Composites Science and Technology 192 (2020) 108099

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Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Limitations on adding nano-fillers to increase the compressive strength of

continuous fibre / epoxy matrix composites
P.-Y. Mechin a , V. Keryvin b ,∗, J.-C. Grandidier c
a
Dassault-Systèmes, CATIA Composites, F-78946 Vélizy-Villacoublay, France
b
Univ. Bretagne Sud, UMR CNRS 6027, IRDL, F-56321 Lorient, France
c
ISAE-ENSMA, UPR CNRS 3346, PPrime, F-86360 Chasseneuil-du-Poitou, France

ARTICLE INFO ABSTRACT

Keywords: The axial compressive strength of continuous fibres reinforced composite laminates is a key design parameter.
A. Nano-particles The mechanism at stake is the micro-buckling instability of fibres, which is contained by the shear stiffness of
Polymer-matrix composites their neighbourhood, and particularly that of the matrix. Adding nano-fillers to polymer matrices increase this
B. Strength
property. Therefore, the compressive strength should in turn be enhanced. In this study, we exhibit some limits
Debonding
of this statement by studying two epoxy resins and two carbon fibres. We show that in some cases premature
C. Failure criterion
damage may occur close to the fibre/matrix interface. We provide qualitative and quantitative explanations
supported by failure analyses and compressive strength estimations.

1. Introduction fibre. The enhancement of the mechanical properties of resins systems

Carbon Fibre Reinforced Polymers (CFRP) are widely used in nu-
merous industrial fields (aeronautics, offshore, renewable energies,
marine industry) or specific custom applications (leisure, racing cars,
racing yachts). One of the key material properties for engineering de-
sign is the axial compressive strength [1]. The underlying compressive
mechanism is the competition between fibres, initially straight (fibre
waviness) due to manufacturing, that bend during the loading and their
neighbourhood that constrain this displacement [2,3]. At some stage,
the containment is no longer strong enough and fibres buckle leading
to kinking bands. In this scenario, the matrix plays a crucial role, via
its stiffness, and particularly its shear stiffness. The higher the stiffness
of the resin is, the higher the compressive strength is.
Several approaches are being considered by chemists, develop-
ing new chemical formulations offering greater rigidity or adding
micro/nano-fillers linked to the thermoset network in order to limit its
ability to deform. Nano-fillers may include nano-silica glass beads, clay
nano-platelets or carbon nanotubes. For example, Jumahat et al. [4]
used an Epikote 828 epoxy resin system with various ratios of nano-
silica fillers. A comparison of the improvement in the resin stiffness and
strength was quantitatively performed. Stiffness increased from 10% to
30% with a nano-fillers content varying from 5 to 25 wt%. Equivalent
observations were made on both yield and ultimate strengths.
Complications in manufacturing continuous fibre composites with
nano-filler containing polymers arise from the issues such as dispersing
fillers or bonding between nano-modified epoxy and the carbon or glass
using nano-fillers has been considered in various studies [5–9]. Tsai and
Cheng [7] observed an 11% increase in compressive strength with 30%
increase in nano-silica content. Quaresimin and Varley [5] reported no
real increase in compressive strength with different nano fillers (nano-
clay, nano-carbon fibre, co-polymers) but a higher resistance to notch
sensitivity for nano-clay and nano-fibre (open-hole compression test).
Uddin and Sun [6] observed an increase of several 10% in off-axis
compression (5–15◦ ) with 15% nano-silica content.
Therefore, nano-fillers may contribute to increase both the stiffness
and strength of the resin. This should in turn increase the compressive
strength of unidirectional plies. In this study, we wonder whether
there might have a limit of the improvement in the axial compres-
sive strength of unidirectional plies using resin with nano-fillers. To
address this question, we use two resin systems (one with and one
without nano-fillers) and two carbon fibres types. The objective is
to propose a qualitative and possibly a quantitative explanation of
the various compressive strength values. The paper is organised as
follows. Careful mechanical tests are performed and estimations using
an engineering analytical criterion are introduced. Results are reviewed
and comparisons between experiments and estimations are made. It will
be shown that nano-fillers do increase the compressive strength to one
exception. This exception will be analysed in details and a mechanistic
and quantitative scenario will be proposed exhibiting some limits of
nano-reinforcement.

