8 Epoxies

Witold Brostow
, Sidney H. Goodman† and Joshua Wahrmund

Laboratory of Advanced Polymers & Optimized Materials (LAPOM), Department of Materials Science and Engineering and
Department of Physics, University of North Texas, Denton TX
†
Consultant, Palos Verdes Estates, CA and Principal Engineer/Scientist (Emeritus), Raytheon/Hughes Aerospace Corp. & Senior Lecturer
(Emeritus), University of Southern California

O U T L I N E

Introduction 191 Applications 243

Detailed Chemistry 192 References 248
Characterization of Epoxies 216

Introduction Castan developed dental fixtures and casings with

this material. His first patent was granted in 1938 [2].
Epoxies are an indispensable class of polymers for In the United States, Dr. Sylvan O. Greenlee dis-
modern industry. These materials are so ubiquitous, covered the same material as Castan, but with a
in fact, that scientists and engineers from a wide higher molecular weight. While working at Devoe
range of disciplines are likely to encounter them in and Raynolds, Greenlee’s intention in synthesizing
quite disparate settings. In recognition of this circum- diglycidal ethers of bisphenol A resins was for the
stance, the present chapter is organized to suit a vari- purpose of surface coatings. His first patent, among
ety of backgrounds: chemists, physicists, materials many others, appeared in 1943.
scientists, engineers, and the like. The essential ele- Also in the early 1940s, Daniel Swern developed
ments of epoxy chemistry are presented first, fol- an alternate route to epoxy formation by formulating
lowed by a host of physical properties and then resins through the reaction of peroxy acids with ole-
applications. In fitting with this aim, we also provide fins. This development is in close resemblance to the
the reader with a review of the measurement techni- current commercial processes used in the creation of
ques relevant to characterizing this material. epoxy compounds as plasticizer-stabilizers.
In the decades that followed, a proliferation of
new epoxies was realized and within the span of 20
History years there were at least 25 different epoxies in
The historical development of epoxy compounds existence. Industrial usage of epoxies also became
dates back to the late nineteenth century with initial widespread with the first commercial production
accounts found as early as 1891. It wasn’t until the beginning in 1947. Since that time, the market for
mid-twentieth century that commercial development epoxy resins has continued its growth due to addi-
was realized [1]. tional applications. Projections show an estimated
In the late 1930s, two researchers independently growth of about 34% annually with a 2015 mar-
synthesized the first epoxy resins from the reaction of ket estimated at $21 billion [3].
bisphenol A with epichlorohydrin. The resulting
diglycidal ether of bisphenol A then became the first Basic Chemistry and Some
commercially available epoxy resin. Dr. Pierre
Castan developed this material in 1936 while working General Remarks
at the De Trey Frères Company in Zurich. The resin The generic term epoxy (epoxide in Europe) is
was thermoset by reaction with phthalic anhydride. now understood to mean the base (thermoplastic,

Handbook of Thermoset Plastics. DOI: http://dx.doi.org/10.1016/B978-1-4557-3107-7.00008-7

© 2014 Elsevier Inc. All rights reserved. 191
192 HANDBOOK OF THERMOSET PLASTICS

uncured) resins as well as the resultant cross-linked involves nucleophilic attack on one of the epoxide
(thermoset, cured) plastic. Chemically, an epoxy carbons by an amine or an anhydride compound
resin contains more than one α-epoxy group situ- (see the next sections for more details). Reviews of
ated terminally, cyclically, or internally in a mole- curing reactions are available in the literature, and
cule; it can be converted to a solid through a terminology has been standardized by the Interna-
thermosetting reaction. tional Union of Pure and Applied Chemistry
The α-epoxy (or 1,2-epoxy) is the most common (IUPAC). An obvious and important difference in
type of functional moiety. Ethylene oxide (Structure the result of the two different curing methods is that
8.1) is the simplest type of 1,2-epoxy. This ring is in homopolymerization the network is only com-
also referred to as the oxirane ring. Another com- posed of the cross-linked epoxy monomers, whereas
mon group in this resin class is the glycidyl group in the bridging reaction the network is composed of
(Structure 8.2). a copolymer of both epoxy monomers and a curing
agent. Therefore, in a bridging reaction the network
O properties are a function of two components, which
H2 C-CH2 allows modifications to be incorporated in either
component. Thus, a rigid epoxy with high strength
Structure 8.1 Ethylene oxide. can be used with an impact-resistant hardener to
CH2 CH CH2 yield a desirable network.
O
In addition, in amine-cured epoxy reactions a
side reaction between the products and reactants
Structure 8.2 Glycidyl group. occurs. Epoxy monomers may be attacked by the
hydroxyl group of the product of the primary amine
The demands of the structural composites field
opened epoxy if either the secondary amine is less
spurred development of high-performance epoxies.
reactive than the hydroxyl group, or by the
These requirements were met by increasing the
hydroxyl group of the final product, in the case of
functionality (number of epoxide groups per mole-
epoxy-rich systems or low-functionality amines.
cule), modifying curing agents, and replacing the
thermally weak aliphatic linkages in glycidyl
groups with rigid bonds.
The ring-opening polymerization and cross- Detailed Chemistry
linking in epoxy resins can be of two general types,
catalyzed homopolymerization or bridging reactions Resin Types
incorporating a co-reactive cross-linking agent into
the network. Homopolymerization, or reactions Diglycidyl Ether of Bisphenol A
between epoxy chains, involves elimination reac- The diglycidyl ether of bisphenol A (DGEBA)
tions on the oxygen atom of the epoxide group continues to this day to represent the most common
using acid or base catalysts, often activated by radi- type of epoxy resin. It is the product of the follow-
ation. The incorporation, or bridging reaction, ing reaction (Scheme 8.1):

O
CH3
Na OH
HO C OH + 2 CI CH2 CH CH2
CH3
Bisphenol A Epichlorohydrin
CH3
– HCI
CICH2CHCH2O C OCH2CHCH2CI
OH CH3 OH

CH3 CH3

CH2 CHCH2 O C OCH2CHCH2 O C O CH2 CH CH2

n
CH3 OH
O CH3 O

Scheme 8.1 Bisphenol A and epichlorohydrin.

8: EPOXIES 193

The basic commercial version of this resin is epichlorohydrin and performing the reaction under
the one having a molecular weight of 380. Purified more alkaline conditions. Tables 8.1 through 8.5
versions (n  0) have molecular weights as low as list some commercial grades of these resins.
344. Higher-molecular-weight versions (n 5 110) Changes in the base resin structure have been
have been produced by reducing the amount of made to adjust final plastics properties. Higher

Table 8.1 Standard Undiluted BIS Resins

Products EEW (g/eq) Viscosity (mPa  s) Color, Max

@ 25°C
D.E.R. 331 (Dow Chemical Co.) 182192 1.11.4 3 104 75 (Platinum Cobalt)


Epon 8280 (Momentive) 185195 1.11.5 3 10 4
1 (Gardner)
Epon 828 (Momentive) 185192 1.11.5 3 10 4
1 (Gardner)
Araldite GY6010 (Huntsman) 182192 1.11.4 3 10 4
1 (Gardner)
Epotuf 37140 (Reichhold) 185 1.25 3 10 4
1 (Gardner)


Special vacuum-casting resin characterized by rapid foam breakdown under vacuum.
NOTE: Standard undiluted resins for all general purposes requiring performance up to 400°F. Aliphatic polyamines or polyamides
satisfactory up to approximately 230°F. Anhydrides, such as phthalic, satisfactory to approximately 200°F. Aromatic amines and anhydrides
satisfactory to 400°F. The anhydrides are effective viscosity reducers to permit higher filler loading.

Table 8.2 Lowest-Viscosity Resins

Products EEW (g/eq) Viscosity (mPa  s) Color, Max

@ 25°C
D.E.R. 332 (Dow Chemical Co.) 171175 46 3 103 75 (Platinum Cobalt)
Epon 825 (Momentive) 175180 5.06.5 3 10 3
250 (Platinum Cobalt)
Araldite GY6004 (Huntsman) 178196 5.06.8 3 10 3
2 (Gardner)
NOTE: The low equivalent weight resins are virtually pure diglycidyl ethers of bisphenol A. They are the lowest viscosity undiluted bisphenol
A resins available. They are so pure; however, that they crystallize during storage. The crystals melt on warming above 125°F.
They fit all the general uses of D.E.R. 330 or D.E.R. 331 resins with the following advantages:
1. Increased HDT
2. Lower viscosity
3. More chemical uniformity
4. Longer pot life with most curing agents
5. Better wetting of glass reinforcements
6. Very pale color
7. Better electrical properties

Table 8.3 High-Viscosity Resins

Products EEW (g/eq) Viscosity(mPa  s) Color, Max

@ 25°C
D.E.R. 317 (Dow Chemical Co.) 192203 1.62.5 3 104 5 (Platinum Cobalt)
D.E.R. 337 (Dow Chemical Co.) 2302501 0.51.5 3 10 4
3 (Platinum Cobalt)
Araldite GY6020 (Ciba-Geigy Corp.) 194208 1.62.0 3 10 4
1 (Gardner)
Epon 830 (Momentive) 190198 1.72.25 3 10 4
250 (Platinum Cobalt)
Epon 834 (Momentive) 230280 0.359.2 3 10 3
200 (Platinum Cobalt)
Extracted from data provided by Dow Chemical Co.
194 HANDBOOK OF THERMOSET PLASTICS

Table 8.4 Low-Melting Solid Resins

Products EEW (g/eq) Viscosity (mPa  s) Color, Max Durran’s

@ 25°C SP (°C)
D.E.R. 661 (Dow Chem Co.) 500560 165250
100 7585
(Platinum
Cobalt)
Epon 1001F (Momentive) 525550 7.09.6

200 79
(Platinum
Cobalt)
Epotuf 37001 (Reichhold) 525 1.0 3 104


3 (Gardner)
Araldite GT7071 500525 200250 1 (Gardner) 7782
(Huntsman)


Solution viscosity for 40 wt.% in diethylene glycol dibutyl ether.



Solution viscosity for 40 wt.% in MEK.




75 wt.% solution in xylene.
NOTE: Primary uses in amine cured protective coatings and for prepreg glass cloth for electrical laminates. D.E.R. 661 resin modified with
polyamines or polyamides is used where high chemically resistant performance is required coupled with a room temperature or low-bake
application.
Blends of ketone solvents (MEK or MIBK) with aromatics (xylene or toluene) are generally suitable for thinning these systems. Higher
boiling solvents, such as glycol ethers, can be used in amounts of 5 to 15% to improve flow and film surface properties, Systems of
D.E.R. 661 resin can be used on all substrates—metal, wood, glass, masonry by all applications—brushing, spraying, dipping, etc.
Coatings end uses include pipe and drum linings, maintenance finishes, and marine finishes.

Table 8.5 High-Molecular-Weight Solid Resins

Products EEW (g/eq) Viscosity @ Color, Max Durran’s

25°C (mPa  s)† SP °C
D.E.R. 667 1.62.0 3 103 1.53.7 3 103
100 (Platinum 120135
(Dow Chem Co.) Cobalt)
Epon 1007F 1.72.2 3 103 50100

200 (Platinum 125
(Momentive) Cobalt)
Araldite GT6097 1.6951,885 3 103 1.82.6 3 103


1 (Gardner)
(Huntsman)
Araldite GT7097 1.5151.920 3 103 W-Y (Gardner) 3 (Gardner)
(Jana)
Epotuf 37006 1.652.00 3 103 Z1Z6 (Gardner) 3 (Gardner) 115130
(Reichhold)
Epotuf 37007 2.02.5 3 103 Z1Z51 3 (Gardner) 115130
(Reichhold)
†
Except where noted


40 wt.% in diethylene glycol monobutyl ether.



40 wt.% in MEK.




40 wt.% in butylcarbitol.
NOTE: Optimum epoxy coating can be obtained by modifying D.E.R. 667 resin with urea, melamine formaldehyde, or phenolic resins.
These systems in the blended solution form have excellent pot life and can be stored for several months without noticeable viscosity
change. To cure the coating, high bakes of 300°400°F from 15 to 30 minutes are required. Phenolic modified systems require the
maximum bake schedule for complete cure. The addition of 1% phosphoric acid will catalyze the cure at somewhat lower temperatures.
Ketones and aromatic solvents are used to thin D.E.R. 667.
End-use applications include tank and drum linings, wire enamels, collapsible tube coatings, and metal furniture finishes.
8: EPOXIES 195

reactivity, greater cross-link density, higher temper- The number of glycidyl groups per molecule
ature, and chemical resistance are obtained by using per resin is a function of the number of available
novolac and some types of peracid epoxies. phenolic hydroxyls in the precursor novolac, the
extent of reaction, and the extent of chain extension
Novolacs of the lowest molecular species during synthesis.
Table 8.6 describes a number of commercial novo-
Novolacs are epoxidized phenolformaldehyde or lac resins.
substituted phenolformaldehyde resins (Structure
8.3).

CH2 CH2 CH2

O CH O
CH O
CH
Peracid Resins
CH2 CH2 CH2
O O O Among the peracid resins, the cyclic types
contribute to higher cross-link densities. These
CH2
CH2
resins have lower viscosities and color com-
CH2
pared to novolac and DGEBA types (Scheme
Structure 8.3 Novolac. 8.2).

Table 8.6 Epoxy Novolac Resins

Products EEW (g/eq) Viscosity Color, Max Durran’s Solvent/%

(mPa  s) SP °C NV
@ 25°C
D.E.N. 431 172179† 1.11.7 3 103
250 -/100
(Dow Chem. Co.) (Platinum
Cobalt)
D.E.N. 438-EK85 176181† 0.61.6 3 103 2 (Gardner) MEK/85
(Dow Chem. Co.)
D.E.N. 438 (Dow 176181 3.14.0 3 104
250 -/100
Chem. Co.) (Platinum
Cobalt)
D.E.N. 438-A85 176181† 0.51.2 3 103 2 (Gardner) Acetone/85
(Dow Chem. Co.)
D.E.N. 438-MK75 176181† 200600 2 (Gardner) MIBK/75
(Dow Chem. Co.)
D.E.N. 439 191210 0.41.0 3 104 3 (Gardner) 4558
(Dow Chem. Co.)
D.E.N. 439-EK85 191210† 0.41.0 3 104 3 (Gardner) MEK/85
(Dow Chem. Co.)
Araldite EPN1138 175182 25 3 104

2 (Gardner) -/100
(Ciba)
Araldite EPN1138 176181† 0.51.2 3 103 2 (Gardner) Acetone/85
A-85 (Ciba)
Araldite EPN1139 172179 1.11.7 3 103

2 (Gardner) -/100
(Ciba)


At 51.7°C



At 52°C
†
On solids
NOTE: The multi-functional epoxy novolacs have greater heat and chemical resistance than Bisphenol A-derived resins when cured with
appropriate hardeners.
196 HANDBOOK OF THERMOSET PLASTICS

O O This type of epoxy has presented toxicity pro-

COOH COH O blems. At least one hydantoin-based product is
+ C=C + C C
being supplied, however, for commercial applica-
Perbenzoic acid Olefin Benzoic acid Epoxy tions, but it requires special handling precautions.
Scheme 8.2 Perbenzoic acid, olefin, benzoic acid,
epoxy. Other Types
Other newer types of polyfunctional resins
A typical resin is illustrated by Structure 8.4:
include tetraglycidyl methylene dianiline (Structure
O 8.5), and a novolac synthesized from bisphenol A
O
CH2 OC
O
(Structure 8.6).
O
O
Structure 8.4 3,4-Epoxycyclohexylmethyl-3, CH2CH CH2
CH2
4-epoxycyclohexane carboxylate. CH2 CHCH2
N N CH2CH CH2
CH2CHCH2
A series of peracid-based resins are also O
O
made for modification of standard resin systems.
They alter such properties as cure rate, flexibility, Structure 8.5 Tetraglycidyl methylene dianiline.
and heat deflection temperature. These resins are
O CH3 O
acyclic aliphatic resins such as epoxidized soya,
CH2 –CH CH2O C CH2
linseed oils, or polybutadiene. Table 8.7 lists com- OCH2 CH

mercial types of peracid epoxies. CH2

CH3
O CH3 O
CH2 –CH CH2O C OCH2 CH CH2
n=3
Hydantoin Resins
CH3
H
The hydantoin resins have shown greater popu-
larity for increasing temperature resistance and Structure 8.6 Novolac synthesized from bisphenol A.
improving mechanical properties, particularly in
structural composites. Numerous structural modifi- To build in flexibility, a series of epoxy resins
cations are feasible with hydantoin resins, as shown is based on glycerol (Structure 8.7), and other
in Figure 8.1. polyglycols (polyethylene and polypropylene, most
often); oils, such as cashew nut oil (Structure 8.8);

Table 8.7 Peracid Epoxies

Products EEW (g/eq) Viscosity/ Color, Max Composition

(mPa  s)
@ 25°C
ERL 4221 131143 350450 1 (Gardner) Epoxy cyclohexyl methyl epoxy
(Union Carbide) cyclohexane carboxylate
ERL 4299 190210 500650 150 Bis(3,4-epoxy cyclohexyl)
(Synasia) (Platinum adipate
Cobalt)
ERL 4234 133154 0.71.7 3 104

2 (Gardner) Epoxy cyclohexyl spiroepoxy
cyclohexane dioxide
Araldite CY-179 130143 100600  Cycloaliphatic diepoxide
(Huntsman)
Araldite CY-184 144172 0.71.0 3 103  Cycloaliphatic diepoxide
Araldite CY-192 150167 430660  Cycloaliphatic diepoxide



At 38°C
8: EPOXIES 197

R2 are macromolecular diacids that co-react easily to

O
O R1 O become part of the cross-linked structure.
I CH2CHCH2 N N CH2CHCH2 The incorporation of such elastomers as modi-
fiers in resin formulations is a very effective way to
O
toughen thermosetting matrices, thus significantly
O R1 R2 O
improving impact and fracture strengths of the
O R2 R1 O
cured multi-phased networks. However, these
II CH2CHCH2 N N N N CH2CHCH2 improvements are achieved at the expense of low-
X ering glass transition temperatures (Tg) of the cured
O O resins. Incorporation of certain oligomeric or poly-
R2 R1
meric thermoplastics, such as polysulfones, poly-
O O
R1 R2 ethersulfones, polymides, or polyetherimides, will
O O
also enhance fracture strengths but without sacrific-
III CH2CHCH2 N N N N CH2CHCH2
X ing Tg or other desirable properties. Further studies
O O with diaminodiphenyl sulfone (DDS)-cured systems
demonstrate that by incorporating both a low level
Figure 8.1 Hydantoin epoxy resin structures. R and
of CTBN (5 parts per hundred, phr) and a practical
R2 can be alkyl groups such as methyl, ethyl, and
level of thermoplastic polysulfone (20 phr), the
pentamethylene; X can be methylene, bis-hydroxy-
fracture toughness of the cured product exhibits an
ethyl esters of various chain lengths, or urethane or
improvement of 300% in fracture energy over the
urea groups.
epoxy/DDS control. The presence of 3 phr CTBN
(Structure 8.11) does not depress the Tg and renders
organic acids, such as dimerized fatty acids the epoxy network more easily toughened by the
(Structure 8.9); and modified bisphenols, such as polysulfone (Structure 8.12).
bisphenol F (Structure 8.10). Amine-terminated elastomers of this same type
CH2 CH CH2 were first introduced in the mid-1970s. Although
OH OH OH
they can also be adducted to DGEBA-type resins,
they are more frequently combined with curing
Structure 8.7 Epoxy resins based on glycerol. agents. Table 8.8 lists some commercial versions of
flexible epoxies.
(CH2) CH (CH2) CH3 Flame retardancy is often introduced into epoxy
7 6
systems with halogen- or phosphorus-based addi-
O O O tives. However, some resins have been provided
CH2 CH CH2 OCH2 CH CH2 which have these constituents pre-reacted in the
resin. Chlorinated and brominated versions of
Structure 8.8 Cashew nut oil.
DGEBA (Structure 8.13) are the most common.
New developments in resin synthesis have con-
O O O O
tinued beyond the more traditional types. Among
CH2 CH CH2 O C CH2 (CH2) C O CH2 CH CH2
n them is a polyfunctional resin based on triyphenyl-
Aliphatic diacid glycidyl esters where n = 0, 2, 4, 5 and 8 hydroxy methane (Structure 8.14). It’s designed for
high- and low-temperature (2195° to 200°C, that
Structure 8.9 Dimerized fatty acid. is 2320° to  390°F) resistance.
A resin having a low-temperature cure
CH2 CH CH2O CH2 OCH2 CH CH2
with high-temperature properties is triglycidyl
O O
p-aminophenol (Structure 8.15).
Structure 8.10 Bisphenol F. Resins having a high resistance to weather degra-
dation and attack by biological organisms have sub-
Also, a whole series of resins is based on stantial amounts of fluorine in the backbone structure
elastomeric modification. The first of this series (Structure 8.16, where Rf 5 C3F7 or C7F15).
used carboxy-terminated polybutadiene/acrylonitrile Epoxy-silicone hybrid resins (Structure 8.17)
(CTBN) liquid elastomers. These telechelic polymers have been developed for use in the molding of
198 HANDBOOK OF THERMOSET PLASTICS

HOOC (CH2 – CH = CH – CH2)X – (CH2 – CH)y COOH

n
CN

CTBN

Structure 8.11 CBTN.

