Article

Durability of Pultruded GFRP through Ten-Year

Outdoor Exposure Test
Itaru Nishizaki, Hiroki Sakuraba * and Tomonori Tomiyama
Received: 1 July 2015; Accepted: 20 November 2015; Published: 30 November 2015
Academic Editors: Raafat El-Hacha and Alexander Böker

Public Works Research Institute, 1-6 Minamihara, Tsukuba, Ibaraki 305-8516, Japan; nisizaki@pwri.go.jp (I.N.);
tomiyama@pwri.go.jp (T.T.)
* Correspondence: hiro-sakura@pwri.go.jp; Tel.: +81-29-879-6763 (ext. 4129); Fax: +81-29-879-6733

Abstract: Pultrusion is an easy molding method of fiber-reinforced polymer (FRP) to obtain a long
composite material with a uniform cross-section at relatively low cost. In some cases, pultruded FRPs
are now used in bridges and deck projects. Since the application of pultruded FRP as a structural
material is increasing, a study on the durability of pultruded FRP under outdoor conditions is
necessary in terms of safety. Some studies have shown that pultruded glass fiber-reinforced polymer
(GFRP) exhibits a slight reduction in mechanical properties during outdoor exposure. Since pultruded
GFRP consists of multi-layers, the change of mechanical properties in each layer is important to
understand. In this study, an outdoor exposure test on pultruded GFRP for 10 years was conducted
with three types of pultruded GFRP, which have different laminate systems, including surface-coated
specimens of each type. Changes of strength and elastic modulus due to outdoor exposure were
discussed with a focus on the contribution of each layer based on the rule of mixtures.

Keywords: pultrusion; GFRP; ten-year outdoor exposure; laminate system; mechanical properties

1. Introduction
Recently, the use of fiber-reinforced polymer (FRP) as a structural material has increased due
to its high resistance to corrosion and low weight. Pultrusion of FRP is a particularly easy method
that can produce long sections of material with a uniform cross-section at relatively low cost. This
makes FRP a structural material which can be used for construction. Information on the durability
of pultruded FRP is important for using FRP safely. There were some studies on the durability of
pultruded FRP used for construction with mainly glass fibers [1–5], but many of them only focused on
moist environments. When the durability of FRP in an ambient condition is considered, an outdoor
exposure test is an important way to understand the durability. As for the use of glass fiber-reinforced
polymer (GFRP) reinforcement, GFRP bars embedded in concrete for seven years were investigated to
assess the structural reliability of a bridge deck reinforced with GFRP bars [6,7]. Some studies on the
durability of press-molded or hand lay-up GFRP investigated by outdoor exposure tests were also
reported [8–10].
A six-year outdoor exposure test for pultruded GFRP was conducted by the authors [11], and it
was shown that a surface coating has a protective effect and reduces the deterioration of mechanical
properties and that uncoated GFRP showed a slight reduction of mechanical properties. However, in
the six-year outdoor test, deteriorated layers of pultruded GFRP were not investigated although they
consisted of multi-layers.
This study presents an outdoor exposure test on pultruded GFRP for 10 years to investigate
layers of GFRP which can deteriorate during outdoor exposure. Three types of pultruded GFRP, with
different laminate systems, were tested, including painted specimens of the GFRP. By calculating the

Polymers 2015, 7, 2494–2503; doi:10.3390/polym7121525 www.mdpi.com/journal/polymers

Polymers 2015,7,7,2494–2503
Polymers2015, page–page

By calculating the contribution ratios of each layer based on the rule of mixtures, deteriorations of
contribution ratios of each layer based on the rule of mixtures, deteriorations of strength and elastic
strength and elastic modulus of the pultruded GFRP are discussed.
modulus of the pultruded GFRP are discussed.

2.2. Experimental
Experimental Section
Section

2.1.Specimen
2.1. Specimen
PultrudedGFRP
Pultruded GFRPplates
platesmade
madeof ofE-glass
E-glassfibers
fibersand
andvinylester
vinylesterresin,
resin,which
whichisisbisphenol
bisphenolAAwith with
styrenesolvent,
styrene solvent, were
were used
used to prepare
to prepare the specimens
the specimens in thisinstudy.
this study. Eachwas
Each plate plate
420was
mm420wide, mm3.2wide,
mm
3.2 mm thick. The laminate systems consist of the combination of three fiber types:
thick. The laminate systems consist of the combination of three fiber types: continuous strand mat continuous strand
mat random
with with random fiber directions,
fiber directions, plain-woven
plain-woven cloth
cloth with with bidirectional
bidirectional fibers and fibers and unidirectional
unidirectional roving, as
roving,inas
shown shown
Figure in Figure
1. Table 1. Table
1 shows three1laminate
shows three laminate
systems systems
that were used that were
in this used
study. in this
Note that study.
since
Note that since the percentages of “Layer system and fiber type” are approximate
the percentages of “Layer system and fiber type” are approximate values, the percentages in R26 do values,
theadd
not percentages in R26
up to exactly do not
100%. Theseadd up towere
plates exactly 100%.
cut into These plates were
620-mm-length cut into
specimens. In 620-mm-length
this study, the
specimens.
direction In this study,
corresponding to the
the direction corresponding
direction of pultrusion is to the direction
defined as the 0˝ofdirection,
pultrusion and is the
defined as
lateral
the 0° direction, and the lateral direction of pultrusion
˝
direction of pultrusion is therefore defined as the 90 direction. is therefore defined as the 90° direction.