∗ Corresponding author.
E-mail address: vincent.keryvin@univ-ubs.fr (V. Keryvin).

https://doi.org/10.1016/j.compscitech.2020.108099
Received 27 July 2019; Received in revised form 17 February 2020; Accepted 20 February 2020
Available online 27 February 2020
0266-3538/© 2020 Elsevier Ltd. All rights reserved.
P.-Y. Mechin et al.
Fig. 1. Experimental four-points bending set-up. (left) Just before fracture. (right) After
fracture that occurred in between the upper rollers at the strain gauge location.
2. Materials and methods
2.1. Materials
The study is focused on both Intermediate Modulus [IM] (IM2C -
Hexcel) and High Modulus [HM] carbon fibres (HR40 - Mitsubishi).
They provide a significant difference in axial stiffness (296 GPa for
IM2C, 373 GPa for HR40 fibres, known from the supplier datasheet).
The associated polymer matrices are epoxy resin systems Se84 LV and
Se84 nano Generation 1 (Gurit products). Therefore four different com-
posite materials are studied in this work. Se84 nano is an equivalent
resin to the Se84 LV which contains nano-fillers (silica nano-particles).
Resins systems have a glass transition temperature (T𝑔 ) around 120 ◦ C.
Plates are manufactured from prepregs, where compaction is operated
every three plies at 3 bars. They are then cured in an autoclave, with a
specific heat-up ramp (composite supplier’s datasheet) and a pressure
of 3 bars. The curing cycle is performed once (one-shot).
2.2. Experimental methods
Four-point bending tests were carried out according to ASTM stan-
dard [10] with a universal testing machine (Instron 5567, 30 kN load
cell) using a distance of 90 mm between the upper rollers, where
pure bending occurs, and a distance of 460 mm between the lower
rollers. Polyethylene plates (3 mm thick) were put under the rollers
(10 mm in diameter) to minimise stress concentrations (see Fig. 1).
Mono-axial strain gauges (10 mm in length - Kyowa) were glued on
both the compression and the tension sides. Ten samples with the
stacking sequence [+45, 09 , −45, 011 , −45, 09 , +45] are tested for
each composite material at 5 mm/min. The laminates are not quasi-
isotropic like those used very often for aeronautical applications. In
our case, this corresponds to a specific application of the materials
used for racing yachts, where compressive strength is the key design
parameter. All the plies in each sample have the same fibre/resin couple
for each kind of coupon. Five were broken with the mould side in
compression, five with the vacuum bagging side in compression. Failure
occurred between the upper rollers as shown in Fig. 1. The force on
the assembly and the two strain gauges signals were recorded during
loading and synchronised. The details of the analysis of the flexural
tests are reported elsewhere [11,12].
Tensile tests on ±45◦ samples are carried out to extract the in-plane
shear behaviour of the unidirectional ply (UD). At least, five samples
with the dimensions 250 × 25 × 2 mm3 composed of 8 plies (symmetric
layup) were tested for sake of reproducibility at 2 mm/min. Experi-
mental details of these tests are also reported in Ref. [11]. The shear
stress 𝜏UD and shear strain 𝛾UD are computed. A non-linear regression
to extract the Ramberg–Osgood (RO) parameters (see. Eq. (1)) is made
for each sample.
( )nUD
𝛾UD 𝜏UD 3 𝜏UD
= + × (1)
𝛾𝑦
UD
𝜏𝑦UD
7 𝜏𝑦 UD
2
Composites Science and Technology 192 (2020) 108099
𝑦 𝑦
It involves material parameters GUD , nUD , 𝛾UD and 𝜏UD . GUD is the shear
𝑦
modulus of the composite. 𝜏UD is a nominal shear yield stress defined
as the shear stress for which a straight line, constructed with a secant
modulus reduced to 70% of the initial shear modulus GUD , intersects
𝑦 𝑦 𝑦
the experimental curve. 𝛾UD is defined by 𝜏UD = GUD × 𝛾UD . Overall
the number of independent material parameters is three and the set
𝑦
(nUD , 𝛾UD , GUD ) will be determined for each material.
Tensile tests are performed on the matrices, following ISO stan-
dard [13], to measure their mechanical properties (Young’s modulus,
Poisson’s ratio, tensile strength) with a universal testing machine (In-
stron 5567, 10 kN load cell). The longitudinal and transverse strains
were measured using a non-contacting 3D optical system (Aramis 5M,
GOM, Germany). Two video cameras (8-bit grey levels, 2050 × 2448
pixels images at 2 Hz) recorded the motion of a random pattern
spray painted on the sample surface, by means of a digital image
correlation (DIC) technique. Five dog-bone samples (gauge length of
25 × 5 × 2 mm3 ) were tested for reproducibility at 1 mm/min.
Tomography measurements are performed to observe the specimens
after failure in four points bending. X-ray computed tomography (XCT,
EasyTom XL Duo - Rx Solutions) is used with a resolution of 1.5 μm
per pixel in all directions (which means 3–4 pixels per fibre) or an
equivalent voxel of 3.38 μm3 . Besides, fracture surfaces are observed
with a camScan MV2300 (Jeol 7000 series - JSM-700F) scanning elec-
tron microscope (SEM). Acceleration voltage is set to 7 kV and image
resolution is 1280 × 1024 pixels. Digital image analyses are carried for
both XCT and SEM using the software FIJI [14].
2.3. Estimation of compressive strength
An analytical model for estimating the compressive strength was
proposed by Budiansky and Fleck [3]. It requires to know the non-
linear shear behaviour of UD 𝛾UD (shear strain) vs. 𝜏UD (shear stress)
for example described by a RO-like behaviour (see Eq. (1)) . The
compressive strength, referred as critical stress generating instability
stab ), is defined as the maximum stress applied on UD before the
(𝜎UD
micro-buckling of the fibre appears, and is given by Eq. (2):
stab GUD
𝜎UD = ( ) (2)
nUD − 1
1 ( )
( ) 𝑦
𝜙0 ∕𝛾UD nUD
3 nUD
1 + nUD
7 nUD − 1
where 𝜙0 is the initial misalignment of the fibre (fibre waviness).
An additional contribution, referred to as a structural effect [15,16],
takes place at the laminate scale and involves the thickness of UD
ply, the stiffness of the off-axis neighbouring plies and the deformation
gradient in bending. This mechanism adds a contribution 𝜎UD stru .
√
stru 𝜋 𝐸𝑚 𝐸𝑓
𝜎UD = 2 𝑟𝑔𝑓 𝑉 (1 − 𝑉𝑓 ) (3)
𝑒𝑏 1 − 𝜈𝑚2 𝑓
where r𝑔𝑓 is the gyration radius of fibre, E𝑚 and 𝜈𝑚 are respectively the
Young’s modulus and the Poisson’s ratio of the matrix, E𝑓 the longi-
tudinal elastic modulus of the fibre, V𝑓 the volume fraction of fibres
and e𝑏 the characteristic thickness of UD involved in the instability
mode (a fraction of the total thickness of UD). For a laminate stacking
under bending, e𝑏 is 0.4 times the thickness of consecutive UD plies
undergoing the higher compressive stress. Details for the calculation of
stru are reported elsewhere [11,16] for sake of clarity. The radius of
𝜎UD
giration is 2 and 1.5 μm respectively for IM2C fibre and HR40 fibre. The
fibre volume fraction is set to 58% according to the prepreg datasheets.
For the various couples fibre/resin considered, the structural effect
has an order of magnitude of ∼ 15% of the stability stress 𝜎UD stab .
The sum of the two contributions (𝜎UD stab and 𝜎 stru ) gives the critical
UD
crit , as proposed in Ref. [16] in the
stress that triggers the instability, 𝜎UD
form of an engineering criterion, very useful for the fast dimensioning
in a design loop. It is nevertheless grounded on a background of solid
numerical simulations describing the possible instabilities [17,18].
P.-Y. Mechin et al. Composites Science and Technology 192 (2020) 108099

