Comparisons of Epoxy
Technology for Protective
Coatings and Linings
in Wastewater Facilities
By John D. Durig, General Polymers, Cincinnati, Ohio, USA
Aeration tank at a wastewater plant. Bis F epoxy resin with an aliphatic or a
Editors Note: This article was first presented at SSPC
99, The Industrial Protective Coatings Conference and
Exhibit, November 14-18, 1999, in Houston, TX, USA,
and published in The Proceedings of the Seminars,
SSPC 99-14, pp. 31-37.
E poxy technology and methods of curing and
reacting with amine-based hardeners have
continued to evolve since the first epoxy patents were is-
sued in the 1930s. The possible reactions combined with
wide-ranging formulation additives have resulted in a myri-
ad of products that can easily confuse decision makers
when it comes to product selection. Adding to the confu-
sion is the wide range of environmental factors that must
be considered when choosing a protective coating system.
This article will identify the primary differences be-
tween three types of epoxies and four types of amine-
based hardeners typically used in coatings for wastewater
treatment facilities. A brief description of chemical struc-
ture will assist those with some chemistry background,
but the important issue is the performance derived from
each specific chemistry. After the discussion of perfor-
mance, combinations of epoxy resins and curing agents
suitable for specific structures and areas in wastewater fa-
cilities will be identified. Finally, to assist decision makers
in selecting the right products, a simple method utilizing
material safety data sheets (MSDS) will be presented.
JPCL May 2000
Copyright 2000, Technology Publishing Company
cycloaliphatic amine curing agent is appropriate.
(Photos courtesy of the author)
Epoxy Resin Technology
There are three types of epoxy resins that find application
in wastewater treatment facilities: bisphenol A, bisphenol
F, and novolac resins. These resins all result from reac-
tions of epichlorohydrin with phenolic compounds. The
type and number of phenolic groups determine both
physical and performance properties of the cured resin.
Bisphenol A Resin Structure
Bisphenol A is a reaction product of phenol and acetone.
Bisphenol A is reacted with epichlorohydrin to form
diglycidylether bisphenol A resin or DGEBA. The resul-
tant epoxy resin is a liquid with a honey-like consistency.
DGEBA is most often used in solvent-free coatings and
flooring systems.
The molecular weight of the formulation is increased
by adding more bisphenol A to liquid DGEBA to form
semi-solid or solid resins. These resins are cut in solvent
to allow their use as maintenance primers for steel or as
corrosion-resistant films.
The higher the molecular weight is, the higher the vis-
49
 centipoises [cP]) that of bisphenol A
Table 1:
resins. Additionally, there is a higher
Typical Epoxy Properties
proportion of trifunctional epoxy mol-
Property DGEBA DGEBF Novolac ecules, which increases the function-
Molecular weight 370 370 504 ality available for crosslinking from
1.9 to 2.1.
Viscosity @ 25 C (77 F) 11,000-15,000 cps 2,500-5,000 cps 20,000-50,000 cps
Epoxide equivalent weight 177-192 159-172 185-200 Novolac Epoxy Resins
Functionality 1.9 2.1 2.6-3.5 Novolacs are modifications of bisphe-
nol F resins formed using excess phe-
nol. Bisphenol F is the simplest novolac resin, but should
not to be confused with its related higher functionality
analogs. Its functionality and performance properties are
quite different than true novolacs. Bisphenol F epoxy
resin performance in wastewater treatment facilities is
between bisphenol A epoxy resin and true novolac. For
the purpose of this article, bisphenol F epoxy resin will
be considered its own class. This will be an important is-
sue for decision makers; some manufacturers do not dis-
tinguish between bisphenol F and other novolac epoxy
resins. Not distinguishing between the two resins can re-
sult in using a product that does not perform adequately
or buying a more expensive and more durable system
than the exposure environment requires.
