Durability of Isophthalic Polyester Composites Used in Civil Engineering Applications

Durability of Isophthalic Polyester Composites Used in

Civil Engineering Applications

H. J. Dagher1, A. Iqbal2, and B. Bogner3

1
Prof. of Civil/Structural Engineering, Director AEWC Center, University of Maine, Orono, ME, USA
2
Engineer, Maine Department of Transportation, Augusta, ME, USA
3
Research Associate, BP Amoco Chemical, Naperville, IL, USA

Received: 6th June 2003; Accepted: 3rd November 2003

SUMMARY

Fiber Reinforced Polymer (FRP) composites are increasingly used in civil infrastructure
applications, primarily because of their high strength-to-weight ratio and corrosion
resistance. Further deployment of FRP in the construction market will be accelerated by
using low-cost, durable matrix materials. In this paper, published research on the
durability of a low-cost matrix, isophthalic polyester (IPE), is reviewed and the results
are compared to the durability of the more expensive vinyl ester (VE). The objective is to
evaluate the suitability of IPE in civil engineering applications, particularly in conjunction
with concrete and high alkaline environments. The analysis indicates that, although
vinyl esters are generally more durable than isophthalic polyesters, the performance
difference does not always appear to be very significant. More importantly, the literature
review revealed that the data on the durability of IPE in concrete and alkaline solutions
is of limited usefulness. Since this is the kind of information needed to evaluate IPE’s
effectiveness in construction applications, further research in these areas is recommended.

INTRODUCTION pilling systems alone costs the U.S. military and

civilian marine and waterfront communities
Once exclusive to the aerospace industry, Fiber $1 billion annually2. Thus, it has become increasingly
Reinforced Polymer (FRP) composites are steadily important to find new materials that promise better
finding their way into civil engineering durability and lower maintenance.
applications where high strength-to-weight ratios
and corrosion resistance can translate to lower
installation and maintenance costs. FRP Figure 1. One of three isopolyester composite bridge
composites are being used as reinforcing bars in sections is crane lifted into place to span a small
concrete, prestressing or post-tensioning elements tributary of The Great Miami River in Hamilton,
in concrete, concrete column wraps for seismic Ohio, USA. Photo by Ben R. Bogner
rehabilitation, bridge deck construction, pilings,
sheet pile retaining walls, offshore structures,
pipelines, as well as for strengthening of beams,
walls and slabs in existing buildings and bridges
(Figures 1, 2 and 3) 1 . They are also been
traditionally used in applications where
electromagnetic properties are important.

The deterioration process of the world’s

infrastructure is continuous and, as a result, so is the
rehabilitation, costing governments billions of dollars
in their maintenance. For example, it is estimated
that the deterioration of wood, concrete, and steel

Polymers & Polymer Composites, Vol. 12, No. 3, 2004 169

 H. J. Dagher, A. Iqbal and B. Bogner

Figure 2. Putruded isopolyester composite profiles Figure 3. A 12.3-meter (40 ft) isopolyester composite
give the top of Stone Mountain, Georgia, USA a bold bridge crosses Pipiwai Stream, Maui, Hawaii, USA.
new look while offering the right combination of Photo courtesy of Ben Bogner.
design flexibility, lightweight, high strength,
corrosion resistance and radio wave transparency.
Photo courtesy of Ben Bogner.

As stated earlier, high-performance FRP composites Table 1. Market prices of commodity resins (2002)
are increasingly becoming a choice for structural
rehabilitation, and niche markets in new construction Resin Type Description $ / lb a
are being developed. One major hindrance to the use General Purpose 0.53 - 0.57
of polymer composites in civil infrastructure is the Polyester
susceptibility of the polymer matrix to weathering Isophthalic 0.70 – 0.80
(Thermoset)
caused by ultra-violet (UV) degradation, moisture, Bisphenol-A 1.20 – 1.50
temperature, and high pH environments3. The marine
Corrosion Resistant 1.47
environment, which can corrode steel by as much as
0.75 mm per year, is considered to be one of the most Vinyl ester Heat and Corrosion
1.61
naturally aggressive4. Resistant
General Purpose 1.16-1.26
In new construction, all-FRP composite structures Epoxy
are often more expensive than traditional concrete Compounds 1.23-2.71
and steel, particularly in applications where high- a
www.PlasticsTechnology.com
strength/weight ratios are not critical or when life-
cycle costs are not considered. To improve the
market viability of FRP composites in civil
engineering applications, it is important, among
other measures, to employ relatively low-cost resin reported to cost $0.70-0.80/lb in 2002. While IPE are
systems. However, low cost cannot come at the less expensive than vinyl esters (VE) and epoxy
expense of performance, particularly long-term resins, they have been reported to be less durable than
durability. Thus, it is important to investigate VE in some end-use environments.
whether valid conclusions about the cost-durability
trade-off can be drawn based on current research or The objectives of the paper are (1) to review and
whether additional investigation is needed. synthesize the literature and present comparative
data on durability of IPE versus VE resins in civil
Commodity thermosetting resin prices in the USA engineering applications and, (2) based on that review,
from the year 2002 are listed in Table 1. Of the resins to propose additional durability research work that
in Table 1, this paper focuses on the durability of needs to be done on IPE resins for specific civil
relatively inexpensive isophthalic polyesters (IPE), engineering end-use environments.