CH3
O

C O S O

CH3 O n

Structure 8.12 Polysulfone.

Br CH3 Br O
O O
O CH2CH CH2
CH2 CH CH2O C OCH2 CH CH2
CH2CH CH2 O N
Br CH3
Br CH2CH CH2
O
Structure 8.13 Brominated DGEBA.
Structure 8.15 Triglycidyl p-aminophenol.
O O
CH2CH CH2O CH O CH2CH CH2

O CF3 CF3 O
O
O CH2CH CH2 CH2CH CH2 O C C O CH2CH2CH

CF3 Rf CF3
Structure 8.14 Polyfunctional resin based on
riyphenyl-hydroxy methane. Structure 8.16 Epoxy with fluorine backbone.

Table 8.8 Flexible Epoxy Resins

Products EEW Viscosity (mPa  s) Color, Max Type

(g/eq) @ 25°C
D.E.R. 736 (Dow 175205 3060 125 (Platinum Polyglycol
Chem. Co.) Cobalt)
D.E.R. 732 (Dow 310330 6070 60 (Platinum Polyglycol
Chem. Co.) Cobalt)
Epon 872 (Momentive) 625725 1.53.8 3 103 10 (Gardner)
Epon 872-x-75 625700 2.02.8 3 10 3
6 (Gardner) 75%NV in
(Momentive) xylene
Araldite GY508 390425 2.05.0 3 103 5 (Gardner) Polyglycol
(Huntsman)
Epotuf 37151 500 5 3 104 5 (Gardner)
(Reichhold)
Heloxy 505 500650 250500 6 (Gardner)
(Momentive)
8: EPOXIES 199

O CH3 CH3
O section on basic chemistry). Although each phe-
CH2 CH CH2O (CH2) Si O Si (CH2) OCH2 CH CH2
nomenon is complicated and the two are in compe-
3 3
tition during the overall curing process,
CH3 CH3 generalizations and simplified models can be made.
During the initial stage of curing, polymerization is
Structure 8.17 Epoxy-silicone hybrid. favored because in the case of catalyzed homopoly-
merization terminal epoxides are the most reactive,
microelectronic packages. A typical structure is the and in the case of co-reactive agents primary reac-
following: tions are more reactive than secondary ones; the
Some properties are listed in Table 8.9. We note terminal epoxide reactivity already mentioned plays
that the tensile elongation at break is inversely a role too. In most cases the polymerization is an
proportional to the brittleness B of the material addition reaction, and thus follows a rate equation
[3a,4,5,6,7]. for addition polymerization. The molecular weight
of the growing polymer increases until the molecu-
Curing Process, Curatives, and lar weight approaches infinity, so that all monomers
are connected by at least one bond and a network is
Cross-Linking Reactions formed. At this point, called the gel point, the poly-
Epoxy curing involves two phenomena, polymer- mer possesses high molecular weight and few
ization and cross-linking (see also the introductory cross-links, and thus behaves much like a very

Table 8.9 Silicone Epoxies

Properties ASTM Test Molding and

Method Encapsulating
Compound
Melt flow (gm./10 min.) D1238
Melting temperature, °C Thermoset
Tm (semicrystalline)
Tg (amorphous)
Processing temperature range, °F. (C 5 compression; C:350
T 5 transfer; I 5 injection; E 5 extrusion)
Molding pressure range, 103 p.s.i. 0.41.0
Mold (linear) shrinkage, in./in. D955 0.0050.006
Tensile strength at break, p.s.i. D638 5008,000
Elongation at break/% D638 60
Tensile yield strength, p.s.i. D638
Compressive strength (rupture or yield) p.s.i. D695 28,000
Flexural strength (rupture or yield), p.s.i. D790 17,000
Izod impact strength, ft.-lb./in. of notch (1/8-in. thick D256A 0.3
specimen)
Hardness shore D2240 A6895
26
Linear thermal expansivity, 10 cm/icm/°C D696 30200
24
Thermal conductivity, 10 J-cm/s-cm °C 2
C177 67
Specific gravity D792 1.21.84
Water absorption 24 hr. (1/8-in. thick specimen), % D570 0.2
Dielectric strength (1/8-in. thick specimen), D149 246500
short time, v./mil
200 HANDBOOK OF THERMOSET PLASTICS

high-molecular-weight thermoplastic. From the gel inappropriate circumstances. Consultation with

point, cross-linking becomes the dominant phenom- established epoxy formulation chemists is rigor-
enon due to the lack of free monomers. Cross- ously advised before indiscriminate changes in
linking involves interchain bonding of intrachain formula or cure conditions are made to effect
reactive sites, either intrachain epoxides or second- property changes.
ary sites on co-reactive agents.
Although cross-linking is a different phenome-
non, the rate of chemical conversion of the epoxide Stoichiometry
groups is unaffected in most epoxy systems. The In the same vein, attention must be paid to the
cross-linking reactions produce a growing network stoichiometric relationships between curing agents
and reduce the mobility of the chain segments. The and resins. Catalytic curatives are added at rela-
growth of the network results in mechanical and tively low levels (0 to 5 phr of resin). Because their
thermal stabilization of the structure, resulting in behavior during cure is truly catalytic, the applica-
increasing modulus and glass transition and degra- tion principles that apply to other catalytic poly-
dation temperatures. At a certain high degree of merizations (e.g. with polyester resins) are the
cross-linking, the increasing molecular weight of same with epoxies.
the structure exceeds the molecular weight for On the other hand, multifunctional co-reactants
which it is thermodynamically stable as a rubber, require that the user address the stoichiometric bal-
and the material transforms into a glass, a process ance between the reacting species. An epoxy for-
called vitrification. In a glassy state, the mobility of mulator will often establish the correct reactive
reactants is severely restricted, reducing the rate of ratio and supply the system accordingly. Many
the reaction to a diffusion-controlled reaction, users, however, develop individualistic recipes
which is much slower. Further conversion is still and must therefore be able to calculate and opti-
possible, however, the rate is much slower since mize the proportions of curatives and resins. An
the process relies on diffusion rather than mobility example of a simple stoichiometric calculation
to bring the reactants together. When the cross- for DGEBA and a typical polyamine is shown in
linking reaction exhausts all the reactive sites avail- Table 8.10.
able, the resulting structure is hard (high modulus) Often a commercial curing agent’s chemical
and insoluble due to a high degree of interchain structure is kept proprietary or the amount of reac-
bonding. tive functional group is ambiguous. In such cases,
The conversion of epoxy resins from the ther- the vendor provides an amine or active hydrogen
moplastic state to tough, hard, thermoset solids equivalent from which an appropriate mix ratio can
can occur via a variety of cross-linking mechan- be calculated. It is also important when performing
isms. Epoxies can catalytically homopolymerize stoichiometric balances to be aware of reactive
or form a heteropolymer by co-reacting through groups that may be bifunctional (e.g. anhydride,
their functional epoxide groups with different olefin).
curatives. In epoxy technology, curatives are most Experience has determined that a precise stoi-
frequently called curing agents. Often the terms chiometric balance does not always produce a
hardener, activator, or catalyst are applied to spe- cured resin system having optimized properties.
cific types of curing agents. It is advisable to Consequently, a formulator will run experiments to
distinguish clearly between true catalytic curing establish the variance of properties of interest with
agents that participate in the cross-linking via the mix ratio. Figure 8.2 shows such a variance. Note
traditional chemical concept of catalysis, and mul- that the optimum level of TETA is about 12.5 phr,
tifunctional cross-linking agents that become almost exactly the theoretical value calculated in
chemically bound in the final three-dimensional Table 8.10. It is not uncommon, however, for the
structure. The latter, therefore, can strongly influ- mix ratio to vary by 80 to 110% of theoretical.
ence the properties of the end plastic. Too often The selected and optimized ratio will subsequently
this fact is overlooked or not understood, causing be published in data sheets or on package labels for
non-optimized formulations to be used under the user’s convenience, or the vendor will
8: EPOXIES 201

Table 8.10 Example of a Stoichiometric Calculation

Resin: DGEBA
Amine Curative: Triethylene Tetramine (TETA)
H2N(CH2)2NH(CH2)2NH(CH2)2NH2
Molecular weight of amine:
6 carbons 5 6 3 12 5 72
4 nitrogens 5 4 3 14 5 56
18 hydrogens 5 18 3 1 5 18
----
Molecular weight 5 146
There are 6 amine hydrogens functionally reactive (bolded) with an epoxy group. Therefore
146 grams/mol 5 24.3 grams/equivalent
6 equivalents/mol
Thus, 24.3 grams of TETA are used per equivalent of epoxy. If the DGEBA has an equivalent weight of 190 (380 g/mol/2 eq./mol), then
24.3 grams of TETA are used with 190 grams of DGEBA, or 24.3/190 5 12.8 grams of TETA per hundred grams of DGEBA.

Table 8.11 Variation of Hardness with Mix Ratio

120 6
Volume resistivity at 115°C

Weight Ratio Barcol Shore

Deflection temperature,°C

110 DETA 5 Versamid Hardness Hardness

ohm cm x 10–10

125/ERL- Impressor Durometer

100 4 2795 Model A
GYZJ-935
90 3
TET 40/60 6065 —
80 2 50/50 2025 —
1 60/40 — 90
70
8 9 10 11 12 13 14 65/35 — 85
Phr of curing agent
70/30 — 50
Figure 8.2 Effect of concentration of DETA and 75/25  30
TETA on deflection temperatures of DGEBA [8].
80/20 5

prepackage the resin and curing agent in an appro-

class includes Lewis bases, primary and secondary
priate volumetric or weight proportion.
amines and amides, and other nitrogen-containing
Earlier, the ambiguousness of establishing an
compounds.
accurate equivalency was mentioned. Such a situa-
tion arises, for example, with aminopolyamides,
whose structure is too complex to determine the Alkaline Curing Agents
number of hydrogens that will coreact with oxirane
rings. Table 8.11 shows the variance of hardness Lewis Bases
obtained with a wide spread of curing agent levels. Lewis bases contain an atom with an unshared
The final use ratio is selected, in these cases, based electron in the outer orbital. The main types of
on the best combination of desired cured-resin Lewis bases used in epoxy resin chemistry are ter-
properties. tiary amines. They catalyze epoxy polymerization
Epoxy curing agents can be divided into two if some hydroxyl-containing molecules are present
major classes: alkaline and acidic. The alkaline (Scheme 8.3).
202 HANDBOOK OF THERMOSET PLASTICS

O O
–
R3N + CH2 CH R3N+ + CH2 CH CH2CH –CH2CH—
–
O O

CH2 CH

Scheme 8.3 Tertiary amine catalyzing epoxy polymerization.

Primarily used in adhesives, laminating, and The hydroxyls formed are further reactive, how-
coatings, the tertiary amines are widely used as ever, the tertiary amine is generally too sterically
accelerators for acid anhydride and aromatic amine hindered to contribute much to the cure.
curing agents. They are rarely used at more than Aliphatic amines constitute the largest group of
1.5 phr unless they are used for low-temperature epoxy curing agents. They can be used as is or
curing of epoxy adhesive formulas, in which case adducted to modify volatility, toxicity, reactivity,
they may be used as high as 15 phr. Excess tertiary and stoichiometry. They are characterized by short
amine does degrade cured-resin properties. pot lives and high exotherms. They are skin sensiti-
Many of the popular tertiary amines contain zers, and some can cause respiratory difficulties.
hydroxyl groups for enhanced reactivity. Examples Aliphatic amine curing agents can add to the
of tertiary amines include tris(dimethylamino- yellowing of epoxy thermosets when exposed to
methyl)phenol (DMP-30), dimethylaminoethanol ultraviolet light during weathering. In thin films,
(S-1), diethylaminoethanol (S-2), benzyldimethyla- the lower amines may also exhibit whitening with a
mine, α-methylbenzyldimethylamine, and triethyl- hazy appearance on the film surface caused by the
and trimethylamine. reaction of primary amine groups with atmospheric
Cured systems behave similarly to aliphatic carbon dioxide to form incompatible amine
amines in large masses: the more steric hindrance carbonates.
of the nitrogen, the less reactive the catalyst. Primary amines can be used as latent curing
A tertiary amine salt (DMP-30 tri-2-ethyl hexoate) agents via reaction with a ketone (MEK, MIBK) to
has been used in electrical applications because of form the ketimine derivative, which is reasonably
improved resistance to humidity and good metal adhe- stable in admixture with epoxy resin. When exposed
sion. Chemical resistance, however, is poor, and all to atmospheric moisture in thin films, the ketimine
properties drop rapidly with increasing temperature. readily hydrolyzes to regenerate the amine and
ketone. The amine proceeds to cure the resin, and
Primary and Secondary Aliphatic the volatile ketone vaporizes from the film.
Amines The most common aliphatic polyamines are those
that belong to the following homologous series:
The epoxyprimary amine reaction is in Scheme diethylene triamine (DETA), triethylenetetramine
8.4: (TETA), and tetraethylene pentamine (TEPA).
The epoxysecondary amine reaction is in Typical properties are shown in Table 8.12. Systems
Scheme 8.5: cured with these three curing agents generally have
OH
similar properties, particularly electrical and chemi-
O
RNH2 + CH2 CH R’
H
RNCH2 CHR’
cal resistance. Another common aliphatic amine,
diethylaminopropylamine (DEAPA), provides more
Scheme 8.4 Epoxy-primary amine reaction. pot life than the DETA types, and even requires
some heat to complete the cure. DEAPA-cured resins
OH are softer with lower heat deflection temperatures.
OH O
H CH2 CH R’ Trimethyl hexamethylene diamine (TMD) is
RNCH2 CHR’ + CH2 CH R’ RN another useful aliphatic diamine. Compared to other
CH2 CH R’
aliphatic amine curing agents, it is characterized by
OH longer pot life and improved light stability, flexibil-
Scheme 8.5 Epoxysecondary amine reaction. ity, and chemical resistance in cured products.
8: EPOXIES 203

Table 8.12 Comparative Mechanical Properties of DETA and TETA-Cured Epoxy Castings at 25°C

Property DETA (1011 phr) TETA (1314 phr)

Heat deflection temperature/°C 95124 98124
Flexural strength, psi 14,50017,000 13,90017,700
25
Flexural modulus, 3 10 psi 5.05.4 4.44.9
Compressive strength, psi 16,500 16,300
Tensile strength, psi 11,400 11,400
Elongation at break/% 5.5 4.4
Izod impact strength, ft-lb/in. of notch 0.4 0.4
Hardness, Rockwell M 99108 106

TMD is often used in combination with other amine Piperidine (Structure 8.18) has one active hydro-
curing agents. gen for reaction, however, the resultant tertiary
amine has sufficient catalytic strength to promote
Amine Adducts continued polymerization of epoxy.
Adduction of DETA-type curing agents reduces (CH2)
4
their volatility, alters the reaction rate, and/or HN
CH2
increases the mix ratios. The oldest adduct is the (CH2)
4
product of DETA and DGEBA. It provides a short-
er cure time because the adduct is a partially Structure 8.18 Piperidine.
reacted substance with added hydroxyls. Thus, less
It provides long pot life and lower exotherm
reactant in a more accelerated reaction is required
with other properties equivalent to the aliphatic
to reach the gel point.
polyamines. Its toxicity has, however, made it the
Other types of adducts are based on ethylene and
subject of governmental restrictions that have sig-
propylene oxides and alkylene polyamines. Exam-
nificantly limited its use.
ples are N-(2-hydroxypropyl)-ethylenediamine and
N-Aminoethylpiperazine (Structure 8.19) contri-
ethylene oxide/DETA. These adducts tend to be
butes improved impact strength when compared to
more hygroscopic, calling for careful storage. They
the DETA series of hardeners.
are not recommended for casting applications but
do perform well in laminating and patching kits. (CH2)
2
Amine-terminated polyglycols appeared first in H2N (CH2) N
2
NH
the early 1970s to introduce flexibility into the (CH2)
2
three-dimensional cross-linked structure of epoxies.
A series of bi-, tri-, and tetrafunctional polyoxypro- Structure 8.19 N-Aminoethylpiperazine.
pylene amines was commercialized. While provid-
ing for increased flexibility, they also increase pot Although gel time and exotherm are also compa-
life and decrease viscosity of formulations without rable, a post-cure of 38° to 66°C (100° to 150°F) is
the attendant age hardening that accompanies the required for complete cure.
use of nonreactive flexibilizers. Menthanediamine (Structure 8.20) makes proces-
sing easier through reduced viscosity of resin
Cyclic Amines mixtures.
Some applications require only intermediate
cured-resin properties between the aliphatic and CH3
H3C
aromatic amines. The cycloaliphatic amines fill this C NH2
gap. The four major cycloaliphatics are piperidine, H2N CH3
N-aminoethylpiperazine (AEP), menthanediamine,
and m-xylylenediamine (MXDA). Structure 8.20 Menthanediamine.
204 HANDBOOK OF THERMOSET PLASTICS

It improves temperature resistance as compared under ambient temperature is achieved through use
to the aliphatics. Its properties are not as good, of an accelerator (a phenol, tertiary amine salt, sal-
however, as the aromatics. icylic acid) or in combination with another amine
m-Xylylenediamine (Structure 8.21) yields the such as trimethylhexylene diamine.
same properties as menthanediamine but contri-
butes hardly any color to formulations.
Aromatic Amines
CH2 NH2 Aromatic amines generally contribute the best
CH2 NH2 properties of the amine-cured epoxies. Specifically,
they increase temperature and chemical resistance,
Structure 8.21 m-Xylylenediamine. extend pot life (although exotherms remain high),
and always require heat for cure. In addition, in
It is popularly used in so-called “water-white” recent years many aromatics have become increas-
castings. Table 8.13 shows some general properties ingly scrutinized and regulated by government
of the cycloaliphatic amines. agencies because of their potential health hazards.
Isophorone diamine (IPD, Structure 8.22) is a In some instances, it has been guilt by association
unique type of curing agent in that its structure con- because of their structural resemblance to aniline-
tains both a primary cycloaliphatic amine group based suspect carcinogens. One formulator has mar-
and a primary aliphatic amine group. keted an adducted aromatic amine that is reported
to minimize toxicity with minimal loss in proper-
CH3 ties. In any case, the reader is advised to consult
NH2 with vendors regarding the current hazard status
CH3 and proper handling procedures before use.
The three major aromatics are as follows
CH3 CH2NH2 (Structures 8.23, 8.24, and 8.25):
Structure 8.22 Isophorone diamine (IPD).

