Letter

INVESTIGATION OF WATER DIFFUSION IN TRIANGULAR BAR-REINFORCED COMPOSITES

Bryan Pajaritoa,b*, Masatoshi Kubouchib, Saiko Aokib
Department of Chemical Engineering, University of the Philippines,
Diliman, 1101 Philippines
b
Department of Chemical Engineering, Tokyo Institute of Technology,
2-12-1 S4-5 O-okayama, Meguro-ku, Tokyo 152-8552, Japan
a

*Author to whom correspondence should be addressed

Email: bryan.pajarito@gmail.com
Received 31 May 2012; accepted 18 December 2012
ABSTRACT
This work investigated water diffusion in composites consisting of a permeable matrix reinforced with aligned,
impermeable, triangular elements. The triangular elements are expected to induce single axis-, filler orientation-dependent transport behaviour in the composite. Such property is suggested to be useful in slow barrier applications and fast drying processes. To test this idea experimentally, triangular bar-reinforced composite specimens are prepared using thermosetting plastics as representative components. Using water as model diffusant,
specimens undergo absorption-desorption-reabsorption gravimetric experiments at 80oC. It is observed that
diffusivity decreases when the base side of the reinforced triangular bars is exposed to diffusion and increases
when it is the sloped side. Diffusion is also reduced when the triangular bars are in staggered alignment.
Keywords: filler orientation, diffusion, triangular bar, composite

1. INTRODUCTION
Materials utilized in barrier and corrosion protection
applications such as organic coatings and linings
are usually designed with low transport properties,
making them almost impermeable to diffusing fluids. The desired impermeability in these materials
is mostly achieved by using reinforcement. These
reinforcing, impervious fillers are hard, brittle, and
are available in different types. Composite materials
can be divided into three classes according to the
type of reinforcement used [1-3]: one-dimensional
(fibres, whiskers); two-dimensional (flakes, platelets, disks, ribbons); and three-dimensional (spheres,
beads). Among the different types of fillers, fibres
and flakes are more efficient reinforcements than
spheres in terms of mechanical and barrier property
enhancement. While fibres give higher moduli and
strength, flakes are advantageous when properties in
a plane are considered due to their capability to reinforce in two dimensions [2,3].
Many researchers have investigated diffusion in
flake-reinforced composites using analytical, numerical and experimental methods. Most analytical
formulations and numerical simulations of diffusion
in these composites are performed based in the assumption that all flakes are oriented perpendicular
to the diffusion direction. At this orientation, flakes
Advanced Composites Letters, Vol. 21, Iss. 6, 2012

decrease the area available for diffusion and increase

the path length of diffusing species in the composite
[4-7]. The analytical and numerical models developed and studied in literature have considered several parameters such as flake aspect ratio, volume
fraction, spacing, relative alignment, random dispersion, size distribution, and filler shape for prediction
of effective diffusion in permeable media containing orthogonal flakes [4-17]. A few researchers have
also expected diffusion in a composite with aligned
flakes to be highly anisotropic; while transport perpendicular to overlapping flakes is slow, transport
parallel to the flakes is fast. Eitzman et al. [15] suggested a simple model which predicts diffusion to be
faster parallel to flakes than perpendicular to flakes.
The model is somewhat similar to spheres and is
verified by Monte Carlo simulations. Their experiments in carbon transport across silicone rubber
membranes containing mica and vermiculite flakes
concluded that tipping the flakes results to fast
transport. Ly and Cheng [16] proposed a geometrical model for estimating diffusion in heterogeneous
media with impermeable flakes arranged in parallel
arrays of variable orientation. Using random walk
simulations for model validation, transport is predicted to increase when the angle between diffusion
direction and flakes is decreased. With electrical
conductivity measurements in mica-filled polyvinyl
137

Bryan Pajarito, Masatoshi Kubouchi, Saiko Aoki

tion-dependent diffusion in a permeable matrix containing aligned impermeable triangular elements.

