Composites: Part B 72 (2015) 175182

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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

Improved mechanical properties of an epoxy glassber composite

reinforced with surface organomodied nanoclays
G.J. Withers a, Y. Yu a, V.N. Khabashesku b, L. Cercone a, V.G. Hadjiev c, J.M. Souza a, D.C. Davis b,d,
a
Milliken Pipe Wrap, Houston, TX 77060, USA
b
Department of Chemical & Biomolecular Engineering, University of Houston, Houston, TX 77204, USA
c
Texas Center for Superconductivity, University of Houston, TX 77204, USA
d
DCD Consulting, LLC, League City, TX 77573, USA

a r t i c l e i n f o a b s t r a c t

Article history: An organomodied surface nanoclay reinforced epoxy glass-ber composite is evaluated for properties of
Received 1 August 2014 mechanical strength, stiffness, ductility and fatigue life, and compared with the pristine or epoxy
Received in revised form 3 December 2014 glass-ber composite material not reinforced with nanoclays. The results from monotonic tensile tests
Accepted 4 December 2014
of the nanoclay reinforced composite material at 60 C in air showed an average 11.7% improvement
Available online 10 December 2014
in the ultimate tensile strength, 10.6% improvement in tensile modulus, and 10.5% improvement in ten-
sile ductility vs. these mechanical properties obtained for the pristine material. From tensiontension
Keywords:
fatigue tests at a stress-ratio = +0.9 and at 60 C in air, the nanoclay reinforced composite had a 7.9%
A. Polymer-matrix composites (PMCs)
A. Nano-structures
greater fatigue strength and a fatigue life over a decade longer or 1000% greater than the pristine
B. Mechanical properties composite when extrapolated to 109 cycles or a simulated 10-year cyclic life. Electron microscopy and
D. Electron microscopy Raman spectroscopy of the fracture and failure modes of the test specimens were used to support the
results and conclusions. This nanocomposite could be used as a new and improved material for repair
or rehabilitation of external surface wall corrosion or physical damage on piping and vessels found in
petrochemical process plants and facilities to extend their operational life.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Over the past decade or more there have been numerous stud-
ies of organomodied surface nanoclay-reinforced epoxy nano-
composites for improved mechanical properties and comparisons
with the non-reinforced or pristine material counterparts [1]. Stud-
ies show that with a small amount, such as <5 weight percentage
(wt.%), of nanoclays dispersed in an epoxy resin a substantial
improvement in the mechanical properties over the pristine mate-
rial can be achieved [26]. These organomodied nanoclays had an
intercalated or the preferred exfoliated morphology where the
platelets or layers are well separated with a wide gallery d-spacing
(>50 ) and randomly dispersed throughout the polymer matrix.
The polymer matrix would hence have more surface areas (up to
hundreds of m2/g) to bond with the reinforcing organomodied
clay layers, that seemingly act as nano-level entanglers with
the polymer chains [7]. The degree of an intercalated or exfoliated
morphology is dependent on the nanoclay composite curing agent,
Corresponding author at: DCD Consulting, LLC, League City, TX 77573, USA. Tel.:
+1 (832) 434 9716.
E-mail addresses: danielhelen@msn.com, dcdavis2@uh.edu (D.C. Davis).
the surface modication, and the processing method [1]. Chan et al.
[8] evaluated the strength and stiffness property improvements of
a surface organomodied nanoclay-epoxy composite. Increases in
the modulus and tensile strength, 34% and 25% respectively, were
found with 5 wt.% nanoclays dispersed in the epoxy resin compos-
ite sample. To achieve these property improvements Chan et al.
employed a centrifuging process in a vacuum environment to
remove air bubbles entrapped in or between the nanoclay platelets
that would negatively impact the mechanical property improve-
ments. Akbari and Bagheri [9] studied a surface modied nano-
clay-epoxy composite and observed mixed results. The stiffness
increased, but the exural and compressive strengths decreased
with increasing clay content. It is believed that the intercalated
instead of exfoliated clay morphology, in this case, had limited
the clay-matrix interactions and in turn lowered the effectiveness
of the clay in strengthening the epoxy. Using X-ray diffraction
(XRD) measurements and transmission electron microscopy
(TEM) observations the d-spacing between organoclay layers were
found to be around 45 with the addition of 5 wt.% nanoclays in
the epoxy matrix. Ha et al. [10] studied the effects of temperature,
at 30 C, 25 C, 40 C, and 70 C, on the mechanical behavior of
silane treated clay-epoxy nanocomposites. Ha et al. found the