Top coat (30μm) &

Intermediate coat (30μm)
(Only for the coated specimens)
Continuous Strand Mat (CSM)
Thickness: 3.2mm

Cloth fiber

Roving fiber (ROV)

Cloth fiber
Continuous Strand Mat (CSM)

Figure1.1.AAschematic
Figure schematicillustration
illustrationofofcross-section
cross-sectionofofthe
thespecimens.
specimens.

Table1.1.Laminate
Table Laminatesystem
systemofofthe
thespecimens.
specimens.

Layer
Layer system
System andand fiber
Fiber type
Type (the
(the values
Values showthe
Show theVolume
volumeFiber
fiberContent
content
Code
Code (%)
VVf f(%) ratio
Ratio of of
thethe corresponding
Corresponding layerininVolume
Layer volumeFraction)
fraction)
R43 43 CSM 9.5%/Cloth 19%/ROV 43%/Cloth 19%/CSM 9.5%
R43 43 CSM 9.5%/Cloth 19%/ROV 43%/Cloth 19%/CSM 9.5%
R26 39 CSM 16%/Cloth 21.5%/ROV 26%/Cloth 21.5%/CSM 16%
R26 39 CSM 16%/Cloth 21.5%/ROV 26%/Cloth 21.5%/CSM 16%
R12
R12 36
36 CSMCSM 21%/Cloth
21%/Cloth 23%/ROV
23%/ROV 12%/Cloth23%/CSM
12%/Cloth 23%/CSM21% 21%

Coated and uncoated specimens were also prepared for all cases. Coated specimens were coated
withCoated and intermediate
an epoxy uncoated specimens
coatingwere
withalso preparedthickness
a designed for all cases.
of 30Coated
μm and specimens were with
then coated coated
an
with an epoxy intermediate coating with a designed thickness of 30 µm and then
acrylurethane resin top coating with a designed thickness of 30 μm by using a brush. The thicknesses coated with an
acrylurethane resin top
of the intermediate andcoating
the topwith a designed
coating thickness ofbased
were determined 30 µm onby using a brush. specification
manufacturer’s The thicknessesand
ofcontrolled
the intermediate and the top coating were determined based on manufacturer’s
by measuring their weights. The actual thicknesses of the intermediate and the top coating specification and
controlled by measuring
were measured by usingtheir weights.
a digital The actual thicknesses
stereomicroscope, and it wasof confirmed
the intermediate
that theand the top
actual coating
thicknesses
were
had ameasured
range from by 70
using a digital
to 75 μm. Two stereomicroscope,
sets of specimens and it was
were confirmed
prepared that
for all the actual thicknesses
cases.
had a Anrange from 70 to 75 µm. Two sets of specimens were prepared for all cases.
exposure test was carried out for 10 years (from June 2003 to July 2013), in Tsukuba,
An exposure
which is located neartest Tokyo
was carried
and hasoutafor 10 years
moderate (from with
climate June an
2003 to July
annual mean2013), in Tsukuba,
temperature of which
14.3 °C
isand
located near Tokyo
an annual rain falland has amm.
of 1326 moderate climate test
The exposure withwasan first
annual mean
started to temperature
investigate the 14.3 ˝ Cof
of safety
and an annual
pultruded GFRPrainfor
falluse
of 1326
as amm. The exposure
structural material.testFigure
was first startedthe
2 shows to investigate
maximum, the safetyand
average of
pultruded
minimumGFRP for use asata the
temperatures structural
Tsukuba material. Figure
exposure site.2The
shows the maximum,
temperatures wereaverage
measuredandatminimum
intervals
temperatures at the Tsukuba exposure site. The temperatures were
of one hour for 10 years, and they were averaged monthly. The maximum and minimum measured at intervals of one hour
for 10 years, and
temperatures they were
reached averaged
31.5 and −3.1 °C,monthly. The maximum
respectively, as shownand minimum
in Figure 2. temperatures reached
31.5 and ˝ C, respectively, as shown
The´3.1
specimens were placed facing in Figure
south on 2.
a 5° slope using steel exposure racks, and Figure 3
shows specimens placed by using the steel exposure racks. One set of specimens was retrieved after
one year and the other set was retrieved after 10 years.

2495
2
Polymers 2015, 7, 2494–2503

The specimens were placed facing south on a 5˝ slope using steel exposure racks, and Figure 3
shows specimens placed by using the steel exposure racks. One set of specimens was retrieved after
one year
Polymers and
2015, 7, the other set was retrieved after 10 years.
page–page
Polymers 2015, 7, page–page

35
35 max.
30 max.
avg.
30 avg.

Celsius)
min.
(degreesCelsius)
25 min.
25
20
20
Temperature(degrees

15
15
10
10
Temperature

5
5
0
0
-5
-5
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Figure
Figure 2.
2. Maximum,
Maximum, average
average and
and minimum
minimum temperatures
temperatures each month at Tsukuba
Figure 2. Maximum, average and minimum temperatures each month at Tsukuba exposure
exposure site.
site.

Figure 3. Specimens placed on exposure racks facing south on a 5° slope.

