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COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 67 (2007) 20272035
www.elsevier.com/locate/compscitech

Controlled interfacial adhesion of Twaron aramid bres in


composites by the nish formulation
Pieter J. de Lange a,*, Peter G. Akker a, Edith Mader b, Shang-Lin Gao b,
Warawan Prasithphol c, Robert J. Young c
a

Teijin Twaron Research, Department of QRF, Arnhem, The Netherlands


b
Leibniz Institute of Polymer Research, Dresden, Germany
School of Materials, University of Manchester, Manchester, M1 7HS, UK
Received 17 October 2006; accepted 30 November 2006
Available online 21 December 2006

Abstract
In order to investigate the eect of oily nish components on the interphase strength of aramid-epoxy composites, Twaron aramid
yarn has been treated in a one step nish process with combinations of adhesion improving (epoxy-amine) components and processability improving (oily) components. Variations in the macroscopic composite properties (compression shear strength and transverse tensile
strength) as a function of the amount of oil are very well predicted by micro-mechanical adhesion results from single lament pull out
measurements and micro Raman spectroscopy. They can be explained by dierences in the amount and distribution of epoxy, xated to
the yarn surface, shown by XPS, contact angle measurements and atomic force microscopy.
 2006 Elsevier Ltd. All rights reserved.
Keywords: A. Aramid bre; A. Polymermatrix composites; B. Surface treatments; B. Interphase; B. Interfacial strength

1. Introduction
Aramid bres are used as reinforcements in high performance composites, e.g. in aerospace applications, but they
are also used extensively as reinforcements for rubber, tires,
plastics, and concrete. The employing aramid bres as reinforcements have been limited by poor brematrix interfacial adhesion, however, because of the diculties
associated with to aramid bre surface having no sucient
reactive functional groups for covalent bonding with
matrix resin. The aramid bre consists of relatively rigid
polymer chains with linked benzene rings and amide bonds
having high crystallinity. In order to reach optimal
mechanical properties of these composite materials, significant research eorts have been directed towards characterization and improvement of the brematrix interfacial

Corresponding author. Tel.: +31 26 3665289; fax: +31 26 3665432.


E-mail address: Pieter.delange@twaron.com (P.J. de Lange).

0266-3538/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.11.018

adhesion by various bre surface treatments. Commercially, a typical chemical treatment of special Twaron aramid bre types for improvement of adhesion to epoxy and
rubber matrices is the application of an epoxy-based nish
to their surface, and subsequent curing thereof [1]. In addition to adhesion active components, a certain amount of an
oily nish component is always applied to the bre surface. The use of these nish components is essential in controlling the processing of the bre, both in the production
step as well as in consecutive process steps, such as twisting
and cabling. However, besides this positive eect on the
processability of the yarns, the oily components in the nish might weaken the interphase by forming a weak boundary layer and thus deteriorate the adhesion strength.
Moreover, they dilute the epoxy/amine system during the
short curing process, in case of combined application. To
the best of the knowledge of the authors, comparative
experimental information of how the oily components
aect the bre/resin interphase and composite mechanical
properties has been scarcely reported in the literature.

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P.J. de Lange et al. / Composites Science and Technology 67 (2007) 20272035

To develop new and improved surface-treated aramid


bre types, aimed at increasing composites performance,
the fundamental knowledge in both material surface and
composite interphase is required. A combination of analytical techniques has been used in the past to study the relationship between the bre surface (with or without
adhesion activation treatment), the resulting microscopic
interphase structure and the macroscopic composite properties, including the brematrix adhesion [24], such as
X-ray photoelectron spectroscopy (XPS), static (time-ofight) secondary ion mass Spectrometry (ToFSIMS), low
energy ion scattering (LEIS), inverse gas chromatography
(IGC), atomic force microscopy (AFM) and micro-Raman
spectroscopy. These techniques allow to study the local
surface chemistry (XPS, ToFSIMS, LEIS), the surface
polarity, and possible presence of acid/base interactions
(IGC), the physical surface microstructure (AFM), and
the local, i.e. micro-mechanical properties of the interphase
region (nanoindentation, pull-out, micro-Raman). The analytical observations can then be correlated with the bre
matrix adhesion strength and toughness, measured e.g. in
bre pull-out tests, and with the macroscopic mechanical
properties of the composite, from transverse tensile strength
and compression shear strength measurements.
In this study, we investigated in detail the eects of the
oily components in the nish. One basic Twaron yarn type
was selected, which was treated in a one step nish with a
combination of an adhesion active nish, based on an
epoxy-amine system, and a processability improving oily
nish with varying ratios. XPS, contact angle measurements, and AFM have been used to characterize the surface properties of these treated bres. The interphase
properties of the bres in an epoxy matrix were studied
by single bre pull out tests and micro-Raman spectroscopic analysis upon single-bre fragmentation geometry
specimens. Finally, the relation to the macroscopic composite properties was established by mechanical evaluation
of unidirectional bre/epoxy composites.

plished by drawing the nished yarn over a hot metal plate


(240 C) for 5 s.
The bulk composites were prepared as unidirectional
laminates with a size of 300 300 mm and a thickness of
4 mm by impregnating the aramid strands continuously
with the epoxy resin system, using a drum winding technique to manufacture a single prepreg layer, and following
by a subsequent hot pressing process. In preparation of single bre model microcomposites, a commercial DGEBAbased epoxy resin Bakelite EPR L20 and curing agent
Bakelite EPH 161 were used in 100:34 weight ratio (manufacturer: Hexion Speciality Chemicals). The curing conditions used in the study were similar to those
recommended by the manufacturer (6 h, 80 C).
2.2. Characterisation
2.2.1. X-ray photoelectron spectroscopy (XPS)
XPS measurements were carried out on a VG Escalab
MKII instrument, making use of non-monochromated Al
Ka radiation from a dual AlMg anode. The analyzer
was operated in constant analyzer energy (CAE) mode,
with a pass-energy of 50 eV for elemental quantication
purposes and 20 eV for C1s peak shape comparison purposes. Intensities were converted to elemental concentrations using Wagner sensitivity factors. Data processing
was performed with VG Eclips software. Before XPS analysis, all Twaron yarn samples were subjected to a Soxhlett
extraction (4 h) with ethanol.
2.2.2. Contact angle measurement
To predict the wetting behaviour during composite processing, the contact angles of dierently surface treated aramid bres as control and extracted samples with water were
determined. A single bre Wilhelmy technique [5] enabled
to determine both the advancing and receding angle. A
SS GmbH) was used.
very sensitive tensiometer K14 (KRU
For each sample 25 single bres were measured to get a
good average value.

2. Experimental
2.1. Materials
Para-aramid yarn from Teijin Twaron, Arnhem, The
Netherlands, was used for the investigation. One basic yarn
type (Twaron 2200, 1680 dtex, f1000) was selected and
treated with a combination of an adhesion active model
nish and a processability improving oily nish, in six
dierent ratios. The adhesion active model nish is an
epoxy-amine system, which contains the diglycidylether
of glycerol as epoxy, and piperazine as amine, in 9:1 weight
ratio. The oily part of the nish consists of a fatty acid
polyglycol ester. The amount of applied epoxy-amine was
xed on 0.3% (weight on yarn). The amount of oily
nish was varied between 0% and 4.8% (weight on yarn).
After application of the combined nish, the yarn was
dried for 5 s in a hot air oven, while curing was accom-

2.2.3. Atomic force microscopy (AFM)


An AFM (Digital Instruments D3100, USA) was used
as a bre surface topography imaging tool in tapping
mode. The cantilever (ULTRASHARP NSC15-F/5, MikroMasch, Estonia) has a normal spring constant of
40.9 N/m, a tip cone angle of 20, radius of 10 nm and
modulus of 160 GPa to assure good imaging resolution.
Image surface area dierence ratio (Sdr, Eq. (1)) as one
roughness parameter derived from ASME B46.1 expresses
the percentage ratio of the three-dimensional area of all of
the triangles formed by three adjacent data points (taking
the z height into account), AT, to the projected two-dimensional surface area in the at xy plane, A0, as shown
below:


AT
S dr
 1  100%:
1
A0

P.J. de Lange et al. / Composites Science and Technology 67 (2007) 20272035

2.2.4. Single-bre pull-out test (SFPO)


Using a self-made embedding apparatus enabling PCcontrolled temperature and time cycles, the model microcomposites for the single bre pull-out test were prepared
by accurately embedding the single bres in matrix with
embedding lengths of 100 through 200 lm. The pull-out test
was carried out on a self-made pull-out apparatus with force
accuracy of 1 mN and displacement accuracy of 0.07 lm
with identical pull-out velocities (0.01 lm s1) at ambient
temperature. From each forcedisplacement-curve, the
force at debonding or kink point Fd, the maximum force
Fmax, and the embedded length le were determined. The bre
diameter d = 2rf of each pulled-out bre piece was measured
microscopically. Each bre/epoxy combination was evaluated by about 1520 single tests. As a relative measure of
interfacial adhesion of dierently sized bres, the apparent
adhesion strength sapp, for each specimen was calculated
from the equation
sapp

F max
:
pdle

In this traditional data reduction practice, the maximum


external force Fmax applied to the bre is taken to correspond to the complete interface debonding [69]. A more
dierentiating approach determines the force, Fd, the
point when initial bre debonding from the matrix may
start, as seen from a kink in the forcedisplacement curve.
Further increase of the external load leads to interfacial
crack propagation and additional friction in the debonded
regions. Then, the local interfacial adhesion strength, sd,
can be determined by using the algorithm described previously [10], in which the raw data was considered including
the whole forcedisplacement curve, the specimen geometry, the embedded area, and the properties of the bre
and the matrix. We also calculated an energy parameter
which characterizes debonding the bre from the polymer
matrix, namely, the critical interphase energy release rate,
Gic. On the assumption that the pull-out process is governed by an energy criterion, Gic can be regarded as a
constant value. The debond force, Fd, is related to Gic
by the equation [11]:

p
F d pr2f p p2  qGic ;
3
where p and q(Gic) are terms depending on bre and matrix
mechanical properties and specimen geometry; their
expressions and the derivation are given in the reference
[10], based on the theory originally presented by Nairn [12].
2.2.5. Micro-Raman spectroscopy
Single bre model composites as fragmentation geometry specimens with bres 23 mm long were prepared with
an epoxy resin matrix as described in detail elsewhere [13].
The model composites were deformed using a Minimat
straining rig and the composite strain monitored using
the strain gauges. The Minimat, with a specimen mounted,
was attached to the stage of the microscope so that the bre

2029

could be observed as the load was increased. The laser


beam was focused on the bre inside the resin matrix using
a 50 objective lens and a near-IR 785 nm laser was used to
obtain the Raman spectra. An exposure time of 3 s and ve
accumulations were employed. The shift of 1612 cm1
Raman band along the length of the bre at each level of
matrix strain applied was examined. A separate experiment
upon the deformation of the bres in air showed that band
shifted at a rate of 3.6 0.1 cm1/% strain. The matrix
strain was increased in increments from 0% to 0.5%,
1.0% and 1.5%. The measurements were taken at every
10 lm at both ends of the bre and every 40 lm along
the middle of the bres.
2.2.6. Composite mechanical testing
The mechanical properties of the unidirectional composites were determined by transverse tensile test and compression shear test, since it was pointed out in previous work [5]
that the adhesion relevance is highest, if epoxy resin
matrix composites are considered. The testing conditions
were chosen according to ISO 527.
3. Results and discussion
3.1. Chemical composition and wettability
XPS analysis was used to characterise the chemical
structure of the nish-treated bre surfaces after the curing
process. Before each analysis, a solvent extraction with ethanol was carried out, which removes the oily nish components and possible residual epoxide. In this way the
technique can be used to determine only the amount of
epoxide which is xated to the aramid surface by the curing
process, and which will be responsible for adhesion
improvement in consecutive adhesion tests [4].
The results of XPS analysis of the solvent extracted
Twaron samples, treated with nishes of varying oil to
epoxy-amine ratio, are given in Table 1. The oxygen percentage of all nish treated samples is higher than the
untreated reference sample. This is explained by the presence of cured epoxy-amine on the surface, which is relative
(in comparison to aramid) oxygen rich. The nitrogen
percentage of all nish treated samples is lower than the

Table 1
XPS elemental analysis of solvent extracted Twaron samples
Applied nish (wt%-on-yarn)

Atomic %

Oil

Cl

Na

67.8
69.8
69.1
68.5
69.5
75.4
76.4
77.8

22.4
22.6
23.4
23.7
22.6
15.3
11.6
11.1

6.8
5.4
5.6
6.6
7.0
9.0
11.8
11.1

1.2
1.8
1.7
1.0
0.7
0.4
0.0

0.2
0.2
0.0
0.0
0.0
0.0
0.1

0.4
0.3
0.2
0.4
0.2
0.0
0.1

Epoxy-amine

0.0
0.3
0.3
0.3
0.6
0.3
1.2
0.3
2.4
0.3
4.8
0.3
Untreated reference Twaron
Aramid, theoretical

P.J. de Lange et al. / Composites Science and Technology 67 (2007) 20272035

untreated reference sample. This is also caused by the cured


epoxy-amine on the surface, which attenuates the nitrogen
signal from aramid. Although the epoxy-amine contains
some nitrogen from piperazine, the amount is low in comparison to aramid, which explains the decrease.
All nish treated samples show a clear chlorine signal.
This can be attributed to the epoxy compound, which contains (as commercial product) a small amount of covalently
bonded chlorine. Therefore, the chlorine can be used as tracer for the epoxy present at the bre surface.
Fig. 1 illustrates the eect of increasing the concentration of oil in the nish on the chlorine/epoxy content
determined by XPS. Above a level of 0.3% of oil, the
chlorine percentage decreases with increasing amount of
oil in the nish. This can easily be explained by a dilution
eect. The oil and the epoxy-amine are cured together on
the bre surface. During the curing process, the epoxy
and amine molecules have to nd (besides each other)
the bre surface and react there, in order to form a xated surface layer which will be responsible for adhesion
activation. With increasing amount of oil and a constant
number of epoxy and amine molecules, the number of
epoxy and amine molecules which will nd the surface
and react there will go down. This is observed in the
XPS measurements, since a solvent extraction is carried
out before the analysis, which removes the oil and all
epoxy and amine molecules which are not xated to the
aramid surface.
Furthermore, it is remarkable that the maximum
amount of chlorine/epoxy is not found for the sample without oil. The explanation might be that the presence and
amount of oil has a signicant eect on the distribution
of epoxy over the surface. In case of a more inhomogeneous distribution of the epoxy over the surface, the measured chlorine percentage will directly go down due to
the surface sensitivity of XPS. This might be the case for
the sample without oil.

All observations in the chlorine percentage are conrmed by the nitrogen percentage, also given in Fig. 1.
The two curves show a perfect opposite behaviour, as
expected; the more epoxy is present at the surface, the
higher is the chlorine signal, and the lower is the nitrogen
signal from the underlying aramid. For high oil levels,
e.g., the chorine percentage decreases to low values, indicating almost no epoxy at the surface, while the nitrogen
percentage rises to a value close to the expected percentage
of aramid. Note that the sum of the nitrogen and chlorine
percentage is lower than 10%, this means that the observed
anti-correlation is real and not caused by normalisation of
the sum of all elemental percentages to 100%.
In addition to determination of the atomic percentages,
XPS was used to probe the chemical binding state of the
carbon and oxygen surface atoms. Fig. 2 shows an overlay
of the C1s signals of the (solvent extracted) samples, prepared with varying amounts of oil. Starting with the sample
without oil, the curve basically consists of a CC contribution at 284.5 eV binding energy, and a CO contribution at
286 eV binding energy. The CC contribution can partly be
attributed to aramid and partly to cured epoxy-amine
structures, while the CO contribution is mainly arising
from the cured epoxy-amine structures. Note that a reference C1s spectrum of pure aramid [4] contains a CN
contribution, on approximately the same position as the
CO, and a C(@O)N contribution on 288 eV, but these
contributions are relatively small. This means that the signal at the CO position can be used as a measure for the
amount of epoxy-amine present at the surface.
Going from the sample without oil, to the sample with
0.3% oil, an increase of the CO contribution is observed,
which implies more xated epoxy-amine on the surface.
This is consistent with Fig. 1. If the amount of oil is further
increased, the CO contribution/xated epoxy-amine goes
through a maximum at 0.6% oil, and decreases then for
higher oil amounts, due to the dilution eect. So qualitatively

10

Chlorine percentage

2
1.8

1.6

1.4

1.2

Cl
N

0.8

0.6

0.4

0.2

Nitrogen percentage

2030

0
0

Amount of oil (w.o.y., %)


Fig. 1. Change in chlorine and nitrogen content of aramid bres with the amount of oil in the nish, measured with XPS after solvent extraction.

P.J. de Lange et al. / Composites Science and Technology 67 (2007) 20272035

2031

100

0.0%
0.3%
0.6%
1.2%
2.4%
4.8%

90
80
70

Intensity

60
50
40
30
20
10
0
293

291

289

287

285

283

281

Binding energy (eV)


Fig. 2. Changes of C1s spectra with the amount of oil, measured with XPS after solvent extraction.

the same as in Fig. 1 is observed, only the maximum is


shifted from 0.3% of oil to 0.6% of oil. Note that for the
highest oil levels the C(@O)N contribution from aramid
becomes visible at 288 eV.
Fig. 3 shows an overlay of the O1s signals of the dierent samples (The oxygen signal in the sample prepared with
0.3% oil is missing due to a recording error). All O1s signals consist of two main contributions. The left contribution at high binding energy (532 eV) can be attributed to
single bonded oxygen from the epoxy-amine structure,
the right contribution at low binding energy (530.5 eV)
can be attributed to double bonded oxygen from aramid.
With increasing amount of oil, the relative aramid
contribution rst goes down (0.6% oil), and then goes up
again (1.2%, 2.4%, 4.8%). With the limited number of

measurements, the minimum aramid contribution


(=maximum epoxy-amine contribution) is found for 0.6%
of oil, consistent with the result from the C1s signal.
So the XPS measurements show a maximum amount of
xated epoxy-amine for an oil level in the range of 0.3
0.6%. Without oil, the distribution of the epoxy-amine
might be inhomogeneous, while for higher oil-levels than
0.30.6% the dilution of the epoxy-amine by the oil
becomes more important. This dilution could cause dierent surface topography in nanometer region and/or inuence the surface free energy of the aramid bres and in
turn the adhesion strength towards polymer matrices in
composites.
Table 2 summarizes advancing and receding contact
angles with water of extracted Twaron samples. In agreement

100
90
80

Intensity

70
60

0.0%
0.6%
1.2%
2.4%
4.8%

50
40
30
20
10
0
538

536

534

532

530

528

526

Binding energy (eV)


Fig. 3. Changes of O1s spectra with the amount of oil, measured with XPS after solvent extraction.

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P.J. de Lange et al. / Composites Science and Technology 67 (2007) 20272035

Table 2
Contact angles of selected extracted Twaron samples with bi-distilled
water

and bre with 4.8% oil show the similar C1s, N1s and O1s
signals.

Applied nish
[wt%-on-yarn]

Contact angles (CA) s.d. []

3.3. Interfacial adhesion

Oil

Epoxy-amine

CA advancing

CA receding

CA hysteresis

0.0
0.6
4.8

0.3
0.3
0.3

79.0 6.0
74.2 8.3
80.8 7.6

46.7 11.0
30.6 8.1
49.0 15.7

32.3
43.6
31.8

with the CO contribution determined from the C1s signal,


the lowest surface contact angles (both advancing and
receding) were determined for the Twaron sample having
0.6% oil together with 0.3% epoxy-amine. This is an indication of more hydrophilic behaviour and increased surface
free energy, caused by the presence of the (maximum)
amount of xated epoxy on the bre surface. This maximum amount of xated epoxide probably also leads to
the highest surface roughness, which would explain the signicant contact angle hysteresis found for this sample.
3.2. Surface topography
Fig. 4 compares height images of the selected oil/epoxy
amine nished Twaron samples after solvent extraction. In
all images, the xated epoxy (which is not removed by the
extraction) seems to be inhomogeneously distributed, and
visible in small islets. With increasing oil content, the nanosize of these epoxy islets increases from about 50 nm for
0% oil to about 100 nm for 0.3% oil, resulting in lower surface area, i.e., Image surface area dierence ratio decreases
from 1.2% to 0.6%. Interestingly, the islets are distributed
on all bre surface, therefore, the oil turns out to have a
positive eect on the distribution of epoxy over the surface
at low content. When the oil content increases to 4.8% and
size of the islets increases to about 200 nm, however, the
islets appear to only partly cover the bre surface which
leads to possible poor interfacial adhesion as conrmed
in following part of the paper. It is also consistent with
the aforementioned XPS results, where the untreated bre

Fig. 5 summarizes the apparent shear strength of all nished Twaron samples determined from the maximum
forces of the forcedisplacement curves of single bre
pull-out test. The data shows an increase of the adhesion
strength with a decrease of the amount of oily components
in the epoxy-amine nishes. On the contrary the pure
epoxy-amine nish proved somewhat lower adhesion
strength. As assumed by XPS surface investigation, the
chlorine content (measured after extraction) represents
the amount of (xated) epoxy species on the outermost surface layer. Only these xated epoxy species have the ability
to covalently bond with the surrounding epoxy resin
matrix, and will contribute in the brematrix adhesion.
So the ndings with respect to adhesion strength correlate
very well with the XPS results.
This is even more emphasized in Fig. 6. Here, relative
values of the critical energy release rates, determined from
the forcedisplacement curves, are plotted as a function of
the amount of oil. In the same gure, the chlorine contents
determined from XPS investigation are plotted. The two
curves correlate very well. Both chemical and micromechanical data highlight same tendencies.
3.4. Micro-Raman spectroscopy
The variations of Raman band position along the length
of the bre in the composite were determined at dierent
matrix strain levels. The band positions were converted
to bre strain in the composite specimens by using the measured rate of shift of the Raman band with strain of the
bre in air (3.6 cm1/%).
The level of interfacial adhesion was evaluated from the
stress transfer length (lt). This is dened as the length over
which the strain in the bre builds up to the plateau value
[14] and it has been found [13] that there is a good

Fig. 4. AFM height images of (solvent extracted) Twaron samples, for dierent amounts of oil: (a) 0%; (b) 0.3%; (c) 4.8%.

P.J. de Lange et al. / Composites Science and Technology 67 (2007) 20272035

2033

Apparent Shear Strength [MPa]

60

50

40

30
20

10

0
0

Amount of oil (w.o.y., %)


Fig. 5. Apparent shear strength determined from single bre pull-out tests with epoxy resin in dependence of the oil content in the nish of Twaron bres.

120

Critical energy release rate


(scaled)
Chlorine content (from XPS)

Relative percentage

100
80
60
40
20
0
0

Amount of oil (w.o.y., %)


Fig. 6. Relative values of critical energy release rates determined from single bre pull-out tests with epoxy resin and chlorine content determined from
XPS in dependence of the oil content in the nish of Twaron bres.

correlation between lt and the interfacial shear strength in


the composite. The stress transfer length was found to
increase with increasing matrix strain due to phenomena
such as non-linear matrix deformation, yielding of the
matrix or debonding that might occur locally at the interface around the bre end. For a given level of matrix
strain, a low value of lt indicates good stress transfer,
whereas a higher value indicates poorer stress transfer.
The variations of stress transfer length obtained at a matrix
strain of 1.5% from averaging the values at both ends of
the bres with six dierent levels of oil content in the
applied nish are shown in Fig. 7. The shortest transfer
length and hence the best adhesion is found for about
1.0% of oil in the applied nish, consistent with the results
from the other experiments.
3.5. Composite mechanical properties
The transverse tensile strength and compression shear
strength as a function of the oil content on the Twaron
bres are presented in Figs. 8 and 9, respectively. Although

the specimen loading is dierently for these tests, the two


strengths determined show well agreeing tendencies in
dependence of the oil content on the Twaron bres. In both
cases, maximum strength is not found for samples without
oil, but for samples with oil amounts around 0.6%. And the
strength goes down at oil levels above 1%. These macroscopic composite properties are very well predicted by the
micro-mechanical adhesion study, carried out with SFPO
and Raman. The more fundamental explanation is given
by the results of the analytical characterization.
4. Conclusions
One basic Twaron yarn type has been treated with a
combination of an adhesion active nish, based on an
epoxy-amine system, and varying amounts of a processability improving oily nish. It was shown with XPS that
the amount of xated epoxy, detected at the bre surface
after solvent extraction, gradually decreases with increasing
oil content of the nish formulation. This can be explained
by dilution of the epoxy/amine system by the oil

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P.J. de Lange et al. / Composites Science and Technology 67 (2007) 20272035

Stress Transfer Length lt [um]

500

400

300

200

100

0
0

Amount of oil (w.o.y., %)


Fig. 7. Variation of stress transfer length, lt, determined from the micro-Raman spectroscopic analysis, with the oil content in the nish of Twaron bres
for a matrix strain of 1.5%.

Transverse tensile strength [MPa]

30
28
26
24
22
20
18
16
14
0

Amount of oil (w.o.y., %)

Compression shear strength [MPa]

Fig. 8. Transverse tensile strength of Twaron/epoxy composites as a function of the oil content in the nish of Twaron bres. The insert shows a schematic
of the specimen loading.

60

58
56

54

52
50

48
0

Amount of oil (w.o.y., %)


Fig. 9. Compression shear strength of Twaron/epoxy composites as a function of the oil content in the nish of Twaron bres. The insert shows a
schematic of the specimen loading.

P.J. de Lange et al. / Composites Science and Technology 67 (2007) 20272035

components. With increasing amount of oil and a constant


number of epoxy and amine molecules, the number of
epoxy and amine molecules which will nd the yarn surface
and react there, during the curing process, will go down.
This is observed with XPS, due to the fact that a solvent
extraction is carried out before the analysis, which removes
all the oil and the loose epoxy and amine molecules.
However, the maximum amount of xated epoxy is not
found in case of absence of oil. A small amount of oil seems
to be required to improve the distribution of the epoxy over
the bre surface. These ndings are conrmed with surface
contact angle measurements. The lowest advancing and
receding angle, and thus the highest hydrophilic behaviour,
is found for the (extracted) Twaron sample having 0.6% oil
together with 0.3% epoxy-amine. The eect of the oil content on the distribution of the xated epoxy is further illustrated by surface topography measurements with AFM.
The size of the observed epoxy islets increases from
50 nm to about 200 nm with increasing oil content.
The eect of the variation in the chemical surface structure of the bres, as shown by the analytical techniques, is
clearly demonstrated in a micro-mechanical adhesion study
in an epoxy matrix. The critical energy release rate, which
can be determined from the forcedisplacement curve in
single lament pull out measurements, and which is a measure for the local microscopic strength of the interphase,
correlates very well with the amount of xated epoxy, as
determined with XPS. And also the stress transfer length,
derived from micro-Raman spectroscopy, indicates an
optimum adhesion for about 1% of oil in the applied nish.
So qualitatively the same trend is found. This suggests
strongly that the amount of xated epoxide on the bre
surface, as measured with XPS, is a determining factor in
the microscopic adhesion to an epoxy matrix.
Furthermore, it can be concluded that the macroscopic composite properties, tested in unidirectional laminates using the same epoxy matrix, is very well predicted
by the micro-mechanical adhesion study (SFPO and
Raman). The curves of the transverse tensile strength and
the compression shear strength, both as a function of the
amount of oil, are showing the same behaviour as the
curves of the critical energy release rate and the (inverted)
stress transfer length. In all cases, maximum performance is
not found for samples without oil, but for samples with oil
amounts between 0.3% and 1%. The correlation of the
microscopic adhesion with the analytical characterization
results, i.e. the amount and distribution of xated epoxy,
is now giving a clear explanation for this behaviour.

2035

Finally, it can be concluded that the presence of a small


amount of oil on commercially adhesion activated Twaron
yarns, required to improve the processing behaviour of the
yarns, is not directly decreasing the adhesion to epoxy, but
is even working positive. And there is a relative broad
safe oil range, i.e. small uctuations in the amount of
oil will not directly destroy the adhesion. This was already
known from other, more practical, industrial investigations, but this study gives a quantitative conrmation
and additional understanding of the fundamental principles behind this knowledge.
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