The viscosity of novolac resins is significantly higher
than that of bisphenol F resins. As important, the func-
Secondary containment at a wastewater treatment facility. An epoxy
tionality is considerably greater. The higher viscosity and
novolac resin or a Bis F epoxy resin is appropriate along with a
cycloaliphatic amine curing agent. greater functionality of the novolacs make their heat and
chemical resistance properties superior to those of
bisphenol F. Table 1 summarizes the key chemical prop-
erties of the epoxy resins described.
cosity and functionality of the resin are. Therefore, in-
creasing molecular weight brings the resin to a consisten- Performance Differences
cy that requires solvent to allow for application to the among Bisphenol A, Bisphenol F,
substrate. and Novolac Resins
Functionality is fundamentally the number of sites Bisphenol A epoxy resin is the workhorse resin for the
available for reaction with curing agents. More reactive majority of chemically curing epoxy coatings for concrete
sites per molecule result in a tighter and more three-di- and steel. It is used extensively because of its excellent
mensional crosslink density. Increasing functionality thus adhesion, toughness, wear resistance, and chemical resis-
increases strength and chemical resistance, thus allowing tance.
the resins to be used in maintenance primers. Bisphenol F resins have been steadily gaining ground
in civil engineering applications because of their resis-
Bisphenol F Resin Structure tance to a wider range of chemicals. There are two
Bisphenol F is similar to bisphenol A except phenol is re- main reasons for their chemical resistance properties.
acted with formaldehyde rather than acetone. The resul- First, bisphenol F systems have slightly higher function-
tant phenolic chemical does not have the two methyl ality than bisphenol A. The higher functionality pro-
groups that are present between the ring structures in vides more reaction sites, leading to a tighter and more
bisphenol A resins. Bisphenol F is reacted with epichloro- three-dimensional crosslink density. Crosslink density
hydrin to form diglycidylether bisphenol F (DGEBF) determines chemical resistance. Second, relative to
resins. Because of the missing methyl groups, the viscosi- bisphenol A resins, bisphenol F resins have lower vis-
ty of bisphenol F resins are typically 1/3 (2,500-5,000 cosity. Lower viscosity means fewer additives and dilu-

50 JPCL May 2000

Copyright 2000, Technology Publishing Company
 Amine-Based
Table 2: Epoxy Curing Agents
Relative Performance Properties of Epoxy Resins For most coatings, the ambient tem-
Bis A Bis F Novolac perature curing requirements demand
Performance Property* Epoxy Epoxy Epoxy the use of amine-based curing agents.
While the epoxy resin selection sets
Adhesion 3 3 3
some limits on performance, the type
UV protection 1 1 1
of curing agent provides significant
Abrasion resistance 3 3 3 performance enhancements. Under-
VOCs 2 3 3 standing the chemistry of basic curing
Crystallization 1 3 3 agents will assist in recognizing the
performance differences they impart.
Moisture tolerance 3 3 3
The classes of amine hardeners in-
Heat resistance 1 2 3
clude
Chemical resistance 1 2 3 aliphatic amines,
Sulfuric acid 1 2 3 polyamides and amidoamines,
Acetone 1 2 3 cycloaliphatic amines, and
aromatic amines.
Methanol 1 2 3
Sodium hydroxide 3 3 3
Aliphatic Amines
Organic acids 1 2 3 and their Modifications
Aliphatic ethylene amines were the
*Key: Scale is from 1 to 3, with 3 reflecting the highest performance among the epoxies described.
first amine hardeners used in epoxy
coatings. They are simple commodity
chemicals that were available to react
ents are needed to enhance application properties. Addi- with epoxies. They include aminoethyl piperazine (AEP),
tives and diluents diminish the crosslink density, which diethylene triamine (DETA), ethylene diamine (EDA), and
in turn lowers chemical resistance of any epoxy system. triethylene tetramine (TETA). The benefits of using these
(Keep in mind, however, that resin content must be bal- amines include high reactivity (fast cure) at ambient tem-
anced by formulators who impart other desirable prop- perature and excellent solvent resistance because of their
erties by this means. Therefore, even with a pure high functionality. Disadvantages such as limited flexibili-
bisphenol F resin system, additives are necessary to pro- ty and inefficient chemical reaction with the epoxy resin,
vide the right surface appearance and application prop- which leads to surface carbonation or blushing, have rele-
erties.) gated these amines to an additive status in their pure
Compared to bisphenol A resins, bisphenol F resins state. Modifications such as adduction or pre-reaction
also have less of a tendency to crystallize at low tempera- with a small amount of epoxy overcome flexibility prob-
tures. Heating the resin will re-liquefy the crystals, but lems and improve compatibility with epoxy resins to re-
heating is difficult to do on a job site. If crystallization is duce surface defects. Formulators generally use these
severe, the crystals may appear in the final film. modified ethylene amines with other hardeners to obtain
Novolac resins provide two important performance ad- desired performance properties.