Table 1
Mechanical properties of the two resins from tensile tests.
Matrix Young’s modulus [GPa] Poisson’s ratio [-] Tensile strength [MPa]
Se84LV 3.0 ± 0.4 0.40 ± 0.01 82 ± 5
Se84nano 5.0 ± 0.7 0.36 ± 0.01 71 ± 2

Table 2
Experimental results and estimations for the four composite materials considered (see
the main text for details).
Matrix Se84LV Se84nano Se84LV Se84nano
Fibre IM (IM2C) IM (IM2C) HM (HR40) HM (HR40)
Shear behaviour - Ramberg Osgood parameters
GUD [GPa] 4.63 ± 0.16 6.45 ± 0.05 4.52 ± 0.09 6.60 ± 0.29
𝑦
𝛾UD [%] 1.16 ± 0.01 0.98 ± 0.01 1.14 ± 0.05 0.93 ± 0.04
nUD [-] 6.90 ± 0.10 8.51 ± 0.42 4.80 ± 0.44 6.24 ± 0.45 Fig. 2. Shear behaviour of UDs for both IM & HM fibres and both Se84 nano & Se84
Shear behaviour - Fracture parameters LV resins, for representative samples.
fail
𝛾UD [%] 14.3 ± 1.7 8.2 ± 0.7 6.1 ± 0.8 1.52 ± 0.21
fail
𝜏UD [GPa] 70 ± 3 68 ± 2 60 ± 2 64 ± 2
Compression strength estimation
𝜙0 [◦ ] 1.5 1.5 2.0 2.0
stab
𝜎UD [MPa] 1257 1575 1029 1290
stru
𝜎UD [MPa] 233 290 175 216
crit
𝜎UD [MPa] 1490 1865 1204 1506
Compression strength measured
fail
𝜎UD [MPa] 1534 ± 51 1762 ± 89 1165 ± 50 1230 ± 90

Two different initial misalignment angles 𝜙0 are considered depend-

ing on the fibre type. The choice for IM2C fibres is made following
the literature [1,19] and set to 1.5◦ . The bending stiffness of the fibre
is supposed to have an influence on this fibre waviness that develops
during the curing stage [20]. The higher the bending stiffness is, the
lower this angle is. HR40 fibres are stiffer (by 30%) than IM2C fibres
but have a smaller diameter (by 30%) so that the bending stiffness is
4 times smaller. We therefore set 𝜙0 to a higher value of 2.0◦ . Let us
note that the values chosen do not have a significant importance in the
context of the comparison of the effect of nano-fillers using the same
fibres and the same manufacturing process on the compressive strength.