Triangular bars are used to represent the triangular
elements in the composite. During manual fabrication of specimens, cured thermosetting plastics are
used to model the permeable matrix and impermeWith diffusion strongly dependent on the orientation able reinforcement of the hypothetical composite.
of the flakes, consider now a hypothetical compos- Using water as the model diffusant, absorption-deite material shown in Fig. 1. A permeable matrix is sorption-reabsorption experiments are performed on
reinforced with impermeable triangular elements ar- the composite specimens. Diffusion parameters are
161-174.
ranged in parallel arrays. While anisotropic diffusion calculated from the monitored weight of the speci12. Fredrickson, G., and Bicerano, J., Barrier properties of oriented disk composites, J. Chem. Phys.,
in flakes occurs along the orthogonal axes, effective mens during experiment. Effects of triangular bar
110/4 (1999), 2181-2188.
diffusion
triangular
elementsofisglass
expected
to be de-composites,
exposedJ. Mater.
side and alignment on water transport in
13. Brydges, W., Gulati,
S., andinBaum,
G., Permeability
ribbon-reinforced
Sci., 10/12 (1975),
2044-2049.
pendent
on a single axis and exposed filler orienta- composite specimens are also discussed.
14. Swannack, C., Cox, C., Liakos, A., and Hirt, D., A three-dimensional simulation of barrier properties
It J.isMembr.
assumed
in this
configuration
of trianof nanocompositetion.
films,
Sci., that
263/1-2
(2005),
47-56.
15. Eitzmann, D., Melkote,
R., and Cussler,
Barrier membranes
tipped impermeable
flakes,
gular elements
insideE.aL.,
permeable
matrix,with
diffusion
2. EXPERIMENTAL
AIChE J., 42/1 (1996),
2-9.
is slower at the base side as compared to diffusion 2.1 Specimen Preparation
16. Ly, Y., and Cheng, Y., Diffusion in heterogeneous media containing impermeable domains arranged
the sloped
sideJ.of
the composite
material.
The Alicyclic type epoxy resin (ECR-1105, Sumitomo
in parallel arrays at
of variable
orientation,
Membr.
Sci., 133/2 (1997),
207-215.
17. White, J. and Cussler,
Anisotropic
transport instructure
water swollen
flake-filledBakelite
membranes,
idea forE.theL.,presented
composite
is derived
Co.,J. Ltd.) cured with methyltetrahydrophMembr. Sci., 278/1-2 (2006), 225-231.
from studies of anisotropic diffusion in flake-rein- thalic anhydride (ECH-202, Sumitomo Bakelite
18. Yurev, S. V. and Lushchik, V. V., Determining the diffusion coefficient of a liquid medium in
forced
composites.
The50-53.
base side of the hypothetical Co., Ltd.) was chosen as the permeable matrix of the
polymeric materials,
Mater.
Sci., 10/1 (1975)
19. Crank, J. (1975)composite
The Mathematics
of Diffusion,
Oxford,
Clarendon Press.
material
in Fig.
1 simulates
flake-filled composite specimens. Cured bisphenol A vinyl es20. Lee, S. and Rockett, T. J., Interactions of water with unsaturated polyester, vinyl ester and acrylic
composite containing aligned, orthogonal flakes, ter resin (Ripoxy R-804, Showa Highpolymer Co.,
resins, Polymer, 33/17 (1992) 3691-3697.
while A.,
theand
sloped
side O.,
mimics
composite
was ester
used as the model impermeable reinforce21. Alvarez, V., Vazquez,
de la Osa,
Cyclicflake-filled
water absorption
behaviour ofLtd.)
glass-vinyl
and glass-epoxy composites,
Compos.flakes.
Mater., It
41/10
(2007)suggested
1275-1289. in this ment of the composite specimens since cured vinyl
containingJ.tipped
is also
22. Bond, D. and Smith, P., Modeling the transport of low-molecular-weight penetrants within polymer
work
that
such
filler
orientation-dependent
transport esters have lower water absorption than cured epoxmatrix composites,
Appl.
Mech.
Rev.,
59 (2006)
249-268.
composite
material and
is useies due
to their different chemical structures.
23. Fan, X. J., Lee,property
S. W. R., of
andhypothetical
Han, Q., Experimental
investigations
model study
of moisture
behaviors in polymeric
Microelectron.
Reliab., 49 (2009)
861-871.
ful inmaterials,
barrier and
drying processes.
A typical
application of the composite is to use its base side as a Triangular bar fillers made of cured vinyl ester were
barrier to diffusing fluids. After partial saturation of prepared as follows. For a batch of triangular bar
the composites permeable matrix, the diffused liq- fillers, 50 g of vinyl ester resin was mechanically
uid is removed by exposing the composites sloped mixed with 0.2 g of methyl ethyl ketone peroxide
side to a drying medium. While the base side of the and 0.2 g of 6% cobalt naphthenate. The resulting
composite slows down diffusion of fluids, the sloped polymer mixture was degassed and poured into a
side enhances drying, removal of diffused fluids, special mold (sprayed with mold release agent Daiand fast recovery of material properties.
free GA-7500, Daikin Industries, Ltd.) specifically
fabricated for curing triangular bar fillers with base,
This work investigates the expected filler orienta- height, and width of 5 mm, 1.6 mm, and 120 mm,

respectively. The mold was then placed inside a con

vection oven and was heated for 2 h at 50oC, fol
lowed by 3 h at 100oC for post-curing. A batch could

produce a maximum of 42 cured triangular bars. It

should be noted, however, that it is difficult to pro

duce defect-free triangular bar fillers due to trapped

air in the small triangular channels of the special

mold. The trapped air usually results to voids in

side the triangular bar fillers after curing. The brittle

nature of cured vinyl ester resin also contributes to

preliminary cracks and early breakage of some tri

angular bar fillers. Those triangular bar fillers that

are fully cured with small defects were selected and

trimmed for filler assembly.

alcohol membranes swollen in aqueous ionic solutions, White and Cussler [17] showed composites
with aligned inorganic flakes have permeabilities
that are lower perpendicular to the flakes than parallel to the flakes.