Because the aliphatic amine group (methylene- NH2

bridged) is considerably more reactive than the NH2

ring-attached group, this material lends itself well
to B-staging applications. Complete cure with IPD Structure 8.23 MPDA.

Table 8.13 Mechanical Properties of Cycloaliphatic Amine-Cured Epoxy Resins

Piperidine Aminoethyl Menthanediamine Meta-

piperazine xylylenediamine
Heat deflection 75110 100120 148158 130150
temperature/°C
Flexural modulus, 4.36
psi 3 1025
Flexural strength, psi 13,50015,500 15,50017,500
Compressive 13,00016,000 8,700 10,500 15,200
strength, psi
Tensile strength, psi 7,0009,500 9,000 9,000 10,600
Ultimate elongation, % 6.08.5 8.8 2.9 6.7
Izod impact strength, 0.30.5 1.01.2 0.30.4
ft-lb/in. of notch
Rockwell M hardness 9096 95105 105
8: EPOXIES 205

H2N CH2 NH2

DADS have been adducted with styrene oxide, phe-
nyl glycidyl ether, cresyl glycidyl ether, and low-
Structure 8.24 MDA. molecular-weight DGEBA. Accelerators such as
phenols or organic acids, (e.g. salicylic) are added
O
to the adduct to promote ambient temperature
H2N S NH2
cures. The adducts are usually dark in color and
high in viscosity. They tend to produce brittle films
O
unless nonreactive diluents such as dibutyl phthal-
Structure 8.25 DADS. ate or benzoyl alcohol are added to reduce viscosity
and flexibilize the formulation.
Because of their reduced reactivity, these materi- A series of composites has been formulated
als lend themselves to formulations that are easily using new novel bisimide amines (Structure 8.26)
B-staged. Typically, these B-stage systems are as the epoxy curative. These curing agents have the
stable at room temperature for months. Molding following structure
compounds, tape adhesives, and laminating pre-
pregs are key applications for such formulas. O CF3 O

MPDA contributes cured resin temperature resis- C C C

H2N Ar N N Ar NH2
tance of 150° to 177°C (300° to 350°F) as com- C CF3 C
pared to 93° to 107°C (200° to 225°F) for O O
aliphatics. It is a skin and clothing stainer and must
Structure 8.26 Bisimide amine curing agent.
be melted into resins. MDA’s properties are some-
what less than MPDA, however, because its polar-
ity is less, it contributes improved dielectric Typical amines used include DADS and MDA in
constant and loss factor. DADS yields the highest the Ar structure. The increased aromaticity creates
heat deflection temperature of the aromatic amines. higher temperature and improved moisture resis-
With proper selection of resin, systems resistant to tance over current epoxy/graphite systems.
204°C (400°F) are common.
A series of eutectic blends of MPDA and MDA Polyamides
has been commercialized, and there are many
blends with proprietary additives to retard crystalli- The polyamides used to cure epoxies are amino-
zation. This tends to maintain hardener liquidity polyamides (Structure 8.27). The literature also
and allows one to mix resin and hardener at lower refers to them as amidopolyamines. They are fun-
temperatures. This step then extends pot life and damentally dimerized or polymerized fatty acids
improves handling. Table 8.14 lists typical proper- that have been co-reacted with various aliphatic
ties of aromatic amine-cured epoxy. amines such as ethylenediamine, DETA, TETA,
Aromatic amine adducts have also been prepared and TEPA (where R 5 other dimer units and amine
for the coatings industry. MPDA, MDA, and units).

Table 8.14 Properties of Aromatic Amine-Cured Epoxy Resins

Property MPDA MDA DDS Eutectic

Heat deflection temp., °C 150 144 190 145
25
Flexural modulus, psi 3 10 4.0 3.9 4.4
Flexural strength, psi 15,500 17,500 17,900 16,400
Compressive strength, psi 10,500 10,500 10,500
Tensile strength, psi 8,000 8,100 8,550 8,000
Elongation at break/% 3.0 4.4 3.3 4.8
Izod impact strength, ft-lb/in. of notch 0.20.3 0.30.5 0.5
Rockwell M hardness 108 106 110 105110
206 HANDBOOK OF THERMOSET PLASTICS

O Typical are 2-ethyl, 3-methyl, and 2-ethyl-4-methyl

H H
(CH2) C N (CH2) NR imidazoles (Structure 8.29).
7 2
O
H H
(CH2) C N (CH2) NR N
7
2 CH CH3
CH3CH2 C CH2
(CH2) CH = CH (CH2) CH3
2 4 N
H

(CH2) CH3
5 Structure 8.29 Imidazole.
Structure 8.27 Aminopolyamide.
Heat is required for full cure of these systems,
The resultant molecules are very large and con- and the final resin exhibits high temperature, elec-
tain varying levels of primary and secondary amine trical, and chemical resistance.
hydrogens, reactive amides, and carboxyl groups,
all of which can contribute to epoxy curing.
Establishment of mix ratios is thus more a function Acid-Curing Agents
of property selection than of stoichiometric balance The acidic class of epoxy curing agents includes
(see the earlier discussion on stoichiometry). Lewis acids, phenols, organic acids, carboxylic acid
Formulations made from these polyamides are the anhydrides, and thiols.
bases of “user-friendly” systems because the toler-
ances on mix ratio are very broad. Although the resul-
tant properties do vary, these systems find application Lewis Acids
in uses that do not require optimized, highly specific Lewis acids contain empty orbitals in the atomic
properties; for example, in two-tube household glues outer shell. Metal halides, like zinc, aluminum and
where ease of mixing volumetrically is more impor- ferric chlorides, and adducted BF3 compounds
tant than maximum shear strength. (e.g. BF3-monoethylamine or BF3-etherate) are the
The aminopolyamides introduce considerably most commonly used to cure epoxies. Most Lewis
reduced volatility and dermatitic potential, acids are latent catalysts used in heat-curing
increased flexibility and impact strength, and water stable one-can systems with room temperature
resistance (even to the point of effecting underwa- shelf lives of up to one year. Although the electri-
ter cure). They have poor chemical resistance and cal properties are good, metallic corrosion can
low heat deflection temperature. Principal applica- occur from decomposition by-products, thus pre-
tions are coatings and adhesives with lesser use in cluding them from numerous insulation and encap-
laminates and castings. sulation applications.
Trifluoromethane sulfonic acid (triflic acid) and
Other Amines its salts have been used to catalyze hydroxyl/epoxy
Other amine-containing curatives fall into the reactions for coatings applications. Blocking these
catalytic class of curing agents. Dicydiandiamide acids with selected amines provides extended shelf
(Structure 8.28) has been long popular for use in stability. Heating unblocks the compound and
stable one-can systems. allows the catalysis of the polymerization to pro-
This material is used in catalytic quantities even ceed. Diethylammonium tritiate has co-cured
epoxies with polyols, phenolics, and aminoplasts,
NH as well as homopolymerized DGEBA. As a result,
H2NCNHC N
new one-component, very-high-solids epoxy coat-
ings have been commercialized.
Structure 8.28 Dicydiandiamide.

Phenols
though its breakdown products have been shown to Phenols will react with epoxies, however, they
participate in co-reactive cross-linking. Various are seldom used as the sole curing agents. They
imidazoles have been used for similar applications. perform much better as reactive accelerators for
8: EPOXIES 207

other curing agents. Phenols can etherify epoxies as dimerized and trimerized fatty acids, phthalic,
follows (Scheme 8.6): oxalic, and maleic acid, and carboxy-terminated
polyesters.
OH
O OH OR
R+ C C ROH C C
Cyclic Anhydrides
Scheme 8.6 Phenol etherifying expoxy. The cyclic anhydrides have been used most suc-
cessfully with epoxy resins. Ring opening is
Typical phenols are phenol-formaldehyde resoles effected by the presence of active hydrogens pres-
and novolacs and substituted phenols. ent as hydroxyls or water, or by a Lewis base
(Scheme 8.8).
Organic Acids Anhydrides are the second largest curatives for
epoxies and are especially suited for electrical insu-
Organic acids are infrequently used alone as cur- lation applications. While they are not skin-sensitiz-
ing agents. The reaction mechanism is the key to ing, their vapors can be irritating. The liquid
the utility of the acid anhydrides. The esterification anhydrides are easily blended into epoxy resins.
proceeds as follows (Scheme 8.7): The solid anhydrides, on the other hand, need heat
and extremely good mixing for proper blending.
O O O OH
Formulations have low viscosity, long pot life, and
COH + C C COC C
low exotherm. They have higher temperature resis-
tance than the aliphatic amines, although not as
Scheme 8.7 Esterification by organic acid.
good as some of the aromatic amines. Elevated
temperature cure and post-curing are generally
The alcoholic hydroxyl that is formed can etheri- required.
fy as described for the phenols. Both the esterifica- Because of the competing esterification and
tion and etherification reaction are temperature etherification reactions, cure schedules are often
dependent. High temperatures promote ester forma- detailed and relatively complex. Consideration
tion, and low temperatures promote ether forma- must be given to gel time/temperature, post-cure
tion. Steric considerations, such as position of the time/temperature, presence or absence and type of
oxirane ring and nature of the carboxyl group, will accelerator, amount of hydroxyl groups present,
also influence the course of these reactions. anhydride/epoxy (A/E) ratio and stoichiometry, and
Tertiary amines tend to enhance esterification and amount of free acid.
retard etherification. Tertiary amines are the most favored accelera-
When organic acids are used, they act as accel- tors, typical ones being BDMA and DMP-30,
erators like the phenols. Typical acids include which promote esterification, as mentioned earlier.

O
COH

COH
O
O O O OH
2O
H

C
+ C C C O C C
O
O
C RO
H COH
O

C OR

Scheme 8.8 Ring opening with Lewis base.

208 HANDBOOK OF THERMOSET PLASTICS

Acid accelerators, like BF3 complexes, phenols, Dodecenylsuccinic anhydride (DDSA, Structure
and dibasic acids, promote etherification. These 8.33) is another easily mixed liquid anhydride. The
considerations strongly influence the optimization dodecenyl group contributes added flexibility and
of the A/E ratio and thus the cured resin properties. impact resistance to systems. In addition, this anhy-
Phthalic anhydride (PA, Structure 8.30), the least dride yields the most outstanding electrical resis-
expensive anhydride, is used where formulation tance properties of this class of curatives. It has a
cost is of primary importance and overall perfor- high equivalent weight, so to optimize cost vs.
mance is secondary. properties, it is frequently admixed with other
anhydrides.
O
C
O O
C CH3 (CH2) CH C
11
O O
H2 C C
Structure 8.30 PA. O

Structure 8.33 DDSA.

It is used in laminates, castings, and pottings,
and provides medium-range heat deflection tem-
peratures. PA sublimes readily and must be reacted Tetrahydrophthalic and maleic anhydrides
quickly with resin. It yields low exotherms in the (ATHA and MA) are primarily used in anhydride
production of large castings. blends. The ATHA can cause darkening of cured
Hexahydrophthalic anhydride (HHPA, Structure resins, but contributes to lower cost while yielding
8.31) is a low melting solid providing good properties similar to HHPA. MA by itself produces
general-purpose properties. very brittle systems. In blends, however, it contri-
butes to compressive strength with some loss in
tensile and flexural strength.
O
Pyromellitic dianhydride (PMDA, Structure
C
O
8.34) is a high melting solid of limited solubility in
C epoxies. Blending with other anhydrides is common
O in order to facilitate incorporation into formula-
tions. PMDA 1 MA blends exhibit heat deflection
Structure 8.31 HHPA. temperatures around 250°C (480°F). This curing
agent is one of the earliest dianhydrides developed
In electrical encapsulation and filament winding, it to maximize temperature resistance by significantly
adds resilience without significant loss in mechanical increasing cross-link density. Tensile and flexural
properties. It does not sublime like PA, and epoxy strengths are reduced as a result, but electrical
mixtures have lower viscosities combined with long properties are maintained.
pot life, low exotherm, and very light color.
Nadic methyl anhydride (NMA, Structure 8.32), O O
is also used in electrical laminating and filament C C
winding. It is a liquid easily blended into resins. O O
C C
Cured products have light color, excellent arc resis-
O O
tance, and high heat deflection temperature.
Structure 8.34 PMDA.
O
C Two other high-melting solid anhydrides that
CH2
O provide high-temperature-resistant epoxy systems
CH3 C
are trimellitic anhydride (TMAh, Structure 8.35)
O
and benzophenonetetracarboxylic dianhydride
Structure 8.32 NMA. (BTDA, Structure 8.36).
8: EPOXIES 209

O O formed by the adduction reaction of maleic anhy-

HOC C dride with a liquid polybutadiene containing a high
O level of terminal unsaturation. Thus, anhydride
C
groups are positioned along the poly-BD chain
O
(Structure 8.38), yielding a polyanhydride that, in
Structure 8.35 TMAh. admixture with an epoxy resin, produces a high
degree of cross-linking.
O O Such curing agents are characterized by low-cure
O
C C temperatures (120° to 130°C) with shorter cure
C
O O times and enhanced toughness properties (i.e. high-
C C
er impact resistance while maintaining or improv-
O O ing hardness and Tg). These two package systems
Structure 8.36 BTDA. yield initial mix viscosities in the 800 to 2000 cen-
tipoise range and workable pot lives up to 3 to 4
hours, depending on operating temperature. RTM
They have found wide use in molding powders
injection, composite fabrication, and filament wind-
and prepreg for laminating. Heat deflection tem-
ing are among established uses for these systems.
peratures of 200° to 300°C (390° to 570°F) are
Many of the solid anhydrides can be blended
common.
into eutectic liquids for improved mixing into resin
Chlorendic anhydride (Structure 8.37) is the
formulas. The eutectics may be liquid at room or
major halogenated anhydride for incorporation of
near-room temperature. Examples include a 70/30
flame resistance into cured systems. It contains
mix of chlorendic and HHPA, a 75/25 NMA/
57% chlorine, yet holds good electrical and
ATHA, and a 50/50 DDSA/HHPA, all of which
mechanical properties to its heat deflection temper-
have melting points below 25°C (77°F). Table 8.15
ature (200°C or 390°F).
describes some generalized properties of various
CI O
anhydride-cured epoxies. Figure 8.3 compares the
relative reactivity of anhydride curing agents to
CI C
those of the other curing agents described here.
CI C CI O
CI
C Polysulfides and Mercaptans
CI O Several liquid polysulfide polymers have been
Structure 8.37 Chlorendic anhydride. available for curing and modifying epoxies for
many years. They have the general structure:
Another anhydride curing agent of the aliphatic
HS C2 H4 OCH2 OC2 H4 SS
ð Þn
type that has achieved some degree of commercial
use is maleinized polybutadiene. This product is 
C2 H4 OCH2 OC2 H4 
SH

C C
C= O
C C

C C C C C C C
C C C C C = C C

C C C
C C C
n

Structure 8.38 Polybutadiene chain.

210 HANDBOOK OF THERMOSET PLASTICS

Table 8.15 Mechanical and Electrical Properties of Anhydride-Hardened Epoxy Resins

Property DDSA PA HHPA NMA PMDA/ Chlorendic

(130 phr) (75 phr) (80 phr) (80 phr) MA 17/ (110 phr)
23
Heat deflection 6670 110152 110130 150175 225 145190
temperature/°C
Flexural 3.8 4.02 4.01 4.4 4.2 5.2
modulus,
psi 3 1025
Flexural strength, 13,500 16,000 18,800 14,000 10,940 17,000
psi
Compressive 10,600 22,000 16,800 18,300 46,000 20,500
strength, psi
Tensile strength, 8,100 11,800 11,400 10,000 3,670 12,000
psi
Elongation at 4.5 4.8 7.4 2.5 0.9 2.6
break/%
Izod impact 0.30.4 0.46 0.30.4 0.48 0.34
strength ft-lb/in
of notch
Rockwell M 100 105 111 109 111
hardness
Dielectric 3.1/2.8 4.0/3.5 4.0/3.5 3.15/3.0 3.73/ 3.4/3.0
constant 3.34
60/106 cps
Dissipation factor .001.01 .001/.02 .007/.02 .002/.02 .007/ .003/.02
60/106 cps 026

These end groups are mercaptan terminated and the property goals, but many additives, reactive and non-
end groups are sufficiently acidic to create a gel, reactive, can be included for further optimization. The
but generally not strong enough to complete cure. epoxy resin formulator’s skill lies in his/her ability to
Consequently, they are added as reactive modifiers effect the appropriate handling, curing, processing,
to other curing agent formulas. They impart impact and property tradeoffs needed by deftly manipulating
resistance and toughness, increased flexibility, and the plethora of potential recipe ingredients.
reduced shrinkage. Table 8.16 describes a typical epoxy formula-
Polymercaptans can cure at temperatures as low tion. By adjusting the type and quantity of ingredi-
as 240°C (240°F), allowing them to be used in ents in the table, the formulator can create systems
adhesive formulations requiring rapid cure, such as that vary from stable free-flowing molding powders
bonding of highway markers (where traffic must be to highly viscous caulks and adhesives to clear,
allowed to resume in a matter of hours) and repair water-thin, castable liquids. With the conclusion of
and patch kits (so-called 5-minute systems). our summary of resins, curatives and catalysts, we
next briefly review the remaining ingredients.
Formulation Principles
Epoxy resins have achieved their commercial suc- Epoxy-Containing Reactive Diluents
cess due in no small way to their amenability to a Epoxy-containing reactive (diluents are either
variety of formulating techniques. Not only can differ- low-viscosity epoxy resins or monoepoxides. They
ent resins and curatives be brought together to achieve are called reactive because the epoxide moieties will
8: EPOXIES 211

24
22
20
72-96 hours 6 months
18
Pot life honrs (1 lb mass)

16
14

12
10
Primery amine

Polyamide
Tertiery amine

6
4
2

0
Aliphatic amine Aromatic amine Heterocyclicc amine Anhydride Lewis acid

Figure 8.3 Pot life of curing agent/diglycidyl ether of bisphenol-A (DGEBPA) [9].

