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1996 - Kevlar Fiber Epoxy Adhesion and Its Effect On Composite Mechanical and Fracture Properties by Plasma and Chemical Treatment

Plasma and chemical treatments were used to modify Kevlar 49 fibers to improve adhesion with epoxy resin. Scanning electron microscopy, X-ray photoelectron spectroscopy, and static secondary ion mass spectroscopy identified changes to the fiber surface topology and chemistry after treatments. Short-beam and T-peel tests showed improved interlaminar shear and peel strengths between fiber and resin with plasma and chlorosulfonation treatments, though fiber/matrix bonding was a minor factor in toughness. Fractography revealed treatment often changed failure from the interface to fiber pull-out or breaking.

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0% found this document useful (0 votes)
48 views14 pages

1996 - Kevlar Fiber Epoxy Adhesion and Its Effect On Composite Mechanical and Fracture Properties by Plasma and Chemical Treatment

Plasma and chemical treatments were used to modify Kevlar 49 fibers to improve adhesion with epoxy resin. Scanning electron microscopy, X-ray photoelectron spectroscopy, and static secondary ion mass spectroscopy identified changes to the fiber surface topology and chemistry after treatments. Short-beam and T-peel tests showed improved interlaminar shear and peel strengths between fiber and resin with plasma and chlorosulfonation treatments, though fiber/matrix bonding was a minor factor in toughness. Fractography revealed treatment often changed failure from the interface to fiber pull-out or breaking.

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© © All Rights Reserved
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Kevlar Fiber-Epoxy Adhesion and Its Effect on Composite

Mechanical and Fracture Properties by Plasma


and Chemical Treatment

S. R. WU, C. S. SHEU, and S. S. SHYU*

Department of Chemical Engineering, National Central University, Chung-Li, Taiwan 320, Republic of China

SYNOPSIS

Kevlar 49 fibers were surface-modified by NH3-, 02-,and H,O-plasma etching and chlo-
rosulfonation and subsequent reaction with some reagents (glycine, deionized water, eth-
ylenediamine, and 1-butanol) to improve the adhesion to epoxy resin. After these treatments,
the changes in fiber topography, chemical compositions of the fiber surfaces, and the surface
functional groups introduced to the surface of fibers were identified by SEM, XPS, and
static SIMS. Interlaminar shear strength (ILSS) and T-peel strength between the fiber
and epoxy resin, as measured by the short-beam test and T-peel test, were remarkedly
improved by gas plasma and chlorosulfonation (0.1% and 0.25% C1SO3H at 30 s). However,
from the results of similar Glc values of the treated and untreated fiber composites, it is
clear that the fiber/matrix interfacial bond strength is only a minor contributor to Glc.
SEM was also used to study the surface topography of the fracture surfaces of composites
in T-peel test. It could be seen from SEM observations that the improvement of fiber/
matrix interfacial bond strength often accompanied a change in fracture mode from the
interface of fiber/epoxy resins to the fiber fibrillation and the resins. 0 1996 John Wiley &
Sons, Inc.

INTRODUCTION energy, surface roughness, and polar groups on the


surface. All these would improve the adhesion be-
The use of plasma and chemical treatment to in- tween the fiber and matrix.
crease the interfacial bonding of the fiber to the ma- This study examines the effects of plasma and
trix has been known for a considerable chemical treatment on the mechanical behavior of
Kevlar aramid [PPTA; poly(p-phenylene tere- Kevlar 49 fiber/epoxy laminates. Scanning electron
phthalamide)] fiber is widely used in the manufac- microscopy (SEM) was used to characterize the
ture of advanced composites. This has been due to changes in fiber topography and the fracture surfaces
major advances in composite mechanical properties of fibers. The surface compositions and chemical
that have resulted from the use of the stiffness, high structures of modified fibers were analyzed by X-
fracture strain, and low-density reinforcing fibers. ray photoelectron spectroscopy (XPS) and static
However, the adhesion between Kevlar fibers and secondary ion mass spectrometry (SSIMS). The
most matrices is poor, due to the high crystallinity double cantilever beam (DCB) method was used to
leading a chemically inactive surface and the rela- measure toughness, GIC. The short-beam method
tively smooth surface of the fiber. Fiber-surface was used to measure the interlaminar shear strength
modification results in improved wettability, surface (ILSS) of laminates. The T-peel test was used to
measure the T-peel strength of laminates. After
these tests, we can further realize the mechanical
* To whom all correspondence should be addressed.
Journal of Applied Polymer Science, Vol. 62, 1347-1360 (1996)
and fracture properties of Kevlar 49 fiber compos-
0 1996 John Wiley & Sons, Inc. CCC 0021-8995/96/091347-14 ites.

