EPOXY RESINS
L.S. Penn and €3. Wang
3.1 INTRODUCTION
Epoxy resin systems have achieved acceptance
as adhesives, potting compounds, molding
compounds and as matrices for continuous fil-
ament composites used in structural
applications. In this chapter, we discuss epoxy
resins in their role as matrices in fiber compos-
ites. In this role, they possess several
advantages over other types of polymers. The
main advantages are:
0 inherently polar nature that confers excel-
lent adhesion to a wide variety of fibers;
0 relatively low cure shrinkage that makes
dimensional accuracy of fabricated struc-
tures easier to obtain;
0 no volatile by-products of the curing reac-
tion to cause undesired bubble or void
formation;
0 crossIinked structure that confers excellent
resistance to hostile environments, both
aqueous and nonaqueous.
In addition to these advantages, epoxy resins
have tremendous versatility because they can
be formulated to meet a broad range of specific
processing and performance requirements. To
know how to take advantage of the formula-
tion options, the engineer needs to have an
elementary understanding of epoxy resin
chemistry and structure-property relation-
ships. This chapter attempts to provide that by
presenting information about the resin system
constituents, how they react together to form a
Handbook of Composites.Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
3
crossllnked network and how they lead to dif-
ferent processing parameters and final
properties in the formulated system. The
chapter also describes the role of cure moni-
toring and property evaluation in epoxy resin
system technology.
3.2 GENERAL DESCRIPTION OF
THERMOSETTING SYSTEMS
3.2.1 DEFINITIONS
According to common chemical practice, mol-
ecules can be classified by the functional
groups they contain. Thus, a molecule contain-
ing the epoxide group (shown below) as part
of its structure is called an epoxide, regardless
of the remaining details of the molecule.
/O\
-c-c-
I I
In practice, other types of molecules are added
to the epoxide to formulate a thermosetting
system, i.e. one that will undergo a curing
reaction to harden into a rigid form. The con-
fusing practice has been followed of referring
to both the epoxide alone and the formulated
system as 'epoxy resin'. One must determine
which is truly intended by the context in
which it is used. For the purposes of clarity in
this chapter, we will use epoxide when refer-
ring to the epoxide constituent alone and will

use the term epoxy resin when referring to the
uncured or cured formulated system.
3.2.2 THE THERMOSETTING (CURING)
REACTION
The thermosetting reaction is the joining of
many small molecules by chemical reaction to
produce an extended network structure.
Although this process is a polymerization, it is
distinct from the type of polymerization that
forms many individual long chains; the ther-
mosetting reaction unifies all the constituent
monomers into a single large molecule extend-
ing to the boundaries of the material.
Epoxide molecules in the pure state at room
temperature normally do not react with each
other and can sit for years in a dry container
without mutual reaction. The types of chemi-
cals added to the epoxide to effect network
formation fall into two categories: curing
agents and catalysts. Curing agents, some-
times called hardeners, are added in
significant amounts to the epoxide and react
with it to become a part of the crosslinked net-
work. These curing agents can be aliphatic
amines, aromatic amines, or anhydrides.
Catalysts, on the other hand, are added in
extremely small amounts to cause the epoxide
molecules to react directly with each other, i.e.
to homopolymerize. Sometimes the chemicals
used as catalysts for homopolymerization can
be used for another purpose; when added in
small amounts to epoxide-curing agent mix-
tures, they will accelerate the curing reaction.
In this role they are called accelerators rather
than catalysts.
In the sections below, we discuss the chem-
ical reactions involved in network formation,
both when the different curing agents are used
and when homopolymerization occurs.
Amine curing
In amine curing agents, each hydrogen on an
amine nitrogen is reactive and can open one
epoxide ring to form a covalent bond 1-5.
General descripfion of thermoseffingsystems 49
When the amine nitrogen contains two hydro-
gens, each reacts with a different epoxide ring.
This scheme is shown in Fig. 3.1, where the
developing network is evident. This scheme
applies to both aliphatic and aromatic amine
curing agents. The reaction between epoxide
and amine produces a C-N bond, whose envi-
ronmental resistance is good, but whose
stability to elevated temperature is highly
dependent on the adjacent molecular structure.
- OH
I
CH-CH,
\ /
cH2-m-
OH
I
- I
OH
CH-CH2
/N-R-y OH
I
CH,-CH-
Fig. 3.1 Reaction scheme for the reaction between
epoxide and amine curing agent. Each hydrogen
reacts with an individual expoxide group. Thus the
primary amine group acts bifunctionally and the
secondary amine group acts monofunctionally. The
epoxide group acts monofunctionally.
From the reaction scheme, it is obvious that
the correct relative amounts of epoxide and
amine curing agent must be used. If there is ,an
imbalance, unreacted functional groups will
be present and the full properties of a com-
plete network will not be developed. The
correct amounts by weight to combine are
determined by computing the weight of cur-
ing agent that contains one chemical
equivalent of amine hydrogens and matching
that with the weight of epoxide that contains
one chemical equivalent of epoxide groups.
50 Epoxy resins