Figure 3. Specimens placed on exposure racks facing south on a 5° slope.
Figure 3. Specimens placed on exposure racks facing south on a 5˝ slope.
Table 2 shows the tensile strength and modulus of the raw materials that are provided by
Table 22 shows
Table showsthethetensile
tensilestrength
strengthand
andmodulus
modulusof of
thethe
rawraw materials
materials thatthat
are are provided
provided by
by the
the manufacturers and used to design the laminate systems. Despite the same fiber, the tensile
the manufacturers and used to design the laminate systems. Despite the same fiber,
manufacturers and used to design the laminate systems. Despite the same fiber, the tensile modulus the tensile
modulus and strength of the continuous strand mat (CSM) are lower than those of the glass fiber
modulus
and andofstrength
strength of the continuous
the continuous strand matstrand
(CSM)mat (CSM)than
are lower are lower than
those of thethose
glass of thebecause
fiber glass fiber
the
because the CSM has random fiber directions.
because the CSM has random
CSM has random fiber directions. fiber directions.
Table 2. Mechanical properties of each layer of the specimens.
Table 2. Mechanical properties of each layer of the specimens.
Table 2. Mechanical properties of each layer of the specimens.
Mechanical properties Glass fiber Continuous strand mat (CSM) Matrix resin
Mechanical properties Glass fiber Continuous strand mat (CSM) Matrix resin
Mechanical Properties
Tensile modulus (GPa) Glass 75
Fiber Continuous Strand
26.9 Mat (CSM) Matrix
1.875 Resin
Tensile modulus (GPa) 75 26.9 1.875
Tensile
Tensile strength
modulus (MPa)
(GPa) 2,500
75 188.5
26.9 62.5
1.875
Tensile strength (MPa) 2,500 188.5 62.5
Tensile strength (MPa) 2,500 188.5 62.5
Tensile modulus and strength based on the rule of mixtures were calculated by Equations (1)
Tensile modulus and strength based on the rule of mixtures were calculated by Equations (1)
and (2). The rule
Tensile of mixtures
modulus and is usually used for on
unidirectional
the rule FRP, but in thiswere study it was used by to
and (2). The rule of mixtures isstrength
usually used based for unidirectional of mixtures
FRP, but in this studycalculated
it was used to
calculate
Equations the contribution
(1)contribution ratios
and (2). Theratiosrule of of each layer in the laminates. The contribution of plain-woven cloth
calculate the of mixtures
each layerisinusually used forThe
the laminates. unidirectional
contributionFRP, but in this study
of plain-woven cloth
was
it divided
was used tobyby two
calculatebecause half
the contribution of the fibers are oriented to the lateral direction of the testing
was divided two because half of the ratiosfibers of areeach layer in
oriented to the
the laminates.
lateral directionThe contribution
of the testing of
direction.
plain-woven Upon calculating
cloth was divided the bytensile modulushalf
two because and strength forare
theoriented
90° direction, Vrov was assumed
direction. Upon calculating the tensile modulus andofstrengththe fibers for the to the lateral
90° direction, Vrov was direction
assumed of
to
thebe zerodirection.
testing because the Upon roving layer the
calculating cantensile
contribute
modulus mainly
and to the 0°
strength fordirection.
the 90 In Equation
˝ direction, V (2),
was
to be zero because the roving layer can contribute mainly to the 0° direction. In Equation rov (2),
the empirical
assumed to becoefficient
zero because for tensile strength
layeris usually obtained by atotest
theand the previous
0˝ direction. studies [12]
the empirical coefficient for the roving
tensile strength can
is contribute
usually mainly
obtained by a test and the previousIn Equation
studies [12](2),
suggest
the that the
empirical coefficient
coefficient for for unidirectional
tensile strength is GFRP
usually is approximately 0.75.
andEach term in Equation (2)
suggest that the coefficient for unidirectional GFRP isobtained by a test
approximately 0.75. the previous
Each studies [12]
term in Equation (2)
shows
suggest the contribution
that of
the coefficient each layer to
for unidirectional the strength,
GFRP is hence the ratio
approximately of contribution of each layer was
shows the contribution of each layer to the strength, hence the ratio of0.75. Each term
contribution of ineachEquation
layer was (2)
calculated
shows by Equationsof(3)–(6).
the contribution each layer to the strength, hence the ratio of contribution of each layer was
calculated by Equations (3)–(6).
calculated by Equations  (3)–(6).E f ⋅V 
= cloth + ECSM ⋅ VCSM + Em ⋅ (1 − Vrov − Vcloth − VCSM ) 
+ Ef ⋅ Vcloth
E Eff⋅⋅V
Ett = E Vrov
rov +
2 + E CSM ⋅ VCSM + E m ⋅ (1 − V rov − V cloth − VCSM ) 
(1)
(1)
 2 
where Et is the tensile modulus of the FRP (GPa), 2496
Ef is the tensile modulus of the glass fiber (GPa),
where Et is the tensile modulus of the FRP (GPa), Ef is the tensile modulus of the glass fiber (GPa),
Em is the tensile modulus of the matrix resin (GPa), ECSM is the tensile modulus of the CSM (GPa),
Em is the tensile modulus of the matrix resin (GPa), ECSM is the tensile modulus of the CSM (GPa),
Vrov is the volume fiber content ratio of the roving layer (for the tensing direction), Vcloth is the volume
Vrov is the volume fiber content ratio of the roving layer (for the tensing direction), Vcloth is the volume
fiber content ratio of the cloth, VCSM is the volume fiber content ratio of the CSM.
Polymers 2015, 7, 2494–2503