Fig. 1: A composite consisting of a permeable matrix

impermeable
Fig. 1: A compositereinforced
consisting of with
a permeable
matrix reinforced
with
elements.
triangular
impermeable
triangular
elements.triangularThe

138

bar fillers were manually assembled

Advanced Composites Letters, Vol. 21, Iss. 6, 2012

Investigation of Water Diffusion in Triangular Bar-Reinforced

Composites

Table 1:
Preparedfor
specimens
for water absorption-deTable 1: Prepared
specimens
water absorption-desorption-reabsorption
tests
sorption-reabsorption
tests

Specimen
VE
EP
A
B
C
D

Exposed side of
Filler
Remarks
triangular bar fillers alignment
pure vinyl ester
pure epoxy
sloped
parallel
composite
base
parallel
composite
sloped
staggered
composite
base
staggered
composite

edges, the composite specimen was again stored in

a convective air oven at 50 oC for at least 100 h and
the weight increase due
was weighed again to obtain

Fig. 2: Layer-wise assembly of triangular bar fillers and to the applied foil and adhesive
before proceeding to
Fig. 2: Layer-wise assembly of triangular bar fillers and mold setup.
mold setup.

the experiments.
ester specimens were
in a layer-wise fashion as illustrated in Fig. 2. The Cured pure epoxy and vinyl

arrangement of triangular bars per layer was guided also prepared for testing and comparison. Table 1
1: Prepared specimens for water absorption-desorption-reabsorption tests
by Table
a pattern
laid out in 1-mm
grid paper. Two 3- lists the specimens tested in this work. Triangular

Exposed
side
of
Filler
layer structures
bonded to form bar fillers were oriented inside the epoxy matrix
Specimen were assembled and Remarks
triangular bar fillers alignment
VE
- structure
vinyl ester The tria 6-layer symmetrical
aspurepure
shown.
with the fillers base side or sloped side exposed
EP
epoxy
surface. Triangular bar
sloped bonded
parallel at their
compositeends using
angular barAB fillers were
near the composite specimen
base
parallel
composite
in parallel or staggered
C
sloped
staggered
composite
cyanoacrylate
adhesive
(Aron
Alpha
Extra 2000, fillers could also be aligned
D
base
staggered
composite

Toagosei Co., Ltd.). Each layer

of the resulting sym- arrangement during filler assembly.
Triplicate speci
metrical structure is composed
of
15
triangular
bars
mens
were
prepared
and
tested
for
each specimen

with 1 mm spacing.
Thewere
fillersealed
assembly
used steel
condition
Table through-the-thickness
1.
The edges
with was
stainless
foil to inensure
moisture diffusion in the

10 mm
to reinforce aspecimens
100 edges
x 100during
xwere
composite
speciThe
sealed
with stainless
steel was
foil to
ensure
through-the-thickness
moisture
in its
the
experiments.
Vinyl
ester
used
as
adhesive
for
the
stainless
steel diffusion
foil due to

specimens
during
experiments.
Vinyl ester
usedthe
as adhesive
adhesive and
for sealing
the stainless
steel the
foil composite
due to its
men.
moisture
resistance
at high temperature.
Afterwas
curing
the edges,
2.2
Water
absorption-desorption-reabsorption

moisture
resistance
at high
After
curing
theoCadhesive
and 100
sealing
thewas
edges,
the composite
was
again
stored
intemperature.
a inside
convective
air oven
at 50
for at least
h and
weighed
again to
The completespecimen
filler assembly
was then
placed
gravimetric
tests

specimen
was
again
stored
in
a
convective
air
oven
at
50
C
for
at
least
100
h
and
was
weighed
again to
themetal
weight
increase
to plates
the applied
foildetermining
and adhesivethe
before
proceeding
theto
experiments.
a 190 x 190 obtain
x 10 mm
mold.
The due
metal
After
weight
increase todue
ap
obtain
the
weight
increase
due
to specimens
the
foil
and
before
proceeding
theedges,
experiments.
Cured
pure
epoxy
and
vinyl
ester
were
alsoadhesive
prepared
for testing
Table 1 lists the

