physical electrical a
Abstract-This summarizes the important physical and electrical Ication characteristics of these
characteristics of these diverse and highly useful insulating ma-
complex materials.Two good general reference books on
terials. Factors of chemical structure which influence the resulting
epoxy resins are cited [3] for anyone wishing further
resin properties are discussed. The great variety of properties which
details. Contrary to many other classes of plastics, such
can be achieved through variations in this one class of resins is
as polyethylene, polypropylene, polyearbonate, poly-
emphasized. A range of applications of these resins is mentioned
and illustrated. methyl methacrylate, etc., the epoxy resins are a much
more diverse class of resins chemically and in their physical
INTRODUCTION properties. They have one common chemical charac-
IN this paper we will review the present state of the teristic, which is the epoxy carbon-oxygen-carbon three-
application of epoxy resins in electrical apparatus. atom ring group in the unpolymerized molecule
These resins have seen some commercial use for more than H 0 H
25 years so they cannot be considered new babies, but
their application in electrical apparatus must still be R,-C C-R2.
considered in its youth. Their use has been growing steadily
over the past two decades. While the volume of use of This ring can be opened by chemical reaction to link two
these resins is small compared to resins like polyethylene, adjoining molecules
the quantity is still impressive. For example, the epoxy
production for all uses was 99 000 metric tons in 1973 0
[1], 19 percent greater than 1972. Of this total, 9 percent
is attributed to electrical laminates and 8 percent to H C-C-H
casting and molding resins, part of which was in electrical
applications. This can be compared to 1.25 million metric R1 R2
tons of high-density polyethylene and 2.6 million metric
tons of low-density polyethylene produced in 1973. The This reaction is catalyzed by a great many organic acid
total use of all plastics in the electrical industry was or basic compounds, which often combine with one (or
743 000 metric tons in 1973, of which only 1-2 percent both) of the two reactive "free" bonds produced by the
was epoxy resins. ring opening.
Epoxy resins have found application where their unique Some of the differences between the thousands of epoxy
or superior properties would warrant a somewhat higher resin types exist in the primary epoxy compound. Another
cost. They are castable into rigid, strong, three-dimen- wide degree of variation results from the selection of acid
sional structures, and impregnable as fluids into porous or basic "hardener" which is used to react to open the
reinforcing structures, where they are converted by epoxy ring. A third order of variation is an accelerator
polymerization to solid, which effectively fills the pores, compound which is sometimes, but not always, added
properties which the thermoplastic resins do not have. (usually in much smaller proportion) to speed up the
They are also used as coatings for conductors, etc. Atten- reaction. Most, if not all, of these components end up
tion should be drawn to the survey of cast and molded chemically reacted or combined into the final solid mass
resin applications in high-voltage power systems, which which is, in effect, one giant molecule. Often both the
appeared in the 1972 CIGRE Proceedings [2]. This primary epoxy and the hardener molecules are difune-
survey, covering a large part of European and U.S. ap- tional, having, respectively, two epoxy rings or two reac-
plications, classified the applications as bushings, cable tive basic groups, thus permitting linkage to other mole-
terminations, instrument transformers, various post and cules in four directions. The possible permutations of
support insulators, and parts for circuit breakers. A molecular growth are often so great that the exact struc-
majority of the uses were epoxy, although butyl or ethyl- ture of any one resin is so complex as to defy determination
ene-propylene-type rubbers competed with them for except in a general way. Nevertheless, if the same propor-
application to small instrument transformers. tions of starting components are used and the same sched-
ule of curing time and temperatures are used, the resulting
CHEMICAL NATURE OF EPOXY RESINS solid-resin characteristics can be reproduced quite well
A brief explanation of the chemistry of epoxy resins timxe after time.
can guide the "lay" electrical engineer to understand the It is important to the various possible electrical ap-
plications to know the main types of resin used and how
Manuscript received March 18, 1974.