Anhydride curing functions as a catalyst to speed up the epox-

ide-curing agent reaction. (Acceleratorswill be
In anhydride curing agents, the anhydride
discussed later.) Figure 3.2 shows an idealized
groups themselves must be cleaved asymmet-
scheme, where the cleaved anhydride reacts
rically to start the r e a ~ t i o n ' ~Initial
, ~ . cleavage
with an epoxide ring carbon, opening the ring
is accomplished with the help of a small
in the process. The negatively charged oxygen
amount of accelerator,which is a chemical that
formed by the opening of the epoxide ring can
proceed to react with a different anhydride
group, perpetuating the reaction. In this ideal-
0 ized developing network, each anhydride
0-
II I group is bifunctional, i.e. it links to two differ-
NR3 (Accelerator) ent epoxide molecules. In practice, the high
temperatures required for anhydride cure, plus
C' the presence of accelerator, provides conditions
/I
0
+ for some extent of epoxide homopoly-
merization (described later) to take place,
0-
making the actual curing reaction much more
0-
I I complex than depicted in Fig. 3.2. The reaction
{c=o fC=O
between epoxide and anhydride produces pri-
marily ester linkages, which have good
L=o L += o stability to elevated temperatures and to most
+ /O\ hostile environments except bases.
Not surprisingly, the correct amount of
I anhydride curing agent relative to the epoxide
must be used to obtain a well developed net-
CC'O Cc=O
work and the associated good properties. The
L += o 'C= 0
+ correct amounts by weight to combine are esti-
mated by examining the reaction scheme and
0- 0- computing the weight of curing agent needed
I I to react completely with a given weight of
c= 0 epoxide. The simplified reaction scheme of
Fig. 3.2 proposes that one anhydride group
I
LI o reacts with two epoxide groups and one epox-
0 0 ide group reacts with two anhydride groups,
I I
o-cH~-c------c-cH*-o making the number of anhydride groups con-
I I
c= 0 c= 0 sumed equal to the number of epoxide groups
consumed in the reaction.
(c=o
+ L + O
Catalytic curing (homopolymerization)
The remaining route to formation of a
crosslinked network from epoxide molecules
Fig. 3.2 Simplified reaction scheme for the reaction
requires homopolymerization'4~7.This can be
between epoxide and anhydride curing agent. After
cleavage, each anhydride group reacts with two brought about if small amounts of certain
epoxide groups and each epoxide group reacts with Lewis acids or Lewis bases are added. These
two anhydride groups. Thus both the epoxide operate as true catalysts by initiating a self-
group and the anhydride group act bifunctionally. perpetuating cationic (Lewis acid) or anionic
 Constituents used in formulated systems 51

/O\ +
R3N -I-CH2-m- +R,NCH2-CH-a2-
I
0-

/O\
CH2-CH- +
+ R3NCH2- CH- CH2-
I
P
cH2-CH-
I
0-
Fig. 3.3 Reaction scheme for the homopolymerization of epoxide. After ring opening, each epoxide group
reacts with two other epoxide groups. Thus the epoxide group acts bifunctionally.

(Lewis base) polymerization. A simplified 3.3 CONSTITUENTS USED IN FORMULATED

reaction scheme initiated by a Lewis base is
shown in Fig. 3.3. Homopolymerization
results in the formation of a network of ether
linkages, which has outstanding elevated-tem-
perature stability and resistance to hostile
environments.
SYSTEMS
3.3.1 EPOXIDES
Although many different types of epoxides are
available, only a few are favored for use in
matrices in fiber compositess-lO.These are
shown in Table 3.1.

Table 3.1 Structures and characteristics of commonly used epoxides

Epoxy equivalent Viscosity at 25"C, Comments
weighf, g/eq Pa s (cP)

Diglycidyl ether of bisphenol A (DGEBA)

171-177 3.5-5.5 May crystallize on storage.

(3500-5500) Example: DER 332 (Dow).
180-188 6.5-9.6 Contains small amount of higher polymer
(6500-9500) to prevent crystallization.Examples: DER 330
(Dow) Epon 826 (Shell).
185-200 10.0-19.0 Contains small amount of higher polymer to
(10 000-19 000) prevent crystallizalion.
Example: Epi-Rez 510 (Hi-Tek Polymers),
DER 331 (Dow), and GY 6010 (Ciba).
450-550 Melting point n = 2; used in prepregs. Examples: Epon 1001
65-76°C (149-167°F) (Shell)and DER 661 (Dow).
52 Epoxy resins

Table 3.1 Continued

Epoxy equivalent Viscosity at 25"C, Comments

weight, g/eq Pa s (cP)

Diglycidyl ether of bisphenol F (DGEBF)

/O\ /O\
CH2- CH- CH2- 0 0 - CH2 -CH- CH2

158-165 5.0-8.0 Isomeric mixture that will not crystallize on

(5000-8000) storage. Example: GY 281 (Ciba).

Polyglycidyl ether of phenol-formaldehyde Novolac

172-179 1.l-1.7 (1100-1700) Example: DEN 431 (Dow).

at 52°C (126°F)
176-181 20.0-50.0 (20 000-50 000) Example: DEN 438 (Dow).
at 52°C (126°F)
191-210 4.0-10.0 (4000-10 000) Example: DEN 439 (Dow).
at 52°C (126°F)

Polyglycidyl ether of o-cresol-formaldehyde Novolac

200 Melting point Used for high-temperature service: R represents

35°C (95°F) chlorohydrins, glycols, and/or polymeric ethers.
Molecular weight = 540. Example: ECN 1235
(Ciba).
225 Melting point Same as above, but molecular weight = 1080.
73°C (163°F) Example: ECN 1273 (Ciba).
230 Melting point Same as above, but molecular weight = 1170.
80°C (176°F) Example: ECN 1280 (Ciba).
235 Melting point Same as above, but molecular weight = 1270.
99°C (210°F) Example: ECN 1299 (Ciba).
 Constituents used in formulated systems 53

Table 3.1 Continued

Epoxy equivalent Viscosity at 25"C, Comments

weight, g/eq Pa s (cP)

N, N, N', N', - Tetraglycidyl methylenedianiline

117-133 10.0-15.0 (10 000-15 000) Used for prepregs. Example: MY 720 (Ciba).