Table 8.16 Typical Epoxy Formula

Monoepoxides are often skin sensitizers, yet

provide very effective viscosity reduction at low
Resin Side Curative Side
Epoxy resin(s) Curing agent(s)
concentrations. They can adversely affect final
physical properties. Figure 8.4 shows viscosity
Epoxide-containing reactive Catalysts and reductions obtainable from typical monoepoxides.
diluents Accelerators
Table 8.19 shows the effect of diluents on the prop-
Non reactive diluents and erties of a DGEBA 1 TETA system.
resinous modifiers

The low-viscosity epoxies (e.g. butadiene diox-
Fillers (reinforcing and/or ide, resorcinol diglycidyl ether) are used at higher
non-reinforced)

concentrations to get equivalent viscosity reduction.
Colorants (pigments and These diluents do not degrade properties at normal
dyes)

use levels and can, in some cases, even improve
selected final properties. In recent years, toxicologi-
Rheological additives
(thixotropes, viscosity cal problems have been uncovered with regard to
suppressants)

some of the traditional resins (e.g. vinylcyclohex-
ene dioxide) and they have been discontinued.
Property promoters (wetting
agents, adhesion promoters,
flame retardant additives)

Resinous Modifiers
Processing aids (deaerating Resinous modifiers include poly(vinyl chloride)
agents, mold release (PVC), polyesters, polyurethanes, silicones, furfur-
agents)


als, acrylics, and butadieneacrylonitrile resins.


In one-can systems, both sides are combined together and are Coal tar and phenolic modifiers are also used.
stored under shelf-stable conditions until ready for use. These materials are added to impart or enhance



May be commonly added to either or both sides provided no
interfering reactions can take place.
specialized properties. Often the property enhance-
ment of the modified epoxy is a direct result of the
react with the curing agents and their presence must contribution of a characteristic property of the
be accounted for in the stoichiometric analysis. added modifier resin. In some instances, the modi-
Tables 8.17 and 8.18 list commercial DGEBA resins fying resin is sufficiently low cost and can act as
that have been pre-diluted with reactive diluents. an extender in the formula.
212 HANDBOOK OF THERMOSET PLASTICS

Table 8.17 Low-Viscosity Diluted Resins

Products EEW Viscosity Color, Max Diluent

(mPa  s) 25°C
D.E.R. 324 (Dow 195204 600800 1 (Gardner) Alkyl glycidyl ether
Chem. Co.)
Araldite GY506 175189 500700 1 (Gardner) BGE-12%
(Huntsman)
Araldite GY507 180192 500700 3 (Gardner) CGE
(Huntsman)
Araldite GY509 189200 500700 1 (Gardner) Epoxide 7
(Huntsman)
Epon 815C 180195 500700 1 (Gardner) BGE-12%
(Momentive)
Epon 813 180200 500700 75 (Platinum CGE
(Momentive) Cobalt)
Epon 8132 195215 500700 1 (Gardner) Epon 828/Heloxy 8
(Momentive) blend
Epotuf 37130 175185 500700 2 (Gardner) BGE-12%
(Reichhold)
Epotuf 37137 175950 500700 3 (Gardner) CGE
(Reichhold)
NOTE: These resins are similar to the D.E.R. 331 resin diluted with a reactive diluent to reduce viscosity. This permits easier laminating
and/or higher filler loading for cost reduction. The resins are suitable for most general purposes where use temperatures will not exceed
200°F and are generally used with polyamine or polyamide hardeners.

Table 8.18 Medium-Viscosity Diluted Resins

Products EEW Viscosity (mPa  s) 25°C Color, Max Diluent

Araldite GY502 (Huntsman) 232238 2.13.6 3 10 3
3 DBP
Epon 824 (Momentive) 192204 4.07.0 3 10 3
1
Epon 8131 (Momentive) 245275 1.11.6 3 10 3
5 Heloxy 505
Epon 8161 (Momentive) 200214 1.82.4 3 10 3
1
NOTE: General comments on utility of PGE-containing resins same as for D.E.R. 330 and D.E.R. 331 resins, but the PGE introduces
greater toxicity and dermatitis problems. The DBP-modified resins are generally suitable for uses only at ambient temperatures, are cured
with polyamines and polyamides, and are generally softer, less brittle, and less solvent resistant than 100% reactive resins.

Among the many properties affected by resinous can be sufficiently mobile that they can ulti-
modifiers are flexibility, toughness and impact mately migrate out of the polymerized mass. Such
strength, peel strength, adhesion to substrates, and migration is of long duration and controllable to
chalk resistance of coatings. some degree. The benefits of adding nonreactives
may often offset the migration problem. Primary
benefits include viscosity and cost reduction, ex-
Nonreactive Diluents tension of pot life, and decrease in exotherm.
Nonreactive diluents are the equivalent of sec- Consistent with plasticization in other plastics, the
ondary plasticizers used with vinyls. They do not nonreactives tend to degrade mechanics, electrical,
participate in the cross-linking reaction and, in fact, and resistance properties as their concentration
8: EPOXIES 213

butyt glycidyl ether

8000 Aliphatic C.,–C., monoglycidyl ether
Cresyl glycidyl ether
Neopentyl glycol diglycidyl ether
7000

6000

5000

Viscosthy. cps

4000

3000

2000

1000

5 10 15 20 25 30
Diluent. percent by weight

Figure 8.4 Comparison of diluent efficiencies [10].

increases. Typical nonreactive diluents include general effects of some commonly used fillers in
monomelic styrene, bisphenols, hydrocarbon oils, epoxies.
and phthalate ester plasticizers like dioctyl and Silver coated glass spheres have been used to
dibutyl phthalate. replace very expensive powdered silver and gold to
create electrical conductivity in epoxy systems. On
a volume basis, the use of these spheres can pro-
Fillers
vide equivalent conductivity at one-twentieth the
Fillers play a primary role in epoxy resin formu- cost of silver. Table 8.21 compares the electrical
lation. Reinforcing fibers such as glass, graphite, conductivity of various metals and filled conductive
and polyaramid improve mechanical properties to epoxies. Table 8.22 compares the thermal conduc-
such an extent that epoxies can be used in many tivity of metals, oxides, and filled conductive
structural applications. Non-reinforcing fillers epoxies.
include powdered metals (electrical and thermal Polyvinylidene chloride (PVDC) microspheres
conductivity), alumina (thermal conductivity), silica are used as a low-cost syntactic foam filler. They
(cost reduction, minor strength enhancement, reduc- react, however, with amines and melt if the
tion of wear rates), mica (electrical resistance), talc exotherm gets too high. Recent work has produced
and calcium carbonate (cost reduction), barium sul- a series of PVDC spheres that is stable if blended
fate (barites, density control), and carbon and in the resin first and castings are limited to 1.5
graphite powders (lubricity). Increasing filler con- inches of thickness. Comparative costs of micro-
tent generally increases viscosity and makes proces- spheres versus other fillers are shown in
sing more difficult. Specific gravity usually Table 8.23.
increases, although some fillers like hollow glass or Studies on the addition of fluorinated polymer
phenolic microballoons create syntactic foams of to epoxy show an enhancement of mechanical
significantly reduced density. Table 8.20 shows the and tribological (wear) properties at different
214 HANDBOOK OF THERMOSET PLASTICS

Table 8.19 Effect of Diluent on Properties of TETA-Cured DGEBA

Diluent and Pot Exotherm, Water Flexural DT, Weight

Mixed Life (°C) Absorption, Strength, (°C) Loss in
Viscosity, at Weight (psi) 48 hr at
Centipoises 23°C Increase (%) 200°C (%)
None 40 200 0.73 20,300 120 1.89
Octylene oxide:
1,500 55 205 1.10 14,185 74 5.20
500 72 180 1.18 11,440 65 Unstable
200 100 164 1.04 7,797 58 Unstable
Styrene oxide:
1,500 48 200 0.71 19,403 93 2.39
500 69 193 0.80 18,854 82 4.29
200 84 178 1.06 16,303 70 6.20
3(Pentadecyl)
phenol glycidyl
ether:
1,500 54 164 1.19 14,010 76 2.84
500 68 148 1.48 6,443 55 4.15
Butyl glycidyl
ether:
1,500 55 204 1.01 18,433 101 2.12
500 63 207 1.32 17,237 85 2.72
200 76 193 1.63 16,400 75 3.77
Phenyl glycidyl
ether:
1,500 47 198 1.04 19,717  2.37
500 49 209 1.26 19,523  3.28
200 54 198 1.35 19,600  4.93
Cresyl glycidyl
ether:
1,500 46 202 0.98 22,067 92 2.98
500 46 204 1.24 20,000 78 4.40
200 51 201 1.35 15,230 63 6.58

concentrations. The introduction of fluorinated poly control of structure, particle size, and reinforcement
(aryl ether ketone) in particular reveals increased characteristics is obtained.
scratch resistance and lowering of both static and
dynamic friction with increased concentration.
The use of synthetic sodium aluminum silicate in Colorants and Dyes
epoxy coatings provides improved opacity over tita- A wide variety of colorants can be used with
nium dioxide. These new silicates are prepared by epoxies. Dyes are less frequently used because of the
the reaction of aluminum sulfate and sodium sili- natural tendency of clear epoxies to yellow when
cate as opposed to being mined naturally. Better exposed to ultraviolet light. Some blue dyes are
Table 8.20 Effects of Some Commonly Used Fillers on Properties
Filler Application Effects

Increase Decrease

Thermal Thermal-shock Impact Compressive Arc Machina Electrical Cost Crac Exoth Coeffi Density Setting Shrinkage
conductivity resistance resistance strength resistance bility conduc king erm cient
tivity expan
sion

Bulk fillers:

Sand X X K X X X

Silica X X K X X X

Talc K X X

Clay X X K X X X X

Calcium carbonate K X X X

Calcium sulfate X X K X X X X
(anhydrous)

Reinforcing:

Mica X K X X X

Wollastonite X X K X X

Chopped glass X K X

Wood flour X X X X K

Sawdust X X X X K

Specially:

Quartz X X X X K X

Alumina X X X X K X

Hydrate alumina K X

Li Al silicate X X X X K X

Beryl X X X X K X

Silica aerogel K

Bentonite K

Graphite X K

Powder metals X X X X X X X X X X X

Ceramic spheres K

K: Major use
X: Minor use
216 HANDBOOK OF THERMOSET PLASTICS

Table 8.21 Electrical Conductivity of Metals, diluents) and thixotropic agents. Pyrolitic silicas,
Conductive Plastics, and Various Insulation bentonite clays, and Castor oil derivatives are the
Materials at 25°C most common thixotropes. New hydrophobic fumed
silicas have received much attention as
Specific ρ 5 Volume
stable thickening agents (see Figure 8.5).
Gravity Resistivity
(g/cm3) (ohm cm) New developments in property modification
have been primarily in the areas of improved adhe-
Silver 10.5 1.6 3 1026 sion via nonsilane adhesion promoters (organome-
Copper 8.9 1.8 3 1026 tallics), improved strength-to-weight reinforcing
Gold 19.3 2.3 3 1026 fibers (polyaramids), and improved flame retar-
dants. One study assessed the effect of tris(dibro-
Aluminum 2.7 2.9 3 1026
mopropyl)phosphate and dechlorane on epoxy
Nickel 8.9 10 3 1026 flammability. Table 8.25 shows a number of flame
Platinum 21.5 21.5 3 1026 retardant additives used with or without haloge-
Eutectic — 2030 3 1026 nated epoxies. Organophosphorus polyols can be
solders co-reacted into epoxies to enhance flame retardance
of epoxy prepreg material used to make printed cir-
Good silver- — 1.0 3 1024
filled inks and cuit boards (see Table 8.26).
coatings
Good silver- — 1.0 3 1023
filled epoxy Characterization of Epoxies
adhesives
The properties of epoxy resins can vary over a
Graphite — 1.3 3 1023 wide range depending on the selection of a formu-
Low cost — 1.0 3 1022 lation’s ingredients, their relative proportions, the
silver-filled processing of the formula, and the configuration
epoxy and environment of the final part.
adhesives As with any versatile class of resins (e.g. vinyls,
Graphite or — 102 to 10 polyesters), it becomes difficult to present an all-
carbon-filled inclusive tabulation of the properties for every pos-
coatings sible formulation. Table 8.27ad) presents a sum-
Oxide-filled 1.52.5 10141015 mary of some of the most important properties of
epoxy some basic epoxy configurations. The data allows
adhesives the reader to make some broad stroke comparisons
Unfilled epoxy 1.1 10141015 with similar data of other plastics. Ultimately, how-
adhesives ever, consultation with epoxy formulators and
review of vendor data sheets/literature combined
Mica, — 1016
polystyrene,
with effective and application-specific testing, pro-
and other best vides the most appropriate database from which
dielectrics design decisions can be made.
Some generalizations about epoxy resin proper-
ties are possible. Liquid resins and curatives can
effective in deferring the perception of yellowing.
form low-viscosity, easily modified systems. They
Table 8.24(a,b) lists many of the pigments found
can cure at temperatures from 240°C (104°F) to
acceptable for use in epoxy systems. Most inorganics,
200°C (392°F), depending on the curing agents
except chrome greens, natural siennas and ochers,
used. They exhibit very low shrinkage and do not
and zinc sulfide white, are used. Organic pigments
evolve volatile by-products during cure. Cure sche-
are generally limited to carbon blacks and phthalates.
dules can be varied within wide boundaries to
accommodate different processing methods and
Other Additives applications.
Rheological additives include viscosity depres- Because of the presence of significant polarity,
sants (usually solvents, surface activators, or epoxies wet and adhere exceptionally well with
8: EPOXIES 217

Table 8.22 Thermal Conductivity of Metals, Oxides, and Conductive Adhesives

Thermal Conductivity at 25°C (Btu/hr °F ft


/ft)

Silver 240
Copper 220
Beryllium oxide 130
Aluminum 110
Steel 40
Eutectic solders 2030
Aluminum oxide 20
Best silver-filled epoxy adhesives 1 to 4
Aluminum-filled (50%) epoxy 1 to 2
2 3
Epoxy filled with 75% by wt. Al O 0.8 to 1
Epoxy filled with 50% by wt. Al2O3 0.3 to 0.4
2 3
Epoxy filled with 25% by wt. Al O 0.2 to 0.3
Unfilled epoxies 0.1 to 0.15
Foamed plastics 0.01 to 0.03
Air 0.015
Conversion of Thermal Conductivity Units
g J/cm s °C/cm
2
w/cm2 °C/cm Btu/ft2hr °F/ft Btu/ft2hr °F/in
4.184 4.19 242 2900
0.96 1.0 58 690
22
1.73 3 10 0.0173 1.0 12.0
23 23
1.44 3 10 1.44 3 10 0.083 1.0
Heat transfer formula: k 5 thermal conductivity
q kΔT
x
ΔT 5 temperature drop across material
q 5 heat flow/unit area
x 5 material thickness

many surfaces. Mechanical properties of cast epoxy either. Under some conditions of high heat and
exceed most other castable plastics. Epoxies are humidity (.120°C, 250°F, 95% RH), significant
excellent electrical and thermal insulators. They loss of properties has been recorded. Polymer
can be formulated to resist temperatures as high as breakdown (reversion) as occurs with some sili-
290°C (550°F). They are selectively resistant to a cones and polyurethanes is, however, quite rare.
broad range of environments and chemicals. They As mentioned earlier, it is nearly impossible to
are highly resistant to caustics, oils, and many sol- present an exhaustive account of physical properties
vents with fair acid resistance. Chlorinated hydro- for any material. Despite this, for the remainder of
carbons and some organic acids will attack epoxy this section we provide the reader with some back-
systems. Epoxies discolor when exposed to ultravi- ground on measurement apparatuses that are useful
olet energy. They tend towards brittleness but can in determining thermal and physical properties of
be toughened at lower use temperatures (.104°C, epoxies. This discussion of experimental techniques
200°F). Many epoxies and curing agents are skin applies just as well to other similar classes of mate-
sensitizers. Although they are not the most expen- rials. However, we provide specific emphasis on
sive of thermosets, they are not the least expensive these techniques as relevant to epoxies.
218 HANDBOOK OF THERMOSET PLASTICS

Table 8.23 Comparative Costs of Fillers and Extenders

Name Specific Gravity (g/ml) Cost ($/lb) Volume Cost ($/ft3)

Typical resin 1.2 0.70 52.40
Glass fiber 2.5 0.75 117.00
Expanded PVDC microsperes 0.032 6.62 13.22
Hollow glass spheres 0.15 1.64 15.35
Solid glass spheres 2.48 0.33 51.07
Calcium carbonate 2.7 0.04 6.74
Aluminum trihydrate 2.4 0.25 37.44
Phenolic microballoons 0.17 3.75 39.78

Table 8.24(a) Applicability of Colorants to Epoxy Resins

Application Key
4  Recommended 3-Applicable
2 - Limited conditions 1-Economy, low quality

Table 8.24(b) Applicability of Colorants to Epoxy Resins

Pigment Type Shades Applicability Rating

Violets, maroons, and reds
Cadmium sulfoselenide1 Maroon to light red 4
Quinacridone Maroon to medium red 4
Bon (2B-Ca salt) Maroon to light red 3
Bon (28-Mn salt) Maroon to light red 4
Lithol rubine Bluish red 2
Ba and Ca lithols Maroon to light red 2
Pigment scarlet Bluish red 4
2
Thioindigoid Maroon 3
PTA toners Violet to medium red 2
Red lake C Light red 1
Pyrazolone Light red 3
Naphthol Light red to dark red 3
Iron oxide Maroons and brick reds 4
High molecular weight desazo red Medium to light red 2
Vat reds Medium reds 2
Orange and yellows
Cadmium sulfoselenide3 Orange to very light yellow 4
4
Chrome yellow Medium to very light yellow 4
(Continued )
8: EPOXIES 219

Table 8.24(b) (Continued)

Pigment Type Shades Applicability Rating

5
Chrome orange Yellowish to red orange 3
6
Molybdate orange Orange and orange red 3
Vat colors Oranges and yellows 2
Benzidine yellow Light yellow 4
Benzidine yellow, xylidide Light to deep yellow 4
Nickel-azo (“greengold”) Greenish yellow 4
7
Strontium yellow Very light yellow 4
Zinc chromate Light yellow 4
8
Ni-Ti yellow Very light yellow 4
Iron Oxide Reddish to yellow tan 4
Greens and blues
Phthalocyanine9 Blue and green 4
PTA/PMA toners Blue and green 2
Chromium oxide Dull green 4
Hydrated chromium oxide Bluish green 4
Chrome green Dark bluish to light yellow-green 4
Pigment green B Dark green 3
10
Iron blue Dark blue 4
Ultramarine Blues and violets 2
Indanthrone Blue 4
Cobalt blue Blue 4
White
Titanium dioxide, rutile White 4
Titanium dioxide, anatase White 4
Zinc oxide White 4
11
Antimony oxide White 4
Blacks and browns
Channel black Jet black 4
Furnace black Black 4
Lamp black Bluish black 4
Iron oxide Brown and black 4
Bone black Black 4
Soluble dyes
Oil soluble
Azo Yellow to red (red) green, 2
Anthraquinone blue, black, brown
(Continued )
220 HANDBOOK OF THERMOSET PLASTICS

Table 8.24(b) (Continued)

Pigment Type Shades Applicability Rating

Acetate dyes Wide range 2
Basic dye bases Wide range 1
1
Discolors with S or Cu metal contact.
2
Varies within class.
3
Discolors in contact with copper.
4
Stains with sulfide.
5
Stains with sulfide.
6
Stains with sulfide.
7
Sulfide-stable.
8
Sulfide-stable.
9
The very red shades of blue crystallize in aromatics.
10
Color destroyed in reducing atmosphere.
11
Mostly used as flame proofer with Cl and Br.