170 Polymers & Polymer Composites, Vol. 12, No. 3, 2004

 Durability of Isophthalic Polyester Composites Used in Civil Engineering Applications
CHEMISTRY AND PRODUCTION OF IPE
Thermosetting polyesters are generally produced
from phthalic and maleic anhydrides and
polyfunctional alcohols, which are catalyzed using
peroxides that produce free radicals. Phthalic acid
is saturated, and maleic acid is unsaturated. They
can be mixed in various proportions to control the
reactivity of the resulting polyester resin. Phthalic
acid can be obtained in ortho-, iso-, and tere-forms
(isomers) according to the position of the acid groups
around the benzene ring, as shown in Figure 4. If an
iso acid such as isophthalic acid is used, the resulting
polymer is called Isophthalic polyester, also
commonly called isopolyester. Because of the
presence of the double bond, these polymers are
unsaturated and comprise the thermoset type of
polyester, in contrast to saturated polyesters such as
PET (polyethylene terephthalate). Isophthalic
polyesters are generally copolymers of maleic acid-
propylene-glycol-isophthalic acid5 in the molar ratio
of 1-2-1, formed through a condensation reaction.
Styrene monomer is the usual solvent/carrier
(approx. 40-50 wt%) used as cross-linking agent.
Isophthalic polyesters are considered a premium
grade of polyesters in the market.
Isophthalic acids are used to obtain resins that have
a better resistance to aqueous environments, and to
improve strength and chemical resistance. 1, 2
propylene glycol is the preferred polyfunctional
alcohol because it forms polyesters that are compatible
with styrene and show little tendency to crystallize;
it is also readily available at low cost. Higher molecular
weight isophthalic resins have higher tensile and
flexural strengths than lower molecular weight
phthalic resins. This may be because isophthalic
acids usually form more linear, higher molecular
weight polymers than orthophthalics. Orthophthalics
have lower amounts of maleic acid/anhydride, leading
to a less dense network, and they are therefore more
sensitive to hydrolytic attack. The ortho isomer is
Figure 4. Chemical structures of the isomers of Phthalic acid.
HOOC
6 1 2 1
1 COOH
5
3 6
6 COOH
4 2
COOH 5 4
3
Phthalic Acid (ortho) Isophthalic Acid
Polymers & Polymer Composites, Vol. 12, No. 3, 2004
also more hydrophilic thanthe meta (iso) isomer,
whose >C-O bond is much more stable5.
Unsaturated polyesters, particularly the isophthalic
acid-based varieties are well known for their resistance
to acids and mildly alkaline environments. Isophthalic
polyester is the most commonly used resin category
(holding 65% of the market) for corrosion-resistant
structures such as pipes, gasoline and sewage tanks,
ducts, etc.6 The other major resin category used is the
vinyl esters with 22% of the market. Isophthalic
polyesters are less expensive than vinyl esters and
epoxy resins, and are more commonly used in
corrosion applications in civil engineering projects.
One example of an isophthalic polyester application
is the Amoco Corporation’s use of glass-reinforced
IPE for underground fuel storage. Amoco’s experience
is that the composite has performed well, even after
20 years of continuous use7.
The reason isophtalic acid based polyesters are
preferred over orthopolyesters for structural
composites are their overall better physical properties.
Isophtalic acid polyesters have higher upper
temperature use limits, are more resistant to
degradation by water and chemicals and are more
impact resistant26.
LITERATURE REVIEW: DURABILITY OF
ISOPHTHALIC POLYESTER
Both isophthalic polyester and vinyl ester have been
used in civil construction where corrosion is a concern.
Although numerous research articles have been
published on the durability of FRP composites in
general, only a small subset of these articles addresses
the durability of isophthalic polyester. This section
describes, compares, and synthesizes findings from
these articles to help draw conclusions on the suitability
of fiber-reinforced isophthalic polyester as compared
to vinyl ester for civil infrastructure uses.
2
3
HOOC COOH
5 4
Terephthalic Acid
171
 H. J. Dagher, A. Iqbal and B. Bogner
When the durability of a fiber-reinforced polymer is
of concern, the matrix material may be considered
the weakest link in the composite.8 For civil
infrastructure end-uses, the matrix material is often
evaluated to determine its durability when subjected
to at least three factors: (1) photo-initiated oxidation
(UV), (2) hygrothermal changes and (3) alkaline and
saline environments. As detailed in the remainder
of this section, these factors are evaluated because a
majority of outdoor civil infrastructure materials are
subjected to these conditions under the normal
course of their life.
