ith cyanate and amine. But, the moisture th e DGEBA epoxy -cyanate system, Tg val ue was
abso rpt ion is much less in epoxy -cyanate systems fo und to be sli ghtly hi gher with respect to the Tg of
when co mpared with e poxy-amine system (). DGEB A epoxy -cyanate system. Tho ugh the PES
Further, it was observed th at the presence of EPN m mod ified epoxy-cyanate system shows less Tg. the

262
Suguna Lakshmi & Reddy : Modification of epoxy system for industrial application
moi sture resis tance property has not been
compromised. Thus, the PES modified epoxy-cyanate
system shows good Tg (210C) and low moisture
absorption (1 .6%). The low moisture absorption in the
case of cyanate-cured epoxies may be due to the
formation of strong networks and the absence of
hydrophilic amino groups to some extent.
Scanning electron microscopy (SEM)
There are reports on toughening of the highly
crosslinked thermosetting polymers with hi gh
modulus and high Tg thermoplastics as studied by
SEM 24 - 26 . In a thermoset/thermoplastic blend the
components are usually mixed together and the
crosslinking of the epoxy occurs in situ. The increase
of the molecular weight of the epoxy during curing
may result in phase separation even if the temperature
27
is kept constant . One of the most studi ed
thermoplastics for the modification of epoxy resin is
the polyether sulphone (PES). PES is added to
increase viscosity during hot lay up of the prepregs
28
for the manufacture of composites .
Morphology
SEM photographs of the cold snap surfaces for the
cured systems are given in photomicrographs I to Ill
(Fig. 4). The cyanate ester homopolymer (I)
morphology appears to be transparent and
homogeneous under the magnification at 800 x. The
blend of DGEBA and EPN with cyanate ester
monomer (II) appears nearly transparent.
Nevertheless, so me amount of phase separation was
observed which may be the immiscible region s
formed during the reaction of epoxies with cyanate
ester monomer. The phase separation of PES in
epoxy-cyanate ester (III) was observed at 800 x
magnification . During the curing reaction, the epoxy
rings opens up and produce polar hydroxyl groups.
The related enthalpy of mixing seems to cause the
PES to separate from the solution. On the other hand,
with more than 20% of polysulphone content, the
cyanate ester/polysulphone blends were phase
separated by spinodal decomposition 27 . The phase
separation during the curing process seems to be an
important parameter because it provides a two-phase
Table 4-Mechanical properti es of the modified epoxy composite
Properties Resin content Flexural Flexural
(Volume%) strength (Mpa) modulus (Gpa)
Values 55 750 55
Articles
system to allow the formation of micro-voids for the
shrinkage compensation. Phase separation may be
caused by a change in the miscibility of the monomer,
prepolymer and catalyst during curing. Therefore, the
thermoplastic/thermosetting system undergoes several
steps before it reaches a maximum reaction rate point.
Initially before the reaction, at room temperature, the
two systems remain separately. Phase one remair s as
a continuous phase and the phase two may perhaps be
dispersed in the continuous phase. During heating, the
systems become miscible and transparent. Further, the
reaction takes place in the miscible systems to form
highly crosslinked having hi gh molecular weight
micro-gels. This decreases the miscibility of the
overall reacting system and at this point phase
separation occurs. The separated micro-gel gets
crosslinks themselves to produce a macrostructure
and di splays as co-continuous phases in the two phase
network structure.
Evaluation of carbon fiber laminate properties
The mechanical properties of the laminates are
given in Table 4. It can be seen that the flexural and
tensile properties are good while the fracture
toughness properties are high in the order of 0.32
(KJ/M 2)29 , compared to standard epoxy system (0.080
KJ/M2)3o_
Conclusion
DGEBA epoxy resm was modified with EPN ,
cyanate ester and PES to obtain an epoxy resi n
system, which offers improved properties. The EPN
was included to enhance the degree of cross-linking
while the cyanate ester was introduced to improve the
moisture resistance and to establish the less densed
crosslinked structure upon curing. Further, the
cyanate ester monomer was prepolymerised by
varying the catalyst and co-catalyst concentration.
The liquid cyanate ester prepolymer had a pot life of
25 days. The cyanate ester prepolymer-epoxy blend
offers process advantage for making epoxy prepregs .
The DGEBA epoxy resin modified system shows high
glass transition temperature and low moi sture
absorption. The morphology study of PES modified
epoxy resin system by SEM shows phase separation.
Tensile strength Tensile Fracture toughness (KJ/M 2)
(Mpa) modulus (Gpa) G1c Gnc
560 61 0.32 1.16
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Articles Indian J. Chem. Tec hn o l. , May 2003

The related enthalpy of mixing of epoxy with PES, 12 Hedri ck 1 C , Yilgor I, Wilkes G C & McGra th J E, Polym
Bull, 13 ( 1985) 20 I.
which seems to cause the PES to separate. The
13 Cecere 1 A & McGrath 1 E, Polym Prep, 27 (1986) 299.
flexural, tensile and toughness properties of the
14 Raghava R S 1, Polym Sci, Polym Phys Edn, 25 (1987) 101 7.
composite, are seems to be very good. 15 Rag hava R S 1, Polym Sci, Polym Phys Edn, 26 ( 1988) 65.
16 Grigat E & Putter R, Angew Chem lnt Edn, ( 1993) 6.
Acknowledgement 17 Alan 1 Russel & Ken N Street, Key Eng Mat, 37 ( 1989) 199.
One of the authors (MS) is grateful to Mr M K 18 Simon S L & Gillham 1 K, Am Chem Soc Eng, 54 (1986)
Sridhar, Ms P Kanakalatha, and Ms Chandra Ajay, 107 .
National Aerospace Laboratories, Bangalore for their 19 Liu H & George G A, Polymer, 37 (1996) 3675.
20 Osei-Owusu A Martin G C & Gotro 1 T, Polym Eng Sci, 32
help in the present work.
(1992) 535.
21 Harismendy I, Gomez C, Ormaetxea M, Martin M D, Ecei za
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