Triglycidyl p-aminophenol
/O\
O-CH2-CH- CH2
I

I
/O\ / N\ /O\
CH2-CH-CH2 CH2-CH- CH2
95-107 0.55-0.85 (550-850) Used extensively for prepregs and adhesives.
Example: MY 0510 (Ciba).

Conspicuously, these epoxides all contain aro- achieve cure with amine curing agents fall in a
matic rings in their structures. Aromatic rings wide range, from 25°C to nearly 200"C,
confer mechanical rigidity and thermal stabil- depending on the chemical structure of the
ity to the crosslinked network. It is also worth amine. The first five entries in the table are
noting that some of the epoxides in the table aliphatic amines, which can cure epoxides at
have two epoxide functional groups, while room temperature or only slightly above.
others have three or four or more. Whether a Aliphatic amine-cured systems also tend to
network is developed by mixing the epoxide have low glass transition temperatures, T , (the
with a curing agent or is developed from epox- temperature at which the mechanical behavior
ide alone by catalytic homopolymerization, a changes from rigid to rubbery) and cannot be
large number of the molecules in a given for- used in composites that will experience high
mulation must be able to react with more than temperature use.
two other molecules in order to form a Most other entries in the table are aromatic
crosslinked network instead of merely form- amines, whose ring structures confer solidity
ing linear chains. and mechanical rigidity. These amine curing
agents require elevated temperature cure, but
the networks they produce have high glass
3.3.2 AMINE CURING AGENTS
transition temperatures and are suitable for
Table 3.2 presents commonly used amine cur- use in composites that will be exposed to ele-
ing agents. The temperatures required to vated temperatures in service.
54 Epoxy resins

Table 3.2 Structures and characteristics of commonly used amine curing agents

Amine hydrogen Viscosity at 25°C (77"F), Comments

equiv. weight, gleq Pa s (cP)

Diethylenetriamine (DETA)

HzN-CH2-CH2-NH- CH2-CH2 -NH2

20.6 0.00554.0085 Available from Dow as DEH 20.

5.5-8.5)

Triethylenetriamine(TETA)

H2Nf (CH2)z-NH CH2-CH2 -NH;!

24.4 0.020-0.023 Available from Dow as DEH 24.

(20-23)

Diethylaminepropylamine (DEAPA)

CH3- CH2,
- (CHZ)3- NH2
CH3- CH2
65 50 Available from Union Carbide.
(5000)

Tetraethylenepentamine(TEPA)

26-27 0.055 Available from Dow as DEH 26.

(55)

Aliphatic polyether triamine (APTA)

H2C f-0 - CH2- CH-(CH3) NH2

I
CH3 - CH2 - C - CH2 f-0 -CH2- CH-(CH,) NH2
Y
I
H2C f-0 - CH2- CH-(CH3) %NH2
77-82 0.072-0.080 x + y + z = 5.3. Available from Texaco as
(72-80) Jeffamine T 403.
 Constituents used in formulated systems 55

Table 3.2 Continued

Amine hydrogen Viscosity at 25°C (77"F), Comments

equiv. weight, g/eq Pa s (cP)

4,4'-Methylenedianiline (MDA)

50 Melting point Available from Ciba as HT 972 and from

89°C (192") Pacific Anchor as Ancamine DDM.

rn-Phenylenediamine (MPDA)
NH2
I

27 Melting point Available from E.I. duPont de Nemours &

60°C (140°F) Company.

44' -Diaminodiphenylsulfone (DDS)

0

62 Melting point 170-180°C Used mainly in prepregs; yields good shelf life and
(338-356°F) high-temperature properties. Available from
Ciba as HT 976.

3,3' -Diaminodiphenylsulf one

0

P- .S
It
I1
0

62 Melting point 174178°C Used mainly in prepregs; reacts more slowly than
(345-352°F) 4,4' analog. Available from Ciba as HT 9720.
56 Epoxy resins

Table 3.2 Continued

Amine hydrogen Viscosity at 25°C (77"F), Comments

equiv. weight, gleq Pa s (cP)

40% MPDA-60%MDA

38 1.50 Eutectic mixture. Available from UniRoyal

(1500) as Tonox 60-40

Dicyandiamide (DICY)

28 Melting point 207-209°C Slow reacting. Used for prepregs. Available from
(405408°F) Cytec Ind.

3.3.3 ANHYDRIDE CURING AGENTS Elevated temperature, typically in the range

Table 3.3 presents commonly used anhydride 100-200°C, is required to achieve cure with
curing agents. Their structures vary widely anhydride curing agents. The glass transition
and some are liquid at room temperature temperatures of anhydride-cured systems are
whereas others must be heated to liquefy. high.

Table 3.3 Structures and characteristics of commonly used anhydride curing agents

Anhydride equiv. Melting point, "C ("F) Comments

zueigkt, g/eq

Phthalic anhydride (PA)

148 130 (266) Available from Amoco.

 Constituents used in formulated systems 57

Table 3.3 Continued

Anhydride equiv. Melting point, "C ( O F ) Comments

weight, g/eq

Hexahydrophthalic anhydride (HHPA)

154 40 (104) Available from Pacific Anchor as Ancadride

MHHPA and from Ciba as HT 907.

Nadic methyl anhydride (NMA) maleic anhydride adduct of methyl cyclopentadiene

180 Liquid at 25°C (77°F) Widely used for prepegs. Available from Pacific
(0.200 Pa s) 200 cP Anchor as Anhydride METHPA and from
Ciba as HY 906.

