Composites Science and Technology 129 (2016) 61e69

Contents lists available at ScienceDirect

Composites Science and Technology

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

Enhancing the impact and flexural strength of PP/LLDPE/TiO2/SEBS

nano-composites by using Taguchi methodology
Mohsen Ayaz a, *, Sajjad Daneshpayeh b, Ali Noroozi b
a
Faculty of Mechanical Engineering, Malek Ashtar University of Technology, Tehran, Iran
b
Faculty of Mechanical Engineering, Shahid Rajaee Teacher Training University, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The present study was an attempt to maximize the impact and flexural strength of polypropylene/linear
Received 4 February 2016 low-density polyethylene/nano-titanium dioxide/styrene-ethylene-butylene-styrene (PP/LLDPE/TiO2/
Received in revised form SEBS) nano-composites simultaneously by optimizing the LLDPE, TiO2, and SEBS. An L9 orthogonal array
11 April 2016
of Taguchi method was used for the experimental design to extract the optimal level of parameters by
Accepted 13 April 2016
Available online 14 April 2016
signal to noise (S/N) ratio. The S/N ratios results were then investigated by grey relational analysis (GRA)
in order to determine optimal condition of the impact and flexural strength. Simultaneous enhancement
of the impact and flexural strength was achieved by 33.85% under optimal condition, i.e. 40 wt% LLDPE,
Keywords:
PP/LLDPE/TiO2/SEBS nano-composite
2 wt% TiO2 and 6 wt% SEBS. The effectiveness of the proposed approach was demonstrated through
Impact strength confirmation tests at the optimal levels of parameters.
Flexural strength © 2016 Elsevier Ltd. All rights reserved.
Taguchi method
Grey relational analysis

1. Introduction strength and Young's modulus of the composites deteriorated.

Polypropylene (PP) has been used as the matrix material in a
commercial form due to its many good properties, such as light
weight, easy processability, relatively low cost, excellent heat
distortion temperature and its durability [1,2]. However, PP has
certain drawbacks that limit its usage in some applications. One of
these drawbacks is its poor impact strength especially at low
temperature due to the inherently high glass transition tempera-
ture (Tg) and high crystallinity [3]. Adding flexible polymers such as
linear low-density polyethylene (LLDPE) is one of the most efficient
methods to toughen PP for different high performance applications.
Blending of PP and LLDPE has been attempted to achieve
improvement in chemical, physical and mechanical properties,
where PP ensures good processability and insensitivity to moisture,
while LLDPE contributes impact properties. Hassan et al. [4] re-
ported improvement in the impact strength of PP by melt blending
with natural rubber and LLDPE. Younesi et al. [5] investigated the
effect of LLDPE on the mechanical properties of PP/LLDPE and
recognized that by adding LLDPE to this composite, the impact
strength was enhanced significantly, while their ultimate tensile
* Corresponding author.
E-mail address: mohsen.ayaz@yahoo.com (M. Ayaz).
Nayak et al. [6] stated that by incorporation of LLDPE to the polymer
matrix composites, the impact strength of composites increased
while the flexural strength decreased. Balakrishnan et al. [7] re-
ported that the LLDPE improved the impact strength of polymer
nano-composites, while decreased the tensile and flexural strength.
As clear from literature review, the incorporation of LLDPE to PP
led to a decrease in some mechanical properties such as flexural
strength. Nano-particles had been extensively used to overcome
these limitations because of their high specific surface area, which
can act as a stress-transfer interface [3]. Titanium dioxide (TiO2) is
one of the most important nano-particles because of some char-
acteristics such as photoelectric conversion, photocatalytic activity,
antibacterial activity, odor inhibition and self-cleaning mechanism
[8]. These characteristics make TiO2 a perfect inorganic reinforcing
component in fabricating nano-composites with desirable me-
chanical properties. Supaphol et al. [9] reported that the presence
of the TiO2 nano-particles within the PP matrix increased the
impact and flexural strength of the nano-composites. Rusu and
Rusu [10] observed noticeable enhancements in the flexural
strength of nylon6/TiO2 nano-composites. Enhancements in the
flexural properties of polyamide6/PP blend were reported by Ou
et al. [11]. Deka and Maji [12] observed that both flexural and
tensile properties of polymer nano-composite were enhanced up to
the addition of 3 wt% TiO2, beyond that these values decreased.