3. Results

The mechanical properties of the two matrices are reported in
Table 1. The four fibre/resin systems are compared in this Section
regarding the various mechanical properties considered along with
estimations of the compressive strength related the micro-buckling
mechanism. First of all, the shear behaviour of unidirectional plies is
reported. Then, the compressive strength is estimated and compared
to experimental results. All values are reported in Table 2. These
quantitative results are finally related to tomography observations.
3.1. In-plane shear behaviour of the unidirectional plies
Representative behaviours of the four composite materials are plot-
ted in Fig. 2. For a given fibre (IM or HM), the effect of nano-fillers is
to increase the stiffness all long the deformation process (see Fig. 2);
Se84nano curves being above Se84LV ones. It increases (see Table 2)
the shear elastic stiffness (+30%) and the hardening exponent nUD ,
𝑦
decreases the shear yield strain (𝛾UD ) and decreases sharply the failure
shear strain values (the shear strength values are not very affected).
For a given matrix, considering the scattering, IM and HM fibres
exhibit similar RO parameters describing the non linear behaviour. In
terms of failure, the failure shear strain values decrease moderately,
whereas the shear strength values are not very affected. As for the hard-
ening exponent nUD , it remains quasi unchanged. The only exception to
these tendencies is the Se84LV-HM couple where nUD decreases sharply
with respect to Se84LV-IM or Se84nano-IM.
Fig. 3. XCT scan of Se84LV-IM after failure.
3.2. Compressive strength estimation and comparison to experimental val-
ues
Using the parameters extracted from the RO fit, the compressive
strength is estimated (see Section 2.3) and reported in Table 2. For a
given fibre (IM or HM), the effect of nano-fillers is expected to increase
the compressive strength. At the contrary, for a given resin, HM fibres
are expected to decrease this strength. The experimental results follow
exactly the same tendencies. In particular, the effect of nano-fillers is
to increase the compressive strength.
3.3. Tomography observations
A typical XCT picture is shown in Fig. 3. For all materials, kinking
bands are observed, validating the scenario of fibre micro-buckling
failure mechanism.
4. Discussion
4.1. Relevance of the micro-buckling model for estimating the compressive
strength
The estimated compressive strength for three of the four fibre/resin
couples of this study, namely Se84LV-IM , Se84LV-HM and Se84nano-
IM , is in very good agreement with experimental results (less than

3
P.-Y. Mechin et al.
Fig. 4. Fracture surfaces of Se84 LV-HM with: (top) Kinking-bands in the UD layer
visible for a large number of fibres, (bottom) Details of the kinking-band showing the
cohesion between fibre and resin.
10% difference), see Table 2. More particularly the estimated ranking
is in complete relevance with the experimental one. This capacity
emphasises the relevance of this engineering criterion for being used
in fast dimensioning design of composites structures for which the key
design constraint is compression.
4.2. Premature compressive failure for Se84nano-HM
In sharp contrast, for the Se84nano-HM couple, the model estima-
tion and the experimental result differ by ∼ 20%. Possible reasons
are sought in this paragraph. Kinking bands are observed like for
the other couples by means of tomography. The failure mechanism
is therefore fibre buckling. Supplementary fractography observations
are carried out by SEM to go down at the constituent scale. This is
made first on Se84LV-HM and illustrated in Fig. 4. We observe that
the interface between the fibre and the matrix resin is strong enough
to accommodate the deformation. Classical fracture surfaces of fibres
indicate that they failed by bending (see e.g. [21]). On the contrary, as
illustrated in Fig. 5, for the couple Se84nano-HM, massive debonding
is observed at the fibre/resin interface.
This is to put in perspective with respect to the IPS tests results. The
mechanism at stake during IPS is mostly elasto-viscoplasticity. Damage
occurs in the very late stages of deformation (there is no acoustic
emission signal linked with possible damage for instance). There are
indeed no obvious reasons why failure should be fibre-dominated.
Failure strains for Se84LV-IM and Se84LV-HM are quite similar. It is
nevertheless not the case for Se84nano-IM and Se84nano-HM for which
failure strains are very different. Since failure strains of Se84LV-IM and
Se84nano-IM are also quite similar, the origin of a low level of failure
shear strain for Se84nano-HM might be sought at the interface scale.
4
Composites Science and Technology 192 (2020) 108099
Fig. 5. Fracture surfaces of Se84 nano-HM with decohesion between fibres and matrix:
(top) Details of the kinking-band showing the decohesion between fibre and resin.
(bottom) Magnification of previous picture.
Based on these observations, we suggest a possible mechanistic
scenario for this premature failure. (We refer to this failure as premature
since the experimental strength value is not in line with its estimation,
contrarily to the three other materials studied.) The more misaligned
fibres that have the highest propensity to buckle are contained by the
stiffness of the surrounding environnement (matrix, interface, fibres).
At some stage of the loading, damage occurs in the form of matrix
cracking and/or interface debonding (see Fig. 4). This lowers drastically
the stiffness of the surrounding environment of the candidate fibres
for buckling, thus reducing the containment. Therefore, buckling then
kinking occur, in a premature way with respect to materials that failed
without damage. This scenario is supported by assumptions made by
Steif to estimate the compressive strength of weakly bonded fibre
composites [22]. The damage of this interface is to be compared with
the low resistance observed on the ±45◦ tests previously carried out
(cf. Table 2). Indeed, if the fibre/resin debonding appears prematurely,
this might be one element to explain a lower failure shear strain of UD
ply.
fail stab )
4.3. Critical shear failure (𝛾UD ) vs. shear strain at instability (𝛾UD
Based on this scenario, it is possible to revisit the estimation of
the instability onset to compare with experimental results. The micro-
buckling model (see Ref. [3] for details) calculates the maximum
allowable shear strain around a candidate fibre for buckling, called
stab , see Eq. (4).
critical shear strain at instability 𝛾UD
[ (
stab 𝑦 )]1∕nUD 𝑦
𝛾UD 7 𝜙0 ∕𝛾UD 𝜙0 ∕𝛾UD
𝑦 = + (4)
𝛾UD 3 nUD − 1 nUD − 1
P.-Y. Mechin et al. Composites Science and Technology 192 (2020) 108099