" *
Ef ¨ Vcloth
Et “ Ef ¨ Vrov ` ` ECSM ¨ VCSM ` Em ¨ p1 ´ Vrov ´ Vcloth ´ VCSM q (1)
2
PolymersE2015, 7, page–page
where t is the tensile modulus of the FRP (GPa), Ef is the tensile modulus of the glass fiber (GPa), Em
is the tensile modulus of the matrix resin (GPa), ECSM is the tensile modulus of the CSM (GPa), V rov is
 Ff ⋅roving
Vcloth layer (for the tensing direction), Vcloth is the 
the volume fiber F =content
K ⋅  Fratio of the
f⋅ Vrov + + FCSM ⋅ VCSM + Fm ⋅ (1 − Vrov − Vcloth − VCSM )  volume fiber(2)
content ratio of the cloth,  VCSM is the2volume fiber content ratio of the CSM. 
" *
where F is the tensile strength F of ¨the
V FRP (MPa), K is the empirical coefficient for tensile strength,
F “ K ¨ Ff ¨ Vrov ` f cloth ` FCSM ¨ VCSM ` Fm ¨ p1 ´ Vrov ´ Vcloth ´ VCSM q (2)
Ff is the tensile strength of the glass2 fiber (MPa), Fm is the tensile strength of the matrix resin (MPa),
FCSM is the tensile strength of the CSM (MPa), Vrov is the volume fiber content ratio of the roving layer
(for theFtensing
where is the tensile strength
direction), ofisthe
Vcloth theFRP (MPa),
volume K iscontent
fiber the empirical
ratio ofcoefficient for
the cloth, V tensile strength, Ff is
CSM is the volume fiber
the tensile
content strength
ratio of the of the glass fiber (MPa), Fm is the tensile strength of the matrix resin (MPa), FCSM is
CSM.
the tensile strength of the CSM (MPa), V rov is the volume fiber content ratio of the roving layer (for the
tensing direction), V cloth is the volume fiber = K ⋅ Fratio
Rrovcontent f⋅ Vrov F cloth, VCSM is the volume fiber content
of the (3)
ratio of the CSM.
K ⋅ Ff ⋅V rov {F
RRrov =“ K ¨ Ff ¨ Vcloth
cloth F (3)
(4)
K ¨ Ff2¨ Vcloth
Rcloth “ {F (4)
RCSM = K ⋅ FCSM2 ⋅VCSM F (5)
RCSM “ K ¨ FCSM ¨ VCSM {F (5)
Rm = K ⋅ Fm ⋅ (1 − Vrov − Vcloth − VCSM ) F (6)
Rm “ K ¨ Fm ¨ p1 ´ Vrov ´ Vcloth ´ VCSM q{F (6)
where RRrov is the contribution ratio of the roving layer, Rcloth is the contribution ratio of the cloth layer,
where rov is the contribution ratio of the roving layer, Rcloth is the contribution ratio of the cloth layer,
RCSM is the contribution ratio of the CSM layer, Rm is the contribution ratio of the matrix resin.
RCSM is the contribution ratio of the CSM layer, Rm is the contribution ratio of the matrix resin.

2.2.
2.2. Testing Method
Testing Method
Tensile tests in
Tensile tests in the
the 00°˝ and
and 90°
90˝ directions
directions and
and anan in-plane
in-plane shear
shear test
test (tensile
(tensile test
test at
at aa 45°
45˝ direction)
direction)
were carried
were carried out,
out, and
and Figure
Figure 44 shows
shows the
the definition of the
definition of the testing
testing directions.
directions. The
The specimens
specimens retrieved
retrieved
from
from the exposure test were washed with water, and five coupons were taken for each test. Note that
the exposure test were washed with water, and five coupons were taken for each test. Note that
the portions of
the portions of each
each plate
platewhich
whichwere
werewithin
withina a5 cm
5 cm distance
distance from
from thethe edges
edges were
were notnotused used for
for the
the tests to avoid disturbance from
tests to avoid disturbance from the edges.the edges.

Specimen Coupon for in-plane shear test, 45°

The portion of 5cm from

Direction of pultrusion
the edges was not used
Testing direction

(direction of roving fibers)

for the counpos

Testing direction

Coupon for tensile test, 90° Coupon for tensile test, 0°

Figure
Figure 4.
4. Test
Test coupons
coupons cut
cut out
out from the exposed
from the exposed specimens.
specimens.

The tensile tests were carried out based on ISO 3268. The coupons were 250 mm long and 25 mm
The tensile tests were carried out based on ISO 3268. The coupons were 250 mm long and 25 mm
wide, and the test speed was 1 mm/min. Equation (7) was used to calculate the tensile strength.
wide, and the test speed was 1 mm/min. Equation (7) was used to calculate the tensile strength. For
For the coated specimens, the designed thickness of the paint layer (120 μm) was subtracted from
the coated specimens, the designed thickness of the paint layer (120 µm) was subtracted from the
the measured value.
measured value.
Pt
σt = (7)
bh
2497
where, σt is the tensile strength (MPa), Pt is the maximum tensile load (N), b is the width of the coupon
(mm), h is the thickness of the coupon (mm).
Equations (8) and (9) were used to calculate the coefficient of variation (CV) based on the results
Polymers 2015, 7, 2494–2503

Pt
σt “ (7)
bh
where, σt is the tensile strength (MPa), Pt is the maximum tensile load (N), b is the width of the
coupon (mm), h is the thickness of the coupon (mm).
Equations (8) and (9) were used to calculate the coefficient of variation (CV) based on the results
of five coupons.
SDts
CVts “ (8)
σt
SDtm
CVtm “ (9)
Et
where CVts is the coefficient of variation for the tensile strength, SDts is the standard deviation for the
tensile strength (MPa), σt is the averaged tensile strength (MPa), CVtm is the coefficient of variation for
the tensile modulus, SDtm is the standard deviation for the tensile modulus (GPa), Et is the averaged
tensile modulus (GPa).
The in-plane shear test (tensile test at a 45˝ direction) was carried out based on JIS 7059. The
coupons were 250 mm long and 25 mm wide, and the test speed was 1 mm/min. Equation (10) was
used to calculate the in-plane shear strength. For the coated specimens, the designed thickness of the
paint layer (120 µm) was subtracted from the measured value.