http://dx.doi.org/10.1016/j.compscitech.2016.04.015
0266-3538/© 2016 Elsevier Ltd. All rights reserved.
62 M. Ayaz et al. / Composites Science and Technology 129 (2016) 61e69
Zapata et al. [13] stated that an increase of Young's modulus and
yield stress in LLDPE/TiO2 was achieved by 50% compared to neat
LLDPE. A great effort has also been devoted to the mechanical
properties of TiO2 nano-particles during the last decades and this is
still an area of substantial scientific and commercial interest
[14e17]. However, thermoplastic nano-composites based on blends
of two or more polymeric materials, i.e. binary or ternary blends,
seem to be a new approach in the nano-composites studies. In this
respect, the dispersion of TiO2 nano-particles into PP/LLDPE ma-
trixes can be emerged as a new approach.
Nano-particles have a much higher surface-to-volume ratio
than conventional micron-particles, and with decreasing particle
size the number of molecules presents on the surface increases
enormously. Hence, interparticle attraction through forces such as
van der Waals and electrostatic forces becomes stronger resulting
in a high surface energy and a tendency to agglomerate during melt
blending [3]. Styrene-ethylene/butylene-styrene (SEBS) as a
coupling agent can reduce or remove the influence of van der Waals
forces and improve the compatibility between the hydrophobic PP
matrix and the TiO2 nano-particles. TiO2 is a nano-filler with a large
number of hydroxyl groups on its surface that generate strong
fillerefiller interactions. The mid-block of SEBS can react with hy-
droxyl groups of the TiO2 surfaces and reduce the high surface
energy difference between PP and the TiO2 nano-particles. A good
dispersion and a strong interface can be obtained by incorporating
SEBS to the nano-TiO2 replacing hydroxyl groups on the nano-
particle surface that interact with the polymeric matrix [18]. Par-
ameswaranpillai et al. [19] reported that the SEBS acted as an
excellent dispersing agent by preventing the agglomeration of
nano-fillers and improved dispersion and strengthened the inter-
face between the fillers and the matrix. Kusmono et al. [20] used
SEBS up to 30 wt% into polyamide6/PP nano-composites and ob-
tained higher tensile and impact strength. Kuboki et al. [21] stated
that the SEBS improved the tensile and flexural strength of the PP
composites.
A review of the existing literature revealed that most of the
studies conducted by researchers on properties of polymer nano-
composites involve changing one of the independent parameters
at a time while maintaining the others at fixed level. For this pur-
pose, in this research an experimental design based on orthogonal
array of Taguchi method was applied. Using signal to noise (S/N)
ratio and orthogonal array of Taguchi method, a balanced com-
parison of levels of the parameters and significant reduction in the
total number of required tests can both be achieved [22,23].
Furthermore, analysis of variance (ANOVA) has been used to
determine the percentage contribution of each input parameters on
the impact and flexural strength. However, the Taguchi experi-
mental design method can only control the optimization of a single
response. Hence, multiple responses were integrated based on the
grey relational analysis (GRA) and Taguchi method to determine
the optimized combination of parameter levels, in order to enhance
the mechanical properties of PP/LLDPE/TiO2/SEBS nano-
composites.
2. Experimental
2.1. Materials
TiO2 powder (rutile crystal forms) with the average size of
30 nm and density of 4.23 g/cm3 was provided by Iranian Nano-
materials Pioneers (INP). The polymers used in this study were
polypropylene (Grade name PP-Z30S, MFI-25 g/10 min measured at
230
C, standard weight 2.16 kg, density 0.9 g/cm3) and linear low-
density polyethylene (Grade name LLDPE-0209, MFI-0.9 g/10 min
measured at 190
C, standard weight 2.16 kg, density 0.92 g/cm3)
supplied by Arak Petrochemical Company, Iran. Styrene-ethylene/
butylene-styrene (Grade name SEBS-G1652, MFI-5 g/10 min
measured at 230
C, standard weight 5 kg, density 0.91 g/cm3) as a
coupling agent was supplied by KRATON Polymers, USA.
The compounding was carried out using a co-rotating screw
extruder (ZSK 25 P8.2E WLE) within 170e190
C temperature
range. The obtained compounds were injection molded to prepare
the test samples by an injection molding machine (IMAN MACHINE,
maximum shot weight per part: 125 g) in the temperature profile of
190e200e210
C and the samples were prepared.
2.2. Mechanical testing
Izod impact test was carried out on notched specimens using a
RESIL IMPACTOR instrument (Italy) according to ASTM D256 with
an impact speed of 3.46 m/s. Flexural test was also performed by
using a three-point bending machine (Zwick/Roell, Germany) with
a support span length of 50 mm and a crosshead speed of 3 mm/
min. All measurements were conducted up to a flexural strain equal
to 5%, according to the ASTM D790 standard at room temperature.
2.3. Scanning electron microscopy (SEM)
The fracture surface of impact specimens was investigated using
VEGATESCAN Scanning Electron Microscopy (SEM) at an accelera-
tion voltage of 20 kV. SEM was used to characterize the state of
dispersion in the nano-composites. The fracture surface was
sputter-coated a thin goldepalladium layer in vacuum chamber for
conductivity before examination.
2.4. Design of experiments (DOE)
The experimental design was performed based on the orthog-
onal array of Taguchi method to evaluate the influence of param-
eters such as LLDPE (20, 40, 60 wt%), TiO2 (0, 2, 4 wt%) and SEBS (0,
3, 6 wt%) on the mechanical properties of PP polymer matrix. The
considered parameters and their levels were listed in Table 1. The
design was composed of 3 variables set at 3-levels each, where the
impact and flexural strength were the dependent variables. Ac-
cording to the standard orthogonal array of Taguchi method, the
design required a total of 9 experiments. The average of experi-
mental results with three replicates and standard deviation of each
experiment by using the L9 orthogonal array were listed in Table 2.
3. Results and discussion
3.1. Analysis of S/N ratios
In analyzing the results, Taguchi recommended the use of the
signal to noise (S/N) ratio to specify the quality of the characteristics
applied. The term ‘signal’ indicates the desirable value (mean) for
the output characteristic and the term ‘noise’ indicates the unde-
sirable value (standard deviation) for the output characteristic. A
high S/N ratio indicates that the signal is much higher than the
random effect of the noise parameters. Depending on the
Table 1
Levels of the parameters used in studying of the LLDPE, TiO2 and SEBS.
Parameters Levels
1 2 3
LLDPE (wt%) 20 40 60
TiO2 (wt%) 0 2 4
SEBS (wt%) 0 3 6
 M. Ayaz et al. / Composites Science and Technology 129 (2016) 61e69 63

Table 2
The experimental results for L9 orthogonal array.

