JOURNAL OF

COMPOSITE
Article M AT E R I A L S
Journal of Composite Materials
2014, Vol 48(2) 165–177
! The Author(s) 2012
Thermal performance and flame Reprints and permissions:
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retardancy studies of vinyl ester and DOI: 10.1177/0021998312469990
jcm.sagepub.com
glass fiber reinforced plastic composites
containing nanoclay

Hong-Gang Zhu1, Ming-Yang Liu2, Richard KK Yuen3,

Christopher KY Leung1 and Jang-Kyo Kim2

Abstract
The thermomechanical properties, thermal stability and flame retardancy of the organoclay-vinyl ester nanocomposites
and the glass fiber reinforced plastic composites made from the vinyl ester nanocomposites matrix were studied. The
results show that nanoclay addition increases both the storage modulus and glass transition temperature of the vinyl
ester and glass fiber reinforced plastic composites due to the reinforcing effects and the molecular relaxing constraining
effects of clay platelets. Both the vinyl ester and glass fiber reinforced plastic composites show different thermal deg-
radation behaviors in nitrogen and in air due to the oxidizing effect of oxygen. Nanoclay has little effect on the thermal
stability of vinyl ester in nitrogen, while increases the 2nd peak decomposition temperature of vinyl ester in air, resulting
from the shielding effect of silicate platelets. However, the thermal stability of the glass fiber reinforced plastic compos-
ites in both atmospheres is reduced by nanoclay with unknown reasons. The flame retardancy of vinyl ester and glass
fiber reinforced plastic composites is significantly improved due to clay that promotes the formation of carbonaceous
char platelets acting as mass and heat barrier. Glass fiber reinforcement alters the thermal dynamic, thermal degradation
and combustion behaviors of the vinyl ester nanocomposites.

Keywords
Organoclay-vinyl ester nanocomposite, glass fiber reinforced plastic, thermomechanical property, thermal stability, flame
retardancy

at elevated temperatures or in fire.1–7 Such findings

Introduction
The interests in the use of fiber-reinforced plastic (FRP)
composites in the construction industry have increased
significantly in the past several decades. Application of
FRP composites includes FRP structural components,
for example bridge deck elements, FRP reinforcing
bars and FRP sheets/laminates for rehabilitation/
strengthening of concrete structures. The main advan-
tages of FRP composites are high specific strength and
high specific modulus, good corrosion resistance and
ease of handling. In civil engineering applications,
materials are always exposed to various adverse envir-
onments, such as high humidity, basics/acids/salts, ele-
vated temperature and fire, etc. Previous studies have
shown that FRP composites may suffer severe reduc-
tions in mechanical properties and structural integrity
have hindered the widespread utilization of FRP com-
posites under adverse environments.8–10
When exposed to high temperatures or fire, both the
matrix material and fiber reinforcement of FRP
1
Department of Civil and Environmental Engineering, Hong Kong
University of Science and Technology, China
2
Department of Mechanical Engineering, Hong Kong University of Science
and Technology, China
3
Department of Building and Construction, City University of Hong
Kong, China
Corresponding author:
Hong-Gang Zhu, Department of Civil and Environmental Engineering,
Hong Kong University of Science and Technology, Clear Water Bay,
Hong Kong, China.
Email: cezhuhg@ust.hk