Durability results from 16 different studies of IPE and
VE are compiled for easy reference in Table 2, and
some are discussed in more detail below. The table
describes the testing environment (Column 1), the
type of specimen used (Column 2), the duration of the
test (Column 3), the percent reduction in strength for
both IPE (Column 4) and VE (Column 5) as applicable,
relevant comments on the study (Column 6), and it
also gives the author and year of publication (Column
7). The strength reduction (Columns 4 and 5) may
refer to any of the following: the tensile strength,
direct shear strength, interlaminar shear strength
(ILSS), flexural strength, or hoop tension strength, as
indicated in the Table. Individual cells in the strength
reduction columns 4 and 5 may have multiple entries
separated by “/”. Each of these corresponds to multiple
testing environments, specimen types, or tests
durations indicated in columns 1, 2, and 3.
Tannous et al. (1999)9 conducted a study on the effects
of water, concrete pore solution (pH=12), HCl (pH=3),
sea water, and temperature (25°C and 60°C), on
pultruded alkali-resistant (AR) glass fiber reinforced
polyester and vinyl ester composite 10 mm and 20 mm
bars where the intended end-use was as a reinforcement
for concrete beams. (The article does not identify the
type of polyester used.) In addition to testing individual
“bare” bars directly under different exposure
conditions, the authors also tested the bars embedded
in 8” x 16” x 8’ concrete beams. The beams were
subjected to de-icing solutions for one- and two-year
periods; the results are shown in Table 2.
In summary, the concrete pore water solution, calcium
hydroxide (Ca(OH)2) with pH=12 at 60°C was the
most detrimental environment to the tensile strength
of the “bare” bars. The tensile strength of 10 mm
polyester bars was reduced by 28% after 6 months of
exposure, whereas that of vinyl ester was reduced by
23%. The reduction in Modulus of Elasticity (MOE)
for both types of bars was reported to be less than 5%
for all tests.
172
After two years of exposure to de-icing salt, the
concrete beam tests indicated that IPE bars exhibited
a reduction in strength of 34%, whereas VE bars
exhibited a somewhat smaller reduction in tensile
strength of 28%. The authors concluded that the
vinyl ester used in the study exhibited lower diffusivity
and provided a better protection for the glass fiber
against chemical attack than IPE.
Tannous and Saadatmanesh (1998)10 published a
study in the ACI Materials Journal similar to the one
described in the previous paragraphs. The difference
between the two studies appears to be the use of AR
glass reinforcement in the 1999 study9, but not in the
1998 study.10 Results from both studies are very
similar, as may be seen in Table 2.
Porter et al. (1997)11, 12 also studied the durability of
FRP reinforcing bars for concrete. The authors tested
three types of rebars: Type A and B made with
isophthalic polyester (two different manufacturers)
and Type C made with bisphenol-A vinyl ester GFRP.
The rebars had a helical wrap to induce better
mechanical gripping with concrete. The specimens
were aged in the concrete pore solution of pH=13 at
60°C for 81 days. The results indicate that both IPE
and VE GFRP (rebar types B and C) lost approximately
65% of their tensile strength in 81 days. IPE rebar type
C lost 48% of its tensile strength, which was less than
the VE rebar. The authors also used FRP rebars to
construct and test 18 prestressed concrete beams
(40% UTS prestressing) but did not specifically state
whether the resin used was VE or IPE. One-half of the
beams were exposed in a high alkaline aging bath.
The authors concluded that stress-corrosion appeared
to have a severe effect on the GFRP (glass FRP)
reinforcement, based on the scatter of the bending
test results for the aged beams.
Shao, Y. and Kouadio, S. (2002)2 studied the effect of
water absorption (260 days) and temperature (23°C,
70°C and 100°C) on fiberglass pultruded isophthalic
polyester sheet piles. The U. S. Army Corps of
Engineers established a performance specification to
be used in composite sheet piling systems, which
limits water absorption to 5% and maximum reduction
in EI (flexural stiffness) to 10%. The pultruded sheet
piles studied by Shao saw a maximum of 3.1% water
absorption in the webs and 1.7 % in the flanges. The
authors estimated that the web, which is 1/8” thick,
would take 14.5 years to reach saturation. Also, no
significant reduction in MOE was observed in any of
the accelerated tests. However, the tensile strength of
the composite was expected to decrease by as much
as 60% after saturation. After 190 days of immersion
Polymers & Polymer Composites, Vol. 12, No. 3, 2004
 Table 2. Summary of Published Test Results on Durability of Isophthalic Polyesters and Vinyl esters