Runs PP (wt LLDPE (wt TiO2 (wt SEBS (wt Impact strength (J/ Standard deviation of impact Flexural strength Standard deviation of flexural
%) %) %) %) m) strength (MPa) strength

1 80 20 0 0 44 1.00000 72 3.46410
2 75 20 2 3 87 1.00000 78 1.00000
3 70 20 4 6 62 1.73205 67 1.00000
4 57 40 0 3 69 1.00000 62 2.00000
5 52 40 2 6 126 0.00000 71 1.00000
6 56 40 4 0 58 1.00000 56 2.00000
7 34 60 0 6 138 1.00000 59 1.15470
8 38 60 2 0 93 2.00000 51 1.00000
9 33 60 4 3 119 1.73205 54 2.00000

experimental objective, Taguchi method optimizes the process Table 4

parameters in order to minimize standard deviation using one of S/N ratio of impact strength by parameter levels (LB).

the objective functions such as: ‘‘the-nominal-the-best (NB)’’, ‘‘the- Levels S/N ratio
larger-the-better (LB)’’, or ‘‘the-smaller-the- better (SB)’’. In this LLDPE TiO2 SEBS
study, the higher impact and flexural strength were expected. Thus,
1 35.76 37.41 35.76
S/N ratio characteristic of LB was applied in the analysis by the
2 38.01 40.05 39.02
following equation: 3 41.22 37.54 40.21
!! Delta 5.46 2.64 4.45
S 1X n
1 Rank 1 3 2
¼ 10 log10 (1)
N n i¼0 y2i

where n is the number of repeated experiment (in the present
study n ¼ 3) and yi is the response measured to the ith time [24,25].
The S/N ratio values were calculated using MINITAB® 17 software
for the impact and flexural strength by taking into consideration Eq.
(1), as shown in Table 3.
3.2. Results of S/N ratios for the impact strength
The average values of the S/N ratios of the impact strength for
each level of the parameters were given in Table 4. These values
were also shown by main effect plots in Fig. 1. Main effect plots
reveal the level to be chosen for optimum parameters, i.e. the level
with the highest point on the plots. The highest S/N ratio always
yields the optimum quality with minimum variance. Therefore, the
level with a higher value reveals the optimum level of each
parameter. The rank and delta values have been used to specify the
most significant parameters. Delta values for every given parameter
in Table 4 show the difference between the highest and the lowest
S/N ratios.
It is clear from Table 4 and Fig. 1 that the LLDPE was the most
significant parameter affecting the impact strength of PP/LLDPE/
TiO2/SEBS nano-composite followed by the SEBS and TiO2. It can
also be understood from Fig. 1 that as the content of LLDPE and
SEBS varied from low to high values, the impact strength showed
an increase by 55.4% and 46.4%, respectively. In addition, the in-
crease in the TiO2 from 0 to 2 wt% resulted in an enhancement in
the impact strength by 19.5%, while the increase in the TiO2 from 2
to 4 wt% resulted in a decrease in the impact strength by 23.7%. The
enhancement of the impact strength can be attributed to a good
dispersion of TiO2 nano-particles and strong interfacial interactions
with the PP matrix, that favor the pinning of cracks as can be seen
from the SEM images in Fig. 2a. Similar results were reported by
Wacharawichananat et al. [26] that stated by addition of the TiO2
nano-particles within PP polymer matrix (about 1 wt%), the impact
strength of polymer nano-composite increased. Cioni et al. [27] also
reported an extraordinary improvement in the impact strength by
addition of nano-particles to polymer matrix, attributed to the
formation of a continuous monolayer of hydrophobic alkyl chains
on the nano-particles that promoted a more uniform filler disper-
sion and matrix-particle debonding. These mechanisms allowed
higher energy absorption during fracture. However, similar to re-
sults of this research, Altan and Yildirim [28] reported that by
addition of the nano-TiO2 up to 3 wt% in the PP matrix, the impact
strength of polymer nano-composite decreased. This can be due to
the filler agglomerates that acted as failure initiation sites and
facilitated crack propagation, as shown in Fig. 2b. But the presence
of SEBS in the PP/LLDPE/TiO2 nano-composites made a dramatic
change, so that the TiO2-PP interface enhanced and agglomeration
was reduced, resulted in an increase in the impact strength
compared to the PP/LLDPE/TiO2 nano-composites without SEBS
(Fig. 2c) [3]. Parameswaranpillai et al. [19] reported an increase in
the impact strength by addition of SEBS to PP/graphene nano-
composites and described this situation by any of the three

Table 3
The results of S/N ratio of LB for the impact and flexural strength.

Runs LLDPE (wt%) TiO2 (wt%) SEBS (wt%) S/N ratios of impact strength S/N ratios of flexural strength

1 20 0 0 32.6647 37.1243
2 20 2 3 38.7892 37.8419
3 20 4 6 35.8388 36.5196
4 40 0 3 36.7714 35.8388
5 40 2 6 42.0069 37.1450
6 40 4 0 35.2610 34.9556
7 60 0 6 42.7917 35.3720
8 60 2 0 39.3625 34.1481
9 60 4 3 41.5085 34.6359
64 M. Ayaz et al. / Composites Science and Technology 129 (2016) 61e69

Fig. 1. Main effects plots for S/N ratios of impact strength.