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166
composites would be subjected to an elevated tem-
perature. Though the fiber reinforcements commonly
used for the preparation of FRP composites applied in
civil engineering, such as basalt, carbon and glass
fibers, show different behaviors at elevated tempera-
tures 11–13 depending on their composition, these
fibers are relatively stable below 700 C, but would
also show significant degradation with further increas-
ing temperature. However, there are also some glass
fibers exhibiting significant mechanical property deg-
radation at moderately low temperatures, often below
500 C. For the matrix materials, such as epoxy, poly-
ester and vinyl ester, they may become rubbery with
concomitant reductions in stiffness and stress-transfer
capacity at elevated temperatures,1 leading to degrad-
ation in the mechanical properties of FRP composites.
In severe cases, the matrix materials (and even the
fiber reinforcements) would thermally decompose
with the release of volatile decomposition products
and eventually burn with the release of heat, toxic
smoke and toxic fume,14 resulting in loss of structural
integrity and load bearing capacity of FRP compos-
ites. The poor thermal performance and fire resistance
of FRP composites are caused primarily by the poor
thermal performance and high flammability of matrix
materials. To address the above issues, specialty poly-
mer resins with high temperature resistance have been
developed, but they are often too expensive and diffi-
cult to process for use in the cost-conscious construc-
tion industry.
Therefore, suitable alternative measures need to be
taken to achieve the thermal performance and fire resist-
ance of FRP composites. Introducing inorganic fillers
into the polymer matrix has been considered another
alternative solution. Especially with the development
of nanotechnology, nanoscopic fillers, such as nanoclay,
carbon nanotubes, carbon nanofibers and polyhedral
oligomeric silsesquioxanes (POSS), etc., have been
employed with varied success.15–21 Compared to con-
ventional microscopic fillers, nanoparticles are capable
of markedly improving certain properties at a fraction of
filler concentration, often less than 5 wt% of the resin
content. The nanoclay, consisting of nanoscale silicate
sheets and other mineral oxides with layered structure,
possesses unique capabilities valuable to polymer that
cannot be found in conventional microscopic reinforce-
ments. Apart from the improved mechanical properties,
the excellent barrier capability arising from the extre-
mely high aspect ratio of nanoclay plates is one of the
most attractive properties of polymer-clay nanocompo-
sites which are particularly useful in civil engineering
applications.22–24 The barrier characteristics are mani-
fested in terms of reduced permeability of moisture,
gases and solvents, improved chemical resistance,
reduced swelling by solvents, improved dimensional
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Journal of Composite Materials 48(2)
stability, improved thermal stability and higher flame
retardancy.15,16,25,26
Using polymer-clay nanocomposite as matrix mater-
ial to improve the mechanical properties and durability
of FRP composites have been studied exten-
sively.22,27–30 However, few researches have been
devoted to understanding the effects of polymer-clay
nanocomposite matrix on the thermal performance
and fire resistance of FRP composites. This study, as
part of a large project on civil engineering application
of polymer-clay nanocomposites,22–24 was hence under-
taken to address the above issue. The thermomechani-
cal properties, thermal stability and fire retardancy of
the organoclay-vinyl ester (VE, clay-VE) nanocompo-
sites and the GFRP composites made from the VE
nanocomposites matrix were investigated using various
characterization tools in this study.
Experimental
Materials and preparation of VE nanocomposites
and GFRP composites
The clay-VE nanocomposite was prepared from bisphe-
nol A epoxy vinyl ester resin (SWANCOR 901-35,
Swancor Ind. Co., LTD), consisting of 65% resin and
35% styrene. The initiator and accelerator employed
for the curing of VE resin were 30 wt% methyl ethyl
ketone peroxide (MEKP) and 6 wt% cobalt naphthe-
nate (Sigma-Aldrich Co. LLC), respectively. The orga-
noclay used for nanocomposite preparation was
Nanomer I.30P organoclay (Nanocor, Inc.), which is
montmorillonite modified with 33 wt% primary octade-
cylamine. A sequential mixing method31 was used to
prepare the clay-VE nanocomposites, and nanocompo-
sites with varying organoclay contents of 0, 3 and
5 wt% were prepared. To prepare the nanocomposites,
desired amount of I.30P organclay was mixed with styr-
ene (99%, Sigma-Aldrich Co. LLC) to obtain a 20 wt%
clay/styrene mixture, which was ultrasonicated for 1 h
at room temperature in an ultrasonication bath
(Bransonic 1510-DTH, Branson Ultrasonics Co.). VE
resin was then added into the mixture and subjected to
high speed shear mixing (Charles Ross and Son Co.) at
a rate of 3500 r/min for 2 h at room temperature. After
the mixture was ultrasonicated for 15 min using an
ultrasonic liquid processor (Sonicator 3000, Misonix,
Inc.), 2 phr initiator and 0.3 phr accelerator were
added into the clay–resin mixture followed by manual
stirring. The clay-resin solution was then cast into an
aluminum mold of 150 mm wide  200 mm long  1 mm
or 5 mm thick, which was cured at room temperature
for 24 h, followed by postcuring at 105 C for 2 h.
Unidirectional E-glass fabrics (UD Fabric 920F,
Han Kuk Fiber Glass Co., LTD) with a silane sizing
Zhu et al.
content below 0.5 wt% were used as the reinforcement
of GFRP composites. The average filament diameter
and strand count of the glass fabric were 15  1 mm
and 950  50 tex, respectively. A vacuum-assisted
hand lay-up method was used to prepare GFRP com-
posite laminates with the VE nanocomposites matrix.
The glass fabrics were stacked in the same fiber orien-
tation with the matrix resin applied in-between until the
desired number of plies was laid. After degassing to
remove entrapped voids, the wet GFRP laminates
were cured between peel ply-coated polypropylene
plates in a Teflon mold at room temperature on a
press, so as to maintain the consistent resin content of
about 40 vol.%. The curing process employed for