http://dx.doi.org/10.1016/j.compositesb.2014.12.008
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176 G.J. Withers et al. / Composites: Part B 72 (2015) 175182
tensile strength and modulus values were the greatest at 30 C
and decreased as the test temperature increased above 25 C. At
70 C both the nanoclay-reinforced epoxy and the pristine epoxy
material strength and stiffness values had decreased to less than
10% of their values at 25 C. The silane treated clay-epoxy material
had superior mechanical properties compared to the untreated
clay (Cloisite Na+) epoxy composite at all temperatures appar-
ently because of better interfacial adhesion between the epoxy
and the nanoclay layers.
To present the literature discussion has been on the effect of
addition of nanoclay llers on the mechanical properties of poly-
meric or specically epoxy resin systems. What follows are results
from some of the limited number of studies that have been con-
ducted on the effects of adding nanoclays into epoxy-long contin-
uous ber composite laminate materials. Polymer-ber composites
have three primary components, the bers which generally carry
the load imposed on the composite, the matrix which provides
bulk to the composite and transfers load between bers, and the
ber/fabric-matrix interfaces [11] which must have sufcient
interfacial strength for loads to transverse the interface without
inducing cracking and delamination. Aktas and Altan [12] studied
glass ber reinforced waterborne epoxy matrix laminates for the
exural strength, stiffness and interlaminar shear strength. The
nanoclays were dispersed in the epoxy resin at contents 0.1, 0.2,
0.5, 1.0, and 2.0 wt.% and the mixture was degassed to remove
air bubbles that result from the agitation of mixing. TEM and
XRD analyses showed that through 0.5 wt.% fabricated samples,
the nanoclays were well dispersed and exfoliated. The nanoclay
reinforced epoxyglass ber composite laminates were fabricated
using a hot press. Mechanical testing of samples fabricated at
0.5 wt.% nanoclay content showed improvements of the exural
strength (8%), exural stiffness (12%) and interlaminar shear (5%).
Samples fabricated with 1.0 and 2.0 wt.% nanoclay reinforcements,
in this case the high aspect ratio clay platelets seem to form inter-
calated stacks or clusters, which resulted in a reduction in
mechanical capabilities of these nanoclay reinforced epoxyglass
ber composites. Aktas and Altan in scanning electron microscopy
(SEM) evaluations of the fracture surfaces of the 60.5 wt.% nano-
clay reinforced epoxyglass ber composite showed more clay/
resin residue remaining on the ber surfaces suggesting improved
ber-matrix adhesion contributed to the improved mechanical
properties of the nano-reinforced materials as compared to the
pristine composite. Xu and Hoa [13] fabricated a nanoclay modi-
ed high temperature epoxycarbon ber composite through hot
melt lay-up plus vacuum bag degassing to minimize air pockets
in the resin and nally an autoclave process for improved laminate
quality. At a loading of 2 parts per hundred (phr) of organomodi-
ed clays in the epoxy, the exural strength and the interlaminar
fracture toughness (GIc) increased by 38% and 53%, respectively.
The fracture surfaces of the nanoclay reinforced samples showed
signicant bonding of the clay/resin to the bers which supports
the nding of improved mechanical properties with respect to
the pristine samples. Nanoclay loadings in the epoxycarbon ber
composite beyond 4 phr resulted in a decrease in the upward trend
for mechanical properties. Bozkurt et al. [14] evaluated 1 wt.%
through 10 wt.% surface modied montmorillonite layered alu-
minoclay reinforced epoxyglass ber composites and a non-sur-
face modied clay epoxyglass ber composite for strength,
stiffness and fracture toughness improvements. Mechanical prop-
erties continually increased through 6 wt.% loadings as XRD and
TEM evaluations indicated that clay layer intercalation and disper-
sion was good through 6 wt.% surface modied nanoclay loaded
material. Thereafter mechanical property values were seen to gen-