% Reduction in Strength
Testing Environment and Specimen Duration
Isopolyester Vinyl ester Comments (6) References (7)
Material Under Test (1) (2) (3)
(4) (5)
Water at 25°C 10 mm / 20 mm 7/6 6/6
6 months
Alkali Resistant Glass Fiber AR GFRP Rod (tension) (tension)
Concrete Pore solution
10 mm / 20 mm 21 / 13 13 / 10
pH=12, Ca(OH), 25°C 6 months
AR GFRP Rod (tension) (tension)
Alkali Resistant Glass Fiber
Concrete Pore solution High temperature tests in concrete pore
10 mm / 20 mm 28 / 17 23 / 14
pH=12, Ca(OH), 60°C 6 months solution are not valid for long-term
AR GFRP Rod (tension) (tension)
Alkali Resistant Glass Fiber durability
HCl, Ph=3, 25°C 10 mm / 20 mm 12 / 10 13 / 7
6 months Tannous9
Alkali Resistant Glass Fiber AR GFRP Rod (tension) (tension)
Sea Water at 25°C 10 mm / 20 mm 17 / 7 15 / 6
6 months
Alkali Resistant Glass Fiber AR GFRP Rod (tension) (tension)

Polymers & Polymer Composites, Vol. 12, No. 3, 2004

De Icing Salt Soln.
10 mm / 20 mm (tension) (tension)
NaCl+MgCl2 (2:1molar ratio) 6 Months
AR GFRP Rod 26 / 9 25 / 8
7% by weight
GFRP reinforced Concrete Beam was tested in 4-point flexure. Loss in
10 mm AR GFRP Rod in 1 and 2 26 / 34 25 / 28
Beam subjected to strength was measured from calculated
concrete beam year (tension) (tension)
De-Icing salt tension stress in the rods at failure
6/5 3/4
Water at 25°C 10 mm / 20 mm GFRP Rod 6 months
(tension) (tension)
Concrete Pore solution 25 / 19 13 / 11
10 mm / 20 mm GFRP Rod 6 months
pH=12, Ca(OH), 25°C (tension) (tension)
Concrete Pore solution 29 / 20 20 / 12
10 mm / 20 mm GFRP Rod 6 months
pH=12, Ca(OH), 60°C (tension) (tension)
7/6 4/4 Tannous10
HCl, Ph=3, 25°C 10 mm / 20 mm GFRP Rod 6 months
(tension) (tension)
Durability of Isophthalic Polyester Composites Used in Civil Engineering Applications

Sea Water at 25°C 11 / 8 6/5

10 mm / 20 mm GFRP Rod 6 months
NaCl soln., 3.5 % by weight (tension) (tension)
De Icing Salt Soln.
29 / 11 24 / 8 The tests with CaCl2 instead of MgCl2 had
NaCl+MgCl2 (2:1 molar ratio) 10 mm / 20 mm GFRP Rod 6 months
(tension) (tension) very similar results.
7% by weight

173
 Table 2. Summary of Published Test Results on Durability of Isophthalic Polyesters and Vinyl esters (Continued)

174
% Reduction in Strength
Testing Environment and Specimen Duration
Isopolyester Vinyl ester Comments (6) References (7)
Material Under Test (1) (2) (3)
(4) (5)
UV radiation
10 mm / 20 mm GFRP Rod 6 months None none The loss in strength was within 3%
31.7 x 10-6 L/sec/cm2
Beams were tested in 4-point flexure. Tannous10
10 mm rod in Concrete
10 mm Rod Reinforced 1 and 2 10/13 8/11 The control beams lost only 4% strength
beam submerged in
concrete Beam year (tension) (tension) after 1 year. The reinforcement ratio
De-Icing Salt
was 0.18%.
Concrete Pore Solution Tested for only 81 days. This time period
pH=13, 60°C, simulating GFRP #3 rebar 3 months 66 65 may not be long enough to achieve Porter11,12
50 year weathering equilibrium moisture content
17/50 Total moisture absorption is independent
Water at 23°C / 70°C Pultruded GFRP Sheet pile 6 months
(tension) of temperature (tap or salt water)
17/56
Water at 23°C / 70°C Pultruded GFRP Sheet pile 9.6 months Shao2
(tension)
Freeze-thaw cycle None ASTM C 666, tested after saturation at
Pultruded GFRP Sheet pile 564 cycles
4.4°C to -17°C (tension) 192 days
Mass loss of polyester after drying
20 None
Cast resin 18 months indicating hydrolysis
(tension) (tension)
(permanent damage)
H. J. Dagher, A. Iqbal and B. Bogner

Sea Water at 50 °C Davies13

Accelerated tests at high temperature are
35 25
Stitched Composite 18 months adequate for water and salt solution but
(shear) (shear)
not pore solution.
Pore solution absorption data does not
follow Arrhenius plots indicating that
Concrete Pore solution 60 20
Cast resin 12 months using temperature as a accelerating factor
at 22°C (tension) (tension)
is not valid for pore solution due to the
significant damage to resin material.
Chin3
Cast resin properties are different from
those of a reinforced composite. While
Concrete Pore solution 70 60
Cast resin 5 months this is useful, it is more appropriate to
at 60°C (tension) (tension)
test the final product or system than the
constituent materials.

Polymers & Polymer Composites, Vol. 12, No. 3, 2004

 Table 2. Summary of Published Test Results on Durability of Isophthalic Polyesters and Vinyl esters (Continued)

% Reduction in Strength
Testing Environment and Specimen Duration
Isopolyester Vinyl ester Comments (6) References (7)
Material Under Test (1) (2) (3)
(4) (5)
Isophthalic polyester was pultruded, VE was
hand lay-up. Mass uptake of IPE was twice
85 14 that of VE.
10% NaOH at 25°C GFRP 9 months
(tension) (tension)
Isophthalic polyesters fare better in acidic
environments. The IPE resin is more soluble
in water and salt solution compared to VE. Sonawala4
Different manufacturing processes were
30 50 used, so direct comparison of IPE and VE is
Non reactive Toluene GFRP 9 months not possible. Pultrusion creates more void
(tension) (tension)
content and can expose more fibers near
the surface.
45 50 Isophthalic polyesters fare better in acidic
35% Sulphuric Acid GFRP 5 months Pai14,15

Polymers & Polymer Composites, Vol. 12, No. 3, 2004

(ILSS) (ILSS) environment
30
Water at 60°C GFRP 7 months IPE twice as durable as OPE Casting5
(tension)

