Mechanical characterisation of Carbon nanober/epoxy

composites produced with dierent dispersion

strategies
A. Ortona
1
, A. Danani, E. Riboldi, G. Scocchi.
ICIMSI-SUPSI, Galleria 2, Manno, 6928 Switzerland
1 Introduction
Presently with the term carbon nanober the scientic commu-
nity refers to a distinction in size scale with other forms of carbon
reinforcements (e.g. carbon bers. In the past, similar structures
were called either lamentous carbon, carbon laments and
carbon whiskers [1] [2]. Carbon nanobers (CNF) are brous
structures with diameters around hundreds of nanometers and
lengths around hundreds of microns. The nanobers carbon struc-
ture presents dierent arrangements of graphene sheets [8]. Be-
cause of their history, there is no strict classication of nanober
structures. In 1985, Kroto and coworkers discovered a new form
of carbon, the C-60, also called buckminsterfullerene [3]. This
discovery, followed by the discovery of carbon nanotubes (CNT)
in 1991 by Iijimas [4], brought new interest in the eld of nano-
reinforcements. It is clear that the smaller the diameter of a ber
the higher are its bulk properties due to the diminished probabil-
ity of critical surface aws with decreasing specimen volume [6].
For this reason, nanotubes have extraordinary mechanical prop-
erties [5], and combining them with polymers or other matrices
form the so-called Carbon Nanotubes Composites[7]), they can
improve plain polymer mechanical properties. On the other hand,
this kind of reinforcement has to-date high manufacturing costs.
1
The main dierence between CNF and CNT is the shape and
stacking of the graphene sheets, that in CNF are arranged in
stacked cones or plates.
CNF represent an interesting economic alternative to CNT for
lower mechanical properties applications. In general mechanical
properties of epoxy reinforced composites are strongly dependent
on bonding of the carbon nano-reinforcement (CNR) to the host
matrix. For this reason, CNR functionalization has become an
argument of strong interest [9][10],[11]. CNR dispersion is also
very important to evenly distribute mechanical loads to the re-
inforcement that is due to the high surface area of the reinforce-
ment (Table.1). Nano reinforcements have been successfully dis-
persed through a number of techniques which release kinetic en-
ergy to the mixture breaking the bonding energy of the aggre-
gates. Probably, the most used technique, which employs ultra-
sounds, is the so called sonication that is because of the lab
scale equipment availability. Bath and Tip sonication have been
employed to disperse CNT and CNF into soft and hard epoxies
[10] [12][13][14][15][16][17][18][31][32]. This method seems very
eective, beside the ber shortening due to the energy levels and
the need of cooling to avoid excessive mixture heating. Other
dispersing methods force the mixture to pass between small gaps
among rotating cylinders (Calendering) [19][20][21] or between
rotating disks [22][23]. Both methods employ high shear stresses
to disperse agglomerates. In calendaring a rst primary disper-
sion of the agglomerates is achieved in the turbulent region before
the rolls, while the nal exfoliation and dispersion of the CNRs
occurs in space between the rolls (some microns). This method
is widely used in the ink industry and can thus easily up scaled.
Dispersing the CNR directly into epoxy gives rise to problems
due to resin wetting and high viscosity. Many strategies using this
method have been pursued [19][20][21][22][23]. Conversely some
researchers dispersed the CNR into the hardener [10][18][27], or
even into the already mixed two components [28]. Results are
strongly dependent on the dispersion method, manufacturing,
2
functionalization of the CNRs and on the resin adopted. In gen-
eral there are improvements in mechanical properties especially
in composite fracture toughness. Another dispersion method im-
plies the use of solvents to pre treat the CNRs. Among the
used solvents are: Chloroform [25], Acetone [19][13][15], Ethanol
[14][15][17][26], THF [14], DMF [15][16], Dichloroethane [16], Toluene
[11] and Water with surfactant [18].
Results are very dicult to compare. For instance, some authors
intentionally leave quantity of solvents to soften the polymer to a
rubbery state [12][25]: in this case adding CNR will always lead
to mechanical properties increase. Other authors used very low
amounts of hardener and used dierent forms of functionalization
[31][32][33]. If solvents are not present or have been evaporated
before polymerization, composite mechanical properties generally
improve for low CNR quantities, but decrease for higher CNR
content.