0 Heat of Reaction
Due to the high potential energy of the ring-
10 strained epoxide groups in the uncured resin, there
is a large Gibbs function difference associated with
20
the ring-opening reaction. Since the Gibbs function
change (ΔG) is expressed in the form of both
enthalpic (ΔH) and entropic (ΔS) contributions,
30
the reaction is called exergenic. Although structural
changes will result in a significant entropy change,
40 the enthalpy change is the dominant effect. That
Sag value (mW)

change in this case results in the evolution of ther-

60 mal energy or heat, an exothermic reaction. Since
the opening of the epoxide rings have much higher
60 energy (and enthalpy) differences than the other
reactions, the amount of heat evolved and the rate
70
of evolution will correspond to the number of epox-
ide groups reacting and the rate of the reaction.
Reactions that generate heat are studied by calo-
80 rimetry. Many types of calorimeters exist, although
only a few are appropriate for polymerization reac-
90 tions. The standard technique for quantitative eval-
uation is the measurement of the change in
100 enthalpy using Differential Scanning Calorimetry
(DSC) since the heat flow during a constant pres-
1 2 3 4 5
sure reaction is defined as the change in enthalpy
Weight % loading
of the system.
New hydrophobic fumed silica Two types of DSCs are available, a heat-flux
120 m2/g hydrophobic fumed silica
Hydrophilic fumed silica
DSC (based on the Boersma [12] design) and a
220 m2/g hydrophobic fumed silica power-compensation DSC. The heat-flux DSC,
Defribrillated asbestos shown in Figure 8.6, measures the difference in
Treated clay temperature between a sample and reference heated
at a programmed rate in a common oven using ther-
Figure 8.5 Sag values of epoxy sealants after mocouples attached to the bottom of the sample
aging 4 weeks as a function of loading [11]. holders. The power-compensation DSC [13,14], in
8: EPOXIES 221

Table 8.25 Flame-Retardant Additives for Epoxy Resins

Additive Level Manufacturer

Needed (%)
Phosphorus
compounds
Triphenylphosphine 510 BASF Wyandotte, M&T Chemical
Tris-β-chloroethyl 510 Stauffer Chemical
phosphate
Hydrates
Alumina trihydrate 2025 Alcoa, Kaiser, Reynolds, others
Halogenated
compounds
Octabromobiphenyl 2025 White Chemical
Decabromobiphenyl 2025 Velsicol
Decabromobiphenyl 2025 Dow Chemical, Great Lakes Chemical, Saytech
Dechlorane 2030 Hooker Chemical
Synergists

Antimony oxide 210 Chemetron, Harshaw, M&T Chemical, McGean, NL
Industries, Nyacol, Samincorp
Zinc borate 210 U.S. Borax & Chemical Corp.
Molybdic oxide 57 Climax Molybdenum Co.


Used in conjunction with other flame-retardant additives.

Table 8.26 Flame Retardance of FR-T in Epoxy Resin Castings
(various sources)

Flame Retardant FR-T (wt%) UL-94 Rating Average Burn LO1

TBBP-A Times (sec)
None None Burn  19.8
0 26 V-O 1.8 32.7
7 9 V-O 1.4 34.3
7 5 V-O 2.5 31.0
14 0 V-O 3.8 30.4


Castings cured with Nadie® methyl anhydride/phthalic anhydride (2/1), Trademark of Allied Corporation.



ASTM D2863

Figure 8.7, employs separate heating elements and calculated differently. Since the heat-flux DSC
thermocouples for sample and reference applying measures the temperature difference between the
separate currents to the heaters to maintain a null sample and reference cells, calculation of the heat
difference in the temperature. flow requires an accurate temperature and sample
Both types of DSC instruments generate plots of dependent thermal resistance value of the system as
heat flow as a function of the programmed temper- a proportionality factor [15]. The power-
ature. However, due to the difference in measure- compensation DSC also requires a thermal resis-
ment techniques, the heat flow ordinate value is tance value; however, that value represents the
Table 8.27(a) General Properties of Epoxies

Materials Properties ASTM Test Method Epoxy

Casting Resins and Compounds
Unfilled Silicafilied Aluminum-filled
Processing 1a. Melt flow (gm./10 min.) D1238
1. Melting temperature, °C.
Tm(semicrystalline) Thermoset Thermoset Thermoset
Tg (amorphous)
2. Processing temperature
range, °F
(C 5 compression;
T 5 transfer:
I 5 injection; E—extrusion)
3. Molding pressure range,
103 p.s.i.
4. Compression ratio
5. Mold (linear) shrinkage, D955 0.0010.010 0,00050.008 0.0010.005
in./in.
Mechanical 6. Tensile strength at break, D638 400013,000 700013,000 700012,000
p.s.i.
7. Elongation at break/% D638 36 13 0.53
8. Tensile yield strength, D638
p.s.i
9. Compressive strength D695 15,00025,000 15,00035,000 15,00033,000
(rupture or yield), p.s.i.
10. Flexural strength (rupture D790 13,00021,000 800014,000 850024,000
or yield), p.s.i.
11. Tensile modulus, D638 350
103 p.s.i.
12. Compressive modulus. D695
103 p.s.i.
13. Flexural modulus. D790
103 p.s.i. 73°F.
 200°F. D790
250°F. D790
300°F. D790
14. Izod impact strength, D256A 0.21 0 0.30.45 0.41.6
ft.-lb/in. of notch (1/8-in. thick
specimen)
15. Hardness Rockwell D785 M80110 M85120 M5585
Shore/Barcol D2240/ D2583
Thermal 16. Linear isobaric D696 4565 2040 55
expansivity/(1026/°C)
17. Deflection temperature D648 115550 160550 190600
under flexural load, °F.
264 p.s.i.
66 p.s.i. D648
18. Thermal conductivity, 18.8 1428 62104
1024 J.-cm/s-cm2-°C. C177
Physical 19. Specific gravity D792 1.111.40 1 62.0 1.41.8
20. Water absorption (1/8-in. D570 0.080.15 0.040.1 0.14.0
thick specimen).
% 24 hr.
Saturation D570
21. Dielectric strength D149 300500 300550
(1/8-in. thick specimen),
short time, v./mil
Table 8.27(b) General Properties of Epoxies

Materials Properties ASTM Test Epoxy

Method Casting Resins and Compounds
Flexibilized Cycloaliphatic
Processing 1a. Melt flow (gm./10 min.) D1238
1. Melting temperature, °C.
Tm (semicrystalline) Thermoset Thermoset
Tg (amorphous)
2.Processing temperature range, °F.
(C 5 compression; T 5 transfer:
I 5 injection; E 5 extrusion)
3. Molding pressure range, 103 p.s.i.
4. Compression ratio
5. Mold (linear) shrinkage, in./in. D955 0.0010.010
Mechanical 6. Tensile strength at break, p.s.i. D638 200010,000 800012,000
7. Elongation at break, % D638 2085 210
8. Tensile yield strength, p.s.i. D638
9. Compressive strength (rupture or yield), p.s.i. D695 100014,000 15,00020,000
10. Flexural strength (rupture or yield), p.s.i. D790 100013,000 10,00013,000
3
11. Tensile modulus, 10 p.s.i. D638
3
12. Compressive modulus, 10 p.s.i. D695 1350 495
3
13. Flexural modulus. 10 p.s.i. 73°F. D790
200°F. D790
250°F. D790
300°F. D790
14. Izod impact strength, ft.-lb./in. of notch (1/8-in. thick D256A 2.35.0
specimen)
 15. Hardness Rockwell D785
Shore/Barcol D2240/D2583 Shore
06589
Thermal 16. Linear isobaric expansivity/(1026/°C) D696 20100
17.Deflection temperature under flexural load,°F. D648 73250 200450
264 p.s.i.
66 p.s.i. D648
24 2
18. Thermal conductivity, 10 J.-cm/s-cm -°C. C177
Physical 19. Specific gravity D79 0.961.35 1.161.21
20. Water absorption (1/8-in. thick specimen) in %, 24 hr. D570 0.270.06
D570
21. Dielectric strength (1/8-in. thick specimen), short time, v./mil D149 235400
Table 8.27(c) General Properties of Epoxies

Materials Properties ASTM Epoxy

Test Bisphenol Molding Compounds Sheet Molding Compound (SMC)
Method
Glass Fiber- Mineral Filled Low-Density Glass Fiber- Carbon Fiber-
Reinforced Glass Sphere- Reinforced Reinforced
Filled
Processing 1a. Melt flow (gm./ D1238
10 min.)
1. Melting
temperature, °C.
Tm (semicrystalline) Thermoset Thermoset Thermoset Thermoset
Tg (amorphous)
2. Processing C: 300330 C: 250330 C: 250300 C: 250330 C: 250330
temperature range, T: 280380 T: 250380 T: 250300 T: 270330 T: 270330
°F.
(C 5 compression;
T 5 transfer:
I 5 injection;
E 5 extrusion)
3. Molding pressure 15 0.13 0.12 0.52.0 0.52.0
range, 103 p.s.i.
4. Compression ratio 3.07.0 2.03.0 3.07.0 2.0 2.0
5. Mold (linear) D955 0.0010.008 0.0020.010 0.0060.010 0.001 .001
shrinkage, in./in.
Mechanical 6. Tensile strength at D638 500020,000 400010,800 25004000 20,00035,000 40,00050,000
break, p.s.i.
7. Elongation at D638 4 0.52.0 0.523.0
break/%
8. Tensile yield D638
strength, p.s.i.
9. Compressive D695 18,00040,000 18,00040,000 10,00015,000 20,00030,000 30,00040,000
strength (rupture or
yield), p.s.i.
10. Flexural strength D790 800030,000 600018,000 50007000 50,00070,000 75,00095,000
(rupture or yield),
p.s.i.
11. Tensile modulus, D638 3000 350 20004000 10,000
103 p.s.i.
 12. Compressive D695 650
modulus, 103 p.s.i.
13. Flexural modulus, D790 20004500 14002000 500750 20003000 5000
103 p.s.i.
73°F. D790
200°F. D790 15002500
250°F. D790
300°F. D790 12001800
14. Izod Impact. D256A 0.310.0 0.30.5 0.150.25 3040 1620
ft-lb./in. of notch
(


in. Slick
specimen)
15. Rockwell D785 M100112 M100M112
Hardness
Shore/Barcol D2240/ B: 5565 B: 5565
D2583
Thermal 16. Linear isobaric D696 46209 84736 50 13
expansivity/(1026/°C)
17. Deflection D648 225500 225500 200250 550 550
temperature/°F under
flexural load
264 p.s.i.
66 p.s.i. D646
18. Thermal D177 16.741.8 17146 1725 7.17.9 5.96.3
conductivity. 1024 J.-
cm./sec.-cm2-°C
Physical 19. Specific gravity D792 1.62.0 1.62.1 0.751.0 0.10 0.10
20. Water absorption
(1/8-in. thick
specimen). %
24 hr. D570 0.040.20 0.030.20 0.21.0 1.4 1.6
Saturation D570
21. Dielectric D149 250400 250420 380420
strength (1/8-in. thick
specimen), short
time. v./mil
Table 8.27(d) General Properties of Epoxies

Materials Properties ASTM Epoxy

Test Novolak Molding Compounds
Method
Mineral-and- Mineral-and- 60% Glass-Filled,
Glass-Filled, Glass-Filled, Graphite High-Strength
Encapsulation High-Temperature Fiber-
Reinforced
Processing 1a. flow (gm./10 min.) D1238
1. Melting temperature.
°C.
Tm (semicrystalline) Thermoset Thermoset Thermoset Thermoset
Tg (amorphous) 145155 155195
2. Processing C: 280360 T: 340400 C: 290330 C: 290350
temperature range, °F. I: 230350 T: 290330
(C 5 compression; T: 250 380
T 5 transfer;
I 5 injection;
E 5 extrusion)
3. Molding pressure 0.253.0 0.52.5 36 2.55.0
range, 103 p.s.i.
4. Compression ratio 1.52.5 67
5. Mold (linear) D955 0.0040.008 0.0040.007 to max. 0,0002
shrinkage, in./in. 0,0001
Mechanical 6. Tensile strength at D.0638 500012,500 600015,500 20,000 18,00027,000
break, p.s.i.
7. Elongation at break/% D638 0.4
8. Tensile yield strength, D638
p.s.i.
9. Compressive strength D695 24,00048,000 30,00048,000 28,000 30,00038,000
(rupture or yield), p.s.i.
10. Flexural strength D790 10,00021.800 10,00021,800 40,000 50,00070,000
(rupture or yield), p.s.i.
11. Tensile modulus, D638 2100 23002400 6000
103 p.s.i.
12. Compressive D695 660
modulus. 103 p.s.i.
 13. Flexural modulus. D790 14002400 23002400 5500 2.84.2
103 p.s.i. 73°F.
200°F. D790
250°F. D790
300°F. D790
14. Izod impact, ft.-lb./in. D256A 0.30.5 0.40.45 10
01 notch (1/8-in. thick
specimen)
15. Hardness Rockwell D785 M115 R110
Shore/Barcol D2240/ Barcol 7075 Barcol 78 Barcol 6074
D2583
Thermal 16. Linear isobaric D696 1843 35 1.0
expansivity/(1026/°C)
17. Deflection D648 300500 500 500
temperature/°F under
flexural load of 264 p.s.i.
66 p.s.i. D648
18. Thermal conductivity, C177 14130 2434 67
1024 J.-cm/s-cm2-°C.
Physical 19. Specific gravity D792 1.62.05 1.851.94 1.461.50 1.84
20. Water absorption D570 0.040.29 0.150.17 0.4
(1/8-in thick specimen).
% 24 hr.
Saturation D570 0.150.3 0.8
21. Dielectric strength D149 325450 440450 380400
(1/8-in thick specimen),
short time. v./mil
230 HANDBOOK OF THERMOSET PLASTICS

heating elements, not the entire system, and is con- ΔH

stant over a wide operating temperature range [16]. α5 (8.1)
ΔHtotal
The power-compensation DSC maintains the pro-
grammed temperature ramp in both sample and ref-
Alternatively, the difference between the total and
erence, ensuring much better temperature control in
any residual enthalpy changes can be compared to
the sample [17].
the total, where ΔH in Equation 8.1 would be
To determine the extent of a curing reaction or
replaced by (ΔHtotal 2 ΔHresid) [18]. Generally, the
the degree of cure α, the change in enthalpy is
total change in enthalpy is determined using a slow
compared to the total change in enthalpy of the
temperature ramp from a low temperature to a tem-
complete reaction, as illustrated in Figure 8.8.
perature just below the onset of thermal degradation,
as shown in Figure 8.9. There is an equation for the
progress of cure as a function of both temperature
Furnace and time, the progress based on determination of
Sensor disk
Sample
position Reference Pt Covers
(S) position (R)
Purge
gas
entry Pt Thermometers

Sample Reference

Pan Pan

PT 100
sensing
devices
Constantan
thermocouples Individual Heaters
(TC)
Figure 8.7 Schematic of a power-compensation
Figure 8.6 Schematic of a heat-flux DSC. DSC.

26.5

26.4
Heart flow endo up (mW)

26.3
A B

26.2

26.1

26.0
0 5 10 15 20 25 t 30 35 40 45 50 55 60
Time (min)

Figure 8.8 An example of a DSC thermogram showing the portion of the total reaction as measured by the
enthalpic exotherm (reacted at time t).
8: EPOXIES 231

either complex viscosity (see below) or the storage the total enthalpy measurement, as shown in the
modulus (also see below) [19]. chronogram in Figure 8.11 and the thermogram in
The enthalpic reaction changes are measured Figure 8.12. Although the value is reported as the
during isothermal measurements, as shown in degree of cure, it should be understood that the
Figure 8.10. Or, if residual enthalpies are used, actual degree of cure is not necessarily equal to this
then an isotherm is followed by a similar ramp as value since an assumption has been made that the

68.0

66.0

64.0

62.0

60.0
Heat flow (mW)

58.0

56.0

54.0

52.0

50.0

48.0

46.0

44.0

100.0 150.0 200.0 250.0 300.0

Temperature (°C)

Figure 8.9 An example of a DSC thermogram showing the total ΔH from a slow temperature scan.

62.8
62.6
62.4
62.2
62.0
Heat flow (mW)

61.8
61.6
61.4
61.2
61.0
60.8
60.6
60.4
60.2

50.0 100.0 150.0

Time (minutes)

Figure 8.10 An example of a DSC thermogram showing a series of isothermal measurements.

232 HANDBOOK OF THERMOSET PLASTICS

total enthalpy represents complete or 100% The rate of the curing reaction can be deter-
conversion. mined from the isothermal data used to determine
The reaction rate dα/dt is related to the heat the degree of cure. Since the enthalpy change is
flow dH/dt by the relationship (Equation 8.2): plotted as a function of time, the rate of change in
time dH/dt will represent the rate of the reaction.
dα 1 dH Non-isothermal methods are abundant, utilizing
5 (8.2)
dt ΔH total dt a single temperature scan run to monitor reaction
enthalpic change [20], as in Figure 8.13, or using a
series of scans with different rates, as shown in
Figure 8.14. These are advantageous due to the
shorter time to run the experiments and avoidance
300 of estimation of the lost area at the beginning of
Heating
50 Temperature ramp the isothermals. However, non-isothermal experi-
200
Isotherm ments are generally less accurate than isothermal
Head flow endo up (mW)

100
ones.