erally decline for both the surface modied and non-modied sur-
face nanoclay composites. It is suspected that at high nanoclay
loadings the existence of agglomerates and air bubble voids in
the epoxy matrix between clay layers deteriorated the mechanical
properties. In a dynamic mechanical analysis (DMA) of the com-
posite material at 6 wt.% clay content, the storage and loss moduli
of the laminates increased probably due to the restricted molecular
motion. The glass transition temperature (Tg) of the laminates
increased by 5% at 10 wt.% surface modied nanoclay loading. It
is believed this improvement in Tg over the 110 wt.% range of
nanoclay loadings is due to the restricted mobility of polymer mol-
ecules. Khan et al. [15] presented a more recent study of tension
tension (TT) fatigue of organoclay (octadeclyamine modied
montmorillonite) reinforced epoxycarbon ber composites. The
organoclay content was at 1, 3, and 5 wt.% of the epoxy hardener
mixture. The organoclay solution was further high shear mixed,
sonicated and degassed to remove air voids and bubbles. TEM
images indicated full intercalation and partial exfoliation of
nanoclay dispersion in the mixture. A nanoclay reinforced
epoxycarbon ber composite laminate and a similar pristine lam-
inate were fabricated each using a hot press for panel dimensions
300 mm square by thickness 2.5 mm. Tensile and fatigue
straight-bar specimens were cut from the panels. The ultimate ten-
sile strength (rUTS) and strain-at-failure or ductility (ef) of the
nanoclay reinforced composite peaked at 3 wt.% clay loading while
the tensile stiffness continued to increase through 5 wt.% clay
loading. The TT fatigue tests were loaded at a stress-ratio (or
R-ratio) = (rmin/rmax) = +0.1. The maximum stress (rmax) levels of
the cycle was 90%, 80%, 60% and 45% of the rUTS of the composite
and rmin would be in each case 10% of rmax. The rmax vs. Nf
(cycles-to-failure) data showed the nanoclay reinforced epoxy
carbon ber composites had a consistently greater fatigue strength
and life as compared to the pristine composite. SEM images of the
nanocomposite fracture surfaces showed features of a more
toughen epoxy matrix and greater ber-epoxy matrix interfacial
bonding. Khan et al. concluded that these microstructural observa-
tions illustrated the primary reasons for the improved tensile
strength and fatigue performance in this nanoclay reinforced
composite.
Herein an organomodied nanoclay reinforced epoxy glassber
composite laminate is evaluated for fatigue life properties as well
as mechanical strength, stiffness and ductility, and compared with
the pristine composite material not reinforced with nanoclays. The
nanoclays are dispersed in the epoxy resin at 2 and 4 wt.% levels
with respect to the epoxy. The TT fatigue tests are at a
R-ratio = +0.9. The test temperature for all tensile and fatigue tests
is 60 C. This fatigue loading R-ratio and elevated temperature test-
ing scheme could be characterized as vibro-creep [16]. This current
study aims to demonstrate under these loading conditions
improvements in these mechanical properties can be obtained
for the epoxy glassber nanocomposite as compared to the
non-reinforced composite. This epoxy glassber composite is
used in applications as patches and wrap materials for repair or
rehabilitation to external surface walls physical damage or
corrosion suffered by piping and vessels found in petrochemical
processing plants and other facilities [17,18]. The nanoclay rein-
forcement in the epoxy glassber composite is expected to extend
the operational capabilities of these repaired and rehabilitated
structures.
2. Materials and fabrication
The composite materials being studied consists of a fabric of e-
glass bers with an epoxy matrix and a nanocomposite with dis-
persed reinforcing organomodied surface nanoclays. The glass
composition meets the certication for e-glass as dened by
ASTMs D578-00 Standards Specication for Glass Fiber Strands.
According to the manufacturer the 1113 lm diameter bers are
 G.J. Withers et al. / Composites: Part B 72 (2015) 175182 177