The author is with the Westinghouse Electric Corporation,
they relate to the resulting physical and electrical charac-
Pittsburgh, Pa. 15235. teristics. Some of the initial epoxy compounds are liquid
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122 IEEE TRANSACTIONS ON ELECTRICAL INSULATION, DECEMBER 1974
and others are low-melting solids, the latter having to be or stresses. After the resin starts to "gel" or form a three-
melted to produce polymerization. This is also the case dimensional network, then internal stress may develop
with the hardener component. Amine-type hardeners are and lead to cracks. Thermal contraction shrinkage also
usually liquid and often anhydride hardeners are solid, the occurs after curing or polymerization of the resin. The
latter having to be dissolved or melted into the epoxy magnitude of this is dependent on the curing temperature
compound to produce the reactive mixture. The structure (including overheating from the heat of polymerization)
of the primary epoxy or anhydride molecule determines difference above the operating temperature. This is re-
whether it will be a semicrystalline solid. Simple regular duced by the amount and type of filler. Avoiding adverse
polar molecule structures crystallize more readily, whereas effects from this is part of the application technology.
compounds having a very complex irregular shape, or
considerable portion of hydrocarbon (-CH2-CH2-CH2-) PHYSICAL PROPERTIES OF EPOXY RESINS
chain are more likely to be liquids. In the case of epoxy The wide variety of epoxy resins have correspondingly
monomer liquids, the viscosity increases with molecular wide ranges of properties. Therefore, only the range of
size,'and these higher molecular weight compounds are properties (see Table I) and their dependence on resin
more difficult to use as impregnating compounds because type, curing conditions, etc., can be indicated in a short
they flow slowly through pores. Increased temperature survey such as this.
to reduce the viscosity during impregnation or casting The filled resin density, of course, decreases in propor-
facilities, may be absolutely necessary, in such applications. tion to the filler density and its percentage. As much as
Polymerization rates are determined by the type of 80-percent silica by weight can be incorporated, but the
hardener and accelerator, if used. Amine hardeners pro- higher percentages are increasingly more difficult to cast
duce rapid polymerization and are used for room tem- and mix. Correspondingly, the coefficient of thermal
perature cure resins. Anhydride hardeners require higher expansion is reduced by the filler and its own coefficient. It
temperatures to initiate polymerization reactions. With is possible to match the expansion coefficient of copper,
anhydride resins, the epoxy and hardener mixture/solution aluminum, or steel over a fairly wide temperature range
must usually be heated to 100'C or higher to produce using proper fillers and percentages. Matching the thermal
polymerization. The rate of polymerization increases expansion coefficient of internal embedded conductors,
with the temperature, as is typical of chemical reactions. etc., can be very important in electrical applications to
Further curing or polymerization and associated physical avoid stress cracking or separation of the resin from the
and electrical changes may proceed slowly (perhaps in metal, which might lead to partial discharges. The thermal
service) long past the initial curing time, if it was too conductivity can be more than doubled with high per-
short for the temperature used. centages of fillers having higher thermal conductivities
Epoxy resins, as do all resins, increase in density or than the resin itself.
shrink during polymerization. This is due to replacement Epoxy resins can be reinforced, of course, with fibrous
of many intermolecular spacings with closer interatomic fillers to achieve very high tensile strengths. Fibers such
bonds or intramolecular spacings, which contracts the as glass, which have a higher elastic modulus, as well as
structure. In this respect, epoxy resins are usually superior strength, than the resin itself, are the most effective. The
to polyester resins since the latter are usually formed from strength to weight ratio which can be achieved is higher
lower molecular weight, smaller molecules, whereas most than with steel.
epoxy monomer molecules are initially higher molecular The physical strength of resins increases throughout
weight. Thus fewer new interatomic bonds will be formed the curing cycle, as more interatomic linkages develop,
in converting epoxies to high-molecular weight resins. but tends to level off with an optimum curing time and
Typically, polyester resins incorporating styrene shrink temperature. Further heating at elevated temperature
8-10 percent on polymerization, whereas epoxy resins
shrink 1-5 percent, depending, of course, on the initial TABLE I
molecule. This shrinkage is further reduced to levels of as EPoxY RESIN PHYSICAL PROPERTIES
low as 0.25 percent apparent by the incorporation of a
Silica
high-volume percent of a nonshrinking filler such as Unfilled Filled
silica. Some of the shrinkage with fillers may be distributed
on a microseopic basis throughout the body of the filled Density, gins/cc 1.11-1.40 1.6-2.0
resin. Coefficient of thermal expansion, 4-10 1.2-4.0
x 10-5 (cm/cm/°C)
Resin shrinkage during casting or impregnation is an
important consideration in the resulting application since Thermal conductivity
(10-4 cal/sec/cm2/°C/cm
4.0-5.0 10-20
it can produce internal separation o_f the resin from solid
parts into which it is cast. It can also introduce significant Tensile strength, (psi) 4000-13,000 7-13,000
mechanical stresses within the resin, and pressure on Elongation, (%) 3.6-6.0 1.0-3.0
solid embedded parts. Part of the total shrinkage of the Compressive strength, (psi) 15-25,000 15-35,000
order of 2 or more may occur while the resin is still liquid. Heat distortion temperature, (C) <25-290
This liquid shrinkage will not cause internal separations (264 psi stress)
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DAKIN: APPLICATION OF EPOXY RESINS 123
would lead slowly to degradation, particularly in the
presence of oxygen.