Fig. 2. SEM images of the samples with: a) LLDPE ¼ 60, TiO2 ¼ 2, SEBS ¼ 0 wt%, b) LLDPE ¼ 40, TiO2 ¼ 4, SEBS ¼ 0 wt%, c) LLDPE ¼ 40, TiO2 ¼ 2, SEBS ¼ 6 wt%.

mechanisms. (i) SEBS phase formed a coating or wrapping over the
nano-fillers and reduced the unfavorable interactions between the
filler and the matrix, (ii) Presence of SEBS retarded the rate of
agglomeration of nano-fillers by forming layers over the surface of
filler, (iii) SEBS facilitated the rejection of nano-particles from PP
matrix by providing less unfavorable interactions, during the
crystallization of PP matrix.
Another remark on the results of S/N ratio analysis in Fig. 1 is
that the optimal level of parameters for maximizing the impact
strength were obtained at level 3 of LLDPE (60 wt%), level 2 of TiO2
(2 wt%) and level 3 of SEBS (6 wt%). In order to understand the
complete effect of the parameters influencing impact strength, the
interactions between the parameters have to be taken into account.
The interaction plot between the three parameters studied in this
work namely LLDPE, TiO2 and SEBS was shown in Fig. 3. The vertical
axis shows the average of the impact strength, while the horizontal
axis shows the variation of parameters according to the Taguchi
design. Non-parallel lines show that the interaction between pa-
rameters is significant. From Fig. 3a, it can be observed that the first
interaction occurred between TiO2 and SEBS (TiO2  SEBS) indi-
cated by the non-parallel lines. As clear from the TiO2  SEBS
interaction, for 0 wt% SEBS, the increase in the value of TiO2 from
0 to 4 wt% initially enhanced the impact strength from 44 to 93 J/m,
but eventually decreased them to 58 J/m. For 3 wt% SEBS, a change
in the value of TiO2 from 0 to 4 wt% enhanced the impact strength
up to 119 J/m, while for 6 wt% SEBS, the impact strength reduced to
62 J/m. This may be due to the saturation of the reinforcing action of
the filler. When the coupling agent reached a maximum value, it
can't be effective [29].
The second significant interaction was seen between the LLDPE
and SEBS (Fig. 3b). As clear from Fig. 3b, the increase in the value of
LLDPE from 20 to 60 wt% enhanced the impact strength up to 93
and 138 J/m for 0 and 6 wt% SEBS, respectively. However, for 3 wt%
SEBS, the impact strength initially decreased from 87 to 69 J/m, and
then enhanced up to 119 J/m. The third significant interaction was
seen between the LLDPE and TiO2 (Fig. 3c). From Fig. 3c, at 0 wt%
TiO2, an increase in LLDPE tended to enhance the impact strength
from 44 to 138 J/m; however at 2 wt% TiO2 the impact strength
initially enhanced from 87 to 126 J/m but eventually dropped from
126 to 93 J/m. The opposite effect was observed at 4 wt% TiO2, so
that the increase in LLDPE slightly decreased the impact strength
from 62 to 58 J/m and then considerably enhanced them from 58 to
119 J/m.
Analysis of variance (ANOVA) is also needed for estimating the
error variance of the parameter effects. ANOVA establishes the
relative significance of parameters in terms of their percentage
 M. Ayaz et al. / Composites Science and Technology 129 (2016) 61e69 65

Fig. 3. Interaction plots of a) TiO2  SEBS, b) LLDPE  SEBS, c) LLDPE  TiO2, for impact strength.

contribution to the response [23]. This analysis was performed on Table 6

S/N ratios to obtain the contribution of each parameter. The results S/N ratios of flexural strength by parameter levels (LB).

of ANOVA for S/N ratios of impact strength were given in Table 5. It Levels S/N ratio
can be seen that the LLDPE had the maximum contribution in LLDPE TiO2 SEBS
controlling the impact strength with 47.52% contribution followed
1 37.16 36.11 35.41
by SEBS with 33.54% and TiO2 with 14.05%. The influence of residual
2 35.98 36.38 36.11
error on the impact strength was negligible with 4.89% 3 34.72 35.37 36.35
contribution. Delta 2.44 1.01 0.94
Rank 1 2 3

