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Composites: Part A 40 (2009) 2038–2045

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Thermal aging of fiberglass/carbon-fiber hybrid composites

E. Barjasteh a, E.J. Bosze b, Y.I. Tsai a, S.R. Nutt a,*
Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, CA 90089, United States
Composite Technology Corporation, Irvine, CA 92614, United States

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

Article history: Thermal oxidation of a unidirectional carbon-fiber/glass-fiber hybrid composite was investigated to
Received 23 March 2009 determine oxidation kinetics and degradation mechanisms. The epoxy composite rods were comprised
Received in revised form 7 August 2009 of a carbon-fiber core and a glass-fiber shell. A reaction–diffusion model was developed for each of the
Accepted 28 September 2009
two hybrid sections to obtain the oxygen-concentration profile and the thickness of the oxidized layer
(TOL) within the composite rods. The TOL was measured experimentally for samples exposed at 180 °C
and 200 °C for up to 8736 h, and measured values were similar to the modeling predictions. The glass-
fiber shell functioned as a protective layer, limiting the oxidation of carbon-fiber core. A relationship
A. Carbon-fiber
A. Glass-fiber
was derived relating TOL to tensile strength of the hybrid composite. The tensile strength remained
B. Environmental degradation essentially unchanged by thermal oxidation after 52 weeks of exposure. Inspection of thermally aged
Thermal oxidation capped rods showed no cracking after long-term exposures.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction At high temperatures (approaching the glass transition temper-

ature Tg), polymer composites are susceptible to oxidative degra-
A relatively new application for polymer matrix composites in- dation [5–8]. Although the fibers are stable at such temperatures
volves the support of overhead conductors for power distribution. (less than Tg), the matrix and especially the fiber–matrix interface
In this application, overhead power lines are supported by a unidi- can undergo degradation that affects the physical and mechanical
rectional hybrid (carbon/glass-fiber) composite [1]. In contrast, tra- properties of the structure over time. Matrix oxidation of compos-
ditional Al conductors are supported by steel cable, and this has ites has been investigated for polymers such as polybismaleimide
been the case for the past 100 years. However, the recently devel- [9,10] and amine cured epoxy [11–13]. The oxidation is initially
oped composite-supported conductors, termed ACCC for alumi- limited to a superficial layer until cracks appear in the layer. Cracks
num conductor/composite core, present multiple advantages for open new pathways for oxygen to penetrate the specimen and lead
economic and efficient transmission of electrical power [2]. In par- to more extensive oxidation. This process can continue until the
ticular, the ACCC conductors exhibit greater strength, lower polymer is completely oxidized. During oxidation, polymers un-
weight, and less sag at high temperatures. dergo mass loss, shrinkage, and density increase [14].
Despite the considerable advantages in mechanical perfor- Oxidative degradation of the matrix of polymer composites
mance, long-term durability of composite conductors is a major generally resembles that of the neat polymer. However, the fibers
concern, as overhead conductors are expected to retain properties and the fiber–matrix interface significantly alter the transport
with minimal maintenance over a service life that spans multiple properties of oxygen, introduce anisotropy, and influence the ex-
decades. These concerns stem from the uncertain effects of long- tent of damage within the composite.
term environmental exposure, which includes temperature, mois- Oxidation-induced damage in unidirectional composites is typ-
ture, radiation, and aggressive chemicals, all of which can be exac- ically manifest as matrix cracks [15,16]. Note that cracks initiate in
erbated by cyclic loads. In general, the mechanical and physical the composites because of the stress gradient induced by shrinkage
properties of polymer composites are adversely affected by such of the oxidized matrix [16], but are also depend on the properties
environmental factors [3,4]. Consequently, the ability to forecast of the fiber–matrix interface [17,18] and on fiber orientations [19].
changes in material properties as a function of environmental In particular, oxidation-induced cracks in unidirectional compos-
exposure, particularly bulk mechanical properties, which are af- ites often initiate at fiber tips exposed at surfaces. Furthermore, fi-
fected by the integrity of fiber–matrix interfaces, is required to de- ber orientation affects and sometimes determines the extent of
sign for extended service lives. cracking, particularly in directions parallel to the fiber orientation.
Spontaneous cracks due to matrix oxidation initiate and propagate
* Corresponding author. Tel.: +1 2137401634. within the oxidized layer at the surface of the structure [16].
E-mail address: nutt@usc.edu (S.R. Nutt). Therefore, prediction of the thickness of the oxidized layer, TOL,