Dry at room temperature 11/22/14

(flexure)
IPE derived from neopentyl glycol
or immersed in: Neopentyl
GFRP embedded in glycol 13/7/18
Tap water at room 24 months Bogner17
concrete 7/29/41 (flexure)
temperature
(flexure)
Salt water at room IPE derived from propylene glycol
Propylene
temperature glycol
20
Fresh Water at 22°C 12" diam. GFRP Shell 3 months (hoop These shells are intended to be filled with
tension) concrete and used for Marine piling.
Unexpected differences in 11 months Pando20
10 versus 3 months response attributed to
Durability of Isophthalic Polyester Composites Used in Civil Engineering Applications

Fresh Water at 22°C 24" diam. GFRP Shell 11 months (hoop manufacturing differences
tension)
Rebar in concrete beams The rebars were extracted from the beams
13
submerged in Ca(OH)2 GFRP REBAR 2 months after the beams were tested to failure in 3- Giernaky22
(tension)
solution pH=12.5 at 60°C point bending

175
176
Table 2. Summary of Published Test Results on Durability of Isophthalic Polyesters and Vinyl esters (Continued)

% Reduction in Strength
Testing Environment and Specimen Duration
Isopolyester Vinyl ester Comments (6) References (7)
Material Under Test (1) (2) (3)
(4) (5)

Rebar in concrete beams The rebars were extracted from the beams
13
submerged in Ca(OH) GFRP REBAR 2 months after the beams were tested to failure in 3-
(tension)
solution pH=12.5 at 60 °C point bending
Giernaky22
GFRP Rebar in concrete
13
beams at standard GFRP Rebar 6 months
(tension)
laboratory air

LHHPC: Low Heat High Performance

GFRP Rebar in concrete Concrete was used for low alkalinity
36
beam submerged in water GFRP Rebar 24 months cement to reduce degradation. 53% Svecova23
(tension)
at 60°C reduction was seen when conventional
concrete was used

35
Water at 60°C 9.4 mm GFRP Rebar 5 months
(flexure)
Wang21
17
H. J. Dagher, A. Iqbal and B. Bogner

Water at 60°C 15.9 mm GFRP Rebar 5 months

(flexure)

Salt Fog (ASTM B 117) 12-19 6-8

Pultruded GFRP 18 months Salt fog replicates ocean spray
35°C (tension) (tension)
Malvar24
100% Oxygen, Salt water 19-30 10-38
Pultruded GFRP 18 months
Submersion at 35°C (tension) (tension)

8 8
GFRP 100% Oxygen environment used to
Saline Solution at 60°C 1.5 months (tension (tension Stone25
Laminates & Rods simulate oxidation of plastics
laminates) rods)