with some premature damage (𝛾UD stab > 𝛾 fail ). Interestingly, we have
UD
investigated this possibility with a second batch of Se84nano-HM. In
Fig. 7 we have added the results of this batch (noted Set-2) of the same
fibre/resin couple that exhibited lower failure values. Following our
assumption, since for all samples this time 𝛾UD stab > 𝛾 fail , the instability
UD
should occur prematurely.
We can finally estimate the compressive strength with the same
micro-buckling model [3,16]. Instead of using 𝛾UD stab in the Ramberg–

Osgood description of the shear behaviour, we use the failure shear

strain given in Eq. (5), and a new stability stress 𝜎UD stab-mod is estimated,

from Argon’s equilibrium equation [23].

fail )
𝜏(𝛾UD
stab-mod
𝜎UD = (5)
fail + 𝜙
𝛾UD
Fig. 6. Shear behaviour of UDs for representative samples of the four composite 0
materials. Solid lines stand for the experimental behaviour under shear. Triangle fail of 1.15%
stab
As a numerical value we choose a value for Set-2 of 𝛾UD
symbols stand for the shear strain at instability (𝛾UD ). The green cross stands for
the scattering (one s.d.) in failure values (only one is visible for this magnification of
(the batch mean value minus one standard deviation) corresponding
fail ) = 55 MPa. All other parameters are unchanged. The new
to 𝜏(𝛾UD
Fig. 2).
critical compression stress at instability 𝜎UD stab-mod is then 1185 MPa.