3.3. Results of S/N ratios for the flexural strength

The average values of the S/N ratios of flexural strength for each Naffakh et al. [3] described that the addition of nano-particles to PP
level of the parameters were given in Table 6. These values were led to the increases in the flexural strength, due to the nucleating
also plotted in Fig. 4. It can be seen from Table 6 and Fig. 4 that the effect of nano-particles that were well dispersed within the matrix.
LLDPE was the most significant parameter affecting the flexural However, the higher TiO2 concentrations (2e4 wt%) led to a gradual
strength of PP/LLDPE/TiO2/SEBS nano-composite followed by the decrease in the flexural properties due to particle agglomeration, as
TiO2 and SEBS. As clear from Fig. 4, the flexural strength decreased clear from Fig. 5a. The deterioration of flexural properties at higher
by 65.4% as the LLDPE changed from 20 to 60 wt%, while it showed loadings can be also due to a ductile-to-brittle transition by the
an enhancement by 22.2% as the SEBS changed from 0 to 6 wt%. formation of aggregates. Nevertheless, the SEBS as a coupling agent
Additionally, the flexural strength showed an enhancement by 8.6% led to a fine nano-filler dispersion and a strong interface between
as the TiO2 increased up to 2 wt%, but it dropped by 28.14% as the TiO2 and PP, which improved the flexural properties (Fig. 5b). This
TiO2 increased up to 4 wt%. Similar result was observed by Altan observation can be referred to the fact that a fraction of the TiO2
and Yildirim [28] that stated by adding the TiO2 to PP polymer nano-particles trapped at the PP/SEBS interface, which may rein-
matrix, the flexural strength increases. However, it should be force the interface by filling the voids. The SEBS polymer chains can
highlighted that the enhancement in the flexural properties ach- penetrate between the TiO2 nano-particles in the PP matrix, and
ieved by incorporating 2 wt% TiO2 were considerably larger than help to form nano-bridges between the adjacent TiO2 nano-
those observed in composites reinforced with the equivalent con- particles, which prevent the agglomeration tendency of nano-
centration of other modified or unmodified nano-fillers [30e32]. particles [21]. It can also be observed from the S/N ratio plots in
Fig. 4 that the optimal parameter levels for the highest flexural
strength were obtained at level 1 of LLDPE (20 wt%), level 2 of TiO2
Table 5 (2 wt%) and level 3 of SEBS (6 wt%).
ANOVA results for S/N ratios of impact strength.
Fig. 6 shows the interaction plot between the parameters. From
Source DF Seq SS Adj SS Adj MS F Contribution % these interaction plots, it can be observed that the first interaction
LLDPE 2 45.123 45.123 22.561 9.70 47.52 occurred between TiO2 and SEBS (TiO2  SEBS) indicated by the
TiO2 2 13.339 13.339 6.669 2.87 14.05 non-parallel lines (Fig. 6a). From Fig. 6a, at 0 wt% SEBS, a change in
SEBS 2 31.845 31.845 15.922 6.85 33.54 the value of TiO2 from 0 to 4 wt% initially reduced the flexural
Residual Error 2 4.650 4.650 2.325 4.89
strength from 72 to 51 MPa and eventually enhanced them up to
Total 8 94.956 100
66 M. Ayaz et al. / Composites Science and Technology 129 (2016) 61e69

Fig. 4. Main effects plots for S/N ratios of flexural strength.

Fig. 5. SEM images of the samples with: a) LLDPE ¼ 60, TiO2 ¼ 4, SEBS ¼ 3 wt%, b) LLDPE ¼ 40, TiO2 ¼ 2, SEBS ¼ 6 wt%.

56 MPa. In contrast, as the TiO2 increased from 0 to 4 wt%, the
flexural strength increased from 62 to 78 MPa for 3 wt% SEBS and
59 to 71 MPa for 6 wt% SEBS, and then decreased from 78 to 54 for
3 wt% SEBS and 71 to 67 MPa for 6 wt% SEBS. This implies that the
effect of TiO2 was high when the SEBS was high, but at lower SEBS,
the effect of TiO2 was not so high.
From the second significant interaction between the LLDPE and
SEBS (Fig. 6b), it can be understood that a change in the LLDPE from
20 to 60 wt% showed deterioration of the flexural strength from 72
to 51 MPa for 0 wt% SEBS and 78 to 54 MPa for 3 wt% SEBS. How-
ever, for 6 wt% SEBS, an increase in the LLDPE from 20 to 40 wt%
showed enhancement of the flexural strength from 67 to 71 MPa,
but further increase of the LLDPE from 40 to 60 wt% showed
deterioration of the flexural strength from 71 to 59 MPa. The third
significant interaction was seen between the LLDPE and TiO2
(Fig. 6c). As clear from Fig. 6c, the increase in the value of LLDPE
from 20 to 60 wt% dropped the flexural strength from 72 to 59 MPa
for 0 wt% TiO2, 78 to 51 MPa for 2 wt% TiO2 and 67 to 54 MPa for
6 wt% TiO2. However, deterioration of the flexural strength by the
LLDPE was more considerable at 2 wt% TiO2.
The ANOVA results for the S/N ratios of flexural strength given in
Table 7 show the percentage contribution of each parameter. The
percentage contributions of input parameters in increasing order
were 68.79% for LLDPE, 12.57% for TiO2 and 10.91% for SEBS. The
effect of residual error on the flexural strength in terms of per-
centage contribution was 7.73%.
3.4. Grey relational analysis (GRA)
Grey relational analysis (GRA) is a method for the measurement
of the correlation degree between parameters based on the simi-
larity or difference between them. GRA was used to determine the
absolute value of the data difference between sequences, and it
could be applied to achieve the approximate correlation between
sequences. The grey theory is one of the significant theories for the
uncertainty, multi-response and discrete data. Based on the GRA,
the experimental data of the impact and flexural strength were first
normalized to be in the range of zero to one, known as data pre-
processing [33]. Data pre-processing is usually necessary since
the range and the unit in one data may differ from the others.
Depending on the characteristics of the data sequence, there are
various types of data pre-processing available including: “the-
larger-the-better” (LB), “the-smaller-the- better” (SB), or “the-
nominal-the-best” (NB). As the higher impact and flexural strength
 M. Ayaz et al. / Composites Science and Technology 129 (2016) 61e69 67

Fig. 6. Interaction plots of a) TiO2  SEBS, b) LLDPE  SEBS, c) LLDPE  TiO2, for flexural strength.