vantages over bisphenol F resins. First, novolac resins Other aliphatic amines include hexamethylene diamine
possess greater chemical resistance properties because (HMD) and trimethyl hexamethylene diamine (TMD).
their very high functionality results in a very tight These chemicals share the high reactivity of ethylene
crosslink density. Second, the larger number of aromatic amines, but they offer moderate flexibility because of
ring structures increases heat resistance in the final sys- their greater linearity (compared to ring structures) and
tem. These properties tend to make the pure novolac the presence of two terminal primary amines. These ter-
resin systems more brittle than bisphenol A or bisphenol minal amine groups are unhindered because they are at
F resin systems, but the problem of brittleness is general- opposite ends of the molecule. This accounts for their fast
ly addressed by formulation techniques and hardener se- reaction time. This also allows for greater flexibility be-
lection. An overview of relative performance properties is cause the distance between two reaction sites is maxi-
outlined in Table 2. mized by their location. The closer and greater the num-

JPCL May 2000 51

Copyright 2000, Technology Publishing Company
 ing solvent resistance generally re-
Table 3: quires blending with other more sol-
Relative Performance Differences among Amine Curing Agents vent-resistant hardeners.
Color Low Temp Water Film Heat Solvent Acid Metaxylylene diamine (MXDA) pro-
Stability Viscosity Cure Sensitivity Flexibility Resistance Resistance Resistance vides excellent compatibility with
Excellent Low Good Low Good Excellent Excellent Excellent epoxy because of an aromatic ring
structure, but its relatively low molec-
IPDA DETA MXDA MDA PAR MDA DETA MDA ular weight allows for some blushing
DCH TMD or carbonation to occur. Its heat resis-
TMD MXDA TMD
tance is better than other aliphatic
PEA PEA
amines discussed because of the aro-
DETA AA DCH TMD
PACM PACM IPDA IPDA MXDA matic backbone. But this same aro-
IPDA DCH matic group limits flexibility and re-
DCH DETA PACM PACM DCH DCH silience. The most distinct feature is
DCH MXDA IPDA its ability to cure at lower tempera-
PEA tures than other aliphatics because of
PAR TMD its unhindered primary amines.
AA TMD PACM IPDA
MDA PACM PACM
Polyamides and Amidoamines
PACM IPDA MXDA Polyamides and amidoamines share
AA MDA several significant advantages over
MXDA PEA MXDA TMD aliphatic (ethylene) amines. These ad-
IPDA DETA PAR vantages result from the introduction
AA DCH AA AA of a fatty acid into the backbone of
PAR PAR
the epoxy hardener. Amidoamines are
AA MXDA
PAR AA TMD a reaction product of tall oil fatty acid
DETA DETA (TOFA) and ethylene amines.
PAR DETA PAR Polyamides are based on dimerized
TOFA and ethylene amines. Ami-
PEA doamines have a lower viscosity.
PEA PEA Unique properties include improved
MDA MDA MDA PEA flexibility and wet-out, improved ad-
Poor High Poor High Poor Poor Poor Poor
hesion, and outstanding water resis-
Key: tance. Additionally, corrosivity and
AA: Amidoamines MXDA: Metaxylylene diamine (aliphatic) health hazards are reduced due to
DCH: Diaminocyclohexane (cycloaliphatic) PACM: bis-(p-aminocyclohexyl) methane (cycloaliphatic) lower functionality. (Corrosivity is a
DETA: Diethylene triamine (aliphatic) PAR: Polyamide resin
measure of how rapidly a substance
IPDA: Isophorone diamine (cycloaliphatic) PEA: Polyetheramines (aliphatic)
MDA: Methylene dianiline (aromatic) will corrode or degrade a surface.