Ps
τs “ (10)
2bh
where τ s is the in-plane shear strength (MPa), Ps is the maximum load (N), b is the width of the
coupon (mm), h is the thickness of the coupon (mm).
Equations (11) and (12) were used to calculate the coefficient of variation (CV) based on the results
of five coupons.
SDss
CVss “ (11)
τs
SDsm
CVsm “ (12)
Gs
where CVss is the coefficient of variation for the in-plane shear stress, SDss is the standard deviation for
the in-plan shear stress (MPa), τs is the averaged in-plane shear strength (MPa), CVsm is the coefficient
of variation for the in-plane shear modulus, SDsm is the standard deviation for the in-plane modulus
(GPa), Gs is the averaged in-plane shear modulus (GPa).
Retention ratios are used to discuss the change of the strength and elastic modulus with aging,
and they are defined in Equations (13) and (14).

exposed
ft
Rrs “ 0year
(13)
ft

exposed
Et
Rrm “ 0year
(14)
Et
where Rrs is the retention ratio for the strength, f t exposed is the tensile strength or the in-plane shear
strength after the exposure (MPa), f t 0 year is the tensile strength or in-plane shear strength before the
exposure (MPa), Et exposed is the tensile modulus or in-plane shear modulus after the exposure (GPa),
Rrm is the retention ratio for the elastic modulus, Et 0 year is the tensile modulus or in-plane shear
modulus before the exposure (GPa).

2498
Polymers 2015, 7, 2494–2503

3. Results and Discussions

3.1. Unpainted Specimens

Test results of unpainted specimens are discussed with the contribution ratios based on the rule of
mixtures. Table 3 shows the tensile strength of unpainted specimens in comparison with the calculated
values. The experimental coefficient, K, was set as 1.0 for the calculation. The ratio of the experimental
values over the corresponding calculated values are from 0.532 to 0.832, as shown in Table 3. The
average value of the experiment/calculation ratio among the values of the 0˝ and 90˝ directions
was 0.636, which was smaller than the suggested value, 0.75, for unidirectional FRP in the previous
study [12].

Table 3. Tensile strength of unpainted specimens in comparison with calculated values.

0 Years (MPa); Calculated Value

Testing Direction Code Experiment/Calculation
Coefficient of Variation, CV (K = 1), (MPa)
R43 409.6; CVts : 21.0% 717.5 0.571
0˝ R26 369.0; CVts : 3.6% 524.8 0.703
R12 319.2; CVts : 4.6% 383.5 0.832
R43 135.8; CVts : 2.6% 255.3 0.532
90˝ R26 165.8; CVts : 4.3% 271.3 0.611
R12 156.2; CVts : 3.4% 275.5 0.567
Note that five coupons were used for each test.

Table 4 shows the tensile and in-plane shear strengths of unpainted specimens with the retention
ratios. CVts and CVss of 0 years have a range from 2.6% to 4.3%, except for that of R43 of the 0˝
direction, which is 21.0%. In the case of one year, Rrs shows a range from 0.91 to 1.16, and CVts and
CVss range from 1.0% to 6.2%. In the case of 10 years, Rrs shows a range from 0.67 to 1.07, and CVts
and CVss range from 2.1% to 7.8%. Rrs of R43 at the 0˝ direction is higher than those of the other cases
probably because of its bigger CVts . Overall, Rrs of the 90˝ and 45˝ (in-plane shear) directions show
lower values than that of the 0˝ direction.

Table 4. Tensile and in-plane shear strengths of unpainted specimens with retention ratios.

Strength (MPa); Coefficient of Variation, CV Retention Ratio, Rrs

Testing Direction Code
0 Years 1 Year 10 Years 1 Year 10 Years
R43 409.6; CVts : 21.0% 473.7; CVts : 3.9% 440.1; CVts : 3.6% 1.16 1.07
0˝ R26 369.0; CVts : 3.6% 370.7; CVts : 4.3% 307.1; CVts : 4.0% 1.00 0.83
R12 319.2; CVts : 4.6% 309.2; CVts : 6.2% 266.3; CVts : 7.8% 0.97 0.83
R43 135.8; CVts : 2.6% 134.1; CVts : 1.0% 104.2; CVts : 3.9% 0.99 0.77
90˝ R26 165.8; CVts : 4.3% 150.6; CVts : 5.0% 115.4; CVts : 4.1% 0.91 0.70
R12 156.2; CVts : 3.4% 152.6; CVts : 2.7% 119.8; CVts : 2.6% 0.98 0.77
R43 52.6; CVss : 3.4% 53.1; CVss : 2.4% 40.4; CVss : 5.0% 1.01 0.77
45˝ (In-plane shear) R26 56.9; CVss : 0.8% 62.1; CVss : 3.1% 41.7; CVss : 2.3% 1.09 0.73
R12 58.0; CVss : 4.5% 58.0; CVss : 3.0% 38.9; CVss : 2.1% 1.00 0.67
Note that five coupons were used for each test.

Table 5 shows the contribution ratios of each layer based on the rule of mixtures calculated by
Equations (3)–(6). In the case of the 0˝ direction, Rrov and Rcloth show dominant values, and their
summations give a range from 82.2% to 93.1%. On the other hand, in the case of the 90˝ direction,
Rcloth gives a range from 75.1% to 80.0%. It is thought that the reduction of Rrs of the 90˝ direction
in 10 years can be caused by the deterioration of plain-woven cloth because the contribution ratios
of the plain-woven cloth of the 90˝ direction are dominant. By considering Rcloth of the 90˝ direction,
Rrs of the 45˝ direction (in-plane shear) in 10 years may be also reduced by the deterioration of
plain-woven cloth.