a natural, lustrous, white, continuous lament, and are of high the composite wrap or patch products. Voids and air pockets would
stability and durability. With the exception of sizing ingredients, be found in the cross-sectional microstructure of the epoxyglass
the bers are inorganic, incombustible and will neither expand nor ber (EP-GLF) laminate composite material, as shown in Fig. 2a
contract with moisture changes. Reported room temperature pris- of an actual eld structural repair wrap. Fig. 2b shows portion of
tine tensile strength of e-glass ber is in the range of 3400 MPa and the cross-section of a laminated test specimen with similar
the tensile modulus is 70 GPa. The fabric reinforcement is e-glass microstructural features, but here having voids or air pockets of
bers in bi-directional [0/90] weave yarns approximately 1 mm slightly greater density and greater sizes. The mechanical proper-
wide. ties in these cases would be lower as compared to that which could
The thermoset epoxy used here is a cross-link between an be achieved in higher quality fabrications [24].
epoxy prepolymer and a curing agent which produces a polymer
with excellent chemical and thermal mechanical properties. The
3. Specimen and testing
resulting epoxy resin is versatile with physical properties of high
adhesive strength, good impact resistance, high strength and
From each nanoclay loading levels (0, 2.0 and 4.0 wt.%) of the
hardness, and good electrical insulation properties. However,
305 mm  305 mm square at epoxyglass fabric (EP-GLF) fabri-
epoxies are known to be subject to brittle fracture that could lead
cated panels four (4) straight-side bar (205 mm long  12.5 mm
to less than optimal composite properties under mechanical
wide) specimens were water jet cut for in-plane tensile and six
loadings [19,20].
(6) specimens were for tensiontension (TT) fatigue testing. The
Nanoclay (NC) selected is Cloisite 30B, a commercial product,
thickness (3 mm) of the specimens was that of the fabricated
supplied by Southern Clay Products (Gonzales, TX, USA). Nanoclays
panel. The axial direction [0] of the specimens was the preferred
here are high aspect ratio organomodied layered silicate minerals
strength direction of the bi-directional [0/90] weave yarn glass
that can be platelets as thin as 1 nm [21,22]. Additionally, clays are
fabric layup. The specimens were tabbed on both sides at each
attractive materials for commercial applications because of their
end with then to remain approximately a 140 mm gauge length
natural occurrence and low cost [23]. This nanoclay has a layered
section. This specimen conguration has been used previously for
silicate structure built of oval-shaped platelets of 1 nm thickness
and 200300 nm in length. Cloisite 30B is an organically surface
modied clay by quaternary amines containing a long-chain alkyl
tallow and two hydroxyethyl groups. See Fig. 1 Cloisite 30B is
capable of bonding to epoxy resin compounds either non-cova-
lently through hydrogen bonds or covalently by additional reaction
with the resin compound under a moderate heat. In composite
applications Cloisite 30B usually has an intercalated morphology
with the functional quaternary amines for compatibilization with
polymer matrix and exfoliation.
For fabricating the thermoset epoxyglass ber (EPGLF) nano-
composites, as-received Cloisite 30B nanoclay (NC) at a prescribed
2 and 4 wt.% in respect to the epoxy was dispersed using a hot
plate/magnetic stirrer at 75 C for 30 min in Part B (a blend of
Tetraethlyenepentamine and Nonylphenol). Part A (Bispenol-A
Type Epoxy Resin) and Part B are mixed manually and applied
evenly to both sides of each 6 plies of 305 mm square glass fabric
pieces. Excess resin mixture is removed to better ensure a compact
laminate as the 6 fabric pieces are stacked aligned in the same
preferential ber direction. The balanced and symmetric 6-ply Fig. 2a. Cross-section of actual biaxial EP-GLF composite repair wrap on a pipe.
laminate is compressed uniformly between two 305 mm square View of glass fabric, epoxy matrix, porosity, outgas voids.
at stiff smooth-surface plates under 550 N total force for 24 h at
room temperature in laboratory air for curing. The pristine
epoxyglass ber laminate is fabricated and cured similarly with-
out any added nanoclays. The laminates were not degassed to
Longitudinal Fabric [0o]
remove bubbles or voids, nor run through an autoclave cycle for
further lamination. The objective here is to fabricate test panels
simulating eld or plant environments where degassing or
autoclave facilities would not be available during insulation of
Outgas void