1347
1348 WU, SHEU, AND SHYU

EXPERIMENTAL gold-coated for subsequent examination in a Hitachi


53-2300 scanning electron microscope, Both the sur-
Materials face topography of fibers and the fracture surfaces
All the aramd fabrics used in this study were woven of composites were investigated to assess and com-
from Kevlar 49 fibers [poly(p-phenylene tere- pare the fiber/matrix adhesion and fracture mode
phthalamide)] (PPTA; E. I. du Pont de Nemours) for each composite.
in the form of 1140 denier, style 281. The fabrics
were cleaned successively with 1,2-dichloroethane, X-ray Photoelectron Spectroscopy (XPS)
methanol, and deionized water to remove surface
XPS data for the treated and untreated specimens
contaminants prior to their use, followed by drying
were obtained on a Perkin-Elmer PHI 590 SAM/
at 100°C in a vacuum oven for 12 h before plasma
ESCA instrument, equipped with a Digital PDP 11/
and chemical treatment. The epoxy resin was a
04 computer using a MgKa (hv = 1253.6 eV) X-ray
commercial diglycidyl-type resin (Epon 828, Shell)
and the curing agent was 4,4'-diaminodiphenyl- source (a voltage of 12 keV, a wattage of 250 W, and
a pressure lower than 5 X lo-' Pa). Survey scans
methane (DDM, Merck). Anhydrous ammonia
(0-1000 eV binding energy) to determine the ele-
(99.99%), oxygen gas (99.99%), and deionized water
mental composition of the fibers were run at an an-
were used for plasma treatment. All the other re-
agents used for chemical treatment were purchased alyzer pass energy of 100 eV. High-resolution spectra
were obtained at a pass energy of 15 eV. The atomic
from Merck.
sensitivity factor (ASF) of the elements was consid-
ered in calculating the atomic fraction ratios.
Plasma Treatments
Following the cleaning procedure, the aramid fabrics Static Secondary Ion Mass Spectroscopy (SSIMS)
were surface-modified by plasma etching carried out
in a SAMCO Model BP-1 bell jar plasma reactor. The static SIMS experiments were performed using
The gases used for the plasma treatments were am- a Cameca IMS-4f ion microscope equipped with a
monia, oxygen, and water vapor. After evacuating Cs+ ion source and a magnetic sector mass analyzer.
to a pressure lower than 8 mTorr, the reactor was The primary ion source was 10 keV Cs+ operated at
purged with each gas for three times and then the a current of 10 pA and at a pressure lower than 1.5
chamber pressure was maintained at 0.2 Torr X lo-' Pa. A defocused beam was rastered over an
throughout the plasma treatment processes. Pieces area of 50 X 50 pm. An electron flood gun set at 4.5
of aramid fabric were treated at 30 W of rf (radio keV was used to minimize sample charging.
frequency, 13.56 Mhz) plasma power in each plasma
environment for 15 s to 10 min treatment time. After Kevlar/Epoxy Composite Fabrication
plasma treatment, the samples were left there for
15 min post-treatment to allow for the decay of re- Kevlar/epoxy composites were fabricated from un-
sidual surface radicals. treated, plasma-treated, and chemical-treated fab-
rics and the diglycidyl-type resin (Epon 828, Shell)
and 4,4'-diaminodiphenylmethane (DDM, Merck).
Chemical Treatment The fabrics were impregnated by passing samples
The dried fabric pieces were immersed in a solution through a solution containing the Epon 828, DDM,
of chlorosulfonic acid in dichloromethane with stir- and acetone mixed in a 4 : 1 : 4.8 weight ratio. The
ring at -10°C and the subsequent reaction of resulting samples were dried a t 25°C for 30 min
-S0,Cl groups were converted to other derivatives and then a t 70°C for 20 min. The impregnated fab-
by immersion in a solution of the appropriate re- ric composites (8 piles for the double cantilever
agents (e.g., deionized water, glycine, ethylenedi- beam method, 16 piles for the short-beam method,
amine, and 1-butanol) with stirring a t 25°C. The and 2 piles for the T-peel test) were then cured
acid concentration and reaction time were varied. under ambient conditions for 2 h a t 80°C followed
Then, the treated fabrics were washed and dried. by 2 h at 150°C (heating rate, 3"C/min) a t a pres-
sure of 150 psi. The mold was cooled to room tem-
perature before the pressure was released. The resin
Scanning Electron Microscopy (SEM)
weight fraction in the laminates was approximately
Treated fibers, untreated (control) fibers, and the 32%. The Tg of the laminate was about 152"C,
fracture surfaces of composites were mounted and which was measured using a 910 differential scan-
KEVLAR FIBER-EPOXY ADHESION 1349