This work aims to study the inuence of dispersion strategies
on CNF/epoxy composites for high CNF loadings. The reason
for this investigation is that, despite the large amount of stud-
ies dealing with nanotubes as ller for polymeric materials, not
as much eort has been devoted to the study of CNF reinforced
materials, and in particular to epoxy based ones [36][37]. More-
over, we believe that recent results concerning the role of surfac-
tants in SWNTs/MWNTs dispersion in polymer-based compos-
ites [34][35] can not be assumed to be valid also for CNF without
an appropriate experimental comparison. Investigating dispersion
strategies and nal properties of these nanocomposites will thus
help to elucidate the mechanisms favoring or hindering synthesis
of eective novel materials.
3
2 Experimental
2.1 Pre-dispersion
Several dispersion trials were executed with Tip Sonication (Sono-
plus HD 2200 from Badelin, Germany). CNF pre-dispersion was
carried out with dierent solvents and durations (Table.2). Sam-
ples were sonicated for 30, 60 and 120 minutes at 40W. After son-
ication samples were placed into a oven to dry at 50
o
C overnight.
A SEM view of the pre-dispersion both in acetone (Fig.3) and
ethanol (Fig.4) shows that tip sonication eectively disaggregates
CNF bundles (Fig.1), shorteing at the same time single nano-
bres .
Morover, while drying, combined eects of CNF attraction and
sedimentation bring the CNF to compact lumps (Fig.2) which
need further sonication into the resin to be spread again. In
plain distilled water it was not possible to disperse the CNF be-
cause of the poor wetability of water against CNF. Adding 1%
surfactant(Triton X100 from Aldirch Germany), CNF seem, af-
ter drying, very well dispersed and separated by the surfactant
residues. The problem is that the residual surfactant binds the
CNF (Fig.5).
CNF were pre-dispersed with the aid of a dispersing medium, by
tip sonication. That occurs at expenses of the ber length which is
reduced after sonication. Another issue is on what happens when
taking away from CNF the dispersing medium. Even if no longer
in an interlaced manner, they re-compact again needing further
ultrasonic dispersion when mixed into the resin. To evaluate the
practicability of the dispersion, several samples where produced
with dierent strategies.
4
3 Composite preparation
Materials employed were: CNF GANF1 from Grupo Antolin Spain;
epoxy resin L285 and hardener H287 from MGS KunstHarzPro-
dukte GMBH, Germany. Composites samples were all manufac-
tured adding 2% CNF by weight in the resin. That percentage
represents, from viscosity measurements, the onset of its expo-
nential increase.
Beside plain resin, CNF and the medium (resin, hardener , or
solvent) mixture was previously stirred manually for one minute.
For all the dispersions the sonicator parameters were: power 40
W, cycle 2 (800ms ON, 200 ms OFF). The vessel was cooled with
ice and water. Four dierent strategies were followed to obtain
cured samples. Strategy 1: as received CNF were directly dis-
persed into the resin by sonication for 30. Strategy 2: CNF were
pre-dispersed in acetone (10g/l) for 2h, dried and then added
to the resin and sonicated again for 30. Strategy 3: a batch of
pre-dispersed CNF in isopropanol delivered by the CNF manu-
facturer (15g/l) and CNF in Acetone (15g/l) were dispersed for
30 And 50 respectively. The slurry was than added to the resin
and solvents removed in a ventilated oven at 60
o
C. Strategy 4:
CNF pre dispersed in isopropanol (same parameters than strat-
egy 3), the blend was added to the hardener. Isopropanol was
than removed from the blend with the same procedure adopted
before. Finally epoxy cross-linking was stared by mixing resin
and hardener in a 100:40 ratio by weight. Dierent dispersion
strategies are summarized in (Table.4).
