Materials

Take the Guesswork Out of

FRP Gunnar Bergman,

Swedish Corrosion Institute

Corrosion
 The lifetime of
fiberglass-reinforced
plastic equipment and
piping often depend
upon previous
experience.
Here’s a way to predict
and prolong service life.
B
ecause plastics are often used to solve corrosion
problems of metallics, one may be led to believe
that they cannot be attacked by corrosion. But this
is not true. It is well known in a pulp mill or a chemical plant,
particularly by the maintenance staff, that, in time, corrosion
damage may appear on plastic structures and components. In
many instances, the lifetime or the need for repair of the
structures is determined by the corrosion attack. Depending
on the type of plastic, fabrication method, type of fiber, tem-
perature and other factors, the corrosion rate or changes in
mechanical properties may be negligible over a period of 20
yr or more, or may lead to a failure in a couple of weeks.
From that point of view, metals and plastics or other materi-
als are equal. We can find numerous corrosion-related fail-
ures, as well as successful applications.
Compared with metals, a shortcoming for plastics is that
the corrosion science of the former is more developed. One
reason is certainly that plastic materials are younger than,
for example, steels.
By learning from the history of metal corrosion, we can
foresee the necessary future developments in polymer corro-
sion science. The confidence and the general status of plastic
materials would probably be significantly increased if their so-
called “chemical resistance” could be presented in technical
corrosion terms analogous to metals. An increased knowledge
of the corrosion properties of plastic materials is also necessary
to master existing instances of corrosion damage and is key to
the future development of improved materials and products.
Selecting plastics
Practical experience shows that the reasons and causes
for selecting plastics in process equipment include (1):
• Corrosion damage has occurred repeatedly with vari-
ous steels that have worked well previously, and the corro-
sion resistance of still more-highly alloyed steels is uncer-
tain or they have already failed.
• Unexpected rapid corrosion has occurred on new con-
Copyright 2000 © NACE International, Houston, TX. First presented at
Corrosion 2000, Orlando, FL. Used with permission.
■ Figure 1. FRP (right) replaced a titanium-lined cover
of a bleach tower (left). Unexpectedly, the titanium lining
suffered from uniform corrosion and became thin.
struction of stainless steel, e.g., SS 2343 (Type 316, UNS
S31600) or on more-highly alloyed steels.
• Unexpected rapid corrosion has occurred with ex-
pensive materials, such as titanium and nickel-based
alloys (Figure 1).
• Damage in older constructions made of wood, concrete,
or lead- or brick-lined steel has become difficult to repair.
• No other material was considered with regard either to
the corrosion stresses or mechanical load.
• The corrosive environment may vary inside or outside
the component. Unexpected external corrosion damage,
sometimes under insulation, has occurred due to spills or
from leaking aggressive gases.
• A plastic (solid or lining) is considered the best selec-
tion from a technical/economical viewpoint.
Plastics such as FRP are “traditionally” considered only
where the environment is strongly corrosive to Type 316
stainless steel, for example, and their use in other cases is
often overlooked.
Plastics vs. metals
Corrosion of metals is mostly determined by electro-
chemical processes, while that of FRP or other plastics is
the result of organochemical ones. A vital difference be-
tween metals and plastics is that the structure of the former
is 100% crystalline and the structure of the latter is
semicrystalline or amorphous. Therefore, also physical pro-
cesses like diffusion, osmosis and swelling may play an im-
portant role in the corrosion of plastics. However, there are
still certain similarities. Most types of corrosion found in
metals may also be found in plastics, for instance, uniform
corrosion, selective corrosion, stress corrosion, layer corro-
sion (delamination for FRP) and localized corrosion (pit-
ting) (Figure 2). Some types of metal corrosion, such as
crevice corrosion, may possibly not be found in plastics and
vice-versa (e.g., swelling and osmosis blistering) (Figure 3).
CEP December 2001 www.cepmagazine.org 55
Materials
■ Figure 2. Piping made from stainless steel (top)
and of FRP (bottom). Both materials became thin
due to uniform corrosion attack.