1359-835X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
E. Barjasteh et al. / Composites: Part A 40 (2009) 2038–2045 2039

helps to design more efficient and durable structures and hence to mechanical analysis (DMA) was performed using a dual-cantile-
prevent as much damage as possible. ver-beam clamp (TA Instruments DMA2980) to measure the Tg val-
The purpose of the present work was to determine kinetics of ues of oxidized composite rods and control samples of neat epoxy.
thermal oxidation and associated damage mechanisms for unidi- DMA experiments were performed in accordance with standard
rectional hybrid composites designed to support overhead conduc- protocol (ASTM D7028), and a ramp rate of 5 °C/min was used
tors. A coupled reaction–diffusion model was developed for the for all specimens. The peak in the loss modulus curve was taken
carbon-fiber (CF) core and the glass-fiber (GF) shell to predict the as the Tg value for composite rod samples (normally 225 °C).
oxygen-concentration profile and the TOL. The effect of oxidation The tensile strength of the composite core was measured using
on tensile strength and on crack initiation and propagation in the a computer-controlled load frame (Instron 5585) following ASTM
hybrid composite was analyzed. Finally, a relationship was derived Standard D3916. Composite core samples were mounted in the
to show the dependence of tensile strength on the ratio of TOL to load frame using adhesive gripping in custom-made fixtures. Ten-
thickness of sample (TS) for unidirectional hybrid composites. sile tests were performed by preloading the samples to 4.5 kN and
holding for 5 min to allow load redistribution in the load train. The
load was applied using a crosshead speed of 5 mm/min (0.2 in./
2. Experiments
min) until failure occurred. All tests were conducted at room
2.1. Materials and conditioning temperature.
Oxygen-diffusivity measurements were performed on thin-film
Unidirectional hybrid composite rods were produced by pultru- clear-cast samples using the half-time method [27] (Mocon Com-
sion (Composite Technology Corporation, Irvine, CA). The rods pany, Minneapolis, MN). Table 2 shows the measured transport
were comprised of a carbon-fiber core (CF) surrounded by a coefficients and oxygen solubility values for the hybrid composites.
glass-fiber shell (GF), as shown in Fig. 1. The epoxy matrix was de- Note that D1, the axial diffusivity parallel to the fiber direction, is
calculated based on the Kondo relationship [20], D1 = (1  Vf)  D2/
signed to achieve a high glass-transition temperature (Tg) using a p
proprietary epoxy formulation and an anhydride curing agent. (1–2  (Vf/p)), where Vf is the volume fraction of fibers. Note that
The rod characteristics are shown in Table 1. In addition, control D2, the diffusivity in the transverse direction, is slightly lower than
samples were produced by a clear casting method that involved the diffusivity of the unreinforced epoxy. Oxygen solubility, s, is
curing the neat resin for 1 h at 200 °C. nearly independent of temperature. The surface concentration of
Sample composite rods (9.5-mm diameter) were placed in an air- oxygen was determined based on Henry’s equation, C s ¼ s  P O2 ,
circulated oven at 180 °C and 200 °C and 1-atmosphere pressure for where P O2 is the partial pressure of oxygen in ambient (lab air).
isothermal aging. Samples were separated to allow convection, and Light microscopy of polished sections was used to measure the oxi-
sample ends were capped with a silicone sealant to prevent the end- dized thickness of samples and to detect cracks.
diffusion of oxygen. The weight loss was recorded at intervals using Nanoindentation measurements were performed on resin-
an analytical balance (ACCULABLA-60) with 0.001 mg accuracy. mounted oxidized epoxy samples using a 100 nm Berkovich tip
Samples were cooled in a desiccator for 10 min before every mea- (TriboIndenter, Hysitron, Minneapolis, MN). Tests were carried
surement to prevent moisture adsorption. The same procedure out on samples isothermally aged at 200 °C for 820 h, 1600 h and
was used for clear-cast samples to record weight loss. 3200 h. The loading rate was 1000 lN/s, and the maximum load
used for each test was 5000 lN. Twenty indents were performed
for each specimen with an indentation spacing of 10-lm. Standard
2.2. Mechanical testing and thermal analysis
nanoindentation drift correction measures were applied during the
The mechanical and thermal properties of composite rods were
measured after different thermal oxidation exposure. Dynamic
2.3. Modeling

The most appropriate model to describe the present system is a

reaction–diffusion model that predicts the extent of oxidation and
distribution of oxygen (concentration profile) within the hybrid
composite. Oxygen molecules are assumed to diffuse into the com-
posite and react with the epoxy matrix. Considering the geometry
of the rod, the oxygen balance equation, Fick’s second law, is writ-
ten in cylindrical coordinates.
"   #
@C 1 @ @C 1 @2C @2C XN
¼ Di¼r;h;z r þ 2 þ þ RðCÞ  xO2 Rb ð1Þ
@t r @r @r r @h2 @z2 b¼1

where C is the oxygen concentration within the sample, Dr, Dz and

Dh are the diffusion coefficients, R(C) is the consumption rate of
oxygen, and Rb is the production rate of volatile b.
Several assumptions are made in constructing a model to simu-
late oxygen diffusion in the composite rod. Because the structure is
essentially infinite in the axial (‘‘z”) direction and symmetrical in
the h direction, we assume that the molar mass transfer of oxygen
is unidirectional and occurs in the transverse direction r (perpen-
dicular to the fibers). Hence, the oxygen-concentration gradients
in z and h directions become zero, and the corresponding terms
are eliminated from the balance equation. Furthermore, we neglect
Fig. 1. Cross section of pultruded hybrid composite rod, showing the carbon core the effect of the transfer of gaseous volatiles. These volatiles diffuse
surrounded by the glass shell. toward the surface of the composite rod, while oxygen diffuses in
2040 E. Barjasteh et al. / Composites: Part A 40 (2009) 2038–2045