Temperture (°C)
40
0
30
Isotherm Residual
–100 Molecular Weight, Segment
20
Reaction enthalpy
Heat flow
enthalpy –200 Mobility, Cross-Link Density,
–300 and Glass Transition
10 –400
Epoxy curing involves an increase in both linear
5 –500 molecular weight and cross-link density, both of
5 10 20 30 40 50 60 70 80 85
which result in reduced chain segment mobility.
Time (min)
Increasing the linear molecular weight or cross-link
Figure 8.11 A DSC chronograph showing the density of a polymer chain increases the position of
complete process of determining residual enthalpy, the glass transition temperature Tg, as shown in
including a fast ramp to temperature, a hold time at Figure 8.15. Many thermosetting polymer systems
the isothermal temperature, a quench to low exhibit a relationship between the Tg and the degree
temperature, and a slow temperature scan. of chemical conversion [21]. Most amine-cured

53.0

52.5

52.0
Heat flow (mW)

51.5

51.0

50.5

50.0
Onset 178.3 °C

49.5 Peak 244.65 °C

ΔM –92.6 j/g

125.0 150.0 175.0 200.0 225.0 250.0 275.0

Temperature (°C)

Figure 8.12 An example of a DSC thermogram showing the measurement of residual cure, or residual
enthalpy in a partially cured sample; in this case the sample was cured for 200 minutes at 160°C.
8: EPOXIES 233

68.0
66.0
64.0
62.0
60.0
Heat flow (mW)

58.0
56.0
54.0
52.0
50.0
48.0
46.0
44.0
100.0 150.0 200.0 250.0 300.0
Temperature (°C)

Figure 8.13 An example of a DSC thermogram of a ΔH scan (at 5 K/min) from which the rate of the reaction
can be calculated using a single scan model.

66.0

64.0

62.0

60.0 Peak 196.08 °C

ΔM –557.44 J/g

58.0
Heat flow (mW)

56.0

54.0

52.0 Peak 218.91 °C

ΔH –563.08 J/g
50.0

48.0

46.0

44.0 Peak 238.42 °C

ΔH –499.33 J/g
42.0

125.0 150.0 175.0 200.0 225.0 250.0 275.0 300.0

Temperature (°C)

Figure 8.14 A series of DSC thermograms at different scanning rates (5, 10, and 20 K/min), from which a
time-dependent rate can be calculated.

epoxy systems exhibit a linear relationship, which Descriptions of this shift are modeled as a func-
implies that the change in molecular structure with tion of chemical structure [2427], as well as in
conversion is independent of the cure temperature terms of extensive theoretical treatments based on
[22]. Such a Tg shift, in many circumstances, gives either free volume [2835] or time-dependent
better resolution than exothermic enthalpy changes relaxation [3645] are abundant in the literature.
[23], especially at high and low degrees of cure. Evidence for free volume models comes primarily
234 HANDBOOK OF THERMOSET PLASTICS

41
Half Cp Extrapolated = 178.132 °C

40 Delta Cp = 0.031 J/g °C 150C

Onset = 170.048 °C

39

38
Head flow endo up (mW)

Half Cp Extrapolated = 151.474°C 120C

37
Data Cp = 0.487 J/g°C
Onset = 149.282 °C
36

35

34

33
130 135 140 145 150 155 160 165 170 175 180 185
Temperature (°C)

Figure 8.15 A DSC thermogram showing the difference in Tg of two identical samples cured at different
temperatures.

from the pressure dependence of Tg in both heat capacity between the rubber and the glass
Thermomechanical Analysis (TMA) [46] and DSC [54]. Since this shift is an effect of the heat capac-
[47] measurements, whereas relaxation effects can ity change, resolution of the glass transition can be
be seen in the frequency dependence of Dynamic increased by calculating and plotting the constant
Mechanical Analysis (DMA) [48] as well as the pressure heat capacity (Cp). The Cp curve is calcu-
effect of scanning rate in most thermal analysis lated by comparing the heat flow (or differential
techniques. The Tg can be measured by a variety of power supplied), a baseline, and a reference mate-
techniques, each with certain advantages and disad- rial, usually sapphire, as described in an ASTM
vantages depending on the material and conditions. standard (see ASTM E1269-90) [55]. A power-
Comparisons of techniques show that while sensi- compensation DSC has a long-term energy calibra-
tivity to transitions may vary [49], the value of the tion stability, hence the sapphire measurement is
Tg is similar, given appropriate conditions unnecessary if the curve is available in the software
(Figure 8.15) [50]. or has been run before, provided that the DSC has
been properly calibrated using a high purity heat of
Differential Scanning Calorimetry fusion standard such as indium [48].
The versatility of DSC to measure both
The most often used, but less accurate than other exotherms and Tgs is also a limitation; when mea-
methods of determining the Tg of polymers, is DSC suring an uncured or a partially cured thermoset, a
[51]. The Tg is taken as the temperature at the residual exotherm follows the Tg being measured
inflection point (peak of derivative curve) [52] of sometimes even overlapping it (Figure 8.16).
the baseline shift in heat flow or as the temperature More accurate Tg calculations require stable
at the half-height shift in baseline heat flow. In baselines before and after the transition and the
situations where the Tg is distorted or masked by curing exotherm interferes with the upper baseline.
other events, like curing exotherms or enthalpic In these cases, the Tg can only be determined as the
relaxations, the Tg may be determined by the onset, onset.
but results should be noted as onset values to avoid
confusion. For consistency in reporting, ASTM
standard E1356-91 has been established [53]. Temperature-Modulated DSC
The shift in baseline heat flow associated with An alternative to the measurement of Cp is
the glass transition is a result of the difference in Temperature-Modulated DSC (TMDSC). TMDSC
8: EPOXIES 235

52.5

52.0

51.5
Heat flow (mW)

Onset 102.698°C
51.0

50.5

50.0

49.5

50.0 75.0 100.0 125.0 150.0 175.0

Temperature (°C)

Figure 8.16 An example of a DSC thermogram with the curing exotherm occurring right after the Tg, distorting
both measurements.

utilizes a modulated temperature ramp, much like

dynamic mechanical analysis uses a dynamic force
and dielectric relaxation analysis uses an alternating
current. TMDSC is a derivative of an earlier tech-
Temperature

nique, Alternating Current (AC) Calorimetry. AC

Calorimetry utilizes an oscillating heating ramp,
accomplished by the use of an auxiliary pulsed heat
source (usually a chopped laser) over the linear pro-
grammed heating ramp, to measure the Cp during
the single run experiment. Analogous to Dynamic
Mechanical Analysis (DMA) and Dielectric
Analysis (DEA), TMDSC mathematically deconvo-
lutes [56] the response into two types of signals, an
in-phase and an out-of-phase response to the modu- Time
lations, as well as producing an average heat flow,
which is analogous to the DSC signal using a linear Figure 8.17 Sine wave temperature modulations
heating ramp. There are two primary methods of [58].
performing TMDSC, sinusoidal and square wave
modulation.
The first method, introduced by Reading [57], The two methods can be described by a single
utilizes a sinusoidal modulation superimposed over temperature function (Equation 8.3):
the traditional linear heating ramp or isotherm,
shown in Figure 8.17. The other method, intro- 4 XN ð21Þn21 sin½ð2n 2 1Þω0 t
TðtÞ 5 T0 1 β 0 t 1 T0
duced by Schawe [59], utilizes square wave modu- π n51 ð2n 2 1Þ
lations, as shown in Figure 8.18. (8.3)
236 HANDBOOK OF THERMOSET PLASTICS

including relaxations, crystallizations, and curing

exotherms.
Schawe’s technique [15,63,64] uses a linear
response approach, which includes a dependence on
the phase lag between the signal and response. His
Temperature

approach also begins with the total heat capacity

(CpT 5 hav/qav) and includes a Cp value calculated
as the ratio of the heat flow amplitude to the heat-
ing rate amplitude. However, his value is called the
complex heat capacity (CP
5 Ah/Aq). The reason
for the difference is that from this value, he pro-
poses a separation of the complex heat capacity
(CP
) into two components, real and imaginary
(Equation 8.4):
Time
CP
5 C0P 1 iCvP (8.4)
Figure 8.18 Square wave temperature modulations
[59].
Here, CP0 represents the real, in-phase compo-
nent, termed storage heat capacity, and CPv repre-
sents the imaginary, out-of-phase component,
Here, T0 is the initial temperature, β0 is the called loss heat capacity. The two values are calcu-
underlying heating rate, Ta is the amplitude of the lated using the phase angle (ϕ) between the signal
temperature modulation, and ω0 is the angular fre- and response (Equations 8.5 and 8.6):
quency [60]. In the special case of sinusoidal mod-
ulation, the first harmonic would dominate the C 0P 5 Re½CP
 5 jCP
jcosϕ (8.5)
series.
Although the modulations are related and can be CvP 5 Im½CP
 5 jCP
jsinϕ (8.6)
described by a single function (Equation 8.3), the
methods of evaluation of the signal developed by Hutchinson and Montserrat [65] have evaluated
Reading and Schawe are quite different. Both meth- the various types of modulations based on sine and
ods use a Fourier transform to produce an average square waves and the methods of evaluation and
heating rate (qav), an average heat flow (hav), an constructed a single parameter model to explain
amplitude of heating rate (Aq), an amplitude of and predict the signals generated in TMDSC.
heat flow (Ah), and a phase angle between the heat- As in DMA and DEA measurements, the storage
ing rate and heat flow (ϕ) [61]. However, Reading signal will include the elastic or in-phase response
and Schawe use these values in different ways to of the material, which in this case will be the
calculate the values of the components. molecular level responses, including glass transi-
Reading’s technique [62] produces three values. tions and meltings. The loss signal represents vis-
The total heat flow (HT 5 hav/qav) is usually cous or out-of-phase events, which are the kinetic
expressed as the total heat capacity (CpT) represent- effects, such as stress relaxations, crystallizations,
ing the response to the overall average heating and curing. The total heat capacity is the average
ramp, which is similar to what would be observed signal, which is equivalent to the heat capacity sig-
in linear DSC heat capacity measurements. The nal produced by traditional DSC.
“reversing” component (Cprev 5 Ah/Aq) represents
the ratio of the amplitude of the heat flow to the
amplitude of the heating rate. These two signals are Thermomechanical Analysis
subtracted to yield the “non-reversing” component The Tg can also be measured accurately using
(Cpnrv 5 CpT 2 Cprev). The reversing component thermomechanical analysis (TMA). TMA is the
represents thermally reversible events, such as Tgs measurement of changes in linear or volumetric
and meltings, whereas the non-reversing component dimension as a function of temperature or time
will represent thermally irreversible events, [66]. The Tg appears as an abrupt increase in slope
8: EPOXIES 237

6.78
Glass transition in TMA
6.75

Probe position (mm)

6.70

6.65

Onset X = 163.993 °C
Onset Y = 6.6358 °C
6.60

6.58
60 80 100 120 140 160 180 200 220 240 260
Temperature (°C)

Figure 8.19 An example of a TMA thermogram showing the change in slope of the expansion, or linear
displacement with temperature, with the onset of change in slope representing the Tg.

in the linear thermal expansion curve, shown in Dynamic Mechanical Analysis

Figure 8.19, with the Tg indicated as the calculated Applied
Force Response
onset of the change in slope, as described in ASTM
standard E1545-95a [67]. Volumetric measurements
are performed using a dilatometry cup fitted with a
movable piston. The volume changes are directly
proportional to the linear movement of the piston, Phase Lag
by simple geometry. In addition to the sensitivity
of the technique to the Tg [4], the linear or volu- Figure 8.20 SignalResponse for DMA
metric change in dimension with temperature gives measurements.
insight into molecular structure. The slope of the
dimensional change as a function of temperature is
the isobaric thermal expansivity, as defined by allow the application of a dynamic force in addition
ASTM E228-95 [68]. to the static force of TMA, just as TMDSC allows
TMA instruments employ a low voltage differen- a modulated temperature signal over the linear tem-
tial transducer (LVDT) to measure dimensional perature ramp of DSC.
changes against the probe tip, producing resolution As shown in Figure 8.20, the phase lag between
of linear changes in micro- to nanometer scale. A the applied dynamic force and the response yields a
TMA instrument must be calibrated for height complex modulus, which can be mathematically
using dimensionally precise quartz standards, as separated into storage or in-phase elastic response
well as temperature from the melting (collapse) of E0 and loss or out-of-phase viscous response Ev
a high purity standard such as indium, as described (Equation 8.7):
in ASTM standard E1363-97 [69].
σ

E
5 E0 1 iEv 5 (8.7)
s

Dynamic Mechanical Analysis
Epoxies undergo changes in mechanical behavior The Tg can be measured quite accurately using
as a function of cure. In addition to the shift in Tg, dynamic mechanical analysis (DMA), which can in
there are changes in the viscoelastic behavior [38] the case of highly filled or highly cross-linked poly-
due to both polymerization and cross-linking. mers give better resolution and more information
Dynamic Mechanical Analysis (DMA) instruments than DSC [70] and better reproducibility than older
238 HANDBOOK OF THERMOSET PLASTICS

techniques, such as Vicat softening (ASTM D1525- Thermally Stimulated Depolarization

96) [13] and deflection temperature (ASTM D648-
Another method to measure the change in Tg and
97) [71] standards [72]. The Tg in a DMA measure-
chain segment mobility during the curing process is
ment is often taken as the peak in tangent delta
based on thermally stimulated depolarization cur-
(E”/E’) [73] while ASTM E1640-94 [74] recom-
rents (TSD, TSC) [3]. TSC is basically a low fre-
mends the peak in the loss modulus. Other methods
quency (1022 to 1024 Hz) dielectric relaxation
include the inflection point or the half height value
study [79]. TSC can be performed in either polari-
of the drop in storage modulus (E’), the onset of
zation (TSP) or depolarization (TSD) mode. TSC
the drop in storage modulus, the onset of increase
involves the polarization of electrets, or dipoles
in loss modulus, and the onset of the increase in
within the polymer chain, making it very sensitive,
tangent delta. A DMA thermogram is shown in
even in copolymers [21], highly cross-linked ther-
Figure 8.21 with storage and loss modulae and tan-
mosets, and filled composites. The sensitivity of
gent delta shown.
TSC, specifically TSD, to molecular motion [80]
DMA (and TMA) measure dimensional changes
and chain segment mobility yields well-resolved Tg
and force responses using a variety of fixtures, each
measurements [81,82]. Also, TSC experiments are
with specific applications and benefits.
not affected by mechanical effects like gelation, as
Applications include tensile, compression or expan-
DMA is. TSC measurements exhibit a time depen-
sion (linear and volumetric), flexural and shear
dence that can be measured as the characteristic
[75]. Specialized techniques for shear measure-
Debye [83] relaxation time, which is analogous to
ments include torsional pendulum [76], torsional
the DMA retardation or phase lag time [43,8488].
braid analysis (TBA) [77], and torsional impreg-
A series of relaxation times [89] can be used to cal-
nated cloth analysis (TICA). A DMA instrument
culate the compensation point, which is the conver-
must be calibrated for temperature, height, and
gence of the frequency-dependent relaxation times,
force. The temperature calibration is described by
much like extrapolation to zero heating rate in DSC
ASTM E1867-97 [78] using the melting tempera-
or zero shear in DMA. TSP measures the polariza-
ture of a high purity standard. Height is determined
tion or absorption of charge by the polymer as a
using a quartz height standard. Force motor calibra-
function of time or temperature, whereas TSD stud-
tion is performed by balancing standard weights.
ies the depolarization or release of stored charge in

Figure 8.21 A DMA thermogram using 3-point bending fixtures, showing all the signals used to calculate
the Tg.
8: EPOXIES 239

a polarized sample. TSD is more useful in curing ratio of shear stress (τ) to shear strain rate (dγ/dt,
studies than TSP, hence, emphasis is on TSD. Equation 8.8):
Shifts in the Tg as a function of conversion can be
evaluated in a similar fashion as shifts in DSC. π
η5 dy
(8.8)
Samples are cured at a certain temperature for a dt
certain time. Then, they are quenched and the Tg
determined during a controlled heating ramp, with Viscosity measurements are performed routinely
Tg values plotted as a function of curing conditions on liquids using a variety of methods, including
(time and temperature). capillary, concentric cylinder, cone and plate, and
In TSD a sample is quickly heated to a poling many other viscometers. These techniques are well
temperature where an electric field of predeter- suited to measurements of liquids from low viscos-
mined strength is applied through parallel plates for ity fluids, such as water (1023 Pascal seconds), to
a specific time. For thermosets, the poling tempera- higher viscosity ones, such as syrup (102 Ps), and
ture will be at the curing temperature and the pol- even some polymer melts (102 to 107 Ps). However,
ing time will be a part of the curing time. After measurement of very high viscosity materials from
poling, the sample is quenched to a relatively low heavy pitch (109 Ps) to window glass (1021 Ps) is
temperature, maintaining the electric field. At the beyond the range of most shear measurements.
selected low temperature, the electric field is dis- These high viscosity materials can be studied using
continued and the circuit is shorted to dissipate any DMA. However, DMA measures mechanical or
residual static charges. The sample is heated from Young’s modulus (E), rather than the shear modu-
this low temperature to a temperature higher than lus required for viscosity computation. Young’s
the poling temperature at a slow, controlled rate modulus (E) is related to shear modulus (Gs) by
and any current discharged is measured using a sen- either the Poisson ratio (ν)48 or the bulk modulus
sitive picoammeter (sensitive to 10215 Amperes or (KB) [91], given by Equation 8.9:
107 electrons per second) and plotted against tem-
perature. The TSD temperature program is depicted E 5 2Gs ð1 1 vÞ 5 3KB ð1 2 2vÞ (8.9)
graphically in Figure 8.22. A typical TSD current
thermogram is shown in Figure 8.23. The Poisson ratio, also called the lateral strain
contraction ratio, relates the change in lateral strain
to the longitudinal strain. We note that Equation
Chemoviscosity
8.9 is only an approximation for viscoelastic mate-
The conversion induced change in viscosity, rials. It does apply to elastic materials.
known as chemoviscosity, can be used to monitor
conversion (analogous to Tg shift) and the change
Current
of physical state [90]. Since viscosity η describes a Amp3 Cured at 120°C
material’s resistance to flow, it is defined as the
5e–10

Peak 1=4.48112a-10 @ 134.522

4e–10
E field
3e–10
Temperature

2e–10

1e–10

0
60 70 80 90 100 110 120 130 140
Time Temperature °C

Figure 8.22 Temperature program in TSD with Figure 8.23 TSD plot of discharge current as a
applied electric field shaded. function of temperature.
240 HANDBOOK OF THERMOSET PLASTICS

From the moduli and the frequency (ω) of the is not important in kinetics calculations. After the
measurements, the complex viscosity (η
) can be minimum viscosity, the reaction will proceed,
calculated. It can be similarly separated into storage increasing the molecular weight and the relative
and loss components (Equations 8.10, 8.11, 8.12): viscosity. This increase in viscosity, analogous to
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi the rise in Tg used in previous models, is propor-
E
E02 1 Ev2 tional to the increase in molecular weight, and thus
η
5 η0 2 iη0 5 5 (8.10) the kinetics of the reaction [92].
iω ω
Ev
η0 5 (8.11) Gelation
ω
E0 Gelation refers to the point during the curing
η0 5 (8.12) reaction where the molecular weight approaches the
ω
maximum, usually assumed to be infinite. That is,
The frequency of the dynamic signal has a large all monomers are connected to the network by at
effect on the response, as depicted in Figure 8.24. least one chemical bond. While gelation is a micro-
A single frequency series of isothermal DMA scopic effect, it produces macroscopic effects.
measurements of complex viscosity as a function of Microscopic gelation refers to the definition of the
time, shown in Figure 8.25, exhibits the characteris- gelation phenomenon just provided. Since it occurs
tic changes happening during a curing cycle. An at a defined point in polymerization, it will occur at
epoxy prepreg is heated quickly to the isothermal a specific degree of conversion.
temperature resulting in a temperature-dependent Microscopic gelation is difficult to measure since
drop in viscosity. The minimum viscosity will gen- the measurable properties would be solubility and
erally be a function of the isothermal temperature, molecular weight. However, the consequence of
provided that no significant reaction has occurred, exceeding the microscopic gel point is macroscopic
that is, provided that the heating rate is faster than gelation, which is much easier to measure. The
the time scale of the reaction onset. Of course, the macroscopic gel point is a mechanical property and
value of the minimum viscosity will be determined can be identified by common thermal analysis tech-
by the molecular structure of the components of the niques, including in situ testing. Beyond gelation,
prepreg and the effect of the overall mixture. there is no increase in molecular weight, only an
However, usually the relative viscosities (relative to increase in cross-link density and a decrease in free
other isotherms) are used, so that the absolute value chain segment length [93].