All the samples were cured 24 h at room temperature and post
cured 15 h at 60
o
C. Some samples were cured at 2 bar pressure.
5
4 Characterisation
In order to evaluate the quality of dierent dispersing strategies,
dierent mechanical tests were performed. The results were al-
ways compared with measurements on plain resin (CEC 22-06).
Tensile tests were performed with a Zwick/Roell Z050 Germany.
Norms employed were ISO 527-4. Tensile tests parameters are re-
ported in (Table.5). Hardness samples were obtained casting the
CNF/epoxy mix into a square mould (40mm x 40mm). The ob-
tained block was then machined and its surface prepared for hard-
ness measurement following IS0 2039-2 : 1987. Hardness measure-
ment equipment was: GNEHM H artepr ufer TYP 300.
Abrasion resistance of the composites, compared to that of the
resin, was also measured. Test equipment and procedure are de-
scribed in (Table.3).
Test samples were weighted before and after the wear test and
weight loss calculated.
Finally, fracture surfaces resulting from tensile tests have been
analyzed using a Soligor SZM-645V optical microscope, in order
to retrieve information on rupture mechanisms.
5 Result and discussion
For quasi static tensile tests, plain resin properties were better
than those of the composites (Fig.6). Their elongation at break
was markedly lower than the plain epoxy (Fig.7). Among the pos-
sible explanation there could be still the presence of small defects
from where cracks can start. Elastic modulus was almost simi-
lar (Fig.8) except for the sample pre dispersed with isopropanol
in resin (CEC 25-06); we believe that some solvent was still in
the composite and that was the cause of the lower values. For
the same reason, that was the only exception for the compos-
6
ite hardness (Fig.9) which was generally improved adding CNF
to the resin . Abrasion test data (Fig.10) have a lot of scatter,
but that is in line with the procedure adopted. Taking this vari-
ability in mind, samples directly dispersed into the resin and
cured at ambient pressure seems to be the only composite with
a better behaviour than the neat resin. In general, composite
manufacturing strategy after pre dispersion has dierent impact
on mechanical properties (Table.6). For tensile test, plain resin
properties were better than the reinforced one. Ultimate stress
and elongation at break indicate that there is a variability in me-
chanical properties from one strategy to the other. Depending
on the strategy adopted dierent defects were generated. A frac-
ture surface analysis of the tensile tests samples revealed three
kind of defects: gas bubbles (probably trapped air) (Fig.11), CNF
agglomerates (Fig.12) and uncured resin regions (Fig.13). Since
the elastic modulus of all the samples remains constant , with
the exception of sample CEC-25-06 in which it is clear that the
resin softened due to the presence of left isopropanol, the bulk
reinforced material doesnt change its mechanical properties in
the elastic region. The detrimental eects of these defects starts
for higher loads. Overall the presence of unreacted resin was the
worst defect in terms of properties reduction followed by gas bub-
bles and CNF aggregates.
6 Conclusions
Dispersion of CNF can be performed with solvents like Acetone,
Ethanol, Isopropanol or with water and surfactant. If the slurry is
dried the CNF tend to pack into compact lumps. These lumps are
formed by disaggregated CNF which in the case of water + sur-
factant are bound by it. Up to now the most eective dispersing
stategy was found to be the direct dispersion into the epoxy by tip
sonication before adding the hardener. Further work will be per-
formed in trying to nd a more eective dispersion strategy. That
will be accomplished merging experiments with numerical simu-
7
lation. Modeling strategy will be based on multiscale approaches
[29], applying methods and techniques similar to those used by
Maiti et al. [30] for CNTs based nanocomposites. Our aim is to
retrieve information on the inuence of dierent surfactants on
CNF bundles disaggregation and on the eect of dispersion and
mesoscopic morphology on nal properties of the nanocomposite.
7 Acknowledgements
This work was performed under the CEC-Made-Shoe Integrated
Project funded by the European Commission - 6 FP Priority
IST - NMP (Manufacturing, Products and Service Engineering
2010) Contract N 507378. The authors wish also to thank Prof.
G. Camino and Dr. A. Castrovinci (Politecnico di Torino) for the
SEM images.