Table 1
Characteristics of carbon-fiber core and glass-fiber shell in hybrid composite rod.

ri (mm) r 0 (mm) Glass volume (%) Carbon volume (%) Epoxy volume (%) Cross-sectional area (%)
Carbon core 0 6.8 0 69 31 51
Glass shell 6.8 9.5 64 0 36 49

Table 2
Values of oxygen diffusivity for the hybrid composite components, where axial and transverse diffusivity are represented by D1 and D2, and Cs is the surface concentration of

Temperature (°K) D glass shell (m2 s1) D carbon core (m2 s1) Solubility (104 mol m3 Pa1) Cs (mol m3)
12 12 12 12
D1 (10 ) D2 (10 ) D1 (10 ) D2 (10 )
180 3.75 0.70 2.59 0.70 3.52 7.10
200 5.36 1.10 3.70 1.10 3.52 7.10

the opposite direction, toward the rod center. The geometry and However, the diffusion coefficients are not identical for the two
dimensions of the model system are shown in Fig. 2. sections. The difference stems from multiple factors, including
The mole balance equations for the shell and core of the hybrid the fact that the fiber volume fractions are not the same in the
composite, shown in Eqs. (2) and (3) are: two sections, nor is the path length (tortuosity) [21,22]. In partic-
! ular, the tortuosity, which is inversely related to diffusivity, differs
@C g @ 2 C g 1 @C g in the two sections because of the different diameters of CF and GF
¼ Dglass=epoxy þ  R1 ðC g Þ ð2Þ
@t @r 2 r @r [26].
! The kinetic scheme of the polymer oxidation includes a series of
@C c @ 2 C c 1 @C c
¼ DCarbon=epoxy þ  R2 ðC c Þ ð3Þ chain radical reactions (Eqs. (8)–(13)). These reactions, which gen-
@t @r2 r @r erate a self-initiator, are known as the closed loop standard
mechanistic scheme [6]. The unimolecular decomposition of
where Dglass=epoxy and DCarbon=epoxy are the diffusivities of oxygen
hydroperoxide is considered because of the high temperature
through the glass shell and carbon core, respectively. In these
exposure, and the scheme is shown below:
expressions, R1 ðC g Þ and R2 ðC c Þ are the reaction rates of oxygen with-
in the glass shell and the carbon core, respectively. Initially, C = 0 for

all points in the rod. The boundary conditions are: POOH ! 2P þ H2 O þ vV K1 ð8Þ
r ¼ Ro : Cg ¼ Cs; ð4Þ P þ O2 ! PO2 K2 ð9Þ
r ¼ Rc : Cg ¼ Cc ; ð5Þ PO2 þ PH ! POOH þ P K3 ð10Þ
@C c @C g P þ P ! inactive products K4 ð11Þ
¼ ; ð6Þ
@r @r  
P þ PO2 ! inactive products K5 ð12Þ
@C c
r¼0: ¼0 ð7Þ  
PO2 þ PO2 ! inactive products þ O2 K6 ð13Þ
where Cs is the concentration of oxygen at the surface of composite
rods. where K1–K6 are the reaction rate constants.
Boundary conditions at r = Rc are defined assuming a continu- In the kinetic scheme, only the oxygen reaction rate is heteroge-
ous oxygen concentration at the CF–GF core–shell interface. The neous, and oxygen availability depends on the diffusivity. The oxy-
matrix material in both components is a cyclo-aliphatic epoxy. gen mole balance in cylindrical coordinates is given below.


1.363 mm

Direction 1 is axial 2Ro =9.525 mm

Direction 2 is radial
(a) (b)
Fig. 2. (a) Schematic of composite rod with coordinates. The oxygen diffuses in the radial direction 2. (b) Transverse section of composite rod.
E. Barjasteh et al. / Composites: Part A 40 (2009) 2038–2045 2041

