Epoxy- allyl phenol- bismaleimide matrix system - Property

dependency on epoxy structure

K. Ambika Devi, Bibin John, C. P Reghunadhan Nair and K.N Ninan

Propellants, Polymers, Chemicals and Materials entity
Vikram Sarabhai space Centre
Trivandrum-695022

Abstract
A ternary matrix system constituted by the reactive blending of epoxy- diallyl bisphenol
and bismalemide (EPB) was found to be superior to the epoxy-phenol (EP) system in
respect of its thermal and mechanical properties. The performance of the ternary blend
system depends on the structure of its constituents, particularly the epoxy and
bismaleimide. The influence of the structural variations of the epoxy resin on the thermal,
physical and mechanical properties of the ternary blend was examined. EPB
compositions were prepared using bismaleimide, diallyl bisphenol -A and three different
epoxy resin systems viz. Novolac epoxy (E 1), bisphenol A diglycidyl ether (E 2) and tris (4-
glycidyl oxyphenyl methane) (E3), having different physical, chemical and functionality
characteristics. The cure characterization of these reactive blends were carried out using
techniques such as differential scanning calorimetry and rheological analysis. The
thermograms showed that the temperature of onset of decomposition for the EPB
systems with the above epoxies (identified as E1, E2 and E3) are in the order E3 > E2 >
E1. The mechanical properties - compressive, flexural and interlaminar shear strength -
of the glass composite were found to depend on the epoxy structure. The trend in these
properties was E1 > E3 > E2. The higher crosslink density of the tri functional epoxy
improved the thermal properties of the system. Highest strength values were obtained
for the EPB system containing novolac epoxy.

1 Introduction
The epoxy resin can be formulated in an infinite number of ways to manipulate
characteristics such as system stability, cure kinetics, physical form, Tg, mechanical
performance and chemical resistance. The versatility in form, modification, properties,
hardening methods, cure conditions and application is probably the most outstanding
characteristic of epoxy resin. Its utility can be further widened by the modification of the
same by suitable means to tailor its property to suit the different system requirements.

Elevated temperature base resins are those that cure to yield somewhat inflexible
molecular structures. Rigidity can be built in to the cured matrix in several ways: through
the incorporation of aromatic groups, an increase in the number of reaction sites (epoxy
groups) per molecule or a reduction in the distance between the reaction sites. The three
primary classes of epoxy resins used in composite application are phenolic glycidyl
ethers, aromatic glycidyl amines and cycloaliphatics [1]. In order to improve the thermal
and mechanical properties of epoxy resin, modifying the molecular backbone and /or
increasing the number of epoxide group functionality are employed by many researchers
[2,3].
The introduction of epoxy in to bismaleimide increases the fracture toughness and
fracture energy of epoxy system with modest reduction in both modulus and glass
transition temperature. A modest improvement in lap shear properties is possible, but the
most important benefits will accrue at higher temperatures. The cure reactions of
reactive blends of bismaleimides and epoxies has been studied and reported [4].

1
We have reported a ternary polymer blend of epoxy- allyl phenol and bismaleimide with
improved high temperature performance and comparable mechanical properties in
comparison with epoxy-phenol system [5]. The structural changes and the resulting
property variations of the epoxy and the BMI systems can influence the performance of
the ternary EPB blend. In the present study, the effect of structural variations of epoxy
resin on the performance of EPB co- curing system is presented.

2.Experimental
2.1 Materials
The materials used in the study are Diallyl bisphenol A (DABA)- synthesized from
bisphenol A, Epoxy resin-1- EPN 1139- supplied by M/S Ciba Geigy, Mumbai, Epoxy
resin-2-Ly-556 -supplied by M/S Ciba Geigy, Mumbai, Epoxy resin-3-Tri epoxy- supplied
by M/s Aldrich, USA, Triphenyl phosphine (TPP)-Supplied by E-Merck, 2, 2 –bis 4-(4
maleimidophenoxy) phenyl] propane-BMIP-synthesized in VSSC by a reported
procedure [6], E-Glass cloth- Plain weave, silane treated fabric of thickness 0.25mm
from Unnathi Corporation, India.
2.2 Preparation and characterization of Ternary blend
The preparation and characterization of EPB reactive blend of novolac epoxy diallyl
bisphenol and bismaleimide was reported by us [7]. The same was repeated for the EPB
systems with epoxies E2 and E3.The ternary EPB blends were characterized using
Nicolet 510 P FTIR spectrophotometer, Mettler TA 3000 Thermal analysis system in
conjunction with TC -10A TA processor and standard DSC-2920 analyser, SDT-2960
simultaneous TGA-DTA and Reologica Stress Tech Rheometer.The curing of the
polymer blend was achieved by following the time temperature cure schedule optimized
for the EPB system [7].