were lined with

thin
polyester
sheets,
and
all
con-applied
plied
adhesive
and stainless
steel and
foil comparison.
attothe
Cured
epoxy
ester
specimens
were
also
prepared
for
testing
and
comparison.
Tablethe
1 lists
the
tested
inand
thisvinyl
work.
Triangular
bar
fillers
were
oriented
inside
the
epoxy
matrix
fillers
tact surfacesspecimens
of the pure
mold
setup
were
applied
with
the dried specimens were immersed in deionizedwith
specimens
tested
in
this
work.
Triangular
bar
fillers
were
oriented
inside
the
epoxy
matrix
with
the
fillers
base
side
or
sloped
side
exposed
near
the
composite
specimen
surface.
Triangular
bar
fillers
could
also
be
mold release agent (QZ 13, Nagase ChemteX Corp.) water inside glass containers. Teflon holders were
base side
or sloped
exposed
near
composite
specimen
surface.
Triangular
bar fillers
could alsoand
be
aligned
in matrix
parallel
or side
staggered
arrangement
during
filler
assembly.
Triplicate
specimens
were prepared
The model permeable
was
prepared
by
me- the
used
to avoid
physical
contact
among
immersed
aligned
in
parallel
or
staggered
arrangement
during
filler
assembly.
Triplicate
specimens
were
prepared
and
tested
for
each
specimen
condition
in
Table
1.
chanically mixing 200 g of epoxy resin and 160 g of specimens. The temperature of immersion was kept
tested
foragent.
each specimen
condition
in Table
1.oC for 1200 h using a water bath. After 1200
acid anhydride
curing
The degassed
polymer
at 80
Water
absorption-desorption-reabsorption
tests removed from water immermixture was 2.2
slowly
added
to the mold with the filler h, the gravimetric
specimens were
2.2 Water
absorption-desorption-reabsorption
gravimetric
tests
After
determining
the
weight
increase
due
to
applied
adhesive
and stainless steel foil at the edges, the dried
assembly fixed inside. Afterwards, the mold was sion and were placed inside
a vacuum oven for dryAfter determining
the weight
increase due
to applied
adhesive
and stainless
steel
foil atwere
the edges,
theavoid
dried
specimens
were immersed
in deionized
water
inside glass
containers.
Teflon
holders
used to
closed with a metal plate and was taken to a thermal ing. The temperature of vacuum drying was kept at o
specimens
were among
immersed
in deionized
water
inside
glass
containers.
Teflon
holders
were
used
to
avoid
physical
contact
immersed
specimens.
The
temperature
of
immersion
was
kept
at
80
C
for
1200
h
press for curing. The acid anhydride epoxy matrix 80oC for 300 h. After 300 h, the specimens were im- o
physical
contact
immersed
The temperature
of water
immersion
was kept
at
80
C
for
1200
h
using
a water
bath.among
After 1200
h,o thespecimens.
specimens were
removed from
immersion
and were
placed
inside
o
was cured using
theafollowing
steps:
3 h1200
at 80h,C,the
2 hspecimens
mersed
again
in
deionized
water
for
o300 h at 80 C.
using
water
bath.
After
were
removed
from
water
immersion
and
were
placed
inside
a vacuum oven
for drying. The temperature of vacuum drying was kept at 80 C for 300 h. After 300 h, the
o
at 100oC, andspecimens
h at 120were
C. immersed
Weight
of specimens
monitored
and
recorded
a5 vacuum
oven
for drying.again
The temperature
of
vacuum
drying
was
kept
at 80oof
C for
300 h. After
300 h, the
in deionized
water
for 300
h atwas
80oC.
Weight
specimens
was monitored
o
during
water
absorption-desorption-resorption
tests.
specimens
were
immersed
in deionized water for 300 htests.
at 80Results
C. Weight
of specimens
was monitored
and
recorded
during
water again
absorption-desorption-resorption
are presented
as percent
weight
The cured polymer
composite
specimen
was
then
Resultsofare
as percent
weight
Wt in
and recorded
during
water
tests.
Results
are change
presented
as percent weight
change
W
with
theabsorption-desorption-resorption
initial
dry weight
thepresented
specimens:
t in relation
taken out of the
moldWand
was cut into a 100 x 100 relation with the initial dry weight of the specimens:
change
t in relation with the initial dry weight of the specimens:
mm square plate. The edges of the composite speci(1)
W W
men were polished with waterproof abrasive paper Wt (% ) = Wi Wd 100
(1)
(1)
i
d
100
before storing in a convective air oven at 50oC for Wt (% ) = Wd
Wd uptake/loss
at least 100 h.
The
specimens
weighed
andwith
percent
water
Mt specimen
in relationbefore
with the
and
percent
waterwere
uptake/loss
Mtbefore
in relation
the initial
weight of the
water absorption,
and
water
uptake/loss
Mt in relation
with
the initial
of the
specimen
edge sealing.desorption,
Thepercent
edgesor
were
sealed
with stainless
initial
weight
of theweight
specimen
before
waterbefore
absorp-water absorption,
reabsorption:
desorption,
or reabsorption: moisture tion, desorption, or reabsorption:
steel foil to ensure
through-the-thickness
W W
(2)
diffusion in the specimens during experiments.
M t (% ) = Wi Wb 100
(2)
Vinyl ester was used as adhesive for the stainless
(2)
i
b
M t (% ) = W
100
b
steel foil due to its moisture resistance at high temWb
where
Wi is
specimen
weight
during
perature. After
curing
thetheadhesive
and
sealing
the tests, Wd is the initial, dried specimen weight, and Wb is the baseline
where Wiweight
is the specimen
weight during
tests,
specimen
before immersion,
drying,
andWre-immersion.
d is the initial, dried specimen weight, and Wb is the baseline
specimen weight before immersion, drying, and re-immersion.
Advanced Composites
Letters, Vol.
21, Iss. 6,equilibrium
2012
139
2.3 Estimation
of apparent
water uptake/loss
2.3 Estimation
of apparent equilibrium
water uptake/loss
The
apparent equilibrium
water uptake/loss
M of specimens during absorption, desorption, and
The
apparent
equilibrium
water
uptake/loss
M of by
specimens
during
absorption,
desorption,
and
reabsorption tests was estimated using a method suggested
Yurev and
Lushchik
[18] for thick
polymeric
reabsorption
tests
using
method suggested
by Yurev
Lushchik
[18] for
thickEq.
polymeric
materials.
Using
Mwas
(%)estimated
versus t (h)
dataaobtained
from experiments,
Mand
was
approximated
using
3:

forfillers
each specimen
condition
Table
1. matrix with the fillers
bar
were oriented
insidein the
epoxy
ed
again
in
deionized
water
for
300
h
80ofillers
C. Weight
specimens
was monitored
composite specimen surface. Triangularatbar
couldofalso
be
ater
absorption-desorption-resorption
tests.
Results
are
presented
as
percent
weight
ater
absorption-desorption-reabsorption
gravimetric
tests
t during filler assembly. Triplicate specimens were prepared and
th
the
initial
dry
weight
of
the
specimens:
determining
the
increase
due
to
applied
adhesive
and
stainless
steel
foil
at the edges, the dried
1.
mens were immersed in deionized water insideBryan
glassPajarito,
containers.
Teflon
holders
were Aoki
used to avoid
Masatoshi Kubouchi, Saiko

o
(1)
where
Wi isWthe
specimen
weight
during of
tests,
Wd
cal
among
immersed
specimens.
The
temperature
immersion
was kept at 80 C for 1200
h
ioncontact
gravimetric
tests
i Wd

(%initial,
)stainless
= thedried
100wereweight,
tand
atowater
bath.
After
1200
h,
specimens
removed
from
water
immersion
and
were
placed
inside
isWthe
specimen
and
W
is
the

applied
adhesive
steel
foil
at
the
edges,
the
dried
b
Wd
uum
oven for
drying.
Thespecimen
temperature
of vacuum
drying
kept at 80oAC for 300 h. After 300 h,Bthe
baseline
before
drying,
ater inside
glass
containers.
Teflonweight
holders
wereimmersion,
used towas
avoid
o
o
h at 80
e/loss
Mtemperature
relation
with
the
weight
before
water absorption,
t in
mens
were
immersed
again
in initial
deionized
water
for
300
C.h Weight
of specimens was monitored
and re-immersion.
ns.
The
of immersion
was
keptofatthe
80specimen
C for
1200

ion:
ecorded
during
water
absorption-desorption-resorption
tests.
Results
are
presented as percent weight
mens were removed from water immersion and were placed
inside

o
e
W
in
relation
with
the
initial
dry
weight
of
the
specimens:
e of tvacuum drying
kept at 80
C for 300equilibrium
h. After 300water
h, theup2.3 was
Estimation
of apparent
Wi Wof
o
(2)
b specimens was monitored
ed water for 300take/loss
hMat (80
C.
Weight
100
t %) =

(1)
Wasi percent
Wuptake/loss
rption-resorptionThe
tests.
ResultsW
are
weightM
apparent
equilibrium
water
b presented
d
100
(
)
W
%
=
t
ight of the specimens:
of specimens during absorption,
and
weight, and
Wd desorption,
n weight during tests, Wd is the initial, dried specimen
W is the baseline
reabsorption tests was estimated using
a method b

immersion,
drying,
and re-immersion.
ercent
water
uptake/loss
M
in
relation
with
the
initial
weight
of
the
t
(1) specimen before water absorption,

i Wd suggested by Yurev and Lushchik [18] for thick

ption,
(t % ) =orWreabsorption:

100
D

C
materials. Using Mt (%) versus
t (h) data
Wd polymeric
ent equilibrium
water uptake/loss

obtained M
from of
experiments,
MW
was approximated
W absorption, desorption, and
specimens
during
ium
uptake/loss
specimen
(2)
i
b
with water
the initial
weightEq.
of 3:
the
before
water
absorption,
100

(
)
M
%
=
using
stimated using a method suggested by tYurev and Lushchik
[18] for thick polymeric

b
versus t (h) data obtained from experiments, M was
approximated
using Eq. 3:

(3)
(3)Wb is the baseline

Wi is theW
specimen
weight
during
tests,
W
is
the
initial,
dried
specimen
weight, and
d
Wb
M1
(2)
) = ibefore
M
100
(% ) = drying,
Mimmersion,

t (%
men
weight
and re-immersion.