@½O2  @ 2 ½O2  1 @½O2    pure nitrogen. Each term on the right side of Eq. (16) can be ex-
¼D þ þ k2 ½O2 ½P   k6 ½PO2 2 ð14Þ pressed in terms of oxygen concentration using kinetic equations,
@t @r 2 r @r
leading to a final equation relating the mass loss to the oxygen con-
The relation of O2 consumption rate, R(C), with oxygen concen- centration [9].
tration, C, can be derived by manipulating the differential equa- Fig. 4 shows the weight-loss data of thin-film samples (30 lm)
tions generated from the kinetic scheme [9], yielding versus aging time for exposures at different partial pressures of
  oxygen (1-atmosphere total pressure) at 200 °C. The sample ex-
b½O2  b½O2 
RðCÞ ¼ 2r0 1 ð15Þ posed in nitrogen (inert atmosphere) showed a lower rate of
1 þ b½O2  2ð1 þ b½O2 Þ weight loss than those exposed in oxidizing atmospheres. The rate
where r 0 , is the maximal oxidation rate in oxygen excess, and b is of weight loss increased with increasing oxygen content in the
the reciprocal of the critical oxygen concentration beyond which ambient, indicating that the weight loss resulted mainly from ther-
oxygen excess is reached. These parameters are measured from mal oxidation. In other words, oxidation level is directly propor-
the gravimetric curve presented in the following section. tional to oxygen concentration. The weight-loss data were used
Carbon fibers reportedly can have a stabilizing effect on thermal to calculate the kinetic parameters, r 0 and b; for the oxidation of
aging of composites [23]. At the fiber–matrix interface, the CF ab- anhydride-cured epoxy, as shown in Table 3. These reaction rate
sorbs and deactivates radicals that would potentially react with parameters were adapted for the oxidation of CF–epoxy compos-
diffusing oxygen molecules. The phenomena described here indi- ites following accepted protocols [23].
cate the need for additional equations in the kinetic scheme. As a After the required phenomenological parameters were deter-
result, the reaction rate parameters, r 0 and b, and consequently mined, the two coupled non-analytical differential equations
the expression for the oxidation reaction rate differ for the CF sec- (Eqs. (2) and (3)), were solved. These equations were non-analyti-
tion and the GF section [23]. cal because the expression for the oxygen reaction was nonlinear.
The equations were solved numerically by applying the boundary
and initial conditions, yielding predicted oxygen-concentration
3. Results
profiles within the carbon core, Cc(r, t), and within the glass shell,
Cg (r, t).
3.1. Oxidation thickness
Fig. 5 shows the predicted oxygen-concentration profiles as a
function of radial position within the hybrid composite for differ-
Fig. 3 shows the weight loss of the composite rods as a function
ent aging times. The predicted oxygen concentration decreased
of aging time, indicating that the weight loss increased with expo-
with increasing depth in the GF shell, as expected, and approached
sure time and temperature. The rate of weight loss was relatively
zero at depths of 25–150 lm, depending on aging time. Note that
high in the first 10–20 h, then appeared to reach a steady state
the concentration profiles were essentially the same for aging
for the duration of the aging.
times of 672 and 100 h. The prediction is accurate for longer aging
The total weight change of the hybrid composite is expressed in
times (to be shown below), unless the composite surface under-
Eq. (16) [23]. The weight change resulted from (a) the loss of vol-
goes severe damage, such as surface erosion or cracking.
atiles (V and lo), (b) water elimination from the structure, and
Using Eq. (15), one can calculate the local oxygen consumption
(c) weight gain associated with the oxidation.
at a particular radial position by integrating the local oxygen-con-
1 dm 32 18 d½H2 O M v d½V sumption rate over aging time, Q ¼ 0 RðcÞ  dt. The calculated val-
ð1  wf Þ ¼ RðCÞ    lo ð16Þ
m0 dt q0 q0 dt q0 dt ues can be used to plot the normalized oxygen consumption as a
function of radial position within the hybrid composite. Such a plot
where wf, Mv, m, q0 and lo are the mass fraction of fibers, average is shown in Fig. 6 for different aging times. The plot indicates the
molar mass of volatile fragments, the mass of the specimen, initial amount of epoxy converted to oxidation product (conversion de-
density, and the volatile emission in the absence of oxygen, respec- gree of oxidation). The oxygen consumption decreases with
tively. Volatile emission, lo, was measured from the gravimetric increasing subsurface depth and asymptotically approaches zero,
curve generated during the exposure of a thin-film specimen in because of the shortage of oxygen, as shown by the oxygen-con-
centration gradient (see Fig. 5). Thus, the oxidation thickness for
different exposure times can be determined from the plot by
relative weight change (%)

99.6 100

relative weight (%)

99.2 0 20 40 60 80 pure nitrogen

%15 oxygen
180 C
98.4 o
200 C
pure oxygen

0 500 1000 1500 2000 0 50 100 150 200

aging time (hour) aging time (hour)

Fig. 3. The gravimetric curve obtained for capped composite rods 30.48 mm in Fig. 4. Weight loss of samples (30 ± 5 lm thick) exposed to different partial
length and 9.525 mm in diameter, thermally aged at 180 °C and 200 °C. pressures of oxygen at 200 °C.
2042 E. Barjasteh et al. / Composites: Part A 40 (2009) 2038–2045

Table 3
Reaction rate parameters, r 0 and b, obtained at 180 and 200 °C for the cycloalyaohatic
anhydidride cured epoxy.

Aging temperature (°C) Carbon section Glass section

r0 b r0 b
(103 s1) (l mole1) (103 s1) (l mole1)
180 3.2 93.3 2.9 103.1
200 10.0 69.5 8.9 75

oxygen concentration (mol m )

1 min
5 min
1 hr
100 hr
4 672 hr GF shell CF core

Fig. 7. Transverse cross section of hybrid composite rod thermally aged in air at
180 °C for 672 h. The TOLC is confined to a thin layer at the surface.