GFRP composites was same to that of the VE
nanocomposites.
Characterization of VE nanocomposites
and GFRP composites
The dispersion state of clay in the clay-VE nanocom-
posites was characterized by measuring the interlayer
spacing of clay on an X-ray diffractometer (XRD,
Philips PW1830), which is equipped with a Cu Ka radi-
ation (0.1540562 nm) source and a germanium detector.
The diffraction spectra were obtained at room tempera-
ture at a scanning rate of 0.1 /min from 2 to 10 . The
spacing between the diffraction lattice planes, d, was
calculated using the following Bragg’s law
2d sin  ¼ n
where  is the diffraction angle (in degree) and  is the
wavelength of the incident ray. A transmission electron
microscope (TEM, JEOL 100CX) was also employed to
visually examine the dispersion state of clay in the
nanocomposites at an acceleration voltage of 120 kV.
The thermomechanical properties of clay-VE nano-
composites and GFRP composites were measured on a
dynamic mechanical analyzer (Perkin Elmer DMA 7).
All specimens were subjected to oscillating 3-point
bending from 25 C to 150 C at a heating rate of 8 C/
min in an argon environment according to the specifi-
cation, ASTM D4065. The GFRP composite specimens
were loaded such that the fiber direction coincided with
the longitudinal direction. The thermal stability of both
composites was evaluated on a thermogravimetric ana-
lyzer (Perkin Elmer TGA 7) operating from room tem-
perature to 1000 C. Specimens were heated from room
temperature to 800 C at a heating rate of 20 C/min
under both nitrogen flow and air flow according to
the specification, ASTM E2109-2000. Three specimens
were tested for each set of conditions in the above
DMA and TGA experiments. The fire reaction proper-
ties of VE nanocomposites and GFRP composites were
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167
studied by performing the combustion test using a cone
calorimeter according to the specification, ASTM E
1354-04. Two panel specimens with dimensions of
100 mm  100 mm  5 mm and a weight of 30–50 g
were prepared for each material. All specimens were
tested in the horizontal position at an incidental heat
flux of 35 kW/m2 and an exhaust flow of 24 L/s, and an
external spark was used for ignition. Important flame
retardant parameters, including heat release rate
(HRR), time to ignition/peak HRR, combustion time
and mass remaining were recorded. After completion of
the combustion test, the morphology of combustion
residue was observed using a scanning electron micro-
scope (SEM, JEOL 6300F) at an acceleration voltage of
100 keV.
Results and discussion
Dispersion state of clay in VE nanocomposites
The XRD spectra of neat I.30P organoclay powder and
clay-VE nanocomposites are presented in Figure 1.
The basal reflection peak of (001) plane of clay in its
powder form appeared at 3.7 , equivalent to an inter-
layer spacing of 2.24 nm. However, the clay’s reflection
peak of (001) plane disappeared completely in the spec-
trum of the nanocomposites, suggesting that the reflec-
tion peak has shifted to an angle below 2 . This
indicates that the interlayer spacing of clay in the nano-
composites increased to above 4.4 nm due to intercal-
ð1Þ ation of polymer molecules into the interlayer space
and/or partial exfoliation of clay. The TEM images
shown in Figure 2 confirm the above conclusion. It
can be seen that the clay was broken into thin clay
particles of about 1mm in length with uniform distribu-
tion on the microscopic scale (Figure 2(a) and (c)).
And, the individual clay particles consisting of a few
to tens of silicate layers were mainly intercalated with
1: I.30P clay
2: 5 wt% I.30P
3: 3 wt% I.30P
Intensity (a.u.)
1
2
3
2 4 6 8 10
2θ (degree)
Figure 1. XRD spectra of I.30 P organoclay powder and 3 wt%,
5 wt% clay-VE nanocomposites.
XRD: X-ray diffraction; VE: vinyl ester.
168
Figure 2. TEM images of: (a, b) 3 wt% and (c, d) 5 wt% clay-VE nanocomposites.
TEM: transmission electron microscopy; VE: vinyl ester.
expanded interlayer distance and some being orderly
exfoliated while the high aspect ratio was still main-
tained (Figure 2(b) and (d)). Similar intercalation and
orderly exfoliation behaviors were observed in the
nanocomposites containing epoxy resin and the same
type of I.30P organoclay.25
Thermomechanical properties of VE nanocomposites
and GFRP composites
The storage modulus and tangent d profiles of the clay-
VE nanocomposites and GFRP composites containing
different amounts of clay are shown in Figure 3. The
incorporation of organoclay significantly increased the
storage modulus of VE at temperatures below Tg. A
remarkable 28% increase was noted at room tempera-
ture with 3 wt% organoclay. Moreover, the corres-
ponding glass transition temperature, as indicated by
the abrupt change in storage modulus or the peak
value of the tangent d profile, shifted from 90 C to
117 C by about 27 C due to the same organoclay con-
tent. The improvements in thermomechanical proper-
ties of VE was attributed to the rigid silicate layers that
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Journal of Composite Materials 48(2)
reinforced the VE resin and inhibited the movement of
flexible segments of VE molecule around and between
the silicate layers by strongly interacting with the VE
resin.15,16,27 The thermomechanical properties of the
nanocomposites containing 3 and 5 wt% clay were
almost identical or very similar, except that the storage
modulus of the nanocomposite with 5 wt% clay was
marginally lower than that of 3 wt% clay in the tem-
perature range from about 40 C to 100 C. This obser-
vation is probably attributed to a slightly lower degree
of intercalation and exfoliation of clay in the nanocom-
posites containing a larger amount of clay (as shown in
Figure 2), resulting in less efficient hindrance of molecu-
lar movement of polymer chains by the nanoclay. It is
interesting to note that the increase in storage modulus
due to nanoclay was functionally very similar to the
increase in flexural modulus of the bulk nanocompo-
sites measured in 3-point bending, although the change
in absolute value was relatively smaller in the bulk
mechanical test, as shown in Figure 4. However, there
was a concomitant reduction in flexural strength of
bulk nanocomposites with increase in clay content.
There are three possible reasons for this phenomenon.
Zhu et al. 169