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Table 1
Surface area of dierent carbon reinforcement
Nano reinforcement Surface area (m2/g)
MWCNTs 200
DWCNTs /g 600-800
SWCNTs 1300
CNF 100-200
CF (short carbon bre) 1
Table 2
Pre dispersion experiments
NF g/l solvent surfactant Total time cycle power
5 Distilled water 30 min 2 40 W
5 Distilled water 1 h 2 40 W
5 Distilled water 2 h 2 40 W
5 Distilled water Triton x-100 30 min 2 40 W
5 Distilled water Triton x-100 1 h 2 40 W
5 Distilled water Triton x-100 2 h 2 40 W
5 acetone 30 min 2 40 W
5 acetone 1 h 2 40 W
5 acetone 2 h 2 40 W
5 ethanol 30 min 2 40 W
5 ethanol 1 h 2 40 W
5 ethanol 2 h 2 40 W
10 Distilled water 30 min 2 40 W
10 Distilled water 1 h 2 40 W
10 Distilled water 2 h 2 40 W
10 Distilled water Triton x-100 30 min 2 40 W
10 Distilled water Triton x-100 1 h 2 40 W
10 Distilled water Triton x-100 2 h 2 40 W
10 acetone 30 min 2 40 W
10 acetone 1 h 2 40 W
10 acetone 2 h 2 40 W
10 ethanol 30 min 2 40 W
10 ethanol 1 h 2 40 W
10 ethanol 2 h 2 40 W
Table 3
Abrasion test set up
ABRASION TEST
Procedures
Abrasion device Type : GIBITRE DIN 53 516
TEST PARAMETERS
Environmental temperature [C] 25
Test method B( with piece rotation)
Load normal to the contact surface 5 N 0.1 N)
Abrasion travel 40 m 0.2 m)
12
Table 4
Samples produced with dierent dispersion strategies (D.S.)
Sample ID D.S. CNF in w. Dir. disp.
into
the resin
ACETONE ISOPROPANOL P(bar)
Pre
disp.
and
dryied
Disp.
And
Added
to Resin
Disp.
And
added
to hard-
ner
Disp.
And
added
to resin
CEC MS 22-06 0% 0
CEC MS 23-06 1 2% X 2
CEC MS 24-06 2 2% X 2
CEC MS 25-06 3 2% X 2
CEC MS 26-06 4 2% X 2
CEC MS 27-06 3 2% X 2
CEC MS 28-06 1 2% X 0
CEC MS 01-07 3 2% X 0
Table 5
Tensile test parameters
Preload 10 N
Preload velocity 1 mm/min
Test velocity 1 mm/min
L
0
= initial reference length 50 mm 0.5 mm
Table 6
Composite averaged mechanical properties increse/decrease in respect of plain resin
CEC 22-06
Mech properties Cec 23-06 Cec 24-06 Cec 25-06 Cec 26-06 Cec 27-06 Cec 28-06
Tensile strenght -36% -54% -28% -59% -48% -14%
Elastic Modulus 1% -2% -10% -1% 0% -1%
Elongation at break -62% -73% -42% -77% -68% -38%
Hardness -1% 3% -3% 1% 3% 2%
Wear (mass loss) 0% 11% 17% 8% 4% -11%
13
Fig. 1. SEM image of as received CNF
Fig. 2. SEM image of CNF after 1h sonication in acetone and drying
14
Fig. 3. SEM of CNF after 1h sonication in acetone and drying
Fig. 4. SEM image of CNF after sonication in ethanol for 2h
15
Fig. 5. SEM image of CNF after sonication in H
2
O with TRITON X100 for 2h
Fig. 6. Box plot of the composites tensile strength
16
Fig. 7. Box plot of the composites strain to failure
Fig. 8. Box plot of the composites Elastic Modulus E
17
Fig. 9. Box plot of Composite hardness Rockwell L
Fig. 10. Box plot of weight loss after abrasion tests
18
Fig. 11. Fracture surface (10X magnication); crack was originated from an air
inclusion.
Fig. 12. Fracture surface (10X magnication); crack was originated from a CNF
aggregate.
Fig. 13. Fracture surface (10X magnication ); crack was originated from a
non-crosslinked volume.
19