Cloisite 30B (Epoxy Matrix)

Methyl, tallow, bis-2-hydroxyethyl

CH2CH2OH
Transverse Fabric [90o]
CH3 N+ T

CH2CH2OH
Where T is Tallow
(~65% C18; ~30% C16; ~5% C14) Fig. 2b. Cross-section of biaxial EPGLP composite laminate test specimen. View of
glass fabric, epoxy matrix, porosity, out gas voids. Axial loading direction

Fig. 1. Scheme for Cloisite 30B (Southern Clay Products). horizontal.
178 G.J. Withers et al. / Composites: Part B 72 (2015) 175182

ber reinforced composite laminate strength, stiffness and fatigue

testing and studies [25,26].
The testing and evaluations consisted of uniaxial tensile
strength tests and uniaxial TT fatigue testing, both at 60 C. Test-
ing was conducted using a servo-controlled hydraulic test machine
with frame capacity of 250 kN and load cell capacity of 100 kN. An
installed temperature controlled hot air furnace housed the
specimen gauge section only, maintaining the constant 60 C. The
tensile composite material testing was conducted consistent with
ASTM D3039/3039M-08 ASTM D3039/D3039M Standard Test
Method for Tensile Properties of Polymer Matrix Composite Mate-
rials to obtain the ultimate engineering tensile strength (rUTS),
stiffness or modulus (E) and ductility or strain-to-failure (ef) of
the laminates. The TT fatigue testing was conducted consistent
with ASTM D 3479/D 3479M-Standard Test Method for Tension
Tension Fatigue of Polymer Matrix Composite Materials. The TT Fig. 3. Illustrative stressstrain curves for EP-GLF and NC EP-GLF composites. The
NC reinforced composite consistently showed greater ultimate tensile strength
testing in this case starts with a fast load-up to the mean stress
(rUTS), stiffness (E) and ductility at failure (ef). Test temperature = 60 C.
(ro = 1/2(rmax + rmin)) of the cycle, and thereafter, cyclic loading
continues at a stress-ratio (or R-ratio) = rmin/rmax = +0.9 in a trian-
gular waveform. rmax is the maximum stress limit of the cycle and
rmin is the minimum stress limit of the cycle. The cyclic frequency
(f) = 5 Hz. The constant testing temperature of 60 C would be in
the creep deformation regime of the matrix material [27]. The
aim of these test conditions was to simulate assumed continuous
operations of a pressure vessel, boiler, piping or other civil-
mechanical systems that would have an external surface at an ele-
vated temperature and under a high mean stress with vibratory
loadings superimposed. These vibratory loadings are to simulate
loading (pressure or thermal) uctuations about the mean stress
[28]. As mentioned previously, this cyclic loading and elevated
temperature test condition imposed on a polymeric material could
be categorized as vibro-creep-fatigue [16]. The fatigue testing used
the identical tensile test specimen to obtain the rmax vs. the num-
ber of cycles-to-failure (Nf) data and plots. The EP-GLF composite
fatigue strength at cyclic life (Nf) would be a consequence of this
mechanical loading and elevated temperature (60 C) conditions Fig. 4. Ultimate tensile strength (rUTS) of EP/GLF and NC EP/GLF composites. The
data show a 14.3% greater rUTS for the 2 g NC EP/GLF vs. the neat EP/GLF composite.
and the composite microstructure.
The 4 g NC EP/GLF composite was not evaluated further. Test temperature = 60 C.

4. Results
specimen had the highest rUTS, and the 4 wt.% Cloisite B loaded
specimen showed the rUTS to decline. The decrease found here in
Three formulations of this thermoset epoxyglass ber (EP
composite rUTS at 4 wt.% Cloisite B nanoclay loading and higher
GLP) composite were fabricated, a pristine composite with no rein-
would be consistent with observed behavior in other research
forcing nanoclays (0 wt.% nanoclays), and two EPGLP composites
studies, discussed previously [1214]. At higher nanoclay loadings
with dispersed surface organomodied Cloisite 30B nanoclays in
large aggregates could form in the matrix or there could be poor NC
the matrix at 2.0 and 4.0 wt.% levels in respect to the epoxy. The
exfoliation that causes a reduction in mechanical properties.
three formulations were fabricated into panels and test specimens
The further analyses in this study will be limited to comparing
were water-jet cut for obtaining strength and fatigue mechanical
the 2 wt.% Cloisite B (NC EP-GLF) composite with the pristine
properties. The objectives of this study is not to obtain design
(EP-GLF) composite. The rUTS for the NC EP-GLF reinforced lami-
mechanical properties for these epoxyglass ber composites but
nate in Fig. 4 is shown to average 11.7% greater than the pristine
to assess the relative improvements in mechanical properties that
material. The modulus (E) is 10.6% greater as shown in Fig. 5 and
could be achieved due to additions of nanoclay reinforcements.