Cg(r,t) CC(r,t) subsurface layer (Y), was less extensively oxidized, and the com-
bined thickness of the two layers constituted the total oxidation
0 layer of the composite, or TOL. Aging at 200 °C produced a TOL
0 50 100 150 200 1360 comprised of a single layer (two distinct layers were not detected).
distance from surface of hybrid composite (µm) The measured TOL values for both aging exposure temperatures
are tabulated in Table 4, along with model-based predictions. The
Fig. 5. Simulation prediction of oxygen-concentration profiles for hybrid composite thickness values were determined from the average of 20 thickness
rods, Cc (r, t) and Cg (r, t), in air at 180 °C.
measurements at each temperature. Comparison of the measured
and predicted TOL values reveals a difference of roughly 6%, both
at 180 °C and 200 °C. Note that no evidence of oxidation was de-
normalized local oxygen consumption

tected within the CF core, which is consistent with the model-

0 based calculation.
1 min Predictions of the TOL can be extended to longer aging times
5 min using the model presented here (Eqs. (2) and (3)). To illustrate,
1 hr transverse cross-sections of composite samples aged for 8736 h
100 hr (52 weeks) at 180 °C and 200 °C are shown in Fig. 9a and b, respec-
672 hr tively. Inspection of the oxidized composite rods showed no signif-
0.5 GF shell CF core
icant changes in TOL, even after 52 weeks of aging. This is
illustrated in Fig. 8, which shows the measured TOL values for ther-
mal exposure at 180 °C. The plot also shows the predicted TOL va-
lue of 155 lm, which is similar to the measured TOL (140 lm).
TOL (Note that 180 °C is the maximum anticipated service temperature
Qg(r,t) Qc(r,t)
for the overhead conductors.) No evidence of crack initiation or
propagation was detected, as described in the next section.
0 50 100 150 200 1360
3.2. Cracking
distance from surface of hybrid composite (µ m)

Fig. 6. Normalized oxygen consumption profiles predicted for hybrid composite Aged composite samples were inspected for cracking by prepar-
rods, Qc (r, t) and Qg (r, t), in air at 180 °C. ing transverse and longitudinal polished sections. No evidence of
cracking or other forms of damage was detected in the samples
simply reading the points at which the conversion degree is that were capped prior to aging, even after aging up to 1 year
approximately zero. The oxidation-concentration profiles and (8736 h). The surface layer (S2, shown in Fig. 2), exhibited partial
associated reaction products formed relatively quickly (<100 h), exfoliation of the GFs, limited to 1 or 2 fiber diameters. The matrix
and thicknesses (TOL values) reached a limiting value of in this layer was oxidized and underwent shrinkage, which caused
155 lm. The TOL remained essentially constant after 100 h, even
for isothermal exposures up to 1 year. Table 4
Comparison of experimental measurement of TOLC with predicted values in air
The oxidation thickness was also measured by oxidizing rods
exposed for 672 h at different aging temperatures, 180 °C and 200 °C.
(30.5 mm long) at 180 °C and 200 °C. Polished cross-sections of
aged composite rods were inspected to measure the oxidization Temperature Oxidation Thickness (TOLC)
(°K) Model prediction Experimental measurement
thickness (TOL), as shown in Fig. 7. The oxidation was limited to
(lm) (lm)
two discrete superficial layers within the GF shell. The outermost
layer underwent more extensive oxidation, and was assumed to 180 155 146 ± 18
200 110 117 ± 5
correspond to a 50% conversion of the matrix (see Fig. 6) [6]. The
E. Barjasteh et al. / Composites: Part A 40 (2009) 2038–2045 2043

face. The values were measured by nanoindentation, and show a

clear hardening of the oxidized layer. In addition, the thickness
140 of the oxidized layer (TOL) can be determined from the profile in
Fig. 11 [24], and is taken as the depth at which the modulus values
oxidation thickness (µm)

reach a constant level. In Fig. 11, the TOL is approximately 110 lm,
which is consistent with the results measured from polished