Polymers & Polymer Composites, Vol. 12, No. 3, 2004

 Durability of Isophthalic Polyester Composites Used in Civil Engineering Applications
in 23°C water, the tensile strength was reduced by
17%. At 70°C for the same period the tensile strength
was reduced by 50%. The reduction in tensile strength
after 260 days was very similar to that of the 190-day
immersion. The most interesting data reported by
Shao was that the freeze-thaw cycling (564 cycles
from 4.4°C to -17.2°C), representing 20-30 years of
normal conditions, had virtually no effect on the
tensile properties of the saturated composites.
Davies, P. et al. (2001)13 examined the effect of sea
water and distilled water at 20°C and 50°C for 1.5 and
3.5 years, respectively, on orthophthalic and
isophthalic polyester, vinyl ester, and epoxy glass
fiber composites (6 layers of 0/90) used for marine
applications. The authors reported that all the resin
systems (except epoxy) immersed in sea water at
20°C for 3.5 years returned to their initial weight
within a month after drying at 50°C and showed no
significant degradation. The distilled water absorption
was much faster than that of seawater and was also
more detrimental to the fiber-matrix interface. The
authors mentioned that the lower absorption in
seawater may be a result of hindered diffusion by
large salt ions. They observed that the polyesters lost
about 1% of their initial weight after drying when
subjected to seawater at 50°C for 1.5 years, indicating
that hydrolysis had occurred and that short molecules
had been extracted. The vinyl ester resin absorption
was completely reversible while the epoxy showed
some residual weight gain even after a month of
drying at 50˚C. It was observed that the shear moduli
(in wet condition) of the polyesters reduced by
approximately 50% due to immersion in seawater at
50˚C for 1.5 years. Vinyl ester and epoxy composites
showed approximately 20% reduction for the same
conditions. As for the apparent shear strength for the
same conditions mentioned above, ortho and iso
polyesters showed 40% and 35% reductions,
respectively. The shear strength of the vinyl ester and
epoxy composites was reduced by 25%. The authors
concluded that, while permanent damage is induced
in polyester composites after 1.5 years, the shear
strengths of the vinyl ester and epoxy composites are
much less affected and largely recover after drying.
Chin et al. (2001)3 studied mass uptake due to
immersion of isopolyester and vinyl ester unreinforced
thin sheets in water, salt water, and concrete pore
solutions at 22°C and 60°C for 60 weeks. The authors
found that at 22°C both polymers absorbed (mass
uptake) approximately 0.53% of the solutions with
concrete pore solution being least absorbed (0.5%).
The absorption was characterized by Fickian. In the
60°C test, Isopolyester started to hydrolyze after
Polymers & Polymer Composites, Vol. 12, No. 3, 2004
100 hours and the mass loss was detected by FTIR
tests. Vinyl ester showed almost no hydrolysis (mass
loss) at 40°C or 60°C because the ester functional
groups in vinyl ester are terminal and shielded by
methyl groups. Both polymers exhibited an increase
in Tg (glass transition temperature) by approximately
4°C and 6°C for vinyl ester and isopolyester,
respectively, when immersed either in 60°C or 90°C
for all solutions for periods of 15, 30 and 60 weeks.
The 90°C concrete-pore solution was most detrimental
to isopolyester after a 10-week treatment, thus halting
further tests. The 90°C test temperature may have
been at or above the Tg of this resin, which would
produce premature failures. Tensile strength was
observed to decrease with exposure to time and
temperature. Isopolyester in the pore solution at 90°C
exhibited the highest loss in tensile strength; in fact,
specimens were so severely degraded after 10 weeks
that they could not be tested. In 10 weeks, salt water
at 90°C reduced the tensile strength of the isophthalic
polyester materials by 60%, and water at 90°C reduced
their tensile strength by 40%. The article does not
mention changes in the modulus of elasticity (MOE).
The article also cites other work by Abeysinghe et al.
(1982), who confirmed that the most severe
degradation to isopolyester, including the formation
of disc-shaped surface cracks, is caused by basic
solutions.
Sonawala et al. (1996)4 observed similar results. The
authors reported that the mass uptake of isophthalic
polyester E-glass composite was twice that of vinyl
ester composite after 270 days’ exposure to alkaline
solution (10% NaOH at 25°C). The tensile strength of
the isophthalic polyester was reduced by 85%,
compared to 14% seen in the vinyl ester composite
when exposed to the alkaline solution mentioned
above for 270 days (9 months). It must be noted that
the isophthalic polyester was pultruded and the
vinyl ester composite was made by hand lay-up; thus,
meaningful comparisons cannot be made. The authors
also observed that using a surface veil made of C-glass
or PET had little effect in protecting the glass fibers in
isopolyester composites, but had a positive effect
when used in vinyl ester composites. Sonawala et al.
also tested the same materials in a nonreactive organic
solvent (toluene). They observed that isophthalic
polyester composites fared better (30% mass loss)
than vinyl ester (50% loss) composites.
Pai et al. (1997)14,15 studied the performance of
laminated composites under service conditions by
focusing on the interlaminar shear strength (ILSS),
which is a resin-dominated property. The authors
subjected two different types of polyesters, a vinyl
177
 H. J. Dagher, A. Iqbal and B. Bogner
ester, and three epoxy resins to 15%, 25%, and 30%
sulphuric acid solutions for 5 months. The resins
were used to produce composites with different
glass fiber lay-ups. They found that isophthalic
polyester had the highest ILSS retention values,
indicating that these resins offer better resistance to
acidic environments than epoxies and vinyl esters.
They also reported that the preferred lay-up to
reduce the diffusion of acid and water uses woven
mats instead of CSM at the surfaces. Composites
with CSM on the surfaces showed the highest
diffusion rates.
Casting et al. (1995)5 studied the effect of water
absorption on gel-coated E-glass reinforced
polyesters and concluded that the lifetime of the
isopolyester is twice that of the orthopolyesters. The
unsaturated polyester resin, epoxy resins, and
laminate plies were reported to behave like osmotic
membranes. They also reported that gelcoat blistering
only affects the skin of the composite, and does not
substantially reduce laminate properties. The effect