2499
Polymers 2015, 7, 2494–2503

Table 5. Contribution ratios of each layer based on the rule of mixtures.

Contribution Ratio of Each Layer (%)

Testing Direction Code
RCSM , CSM Rcloth Plain Woven Cloth Rrov , Roving Rm , Matrix
R43 2.1 28.5 64.4 5.0
0˝Polymers 2015, 7, page–page
R26 4.5 39.9 48.3 7.3
R12 7.4 54.0 28.2 10.4
Table 5. Contribution ratios of each layer based on the rule of mixtures.
R43 6.0 80.0 0.0 14.0
90˝ R26 8.7 77.3 0.0 14.1
Testing R12 10.3 Contribution ratio of each layer (%)
75.1 0.0 14.5
Code
direction RCSM, CSM Rcloth Plain woven cloth Rrov, Roving Rm, Matrix
R43 2.1 28.5 64.4 5.0
Table 6 shows the R26 modulus
0° elastic 4.5 of unpainted 39.9 specimens with48.3 the retention
7.3 ratios. CVtm and
R12 7.4 54.0 28.2 10.4
˝ direction,
CVsm in 0 years have a rangeR43
from 1.7%6.0
to 4.3%, except
80.0
for that of R430.0
of the 0 14.0
which is 12.3%.
Rrm of one year shows
90° a range
R26 from8.71.06 to 1.20, and
77.3 a CVtm range 0.0from 1.1%14.1to 4.6%. In the case of
10 years, Rr shows a rangeR12
m
10.3to 1.29, and a75.1
from 1.01 CV range from 0.0 2.1% to 5.8%.
tm
14.5 Rr is higher than
m
those of the tensile and in-plane shear strengths, probably due to the effect of post-curing of the resin.
Table 6 shows the elastic modulus of unpainted specimens with the retention ratios. CVtm and
CVsm in 0 years have a range from 1.7% to 4.3%, except for that of R43 of the 0° direction, which is
12.3%. RrTable 6. Elastic
m of one modulus
year shows of unpainted
a range from 1.06 to specimens
1.20, and with
a CVtmretention ratios.
range from 1.1% to 4.6%.
In the case of 10 years, Rrm shows a range from 1.01 to 1.29, and a CVtm range from 2.1% to 5.8%.
Rrm is higher than those ofElastic
the tensile and (GPa);
Modulus in-plane shear strengths,
Coefficient probably
of Variation, CV due toRetention
the effectRatio,
of Rrm
Testing Direction
post-curing ofCode
the resin. 0 Years 1 Year 10 Years 1 Year 10 Years
R43 Table 20.9;
6. Elastic
CVtm modulus
: 12.3%of unpainted
25.0; CVspecimens
tm : 3.2%
with retention
26.9; CVtm :ratios.
5.2% 1.20 1.29
0˝ R26 19.2; CVtm : 4.3% 20.5; CVtm : 2.0% 20.2; CVtm : 2.5% 1.07 1.05
Testing R12 Code 17.9; CVElastic: modulus (GPa);
19.0; coefficient of variation, CV : 5.8% Retention ratio, Rrm
tm 2.5% CVtm : 3.5% 18.7; CV tm 1.06 1.04
Direction 0 Years 1 Year 10 Years 1 Year 10 Years
R43 R43 12.5; CV
20.9; tmtm:: 2.5%
CV 12.3% 13.4;CV
25.0; CV tm : 1.4% 26.9;13.4;
tm: 3.2% CVtmCV tm :
: 5.2% 1.4%1.20 1.07 1.29 1.07
90˝ 0° R26 R26 12.9; CVCV
19.2; tmtm: :4.0%
4.3% 13.6;CV
20.5; CVtmtm
: 1.1% 20.2;13.9;
: 2.0% CVtmCV tm :
: 2.5% 2.1%1.07 1.06 1.05 1.07
R12 R12 12.8; CVCV
17.9; tmtm: :2.3%
2.5% 14.3;CV
19.0; CVtmtm
: 1.1% 18.7;13.4;
: 3.5% CVtmCV tm :
: 5.8% 2.1%1.06 1.12 1.04 1.05
R43 R43 12.5; CV tm: 2.5%
3.40; CVsm : 3.4% 13.4; CV tm: 1.4%
4.05; CVsm : 2.8% 13.4; CV tm: 1.4%
4.01; CVsm : 2.9%1.07 1.19 1.07 1.18
45˝ (In-plane 90°
R26 R26 12.9;
3.76; CVCV tm: 4.0%
sm : 1.7%
13.6;
4.17;CVCVtm: 1.1%
sm : 1.6%
13.9;3.80;
CVtmCV
: 2.1% :
sm 1.4%1.06 1.11 1.07 1.01
shear modulus)
R12 R12 12.8;
3.49; CVCV tm: 2.3%
sm : 2.9%
14.3;
4.10;CVCVtm: 1.1%
sm : 4.6%
13.4;3.80;
CVtmCV
: 2.1% :
sm 2.7%1.12 1.17 1.05 1.09
R43 3.40; CVsm: 3.4% 4.05; CVsm: 2.8% 4.01; CVsm: 2.9% 1.19 1.18
45° (In-plane Note that five coupons were used for each test.
R26 3.76; CVsm: 1.7% 4.17; CVsm: 1.6% 3.80; CVsm: 1.4% 1.11 1.01
shear modulus)
R12 3.49; CVsm: 2.9% 4.10; CVsm: 4.6% 3.80; CVsm: 2.7% 1.17 1.09
Figure 5 summarizes results Note that five coupons
of unpainted were used forIteach
specimens. test.
is shown that, overall, the strength of
the unpainted Figure
specimens declines
5 summarizes after
results of 10 years of
unpainted outdoor
specimens. exposure
It is shown that, asoverall,
showntheinstrength
Table 4,
of and that
the unpainted
the plain-woven specimens
cloth layers declines
were after 10 years
deteriorated of outdoor
during exposure
10 years as shown in
of outdoor Table 4, and
exposure by that
considering
the plain-woven cloth layers were deteriorated during 10 years of outdoor exposure by considering
the contribution ratios of each layer calculated based on the rule of mixtures. On the other hand, the
the contribution ratios of each layer calculated based on the rule of mixtures. On the other hand,
elastic modulus of the
the elastic unpainted
modulus specimens
of the unpainted shows
specimens a slight
shows increase
a slight increaseas showninin
as shown Table
Table 6. 6.