70 4. Discussion
experimental measurement
The GF shell is intended primarily to prevent galvanic coupling
model-based prediction
between the CF core and the overlaid aluminum wires of the over-
head conductor [1,25]. However, it also acts as a barrier against
oxidization and effectively limits oxidative damage in the hybrid
0 composites to a few fiber diameters. This also prevents oxidative
0 10 20 30 40 50 60 damage of the CF core, which is expected to carry more than 75%
of applied loads. While oxygen diffused into the GF shell, penetra-
aging time (weeks)
tion was limited to a few fiber diameters because the diffusion was
Fig. 8. Experimental measurements and model-based predictions of TOL for coupled to a reaction. Thus, oxygen never reached the CF/GF inter-
different aging time up to 52 weeks at 180 °C. face. Inspection of rods aged for 8736 h showed no evidence of
cracks or other damage. The only change observed was exfoliation
of 1–2 fiber layers at the GF surface. The exfoliation of fibers can be
fiber–matrix interface debonding in the near-surface region [18]. attributed to structural changes in the matrix and shrinkage asso-
The extent of surface exfoliation, which started in the first few ciated with the oxidation reaction, which left surface fibers ex-
weeks of aging, remained unchanged for longer exposures, but posed and debonded.
exfoliation was more severe at higher exposure temperatures. This The limited extent of oxidation was supported by measure-
outermost surface (S2), in which fiber orientations were parallel to ments and model-based predictions of the TOL for the composite
the surface [16,18], inhibited crack initiation and propagation dur- rods, both of which indicated a passivating effect of the oxidized
ing prolonged exposures. layer. The competition between the rate of oxygen diffusion and
the rate of reaction between oxygen and the matrix ultimately
3.3. Mechanical-property retention determined the TOL. Considering the temperature dependence of
diffusion and reaction rates, the ratio of the oxygen-diffusion rate
The tensile strength of the composite rods remained essentially to the oxygen-consumption rate decreased as the temperature in-
unchanged after thermal oxidation, as shown in Fig. 10a and b. creased, and thus the TOL actually decreased with increasing aging
Small variations in the tensile strength of aged samples were temperature [12].
attributed to normal experimental error. In addition, essentially The reaction–diffusion equation presented will provide a valid
two competing effects affected the strength in the early period of prediction of the oxygen concentration profile (and the distribu-
exposure. Additional crosslinking (post-curing) of the matrix tion of oxidation products) for a specified aging period, provided
caused a slight increase in matrix strength, while aging effects, pri- the phenomenological model parameters (D, r 0 , and b) are un-
marily superficial surface damage from oxidation, caused a slight changed during isothermal aging, and no damage occurs to the
decrease in composite strength. sample surface. The model parameters change during aging due
to oxidation and conversion of the matrix. However, for the condi-
3.4. Matrix elastic modulus tions studied here, an accurate prediction of oxygen concentration
and oxidation product after 1 year of exposure is achieved because
Matrix oxidation altered the elastic modulus (E), particularly of the slow conversion rate of the epoxy matrix. Thus, the model
within the oxidized layer. Fig. 11 shows the values of the elastic parameters are assumed to be nearly constant over the one-year
modulus as a function of depth beneath the oxidized sample sur- aging period.

Fig. 9. Transverse cross section of hybrid composite rods thermally aged in air at (a) 180 °C and (b) 200 °C for 8736 h.
2044 E. Barjasteh et al. / Composites: Part A 40 (2009) 2038–2045

100 100
% tensile strength

% tensile strength
80 80


unaged 1 4 20 16 20 36 52
unaged 1 4 20 16 20 36 52
aging time (weeks) aging time (weeks)

(a) (b)
Fig. 10. Tensile strength of the hybrid composite rod exposed at (a) 180 °C and (b) 200 °C in air for 52 weeks.

7 Em ¼ Em-unaged v m-unaged þ Em-aged v m-aged ð18Þ

The changes in matrix modulus were confined to the TOL, while
6 the matrix modulus remained unchanged in the bulk of the com-
oxidation thickness posite (see Fig. 11). Therefore, the modulus of the aged section is
expressed in Eq. (19):
E (Gpa)

Em-aged ¼ 2
r  Em-aged dr ð19Þ
4 r 2o  ðr o  TOLÞ r o TOL

where Em-aged is the local modulus of the aged matrix within the
Vacuum-aged modulus
3 oxidized layer.
Un-aged modulus Finally, Em can be expressed by substituting Eq. (19) into Eq.
0 50 100 150 200 Z ro
2  mm-aged
Distance from surface of sample (µm) Em  Em-unaged v m-unaged þ r  Em-aged dr ð20Þ
r 2o  ðro  TOLÞ2 ro TOL