2 (M 2 M 1 )

Wb

uptake/loss
where
Mspecimen
and M2 weight,
are theuptake/loss
percent
water
timation
of initial,
apparent
equilibrium
water
1
s,
Wd is the
dried
and Wb is
the
baseline
specimen
time
t1 and tat
=time
2tof
, respectively.
he
waterofuptake/loss
specimen
and
t2 = 2tThe
The desorption,
1, respectively.
during
absorption,
and of composite speciapparent
equilibrium
water atof
uptake/loss
2M
1 t1specimens

andpercent
re-immersion.
Fig.
3: Cross-section
optical images
ng a time
t2 was
suchmethod
that theinvolves
inequality
1 < M2suggested
M1 <t2 2such
was
observed.
the calculated
a /time
that
theand
in- If
Yurev
orption
tests
estimated
using aselecting
method
by
Lushchik
[18]
for
thick
polymeric
mens images
A, B, of
C,composite
and D. specimens A, B, C, and D.
Fig. 3: Cross-section optical
If of
ess
than
theMrecorded
maximum
percent
uptake/loss
another t2 using Eq. 3:
equality
1t (h)
< Mdata
/ Mobtained
< 2water
wasfrom
observed.
thethe
calcuals.uptake/loss
Using
versus
experiments,
Mspecimen,
t (%)
was approximated
2
1
ter
a. TheMprocedure
wasMrepeated
until the t2calculated
M the
is recorded
greater
or equal
the
lated
at the selected
is lessdesorption,
than
(3) images of polymer
the cross-section
optical
and thanshows
/loss
during absorption,
M
of specimens
1
value.
M
%
M
=
t
maximum
percent
water
uptake/loss
of
the
specicomposite specimens A, B, C, and D. In specimens
[18] for thick polymeric
thod suggested by Yurev and Lushchik
M
2 M
men, another
t2 is approximated
selected from2using
the
data.
The
tained from experiments,
M was
Eq.
3:1 proce- A and C, the sloped side of the reinforced triangles is
r diffusion coefficient
dure was repeated until the calculated M is greater
first to be exposed during water absorption-desorp(3)
M

1
%)
obtained
from
experiments
the estimated
values,
M1 versus
and
are data
the percent
uptake/loss
ofand
specimen
timeMt1tion-reabsorption
and t2 =water
2t1, respectively.
The
= Mt2 (h)
than
or equalwater
the
maximum
experimental
Mt at
value.
gravimetric
experiments. Speci %

specimens
were
calculated
by Levenberg-Marquardt
The
2 selecting
M
df involves
a1 time t2 such
that the inequality 1 < nonlinear
M2 / M1 < regression.
2mens
was observed.
If
the
calculated
2 M
B and D, on the other hand, have the base side
by Crank
[19]
for
Fickian
diffusion
in amaximum
square
plate
of thickness
2h: of theofreinforced
the
selected
t2 is
less
than the
recorded
percent
water uptake/loss
the specimen,
another
t2 to diffusion. It is
2.4
Calculation
of water
diffusion
coefficient
triangles
exposed

cted
from
the
data.
The
procedure
was
repeated
until
the
calculated
M
is
greater
than
or
equal
the

ptake/loss of specimen
at time
t1 and
2t1, respectively.
The
Using the
recorded
Mt t(%)
t (h) data obtained
2 = versus
expected
that water diffusion in specimens(a)
A and C

(4)
value.
mum
M
t

at theexperimental
inequality
1
<
M
/
M
<
2
was
observed.
If
the
calculated
8
from experiments
and the estimated
M values,
wa- is faster than in specimens B and D due to the dif2
2
1

+ 1 2t another
M
exp of
Dthe
2nspecimen,
4h 2 t
t = M 1
2 coefficients
2
d maximum
percent
water
uptake/loss
2
ter
diffusion
of
specimens
were
calcuference in exposed matrix area available for mass

n =0 2n + 1
the
alculation
of until
water
diffusion
coefficient
was
repeated
the
calculated
M is greater nonlinear
than or equal
lated
by
Levenberg-Marquardt
regression.
transport. Alignment of triangular fillers is also exthe recorded Mt (%) versus t (h) data obtained from experiments
and the estimated M values, water
[19] for Fick(b)
The
model
function
is
given
by
Crank
pected
to
contribute to filler orientation-dependent
ffusion
coefficient.
script waswere
written
in GNU by
Octave
software utilizing
its
leasqr
ion
coefficients
of Aspecimens
calculated
Levenberg-Marquardt
nonlinear
regression. The
ian diffusion
in a square data.
plate of thickness
2h:
diffusion in composites. The alignment of rein a square
diffusion
from experimental
function iscoefficient
given by Crank
[19] for Fickian
diffusion in
plate of thickness 2h:
nt
forced triangles in the matrix is parallel for speci
a obtained from experiments and the estimated M values,
water

mens A and B, and staggered(4)

for specimens C and

calculated by Levenberg-Marquardt
nonlinear
regression.
The 2 2

8
2
D.
Studies
of
diffusion
in
flake-filled
films(c)suggest
SCUSSION
= M plate
1 of thickness22h:2 exp D 2n + 1 t 4 h
ickian diffusion inMat square
(4)
lower
diffusivity
in
staggered
than
in
parallel flake
2
1
+

n =0

tortuosity [4-11,15-17].
networks
due
to
increased
(4)

8
2 2
Hence,
it alsoutilizing
expecteditsthat
diffusion in specimens
D is the water
diffusion
coefficient.
A2 script
was
written
in
GNU
Octave
software
leasqr

+
exp
D
2
n
1

t
4
h

2 2
C
and
D
is
slower
than
in
specimens
A and B due to
2
1
+

n
on to calculate the diffusion coefficient from
data.
experimental

where D is the water diffusion coefficient.