Continuous strand mat (CSM)

Deteriorated layers due to
outdoor exposure
Cloth fiber
After
σ exposure decrease of
Roving fiber (ROV)
strength
Initial
Cloth fiber
Increase of elastic modulus
Continuous strand mat (CSM) ε
Cross-section of unpainted specimens Stress-strain relationship

Figure 5. Summary of results of unpainted specimens.

Figure 5. Summary of results of unpainted specimens.
3.2. Painted Specimens
3.2. Painted Specimens
Test results of painted specimens are discussed by comparing them with the results of the
unpainted specimens. Table 7 shows the tensile and in-plane shear strengths of painted specimens
Test results of painted specimens are discussed by comparing them with the results of the
with retentions ratios. In the case of one year, Rrs shows a range from 0.92 to 1.21, and CVts and CVss
unpainted range
specimens.
from 2.0%Table 7 shows
to 10.7%. theoftensile
In the case 10 years,and in-plane
Rrs shows shear
a range strengths
from 0.86 of painted
to 1.24, which specimens
are higher
with retentions ratios. In the case of one year, Rrs shows a range from 0.92 to 1.21, and CVts and CVss
values than those of unpainted specimens. Rr s of unpainted specimens of the 90° and 45° (in-plane
range from 2.0% to 10.7%. In the case of 10 years, Rrs shows a range from 0.86 to 1.24, which are higher
7
values than those of unpainted specimens. Rrs of unpainted specimens of the 90˝ and 45˝ (in-plane
shear) directions show lower values than those of the 0˝ direction, while Rrs of painted specimens

2500
Polymers 2015, 7, 2494–2503

do not. It is thought that the surface coating prevented the painted specimens from deteriorating by
comparing these results to the results of the retention ratios of the unpainted specimens. The surface
coating seemed to reduce the effect of moisture because it is one of the key factors of deterioration for
pultruded GFRP, such as the reduction of bending strength [13] and mass loss [14].

Table 7. Tensile and in-plane shear strengths of painted specimens with retention ratios.

Tensile Strength (MPa); Coefficient of Variation, CV Retention Ratio, Rrs

Testing Direction Code
0 Years 1 Year 10 Years 1 Year 10 Years
409.6; 496.7; 488.0;
R43 1.21 1.19
CVts : 21.0% CVts : 3.3% CVts : 2.6%

0˝ 369.0; 372.4; 316.4;

R26 1.01 0.86
CVts : 3.6% CVts : 3.1% CVts : 4.9%
319.2; 330.5; 323.8;
R12 1.04 1.01
CVts : 4.6% CVts : 10.7% CVts : 6.7%
135.8; 140.9; 140.9;
R43 1.04 1.04
CVts : 2.6% CVts : 6.3% CVts : 3.3%

90˝ 165.8; 152.1; 162.1;

R26 0.92 0.98
CVts : 4.3% CVts : 2.9% CVts : 2.1%
156.2; 158.5; 150.8;
R12 1.01 0.97
CVts : 3.4% CVts : 3.0% CVts : 2.4%
52.6; 50.1; 49.0;
R43 0.95 0.93
CVss : 3.4% CVss : 2.0% CVss : 0.5%
45˝ (In-plane shear) 56.9; 64.6; 70.8;
R26 1.13 1.24
CVss : 0.8% CVss : 3.0% CVss : 2.5%
58.0; 57.6; 58.9;
R12 0.99 1.02
CVss : 4.5% CVss : 2.6% CVss : 1.2%
Note that five coupons were used for each test.

Table 8 shows the elastic modulus of painted specimens with the retentions ratios. In the case of
one year, Rrm shows a range from 0.89 to 1.20, and CVtm and CVsm range from 1.8% to 7.9%. In the
case of 10 years, the retention ratios show a range from 0.96 to 1.21, and CVtm and CVsm range from
1.7% to 5.0%. Overall, Rrm of painted specimens is higher than those of the tensile and in-plane shear
strengths, which is the same tendency as in the case of unpainted specimens.

Table 8. Elastic modulus of painted specimens with retention ratios.