Fig. 11. Elastic modulus as a function of depth for a clear cast polymer sample
where Em-unaged is the modulus of the vacuum-aged composite. Using
(3 mm thick) aged for 3200 h at 200 °C.
the Em-aged values determined from nanoindentation measure-
ments, a sigmoidal curve was fit to the data points (see Fig. 11) in
The oxygen concentration profiles provide some guidance for order to calculate the integral in Eq. (20). As a result, the variation
the design of hybrid composites for overhead conductors. The con- in ðEm Þaged as expressed in Eq. (20), alters Ec . The ratio of elastic mod-
ductor design features a GF shell to protect the CF core from gal- ulus of the aged matrix to that of the unaged matrix is essentially
vanic corrosion, which also limits thermal oxidation. The findings one.
presented here allow one to estimate the required thickness of a
ðEm Þaged
GF shell to constitute an effective oxygen barrier. In particular, ffi 1:001 ð21Þ
the TOL was 150 lm, indicating that a safe design would include ðEm Þunaged
a shell substantially thicker than the TOL (depending on desired
Thus, tensile strength is directly proportional to elongation at
safety factors and associated risks). Furthermore, the TOL values
break, ef . In the present study, ef was constant for different aging
can be used to estimate the effect on retained tensile strength, as
times. The aged cross-sectional area constituted less than 3% of
described below.
the total cross-sectional area, and had no discernible effect on
When a uniaxial load is applied to the composite, the load is
the failure mode (experimental data showed that ef was
shared by the CF, the GF, and the matrix. Assuming elastic behav-
1.15 ± 0.05% even after aging for 1 year). Hence, the reduction in
iour, the tensile strength of the unaged unidirectional composite
composite tensile strength after long-term aging in oxidizing
can be calculated by applying Hooke’s law [28].
atmospheres is expected to be negligible, an assertion that is sup-
ðdC ÞF ¼ Ec  ðec ÞF ¼ ðEm  v m þ Egf :v gf þ Ecf  v cf Þ  ðec ÞF ð17Þ ported by the results reported here (Fig. 10).
Sample dimensions can significantly affect the strength reten-
where the subscripts c, gf, cf and m represent the composite, glass-
tion in oxidizing environments, as shown in Eq. (20). Oxidation
fiber, carbon-fiber, and the matrix, respectively, and ðdÞF is the ten-
thickness is a surface parameter, and thus the TOL remains the
sile strength of the matrix, E is the Young’s modulus, v is the volume
same in small-diameter or large-diameter structures. Thus,
fraction, and ðeÞF is the elongation at break.
changes in the composite properties related to TOL are relatively
Assuming no variations in the GF and CF modulus values after
more severe for smaller-diameter rods. For example, for rod diam-
aging, the matrix modulus Em varies in Eq. (17). Eq. (18) shows that
m-aged , eters less than 1 mm, the volume fraction of aged and unaged sec-
Em depends on the matrix modulus of the oxidized section, E
tions will be comparable. As a result, for a given TOL, the ratio of
and that of the unaged bulk, Em-unaged .
elastic modulus (and ultimate tensile strength) of aged composites
to that of unaged composites is not equal to one. Consequently,
E. Barjasteh et al. / Composites: Part A 40 (2009) 2038–2045 2045