Corrosion data
For metals, there are well-developed testing methods for
each type of corrosion and the data achieved for specific ma-
terials can easily be compared and be of use in materials se-
lection and design. For plastics, the situation is not as clear-
cut. In manufacturers’ data sheets, corrosion data are never
or seldom presented. Instead, the sheets list the so-called
“chemical resistance” of the material in different environ-
ments as a recommendation for use up to a certain maxi-
■ Figure 3. Swelling damage
of a PVC lining in an FRP
pipe (top) and swelling of the
resin matrix in an FRP
laminate of another pipe
(bottom). The swelling caused
extensive micro-cracking.
■ Figure 4. Successful use
of FRP in a reaction tower
for making iron (III) chloride
by oxidation of an iron (II)
chloride solution with
chlorine gas at 80–90°C.
Upon inspection after 14 yr,
the tower was found to be in
excellent condition.
56 www.cepmagazine.org December 2001 CEP
mum temperature, or, more generally, as “resistant,” “limited
resistance” and “not resistant.” Consequently, there is no in-
formation given about the types of possible attack, how fast
attack proceeds into the wall, and what damage it may
cause. It is therefore difficult to take any possible corrosion
into account when designing a product for a certain lifetime.
The service reliability cannot be assessed and one cannot
compare the resistance of different materials or materials of
the same type, but only of different brands or grades.
Available literature contains many investigations into
the chemical resistance of plastics in various environments.
However, the environmental effect on the material is sel-
dom evaluated and described in technical corrosion terms,
and the investigations are therefore less practical. When se-
lecting a plastic for service in a specific medium, its long-
term corrosion properties need to be known. The engineer
ought to know how different substances in the medium af-
fect the material and which corrosion process might be
critical with regard to service conditions, rate of corrosion
and the desired lifetime.
A complication is that FRP and other plastics are not
specific or standardized materials, but the names stand for
a group of materials. The corrosion properties of FRP, for
instance, may differ depending on factors such as, the type
of resin and curing system used, the type and content of
fiberglass, the laminate structure and the fabrication proce-
dure. Such parameters may be considered as the quality of
the material. Experience about the corrosion performance
of a plastic, or corrosion data obtained from corrosion
analyses, may therefore not be generalized, but must al-
ways be accompanied by a clear-cut definition of the mate-
rial and, preferably, a quality characterization.
Within the chemical process industries (CPI), corrosion
performance of different plastics in various applications
has mostly been gained by full-scale use of the process
components under actual service. Failures have sometimes
generated high costs for repairs or replacement, and for
lost production in cases of unplanned shutdowns. It is un-
satisfactory that the causes of different kind of failures sel-
dom are thoroughly investigated.

Uses and alternative materials ■ Figure 5. FRP is the standard material for many components
Plastic materials are used to a large extent in process at chlor-alkali plants.
equipment in pulp-and-paper plants (mostly in the bleach
and chemical-preparation plants) and in chemical opera-
tions, typically in the manufacture of chlorine, chlorate and pulp mills for up to about 20 yr, and of FRP coupons (sam-
sulfuric acid. Plastics are also used to a great extent in ples of a material used to test its corrosion resistance) ex-
plants that employ different kinds of acid, e.g., hydrochlo- posed in the field (1, 2), a semi-empirical relationship ex-
ric, hydrofluoric, and nitric, as well as metal chlorides, e.g., ists for uniform corrosion of FRP in ClO2:
NaCl, FeCl3, AlCl3, MgCl2 and NiCl2 (Figure 4). They are
also found in equipment in desulfurization plants, such as Φ = B·tα·c·A·e–Ea/RT (1)
flue-gas ducting and scrubbers, as well as those in the off-
shore-oil industry. Sometimes, FRP is used with a thermo- where Φ is the depth of corrosion, mm; B is a special fac-
plastic lining of polypropylene (PP), polyvinyl chloride tor in case of protective deposits on the surface (usually, B
(PVC) or polyvinylidene fluoride (PVDF). The alternatives = 0 or 1); t is the time in service, yr; α is a factor that de-
to plastics vary from case to case, but are in general, high- pends on the thickness and the degree of degradation of the
alloyed stainless steels, titanium, nickel-based alloys or corroded surface layer (usually, α is between 0.5 and 1); c
pure nickel, brick or rubber linings, and enameled steel. is the concentration of chlorine dioxide, g/L; A is a materi-
Now, we will review the performance of FRP in some al constant that depends on the type of resin, the degree of
typical environments. curing and the laminate structure; Ea is the activation ener-
gy of the rate-controlling step of the corrosion process,
Performance in chlorine dioxide J/mol; R is the gas constant, 8.3 J/mol•K; and T is the tem-
Chlorine dioxide (ClO2) is an important bleaching agent perature, K. Note: B = 0 in the case of a deposit on the sur-
for pulp. FRP has long been used for handling streams con- face that gives 100% corrosion protection to the FRP. We
taining ClO2, both in the bleach plant and in the plant that have seen such deposit layers in some instances on FRP
produces it. Alternative materials are titanium (for all con- equipment in plants producing ClO2. The protective layer
centrations and temperatures), brick linings with polyester can be thin and be of a different nature. When there is no
or vinyl ester-based joint mortar, high-alloyed stainless deposit layer, B = 1.