A
script
the
difference
in
the
alignment
of
reinforced
trian
Fig. 4: Weight
of specimens during a) water absorption, b) desorption, and c) reabsorption at 80oC.
was written in GNU Octave software utilizing
its change
gular bars.

( )

( )

A script was written in GNU Octave software utilizing its leasqr

leasqr
function to calculate the diffusion coefficient
SULTS
AND DISCUSSION
nt
from experimental
data.
from experimental data.

3. RESULTS AND DISCUSSION

Polymer composite specimens were prepared in this
work to study filler orientation-dependent diffusion
induced by aligned triangular elements. Triangular
bar fillers were used to represent and model the desired triangular elements in the composite. Fig. 3
140

Fig. 4 shows the percent weight change curves during water absorption, desorption, and reabsorption
as a function of square root time for all specimens
at 80oC. All specimens gained weight during water
absorption and reabsorption, and lose weight during water desorption. Specimen EP has the highest
weight change during exposure to deionized water,
followed by composite specimens, and lastly by
specimen VE. Specimen VE has achieved water
Advanced Composites Letters, Vol. 21, Iss. 6, 2012

Investigation of Water Diffusion in Triangular Bar-Reinforced Composites

(a)

(b)

(c)

Fig. 4: Weight change of specimens during a) water

absorption, b) desorption, and c) reabsorption at 80oC.

VE

saturation during absorption and reabsorption tests

as depicted by its weight change curve. The other
remaining specimens have failed to achieve water saturation during exposure. The weight change
curves of VE and composite specimens during desorption indicate weight loss during the water absorption test. Weight loss during moisture transport
are attributed to diffusion of residual volatiles, hydrolysis of chemical functional groups such epoxy
and ester, diffusion of residuals from cracks, and
leaching [20]. Weight loss is shown to be severe in
composite than in pure resin specimens. This could
be due to degradation of cyanoacrylate adhesive at
high moisture concentration and temperature.
Fig. 5 shows the percent water uptake/loss curves
during absorption, desorption, and reabsorption as
a function of square root time for all specimens at
80oC. Comparing water uptake of specimens during absorption and reabsorption at the same immersion time, water uptake during absorption is lower
as compared during reabsorption. Additional free
volume generated in the specimens during water absorption and desorption at 80oC could result to high-

EP

Fig. 5: Water uptake/loss of specimens during absorption, desorption, and reabsorption at 80oC.

Fig. 5: Water uptake/loss of specimens during absorption, desorption, and reabsorption at 80oC.
Advanced Composites Letters, Vol. 21, Iss. 6, 2012

141

Bryan Pajarito, Masatoshi Kubouchi, Saiko Aoki

er water uptake during reabsorption. The specimens loss of specimens during absorption, desorption,
are made up of cured vinyl ester and epoxy com- and reabsorption assumes effective diffusion across
ponents which are glassy polymers that have time- the materials to be Fickian, characterized by an inidependent properties [19]. During absorption, water tial linear curve of water uptake/loss versus square

molecules stretch the polymer

chains which result root of exposure time and followed by a saturation

to additional free volume. The added free volume or equilibrium stage defined by the parameter M.
will still be available in the polymer network during The double time approach of Yurev and Lushchik
since the stressed poly- [18] was applied in this work to indicate a possible
desorption and reabsorption
VE mer chains of glassy polymers
EP time to relax. value for M which simplifies the determination of

take
The added free volume in the specimens could also D from experimental data. However, a close inspecbe due to irreversible damage during water absorp- tion of experimental data in Fig. 5 shows the percent
tion such as cracks, microcavities, and voids from water uptake/loss curves to be somewhat trending
debonded filler-matrix interphases [21]. Debonding beyond the apparent M values. This observation
and degradation of the interphase between epoxy suggests the behaviour of water uptake/loss in the
matrix and vinyl ester fillers due to fluid sorption- specimens to be non-Fickian, for instance two-stage
induced swelling may result to narrow spaces and sorption [22,23]. In almost all specimens, the first
promote overall water diffusion and transport by linear stage lasts until about t = 20 h0.5, followed
capillary effect. These may facilitate higher effec- by a second linear stage of lower slope. The first
and re- stage of sorption is usually attributed to be Fickian
B
A tive diffusion rates during water desorption
absorption than during absorption.
diffusion-controlled, while the second stage of sorption is described as due to polymer matrix relaxation

The dotted lines in Fig. 5 are plots of Eq.

4
using
upon interaction with the diffusant.

the calculated diffusion parameters listed in Table 2.