ning calorimeter module (DuPont Instruments) at men (2 plies) dimensions were 90 X 11 X 0.25 mm,
a heating rate of 20"C/min in a nitrogen atmo- with a starter crack implanted between two layers.
sphere (flow rate = 20 mL/min). The condition for the T-peel test is the same as for
the short-beam method. The T-peel test was per-
formed by using an Instron, pulling the surfaces
Interlaminar Fracture Energy apart at a rate of crosshead movement 25 mm/min.
The mode I fracture toughnesses, GIc, of the lami- The T-peel strength in gw/cm, W ,is calculated from
nates is given by the double cantilever beam (DCB) W = F/B, where F is the force applied to the joint
method and B is the width of the strip. The T-peel strength
was the average of more than 10 measurements.
- P2dC
3PV -
GIc = - --
2aB 2B da
RESULTS AND DISCUSSION
where P is the applied force in Newtons; V; the
loadline displacement in mm; a, the crack length in Fiber Surface Topography
mm; B, the specimen width in mm; and C, the spec- Plasma Treatment
imen compliance (V/P). Beam specimens (8 plies)
of dimensions 90 X 11 X 1 mm containing a starter The SEM photomicrographs of untreated and
crack implanted between the fourth and fifth layers plasma-treated fiber surfaces are shown in Figure 1.
prior to autoclaving were cut from composite panels. The control fiber surface is quite smooth, as seen in
The starter crack consisted of a 15 X 11 mm strip Figure l(a). No significant change in the surface
of aluminum foil which had been single-folded and texture can be detected after NH3-, 02-, and H20-
was embedded in one edge of the laminate. Speci- plasma treating at 30 W for 10 min, as seen in Figure
mens were tested a t 25°C on an Instron tester at a l(b)-(d), respectively. This result is the same as the
crosshead speed of 2 mm/min. Each reported GIc results obtained by Allred et al.23 in their NH3-
value is the average of more than 10 successful mea- plasma studies and Kupper and Schwartz3 in their
surements. Ar-, N2-,and CO-plasma studies of aramid (Kevlar
49) fibers, which did not exhibit any change in sur-
face topography after plasma treatment. In our lab-
lnterlaminar Shear Strength (ILSS) oratory, Kevlar 149 fibers had been surface-treated
The interlaminar shear strength of laminates was with plasma to modify their surface structures.8-"
determined using the short-beam method by ASTM- All the three plasma treatments roughened the fiber
D-2344-76. Specimen (16 plies) dimensions were surfaces and the etching abilities among different
nominally 16 X 11X 2 mm, with a span to thickness gases is O2 > H 2 0 > NH3. This result is different
ratio of 5. The condition the test specimen and the from the result by using Kevlar 49 fibers, so the
test in an enclosed space was maintained at 23°C etching effects is only a minor contributor to the
and 50% relative humidity. Test the specimen at a interfacial bonding of Kevlar 49 fiber to the epoxy
rate of crosshead movement 0.5 mm/min. in plasma treatment.
The interlaminar shear strength, 7,for the short-
beam test is calculated by the expression Chemical Treatment
After the treatment with 0.25% chlorosulfonic acid
7=-
3P for 15 s, no change in the surface texture was de-
4Bh tected [Fig. 2(a)]. But at higher concentrations of
chlorosulfonic acid and longer reaction times, the
where P is the maximum load in Newtons; B , the fiber surfaces were etched more vigorously, as seen
width of specimen in m; and h, the thickness of in Figure 2(b)-(d). After the treatment with 0.25%
specimen in m. Each reported ILSS value is the av- chlorosulfonic acid for 5 min, the fibers revealed
erage of more than 10 successful measurements. many fragments on the surface, as seen in Figure
2(b). Fibers treated with 1%chlorosulfonic acid for
2.5 and 5 min showed many shallow and discontin-
1-peel Strength
uous grooves along the axial direction of the fiber
The T-peel strength of laminates was determined [Fig. 2(c) and (d)]. The significant change in the
using the T-peel test by ASTM-D-1876-72. Speci- topography of the fiber surfaces was due to the in-
1350 WU, SHEU, AND SHYU

Figure 1 SEM photographs of Kevlar 49 fiber surfaces treated with different plasma
treatments: ( a ) control; ( b ) treated by NH,-plasma at 30 W for 10 min; ( c ) treated by 02-
plasma at 30 W for 10 min; ( d ) treated by H20-plasma at 30 W for 10 min.

complete etching by the higher concentration of ture formula (PPTA),there are two oxygen atoms,
chlorosulfonic acid. The subsequent treatment of two nitrogen atoms, and 14 carbon atoms per re-
chlorosulfonated fibers (0.25% chlorosulfonic acid peating unit of Kevlar. It can be seen from Table I
for 15 s) with glycine, water, ethylenediamine, and that the element analysis result for the control fibers
1-butanol did not detect further change in the fiber- is quite in agreement with the theoretical calcula-
surface topography. tion; however, the surface composition of the control
fibers is significantly different from the bulk. For
the control fiber, the oxygen on the surface is about
XPS Analysis 2.5 times that in the bulk. The difference may be
due to the possible surface o x i d a t i ~ n ' and/or
~ * ~ ~ sur-
Plasma Treatment
face finishes used during fiber fabrication.
Kevlar 49 fiber surfaces modified by NH3-, 02-, and Table I also shows that the surface contents of
H20-plasmatreatment were analyzed by XPS. Table nitrogen increase from 21.6 to 27.3% after 3 min
I summarizes the atomic percentages of carbon, ox- NH3-plasma treatments a t 30 W. This indicates that
ygen, and nitrogen and the atom ratios of N/C and the nitrogen atoms were incorporated into the fiber
O / C for the control and modified fiber surfaces. The surfaces during NH3-plasma discharge. With 30 W
chemical composition of Kevlar 49 fibers examined 02-plasmatreatment for 3 min, the surface oxygen
by a Perkin-Elmer Model 2400 elemental analyzer content increases. This can be explained by surface
is also listed in Table I. For the theoretical com- oxidation during the 02-plasma exposure. With 30
position of Kevlar 49 fibers, according to the struc- W H20-plasma treatment for 3 min, the surface
KEVLAR FIBER-EPOXY ADHESION 1351

Figure 2 SEM photographs of Kevlar 49 fiber surfaces treated with C1S03H: ( a ) 0.25%
ClS03H for 15 s; ( b ) 0.25% CISOBHfor 5 min; ( c ) 1% C1S03H for 2.5 min; ( d ) 1%C1S03H
for 5 min.

contents of each element were changed. It is evident Chemical Treatment


that the high concentration of atomic oxygen gen-
erated in H20-plasma was incorporated into fiber The results of chemical treatment are shown in Ta-
surface during plasma di~charge.'~ ble 11. After chlorosulfonation, the surface contents

Table I ESCA Analysis Results of Surface Composition for Plasma-treated Kevlar 49 Fibers

Atomic Percent Atomic Ratio


Surface Treatment
Conditions C 0 N N/C o/c
Theoretical 77.8 11.1 11.1 0.143 0.143
EA" 74.0 14.4 10.7 0.143 0.192
Controlb 42.9 35.5 21.6 0.503 0.828
NH3-plasma 30 W 3 min 39.2 33.5 27.3 0.696 0.855
02-plasma 30 W 3 min 38.5 42.3 19.2 0.499 1.099
H20-plasma 30 W 3 min 39.1 37.7 23.2 0.593 0.964

a EA: elemental analysis results of the control sample.


Control: 1,2-dichloroethane washed + methanol washed + deionized water washed + dried.
1352 WU, SHEU, AND SHYU

Table I1 ESCA Analysis Results of Surface Composition for Kevlar 49 Fibers

Type of Atomic Percent Atomic Ratio


Surface
Treatment C 0 N S N/C o/c
Theoretical 77.8 11.1 11.1 - 0.143 0.143
Control 42.9 35.5 21.6 - 0.503 0.828
cs 30.7 36.3 12.2 10.0 0.397 1.182
cs + w 36.9 36.6 17.6 14.9 0.570 1.184
+
CS G 33.2 44.2 17.9 4.7 0.539 1.331
CS + E 40.6 27.2 25.0 7.2 0.616 0.670
CS + B 51.4 26.0 14.8 7.8 0.288 0.506

CS: chlorosulfonation (0.25%chlorosulfonicacid in dichloromethanefor 0.25 min); W: 100%deionized water (hydrolysis)


for 15 min; G: 1.0% glycine (in 1,4-dioxane)for 15 min; E: 15% ethylenediamine (in 1,2-dichloroethane)for 15 min; B:
15% 1-butanol (in 1,4-dioxane) for 15 min.

of each element are markedly changed. Another ele- mass of 108 and 112 amu [Fig. 3(b)]. These peaks
ment, sulfur, appeared and the -S0,Cl groups were can be assigned t o [C,H4(NH2),]- and [C-
formed. The subsequent reaction with glycine, C6(NHz)-C]-. This may indicate that at least pri-
deionized water, ethylenediamine, and 1-butanol mary amino groups are formed after NH3-plasma
also changed the surface composition of the fiber. treatment. Figure 3(c) shows the negative ion spec-
This procedure may introduce new functional groups trum of Kevlar 49 fiber treated by 30 W 02-plasma
on the fiber surface. for 3 min. In comparison with Figure 3(a), many
peaks disappeared in the mass ranges of 76, 84-86,
92, and 96-98 amu. There is a lack of aromatic ring
Static SlMS Analysis
fragments and this means that the high concentra-
Plasma Treatment tion of oxygen in plasma led t o extensive damage of
the aromatic ring and polymer backbone.26 After
Figure 3(a) reveals the negative SSIMS spectrum of
the control fiber surfaces. Although a 1-280 amu treatment with H20-plasma a t 30 W for 3 rnin [Fig.
3(d)], relatively high intensities of peaks a t 0-(16),
mass scan was performed during the spectrum
OH-(17), and Oi(32) are found, and there are
acquisition, the spectrum is dominated by peaks
which appear in the mass range less than 100 amu. many new peaks in the mass of 107 [C,H(OH),]-,
T h e negative ion spectra exhibit significant inten- 109 [C,H,(OH),]-, 110 [C,H,(OH)J, 114 [C-
sities for 0-(16), OH-(17), CN-(26), 0,(32), and C,H(OH) -C]-, 119 [C-CC,H(OH),]-, and 136
[ c -C,H(OH),]-. These oxygen-containing frag-
CON-(43). The relatively high intensity of oxygen-
ments result from the large amount of oxygen atom
containing fragments (0-, OH-, and 0,) in the
incorporated into the fiber surface.25
spectrum are observed. This means there is a n ox-
idized layer a t the control fiber surface. T h e high
Chemical Treatment
intensity of the peak at 26 amu due t o CN- origi-
nating from amine group of the PPTA polymer chain After treatment with 0.25% chlorosulfonic acid for
is found. Furthermore, weak PPTA-related frag- 2.5 min, the spectra (not shown) reveal the peak of
ments [C,H,]- ( n = 0-4), [C,H,-CC]- ( n = 0-2), C6H3S-(107). This means that the sulfur-containing
[C-C&,-cC]- ( n = 0-2), [C6H4-CON]-, functionality was introduced into the fiber surface
[C6H4NH2]-,and [CO-c6-CON]- due to aro- by chlorosulfonation treatment.
matic ions are observed in the higher mass range.
Significant “fingerprint” organic fragment ions are
Interlaminar Fracture Energy
capable of providing structural information about
the repeating unit of PPTA [i.e., (--0- The GIc values for the untreated and treated aramid/
C(jH4 -CO -N H -C6H4- N H -),I. epoxy composites, determined from eq. ( l ) , is a
After treatment with 30 W NH3-plasma for 3 min, function of the crack length. All GIc vs. crack length
the negative ion spectrum is similar to t h a t of the graphs exhibited the characteristic R curves asso-
control fiber. But new peaks can be observed in the ciated with fiber bridging. The results show that
KEVLAR FIBER-EPOXY ADHESION 1353

MASS (amu)

Figure 3 ( a ) Negative SSIMS spectrum of untreated (control) Kevlar 49 fibers. ( b )


Negative SSIMS spectrum of Kevlar 49 fibers treated by NH,-plasma at 30 W for 3 min.
( c ) Negative SSIMS spectrum of Kevlar 49 fibers treated by 02-plasma at 30 W for 3 min.
( d ) Negative SSIMS spectrum of Kevlar 49 fibers treated by H,O-plasma a t 30 W for 3
min.

there is no significant change in interlaminar frac- lnterlaminar Shear Strength


ture energy after plasma and chemical treatments
Plasma Treatment
(Figs. 4 and 5). It was found that the interlaminar
fracture energy of the composite is sensitive to and The interlaminar shear strength (ILSS) of the ar-
controlled by the fracture toughness of the matrix amid/epoxy composites was calculated from eq. (2).
resin up to a limiting resin toughness, beyond which Results of the test are shown in Tables I11 and IV.
the interlaminar fracture energy does not increase A marked increase in the apparent ILSS obtained
in the same proportion as that of the m a t r i ~ So,
.~ for the laminate prepared from plasma-treated fiber
the fiber/matrix interfacial bond strength is only a is due to an increase in the fiber/matrix interface
minor factor to GIc values for fiber composites. The strength. The effects of the treatment time on the
appearance of large internal cracks in some fila- ILSS of the fiber treated by various plasma at a
ments could only happen at a higher concentration power level of 30 W is shown in Figure 6. However,
of chlorosulfonic acid. This may cause lower Grc val- a treatment time longer than 5 min did not increase
ues because the crack growth occurred on the fila- the ILSS further in the case of the plasma treatment.
ments, rather on the matrix or interface. Otherwise, The degree of the increase in ILSS among different
there is no significant change in Glc values. plasmas is NH3 > O2 > H 2 0 . The increase in the
1354 WU, SHEU, AND SHYU

Figure 4 Dependence of the critical strain energy release rate of the Kevlar 49 fiber-
epoxy system on the various plasma at 30 W power for 5 min.

ILSS of the plasma-treated samples can be eluci- Chemical Treatment


dated in that the plasma treatments incorporated
some newly formed functionalities onto the fiber Figure 7 shows the effect of the chlorosulfonic acid
surface which would improve the wettability and in- concentration and treatment time on the ILSS. The
crease the surface energy of the fiber surface. Other ILSS was markedly improved by 0.1 and 0.25%
possible factors such as chemical bonding between chlorosulfonic acid treatment for 30 s. But higher
the newly formed functionalities and epoxy resin concentrations of chlorosulfonic acid and longer re-
may also be contributing to the increase in ILSS. action times caused a lower ILSS. This may be due

Figure 5 Dependence of the critical strain energy release rate of the Kevlar 49 fiber-
epoxy system on the various concn of CISOBHat 30 s.
KEVLAR FIBER-EPOXY ADHESION 1355

Table I11 Mechanical ProDerties of Aramid/Epoxs Composites After Plasma Treatment

Plasma Interlaminar Fracture Interlaminar Shear T-peel Strength


Treatment Energy (J m-*) Strength (MPa) (gw/cm)

None 604 f 67 20.6 f 1.2 350 f 25


NH,-plasma
15 s a t 30 W 25.3 f 0.2 550 f 15
1 rnin at 30 W - 30.9 f 0.5 570 f 30
5 rnin at 30 W 617 f 52 33.1 ? 1.2 617 f 32
10 rnin at 30 W - 30.6 f 0.9 583 k 26
0,-plasma
15 s at 30 W - 25.6 f 1.5 400 f 15
1 rnin at 30 W - 27.4 f 0.6 533 f 26
5 rnin at 30 W 594 f 85 29.2 f 1.3 566 2 30
10 rnin a t 30 W - 28.9 f 1.1 573 f 28
H,O-plasma
15 s at 30 W 22.8 f 1.1 450 f 27
1 rnin at 30 W - 25.0 f 0.3 466 f 25
5 rnin at 30 W 602 f 62 27.5 f 0.6 533 f 21
10 rnin at 30 W - 22.5 zk 0.3 433 -t 24

to that the chlorosulfonic acid is capable of pene- addition to the interfacial bonding, the fiber strength
trating the fiber and causing significant disruption is also an important factor for the ILSS in the short-
of the microstructure and strength of the fiber. In beam method.

Table IV Mechanical Properties of Aramid/Epoxy Composites After Chemical Treatment

Interlaminar Interlaminar
Fracture Shear T-peel
Plasma Energy Strength Strength
Treatment Time (rnin) (J m-') (MPa) (gw/cm)

None 604 f 67 20.6 f 1.2 350 f 25


Chlorosulfonation
concn (wt %)
0.1 0.25 - 27.2 f 0.6 413 f 23
0.1 0.5 640 k 72 31.6 f 0.3 533 f 21
0.1 2.5 27.3 f 0.2 520 f 27
0.1 5 - 25.1 f 0.4 346 f 21
0.25 0.25 - 25.1 f 0.3 467 f 17
0.25 0.5 657 f 63 31.4 f 0.5 480 f 21
0.25 2.5 - 19.4 f 0.7 427 f 23
0.25 5 - 15.4 f 0.3 213 f 16
1 0.25 - 20.0 f 0.3 293 f 17
1 0.5 492 f 67 15.0 f 0.7 237 ? 1 3
1 2.5 - 10.0 f 0.7 200 f 10
1 5 8.0 f 0.6 146 f 10
Chlorosulfonation (concn 0.25% for 15 s)/
glycine (concn 1% for 15 min) 26.3 f 0.4 492 f 17
Chlorosulfonation (concn 0.25% for 15 s)/
deionized water (15 min) 25.71 f 0.5 485 f 21
Chlorosulfonation (concn 0.25% for 15 s)/
ethylenediamine (concn 15% for 15 min) 27.68 f 0.5 505 f 21
Chlorosulfonation (concn 0.25% for 15 s)/
1-butanol (concn 15% for 15 min) 24.92 f 0.4 445 f 17
1356 WU, SHEU, AND SHYU

Figure 6 Dependence of the interlaminar shear strength of the Kevlar 49 fiber-epoxy


system on the treatment time of fiber treated by various plasma at 30 W power level.

In this study, 0.25% chlorosulfonic acid and 15 s strength among different plasmas is NH3 > O2
treatment time were selected as the initial conditions > H20. The T-peel strength was shown to increase
prior to further reaction treatment. Table IV shows with increasing treatment time up to 5 min, after
the ILSS of the composite which was posttreated which there was no further increase. These results
with glycine, deionized water, ethylenediamine, and are similar to interlaminar shear strength after
1-butanol. The results suggest that the posttreat- plasma treatment.
ment does not introduce reactive groups into the
fiber surface effectively and may cause the fiber Chemical Treatment
strength decrease. The surface modification with
reactive functional groups and improved the bonding The effect of the chemical treatment on the T-peel
of aramid fibers in epoxy composites can be attained strength is shown in Figure 9. These results suggest
by chlorosulfonation that does not require subse- that an improvement is realized by the introduction
quent reaction with any reagents. of -SOC1, groups, but higher concentrations of
chlorosulfonic acid and longer reaction times would
not enhance the T-peel strength further. This may
T-peel Strength be due to that the fiber strength decreases [Fig. 2(c)
and (d)] with unsuitable treatment. The effects of
Plasma Treatment
the chemical treatment of the fiber surfaces on the
Composite laminates for preliminary evaluation of T-peel strength are also quite similar to that of the
the T-peel strength were performed by ASTM-D- interlaminar shear strength.
1876-72. Figure 8 shows the T-peel strength for
composites containing untreated and plasma-treated
fibers. There is no significant difference in the tensile Fracture Surface Analysis of the T-peel Test
strength between the control and plasma-treated Specimens
Kevlar 49 fiber." Hence, the increase in T-peel Plasma Treatment
strength of the two-ply structure is considered to be
due to significantly enhanced bonding at the inter- The fracture surfaces of the T-peel test specimens
face. These results indicate that at least some co- were examined by SEM. As shown in Figure 10(a),
valent bonds between the new functional groups at the untreated fiber surface after the T-peel test is
the plasma-treated fiber surface and the epoxy resin quite smooth. No resin remains on the surface and
were formed. The degree of the increase in T-peel only a few torn filament skins appeared. Therefore,
KEVLAR FIBER-EPOXY ADHESION 1357

Figure 7 Dependence of the interlaminar shear strength of the Kevlar 49 fiber-epoxy


system on the treatment time of fiber treated by various concn of C1SO3H.

the fracture mode of the untreated composite is at are significant differences between the failure sur-
the interface of the fiber/matrix. This means that face of untreated peel specimens and those of
the interfacial bonding is poor and the interface specimens prepared from plasma-treated fiber.
structure cannot transfer stress effectively. After 30 W NH3-plasma treatment for 10 min [Fig.
The fracture surfaces of the plasma-treated 10(b)],the fracture surface shows some fiber skins
specimens are shown in Figure IO(b)-(d). There and fracture resin left in the resin grooves, which

Figure 8 Dependence of T-peel strength of the Kevlar 49 fiber-epoxy system on the


treatment time of fiber treated by various plasma at 30 W power level.
1358 WU, SHEU, AND SHYU

Figure 9 Dependence of T-peel strength of the Kevlar 49 fiber-epoxy system on the


treatment time of fiber treated by various concn of CIS03H.

are not regular and smooth. After 30 W 02-plasma CONCLUSIONS


treatment for 10 min [Fig. lO(c)], the fracture sur-
face reveals axially split filaments and torn fila-
ment skins. A fibril-like structure of the fracture Plasma and chemical treatment of aramid fibers re-
surface is also observed in the case of the HzO- sults in changes in the interface sensitive mechanical
plasma treatment [Fig. 10(d)].At the same control properties of aramid epoxy composites. Interlaminar
condition, the fracture surface of the H20-plasma shear strength and T-peel strength between the fiber
treatment is more regular and smoother than that and epoxy resin were markedly improved by plasma
of the NH3- and 02-plasma treatment. However, treatment and chlorosulfonation. It was suggested
the peeling of fibrils in the T-peel test specimen that covalent bonding of the epoxy resin with func-
shows that the interfacial bond strength is greater tional groups on fiber surfaces could be a major fac-
than is the filament internal strength. This may tor in the interfacial bond strength of the compos-
be due to the improvement of the interfacial ites. But the decrease in ILSS and T-peel strength
bonding and the weakening of the skin-core was significant when the fiber was treated at a higher
strength by the plasma treatment. concentrations of chlorosulfonic acid or longer re-
action times. Such treatment caused the fiber sur-
faces to be etched vigorously and the decrease in
Chemical Treatment
fiber strength. The postchemical treatments did not
The surface of the chemical-treated specimen after further change the ILSS and T-peel strength. This
the T-peel test was quite similar to the fracture sur- may be due to that the posttreatment did not intro-
face of the plasma-treated specimen. But using duce reactive groups into the fiber surface effectively
higher concentrations of chlorosulfonic acid and and caused the fiber strength decrease. Because the
longer reaction times, large internal cracks [Fig. fiber/matrix interfacial bond strength is only a mi-
1l(a) and (b)] appeared in some filaments and torn nor contributor to GIc and the Glc values of the com-
filament skins over extensive distances were also posite depends mainly on the fracture toughness of
observed. This means that the failure mode changed the matrix resin, any pretreatment of the reinforced
to the fiber fibrillation and the chlorosulfonic acid fiber would not significantly change the GIc values.
may penetrate inside the fiber, destroying the struc- SEM observations show that the improvement of
ture of the fiber. So, the choice of the conditions in fiber /matrix interfacial bond strength is often ac-
chemical treatment is very important. companied by a change in the fracture mode from
KEVLAR FIBER-EPOXY ADHESION 1359

(4 (4
Figure 10 Fracture surfaces of T-peel test specimens for Kevlar 49 fiber-epoxy system:
( a ) control; ( b ) treated by NH3-plasma at 30 W for 10 min; ( c ) treated by O,-plasma at
30 W for 10 min; ( d ) treated by H,O-plasma a t 30 W for 10 min.

(a) (b)
Figure 11 Fracture surfaces of T-peel test specimens for Kevlar 49 fiber-epoxy system
treated by 1%C1SO3H for ( a ) 2.5 min and ( b ) 5 min.
1360 WU, SHEU, AND SHYU

the failure at the interface of fiber/epoxy resins to 14. M. Takayanagi, S. Ueta, W.-Y. Lei, and K. Koga,
the fiber fibrillation and the resins. Polym. J., 1 9 , 4 6 7 (1987).
15. L. S. Penn, G. C. Tesoro, and H. X. Zhou, Polym.
Compos., 9,184 (1988).
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