Neat resin 3wt% clay 5wt% clay

(a) 4 1.0

Storage modulus (GPa)

0.8
3

Loss factor
0.6
2
0.4

1
0.2

0 0.0
25 45 65 85 105 125
Temperature (°C)

Neat resin 3wt% clay 5wt% clay

(b) 18 0.4
16
Storage modulus (GPa)

14 0.3

Loss factor
12
10 0.2
8
6 0.1
4
2 0.0
25 45 65 85 105 125 145
Temperature (°C)

Figure 3. Storage modulus and loss factor profiles of: (a) clay-VE nanocomposites and (b) clay-GFRP composites.
VE: vinyl ester; GFRP: glass fiber reinforced plastic.

(a) 4 (b) 120

Flexural strength (MPa)
Flexural modulus (GPa)

100
102.24
3.26 3.34 80
3 3.24
78.08 75.34
60

2 40
-1 1 3 5 -1 1 3 5
Clay content (wt%) Clay content (wt%)

Figure 4. (a) Flexural modulus and (b) flexural strength of clay-VE nanocomposites plotted as a function of clay content.
VE: vinyl ester.

One is that more air bubbles/voids were entrapped due due to the incorporation of nanoclay. As a result of the
to the viscosity increase of VE resin caused by clay, incorporation of glass fibers with a Young’s modulus of
another is that some clay agglomerates acted as stress 73 GPa, the storage modulus of GFRP composites was
concentrators, and the third is that internal stress was three to four times higher than those of the VE nano-
induced by the different cure speeds in bulk VE and at composites at temperatures below the Tg. Moreover,
the clay–VE interface.32 different to the VE nanocomposites, the storage modu-
The corresponding storage modulus and tangent d lus of GFRP composites was still maintained at
profiles of GFRP composites similarly present substan- 2–5 GPa at temperatures above the Tg, indicating the
tial improvements in the thermomechanical parameters thermal resistance of glass fibers. However, the Tg

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170
of GFRP composites were similar to those of the VE
nanocomposites. This is because that the Tg of GFRP
composites are highly dependent on the properties of
their matrix materials. Although the matrix material
played a minor role in determining the bulk mechanical
properties of GFRP composites, especially the proper-
ties along the fiber direction, addition of clay into the
VE matrix enhanced not only the Tg but also the stor-
age modulus of GFRP composites. This is caused by
both the reinforcing and constraining effects of clay
platelets and the improved bonding29 between matrix
material and fiber. In comparison with the GFRP com-
posite without clay, the storage modulus measured at
32 C and the Tg of the GFRP composite containing
3 wt% clay were 26% and 14 C higher, respectively.
Moreover, at temperatures above the Tg, say 130 C,
the storage modulus of the latter composite containing
nanoclay was still higher than that of the former com-
posite. Similar to the observations for VE nanocompo-
sites with 3 and 5 wt% clay, there were negligible
differences in the thermomechanical properties between
the corresponding GFRP composites.
Thermal stability of VE nanocomposites
and GFRP composites
To evaluate the thermal stability of VE and GFRP
composites containing nanoclay, the thermogravimetric
analysis (TGA) was performed in both nitrogen and
air. Figures 5 and 6 show the percent weight changes
with temperature while Table 1 summarizes the onset
decomposition temperatures at which the mass loss
reaches 10% and the peak decomposition temperatures
where the mass loss rate reaches the highest.
Clay-VE nanocomposites presented different ther-
mal decomposition behaviors in nitrogen and air.
These nanocomposites exhibited single-step decompos-
ition with a few residues left in nitrogen while two-
step decomposition with almost no residue left in
air because of the different thermal degradation
(a) 100
80
Weight (%)
60
40
20
0 0
50 150 250 350
Temperature (°C)
Figure 5. Weight loss curves of clay-VE nanocomposites obtained: (a) in nitrogen and (b) in air.
VE: vinyl ester.
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Journal of Composite Materials 48(2)
mechanisms in different environments. There was no
chemical reaction occurring between the inert nitrogen
gas and nanocomposites even at a high temperature,
and the thermal decomposition was caused mainly by
the scission and cleavage reactions of polymer chains,
such as the organic surfactant of clay, polystyrene
and vinyl ester chains, at an elevated temperature.14,33
In contrast, in air, reactions occurred between the
oxygen and polymer at an elevated temperature with
oxygen acting as an oxidant. The thermal decompos-
ition of nanocomposites in air was hence caused by not
only the scission and cleavage of polymer chains, but
also the oxidization and even combustion of polymer in
the presence of oxygen, heat and combustible vola-
tiles.14,34 Therefore, the first weight loss in air occurred
due to evaporation of volatile products arising from the
scission and oxidization of polymer molecules, while
the second weight loss was induced by the high tem-
perature decomposition of char residues mainly
through thermal oxidation,34 which did not occur in
nitrogen atmosphere. Table 1 indicates that both the
onset decomposition temperature, TO, and the 1st
peak decomposition temperature, TP1, of clay-VE
nanocomposites were generally lower in air than in
nitrogen. One possible reason is that the oxygen con-
tained in air promoted the thermal decomposition of
nanocomposites by oxidizing the polymer molecules.34
In nitrogen, the thermal decomposition behaviors of
the clay-VE nanocomposites were almost identical
regardless of clay content (Figure 5(a)), and only neg-
ligible differences were identified in terms of the onset
and peak decomposition temperatures, indicating that
organoclay had little effect on the thermal stability of
vinyl ester in nitrogen. This can be attributed to the
dual effects of organoclay on the thermal stability of
polymer: (1) the organic modifier in nanoclay decom-
poses between 200 C and 300 C and catalyzes the deg-
radation of polymer; (2) the nanoclay enhances the
thermal stability of polymer due to the strong inter-
action between polymer and silicate layer (restrict the
Neat resin (b) 100 Neat resin
3wt% clay 3wt% clay
5wt% clay 80 5wt% clay
Weight (%)
60
40
20
450 550 650 50 150 250 350 450 550 650
Temperature (°C)
Zhu et al. 171