Table 7 usual to calculate the average value of the grey relational coefficient
ANOVA results for S/N ratios of flexural strength. as the grey relational grade (gi). The grey relational grade is treated
Source DF Seq SS Adj SS Adj MS F Contribution % as the overall response instead of the multiple responses of impact
LLDPE 2 8.957 8.957 4.4786 8.90 68.79
and flexural strength. The grey relational grade (gi) was calculated
TiO2 2 1.637 1.637 0.8183 1.63 12.57 as follows:
SEBS 2 1.419 1.419 0.7094 1.41 10.91
Residual Error 2 1.007 1.0070 0.5034 7.73
Total 8 13.019 100
1Xr
gi ¼ xi ðkÞ (4)
r
k¼1

provide better feature of the mechanical properties, the data se-

quences of responses have LB characteristics. Hence, the original
sequence should be normalized as follows:
yi ðkÞ  minyi ðkÞ
xi ðkÞ ¼
maxyi ðkÞ  minyi ðkÞ
where xi(k) is the normalized value of the kth element in the ith
sequence, yi(k) is the original value, min yi(k) is the smallest value
of yi(k) and max yi(k) is the largest value of yi(k) [33]. The larger
value of normalized results can show the better performance
characteristic, and the best normalized results will be equal to one.
In the GRA, S/N ratio of quality characteristics was normalized at
first to reduce the variability. After data pre-processing, a grey
relational coefficient (xi(k)) was calculated to recognize the rela-
tionship between the optimal (best ¼ 1) and actual normalized
experimental results. The grey relational coefficient xi(k) can be
calculated as follows:
Dmin þ zDmax
xi ðkÞ ¼
D0i ðkÞ þ zDmax
where D0i(k) is the difference of the absolute value between x0(k)
and xi(k), i.e. jx0(k)  xi(k)j, Dmin and Dmax are the minimum and
maximum values of the absolute differences (D0i) of all comparing
sequences, respectively [33]. A value of the z ¼ 0.5 is generally used
when the weighting coefficients of each response are equal.
After calculation of the grey relational coefficient (xi(k)), it is
where r is the number of performance characteristics (2 in present
case) [33]. The data normalized (xi(k)), grey relational coefficient
(xi(k)) and grey relational grade (gi) for each experiment using the
L9 orthogonal array of Taguchi design were listed in Table 8. A
higher grey relational grade (gi) shows that the corresponding S/N
(2)
ratio is closer to the ideally normalized S/N ratio. It was observed
from the results that the experiment number 5 had the highest grey
relational grade (gi); therefore it is optimal parameter setting for
attaining multiple performances simultaneously among 9 experi-
ments. However, the relative importance of the each parameter for
the multiple performance characteristics still needed to be
analyzed in order to determine the optimal combinations of the
parameter levels.
In the present study, S/N ratio analysis was employed for GRA as
the performance index to convert the gi results into a value for the
characteristics in the optimum parameter analysis. As the larger
value of grey relational grade can show the better performance
characteristic, the S/N ratio was calculated using the-larger-the-
better (LB) criterion (Eq. (1)). MINITAB® 17 software was
employed to calculate the average value of the grey relational
(3)
grades for each parameter level, as shown in Table 9. The main
effect analysis was conducted on the numerical values of the grey
relational grade to draw the response graph (Fig. 7). The optimum
level of parameters with respect to maximum grey relational grade,
was level 2 of LLDPE, level 2 of TiO2 and level 3 of SEBS. Therefore,
the higher impact and flexural strength of the PP/LLDPE/TiO2/SEBS
nano-composite can be obtained simultaneously by 40 wt% LLDPE,
2 wt% TiO2, and 6 wt% SEBS. The mechanical properties of PP/
68 M. Ayaz et al. / Composites Science and Technology 129 (2016) 61e69

Table 8
Results of GRA for the impact and flexural strength.

Run xi (k) xi (k) gi

Impact strength Flexural strength Impact strength Flexural strength

1 0.00000 0.80572 0.33333 0.72017 0.526752

2 0.60477 1.00000 0.55852 1.00000 0.779257
3 0.31343 0.64201 0.42138 0.58276 0.502070
4 0.40552 0.45771 0.45684 0.47971 0.468275
5 0.92250 0.81133 0.86580 0.72603 0.795917
6 0.25637 0.21862 0.40205 0.39020 0.396127
7 1.00000 0.33134 1.00000 0.42784 0.713923
8 0.66138 0.00000 0.59622 0.33333 0.464774
9 0.87329 0.13207 0.79781 0.36552 0.581665

Table 9
S/N ratios of grey relational grade by parameter levels (LB). X
q
Y ¼ Ym þ ðYi  Ym Þ (5)
Levels S/N ratio
i¼0
LLDPE TiO2 SEBS

1 5.642 6.356 7.712 where Ym is the total average of the grey relational grade, Yi is the
2 5.576 4.342 5.462 average of the grey relational grade at the optimum level, and q is
3 6.456 6.976 4.500 the number of parameters [35]. The initial conditions of parameters
Delta 0.880 2.634 3.212
were LLDPE1 TiO2 1 SEBS1, which was the experimental number 1 in
Rank 3 2 1
Table 2. As shown in Table 10, the results of confirmation test

Fig. 7. Main effects plot for S/N ratios of grey relational grade.