Dodecenyl succinic anhydride (DDSA)

270 Liquid at 25°C (77°F) Available from Dixie Chemical and from
(0.200 Pa s) 200 cP Humphrey Chemical.
58 Epoxy resins

Table 3.3 Continued

Anhydride equiv. Melfing point, "C ( O F ) Comments

weight, g/eq

Chlorendic anhydride (CAI

371 231-235 Needs no cure accelerator, but is high melting and

(448445) hard to handle; good fire retardant. Available
from Velsicol.

Trimellitic anhydride (TMA)

,o

\\
0

193 161-1 64 Available from Buffalo Color.

(322-327)

Maleic anhydride (MA)

\\
0

100 53 (127) Available from Amoco.

Succinic anhydride (SA)

/p

l0
100 120 (248) Available from Buffalo Color.
 Constituents used in formulated systems 59

Table 3.3 Continued

Anhydride equiv. Melting point, "C ( O F ) Comments

weight, g/eq

Methyltetrahydrophthalicanhydride

166 Liquid at 25°C (77°F) Available from Lindau.

(0.06 Pa s) 60 cP

3,3', 4,4' - Benzophenone-tetracarboxylicdianhydride (BTDA)

0
0 II 0
\\
o/c~cy&o
C
'
// \\
0 0
161 221 (430) Used mainly in powder coatings; when used as
minor component in fiber composite matrix, it
improves high-temperature properties.Available
from Allco.

3.3.4 CATALYSTS FOR useful in prepregs that must be stored for

HOMOPOLYMERIZATION some time without cure advancement prior to
being used in fabrication of a structural com-
Table 3.4 presents some Lewis acids and Lewis
ponent.
bases that have been found effective as cata-
lysts for homopolymerization of epoxides.
Certain Lewis acids, such as boron trifluoride 3.3.5 ACCELERATORS FOR CURING AGENT
(BF,) produce rapid and very exothermic SYSTEMS
homopolymerization and need to be used in
blocked form. BF,, when blocked with Some Lewis acids and Lewis bases can also be
used as accelerators in epoxide-curing agent
monoethyl amine to form the complex
mixtures to speed up a sluggish reaction. They
BF,MEA, is latent at room temperature and
are added in small amounts, only a few weight
becomes active only above 90"C, the tempera-
per cent, empirically determined to give the
ture at which the complex separates. The
best results. Most often they are used to speed
epoxide homopolymerization that occurs
up the curing reaction in epoxide-anhydride
above 90°C is rapid, but has controllable
systems. Table 3.4 indicates which catalysts are
release of heat. Epoxides containing blocked
also used as accelerators and lists additional
Lewis acids as catalysts have been found to be
chemicals used as accelerators only.
60 Epoxy resins

Table 3.4 Structures and characteristics of commonly used catalysts and accelerators

Amine hydrogen Melting point, "C ( O F ) Comments

equiv. weight, g/e9

Benzyldimethylarnine (BDMA)

- Liquid at 25°C (77°F) Lewis base used as an accelerator mainly for

(0.1 Pa s, 100 cP) anhydride mixtures. Avalible from Ciba
as DY 062.

2,4,6-Tris(dimethylaminomethyl)phenol

Liquid at 25°C (77°F) Lewis base used as an accelerator for epoxide

(0.3Pa s, 300 cP) anhydride mixtures to provide room-temperature
cure. Available from Rohm & Haas as DMP-30 and
from Ciba as DY 064.

2-Ethyl-4-methylimidazole (EMI)

CH3- CH2 - C CH
\ /
N
H
Liquid at 25°C (77°F) Lewis base used as an accelerator for epoxide-
(4-8 Pa s, 4000-8000 cP) anhydride mixtures to provide long pot life and
good elevated-temperature properties. Available
from Air Products as EMI-24.
 Constituents used in formulated systems 61

Table 3.4 Continued

Amine hydrogen Melting point, "C ( O F ) Comments

equiv. weight, g/eq

Boron trifluoride-monoethylene amine (BF,MEA)

F
I
F -B:NHz- CH2- CH,
I
F
85-90 (185-194) Blocked Lewis acid; used as an accelerator for
epoxide DDS systems in high temperature
service; provides latency. Available from ATOTech.

3.3.6 DILUENTS epoxide groups. Some of these diluents are

For some types of processing the viscosity of
the uncured resin system needs to be lowered.
When it is not advisable, as in the case of wet
filament winding or hand lay-up, to use
volatile solvents as diluents, reactive diluents
must be used. Table 3.5 lists some acceptable
diluents, all low viscosity liquids containing
monofunctional, i.e. have only one epoxide
group, so they cannot form crosslinks in the
network like bi-, tri- and tetrafunctional mole-
cules do. However, by chemically attaching to
the network, the reactive diluents become a
permanent and stable part of it. Other diluents
are bifunctional and will form crosslinks.

Table 3.5 Structures and characteristics of commonly used, commerciallyavailable epoxide reactive dilutents

Epoxy equivalent Viscosify at 25"C, Comments

weight, g/eq Pa s (cP)

Butyl glycidyl ether (BGE)

/O\
CH3-(CH2)3 -0 - CH2- CH-CH2

130-149 0.002-0.003 Example: RD-1 (Ciba).

(2-3)

Octyl, decyl glycidyl ether blend

/O\
CH3-((CH2)7 - 0 - CH2- CH- CH2

215-235 0.005-0.015 Example: Epotuf 37-057 (Reichhold) and Dy 027

(5-15) (Ciba).
62 Epoxy resins

Table 3.5 Continued

Epoxy equivalent Viscosity at 25"C, Comments

weight,g/eq Pa s (cP)
___ ~~ . _ _ _ _ ~ ~

p - t - Butyl phenyl glycidyl ether

CH3
/O\
0 - CH2 - CH- CH2
I -

220-245 0.015-0.30 Example: Epi-Rez 5014 (Hi-Tek Polymers).