thermal motion of polymer molecular) and the barrier
effect of silicate layer to the release of volatile decom-
position products.35 Some 12% of the total weight still
remained for the clay nanocomposites at about 550 C
corresponding to 0 wt% for the neat VE. This observa-
tion is mostly due to the facts that the decomposition
temperature of clay is much higher than 500 C and
some polymer molecules intercalated in the clay are
protected by clay layers from thermal decomposition.
As shown in Figure 5(b), the thermal decomposition
behaviors of the clay-VE nanocomposites in air were
basically much the same as in nitrogen up to about
450 C. However, the onset decomposition temperature
in air marginally increased with the incorporation of
organoclay, which was different to that in nitrogen.
This is because that, besides the dual effects mentioned
above, the silicate platelets hinders the diffusion of
oxygen which accelerates the degradation of polymer.
Similar to the case in nitrogen, the 1st peak decompos-
ition temperature in air was not affected at all by nano-
clay addition. This may be due to the fact that the
scission and oxidization of polymer molecules occurred
simultaneously in the first weight loss stage, and the
barrier effect of nanoclay to oxygen and volatile
decomposition products diffusion was counteracted.
In contrast, the second peak decomposition tempera-
tures were higher for the nanocomposites than the neat
VE by more than 26 C. This is because that the mass
loss in this stage was caused by the high temperature
decomposition of char residue consisting of polymer
and nanoclay with most of polymer in between the sili-
cate layers. The barrier effect of silicate layer to oxygen
and volatile decomposition products diffusion are
hence much more significant. In this weight loss stage,
the silicate layer acted as a barrier to oxygen and vola-
tile decomposition products, retarding the decompos-
ition and mass loss of char residues. Similar to the
observation in nitrogen, the residue weights of the
nanocomposites were higher than that of the neat
vinyl ester in air, but the amounts of residue in air
were much smaller due to the decomposition of poly-
mer in-between the silicate layers
The TGA curves of GFRP composites containing
clay are shown in Figure 6. Similar to their respect-
ive matrix materials, all three different GFRP compos-
ites showed single-step decomposition in nitrogen.
However, the onset decomposition temperatures of
GFRP composites were significantly lower than those

(a) 100 Neat resin (b) 100 Neat resin

3wt% clay 3wt% clay
95 5wt% clay
95 5wt% clay
Weight (%)

Weight (%)

90 90

85 85

80 80

75 75
50 150 250 350 450 550 650 50 150 250 350 450 550 650
Temperature (°C) Temperature (°C)

Figure 6. Weight loss curves of clay-GFRP composites obtained: (a) in nitrogen and (b) in air.
GFRP: glass fiber reinforced plastic.

Table 1. Characteristic decomposition temperatures of clay-VE nanocomposites and clay-GFRP composites.

In nitrogen In air
Sample
TO (oC) TP1 (oC) TO (oC) TP1 (oC) TP2 (oC) TP3 (oC)

0 wt% nanocomposite 394 437 376 436 527

3 wt% nanocomposite 393 440 382 433 555
5 wt% nanocomposite 394 438 380 434 553
0 wt% GFRP composite 342 439 298 371 421 532
3 wt% GFRP composite 304 427 265 356 419 525
5 wt% GFRP composite 312 432 271 360 424 528
TO: onset decomposition temperature; TP1, TP2 and TP3: peak decomposition temperatures at the 1st, 2nd and 3rd decomposition stages, respectively;
VE: vinyl ester; GFRP: glass fiber reinforced plastic.