2.3 Preparation of Laminates and characterization of composites

Laminates were prepared using the three EPB systems and plane weave glass cloth.
The mechanical properties of the composites were evaluated by determining their
flexural strength, compressive strength and interlaminar shear strength (ILSS) following
the ASTM standard test procedures. The resin content was determined by matrix
digestion method using a muffle furnace.

3 Results and discussion

3.1 Cure characterization of the ternary polymer blend

The IR spectrum of the EPB systems with different epoxies E 1, E2 and E3 recorded
before and after cure reaction confirmed the cure completion. The DSC cure
thermograms of the EPB systems with different epoxies is given in Fig.1. The epoxy –
phenol reaction (100 -150 oC) was found to be not prominent in the case of Tri epoxy.
The phenol-epoxy, Ene reaction and Diel-Alder reaction all occur more or less in the
same temperature regions. The curing of the unsaturated groups of the adduct occur
beyond 250 oC.

2
The rheological cure characterization of the different blends enabled the determination of
gel point and gave a better insight in to the temperature dependence of their cure profile
with change in epoxy structural variations. The dynamic rheograms obtained for the EPB
system with different epoxies showed that the temperatures corresponding to the
gelation and crosslinking are differing slightly with change in epoxy type. The storage
shear modulus vs temperature curves obtained for the three EPB systems are given in
Fig.2.
1000000

100

Storage shear modulus (KPa)

EPB-E1
EPB-E2
EPB-E3

0.01

1E-6
50 100 150 200 250 300

Temperature(oC)
Fig.1 DSC thermograms showing the cure Fig.2 Temperature dependence of Storage and loss
reaction of EPB systems with different epoxies shear modulus of EPB system with different epoxies

The TGA thermograms recorded for the cured DABA-EPN–BMI blends with different
types of epoxies showed that the temperature of initiation (Ti), peak (Tm) and completion
(Ts) of decomposition for the EPB systems with epoxies E1, E2 & E3 are in the order E3 >
E1 >E2 showing that their thermal stabilities are in the same order.

Table 1 Thermal decomposition characteristics of EPB systems with epoxy

variation

Temperature Sample reference

EPB- E1 EPB-E2 EPB- E3

o
Ti ( C) 240 225 275
o
Tm ( C) 430 426 431

Ts (oC) 680 657 671

3. 2 Characterization of the composite

The glass laminates prepared using the three component EPB resin systems containing
different epoxies were characterized for their mechanical and physical properties and the
results are summarized in Table 2.The mechanical properties (compressive, flexural and
interlaminar shear strength) of the composite samples were found to be different for the
systems with different epoxies. The trend in these properties were E1 > E3 > E2. The

3
reduction in strength of the tri epoxy may be due to its very low flexibility caused by the
higher crosslink density while the least strength values reported for the LY-556 may be
due to its increased flexibility resulting from its molecular structure, which caused
comparatively reduced cosslinkages in the system.

Table 2 Mechanical and physical properties of EPB systems with different epoxies

Sample reference
Property EPB-E1 EPB-E2 EPB-E3
ILSS (kg/cm2) 450 380 410
Compressive strength (kg/cm2) 2780 2130 2380
2
Flexural strength (kg/cm ) 5600 5000 4800
Resin content (%) 20.4 21.4 21.6

The resin content in these composites determined by matrix digestion showed a

variation from 20.4 - 21.6 for EPB systems with different epoxies.

4. Conclusion

The structural variation of epoxy was found to influence the properties of the Epoxy-
phenol-bismaleimide composites. The tri epoxy having more crosslinking sites was
found to have improved thermal properties. Their ILSS was found to be higher compared
to the LY-556 based system, while its flexural properties were minimum among the three
systems studied. The resin content was found to be with in a narrow range. All the
strength properties showed maximum value for the EPB system containing novolac
epoxy.

5. Acknowledgements

The authors thank Director VSSC for granting permission to present this paper. The
analytical support given by our colleagues in Analytical and Spectroscopic Division
(ASD) is also acknowledged.

6. Reference
1 ASM Hand Book Vol.-21, 79
2 T. Y.Murata, Y. Nakanishi, US patent 1997, 5623031.
3 C.S Wang, M.C Lee, J. Appl. Poly.Sci.70, 1998, 1907
4 C. Gouri, C.P Reghunadhan Nair and R. Ramaswamy, Polym Int. 50, 2001, 403-411

5 K.Ambika Devi, C.P Reghunadhan Nair, G.Viswanadhan Asari, K.N Ninan “Effect of
bimaleimide on the thermal characteristics of Epoxy- Phenolic- Bismaleimide matrix
system” International conference Thermans -2006 Feb.2006

6 C. P. Reghunadhan Nair, Tania Francis, J Appl. Polym. Sci.74, 1999, 3366

4
7. K. Ambika Devi, Bibin John, C.P. Reghunadhan Nair, K.N Ninan, “Bismaleimide- co-
cured di allyl bisphenol A – epoxy novolac system- Cure and thermal properties”
(communicated to J. Appl. Poly. Sci.)