(15-30)

Phenyl glycidyl ether (PGE)

/O\
0 - CH2 -CH-CH2

150 0.006 Example: Heloxy WC-63 (Wilmington Chemical).

(6)

Cresyl glycidyl ether (CGE)

170-190 0.005-0.050 Less volatile than BGE. Example: Epotuf 37453

(5-50) (Reichhold), and by DY 023 (Ciba).

Diglycidyl ether of 1,4 - butanediol (BDE)

12@140 0.010-0.025 Example: RD-2 (Ciba); not a pure compound.

(10-25)
-~ _____ ~- ~~~~ ~~ ~-
 General principles of formulation 63

Table 3.5 Continued

Epoxy equivalent Viscosity at 25°C’ Comments

weight, g/e9 Pa S ( c ~ )
~

Diglycidyl ether of neopentyl glycol

CH3
13CL145 0.005-0.015 Example: AZ epoxy N (AZS Corp.);not a pure
(5-15) compound.

Diglycidyl ether of polypropylene glycol

r 1

175-205 0.30-0.060 (30-60) n = 4. Example DER 736 (Dow).

305335 0.55-0.100 (55-100) n = 9. Example DER 732 (Dow).

Vinyl cyclohexene dioxide

/O\
A CH - C H ~
O ’ W
76 0.20 Example ERL 4206 (Union Carbide).
(20)

3.4 GENERAL PRINCIPLES OF

FORMULATION
Epoxy resin systems must be formulated on a
rational basis and the chemical structure of the
constituents forms this basis. Many detailed
structure-property relationships can be
reduced to rules of thumb and some of those
we present in this section. The reader should
use these with caution, because often a more
detailed examination of the chemical structure
reveals conflicting trends and experimentation
is needed.
First, the presence of significant amounts of
aliphatic segments in the chemical structure of
the cured network results in lower rigidity and
lower Tg as compared to aromatic rings, or
even saturated rings. Thus, aromatic amine-
cured systems or homopolymerized systems
both have high stiffness and high Tg. whereas
an aliphatic amine-cured system will have a
lower stiffness and lower T,.
In terms of processing and cure, the flexibil-
ity and mobility of aliphatic segments imparts
low viscosity (if a liquid) or low melting point
(if a solid). Constituents whose structures are
mainly aliphatic react rapidly at room temper-
ature. Thus, an aliphatic amine-cured system is
recommended over an aromatic amine-cured
64 Epoxy resins
system if low viscosity for processing and a
room temperature cure are needed1’,12.
Constituents with aromatic ring structures
react sluggishly or not at all at room tempera-
ture13J4.Thus aromatic-amine cured systems
require elevated temperature cures.
As cited earlier in the discussion on cure
reactions, the relative amount of curing agent
to epoxide is important in achieving a well-
developed network. The formulations
presented in Table 3.6 are approximately what
would be used for some specific epoxide-curing
agent formulations. The reader should verify
the correctness of the formulations by comput-
ing the appropriate weight ratios from the
molecular structures given in Tables 3.1, 3.2
and 3.3.
Table 3.6 Formulations for selected epoxy resin
systems
Constituents Epoxide Curing agent
PbV Pbw‘
Diglycidyl ether of
bisphenol A triethylene
tetramine 100 14
Diglycidyl ether of
bisphenol A rneta-
phenylene diamine 100 16
Diglycidyl ether of
bisphenol A
hexahydrophthalic
anhydride 100 90
Parts by weight
Finally, through the chemistry of the constituents
and the network they form, the formulation
d u e n c e s the environmental resistance of the
resin. Thus the formulation must be selected
with the future environmental exposures in
mind. Figure 3.4 compares the environmental
resistance of four important types of epoxy resin
systems: aliphatic amine-cured,aromatic amine-
cured, homopolymerized epoxide (BF,MEA
catalyst) and anhydride-curedI5. The excellent
resistance of the crosslmked network is evident
in all but a few cases; the anhydride-cured sys-
tem is degraded in strong base due to basic
hydrolysis of its ester linkages and both the
anhydride-cured and the homopolymerized sys-
tems are vulnerable to swelling by the strong
solvent, trichloroethylene.
3.5 PROCESSING CONSIDERATIONS IN
EPOXY RESIN COMPOSITES
The goals of the processing procedures used to
make a good quality fiber composite are to
ensure that the resin forms a void-free contin-
uous phase, surrounds each filament, is evenly
distributed, is present in the desired amount
relative to the fiber and is fully cured. The ease
with which these goals can be achieved is
highly dependent on the rheological proper-
ties of the resin as it progresses through its
cure and on the engineer’s ability to evaluate
rheology and degree of cure throughout the
processing cycle.
In the early years of epoxy resin technol-
ogy, processing procedures were developed
by a trial and error approach. This is still a
viable approach, especially for engineers
skilled in the art of thermoset composite pro-
cessing. However, in recent years,
rheologica116-18 and chemorheologica119~20
models that relate viscosity, rigidity and
degree of cure to time and temperature have
been developed. These models predict rheo-
logical changes during cure and can serve as
an aid to processing and cure cycle develop-
ment.
3.5.1 PROCESSING VARIABLES EARLY IN CURE
One of the major concerns in the early stages
of composite processing is resin viscosity.
Sometimes, the freshly mixed, uncured resin
formulation is inherently fluid enough to pen-
etrate the fiber bundle and surround each
filament. (Tables 3.1, 3.2 and 3.3 give viscosity
values for several epoxides and curing
agents.) Often, however, the viscosity of the
uncured resin system is too high and must be
 Processing considerations in epoxy resin composites 65