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172
Table 2. Fire reaction properties of clay-VE nanocomposites and clay-GFRP composites.
Clay-VE nanocomposites
Sample 0 wt%
Time to ignition (s) 68
Peak HRR (kW/m2) 632
Time to peak HRR (s) 94
Average HRR (kW/m2) 288
Combustion time (s) 99
Mass remaining (%) 4.1
VE: vinyl ester; GFRP: glass fiber reinforced plastic; HRR: heat release rate.
of their matrix materials. This may be attributed to the
lower decomposition temperatures of the sizing mater-
ials, including the silane coupling agents applied to the
glass fibers and the fiber-matrix interfacial material
with a lower cross-linking density than the bulk
matrix material.36,37 While clay had little effect on the
onset decomposition temperatures of the matrix mater-
ials in nitrogen, the onset decomposition temperatures
of GFRP composites were remarkably reduced by clay
addition, but the reason is still unknown. The peak
decomposition temperatures of the matrix materials
and the GFRP composites in nitrogen were similar
and both little affected by the addition of nanoclay.
As a result of the presence of low-molecular weight
sizing material and poorly cross-linked interfacial
materials in GFRP composites and the oxidizing
effect of oxygen, the GFRP composites in air reached
10% mass loss at much lower temperatures and showed
an additional decomposition process at lower tempera-
tures compared with their matrix materials. Therefore,
(1) the GFRP composites in air showed lower on-set
decomposition temperatures than in nitrogen; (2) the
GFRP composites showed three-step decomposition
in air (Figure 6(b)), whereas their matrix materials pre-
sented two-step decomposition (Figure 5(b)); (3) the
onset decomposition temperatures of GFRP compos-
ites were much lower than those of their matrix mater-
ials, while the 2nd and 3rd peak decomposition
temperatures of GFRP composite were similar to the
1st and 2nd peak decomposition temperatures of their
matrix materials. Similar to the observations in nitro-
gen atmosphere, clay addition decreased the onset
decomposition temperatures while marginally affected
the peak decomposition temperatures of GFRP com-
posites in air, though clay addition significantly
enhanced the 2nd peak decomposition temperature of
the VE nanocomposites in air. Further studies should
be conducted to make clear the mechanisms behind
these phenomena.
In summary, the incorporation of nanoclay had little
effect on the thermal stability of VE in nitrogen, while it
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Journal of Composite Materials 48(2)
Clay-GFRP composite
3 wt% 5 wt% 0 wt% 3 wt% 5 wt%
89 75 58 178 120
319 301 911 678 687
229 115 153 363 241
217 210 559 302 410
351 285 199 409 307
7.4 10.6 28.3 31.4 32.2
improved the 2nd peak decomposition temperature of
VE in air. However, the thermal stability of the GFRP
composites in both air and nitrogen was reduced in
terms of both initial and peak decomposition tempera-
tures due to nanoclay. The mechanisms behind the
latter phenomenon are still not clear, and further stu-
dies are needed to give a proper explanation.
Fire reaction properties of VE nanocomposites
and GFRP composites
The cone calorimeter test results of the composites are
summarized in Table 2, while the HRR of the compos-
ites determined from the tests are plotted as a function
of time as shown in Figure 7. For the HRR profile of
neat VE, there was an initial delay period before the
specimen released heat, namely ignited, with the time of
this period defined as the time to ignition. This is
because that, during this period, the exposure time to
the external heat flux is insufficient to heat the VE resin
to the pyrolysis temperature. Following this delay,
there was a rapid rise in the HRR, due to the sudden,
short-term release of heat from the ignition of flam-
mable volatile, in this case mainly low molecular
weight hydrocarbons, released from the materials near
to the VE–fire interface. The HRR of neat VE then
continued to rise rapidly to a peak value with the con-
tinuous combustion of VE resin. Following the peak
HRR, the HRR decreased progressively resulting
from the declining amount of VE resin as well as the
formation and thickening of char layer that slowed the
decomposition and the release of combustible volatile
in the underlying material. Eventually, the heat release
rate become negligible, as the last of the resin is decom-
posed and consumed by combustion.14
Clay addition changed the HRR profiles of VE, con-
sistent with the results of other polymer-clay nanocom-
posites.38 The initial delay period present in the HRR
curves of VE nanocomposites was prolonged by clay
which delayed the decomposition of VE resin and