TMD: Trimethyl hexamethylene diamine (aliphatic)
Generally, this is a measure of impact
on contact with skin and eyes.) This
lower functionality also leads to
ber of reactive amine groups are, the harder and more in- longer usable pot life, less sensitive mix ratios, and signif-
flexible the cure system will become. Their compatibility icantly less risk for carbonation and surface defects than
with epoxy is also better than that of ethylene amines, is the case with aliphatic amines. However, solvent and
but they too require modification to overcome carbona- acid resistance suffer as a result.
tion. TMD is often used as a flow and leveling agent, but Polyamide resins (PAR) and amidoamines (AA) are
cost prohibits its widespread use. used in primers or tie coats for steel and concrete. For
Polyetheramines provide good color retention, good outstanding chemical resistance, however, other amino
flexibility, and reduced carbonation tendencies but react hardeners are selected for topcoats. Modifications such as
more slowly than other aliphatic amines. In addition, oxy- adduction are common to improve compatibility with
genated solvents attack the polyether backbone. Enhanc- epoxy. Solvent resistance can also be improved by formu-
52 JPCL May 2000
Copyright 2000, Technology Publishing Company
 lating with other amine hardeners
such as ethylene amines or other
Table 4:
Epoxy Systems for Components of a Wastewater Treatment Facility
short, highly functional curing agents.
WWT Structures Epoxy Resin Type Curing Agent Type
Cycloaliphatic Amines Administration building floors Bis A Aliphatic, cycloaliphatic
Isophorone diamine (IPDA) and di- Bis F
Aeration tanks Aliphatic, cycloaliphatic
aminocyclohexane (DCH) are the
Aerobic digesters Bis F Aliphatic, cycloaliphatic
most widely used cycloaliphatic
Anaerobic digesters Bis F Aliphatic, cycloaliphatic
amines. This class of amine is charac-
Air pollution control equipment Bis F Aliphatic, cycloaliphatic
terized by an amino group on the six-
Bar screen chamber Bis F Aliphatic, cycloaliphatic
carbon ring structure. Through the
Chemical feed room walls All All
presence of a non-chromophoric ring
Chemical feed room floors All All
structure, IPDA and DCH provide the
Chlorine contact chambers EPN*, Bis F
most light-stable systems of all amine
structures. This structure also pro- Clarifier tanks, steel Bis F Polyamide primer, cycloaliphatic
vides greater heat resistance than lin- topcoat
ear aliphatic amines. Cycloaliphatics Clarifier tanks, concrete Bis A/Bis F Aliphatic, cycloaliphatic
Control room floors Bis A/Bis F Aliphatic, cycloaliphatic
Control room walls Bis A/Bis F Aliphatic, cycloaliphatic
Demineralization units Bis A/Bis F Aliphatic, cycloaliphatic
Distribution chambers Bis A/Bis F Aliphatic, cycloaliphatic
Grit chambers Bis A/Bis F Aliphatic, cycloaliphatic
Influent collection channel Bis A/Bis F Aliphatic, cycloaliphatic
Lift stations Bis A Polyamide, aliphatic
Manholes Bis A Polyamide, aliphatic
Nitrification reactor tanks EPN Cycloaliphatic
Operations building floors Bis F/Bis A Aliphatic, cycloaliphatic
Process building floors Bis F/Bis A Aliphatic, cycloaliphatic
Pump house floors Bis F/Bis A Aliphatic, cycloaliphatic
Secondary containment EPN, Bis F Cycloaliphatic
Sedimentation tanks Bis F/Bis A Aliphatic
Slope/fill Bis A All
Sludge thickeners EPN Aliphatic, cycloaliphatic
Storage tanks, exterior Bis F/Bis A All, not topcoats
Structural steel Bis F/Bis A All, not topcoats
Hydrochloric acid tank in secondary containment at a
desalination water treatment facility. Secondary con- Sumps All All
tainment lining requirements here are similar to those Trenches All All
for secondary containment at wastewater plants.
*Epoxy Novolac

increase rigidity, which improves mechanical strength
over both aliphatic and fatty acid-based amines. They are
slower reacting than aliphatic amines but faster than
polyamides. Chemical resistance (non-solvent) is superior
to aliphatic amines and polyamides. Carbonation is still a
potential problem, but adduction with epoxy has become
standard in the industry to reduce this effect. In general,
accelerators are necessary to complete the reaction be-
tween the epoxy and the hindered ring-bound amine.