smaller-diameter structures are expected to be more susceptible to specimen. Such stress-altered transport properties may well accel-
damage from thermal oxidation. erate thermal aging and the associated effects, including micro-
The oxidation process for the hybrid composites studied here is structural damage.
diffusion-controlled, and thus accurate prediction of the TOL using
the phenomenological model requires accurate measurement of Acknowledgment
diffusivity. The diffusion coefficient is not dependent only on the
temperature that is expressed by the standard Arrhenius law. Financial support from Composite Technology Corporation is
Assuming homogenous oxidation for a thin polymer layer, the gratefully acknowledged. The authors also acknowledge Dr. A.
yield of oxidation (conversion degree) eventually approaches one, Hodge for assistance with nanoindentation experiments.
indicating that the material structure changes and hence, the
transport properties, such as diffusivity, vary over time. In addition, References
diffusivity is dependent on composition, which varies with dis-
tance from the edge of the sample. Therefore, to take into account [1] Alawar A, Bosze EJ, Nutt SR. A composite core conductor for low sag at high
temperatures. IEEE Trans Power Deliv 2005:20.
the effect of diffusivity variation in the phenomenological model, [2] Bosze E J, Alwar A, Bertschger O, Tsai Y, Nutt SR. High-temperature strength
one should measure the diffusion coefficient for different composi- and storage modulus in unidirectional hybrid composites. Compos Sci Technol
tions within the TOL. The oxygen diffusivity within the composite 2006;66:1963–9.
[3] Selzer R, Friedrich K. Mechanical properties and failure behavior of carbon
matrix was calculated from diffusivity data obtained from the bulk fibre-reinforced polymer composites under the influence of moisture.
epoxy using a scaling law [16]. However, a difficulty arises in mak- Composite A 1997;28:595–604.
ing such measurements because of the brittle (and fragile) nature [4] Ellyin F, Master R. Environmental effects on the mechanical properties of glass-
fiber epoxy composite tubular specimens. Compos Sci Technol
of thin oxidized polymer films. Our research group has overcome 2004;64:1863–74.
the former problem by developing a method to make uniform thin [5] Tsotsis T K. Thermo-oxidative aging of composite materials. J Compos Mater
films of epoxy (<10 lm). Such films are presently being used to 1995;29:410–22.
[6] Colin X, Verdu J. Strategy for studying thermal oxidation of organic matrix
perform the requisite diffusivity measurements.
composites. Compos Sci Technol 2005;65:411–9.
[7] Bellenger V, Decelle J, Huet N. Aging of a carbon epoxy composite for
5. Conclusions aeronautic applications. Composite: Part B 2005;36:189–94.
[8] Tsotsis TK. Long-term thermo-oxidative aging in composite materials:
experimental methods. J Compos Mater 1998;58:355–68.
A reaction–diffusion model was applied to the thermal oxida- [9] Colin X, Marais C, Verdu J. Thermal oxidation kinetics for a poly
tion of hybrid GF/CF composites to determine oxygen-concentra- (bismaleimide). J Appl Polym Sci 2001;82:3418–30.
[10] Tandon GP, Pochiraju KV, Schoeppner GA. Modeling of oxidative development
tion profiles and the thickness of the oxidized layer. The in pmr-15 resin. Polym Degrad Stab 2006;91:1861–9.
predictions were compared with experimental measurements of [11] Colin X, Marais C, Verdu J. A new method for predicting the thermal oxidation
oxidized-layer thickness, resulting in an accuracy of >90% for up of thermoset matrices. Application to an amine crosslinked epoxy. Polym Test
to a year of thermal exposure. The TOL grew primarily during ini- [12] Le Huy HM, Bellenger V, Paris M, Verdu J. Thermal oxidation of anhydride
tial stages, although the growth rate decreased with increasing cured epoxies II. depth distribution of oxidation products. Polym Degrad Stab
layer thickness, following parabolic kinetics. The layer did not 1992;35:171–9.
[13] Barjasteh E, Bosze EJ, Nutt SR. Thermal oxidation of anhydride cured epoxy and
grow appreciably after four days of exposure, and even exposures
epoxy matrix composites. SAMPE Proc 2008;52:12.
of 1 year at 180 °C and 200 °C caused no significant thickening. [14] Decelle J, Huet N, Bellenger V. Oxidation induced shrinkage for thermally aged
Thus, the oxidized surface layer effectively functioned as a passive epoxy networks. Polym Degrad Stab 2003;81:239–48.
layer, arresting the diffusion of oxygen and protecting the bulk [15] Schoeppner GA, Tandon GP, Ripberger ER. Anisotropic oxidation and weight
loss in pmr-15 composites. Composites Part A 2007;38:890–904.
epoxy from further oxidation. [16] Colin X, Mavel A, Marais C, Verdu J. Interaction between cracking and
Geometric features of the composite samples significantly influ- oxidation in organic matrix composites. J Compos Mater 2005;39:1371–89.
enced the resistance to aging and associated crack initiation. For [17] Tsotsis TK, Lee SM. Long-term thermo-oxidative aging in composite materials:
failure mechanisms. Compos Sci Technol 1998;58:355–68.
example, the alignment of fibers parallel to the exposed surface [18] Bowles KJ, Madhukar M, Papadopoulos DS, Inghram L, McCorkle L. The effects
effectively inhibited the advancement of the oxidized layer toward of fiber surface modification and thermal aging on composite toughness and
the rod interior. Secondly, no evidence of cracking or other forms of its measurement. J Compos Mater 1997;31(6):552–79.
[19] Salin IM, Seferis JC. Anisotropic effects in thermogravimetry of polymeric
damage was detected during long-term exposures up to 1 year. The composites. J Polym Sci 1993;31:1019–27.
crack resistance was attributed to the orientation of high-strength [20] Kondo K, Taki T. Moisture diffusivity of unidirectional composites. J Compos
fibers parallel to the exposed surface. Strength retention of similar Mater 1982;16:82–93.
[21] Wu YS, Vliet JV, Frijlink HW, Maarschalk KV. The determination of relative
oxidized composites will depend in part on the ratio of the TOL to path length as a measure for tortuosity in compacts using image analysis. Eur J
the sample diameter. However, the strength loss is expected to be Pharmaceut Sci 2006;28:433–40.
negligible in cases where the ratio of the TOL to the sample diam- [22] Matthews GP, Spearing MC. Measurement and modelling of diffusion, porosity
and other pore level characteristics of sandstones. Mar Petrol Geol
eter is small (<0.1).
An issue of practical importance for overhead conductors con- [23] Colin X, Marais CJ, Verdu J. Kinetic modelling of the stabilizing effect of carbon
cerns the possible effect of thermal aging on long-term durability fibres on thermal ageing of thermoset matrix composites. Compos Sci Technol
and retention of mechanical properties. Although the oxidized sur- 2005;65:117–27.
[24] Putthanarat S, Tandon GP, Schoeppner GA. Influence of polishing time on
face layer reaches a self-limiting thickness and may protect the thermo-oxidation characterization of isothermally aged PMR-15 resin. Polym
composite from progressive damage, the surface layer may be dis- Degrad Stab 2007;92:2110–20.
rupted in service by phenomena such as abrasion from overlaid [25] Boyd J, Chang G, Webb W, Speak S. Galvanic corrosion effects on carbon fiber
composites. In: 37th International SAMPE symposium and exhibition:
aluminum strands, cyclic bending loads, thermal cycles, and mois- materials working for you in the 21st century, vol. 435; 1992. p. 1184–98.
ture absorption. Repeated disruption of the layer could negate the [26] Tsai YI, Bosze EJ, Barjasteh E, Nutt SR. Influence of hygrothermal environment
protective effects and lead to progressive damage. Furthermore, on thermal and mechanical properties of carbonfiber/fiber glass composites.
Compos Sci Technol 2009;69:432–7.
the effects of thermal aging may be more pronounced in small- [27] Ziegel KD, Frensdorff HK, Blair DE. Measurement of hydrogen isotope transport
diameter composite rods, in which the oxidized-layer thickness in poly-(vinyl fluoride) films by the permeation-rate method. J Polym Sci: Part
constitutes a larger portion of the rod diameter. In addition, tensile A-2 1969;7:809–19.
[28] Kaw AK. Mechanics of composite materials. CRC Press; 1997. p. 327.
loads encountered in service may affect the transport properties of
oxygen and reaction-generated volatiles within the composite