of plasticization and osmotic delamination is far
more important than gelcoat degradation for long-
term durability. They predicted that delamination
of the plies would occur after 20 to 30 years of
immersion at room temperature. The flexural and
interlaminar shear strengths of isopolyester
composites decreased by about 25-30% after a 30-
week immersion, compared to 40-65% loss observed
in orthopolyester composites.
Tsui et al. (1992)16 studied the performance of an E-
glass reinforced polyester composite used for sewer
lining. The authors reported that external damage
such as scratching and scoring of the resin-rich
barrier (gelcoat) will not severely undermine the
long-term performance of polyesters under acidic
(sulphuric) stress corrosion conditions, because the
failure mechanism is mainly controlled by diffusion
and corrosion.
Bogner and Borja (1998)17 tested thin composite
specimens (3 mm thick x 100 mm x 200mm) using
ASTM C581 and three resin systems: (1) bisphenol-
A vinyl ester controls (Derakane 411-45 supplied
by the Dow Chemical Company); (2) TG-353
isopolyester derived from neopentyl glycol; and
(3) SG-10 isopolyester derived from propylene
glycol. The specimens were embedded in a Portland
cement mixture, and cured for 30 days at room
temperature. The specimens, now embedded in
cured concrete, were conditioned in salt water and
tap water, while controls were allowed to stand at
room temperature. Coupons were removed at one,
178
three, six, twelve, and twenty-four months. They
were visually inspected, and then tested to
determine flexural strength, flexural stiffness, and
Barcol hardness.
The control specimens exposed to dry concrete showed
statistically equivalent flexural strength reductions
after 24 months, ranging from 13% for vinyl ester to
11% for the TG-353 IPE and 7% for the SG-10 IPE.
Flexural modulus reductions were 19% for the vinyl
ester, 0% for the TG-353 and 18% for the SG-10.
Except for the VE, the specimens exposed to wet
concrete at ambient temperature exhibited slightly
more degradation than the dry specimens. Flexural
strength reductions after 24 months were 7% for vinyl
ester, 22% for the TG-353 IPE, and 29% for the SG-10
IPE. Flexural modulus reductions were 19% for the
vinyl ester, 0% for the TG-353, and 18% for the SG-10.
For coupons exposed to the saltwater environment,
flexural strength reductions after 24 months were
18% for vinyl ester, 14% for the TG-353 IPE, and 41%
for the SG-10 IPE. Flexural modulus reductions were
18% for the vinyl ester, 14% for the TG-353, and 12%
for the SG-10.
The isopolyester specimens exhibited no change in
Barcol hardness in any of the conditions, whereas the
vinyl ester specimens showed a 6% reduction when
subjected to salt and tap water. In addition, the
isopolyester resin using neopentyl glycol performed
slightly better than the vinyl ester resin. The authors
concluded that, overall, all three resins would meet
the Amoco Chemicals corrosion criteria of retaining
50% strength after 10 years.
Fatsuki and Uomoto (1995) 18 evaluated the
degradation of the vinyl ester composite bars using
glass, aramid, and carbon fibers subjected to sodium
hydroxide solution (NaOH) at 40°C for 120 days.
The GFRP was subjected to 1.0 mol/l whereas the
AFRP and CFRP were subjected to 2.0 mol/l because
glass fibers are known to be less resistant to alkaline
attack. The objective of the study was to measure
sodium (Na+) ion diffusion into the fibers and
correlate it with tensile strength changes. They
observed that the tensile strength of the GFRP reduced
by 71% whereas the AFRP and CFRP bars showed
almost no change, despite the fact that both AFRP
and CFRP bars were subjected to twice the amount
of Na+ ion concentration compared to GFRP. Test
results showed almost no Na+ ion penetration in
AFRP and CFRP, but substantial penetration was
seen in the GFRP rods in the radial direction. These
Polymers & Polymer Composites, Vol. 12, No. 3, 2004
 Durability of Isophthalic Polyester Composites Used in Civil Engineering Applications
results indicate that the performance of the composite
is not just dependent on the resin’s ability to protect
the fiber. The chemical nature of the fiber itself will
also affect the long-term durability.
These results also indicate that the best composite
material is produced by carefully choosing both the
fiber type and the resin for the specific application.
DISCUSSION OF TEST RESULTS FROM
THE LITERATURE REVIEW
Table 2 summarizes the results of durability studies
on isophthalic polyester GFRP compared to those
conducted on vinyl ester. It can be seen from the
works of Tannous and others4,9,11,12 that highly alkaline
solutions such as sodium hydroxide (NaOH), concrete
pore solution, and deicing salt cause significant
reduction in the tensile strengths of both IPE and VE.
Except for concrete pore solution, which is particularly
harsh on IPE compared to VE composites, in all other
environments, including freeze-thaw, salt solution,
and acidic environments, the difference in durability
between IPE and VE is often quite small or within the
statistical significance of the experiment. In a concrete
pore solution environment at room temperature, the
reduction in tensile strength of IPE is higher than that
of VE, but the difference seems to decrease at higher
temperatures. This effect was observed by Chin et al.
on cast resin as well3. Also, GFRP embedded in
concrete and subjected to de-icing salt showed a
lower reduction in mechanical properties than “bare”
bars directly exposed to the same solution for the
same period of time10,19.
4
Sonawala reported that a highly alkaline sodium
hydroxide solution caused severe strength degradation
(85%) to IPE composites while VE specimens showed
somewhat modest strength reductions (14%). In this
experiment, such a direct comparison cannot be
made because the IPE specimens used by the author
were pultruded, whereas the VE specimens were
made by hand lay-up.
In acidic environments IPE and VE composite
performance were very similar9,10,15. The effect of
water is very minimal on both IPE and VE;9,10 however,
a higher temperature significantly increases
degradation2,5,20. It can be inferred from Table 2 that
the degradation of both IPE and VE composites is very
sensitive to material thickness. Thicker materials
such as larger diameter bars are less affected by
moisture than smaller diameter bars because of
differences in moisture penetration depth9,10,20,21.
Polymers & Polymer Composites, Vol. 12, No. 3, 2004
CONCLUSIONS
Twenty relevant articles were reviewed comparing
the durability of isophthalic polyesters and vinyl