The structural effect contribution 𝜎UD stru is taken as unchanged to 216

MPa even if it should slightly be overestimated since it does not take

into account the fibre/matrix debonding and/or matrix cracking. The
predicted compressive strength is then 1401 MPa to be compared to the
1230 ± 90 MPa of the experiments. This shows that our assumed mech-
anistic scenario of premature embrittlement, initially based on fracture
surface observations, is now reinforced by this quantitative comparison
between an estimation and measured compressive strengths.
Finally, during a parallel experimental campaign we found out
that another batch of Se84nano-HR40 (Set-3) presented compressive
strengths of 1460 ± 45 MPa. Compared to the prediction proposed with
the micro-buckling model (1401 MPa for Set-2 and 1506 MPa for Set-
1), a better agreement between estimation and experiments is obtained.
It could mean that this time for that batch the failure shear strain is
Fig. 7. Shear behaviour of Se84nano-HM couple for two batches. The Set-1 (solid line) fail > 𝛾 stab ). Interestingly, in
higher than the shear strain at instability (𝛾UD UD
is the same as that drawn in Fig. 2. Dot-dash lines stand for the scattering (1 s.d.) in
failure values.
terms of fracture surfaces, this last batch exhibits characteristic features
similar to those observed on Se84nano-IM couple with most of the
Table 3 fibres bounded to resin (see Fig. 8). Therefore, we can conclude that
Estimated shear strains at instability (𝛾UD stab
) of the unidirectional ply and measured compressive failure on the Se84nano-HM couple for this batch is the
fail
failure shear strains (𝛾UD ) for the four composite materials. result of a complete micro-buckling of fibre failure mechanism without
Matrix Se84LV Se84nano Se84LV Se84nano prior damage. This compressive failure allows to benefit from the full
Fibre IM (IM2C) IM (IM2C) HM (HR40) HM (HR40) contribution of the fibre/resin couple to contain the buckling of the
stab
𝛾UD [%] 1.54 1.28 2.10 1.59 fibre.
fail
𝛾UD [%] 14.3 ± 1.7 8.2 ± 0.7 12.4 ± 1.5 1.52 ± 0.21 Eventually a failure map shown in Fig. 9 summarises the different
failure mechanisms for the materials of this study. The compressive
stress 𝜎 ∞ acting on the UD ply is plotted versus the local shear strain
It is interesting to compare the computed values of the shear strain around the bending fibre 𝛾UD as given by Argon [23] and incorporating
at instability (𝛾UDstab ) with the failure shear strains measured (𝛾 fail ). the Ramberg–Osgood shear behaviour 𝛾UD − 𝜏UD obtained by the IPS
UD
These values are reported in Table 3 for the four materials of this tests (see Eq. (1)).
study and also superimposed on the shear behaviours plotted in Fig. 6 𝜏UD
𝑦
(triangles coloured in adequation with the curves). It is observed that 𝜏UD 𝜏UD
for the three first materials, the failure shear strains are higher than the 𝜎 ∞ (𝛾UD ) = = GUD ( )nUD (6)
𝛾UD + 𝜙0 𝜏UD 𝜏UD 𝜙0
3
stability shear strains. Therefore, the instability mode develops before 𝑦 + 𝑦 + 𝑦
stab < 𝛾 fail ). In sharp contrast, for 𝜏UD 7 𝜏UD 𝛾UD
the material undergoes failure (𝛾UD UD
Se84nano-HM the two values are almost the same with a failure shear The competition between micro-buckling of fibres and premature dam-
strain (mean value) slightly lower than the shear strain at instability. age at the interface scale is represented by the shear failure strains
This is emphasised in Fig. 7 (noted Set-1). We propose that in that found from the IPS tests.
stab > 𝛾 fail ), it is possible that premature damage triggers the
case (𝛾UD UD
instability. 4.5. Additional support for the assumption of premature damage at or close
to the fibre/matrix interface
4.4. Variability of failure shear strain and its consequences on compression
micro-buckling The mechanistic assumption of a premature damage close to or at
the fibre/matrix interface explaining the lower compressive strength
It can be observed in Figs. 6 and 7 that, in few cases, for Se84nano- of Se84nano-HM with respect to its estimation is discussed in this
HM, 𝛾UDstab < 𝛾 fail due to the scatter in the shear strain values. Therefore,
UD
paragraph. We first turn our attention to the interface strength. In situ
it is relevant to think that it is liable to find samples that exhibited measurements of the interfacial shear strength (IFSS) between the fibre
an instability mode without some premature damage (𝛾UD stab < 𝛾 fail ) or and the matrix were made. Push-in tests of fibres were carried out
UD