4.1. Tensile testing

Tensile monotonic pull test specimens were loaded at a rate of

220 N/s to avoid including time-dependent strain effects at the test
temperature (60 C). The typical stressstrain curves resulted to
have the classical bi-linear form [29] as shown in Fig. 3. The repre-
sentative curve for the nanoclay (NC) reinforced epoxy (EP)glass
ber (GLF) composite illustrates greater values obtained for the
ultimate tensile strength (rUTS), stiffness value (E) and strain-
at-failure or ductility (ef) in comparison to the EP-GLF pristine
composite.
In Fig. 4 is a comparison of the average rUTS for the three pre-
pared formulations of this thermoset epoxyglass ber (EPGLP) Fig. 5. Tensile modulus (E) of EP-GLF and NC EP-GLF composites. The data show a
composite in this study. The 2 wt.% Cloisite B nanoclay (NC) loaded 5.7% greater E for the NC EP-GLF vs. the EP-GLF composite. Test temperature = 60 C.
 G.J. Withers et al. / Composites: Part B 72 (2015) 175182
the strain-to-failure or ductility (ef) in Fig. 6 is 10.5% greater for the
NC EP-GLF reinforced composite vs. the EPGLP pristine composite
material.
4.2. Tensiontension (TT) fatigue testing
The fatigue testing was conducted as dened previously in a
vibro-creep-fatigue mode, R-ratio = +0.9 at the test tempera-
ture = 60 C, frequency (f) = 5 Hz. Fig. 7 shows a schematic of a total
vibro-creep strain response (e) of this loading to consist of the
quasi-static strain accumulation (eo) due to the initial loading
and the inelastic vibro-creep strain accumulation (ec) response
due to the applied cyclic-time or frequency-dependent loading.
The vibro-creep strain (ec) is shown increasing logarithmically,
with the De responses to the applied stress range Dr = rmaxrmin,
to the total strain accumulation (ef) at the number of cycles-to-fail-
ure (Nf). The nal failure mode in all cases is fatigue dominant.
This fatigue analysis will determine the reduction in strength as
a function of fatigue life for both the NC-reinforced composite and
the pristine composite material. The maximum stress (rmax) vs. the
cycles-to-failure (Nf) curves in Fig. 8 show the NC EP-GLF compos-
ite to have a greater fatigue strength and fatigue life than the
EP-GLF composite over the test data range of >500,000 cycles. Sta-
tistically generated trend lines through each set of fatigue failure
datum points would calculate at 109 cycles to be approximately
10-years of simulated cyclic life at f = 5 Hz. At this point the fatigue
strength of the NC EP-GLF composite (270 MPa) would be 7.9%
higher than that of the EP-GLF material (250 MPa). However, from
Fig. 8 the plotted slope of the rmaxNf curves on the logarithmic
scale at 109 cycles, the fatigue life (Nf) of the NC EP-GLF composite
is calculated to be over a decade longer or signicantly 1000%
greater than the EPGLP composite fatigue life.
Fig. 6. Strain-to-failure or ductility (ef) of EP-GLF and NC EP-GLF composites. The
data show a 10.5% greater ef for the NC EP/GLF vs. the EP-GLF composite. Test
temperature = 60 C.
Fig. 7. Vibro-creep-fatigue strain response schematic.
179
Fague Life
500.00
450.00
Maximum Stress, max (MPa)
400.00 max = -6.47ln(N) + 404.41
350.00
300.00
max = -6.808ln(N) + 391.67
250.00
200.00
1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06
Cycles to Failure, N f
EP/GLF NC EP/GLF
Fig. 8. Fatigue life: Maximum Stress (rmax) in the fatigue cycle vs. cycles to failure
(Nf) at stress ratio (R-ratio) = +0.9. NC EP-GLF composite shows a consistently
greater fatigue strength and projected fatigue life vs. the EP-GLF composite in the
higher cycle regime. Test temperature = 60 C.
4.3. Glass transition temperature testing
The glass transition temperature (Tg) of the composite materials
was measured using a TA Q20 Differential Scanning Calorimeter
(DSC) in accordance with the ASTM E1356 Standard, Test Method
for Assignment of the Glass Transition Temperatures by Differen-
tial Scanning Calorimetry. The heating rate is set at 10 C/min with
temperature ranges between 0 C and 200 C for epoxy base
composites. The addition of 2 wt.% nanoclay decreases the average
Tg of the EPGLP composite from 91.5 C to 74.5 C. This result is
highly possible as previous research suggested that the Tg could
increase or decrease with wt.% content or surface modication of
the nanoclay additives [14]. In any case, the measured Tg for the
NC EP-GLF composite is greater than the extreme possible
operating temperature of 60 C.
5. Discussion of results
Improvements in the ultimate tensile strength, stiffness,
ductility, and fatigue life mechanical properties at 60 C of an
epoxyglass ber (EP-GLF) composite were all improved with
added 2 wt.% organomodied nanoclays in the epoxy resin. As dis-
cussed previously [12] a probably explanation for these improved
properties is that the 2 wt.% nanoclay concentration was sufcient
for adequate reinforcement, and as well, the nanoclays were well
dispersed and exfoliated in the epoxy resin. Nanoclay addition at
4 wt.% showed a decrease in strength value for the nanocomposite.
At 4 wt.% nanoclay concentration in the epoxy resin aggregates are
postulated to have formed that negatively affected the mechanical
properties, as discussed previously [14]. With 2 wt.% nanoclay con-
centration in the EP-GLF composite there was a greater fatigue
strength and projected fatigue life at higher cyclic life for the NC
EP-GLF nanocomposite material as compared to the EP-GLF pris-
tine composite material.
Viewing the failure and fracture modes of the test specimens
provide evidence that the nanoclays had a positive role on the
improved mechanical behavior of this EP-GLF composite. The fail-
ure of the EP-GLF tensile and fatigue specimens, shown in Fig. 9a,
initiated in a matrix dominant mode in tension. The failure path
is at an angle [4560] to the loading direction [0] through the
bi-directional [0/90] woven fabric. The failure mode of the NC
EP-GLF specimens, under both tensile and fatigue loadings,
initiated in a matrix dominant fracture with a path that propagated
180 G.J. Withers et al. / Composites: Part B 72 (2015) 175182