The elastic modulus and softening temperature can be
varied widely with selection of the primary epoxy resin
type. Aromatic epoxies are usually stronger, have higher
elastic moduli and softening temperatures than aliphatic 40
epoxies. Flexibility is introduced by using epoxies which
produce fewer crosslinks between molecular chains and
longer aliphatic: (-CH2-CH2-CHI-) lengths which have
lower intermolecular attractive forces.
The epoxy resins usually have fairly good chemical
solvent and water resistance, much better than polyester
resins or many common thermoplastics. There are, of Temperature _
course, exceptions. Flexibilized resins are more likely to
be swelled by solvents, and aliphatic amine cured resins Fig. 1. Typical temperature variation of tan 5 of epoxy resins.
are attacked more readily. It is best to check references
on the particular resin if there is a serious exposure situa- related with a softening temperature of the resin. Flexi-
tion, because of the wide differences between different bilizing the resin shifts the high-temperature peak toward
resins. lower temperatures. Further curing of the resin, (if it is
Similarly, the thermal stability of different epoxy not sufficiently cured), will shift the peak toward higher
resins varies widely. For example, it is not usually expected temperatures. Increasing the test frequency will also shift
that low-temperature curing or flexible resins would have the curve to higher temperatures. Increasing the polarity
high-temperature thermal stability. Rigid aromatic an- and ionic content of the resin can raise the whole curve
hydride cured epoxies can be made with 130° and 1550 upward. The lower temperature peak, which is not always
Class long time lives. In recent years, 1800 Class rigid observed with all resins, is attributed to small polar side
epoxy resins have been reported. groups in the solid three-dimensional molecular network.
Some epoxy resins have excellent weathering charac- These can sometimes rotate or oscillate, as in a cage,
teristics, and more will be said about this later in the independently of the whole structure. With proper at-
paragraphs on outdoor application of epoxy insulation. tention to resin formulation, it is possible to achieve
low-dissipation factors at elevated temperatures. Values
ELECTRICAL PROPERTIES of 0.01 to 0.02 tan 8 at 150°C have been achieved.
The dielectric constant and loss tangent of epoxy resins
vary widely with the type of resin. Aliphatic amine cured DIELECTRIC STRENGTH
resins are generally high in loss tangent, dielectric con- Data on the dielectric strength of epoxy resins and
stant, and conductivity, but the aromatic amine cured laminates when tested in a conventional ASTM D149
resins are somewhat better. The higher conductivities test manner, using a plate between electrodes (immersed
associated with aliphatic amines are attributed to the in oil to prevent flashover) is not remarkably different
formation of amine salts, or adducts with water, which from many other resin sheets and laminates, showing
are more highly dissociated into separate ions than either values in V/mils which vary about as the inverse square
organic carboxylic acids or amines themselves. In the root of the thickness, being for 1/8-in thickness about
presence of inorganic acids, aliphatic amine cured resins 400 V/mils. Tests of sheet materials in oil or other insulat-
may become quite conducting. The best dielectric prop- ing fluids usually occur with prebreakdown discharges in
erties are obtained with aromatic anhydride cured resins. the fluid at the electrode edges. These discharge streamers
Hardness and high-softening temperatures are usually have high-electric stresses at their termination on the
associated with lower electrical conductivity, dissipation resin surface and result in lower breakdown voltages, and
factor, and dielectric constant, because the internal ionic declining breakdown stresses with increasing thickness.
and dipole mobility is reduced. Conversely, flexible resins Of particular interest is the dielectric strength of cast
are more likely to have higher dielectric losses. The pres- epoxy resins with embedded electrodes, a condition which
ence of ionic-type contaminants, and water may contribute can be readily achieved with these vacuum castable
appreciably to the ac and dc conductivity of more flexible materials. Furthermore, this condition of embedded
resins and others at elevated temperature. conductors is typical of many cast resin applications.