100

75

50

ae
I 25
lm
n
.-C
VI
c1

9 0
$ Sodium hydroxide, 50% Sulfuric acid, 25% Hydrochloric acid, 25%
0 82°C (180°F) 82°C (180°F) 82°C (180°F)
L
E+
0
C
.-c0
C
W
w
E
-c3
c

i
0 100

-E
2
; 75
-
U
W

50

25

0
Distilled water Trichloroethylene Sodium hypochlorite, 6%
54°C (13CPF) 54°C (130°F) 54°C (130°F)
Exposure conditions

Fig. 3.4 Environmental resistance of common cured epoxy systems as indicated by flexural modulus reten-
tion after environmental exposure Is.
Aliphatic amine-cured (TETA),
Aromatic amine-cured (MPDA), @
reduced to achieve the desired flow require-
ments. The two major approaches to reducing
viscosity are thinning the mixture with low
viscosity organic solvents and adding low vis-
cosity reactive diluents, such as those
presented in Table 3.5.
Thinning with organic solvents, although
Homopolymerized (BF,MEA),
Anhydride-cured (PA), mrm
the simplest approach, can result in bubble or
void formation within the composite if the
solvent cannot escape completely. This could
be a problem for component fabrication by
wet filament winding, where layers contain-
ing the freshly mixed epoxy resin system are
placed sequentially on top of one another.
66 Epoxy resins

Filament winding processors do not use sol-
vents to reduce viscosity, rather selecting
lower viscosity resins, reactive diluents, or
diluting with heat. On the other hand, the use
By contrast, reactive diluents, being them-
selves epoxides, chemically react to become a
permanent part of the crosslinked network.
Figure 3.5 shows the relation between L'1SCOS-
'

of small amounts of solvent to reduce resin
viscosity during fabrication of prepreg
(pre-impregnated fiber) presents no prob-
lems, since prepreg is made in the form of
single, thin-layer sheet, tape or tow from
which solvent can vaporize easily and the
prepreg is heat treated to eliminate solvent
and to advance cure.
ity and the amount of diluent added to a
viscous epoxide. Ideally, the engineer wants to
use just enough diluent to lower viscosity as
needed without dramatically altering the
properties of the final cured network.
The length of time that an epoxy resin for-
mulation remains fluid is important.
Liquid-like flow becomes impossible once the
gelation stage, marked by an abrupt increase
in viscosity, is reached. Time to gelation is
called gel time, or sometimes pot life.

A
- 'T
1100
Aliphatic amine curing agents produce pot
lives of the order of minutes or a few hours,
while aromatic amine curing agents produce
pot lives of 24 h or more13,22,23.
Anhydride cur-
ing agents typically produce very long pot
- lives (e.g. two months for NMA) when mixed

- --
m with epoxides. This is because, as already
IS00
i
.- mentioned, the anhydride group is not very
ln
0
1100
reactive with epoxides unless it is cleaved with
, -
0
.-
ln
1100 the aid of an accelerator molecule. Once the
1000 - accelerator is activated, the pot life of the mix-
ture will be shortened to a few hours. Pot life
eo0 - can be controlled over a wide range by careful
800 - use of accelerators.
700 - Each resin formulation has a unique chem-
istry that imparts a set of processing variables
600 - with unique values. Standard laboratory test
500 - methods for processing variables that are
important early in cure are described by the
400 - American Society for Testing and Materials,
$00 - Philadelphia, Pennsylvania.ASTM numbers of
zoo - the procedures for determining resin viscosity,
gel time and melt flow are listed in Table 3.7.
100 -
I
0
l
lll
lrl
l
10
llTable 3.7 Laboratory test methods for measuring
20 30 40 SO 60 70 80 90 IOC

DILUENT, 'Io processing variables

Processing variable Reference

-
Fig. 3.5 Viscosity versus per cent of diluent in epox-
ide-diluent mixturesz1.The epoxide is DGEBA and Viscosity ASTM D2393
the diluent is BDE (diglycidyl ether of 1, 4-butane time (pot life) ASTM D2471
diol). Melt flow ASTM D3795, ASTM D4473
 Processing considerations in epoxy resin composites 67
3.5.2 MONITORING OF CURE
Once the cure is underway in an epoxy resin
system, all of the properties of the system
change rapidly until the final crosslinked net-
work is reached. Not only is flow decreasing
and rigidity increasing, but all other properties
(electrical, chemical, optical, etc.) are chang-
ing. When the curing epoxy resin system is
subjected to temperature and pressure
changes, the resin response will be characteris-
tic of its degree of cure at that moment. Cure
cycle events, such as temperature and pressure
changes, need to be carefully timed with this
in mind.
The degree of cure can be defined in terms
of any one of a large number of chemical or
physical (including mechanical) properties that
change continuously during the curing reac-
tion and reach a constant value at end of the
cure. Evaluation of the degree of cure is usually
based on one of these properties and full cure
is then defined as the point at which this
selected property reaches a constant value.
Originally, the only available methods for
evaluating cure were off-line laboratory meth-
1.24
1.22 -
+
1.20 -
$$ + s t + + $ + +
1.18-
\El
s 1.16 -
.-
c
v)
1.14-
Fig. 3.6 Specific gravity compared with cure time for an aromatic amine-cured epoxy system cured at
120°C26. Volume reduction (densification) during early network formation is rapid and levels off as cure
nears completion.
ods where samples were taken and tested at
intervals in the cure cycle. The time needed to
develop one data point depended on the par-
ticular laboratory method. Off-line testing has
been made more convenient with the develop-
ment of continuous monitoring techniques
(i.e. data points in real time) used on small
dedicated specimens of resin or prepreg.
Recently, real time, in situ methods where cure
can be monitored in the composite structural
component itself have been developed.
Traditional off-line methods
Intermittent off-line methods include chemical
titration of the unreacted epoxide groups pre-
sentz4jz5, specific gravity to measure
densificationzh and differential scanning
calorimetry to measure the residual cure
e~otherm*"~ Figure
~ ~ ~ ~3.6
* .shows a plot of spe-
cific gravity data obtained on specimens cured
for increasing lengths of time at a single tem-
perature. Figure 3.7 shows differential
scanning calorimeter scans for two epoxy resin
specimens of the same formulation, but with
different degrees of cure.
+ +
 Exotherm
A
. I
I I
I I
1 I