-
long x 12.5 mm wide x 3 mm thick. Specimen = failed
UTS N7 396.08 MPa
in tensile
dimensions: 205 mm
strength test. Specimens N2, N5 and N6
o
failed in cyclic fague. Fague loading: R- C.

N f = 60,729

N f = 306

N f = 237,803
Fig. 10. EP-GLF tensile specimen fracture surface at rUTS = 396.08 MPa. Fracture
surface shows a brittle-like matrix and not strong ber-matrix interfacial strength.
Fig. 9a. Failure modes of neat EP-GLF test specimens. Approximate original Test temperature = 60 C.
dimensions: 205 mm long  12.5 mm wide  3 mm thick. Specimen N7 failed in
tensile strength test. Specimens N2, N5 and N6 failed in cyclic fatigue. Fatigue
loading: R-ratio = +0.9. Test temperature for all specimens = 60 C. matrix behavior that would be more susceptible to failure under
Mode I normal loadings. The surfaces of the bers are devoid of a
signicant amount of epoxy matrix residue and there appears to
in the loading direction [0] along the length of the specimen gauge
be weak ber-matrix adhesion. The fracture surface of a NC
section in interlaminar shear, as shown in Fig. 9b. These two differ-
EP-GLF tensile specimen in Fig. 12a suggests a toughened and more
ent failure modes could be referred to as Mode I and Mode II,
ductile epoxy matrix which supports the improved mechanical
respectively. All nal failures of the specimens were by ber rup-
properties measured for the nanocomposite. The micrograph
ture. In a study of a unidirectional glass ber reinforced composite
image in Fig. 12b shows the nanoclay-reinforced matrix to have
by Colombo and Vergani [30], specimen failures initiated by
strong interfacial bonding to the bers which suggests that
interlaminar matrix shear had a greater strength, stiffness and
the NC EP-GLF composite would have improved strength and
fatigue life as compared to specimen failures initiated by tensile
fatigue properties as compared to the pristine composite material.
rupture of the matrix. Allix et al. [31] found that the Mode I
Using a multichannel T64000 Horiba Jobin Yvon Raman micro-
fracture toughness in composites is always much less than Mode
scope Fig. 13a is an optical image of a NC epoxyglass ber com-
II, which would be consistent with the results found with these
posite untested specimen cross-sectional surface and Fig. 13b is a
EP-GLF specimen failures.
Raman spectrographic mapping of the surface. In Fig. 13b the glass
The change in failure modes between the EP-GLF and NC EP-GLF
bers are imaged RED, epoxy GREEN and the organomodied
specimens can possibly be explained by observing the differences
nanoclays BLUE, as obtained by deconvoluting the measured
in the deformation and fracture modes of the specimens. The frac-
spectra into the Raman spectra (Fig. 13c) of the nanocomposite
ture modes of the EP-GLF specimens under both monotonic tensile
components [32,33]. Fig. 13b shows the nanoclays are dispersed
and cyclic loadings, as in Figs. 10 and 11, shows a more brittle-like
mainly in the epoxy matrix-glass ber fabrics. In the lower portion