steels (only where the concentration of ClO2 is low), and,
for certain applications, PVC and fluoroplastics. Among
these materials, FRP is very attractive, but only if the struc-
tures offer a high level of reliability and long lives, without
too much need for repair.
The performance of FRP in ClO2 cannot be generalized
as it varies in different applications. The service lifetime,
or repair interval, is normally determined by uniform cor-
rosion from ClO2 attack. As long as the attack stays within
the so-called corrosion-barrier layer of the laminate (nor-
mally, 2.5 mm thick) it may not influence the strength of
the laminate and, consequently, the service reliability of
the structure. However, the normal procedure with FRP is
to install the equipment and then wait to see how long it
will last or run without the need for repairs. A better strate-
gy would be to design or ensure that the corrosion barrier
of the laminate is thick enough to assure reliability during
a desired service or interval of repair. For this purpose, cor-
rosion design data are needed. ■ Figure 6. As a result of high pH, this FRP piping had to be
Based on corrosion analyses of samples from FRP replaced after a short time when used in a line for warm, outlet brine
equipment used for different ClO2 environments in various in a chlorine plant with membrane cells.

CEP December 2001 www.cepmagazine.org 57

Materials
■ Figure 7. An FRP pipe after 1 yr in chlorine gas. Occasionally, the line was
subjected to liquid chlorine. Half of the wall thickness of the pipe was heavily
attacked. The resin (vinyl ester) in the corroded part was completely degraded
away. Fortunately, the damage was discovered in time.
The practical use of such a relationship can be summa-
rized as follows:
• The service life (regarding ClO2 attack) can be esti-
mated on existing structures. Replacements and repairs can
be made at optimum times.
• The estimated corrosion rate can be taken into account
when the structure is designed. A desired lifetime or inter-
val of repair can be assured.
• The cost-effectiveness of the material can be estimated
more easily, which facilitates materials selection.
Apart from ClO2 attack, FRP may also be attacked by
diffusing water, especially if the temperature is high, above
50°C. Water-related effects and damage to FRP materials are
complex. Moreover, considering the many matrix/fiber/lami-
nate buildup combinations used, this is an extensive subject
to master. Because of its importance, research at SCI in this
field is intensive (3).
Eq. 1 and its use in predicting behavior apply to uni-
form corrosion of FRP. However, this equation does not ac-
count for stress corrosion, which cannot be neglected. SCI
research found that two FRP piping failures occurred after
a short time in ClO2-containing environments because of
acid/fiberglass-related stress corrosion cracking.
Performance in chlorine
FRP has long been the standard material for many com-
ponents in chlor-alkali plants (Figure 5), and for chlorine-
containing environments in general elsewhere. The metal
alternatives are often restricted to titanium, but in a chlo-
rine-production plant, this is not feasible, at least where
there could be stray current from electrolysis cells. More-
over, titanium is highly unsuitable with dry chlorine
(<0.4% water), or where moist chlorine could become dry
by condensation of the moisture. The titanium may ignite
and burn explosively. For certain chlorine-containing envi-
ronments, nickel-based alloys may also be an alternative.