Energy
calls

1
Endotherm . I I I I I I I

Fig. 3.7 Differential scanning calorimeter scans for an epoxy resin system28.Scans for two different speci-
mens, each having a different original degree of cure, are shown, with scan A displaced upward from
scan B for graphical visibility. The height of the residual cure exotherm is inversely related to the original
degree of cure. The higher exotherm peak in B indicates an original degree of cure lower than in A.

Continuous off-line methods include infrared
s p e c t r o s ~ o p y ~ ,parallel
~ ~ , ~ ~ , plate-type bulk
diele~trornetry~’,~~ and dynamic mechanical
s p e ~ t r o m e t r y ~Figure
~ ” ~ . 3.8 shows the results
of infrared monitoring for five different neat
resin specimens, each cured at a different tem-
perature and Fig. 3.9 shows data obtained by
bulk dielectrometry.
The off-line methods, real time or not, are
useful for developing a cure schedule for a
new epoxy resin formulation, for optimizing
processing variables and for quality control of
incoming resins or prepregs. They have also
been used successfully for the development of
mathematical models of cure kinetics.
However, because they are off-line, they can-
not be used for process control.

Fig. 3.8 Degree of cure compared with time for an aromatic amine-cured epoxy systemz8.Data for five
specimens, each cured at a different temperature, are presented.
 Property data for cured epoxy resin systems 69

200 I 1
.1
I f f
I f
1
Decreasing molecular dipole mobility

150 Temperature profile - t

I
I \
0
I
-I
I

increasing molecular dipole mobility

w 100 er; elevation - %r
E C
.-c
0

--------
P
E m
F .-n
.-
v)

I-
v)

50
No further
cure at
temperature

0 I 1 I

0 2 4 6 8
Time - h
Fig. 3.9 Bulk dielectrometry data compared with time for an aliphatic amine-cured epoxy system28.
Dissipation factor (dashed line) is inversely related to rigidity in the developing network. The applied tem-
perature is shown by the solid line.

Modern in situ methods Other examples of in situ monitoring are

In situ methods for cure monitoring are real
time methods that require sensors small
enough to implant and leave in the composite
itself. When the information from in situ mon-
itoring is used as continuous input to an
appropriate process model, it can be used in
process control loops that adjust the process-
ing conditions automatically.
One example of an in situ method is low fre-
quency dielectrometry using a very small
assembly of interdigitated electrodes called a
fringe field sensor. This technique measures
changes in ability of permanent dipoles within
the resin chemical structure to align themselves
with the applied oscillating electric field and
also measures changes in the mobility of ions
present as impurities in the resin3941.Both of
these quantities correlate with resin viscosity in
the early stages of cure and with mechanical
rigidity in the later stages of cure39,40,42.
based on fluorescence spectroscopy of tag
molecules in the resin43,44 and on infrared45,46
and Raman47spectroscopies of the resin mole-
cules themselves. In these methods, optical
fibers are the sensors that transmit the appro-
priate wavelength of light into the curing resin
and also transmit the spectral information
back The spectral changes relate directly
to the chemical changes that occur as the cur-
ing reaction progresses to completion.
3.6 PROPERTY DATA FOR CURED EPOXY
RESIN SYSTEMS
Property data for cured, unreinforced epoxy
resin systems are needed for two purposes.
First, they are useful when selecting the best
fiber and matrix combination for a particular
application. Resin system choices can be
rapidly narrowed down to a few alternatives
70 Epoxy resins

when comparisons of key properties are made and many other properties of the composite can
from existing data tables or manufacturers’ be computed in advance, if one has the corre-
data sheets. sponding values for the fiber and the matrix.
Second, epoxy resin data are required in Tables 3.8, 3.9 and 3.10 present property
micromechanics computations of composite data for three major resin systems: aliphatic
properties. Elastic constants, thermal expansion amine-cured, aromatic amine-cured and anhy-
coefficients, moisture absorption coefficients, dride-cured. Property data for commonly used
Table 3.8 An aliphatic amine-cured epoxy resin system, room-temperature curable1228

Resin system constituents Parts by weight

Epoxy: DGEBA, eg., DER 332 (Dow) 100
Curing agent: APTA, e.g. Jeffamine T-403 (Texaco) 45
Cure cycle: 16 h at 60°C (140°F)for improved properties over room temperature cure
Viscosity at 25°C (77°F) Heat distortion temperature at
0.8 Pa s (800 cP) 1820 kPa (264 psi) 62°C (144°F)
Density of cured resin at 25°C (77°F) Coefficient of linear thermal expansion
1.16 g ~ m - ~ from 298 to 374 K 66x “C-’
Volumetric shrinkage Average specific heat from
After gelation 4.4% l
’ 286 to 367 K 1.75~10~Jkg-lK~~
After cure 4.4%
Coefficient of thermal conductivity
Water absorption, wt. gain after 2 h in At 298 K 0.133 W m-’ K-’ a
boiling water 0.75% a At 318 K 0.174 Wm-’ K-’ a