5
P.-Y. Mechin et al.
Fig. 8. Fracture surface of another batch of Se84 nano-HM (Set-3) : (top) Kinking-bands
in the UD layer visible for a large number of fibres, (bottom) Detail of the kinking-band
showing the cohesion between fibre and resin.
Fig. 9. Compressive stress applied on the most loaded UD ply versus the maximum
local shear strain around the fibre. The stars and dashed lines indicate the failure
strains given by the IPS tests. The wavy pattern represents a micro-buckling instability
without premature damage. The inset concerns the sole Se84nano-HR40 material. The
green wavy with patterns with slits represent micro-buckling instability with large (Set-
2) or moderate premature damage (Set-1) and the plain green wavy pattern represents
micro-buckling instability without premature damage (Set-1). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of
this article.)
on transverse cross sections polished up to 1 μm diamond paste. The
procedure is described in Tan et al. [24] and was followed in complete
accordance. It consists in pressing the surface of carbon fibres with
a diamond flat punch of 4.8 μm in diameter using an instrumented
indentation device (Hysitron TI-980, Bruker, Germany). Chosen carbon
fibres were surrounded by six other fibres in an hexagonal pattern.
Push-in tests were performed under displacement control at 40 nm/s
up to a maximum displacement of 1200 nm followed by unloading to
the initial position. More than 5 fibre tests were carried out for each
laminate. The apparent IFSS (shear-lag estimation) following Ref. [24]
6
Composites Science and Technology 192 (2020) 108099
was found to be 19 ± 4 MPa and 17 ± 4 MPa for Se84nano-HM
and Se84nano-IM, respectively. These numbers made it impossible to
conclude soundly on a weaker interface for Se84nano-HM.
Therefore, we are able to precise our mechanistic assumption. The
interface strength seems not to be the cause for premature failure
given the IFSS values. It is therefore proposed the failure of the matrix
close to or at the fibre/matrix interface to be a possible mechanism of
premature failure for Se84nano-HM. Three concurrent elements are in
favour of this scenario. (i) There is a higher stress in the HM fibres than
in the IM fibres because of their different axial modulus values (375 vs
296 GPa). A larger stress gradient between matrix and fibre is therefore
present. (ii) There is a higher stress in Se84nano matrix compared to
Se84LV because of their different Young’s modulus values (5.5 vs 3.5
GPa, cf. Table 1). (iii) Se84nano matrix has a lower strength compared
to Se84LV (71 vs 82 MPa, cf. Table 1).
5. Conclusion
The effect of nano-fillers on the compressive strength of carbon fibre
composites is quantitatively studied for two epoxy resins (Se84 LV &
Se84 nano) and two different fibres (high modulus and intermediate
modulus fibres). From an experimental point of view, Se84nano resin
provides higher compressive strength results compared to Se84 LV
resin. This result confirms that adding nano-fillers to a resin is suitable
for enhancing this key material property.
Estimations of the compressive strength were made using an engi-
neering failure criterion. This model proposes a combination of a micro-
buckling mechanism and a structural effect related to both the stacking
sequence and loading conditions. The estimations are compared to
experimental results from four points bending tests.
Out of four fibre/resin configurations studied, three provide very
good agreement between experiments and estimations. For a specific
couple (Se84nano-HM), the experiments give lower results. We have
put forward that this is due to a premature damage at or close to
the fibre/resin interface. It is related to the low failure shear strain
values experimentally measured by tensile tests on ±45◦ laminates.
This latter value is compared to the shear strain at instability estimated
from the micro-buckling model. In the case of Se84nano-HM, these
two values are very similar. We have proposed that, considering the
experimental scatter in the failure shear strains, it is liable to have two
scenarios. In the first case, where the failure shear strain is higher than
the shear strain at instability, the instability mode develops without
any premature damage and the structural effect stabilises this mode,
delaying its onset. At the contrary, for the opposite case, damage
appears at the fibre/matrix interface, decreasing drastically the con-
tainment around candidate fibres for buckling. The instability mode is
prematurely triggered. This has been confirmed using different batches
of the same composite material in terms of estimations and fracture
surface analyses.
This paper explores the experimental evidence of the competition
between micro-buckling and premature damage. It provides some nec-
essary elements for a future finite element modelling. In all cases, the
engineering criterion used in this work, is robust enough to give very
useful estimations of the compressive strength. Based on this work, a
new resin system could be proposed to reduce the risk of low com-
pressive strengths using the high modulus fibres, for example in terms
of a better compatibility for this Se84nano resin with high-modulus
HR40 carbon fibres. A direct subsequent study would be to know
the critical amount of nano-fillers that can enhance the compressive
strength without leading to interface damage. The development of such
resins could lead to a new way in the design of composite structures.
Both HR40 & IM2C fibres would then be able to deliver a minimum
compressive strength of 1500 MPa, with a substantially higher stiffness