A relatively new cycloaliphatic amine is bis-(p-aminocy-
JPCL May 2000
Copyright 2000, Technology Publishing Company
clohexyl) methane (PACM). This amine combines the low
temperature cure characteristics of MXDA with the heat
resistance and mechanical strength of the other cy-
cloaliphatics. It is characterized by two ring structures
with ring-bound amines connected by a methylene
bridge. It yields significantly tougher coatings than do
other cycloaliphatics because of its low functionality,
which results in a low crosslink density. It gives better
solvent resistance than that given by PAR but poorer re-
sistance than that given by aliphatics. Its compatibility
53
with epoxy is excellent due to the double ring structure,
and carbonation is less likely than with aliphatic amines. Table 5:
Acid resistance suffers as a result of the long distance be- Index of Epoxy Resins and Curing Agents
tween reactive amines. The unhindered primary amines Chemical Name Abbreviation C.A.S.#
are easily accessible for reaction, which makes this a fast- Resins
reacting system. Adduction is a typical modification to re- Diglycidyl ether bisphenol A Bis A resin 25068-38-6
duce corrosivity and further improve compatibility with epoxy resin liquid (DGEBA)
epoxy. Diglycidyl ether bisphenol A Bis A resin 25036-25-3
epoxy resin solid
Diglycidyl ether bisphenol F Bis F resin 9003-36-5
Aromatic Amines
(DGEBF)
and their Modification 028064-14-4
Epoxy phenol novolac Novolac resin
For years, the most widely used aromatic amine was (EPN)
methylene dianiline (MDA). It offered a long pot life,
the best acid and heat resistance, and excellent mechan- Curing Agents
ical properties. It was also non-corrosive and non-irritat- Aminoethyl piperazine (aliphatic) AEP 140-31-8
ing, moisture insensitive, and flexible. Color stability Ethylene diamine (aliphatic) EDA 107-15-3
Diethylene triamine (aliphatic) DETA 111-40-0
was its major drawback. Unfortunately, it has been
Triethylene tetramine (aliphatic) TETA 112-24-3
found to be systemically toxic. In addition, restrictions 124-09-4
Hexamethylene diamine (aliphatic) HMD
imposed by the U.S. Occupational Safety and Health Ad- Trimethyl hexamethylene diamine TMD 025620-58-0
ministration (OSHA) and health concerns in handling (aliphatic)
MDA have forced most formulators to stop using MDA. Polyetheramines (aliphatic) PEA 9046-10-0
Fortunately, formulators have found alternative Metaxylylene diamine (aliphatic) MXDA 1477-55-0
chemistries to satisfy most of the demands for perfor- Polyamide resins PAR 68410-23-1
mance properties of MDA. Amidoamine resins AA 68953-36-6
Isophorone diamine (cycloaliphatic) IPDA 2855-13-2
Table 3 summarizes the performance differences that
Diaminocyclohexane (cycloaliphatic) DCH 694-83-7
can be expected by most of the types of amine-cured 1761-71-3
bis-(p-aminocyclohexyl) methane PACM
epoxies described above. These differences are relative (cycloaliphatic)
to each other within each class of epoxy. Ultimately, Methylene dianiline (aromatic) MDA 101-77-9
coating performance will depend on the formulators
skill in designing a product for a specific niche or appli-
cation. Nevertheless, this information on relative perfor-
mance can assist decision makers in understanding the
products specified and purchased. MSDSs helps the specifier locate information on the
coatings ingredients and compare generically similar
Practical Application coatings to learn of any significant differences between
of the Chemistry Described them.
To bring this chemistry into the world of wastewater
treatment facilities, Table 4 identifies the appropriate Conclusion
choice of a cured epoxy system for typical structures in This article has identified several variations within an
a wastewater treatment facility. Table 5 gives names of epoxy formulation. Resin options include bisphenol A,
the resins and curing agents discussed, their abbrevia- bisphenol F, and novolac to vary base functionality and
tions, and their Chemical Abstracts Service (C.A.S.) chemical resistance. Modification of the hardener allows
numbers. (The C.A.S. is an organization that provides for enhanced performance, cure properties, chemical re-
an index to information in Chemical Abstracts, which is sistance, flexibility, and light stability. When selecting
published by the American Chemical Society. The C.A.S. epoxies for wastewater facility application, it is important
numbers help readers locate information about particu- to select the best and most appropriate formulation to
lar substances in the Chemical Abstracts.) The material meet the demands of the environment without incurring
safety data sheet (MSDS) of a coating will list the spe- excess cost.
cific curing agents and resins in the coating composi-
tion. The MSDS must list the C.A.S. number of each in-
gredient. Thus, knowing the C.A.S. numbers from
54 JPCL May 2000
Copyright 2000, Technology Publishing Company