At 336 K 0.210 W m-l K-’

Impact strength
(Izod notched bar test)
Shear properties
Failure stress
Modulus of elasticity
Tensile properties
Modulus of elasticity
11.0 J m-’ of notch Compressive properties
Modulus of elasticity
3.48 GPa (504 ksi)
61 MPa (8.85 ksi)
1.27 GPa (184 ksi)
3.24 GPa (470 ksi)

120 I I I I
Cures: 16
._
r 16 h @ 60°C 4 m
Y

0
0 1 2 3 4 5 0 0.8 1.6 2.4 3.2 4.0

Tensile strain % Compressive strain %

~~ -~ ~~~ __

a Cured for 24 h at 60°C (140°F) + 24 h at 77°C (171°F).

 Property data for cured epoxy resin systems 71

Table 3.9 An aromatic amine-cured epoxy resin systemI3

Resin system constituents Parts by weight

Epoxy: DGEBA, e.g. Epon 826 (Shell) 100
Diluent: BDE, e.g. RD-2 (Ciba-Geigy) 25
Curing agent: MDA-MPDA eutectic, e.g. Tonox 6 0 4 0 (UniRoyal) 29
Cure cycle: 3 h at 60°C (140°F) + 2 h at 120°C (248°F)
Viscosity at 25°C (77°F) Water absorption, wt. gain
after 6 h in boiling water 0.93%
1.2 P a s (1200 CP)
Glass transition temperature
Time to reach 2.0 Pa s 6h
130°C (266°F)
Gel time for a 30-g mass at
25°C (77°F) 23 h Heat distortion temperature at
1820 kPa (264 psi) 121°C (250°F)
Density at 25°C (77°F)
Uncured 1.15 Mg m-3
Cured 1.21 Mg m-3 Coefficient of linear thermal expansion
from 298 to 3755 K 6.81 x 10-5oc-1
Volumetric shrinkage
After gelation 3.7% Specific heat
After cure 5.4% At 363 K 1.54 x lo3J kg-' K-'
At 424 K 1.71 x lo3J kg-'K-'
Tensile properties
Modulus of elasticity 2.68 GPa (389 ksi) Coefficient of thermal conductivity
At 325 K 0:243 W m-' K-'
At 356 K 0.244 W rn-' K-'
100 I I I I - 14 At 389 K 0.256 W m-'K-'
Shear properties
80 Failure stress 52 MPa (7.54 ksi)
- 10 Compressive properties
._ Maximum stress 111MPa (16.1 ksi)
h
H
60
- 8 %
VI
Strain at maximum stress 8.0 %
In
VI VI
E
Modulus of elasticity 2.9 GPa (420 Ksi)
E - 6 G
5 40

- 4
20
- 2

0
0 2 4 6 a io-
Strain YO

epoxy resin formulations are often available
from resin suppliers. Data for new or unusual
formulations must be generated by the user.
Whether the data are generated by the resin
supplier or the user, it is important that stan-
dard test procedures be followed. This will
ensure that the resin systems can be compared
on an equal basis. Where standardized test
procedures exist, e.g. as from the American
Society for Testing and Materials, they should
be followed. Where they do not exist, litera-
ture references are helpful. Table 3.11 lists
some commonly tested properties and the
standard methods (American Society for
Testing and Materials) describing the tests.
72 Epoxy resins

Table 3.10 An anhydride-cured epoxy resin systemI5

Resin system constituents Parts by weight
Epoxy: DGEBA, e.g. Epon 828 (Shell) 100
Curing agent: NMA 90
Accelerator: BDMA 1
Cure cycle: 3 h at 120°C (248°F) + 24 h at 150°C (302°F)

Viscosity at 27°C (81°F) 1.78 P a s (1780 cP)

Time to reach 100 Pa s (1000 cP) 556 days
Pot life of a 500 g mass at 23°C (73°F) 4-6 days
Heat distortion temperature at 1820 kPa (264 psi) 121°C (250°F)
Solvent absorption, wt. gain
After 24 h in boiling water 0.67%
After 3 h in boiling acetone 1.9%
Tensile properties At 23°C (73°F) At 100°C (212°F)
Maximum stress 72.4 MPa (10.5 ksi) 46.2 MPa (6.70 ksi)
Strain at maximum stress 2.7% 7.2%
Modulus of elasticity 3.45 GPa (500 ksi) 1.38 GPa (200 ksi)

Table 3.11 Standard test methods for cured epoxy resin systems

Property ASTM
Standard Method
___
Physical and chemical properties:
Specific gravity D792
Chemical resistance D543
Water absorption D570
Light and water exposure D1499
Electrical properties:
Volume resistivity D257
Surface resistivity D257
Dielectric strength D149
Dielectric breakdown voltage D149
Permittivity, dielectric constant D150
Dielectric loss D150
Thermal properties:
Heat deflection temperature D648
Glass transition temperature D4065
Coefficient of linear thermal expansion D696
Coefficient of thermal conductivity C177
Mechanical properties:
Tensile modulus and strength D638
Compressive modulus and strength D695
Flexural modulus and strength D790
Impact resistance D256
Dynamic mechanical properties:
Storage modulus D4065
Loss modulus D4065
Transition temperature D4065

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