to increase the performance of composite structures such as hydrofoils,
wings of aircrafts or wind turbines. The balance between both stiffness
and strength driven design could be enhanced.
P.-Y. Mechin et al.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
CRediT authorship contribution statement
P.-Y. Mechin: Conceptualization, Methodology, Data curation, In-
vestigation, Writing - original draft, Writing- reviewing & editing,
Investigation. V. Keryvin: Conceptualization, Methodology, Valida-
tion, Writing - original draft, Writing - reviewing & editing, Supervi-
sion, Data curation, Investigation. J.-C. Grandidier: Conceptualization,
Methodology, Writing - reviewing & editing, Validation.
Acknowledgements
The authors are grateful to F. Portanguen, H. Bellegou, A. Jegat,
T.S. Guruprasad (IRDL - UBS) and C. Caër (IRDL - ENSTA Bretagne)
for experimental support and Y. Pannier, D. Mellier (PPRIME - EN-
SMA) for their contribution to X-ray scanning tomography scanning
and discussions. We thank K. Cadd & T. Chatteley (Gurit company)
for support and materials. The X-ray scanning tomography apparatus
has been partially financially supported by the French Government
programme ‘‘Investissements d’Avenir’’ France (EQUIPEX GAP, ref.
ANR-11-EQPX-0018) and funding of Europe and Nouvelle-Aquitaine,
France.
References
[1] C. Soutis, Measurement of the static compressive strength of carbon-fibre/epoxy
laminates, Compos. Sci. Technol. 42 (4) (1991) 373–392.
[2] M.R. Wisnom, The effect of fibre waviness on the relationship between compres-
sive and flexural strengths of unidirectional composites, J. Compos. Mater. 28
(1) (1994) 66–76.
[3] B. Budiansky, N. Fleck, Compressive failure of fibre composites, J. Mech. Phys.
Solids 41 (1) (1993) 183–211.
[4] A. Jumahat, C. Soutis, F.R. Jones, A. Hodzic, Effect of silica nanoparticles on
compressive properties of an epoxy polymer, J. Mater. Sci. 45 (21) (2010)
5973–5983.
[5] M. Quaresimin, R.J. Varley, Understanding the effect of nano-modifier addition
upon the properties of fibre reinforced laminates, Compos. Sci. Technol. 68 (3–4)
(2008) 718–726.
[6] M.F. Uddin, C.T. Sun, Strength of unidirectional glass/epoxy composite with
silica nanoparticle-enhanced matrix, Compos. Sci. Technol. 68 (7–8) (2008)
1637–1643.
Composites Science and Technology 192 (2020) 108099
[7] J.L. Tsai, Y.L. Cheng, Investigating silica nanoparticle effect on dynamic
and quasi-static compressive strengths of glass fiber/epoxy nanocomposites, J.
Compos. Mater. 43 (25) (2009) 3143–3155.
[8] Jumahat A., Effect of nanofillers on thermo-mechanical properties of polymers
and composite laminates (Ph.D. thesis), University of Sheffield, UK, 2011.
[9] A. Jumahat, C. Soutis, J. Mahmud, N. Ahmad, Compressive properties of
nanoclay/epoxy nanocomposites, Procedia Eng. 41 (IRIS) (2012) 1607–1613.
[10] ASTM, D790 - standard test method for flexural properties of unreinforced and
reinforced plastics and electrical insulating materials, 2002.
[11] P.-Y. Mechin, V. Keryvin, J.-C. Grandidier, D. Glehen, An experimental protocol
to measure the parameters affecting the compressive strength of CFRP with a
fibre micro-buckling failure criterion, Compos. Struct. 211 (2019) 154–162.
[12] V. Keryvin, A. Marchandise, P.-Y. Mechin, J.-C. Grandidier, Determination of the
longitudinal non linear elastic behaviour and compressive strength of a CFRP ply
by bending tests on laminates, Composites B 187 (2020) 107863.
[13] ISO 527-2. Plastics - Determination of tensile properties - Part 2 Test conditions
for moulding and extrusion plastics, 1996.
[14] J. Schindelin, I. Arganda-Carreras, E. Frise, V. Kaynig, M. Longair, T. Pietzsch,
et al., Fiji: an open-source platform for biological-image analysis, Nat. Methods
9 (7) (2012) 676–682.
[15] M.R. Wisnom, On the high compressive strains achieved in bending test on
unidirectional carbon-fibre/epoxy, Compos. Sci. Technol. 43 (1) (1992) 229–235.
[16] J.C. Grandidier, P. Casari, C. Jochum, A fibre direction compressive failure
criterion for long fibre laminates at ply scale, including stacking sequence and
laminate thickness effects, Compos. Struct. 94 (12) (2012) 3799–3806.
[17] S. Drapier, C. Gardin, J.C. Grandidier, M. Potier-Ferry, Structure effect and
microbuckling, Compos. Sci. Technol. 56 (96) (1996) 861–867.
[18] C. Gardin, J.C. Grandidier, M. Potier-Ferry, Homogenized models for the mod-
elling of instability in long fibre media, Rev. Mec. Appl. Théor. 1 (2002)
171–203.
[19] A. Jumahat, C. Soutis, F. Jones, A. Hodzic, Fracture mechanisms and failure
analysis of carbon fibre/toughened epoxy composites subjected to compressive
loading, Compos. Struct. 92 (2) (2010) 295–305.
[20] C. Jochum, J.C. Grandidier, Smaali M., Proposal for a long-fibre microbuckling
scenario during the cure of a thermosetting matrix, Composites A 39 (1) (2008)
19–28.
[21] M.S. Kumar, K. Raghavendra, M. Ambresh, H. Ramachandra, M. Venkataswamy,
V. Ranganath, Fractographic analysis of compression failures in unidirectional
carbon fiber reinforced plastic composites, Proc. Inst. Mech. Eng. L 229 (6)
(2015) 439–446.
[22] P.S. Steif, A simple model for the compressive failure of weakly bonded,
fiber-reinforced composites, J. Compos. Mater. 22 (9) (1988) 818–828.
[23] A. Argon, Treatise on materials science and technology, in: Fracture of Com-
posites, herman ed, Academy Press, New York, ISBN: 9781483218175, 1972, p.
270, chap. 4.
[24] M. Rodríguez, J.M. Molina-Aldareguía, C. Gonzílez, J. LLorca, A methodology to
measure the interface shear strength by means of the fiber push-in test, Compos.
Sci. Technol. 72 (15) (2012) 1924–1932.