0.5774 3.054e+7

0.5
1 Hz 2.500e+7

0.4
Tangent delta 2.000e+7
2 Hz
Modulus (Pa)

0.3
Tan detta

2 Hz 1.500e+7

0.2
1.000e+7
Storage modulus
0.1 1 Hz
5000000

–0.02748 226844
50 60 80 100 120 140 160 180
Temperature (°C)

Figure 8.24 A series of 3-point bending DMA thermograms taken at different frequencies (1 and 2 Hz) and
showing the response as a function of frequency.
8: EPOXIES 241

Gelation does not significantly affect the chemi- adhesion would identify a different point than
cal conversion or curing reaction, so it does not someone concerned with ensuring dimensional sta-
appear in DSC measurements [94]. However, it bility, and different than a researcher interested in
does have a large influence on the mechanical characterizing the physical state of the material.
properties of the polymer. Gelation affects the stiff- The DMA isothermal plot in Figure 8.26 identifies
ness (modulus), adhesion and general processability the gel point using Gillham’s terminology (i.e. the
of thermosets and composite prepregs, so it is peak in tangent delta). As described earlier, DMA
important from an industrial processing standpoint. transitions exhibit frequency dependence. However,
Gelation appears in the complex modulus, tangent since gelation is an isoconversion event, it is fre-
delta and complex viscosity of DMA measure- quency independent. The gel point is therefore
ments; however, as with many thermal events, there defined as the point where the tangent delta
is no unequivocal definition at which point the becomes frequency independent. However, this
gelation occurs. Gillham [95], who first plotted method requires many measurements at different
gelation curves as part of overall time-temperature- frequencies. The gel point can be defined in terms
transformation (TTT) diagrams developed with of viscosity since it represents the maximum
Enns [96,97], defines it as the peak in the tangent viscosity.
delta of a DMA isotherm; this was also adopted
into ASTM standard D4473-90 [98]. Others define
it as the peak in loss modulus. Some define it by Vitrification
the onset or inflection point of the increase in the Vitrification is defined as the point at which the
storage modulus, whereas others define it as the molecular weight or cross-link density of the curing
onset of the plateau of the maximum of the storage polymer exceeds that which is thermodynamically
modulus. A common method has been to use the stable as a rubber, and the material undergoes a
crossover point, which is where the storage and transition from a rubber to a glass, at which point
loss moduli cross, or are equal, and the tan delta is the reaction dramatically slows due to the reduced
equal to unity. However, this has been shown to be mobility of the reactants. The vitrification point can
inaccurate in many cases and can only be used as be measured using DSC, TMDSC, and DMA.
an approximate measure or as a reference conver- Although vitrification is a thermal transition
sion value for a particular system. This discrepancy from a rubber to a glass and does appear in DSC
lies primarily in the application for which the data measurements, the determination of the point and
is being used. Someone concerned with laminate quantification of the shift in baseline heat flow (Cp)

1.17e+10

140C
1.00e+10
120C
180C

8.00e+9
160C
Viscosity (Pa,s)

6.00e+9

4.00e+9

2.00e+9

–5.30e+9
0 50 100 150 200 250 300
Time (min)

Figure 8.25 A series of isothermal 3-point bending DMA plots of the change in complex viscosity as a function
of time.
242 HANDBOOK OF THERMOSET PLASTICS

Figure 8.26 A DMA isothermal 3-point bending plot showing tangent delta from which gel point can be
defined.

Figure 8.27 TMDSC isotherms showing vitrification as half-height drop in storage Cp.

usually occurs around the end of the curing (since from torsional braid analysis (TBA), a specialized
it is a decrease in the reaction rate) and as such is torsional DMA measurement. Gillham defines the
usually masked by the curing reaction exotherm. vitrification in TBA and DMA measurements as the
This is one of the clearest applications of TMDSC highest tangent delta peak below the melt, which
since the curing exotherm appears in the loss Cp usually corresponds to the maximum value of the
and vitrification appears in the storage Cp [1,2]. A storage modulus during an isothermal experiment.
series of isothermal TMDSC plots identifying the Measurement of vitrification in isothermal DMA
vitrification point are shown in Figure 8.27. and TBA studies are common. DMA isotherms can
DMA has been used extensively to investigate demonstrate vitrification points from parallel plate
the vitrification point, and continues to be the most bending modes as shown in Figure 8.28.
common method. The first epoxy timetempera- Vitrification generally occurs when the increasing
turetransformation (TTT) diagram, proposed by Tg equals the cure temperature [54]. Although the
Gillham and Enns [99], was constructed primarily reaction dramatically slows, it is still significant
8: EPOXIES 243

Figure 8.28 A parallel plate DMA isotherm (160°C) with vitrification defined by the second peak in tangent
delta in time.

until the Tg exceeds the cure temperature by 20 to TTT Diagram

40 K. Gel Rubber
The TMDSC and stepscan DSC techniques gen-
erally provide improved accuracy over DMA in Tgult

identifying vitrification points. In contrast, gelation Vi

Cure temperature

tri
is more readily uncovered by the use of DMA. This fic
at
io Gel Glass
combination of techniques allows for the most n
Ge
accurate determination of TTT diagrams for epoxy lat
ion
systems. The separation between the gelation and
vitrification processes is represented in Figure 8.29; Liquid
Tggel
[100] it was obtained by applying both DMA and
TMDSC. As the conditions are varied between cure
timing and temperature, one can either produce a
Tg0
sol glass, gel glass, or gel rubber as possible end
Sol Glass
states.
In time

Figure 8.29 A typical TTT diagram showing

Applications gelation and vitrification curves.

A high degree of cross-linking and the nature of

the interchain bonds give cured epoxies many desir- optimized by appropriate selection of the epoxy
able characteristics. These include excellent adhe- monomer and the curing agent or catalyst.
sion to many substrates, high strength (tensile, Epoxies find application in five major areas:
compressive and flexural), chemical resistance, coatings, electrical and electronic insulation, adhe-
fatigue resistance, corrosion resistance, and electri- sives, composites, and construction. These categori-
cal resistance. In addition, processing is simplified zations define the nature of the epoxy systems and
by the low shrinkage and lack of volatile by- span all major commercial enterprises. For exam-
products. The properties of uncured epoxy resins ple, the medical and dental field uses epoxy cast-
(i.e. viscosity), and those of their cured counter- ings, encapsulants, and adhesives; space
parts (strength, electrical resistivity), can be exploration uses epoxy composites, adhesives, and
244 HANDBOOK OF THERMOSET PLASTICS

electrical insulation; the automotive industry uses Technology has been developed for curing epoxy
protective coatings and adhesives. resin-based coatings via exposure to ultraviolet light
Because of the ease of application and desirable for a few seconds. The systems contain a photoinitia-
properties, epoxies are widely used for coatings, tor that disassociates under ultraviolet radiation to
corrosion protectants, electric encapsulants, fiber generate cationic species that rapidly polymerize the
optic sheathing, flooring, and adhesives. Given so epoxy resin to yield cross-linked, high-performance
many everyday uses, most hardware stores carry a coatings. The cycloaliphatic type epoxies are particu-
wide variety of epoxy adhesives and coatings. larly amendable to this type of application. They
Coatings make up fully 50% or more of epoxy yield attractive coatings benefits such as low shrink-
resin production. Epoxy’s chemical resistance, age, excellent adhesion to a wide variety of sub-
toughness, durability, and adhesion are the prime strates, excellent weathering resistance, and low
features for this arena. Epoxy resins are used in potential for skin irritation. Coreactants such as poly-
appliance and automotive primers, can coatings, ols are often used to influence film properties.
industrial maintenance paints, and product and The high resistivity and relatively low dissipa-
marine finishes. Figure 8.30 shows an example of tion factors, combined with high mechanical prop-
an epoxy coating. erties, are the characteristics that permit the
Pollution control constraints have prompted devel- widespread use of epoxies in electrical and elec-
opments in water-borne, high solids, and solventless tronic insulation. Encapsulation and coating of tran-
coating systems. A host of epoxy resins and curing sistors, switches, coils, insulators, and integrated
agents have been developed for use as powder coat- circuits are routine. New casting processes are pro-
ings via spray or fluidized bed application techni- viding dimensional stability, eliminating stress
ques. This continues to be a growing field for build-up and surface defects, and significantly
coatings because of two very attractive environmen- reducing demold time. In Europe, epoxies continue
tally friendly features: (1) essentially free of stack to dominate porcelain in large outdoor transfor-
emissions when heat cured and (2) overspray powder mers, switching gear, and high voltage insulators.
is readily recovered for recycling. Powder coatings Figure 8.31 shows an example of an epoxy used in
for such areas as thick-film pipe coatings continue to such applications.
consume large volumes of resin. Two-component,
air-dried, solventless systems are adaptable to new
spray application processes in maintenance coatings.
Two-component, water-based emulsion paints are
being used in architectural applications. Traditional
coal-tar epoxies and zinc-rich wash coat primers
remain staples for maintenance and marine protection
coatings.

Figure 8.31 Electrica V electronic devices

Figure 8.30 Epoxy coated pipe. (Courtesy of Shell encapsulated with epoxy resin. (Courtesy of Shell
Chemical Co./EPONB Resin.) Chemical Co./EPONB Resin.)
8: EPOXIES 245

Encapsulants are being developed based on the are more versatile to formulate, and provide higher
concept of simultaneous interpenetrating networks service temperatures. Successful applications
(SINs). In this situation, two different monomers include skateboards and snow skis.
are polymerized simultaneously to form interpene- Since their introduction, epoxies have been a
trating three-dimensional networks. An example of dominant force in adhesives and bonding. Volatile-
one such system is a SIN based on epoxy and poly free curing and minimal shrinkage, combined with
(n-butyl acrylate). The major advantage of this excellent lap-shear strength, make epoxies the pre-
approach for epoxy castables is improved resistance mier adhesive. Major recent developments have
to crack growth. focused on new latent curatives for one-can systems
Many epoxies are cast for non-electrical applica- that are room temperature stable for over a year,
tions. Novel applications for such structural castings yet will cure in minutes at temperatures as low as
include large bearings for an oceanic oil rig swivel 100°C (212°F). New epoxy systems have success-
buoy (see Figure 8.32), acid-resistant pump impellers, fully bonded to and fined enamel, dentin, and
and sleeves for ship stern-tube assemblies. New deep- cementum in the dental field (see Figure 8.33).
diving submersible have been built from acrylic and The United States Air Force has conducted a
epoxy resins. These are in current use for deep-sea major program to determine whether adhesive
diving exploration and provide a one-person, one- bonding with epoxy could replace rivets that are
atmosphere diving capability to depths of 6,500 feet. traditionally used in aircraft assemblies. The largest
Resin transfer molding (RTM) is a process that adhesively bonded primary structure ever assem-
is very useful in the rapid molding of liquid bled, a 42 foot long by 18 foot wide fuselage sec-
epoxies. Typical parts made via RTM include pro- tion, was thoroughly tested (see Figure 8.34). The
peller blades, industrial fan blades, and support program validated the technology to the point that
beams. New epoxy systems are being examined for new aircraft are using as much adhesive on primary
use in the reaction injection molding (RIM) pro- structures as are currently used for secondary and
cess. RIM has been dominated by urethanes; how- nonstructural aircraft elements.
ever, these new epoxies, particularly reinforced Several factors in the automotive industry have
versions, have higher tensile and flexural moduli, promoted the replacement of welding, riveting, and

Figure 8.32 To assure continuous flow of North Sea Oil, liquid epoxy resin was pumped into 12 mounting
areas of a swivel buoy that weighs 4.6 million pounds. Source: [101].
246 HANDBOOK OF THERMOSET PLASTICS

Figure 8.33 Epoxy enamel coating for teeth. Figure 8.35 Graphite/epoxy violin. (Courtesy of
(Courtesy of Lee Pharmaceuticals.) L.K. John, inventor.)

the Chevrolet Corvette [102] and the Bell/Textron

V-22 [103] TiltRotor aircraft. Epoxies and fiber-
reinforced epoxy composites have also greatly
influenced sports equipment, specifically in tennis,
golf, and cycling.
Glass, graphite, and polyaramid-reinforced epoxy
composites continue to find major use in such
industries as space, printed circuitry, tanks and
pressure vessels, and pipes. Epoxy composites pro-
vide high strength-to-weight ratios; have good ther-
mal, electrical, and chemical resistance; and are
compatible with every reinforced plastics process.
A novel use of graphite/epoxy composite has
been reported in the music field. A violin (see
Figure 8.35) was constructed with the composite
Figure 8.34 PABST program fuselage. (Courtesy of replacing traditional woods. Cost and fabrication
McDonnell Douglas Corp.) time were substantially reduced. The overall tone
balance was rated as good, with excellent high notes
other traditional metal joining processes with epoxy by the concert artists who played the instrument.
adhesive bonding. In car, bus, and truck plants Industrial chemically resistant flooring remains a
adhesive processes reduce noise and eliminate haz- major use of epoxy resins in the construction trade.
ardous materials (e.g. lead) and processes. The Sand-filled compositions having excellent, oil,
adhesives help meet crash, rollover, and other water, solvent, and caustic resistance and superb
safety regulations and reduce weight to improve adhesion to concrete are the primary epoxy systems
fuel efficiency. used. Some decorative “pour-a-floor” systems are
Other properties, such as liquid processability still popular because of the ease of application and
and cured strength control, make epoxies the obvi- excellent adhesion to glass, quartz, marble chips,
ous choice for matrices in fiber-reinforced compo- and other attractive inclusion materials. Other con-
sites. For years now, glass fiber-reinforced epoxies struction uses are coal-tar-based paving materials,
have appeared commonly as major components in grouts, and adhesives for segmental bridge con-
boats, automobiles, aircraft, medical prostheses, struction and airport runway repair (Table 8.28).
and sports equipment. Indeed, many developments Table 8.29 lists commercial manufacturing
were only possible using this material, including information.
8: EPOXIES 247

Table 8.28 Epoxy Resin Demand in Tooling and Casting by Region

2010 2012
Western Europe 281 293
North America 261 271
Japan 87 90
Asia Pacific 249 275
Rest of World 99 107
Total 977 1036
Total Average Annual Growth Rate  3%


Demand expressed in US $ million.
Source: Acmite Market Intelligence Report: World Epoxy Market [104]

Table 8.29 Trade Names & Manufacturers of Epoxy Resins Curing Agents & Formulations

Trade Name Product Manufacturer

Able- Formulations Ablestik Laboratories
Ajicure Curing agents Ajinomoto Co., Inc.
Amicon Formulations Emerson & Cuming, Inc. Grace Speciality
Polymers
Amicure, Curing agents Air Products & Chemicals, Inc.
Ancamine
Araldite Resins, curing agents, Ciba-Geigy Corp., Polymers Div.
formulations
Capcure Curing agents Henkel Corp. Functional Products, Div.
Conapoxy Formulations Cytec, Inc.
DEN, DER, DOW Resins, curing agents Dow Chemical Co.
Duomeen Curing agents Akzo Nobel Chemicals, Inc.
Eccobond Formulations Emerson & Cuming, Inc., Grace Speciality
Polymers
Elastolock Formulations Daich Coatings
Epilink Curing agents Air Products and Chemicals, Inc.
Epo-Tek Formulations Epoxy Technology, Inc.
Epocap, Epocure Formulations Hardman Div., Harcros Chemicals, Inc.
Epon Resins, curing agents Momentive Specialty Chemicals
Eponex Resins Momentive Specialty Chemicals
Eposet, Epoweld Formulations Hardman Div., Harcros Chemicals, Inc.
Epoxi-Patch Formulations Dexter Aerospace Materials Div.
ERL Resins Union Carbide Corp.
Ethacure Curing agents Albermarle Corp.
Genamid Curing agents Henkel Corp. Functional Products, Div.
(Continued )
248 HANDBOOK OF THERMOSET PLASTICS

Table 8.29 (Continued)

Trade Name Product Manufacturer

Heloxy Resins Momentive Specialty Chemicals
Hysol Formulations Henkel Corp.
Insulcast Formulations ITW Polymer Technologies
Megabond Formulations Laticrete
Monopoxy Formulations Hardman Div., Harcros Chemicals, Inc.
Norcast, Norcure Formulations Bradken
Rolox Formulations Hardman Div., Harcros Chemicals, Inc.
Scotch- Formulations 3M Co.
Sonite Formulations Smooth-On, Inc.
Stycast Formulations Emerson & Cuming, Inc., Grace Speciality
Polymers
Tonox Curing agent Uniroyal Chemical Co., Inc.
Tra- Formulations Tra-Con Inc.
Versamid, Curing agents Henkel Corp. Functional Products, Div.
Versamine
Weldfast Formulations Fibercast Co.