hence the generation and release of combustible
Zhu et al.
(a) 700
600
HRR (kW/m2)
500
400
300
200
100
0 0
0 100 200 300
Time (s)
Figure 7. HRR profiles of: (a) clay-VE nanocomposites and (b) clay-GFRP composites.
HRR: heat release rate; VE: vinyl ester; GFRP: glass fiber reinforced plastic.
volatiles. Table 2 indicates that the time to ignition of
VE was increased by 31% with the incorporation of
3 wt% clay. After ignition, the HRR of neat VE
increased rapidly to a peak value, followed by a drastic
decrease to zero in less than about 70 s, whereas the
HRR of the nanocomposites increased to almost a
half value of the peak HRR of neat VE, followed by
an almost constant stage for more than 100 s before
gradual decrease to zero in about 150 s. This is because
compacted carbonaceous char platelets began to form
at the surface of VE nanocomposites after combustion
of the surface resin and increased/thickened with the
proceeding of combustion, while few char formed
during the combustion of neat VE, to be discussed in
the following section on combustion residue character-
ization. The increase in the remaining mass is also a
reflection of char formation. This clay-reinforced char
layer acted as a barrier to both heat and pyrolyzed
flammable volatiles (fuel for combustion), thus lower-
ing the HRR and lengthening the time to peak HRR
and to complete combustion by delaying the decompos-
ition of VE resin underneath as well as reducing the
generation and release rates of combustible vola-
tiles.15,16 With the addition of 3 wt% clay, the peak
HRR and average HRR of VE were reduced by 50%
and 25% respectively, while the time to peak HRR was
increased by 144%. However, clay addition had little
effect on the initial HRR just after ignition. This is
because that, in this period, heat release was mainly
caused by combustion of surface resin and no char
had been formed. Similar to the observations in ther-
momechanical property and thermal stability studies,
the flame retardancy parameters of the composite
with 5% clay are similar or slightly inferior to those
of the composite with 3% clay.
The HRR profiles of GFRP composites were differ-
ent from those of the matrix materials, as a result of the
incorporation of unburned glass fiber with low thermal
conductivity.39 As shown in Figure 7(b), the HRR of
GFRP composites increased rapidly after ignition, just
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173
Neat Resin (b) 1000 Neat Resin
3wt% clay 3wt% clay
5wt% clay
5wt% clay 800
HRR(kW/m2)
600
400
200
400 500 0 100 200 300 400 500
Time (s)
like the matrix materials, due to the combustion of sur-
face resin. However, in the following, the HRR
increased gradually first, with a shoulder present, and
then increased rapidly again to a peak value followed
by a gradual decrease to zero. This is because that the
glass fabric delayed the decomposition and thus com-
bustion of matrix materials, especially those between
the glass fabrics.39 After a period of slow combustion
of the in-between matrix materials (shoulder), delamin-
ation would occurred in the GFRP laminates, resulting
in the 2nd rapid increase stage of HRR as a result of
increase in the composite surface area exposed to heat
flux. Compared with their matrix materials, the time to
ignition, peak HRR and complete combustion were
much longer for the GFRP composites, due to the
shielding effect of glass fiber. In addition, as the surface
area exposed to the heat flux is much larger for GFRP
composites because of delamination, the peak HRR of
GFRP composites was much larger than those of VE
nanocomposites. Moreover, the larger average HRR
for GFRP composites can be attributed to the combus-
tion of sizing material applied to glass fiber.
Similar to the observations for VE nanocomposites,
nanoclay changed both the HRR profiles and the flame
retardancy parameters of GFRP composites. Though
there was no constant stage found in the HRR profiles
of GFRP composites containing clay after the peak
HRR, clay incorporation increased the width of the
shoulder, indicating a slower combustion of the in-
between matrix materials and a delayed delamination
of GFRP composites containing clay. Moreover, orga-
noclay significantly lengthened the times to ignition,
peak HRR and complete combustion and markedly
reduced the peak and average HRR of GFRP compos-
ites, with the change more pronounced for GFRP
composite with 3 wt% clay. Compared with the VE
nanocomposites, the effect of clay on lengthening the
time to ignition is more significant for GFRP compos-
ites due to the synergistic shielding effect of glass fiber,
whereas the effects of clay on lengthening the
174 Journal of Composite Materials 48(2)