LLDPE/TiO2/SEBS nano-composites can be related to thermal and
crystallization behavior as extensively described in our previous
research [34].
3.5. Confirmation experiment
The experimental confirmation test is an important step in
verifying the results obtained based on the Taguchi design. A
selected number of experiments were carried out under optimal
conditions of parameters to validate the feasibility and reproduc-
ibility of the optimization method adopted in this study. The
average of the confirmation tests was compared with the results of
prediction and initial condition in Table 10. The predicted grey
relational grade for the optimal levels of parameters can be calcu-
lated as:
indicated that the value of impact strength was strongly enhanced
from 44 to 127 J/m, while the value of flexural strength was slightly
dropped from 72 to 71 MPa. The predicted grey relational grade
increased up to 0.8421, which was the largest value among all ex-
periments in Table 8. In addition, grey relational grade of confir-
mation experiment was improved by 33.85% from the initial grey
relational grade. Consequently, it clearly showed that the required
performance characteristics namely the impact and flexural
strength have greatly enhanced by using this approach.
4. Conclusions
In the present study, different filler loadings of LLDPE, TiO2 and
SEBS were optimized by Taguchi based grey relational analysis, in
order to enhance the impact and flexural strength of PP/LLDPE/
 M. Ayaz et al. / Composites Science and Technology 129 (2016) 61e69
Table 10
Results of the confirmation experiment for the impact and flexural strength.
Initial conditions
Level LLDPE1, TiO2 1, SEBS1
Impact strength (J/m) 44
Flexural strength (MPa) 72
Grey relational grade 0.5267
Improvement of Grey relational grade from initial ¼ 0.2696 ¼ 33.85%.
TiO2/SEBS nano-composite, simultaneously. From the S/N ratio
analysis, it was found that the maximum impact strength obtained
as follows: LLDPE 60 wt%, TiO2 2 wt%, and SEBS 6 wt%. It was also
found that the maximum flexural strength obtained as follows:
LLDPE 20 wt%, TiO2 2 wt%, and SEBS 6 wt%. Through ANOVA it was
revealed that LLDPE had the maximum contribution in controlling
the impact and flexural properties of PP/LLDPE/TiO2/SEBS nano-
composite. Significant interactions of TiO2  SEBS, LLDPE  SEBS
and LLDPE  TiO2 confirmed that the ideal values of LLDPE, TiO2,
and SEBS of the PP/LLDPE/TiO2/SEBS nano-composites for obtaining
the maximum impact and flexural strength varied with the varia-
tion of each. Finally, according to grey relational analysis in
conjunction with Taguchi design of experiments it was predicted
that the higher impact and flexural strength of PP/LLDPE/TiO2/SEBS
nano-composite simultaneously obtained as follows: LLDPE 40 wt
%, TiO2 2 wt%, and SEBS 6 wt%. The efficiency of Taguchi based grey
relational analysis had been successfully proven by confirmation
experiments at the optimal parameters conditions.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.compscitech.2016.04.015.
References
[1] S.P. Ju, C.C. Chen, T.J. Huang, C.H. Liao, H.L. Chen, Y.C. Chuang, Y.C. Wu,
H.T. Chen, Investigation of the structural and mechanical properties of
polypropylene-based carbon fiber nanocomposites by experimental mea-
surement and molecular dynamics simulation, Comput. Mater. Sci. 115 (2016)
1e10.
[2] P.A. Zapata, F.M. Rabagliati, I. Lieberwirth, F. Catalina, T. Corrales, Study of the
photodegradation of nanocomposites containing TiO2 nanoparticles dispersed
in polyethylene and in poly (ethylene-cooctadecene), Polym. Degrad. Stabil.
109 (2014) 106e114.
[3] M. Naffakh, A.M.D. Pascual, C. Marco, G.J. Ellis, M.A.G. Fatou, Opportunities and
challenges in the use of inorganic fullerene-like nanoparticles to produce
advanced polymer nanocomposites, Prog. Polym. Sci. 38 (2013) 1163e1231.
[4] A. Hassan, M.U. Wahit, C.Y. Chee, Mechanical and morphological properties of
PP/NR/LLDPE ternary blenddeffect of HVA-2, Polym. Test. 22 (2003) 281e290.
[5] M. Younesi, M.E. Bahrololoom, Producing toughened PP/HA-LLDPE ternary
bio-composite using a two-step blending method, Mater. Des. 30 (2009)
4253e4259.
[6] S.K. Nayak, S. Mohanty, Poly (trimethylene) terephthalate/m-LLDPE blend
nanocomposites: evaluation of mechanical, thermal and morphological
behavior, Mat. Sci. Eng. A Struct. 527 (2010) 574e583.
[7] H. Balakrishnan, A. Hassan, M.U. Wahit, A.A. Yussuf, S.B.A. Razak, Novel