UTS = 416.68 MPa

N f = 13,924

Nf =93,457

Nf = 539,293

Fig. 9b. Failure modes of NC EP-GLF test specimens. Approximate original

dimensions: 205 mm long  12.5 mm wide  3 mm thick. Specimen NE3 failed in Fig. 11. EP-GLF fatigue specimen failed at Nf = 237,803 cycles. Fracture surface
tensile strength test. Specimens NE2, NE7 and NE8 failed in cyclic fatigue. Fatigue shows a brittle-like matrix and not strong ber-matrix interfacial strength. Test
loading: R-ratio = +0.9. Test temperature for all specimens = 60 C. temperature = 60 C.
 G.J. Withers et al. / Composites: Part B 72 (2015) 175182 181

Fig. 12. (a and b) NC EP-GLF tensile specimen fracture surface at rUTS = 415.68 MPa. Fracture shows ductile-like matrix features and strong ber-matrix interfacial strength as
matrix remains bonded to bers. Test temperature = 60 C.

Fig. 13a. Optical image of NC EP-GLF specimen fracture surface. Fig. 13b. Raman spectroscopic image of NC EP-GLF specimen fracture surface scan
of area shown in 13a. RED glass bers, GREEN epoxy matrix, BLUE nanoclay.
(For interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)
of Fig. 13b is shown glass ber ends of a fabric piece that is in the
transverse direction (normal to loading direction) of the composite.
Some of the nanoclays appear as large agglomerates (>4 lm), but
most nanoclay particles are much smaller in size and nely
dispersed. In the upper portion of Fig. 13b, nanoclays are shown
dispersed in an epoxyglass ber fabric piece that is aligned in
the longitudinal (loading) direction of the composite laminate.
The darkened region across the near center of the image is thought
to be a very narrow (approximately 10 lm) space between the two
fabric pieces in the laminate. In Fig. 13a optical image the epoxy
matrix has a darker gray color. The epoxyglass ber fabric areas
with nanoclays appear as a light gray or near white colored matter.
Using this unique spectrographic analysis these images clearly
demonstrate that the nanoclays are present over a wide area of this Fig. 13c. Raman spectroscopic spectra.
NC EP-GLF composite microstructure.
182 G.J. Withers et al. / Composites: Part B 72 (2015) 175182
6. Summary and conclusions
This study was to demonstrate that mechanical property
improvements could be obtained in an epoxyglass ber (EP-
GLF) composite laminate reinforced with surface organomodied
nanoclays (NC) under monotonic tensile and vibro-creep-fatigue
loadings at 60 C in comparison with the non-NC reinforced case.
The results showed that the NC reinforced EP-GLF composite
would have a greater strength, stiffness and ductility than the
pristine EP-GLF composite. The NC EP-GLF composite has a greater
fatigue life than the EP-GLF composite at a projected 10-year oper-
ational life. Microscopy and spectroscopy analyses of the fracture
and other surfaces of the NC EP-GLF composite test specimens
show that the nanoclays are widely dispersed in the epoxy matrix
and epoxyglass ber fabrics. Hence, it can be concluded that the
nanoclays apparently toughened the epoxy matrix and strength-
ened the ber-matrix interfaces in the composite to achieve these
mechanical property improvements. This study demonstrated that
nanotechnology can be used to improve the mechanical capabili-
ties of composite structures with far less than ideal microstruc-
tures. Specically this study further demonstrated that this
nanoclay (NC) reinforced EP-GLF composite could be a new and
improved composite wrap material for repair or rehabilitation of
damaged external surface walls of pipes and vessels installed at
petrochemical process plants and other facilities.
Acknowledgments
The authors would like to thank for their assistance in this
study, Dr. Benjamin T.A. Chang, PolyLab, LLC (Houston), for his
thermalmechanical materials analyses, Mr. Matt Potter (Texas
A&M University) for his expertise in mechanical testing and Dr.
James Martinez (NASA Johnson Space Center) for his assistance
with the SEM work. The authors give a special gratitude to Dr.
Ben Schrag, NSF SBIR Program Director, for recommending to fund
this Phase I research under NSF Award No. 1152577.
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