Figure 8. SEM photographs of char from: (a) neat VE; (b) 3 wt% clay-VE; and (c) 5 wt% clay-VE nanocomposites.
SEM: scanning electron microscopy; VE: vinyl ester.

Figure 9. SEM photographs of char from: (a, b) neat GFRP; (c, d) 3 wt% clay-GFRP; and (e, f) 5 wt% clay-GFRP composites.
SEM: scanning electron microscopy; GFRP: glass fiber reinforced plastic.

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Zhu et al.
combustion time and on reducing the peak HRR of
GFRP composites are less significant as a result of
delamination.
Marked reductions in peak HRR have been found
for both VE and GFRP composites with the addition of
nanoclay. Such reductions are of importance for fire
safety, as peak HRR represents the point in a fire
where heat is likely to propagate further, or to ignite
adjacent objects. HRR is a measure of the rate at which
heat is generated by fire, and is the driving force for
fire.40 The plateau HRR without a sharp peak and the
wider initial shoulder indicate more stable heat release
and thus improved fire resistance due to the presence of
nanoclay that functions as barrier to discourage diffu-
sion of heat and flammable decomposition products.
Most undesirable fire products, such as smoke,
toxic gases and environmental temperature which are
threats to life, generally proceed step by step as HRR
increases,40 as such a reduction in HRRs means a
reduction in threat to life.
Morphologies of combustion residue of VE
nanocomposites and GFRP composites
Figure 8 shows the SEM images of the combustion
residue of clay-VE nanocomposites. At the end of
cone calorimeter test, there was almost no residue left
for the neat VE (Figure 8(a)), whereas a large amount
of residue consisting of densely packed char platelets
were found for the VE nanocomposites containing clay,
with small differences in the amount and size of chars
between the composites with 3% and 5% clay. This is
consistent with the results obtained in the cone calor-
imetry tests. During the combustion of VE nanocom-
posites, the silicate platelets with high aspect ratio did
not decompose, gradually forming platelet shaped
aggregates together with decomposed surrounding
polymer chains.15,16 The char platelets in turn acted
as barrier to diffusion of heat and oxygen, as well as
the volatilization of combustible decomposition prod-
ucts of polymer, and hence inhibited the decomposition
and combustion of polymer resin underneath them, fur-
ther promoting the formation of char. Gilman et al.41
reported that the char from the intercalated polymer-
clay nanocomposites also contained the multilayered
silicate structure and this nanocomposite structure
enhanced the performance of the char as a heat and
volatile insulator through reinforcement of the silicate
layers.
The SEM images of the combustion residue of
GFRP composites shown in Figure 9 indicate that
almost all neat VE resin surrounding the fibers was
burnt out, exposing the clean and smooth glass fibers
with few chars attached. In contrast, the GFRP com-
posites containing clay presented a significant amount
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175
of char around the glass fibers due to the presence of
silicate platelets. The residue covering the surface glass
fibers, shown in Figure 9(b) and (c), is believed to be a
blend of burnt polymer and clay. The above findings
for GFRP composites are considered consistent with
the conclusions drawn for the char formation of VE
nanocomposites and for the flame retardancy of
GFRP composites.
Conclusions
The thermomechanical properties, thermal stability and
flame retardancy of the clay-VE nanocomposites and
the GFRP composites made from the VE nanocompo-
sites matrix were studied. The following conclusions are
highlighted from the experimental investigation.
(i) The clay-VE nanocomposites prepared in this
study were characterized as intercalated nanocom-
posites with some orderly exfoliated silicate layers.
(ii) Both the storage modulus in the elastic state and
the glass transition temperature (Tg) of VE and
GFRP composites were significantly improved by
nanoclay due to both the reinforcing and con-
straining effects of clay platelets. However, there
were only negligible differences in the thermome-
chanical properties between VE and GFRP com-
posites with 3 wt% and 5 wt% clay. The storage
modulus of GFRP composites was higher than
those of the VE nanocomposites over the scanning
range due to the incorporation of fiber reinforce-
ments, whereas the Tg of GFRP composites and
the corresponding VE nanocomposites were simi-
lar as the Tg of GFRP composites was dependent
on their matrix materials
(iii) Both the VE and GFRP composites show different
thermal degradation behaviors in nitrogen and in
air, due to the oxidizing effect of oxygen in air. The
onset decomposition temperatures of GFRP com-
posites were lower than those of their matrix
materials in both atmospheres due to the presence
of sizing materials and fiber-matrix interfacial
materials with low decomposition temperatures.
Nanoclay addition had little effect on the thermal
stability of VE in nitrogen, while it increased the
2nd peak decomposition temperature of VE in air,
as a result of the shielding effect of silicate platelets
to the diffusion of oxygen and volatile decompos-
ition products. The thermal stability of GFRP
composites in both atmospheres was reduced by
nanoclay, but the reason is still unclear.
(iv) The effects of nanoclay on improving the fire
retardancy of VE as well as GFRP composites
were significant in terms of all fire reaction proper-
ties measured using a cone calorimeter. The fire
176
retardancy improvement due to nanoclay is
because clay promoted the formation of char plate-
lets acted as mass and heat barrier in the compos-
ites with clay, as proved by the SEM images. The
presence of glass fibers in GFRP composites had a
synergistic shielding effect, giving rise to a different
HRR profiles and a significant increase in ignition
time by more than 65% compared with the VE
nanocomposites.
Funding
Financial support of the work by the Research Grants
Council of Hong Kong SAR (Project codes: 616107, 614067
and 6184/03E), by the Innovation and Technology Fund of
Hong Kong SAR (ITP/036/09NP) and by the Research
Project Competition Grant of HKUST (RPC06/07.EG17) is
gratefully acknowledged.
Acknowledgment
Technical supports from the Materials Characterization and
Preparation Facilities (MCPF), HKUST are much
appreciated.
Conflict of interest
None declared.
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