ester composites for civil infrastructure applications.
These articles present new recently acquired data on
the relative durability of IPE and VE composites and
reveal areas where further research is needed.
Conclusions that can be supported by the data are
presented below, followed by recommendations for
additional research.
Of the twenty articles analyzed, fourteen present
new test data relevant to the durability of IPE
composites. Based on the test data provided in these
articles and summarized in Table 2, the following
conclusions can be drawn:
1. With respect to the accelerated degradation data
reviewed from fourteen different sources, the
strength reductions of isophthalic polyesters
vary considerably depending on the resin,
manufacturing process, and exposure type. Some
examples include a low of no reduction in
strength under seawater immersion for 6 months
at 25°C, a 7% reduction for 6 months exposure
to water at 25°C, and a high of 85% reduction for
GFRP pultruded composites subjected to
immersion in 10% NaOH alkaline solutions at
25°C for 9 months4.
2. Research to date suggests that there is little
difference in tensile strength loss between IPE
and VE in a concrete pore solution.
The papers by Tannous et al.910 provide perhaps
the most extensive test data on the ageing of
isophthalic polyester composites in a concrete
pore solution. The work indicates very small
difference in tensile strength loss of GFRP rods
for IPE (21%-28%) and VE (13%-23%) specimens
subjected to a concrete pore solution pH=12
Ca(OH)2 for 6 months at 25°C and 60°C. Porter et
al26-7 also reported that the tensile strength
reductions for IPE and VE in a concrete pore
solution were very similar for pultruded GFRP
rebars (65% reduction).
3. Although there appears to be little difference in
tensile strength reduction between IPE and VE in
a variety of exposure environments, the VE was
superior with respect to diffusivity and resistance
to chemical attack in non-alkaline environments.
The study by Tannous et al.9 shows little difference
in tensile strength reduction of E-glass isophthalic
179
 H. J. Dagher, A. Iqbal and B. Bogner
polyester composites and vinyl ester bars in a
variety of exposure environments including (a)
water immersion at 25°C for 6 months with a 7%
reduction for IPE versus 5.9% for VE; (b)
immersion in HCl pH=3 25°C solution for
6 months with no reduction for either VE or IPE;
and (c) seawater at 25°C for 6 months with no
reduction for either VE nor IPE. However, the
authors conclude that for the resins tested, “the
VE showed lower diffusivity and better resistance
to chemical attack than the PE.”
4. There is an apparent notable difference in the
degradation of IPE and VE when they are immersed
in NaOH solution, but the data are open to
question. The most severe degradation of
isophthalic polyester (85% loss in tensile strength)
was reported by Sonawala and Spontak4 for GFRP
pultruded composites subjected to immersion in
10% NaOH alkaline solutions at 25°C for 9 months.
The corresponding tensile strength loss for vinyl
ester GFRP in this study was 14%. The concern
here is that the study used two different
manufacturing processes in producing the GFRP,
so it is difficult to compare the data for IPE and
VE. Also, the mass uptake of IPE was twice that of
VE. The IPE loss in strength is reported to be the
result of the attack on ester groups by OH-
(hydroxyl) ions. OH- ions also attack the siloxane
(Si-O-Si) bonds in the glass fiber, causing them to
break down. Polyesters are also more soluble in
water and salt solution than vinyl esters.
5. The utility of test data measuring the durability of
isophthalic resins in concrete pore solution
depends in part on whether a realistic end-use
system was used in the testing. It is important to
test the actual end-use system (resin, additives,
fiber) using the manufacturing process intended
for production. The two journal articles that
report on the durability of isophthalic resins in
concrete pore solution are the works by Tannous
et al.9 and Chin et al.3 Both Tannous and Chin
conditioned the specimens for over 6 months,
which is the minimum time required to obtain
appreciable moisture diffusion. Tannous used 10
mm GFRP rods whereas Chin used cast resins.
However, since the cast resins do not represent
the true end-use properties of a composite,
Tannous’ data is more relevant in this context.
Data by Tannous et al.9 showed VE to have a better
performance than IPE.
6. High temperature has adverse effects on both VE
and IPE composites, but the effect is more
pronounced with IPE. Questions remain as to the
180
validity of temperature-accelerated tests,
particularly using concrete pore solutions3.
7. Reduction in properties under salt water or water
environments depends on the temperature. At
around 25°C, the reduction in tensile strength is
expected to be approximately 10-20%. At
temperatures around 50-70°C, the degradation is
adverse and reduction in tensile strength can be
as high as 50%2, 17, 21, 24.
8. Under acid environments, IPE actually shows
slightly better performance than VE.4, 15
Until more IPE degradation data in concrete pore
solutions become available, solid conclusions on
the suitability of IPE resins embedded in concrete
cannot be drawn. Thus, the following
recommendations are presented:
1. More comparative research is needed on the
durability of IPE versus VE composites in concrete
pore solutions. In this context, the testing of the
final product to be used (the rebar) in concrete is
most appropriate. The manufacturing process
used in producing the test specimens needs to be
consistent for both IPE and VE in order to draw
valid conclusions.
2. Research is needed that reflects more realistically
the end-use applications and environments. The
use of VE composites embedded in concrete
appears to be suitable, assuming that proper
strength reduction factors are used to account for
the end-use environment. On the other hand, IPE
may be suitable for applications where it is in
contact with concrete (such as IPE I-beams
supporting a concrete bridge deck) but not
embedded in concrete (such as rebars), assuming
that it is properly protected from the concrete,
and appropriate strength reduction factors are
used to reflect the end-use environment.
3. Most of the previous testing has been run for less
than two years and temperature was the usual
accelerant. Longer-term, lower temperature tests
should be performed to better define the durability
of IPE resins in actual service.
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182 Polymers & Polymer Composites, Vol. 12, No. 3, 2004