References [10] DiBenedetto M. Using solvents and reactive

diluents in epoxy systems. Mod Paint Coatings,
[1] Bilyeu B, Brostow W, Menard KP. J Mater 70, 7 (July 1980) 39. Aromatic amine adducts
Ed 1999;21:281. for high-performance coatings, Modern Paint
[2] Bilyeu B, Brostow W, Menard K. Division of and Coatings, 71, 7 (July 1981) 36.
polymer materials science & engineering. [11] Cochrane H, Miller D. Hydrophobic fumed sil-
Proc Am Chem Soc 1998;78:232. ica as a rheology control agent for epoxy adhe-
[3] World Epoxy Resin Market. Market Report, sives, sealants. Adhes Age 1982;25(11):22.
Acmite Market Intelligence; 2010. [12] Boersma SL. J Am Ceram Soc 1955;38:281.
[3a] Brostow W, Hagg Lobland HE, Narkis M. J [13] ASTM D1525-96, American Society for
Mater Res 2006;21:2422. Testing and Materials, West Conshohocken
[4] Brostow W, Hagg Lobland HE, Narkis M. (current standard).
Polym Bull 2011;59:1697. [14] Watson ES, O’Neill MJ, Justin J, Brenner N.
[5] Szymczyk A, Roslaniec Z, Zenker M, Garcia- Anal Chem 1964;36:1233.
Gutierrez MC, Hernandez JJ, Rueda DR, et al. [15] Schawe JEK. Thermochim Acta 1995;270:1.
Expr Polym Lett 2011;5:977. [16] Quinn TJ. Temperature. San Diego: Academic
[6] Dorigato A, Pegoretti A, Fambri L, Lonardi Press; 1990.
C, Slouf M, Kolarik J. Expr Polym Lett [17] Hemminger W. In: Mathot VBF, editor.
2011;5:23. Calorimetry and thermal analysis of polymers.
[7] Brostow W, Kovacevic V, Vrsaljko D, Munich: Hanser; 1994. p. 17, Chap. 2.
Whitworth J. J Mater Ed 2010;32:273. [18] Fuller B, Gotro JT, Martin GC. In: Craver C,
[8] Handbook of Epoxy Resins by Lee and Neville. Provder T, editors. Polymer characterization.
Copyright 1967 by McGraw-Hill, Inc. Used Washington D.C.: American Chemical
with permission of McGraw-Hill Book Co. Society; 1990. p. 215, Chap. 12.
[9] Nielsen PO. Properties of epoxy resins, hard- [19] Brostow W, Glass NM. Mater Res Innovat
eners, and modifiers. Adhes Age 1982;25 2003;7:125.
(4):42.
8: EPOXIES 249

[20] Borchardt HJ, Daniels F. J Am Chem Soc [44] Van Krevelen DW. Properties of polymers.
1956;79:41. 3rd ed. Amsterdam: Elsevier; 1990.
[21] Chartoff RP. In: Turi E, editor. Thermal char- [45] Ward IM. Mechanical properties of solid poly-
acterization of polymeric materials. 2nd ed. mers. New York: Wiley; 1983.
San Diego: Academic Press; 1997. p. 484, [46] Zoller P, Kehl TA, Starkweather Jr. HW,
Chap. 3. Jones GA. J Polym Sci Phys 1989;27:993.
[22] Wisanrakkit G, Gillham JK, Craver C, [47] Richardson MJ. In: Mathot VBF, editor.
Provder T, editors. Washington D.C.: Calorimetry and thermal analysis of poly-
American Chemical Society; 1990, Chap. 9. mers. Munich: Hanser; 1994. p. 169, Chap. 6.
[23] Richardson MJ. Pure Appl Chem [48] Menard KP. Dynamic mechanical analysis.
1992;64:1789. 2nd ed. Boca Raton, FL: CRC Press; 2008.
[24] Barton JM. In: Chiu J, editor. Polymer charac- [49] O’Neal HR, Welch S, Rogers J, Guilford S,
terization by thermal methods of analysis. Curran G, Menard KP. J Adv Mater 1995;26:49.
New York: Dekker; 1974. [50] Cassel B, Twombly B. In: Riga AT, Neag
[25] DiBenedetto AT. J Polym Sci Polym Phys CM, editors. Material characterization by
1987;25:1949. TMA. Philadelphia: ASTM; 1991. p. 108.
[26] Stutz H, Illers KH, Mertes J. J Polym Sci [51] Sperling LH. Introduction to physical polymer
Phys 1990;28:1483. science. New York: Wiley; 1986.
[27] Stutz H, Mertes J, Neubecker K. J Polym Sci [52] Bershtein VA, Egorov VM. Differential scan-
Chem 1993;31:1879. ning calorimetry of polymers. New York:
[28] Bauwens JC. Failure of Plastics. Brostow W, Ellis Horwood; 1994.
Corneliussen, R, Chap. 12, Hanser, Munich; [54] Godovsky YK. Thermophysical properties of
1992. polymers. Berlin: Springer Verlag; 1992.
[29] Brostow W, Duffy JV, Lee GF, Madejczyk K. [53] ASTM E1356-91, American Society for
Macromolecules 1991;24:479. Testing and Materials, West Conshohocken
[30] Brostow W. Macromol Symp 1991;41:119. (current standard).
[31] Chinn D, Shim SB, Seferis JC. J Thermal [55] ASTM E1269-90, American Society for
Anal 1996;46:1511. Testing and Materials, West Conshohocken
[32] Hartmann B, Haque MA. J Appl Phys (current standard).
1985;58:2831. [56] Press WH, Flannery BP, Teukolsky SA,
[33] Ibar JP. J Macromol Sci 1979;16:61. Vetterling WT. Convolution and deconvolu-
[34] Jo WH, Ko KJ. Polym Eng Sci 1991;31:239. tion Using the FFT. Numerical recipes in
[35] Maksimov VL. Polym Sci 1994;36:955. FORTRAN: the art of scientific computing.
[36] Fossey SA. In: Performance of Plastics, 2nd ed. Cambridge, England: Cambridge
Brostow W, editor. Chap. 4, Hanser, Munich, University Press; 1992. p. 531537, Ch. 13.
p. 67; 2001. [57] Rhodes MS. Why anhydrides for curing epoxy
[37] Dillman SH, Seferis JC. J Macromol Sci resins. SAMPE J 1993;29(5):7.
1989;26:227. [58] Reading M, Elliot D, Hill V. Proc North
[38] Ferry JD. Viscoelastic properties of polymers. American Therm Anal Soc Conf 1992;21:145.
New York: Wiley; 1980. [59] Schawe J, Marguilies M. US Patent 5549387;
[39] Kubát J, Rigdahl, M. In: Failure of plastics, 1996.
Brostow W, Corneliussen R, editors. Chap. 4, [60] Gopalanarayanan B, Ph.D. Dissertation,
Hanser, Munich, p. 60; 1992. University of North Texas, Denton; 1998.
[40] Marchal E. J Chem Phys 1992;96:4676. [62] Jones KJ, Kinshott I, Reading M, Lacey AA,
[41] Matsuoka S. In: Failure of plastics. Brostow Nikolopoulos C, Pollock HM. Thermochim
W, Corneliussen RD, editors. Chap. 3, Hanser, Acta 1997;304/305:187.
Munich p. 24; 1986. [63] Schawe JEK. Thermochim Acta 1995;260:1.
[42] Mijović J, Schafran B. SAMPE J 1990;26:51. [64] Schawe JEK. Thermochim Acta 1995;261:183.
[43] Sauer BB, Avakian P. Polymer (Guildf) [65] Hutchinson JM, Montserrat S. Thermochim
1992;33:5128. Acta 1996;286:263.
250 HANDBOOK OF THERMOSET PLASTICS

[66] Neag CM. Material characterization by thermo- [86] Halpern V. J Phys D 1992;25:1533.
mechanical analysis. Philadelphia: American [87] Halpern V. Phys Rev B 1997;56:377.
Society for Testing and Materials; 1991. [88] Marchal E. Polymer (Guildf) 1991;32:297.
[67] ASTM E1545-95a, American Society for [89] Ibar JP, Denning P, Thomas T, Bernes A,
Testing and Materials, West Conshohocken deGoys C, Saffell JR, et al. Polymer charac-
(current standard). terization. In: Craver C, Provder T, editors.
[68] ASTM E228-95, American Society for Washington D.C.: American Chemical
Testing and Materials, West Conshohocken Society; 1990. p. 167, Chap. 10.
(current standard). [90] Hinrichs RJ. Chemorheology of thermoset-
[69] ASTM E1363-97, American Society for ting polymers. Washington D.C.: American
Testing and Materials, West Conshohocken Chemical Society; 1983.
(current standard). [91] Birley AW, Haworth B, Batchelor J. Physics
[70] Mallela H, Davis M, Menard KP. Proc of Plastics, Hanser, Munich.
Annu Technol Conf Soc Plast Eng 1994;40: [92] Yousefi A, Lafleur PG, Gauvin R. Polym
2276. Compos 1997;18:157.
[71] ASTM D648-97, American Society for [93] Dušek K, MacKnight WJ. In: Dickie RA,
Testing and Materials, West Conshohocken Labana SS, Bauer RS, editors. Cross-linked
(current standard). polymers. Washington D.C: American
[72] Akay M, Cracknell JG, Farnham HA. Polym Chemical Society; 1988. p. 2, Chap. 1.
Polym Comp 1994;2:317. [94] Prime RB. In: Turi E, editor. Thermal char-
[73] Wilson TW, Fornes RE, Gilbert RD, Memory acterization of polymeric materials. 2nd ed.
JD. In: Dickie RA, Labana SS, Bauer RS, San Diego: Academic Press; 1997. p. 1380,
editors. Cross-linked polymers. Washington Chap. 6.
D.C.: American Chemical Society; 1988, [95] Gillham JK. Polym Eng Sci 1986;26:1429.
Chap. 7. [96] Enns JB, Gillham JK. J Appl Polym Sci
[74] ASTM E1640-94, American Society for 1983;28:2567.
Testing and Materials, West Conshohocken [97] Enns JB, Gillham JK. In: Craver C, editor.
(current standard). Polymer characterization. Washington D.C.:
[75] Cassel B, Twombly B. Am Lab 1991;:34. American Chemical Society; 1983. p. 27,
[76] Schmieder K, Wolf K. Kolloid Zeit Chap. 2.
1952;127:65. [98] ASTM D4473-90, American Society for
[77] Lewis AF, Gillham JK. J Appl Polym Sci Testing and Materials, West Conshohocken
1962;6:422. (current standard).
[78] ASTM E1867-97, American Society for [99] Gillham JK, Enns JB. Trends Polym Sci
Testing and Materials, West Conshohocken 1994;2:406.
(current standard). [100] Bilyeu B, Brostow W, Menard KP. Polym
[79] Mettes DG. In: Lubin G, editor. Handbook Compos 2002;23:1111.
of fiberglass and advanced plastics compo- [101] Wilson JM. Cast epoxies replace metals in
sites. New York: Van Nostrand Reinhold; mechanical designs. Mater Eng 1983;97:28.
1969. [102] Rose M. Automobiles series. Atlanta:
[80] Dias AB, Moura-Ramos JJ, Williams G. Corvette, A&E Network Productions; 1994.
Polymer (Guildf) 1994;35:1253. [103] U.S. Congress Commercial Tiltrotor
[81] Hsiao BS, Sauer BB. J Polym Sci Phys Development Advisory Committee Report,
1993;31:917, Chapter 10 in Ref. 2. based on research and development by Bell
[82] Sauer BB, Avakian P, Cohen GM. Polymer Helicopter/ Textron, Washington, D.C.; 1995.
(Guildf) 1992;33:2666. [104] Acmite Market Intelligence. World epoxy
[83] Debye P. Polar molecules. Chemical resin market. Acmite Market Intelligence:
Catalog, New York; 1929. Author. Retrieved from , http://www.
[84] Halpern V. J Phys C 1994;6:9451. acmite.com/brochure/Brochure-Epoxy-Resin-
[85] Halpern V. J Phys C 1995;7:7687. Market-Report.pdf ., 2010.
8: EPOXIES 251

Further Reading Garn PD, Menis O, Wiedemann HG. In: Wiedemann

HG, editor. Thermal analysis. Basel: Birkhäeser;
Arnold FE, Thoman S. Int SAMPE Tech Conf 1980.
1996;28:222. Greenlee, S., US Patent 2456408; 1948.
Bilyeu B, Brostow W, Menard KP. J Mater Ed Hamerton I. Recent developments in epoxy resins.
2000;22:107. Rapra Technology Ltd; 1996.
Bilyeu B, Brostow W, Menard KP. J Mater Ed Hearle JWS. In: Lemstra PJ, Kleintjens LA, editors.
2001;23:189. Integration of fundamental polymer science and
Bolger JC. Epoxies for manufacturing cars, buses, technology, vol. 3, Part 3. London: Elsevier;
& trucks. Adhes Age 1980;23(12):14. 1989.
Bolger JC, Morana SL. Conductive adhesives: Hill JO. Better thermal analysis and calorimetry. 3rd
how and where they work. Adhes Age 1984;27 ed. Portsmouth, U.K: CPC Reprographics; 1991.
(7):17. Hüls America, Inc., Technical Service Report 22-E-
Bratychak M, Brostow W. Polym Eng Sci 37521, IPD, TMD.
1999;39:1541. Jenkins AD, Kratochvı́l P, Stepto RFT, Suter UW.
Brostow W, Bujard B, Cassidy PE, Hagg HE, Pure Appl Chem 1996;68:2287.
Montemartini PE. Mater Res Innovat 2002;6:7. Kern KT, Ries HR, Long Jr. ER. J Mater Educ
Brostow W, Cassidy PE, Hagg HE, Jaklewicz M, 1994;16:293.
Montemartini PE. Polymer (Guildf) Le Chatelier H. Bull Soc Min Crist 1887;10:204.
2001;42:7971. Lee CY-C, Goldfarb IJ, Craver C, editors. Polymer
Brostow W, Chonkaew W, Datashvili T, Menard characterization. Washington D.C.: American
KP. J Nanosci Nanotech 2009;9:1916. Chemical Society; 1983, Chap. 3.
Brostow W, Kaushik BK, Mall SB, Talwar IM. Lee H. Advances in biomedical adhesives and sea-
Polymer (Guildf) 1992;33:4687. lants. SAMPE J July/1984;20(4):13.
Brown RE, McCrea RE. Competition, chances for Mathot VBF. In: Mathot VBF, editor. Calorimetry
growth for epoxy adhesive markets. Adhes Age and thermal analysis of polymers. Munich:
1982;25(2):21. Hanser; 1994. p. 105, Chap. 5.
Buehner RW, Atzinger GD. Adhes Age 1991;:246. May CA. In: May CA, editor. Epoxy resins: chem-
Burns P. Recent developments in epoxy resins, Term istry and technology. New York: Marcel Dekker;
paper submitted to fulfill requirements of Ch.E. 1988, Ch. 1.
478, University of Southern California; 1984. Melber GE, Gibbons KM, Anderson TF. Organic
Caston P. European Patents CH 211116 (1938), microspheres for super-tough syntactic foams.
DRP 749512 (1938), GB 518057; 1938. Plast Compod 1984;7(2):19.
Creegan KM, et al. Synthesis and characterization Menard KP. Thermal Transitions and their mea-
of C60O, the first fullerene epoxide. J Amer surement, Ch. 8 in Ref. 2.
Chem Soc 1992;114:1103. Naitove MH, Colangelo M. At RP meeting: an
Crozier D, Morse G, Tajima Y. The development upbeat mood, modest advances in technology.
of improved chemical analysis methods for epoxy Plast Techn March 1983;29:48.
resins. SAMPE J 1982;18(5):17. Nernst W, Riesenfeld EH. Chem Ber 1903;36:
Denoms SD. Coloring the tough ones: thermosets. 2086.
Plast Compd 1981;4(3):45. O’Neill MJ. Anal Chem 1964;36:1238.
Dow Corning Corp. Dow Corning 631 semiconduc- Opalicki M, Kenny JM, Nicolais L. J Appl Polym
tor grade molding compound. Bulletin 1980;:. Sci 1996;61:1025.
Fox MA, Whitesell JK. Organic chemistry. Boston: Riew LK, et. al., Toughened epoxy resins: pre-
Jones and Bartlett Publishers; 1994. formed particles as toughened adhesive joints.
Fritz ER, Green J. New flame retardant for epoxy glass Proceedings of the 15th annual meeting of the
laminates. Printed Circuit Fab 1983;6(5):55. adhesion society, Hilton Head, SC, (1619 Feb.
Gallagher PK. In: Turi E, editor. Thermal charac- 1992) 166171.
terization of polymeric materials. 2nd ed. San Rohn CL. Analytical polymer rheology. Munich:
Diego: Academic Press; 1997. Hanser; 1995.
252 HANDBOOK OF THERMOSET PLASTICS

Schwartz S, Goodman S. S.H. Plastics materials Vazirani HN. Flexible epoxy resins. Adhes Age
and processes. New York: Van Nostrand 1980;23(10):31.
Reinhold Co.; 1982. Villani T. Epoxy. Modern plastics encyclopedia, vol.
Scola DA, Peter RH. The properties of novel bisi- 58. New York: McGraw-Hill Inc.; 1981, 10A.
mide amine cured epoxy/celion 6000 graphite Waddill HG. Reaction injection molding (RIM)
fiber composites. SAMPE J 1982;18(1):16. with epoxy resin systems. Presentation to the
Skiest I. Epoxy resins. New York: Reinhold 35th Annual Technical Conference, Reinforced
Publishing Co.; 1958. Plastics-Composites Institute, The Society of the
Sperling LH. Interpenetrating polymer networks: a Plastics Industry, Inc., Section 22-B; 1980 1.
new class of materials. Mater Eng 1980;92(3):67. Wason SK. Synthetic sodium aluminum silicates.
Speyer RF. Thermal analysis of materials. New Plast Compod 1983;6(5):29.
York: Marcel Dekker; 1994. Wehrenberg RH. Epoxies: versatile, new materials
Storck WJ, Layman PL, McCoy M, Reisch MS, for RIM. Mater Eng 1980;91(6):42.
Thayer AM, Tremblay JF. Chem Eng News Weiss J. Epoxy hydantoins as matrix resins. NASA
1999;77:32. Contractor Report 166024, Contract NASI-
Sullivan P, Seidel G. Phys Rev 1968;173:679. 16551, NASA Langley Research Center,
Twarowski TE, Geil PH. Characterization studies of Hampton, Virginia; March 1983.
fluorinated resins: naval experimental resin CS/ISA Wunderlich B. Thermal analysis. San Diego:
as a structural material and for use in blends and Academic Press; 1990.
composites. Urbana, IL: National Center for Wunderlich B. In: Turi E, editor. Thermal charac-
Composite Material Research, University of Illinois; terization of polymeric materials. 2nd ed. San
1989, ONR-URI Report NCCMR-89-#0013. Diego: Academic Press; 1997.