Molecular chlorine in a moist environment or in an aque-
ous solution causes the same type of attack on FRP as does
ClO2 — uniform corrosion gradually reduces the thickness of
the laminate, but a layer of corroded material may remain on
the surface (the“chlorine butter” layer). Research shows that
Eq. 1 also can be used to estimate such attack caused by
molecular chlorine in moist, gaseous environments or in aque-
ous solutions, at different temperatures and concentrations.
58 www.cepmagazine.org December 2001 CEP
A knowledge of chlorine chemistry is needed in the de-
sign of FRP structures for different chlorine environments.
This entails finding data for certain equilibrium constants
and the solubility of chlorine in the actual environment.
The active form of chlorine in an aqueous solution depends
on pH, and is controlled by the following two equilibria:
Cl2 + H2O = HClO + H+ + Cl– (2)
HClO = H+ + ClO– (3)
The importance of pH is illustrated by two cases in two
chlorine plants. The first plant uses mercury cells and the
second, membrane-cell technology. In the mercury-cell
plant, the outlet brine has a pH of 2–2.5 and is at about
80°C. FRP piping of standard grade (2.5 mm corrosion-
barrier layer and made with a chemical-resistant resin)
was replaced after 14 yr. Uniform corrosion from chlorine
attack had entirely consumed the barrier layer of the lami-
nate; the corrosion depth was about 2.7 mm. The chlorine
concentration in the solution was about 0.3–0.4 g/L. A
lifetime of 14 yr is generally considered satisfactory.
However, by choosing a thicker barrier layer and also a
more corrosion-resistant type of resin, such as a novolac-
epoxy-based vinyl ester, the lifetime can be prolonged to
20 yr or more.
Considering the good performance of FRP piping for out-
let brine in many chlorine plants, such piping was also cho-
sen for the outlet brine in the chlorine plant with the mem-
brane cells. However, after only one year of operation, all
piping in this application was severely corroded and had to
be replaced (Figure 6). The outlet brine had a pH of 4–5 and
was also around 80°C. The plant did not understood why
FRP did not perform well. Studies showed that laminate
quality or improper choice of resin type was not the reason.
However, owing to the higher pH of this solution, the
chlorine species in it was, to a great extent, hypochlorous
acid (about 2.5–3.5 g/L). The content of molecular chlorine
in the solution was 0.3–0.5 g/L. In the brine from the mer-
cury cells, the hypochlorous acid concentration was more
than a hundred times less (about 0.02 g/L) due to the lower
pH. The content of molecular chlorine in the solution was,
however, about the same.
For some reason, hypochlorous acid is strongly corrosive
toward FRP. It causes a gradual reduction in thickness of
the material without any obvious surface-layer corrosion.
Corrosion testing of clear castings of different commercial
types of resin in an environment containing 0.8–1.5 g/L of
hypochlorous acid, but no molecular chlorine, at 80°C
showed that the corrosion rate was 4–6 mm/yr. Further, it

was shown that the presence of fiberglass enhanced the cor-
rosion rate significantly. With such corrosion data, it is easy
to understand the corrosion behavior of the FRP piping for
outlet brine in the plant with the membrane cells. These two
cases demonstrate clearly the importance of having relevant
corrosion data for predicting service performance of FRP in
chlorine-containing environments.
The mechanisms of corrosion of FRP in dry chlorine gas
differ somewhat from that in moist gas. For dry gas, the
chlorine causes mainly a chlorination of the resin. Depend-
ing on the type of resin in the laminate, this is not necessar-
ily accompanied by a significant degradation of the resin
matrix. However, hydrochloric acid is formed in the chlori-
nation process. The diffusion rate of the acid in the laminate
is much faster than that of chlorine. This has, for example,
caused hydrochloric-acid corrosion on titanium that was
protected from direct contact with dry chlorine by a thick
coating of FRP. Moreover, such formation of hydrochloric
acid in a chlorine-exposed laminate has sometimes caused
stress-corrosion cracking in joints of FRP piping.
FRP piping is unsuitable where it could contact liquid
chlorine. When FRP piping is used for gasified chlorine, it
is strongly recommended that effective measures are taken
against ingress or formation of liquid. Otherwise, the plas-
tic may fail after a short period (Figure 7). A common
cause of liquid chlorine in such piping is that the gas con-
denses due to cooling from the outside. That can happen in
uninsulated lines when the flowrate is low.