Rather than use the maximum percent water uptake/ Fig. 6 shows the effect of triangular bar filler ex
loss as the apparent equilibrium value M [20,21], oposed side and alignment on the average diffusion

Fig. 5: Eq.
Water3uptake/loss
of specimens
during absorption, desorption,
and reabsorption
C.
was used
for approximation,
as the method
wasat 80 coefficient
of composite specimens
during water ab

specifically designed for thick polymeric specimens sorption, desorption, and reabsorption at 80oC. As

[18]. The calculated M value was then used for data

diffusion

C fitting via Eq. 4 to compute the effective

D
(a)
coefficient D of specimens during water absorp
tion, desorption, and reabsorption. All specimens

show high moisture diffusivity during desorption,

followed by reabsorption, then absorption. All com

posite specimens have low diffusivities than epoxy

matrix during water absorption. During desorption,

the diffusivities of composite specimens are higher

than epoxy matrix except specimen D. During re

absorption, the diffusivities of composite specimens

are higher than epoxy matrix except specimen C.

The higher diffusivity of composites than their ma

trices during diffusion is usually an indication of

(b)
filler-matrix interphase degradation [21].

The use of Eq. 4 in describing the water uptake and

2: Diffusionparameters
parameters of specimens
TableTable
2: Diffusion
of specimens

Absorption
Specimen
M (%) D (mm2/h)
VE
1.5466 0.0488
EP
3.1929 0.0280
A
2.5242 0.0245
B
2.5806 0.0194
C
2.8166 0.0187
D
2.8776 0.0174

142

Desorption
M (%) D (mm2/h)
1.5983 0.1987
2.8233 0.1673
2.6936 0.2242
2.6297 0.1993
2.6899 0.2144
2.6192 0.1569

Reabsorption
M (%) D (mm2/h)
1.6020 0.1398
2.6074 0.0913
2.5382 0.0978
2.5109 0.0969
2.5238 0.0820
2.3981 0.0917

filler a) exposed side and

Fig. 6: Effect of triangular bar

b) alignment on average diffusion

coefficient of compos
ite specimens.

Advanced Composites Letters, Vol. 21, Iss. 6, 2012

Fig. 6: Effect of triangular bar filler a) exposed side and b) alignment on average diffusion coefficient of co

Investigation of Water Diffusion in Triangular Bar-Reinforced Composites

shown from the results during absorption and desorption in Fig. 6a, diffusion is slow when base side
of triangular bar fillers is exposed to diffusion, and
fast when sloped side is otherwise exposed. Orienting the base side of triangular bar fillers outward in
the composite reduces the available area of permeable epoxy matrix for water absorption and desorption. On the other hand, results shown in Fig. 6b
describe the effect of filler alignment in water diffusion. In parallel alignment, diffusion resistance
is mainly from the epoxy matrix and presence of
slits between triangular bars. Aligning the bars in
staggered configuration contributes additional resistance to transport by increasing the path length
of diffusing water molecules in the composite. The
resulting effect, known as wiggling in flake barrier
films [4-11,15-17], is due to increased tortuosity of
the composite at staggered alignment of triangular
bar fillers.
4. CONCLUSIONS
Reinforcing a permeable matrix with aligned, impermeable triangular elements could result to a
composite material with single axis-, filler orientation-dependent diffusion behaviour. To test this idea
experimentally, this work used cured epoxy and
vinyl ester to represent the permeable and impermeable component of the composite, respectively.
Water was chosen as the diffusing fluid, and absorption-desorption-reabsorption tests were performed
on specimens at 80oC. Percent weight change curves
of specimens show weight gain during absorption
and reabsorption, and weight loss during desorption. Weight change values of polymer composite
specimens fall between the values of pure epoxy
and vinyl ester specimens. Water uptake of specimens during absorption is lower than during reabsorption. The result is related to the generation of
additional free volume in the specimens due to the
time-dependent properties of glassy polymers and
irreversible damage sustained during water absorption and desorption. The calculated diffusion coefficients of specimens show high water diffusivity during desorption, followed by reabsorption, and then
absorption. Moisture diffusivity of composite specimens are found to be lower than pure matrix resin
during absorption and higher during desorption and
reabsorption, indicating fast water transport at the
local, degraded interphase regions. The calculated
diffusion coefficients also reveal filler orientationdependent transport in composite specimens. Diffusion is slow when base side of triangular elements is
exposed to diffusion, and it is fast when the sloped
side of triangular elements is exposed. Exposing the
Advanced Composites Letters, Vol. 21, Iss. 6, 2012

base side of triangular elements to diffusion reduces

the available area of permeable matrix for transport.
Diffusion is also reduced when the triangular elements are arranged in staggered alignment due to
increased path length of diffusing molecules in the
composite.
ACKNOWLEDGEMENTS
The authors are grateful to The Hitachi Scholarship
Foundation (HSF) for financial support.
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Advanced Composites Letters, Vol. 21, Iss. 6, 2012