The typical 60-Hz dielectric loss tangent variation with With embedded conductors or electrodes, predischarges
temperature of epoxy resins is illustrated in Fig. 1, sche- in the immersion medium are avoided and strengths more
matically. It consists sometimes of a lower temperature representative of the resin itself are achieved. Fig. 2(a)
tan 8 peak followed at higher temperatures with a flat or and 2(b) are cast epoxy breakdown values published by
slightly rising section, and at the highest temperature Professor Kind's Laboratory at the Technical University
with a rapid increase in tan 8. The temperature at which of Braunschweig [4]. These figures show several points.
the high-temperature increase begins can often be cor- 1) The low-frequency 50- (or 60-) Hz breakdown volt-
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124 IEEE TRANSACTIONS ON ELECTRICAL INSULATION) DECEMBER 1974
(a) (b)
Fig. 3. (a) Cast epoxy condenser-type bushings with porcelain
weather sheds (Westinghouse), 25 kV, 1200 and 400 A; 34.5
kV, 400 A. (b) Comparison of paper-Micarta and cast epoxy
condenser bushings, with porcelain weather sheds, 34.5-kV rating
(Westinghouse).
the fibers, followed by internal tracking and eventual The epoxy resins are also used widely, often modified
breakdown in wet conditions. by combination with other types of polymerizable com-
pounds, as wire enamel coatings. A more recent develop-
APPLICATIONS ment is the application of uncured solid epoxy resins as a
The application of epoxy resins has been expanded powder, which is subsequently melted and cured to thick
steadily as the technology of formulating improved elec- coatings, to bus bar, and other irregular large and small
trical and mechanical properties and processing techniques conductor shapes. Coatings as thick as 0.04 in may be
developed. applied at one time. The powder is initially adhered to the
Impregnation of rotating machine insulation with conductor surface by sticking by slight melting by heat
polymerizable liquid epoxies followed by curing in situ of the conductor piece, which is preheated; or it may be
is an important application. Epoxy resins have superior adhered by electrostatic attraction.
properties in chemical and water resistance to previously The applications involving cast resins and outdoor use
used polyester resins. Vacuum impregnation of small pores are particularly emphasized in this paper. These applica-
is more difficult, however, when the viscosity is high. It is tions are outlined in [2] and mentioned in the Introduc-
estimated that a majority of the high-voltage generators tion. Only a few examples are cited here. See also [13].
and motors throughout the world are now being im- Earlier applications of cast epoxy have been indoors or
pregnated with some form of epoxy resin. Polymerizable, protected, because of the uncertainty and apprehension
"B stage," impregnated semisolid mica paper tapes are regarding the weathering, tracking, and reliability in
also now available for taping coils. These must be con- outdoor environments. Among these applications are cast
solidated onto the coil with high pressure during curing epoxy condenser bushings shown in Fig. 3 (a) and 3 (b), in
to achieve satisfactory dielectric strength. this case supplied in a porcelain weather casing.
Epoxy resins are also coated onto paper for winding More than ten years ago, systematic outdoor exposure
condenser bushings, in much the same way as other resins tests under voltage were initiated of a great variety of
have been used, (shellac, phenolics, etc.). Improved bushings and insulator specimens with primary emphasis
results are claimed. on proving the reliability of epoxy resins which had been
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126 IEEE TRANiSACTIONS ON ELECTRICAL INSULATION, DECEMBER 1974
(a)
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DAKIN: APPLICATION OF EPOXY RESINS 127
(a)
(b)
(c)
Fig. 6. (a) Wall mounted cast epoxy current transformer (Mess-
wandlerbau). (b) 20-kV cast epoxy transformer in North Germany
(Messwandlerbau). (c) 60-kV cast epoxy current transformer in
an outdoor application (Messwandlerbau).
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128 IEEE TRANSACTIONS ON ELECTRICAL INSULATION, DECEMBER 1974
Fig. 10. Cast epoxy foil wound coil for 15-kV, 50-kVA (listribution
transformer (used in oil) (Westinghouse).
(a)