Performance in chlorate environments
In pulp mills, FRP is used in tanks and piping for con-
centrated, warm solutions of sodium chlorate. Alternatives
are usually stainless steels. A pulp mill in Sweden found
FRP to be a successful alternative to two types of stainless
steel for storing sodium chlorate at about 70°C. In 1970,
the mill put a Type 304 stainless steel chlorate-dissolving
tank in operation. After 6 months, a number of stress corro-
sion cracks were found. Consequently, the tank was lined
Literature Cited
1. Bergman, G., “Corrosion of Plastics and Rubber in Process Equip-
ment – Experiences from the Pulp and Paper Industry,” TAPPI Press,
Atlanta, GA (1995).
2. Bergman, G., “Corrosion Resistance of Glass-fibre Reinforced Plas-
tics (GRP) in Chlorine Dioxide Environments.” in “Pulp and Paper
Corrosion Problems,” Vol. 5, Proc. Fifth International Symposium on
Corrosion in the Pulp and Paper Industry, Vancouver, Canada, pp.
105–109 (June 3–6, 1986).
3. Bergman, G., “Corrosion of Glass-fibre Reinforced Ester Plastics
(GRP) used in Pulp Mill Applications — Effects and Damage Main-
ly Related to the Influence of Water,” in “Pulp and Paper Corrosion
Problems,” Vol. 6B, Proc. 6th International Symposium on Corro-
sion in the Pulp and Paper Industry, Helsinki, Finland, pp. 386–400
(Aug. 29–Sept. 1, 1989).
■ Figure 8. This 27-
year-old FRP chlorate
tank, in the Mörrum,
Sweden mill continues
to hold up well.
with Type 316, but the lining was attacked after 1.5 yr; this
time by localized corrosion of the plate. The tank was re-
placed with an FRP tank in 1972 (Figure 8). The laminate
was built up with an epoxy-based vinyl ester resin. The
tank is still in service, with no need for repairs during its
27 years of operation, apart from replacing a stainless steel
heater in its bottom, which suffered badly from corrosion.
The experience with FRP tanks and pipings for sodium
chlorate solutions in pulp mills has mostly been good. Fail-
ures have been caused by poor-quality construction or by
the laminate. For example, one FRP tank burst after 8 yr
because the chlorate penetrated and weakened a vertical
joint of inferior quality. In modern production plants of
sodium chlorate, FRP structures dominate. However, for
equipment in contact with the chlorate electrolyte, the FRP
is lined with fluorinated ethylene propylene (FEP), because
the electrolyte contains hypochlorous acid (about 1 g/L)
and is therefore strongly corrosive to FRP. Titanium is a
strong candidate among the metals for this environment,
but it cannot be used in the electrolysis cells or in the pip-
ing close to the cells due to risks related to stray current.
Concluding remarks
Confidence, cost-effectiveness and assurance of a high
level of service reliability during a desired lifetime or
maintenance interval are some key factors that affect the
choice of material for a specific environment. Increased
corrosion studies of plastics in different environments
would certainly benefit, support and facilitate the choice of
such materials in many future applications and help in de-
veloping of new materials and products. ◆
GUNNAR BERGMAN is group leader for the section Corrosion Properties of
Polymeric Materials at the R&D department of the Swedish Corrosion
Institute (Kräftriket 23A, SE-104 05, Stockholm, Sweden; Phone:+46-
86741728; Fax: +46-86741780; E-mail: gunnar.bergman@corr-institute.se).
He has 20 years of experience in the use of plastics and rubber in process
equipment within the pulp-and-paper and chemical process industries. He
has a MSc degree in chemical engineering from the Royal Institute of
Technology, Stockholm, with a major in polymer technology. Bergman is a
member of the Technical Association of the Pulp and Paper Industry
(TAPPI), NACE International, the Society of Plastics Engineers (SPE) and the
Institute of Materials (U.K.). More information about his research activities
can be found at www.corr-institute.se.
CEP December 2001 www.cepmagazine.org 59