toughened polylactic acid nanocomposite: mechanical, thermal and
morphological properties, Mater. Des. 31 (2010) 3289e3298.
[8] M. Rana, B. Hao, L. Mu, L. Chen, P.C. Ma, Development of multi-functional
cotton fabrics with Ag/AgBreTiO2 nanocomposite coating, Compos. Sci.
Technol. 122 (2016) 104e112.
[9] P. Supaphol, P. Thanomkiat, J. Junkasem, R. Dangtungez, Non-isothermal melt
crystallization and mechanical properties of titanium(IV) oxide nanoparticle-
filled isotactic polypropylene, Polym. Test. 26 (2007) 20e37.
[10] G. Rusu, E. Rusu, Nylon 6/TiO2 composites by in situ anionic ring-opening
polymerization of caprolactam: synthesis, characterization and properties,
Int. J. Polym. Anal. Charact. 16 (2011) 561e583.
[11] B. Ou, D. Li, Y. Liu, Compatibilizing effect of maleated polypropylene on the
mechanical properties of injection molded polypropylene/polyamide 6/func-
tionalized-TiO2 nanocomposites, Compos. Sci. Technol. 69 (2009) 421e426.
[12] B.K. Deka, T.K. Maji, Effect of TiO2 and nanoclay on the properties of wood
polymer nanocomposite, Compos. Part A Appl. S 42 (2011) 2117e2125.
69
Optimal conditions
Experimental Prediction
LLDPE2, TiO2 2, SEBS3 LLDPE2, TiO2 2, SEBS3
127 118.3
71 69.4
0.7963 0.8421
[13] P.A. Zapata, H. Palza, L.S. Cruz, I. Lieberwirth, F. Catalina, T. Corrales,
F.M. Rabagliati, Polyethylene and poly(ethylene-co-1-octadecene) composites
with TiO2 based, nanoparticles by metallocenic “in situ” polymerization,
Polymer 54 (2013) 2690e2698.
[14] S.K. Esthappan, S.K. Kuttappan, R. Joseph, Thermal and mechanical properties
of polypropylene/titanium dioxide nanocomposite fibers, Mater. Des. 37
(2012) 537e542.
[15] B. Oua, D. Li, Y. Liu, Compatibilizing effect of maleated polypropylene on the
mechanical properties of injection molded polypropylene/polyamide 6/func-
tionalized-TiO2 nanocomposites, Compos. Sci. Technol. 69 (2009) 421e426.
[16] N. Patra, M. Salerno, P.D. Cozzoli, A.C. Barone, L. Ceseracciu, F. Pignatelli,
R. Carzino, L. Marini, A. Athanassiou, Thermal and mechanical characterization
of poly(methyl methacrylate) nanocomposites filled with TiO2 nanorods,
Compos. Part B Eng. 43 (2012) 3114e3119.
[17] L.M. Hamming, R. Qiao, P.B. Messersmith, L.C. Brinson, Effects of dispersion
and interfacial modification on the macroscale properties of TiO2 polymer-
ematrix nanocomposites, Compos. Sci. Technol. 69 (2009) 1880e1886.
[18] M. Altan, H. Yildirim, Mechanical and antibacterial properties of injection
molded polypropylene/TiO2 nano-composites: effects of surface modification,
J. Mater. Sci. Technol. 28 (2012) 686e692.
[19] J. Parameswaranpillai, G. Joseph, K.P. Shinu, P.R. Sreejesh, S. Jose, N.V. Salim,
N. Hameed, The role of SEBS in tailoring the interface between the polymer
matrix and exfoliated graphene nanoplatelets in hybrid composites, Mater.
Chem. Phys. 163 (2015) 182e189.
[20] Kusmono, Z.M. Ishak, W.S. Chow, T. Takeichib, Rochmadi, Compatibilizing
effect of SEBS-g-MA on the mechanical properties of different types of OMMT
filled polyamide 6/polypropylene nanocomposites, Compos. Part A Appl. 39
(2008) 1802e1814.
[21] T. Kuboki, Y.H. Lee, C.B. Park, M. Sain, Effects of styr-
eneeethyleneebutyleneestyrene based additives on the mechanical proper-
ties of rice hull/polypropylene composites, Polym. Eng. Sci. 47 (2007)
1148e1155.
[22] G. Taguchi, Introduction to Quality Engineering, Asian Productivity Organi-
zation, Tokyo, 1990.
[23] P.J. Ross, Taguchi Techniques for Quality Engineering, McGraw-Hill, New York,
1996.
[24] F. Stan, L.I. Sandu, C. Fetecau, Effect of processing parameters and strain rate
on mechanical properties of carbon nanotubeefilled polypropylene nano-
composites, Compos. Part B Eng. 59 (2014) 109e122.
[25] J.C.C. Rubio, L.J. Silva, W.O. Leite, T.H. Panzera, S.L.M.R. Filho, J.P. Davim, In-
vestigations on the drilling process of unreinforced and reinforced polyamides
using Taguchi method, Compos. Part B Eng. 55 (2013) 338e344.
[26] S. Wacharawichananat, S. Thongyai, T. Tipsri, Effect of mixing conditions and
particle sizes of titanium dioxide on mechanical and morphological properties
of polypropylene/titanium dioxide composites, Iran. Polym. J. 18 (2009)
607e616.
[27] B. Cioni, A. Lazzeri, The role of interfacial interactions in the toughening of
precipitated calcium carbonate-polypropylene nanocomposites, Compos.
Interface 17 (2010) 543e549.
[28] M. Altan, H. Yildirim, