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SCIENCE AND
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Composites Science and Technology 67 (2007) 20272035
www.elsevier.com/locate/compscitech
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
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.
2028
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-
F max
:
pdle
2029
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
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
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
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
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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]
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
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%.
2033
60
50
40
30
20
10
0
0
120
Relative percentage
100
80
60
40
20
0
0
2034
500
400
300
200
100
0
0
30
28
26
24
22
20
18
16
14
0
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
2035