Elastic Modulus (GPa); Coefficient of Variation, CV Retention Ratio, Rrm

Testing Direction Code
0 Years 1 Year 10 Years 1 Year 10 Years
20.9; 25.0; 25.2;
R43 1.20 1.21
CVtm : 12.3% CVtm : 3.8% CVtm : 3.4%

0˝ 19.2; 20.7; 18.5;

R26 1.08 0.96
CVtm : 4.3% CVtm : 2.0% CVtm : 4.3%
17.9; 19.5; 19.0;
R12 1.09 1.06
CVtm : 2.5% CVtm : 7.9% CVtm : 4.4%
12.5; 13.1; 13.8;
R43 1.05 1.10
CVtm : 2.5% CVtm : 2.5% CVtm : 1.8%

90˝ 12.9; 11.5; 14.0;

R26 0.89 1.08
CVtm : 4.0% CVtm : 4.3% CVtm : 3.1%
12.8; 13.8; 13.7;
R12 1.08 1.07
CVtm : 2.3% CVtm : 2.6% CVtm : 1.7%
3.40; 4.03; 3.99;
R43 1.19 1.17
CVsm : 3.4% CVsm : 3.7% CVsm : 2.6%
45˝ (In-plane shear) 3.76; 4.49; 4.44;
R26 1.19 1.18
CVsm : 1.7% CVsm : 7.7% CVsm : 5.0%
3.49; 4.11; 4.12;
R12 1.18 1.18
CVsm : 2.9% CVsm : 1.8% CVsm : 3.3%
Note that five coupons were used for each test.

2501
Polymers 2015, 7, 2494–2503
Polymers 2015, 7, page–page

Figure66 summarizes
Figure summarizesthe theresults
resultsof
ofthe
thepainted
paintedspecimens.
specimens.In Incontrast
contrastto to the
the case
case of
of the
the unpainted
unpainted
specimens, the
specimens, the strength
strength of
of the
the painted
painted specimens
specimens after
after 10
10 years
years ofof outdoor
outdoor exposure
exposure indicates
indicates aa close
close
valueto
value to the
the one
one before
before outdoor
outdoor exposure,
exposure,as asshown
shownin in Table
Table7.7.ItIt is
is thought
thought that
that aa surface
surface coating
coating can
can
preventthe
prevent theplain-woven
plain-woven clothcloth layers
layers fromfrom deteriorating
deteriorating due todue
outdoor to outdoor
exposure.exposure.
The elasticThe elastic
modulus
modulus
of of thespecimens
the painted painted specimens showsincrease
shows a slight a slight increase
as shown asin
shown
Tablein 8,Table
which8,iswhich is also observed
also observed in the
in the
case ofcase of the unpainted
the unpainted specimens.
specimens.

Continuous strand mat (CSM)

Coating material

Cloth fiber After exposure

σ
Roving fiber (ROV) Initial ≈ After exposure
Initial
Cloth fiber Increase of elastic modulus
ε
Continuous strand mat (CSM) Stress-strain relationship
Cross-section of painted specimens Coating material

Figure 6. Summary
Figure 6. Summary of
of results
results of
of painted
painted specimens.
specimens.

4. Conclusions
4. Conclusions
The
The main
main conclusions
conclusions from
fromthethepresent
presentstudy
studycan canbe
besummarized
summarizedas asfollows:
follows:
In
In the
the case of the unpainted
unpainted specimens,
specimens,thethetensile
tensileand
andin-plane
in-planeshear
shearstrengths
strengths after
after 1010 years
years of
of outdoor
outdoor exposure
exposure werelower
were lowerthanthanthose
thoseofofthe
theones
ones before
before the
the exposure test. By calculating
calculating thethe
contribution
contribution ratios
ratios of
of each
each layer,
layer,plain-woven
plain-woven cloth,
cloth, which
which had
had aa relatively
relatively higher
higher contribution
contribution ratio
ratio
than
than the
the other
other layers,
layers, seemed
seemed to to deteriorate
deteriorate during
during thethe 10-year
10-year exposure.
exposure. For For the
the elastic
elastic modulus
modulus of of
the
the unpainted
unpainted specimens,
specimens, aa slight
slight increase
increase was
was observed,
observed, probably
probably duedue to
to the
the effect
effect of
of post-curing
post-curing of of
the resin.
the resin.
In
In the
the case
case ofof the
the painted
painted specimens,
specimens, thethe tensile
tensile and
and in-plane
in-plane shear
shear strengths
strengths after
after 10
10 years
years ofof
outdoor
outdoor exposure
exposure were
were close
close to
to the
the ones
ones before
before thethe exposure
exposure test,
test, which
which were
were caused
caused by by the
the effect
effect of
of
the
the surface
surface paint.
paint. However,
However, further
further studies
studies are
are needed
needed toto understand
understand how how thethe surface
surface paint
paint protects
protects
the
the painted
painted specimens.
specimens. For the elastic modulus of the painted painted specimens,
specimens, as they they have
have the
the same
same
tendency
tendency as as the
the unpainted
unpainted specimens,
specimens,aaslight
slightincrease
increasewaswasobserved.
observed.
Acknowledgments: The
Acknowledgments: The authors
authors gratefully
gratefully acknowledge
acknowledge the
the assistance
assistance by
by Asahi
Asahi Glass
Glass Matex
MatexCo.,
Co.,Ltd.
Ltd. for
for
providingthe
providing thespecimens.
specimens.
Author contributions: The authors
Author Contributions: authors dedicated
dedicated themselves
themselves to to conduct
conduct this
this experimental
experimental work.
work. Itaru
Itaru Nishizaki
Nishizaki
planned
planned and supervised the entire experimental work, and Tomonori Tomiyama prepared the specimens and
and supervised the entire experimental work, and Tomonori Tomiyama prepared the specimens and
placed at the exposure sites. Hiroki Sakuraba conducted the material tests and analyzed experimental results. All
placed at the exposure sites. Hiroki Sakuraba conducted the material tests and analyzed experimental results.
the authors edited the manuscript especially on their tasks.
All the authors edited the manuscript especially on their tasks.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
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© 2015 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons by Attribution
(CC-BY) license (http://creativecommons.org/licenses/by/4.0/).

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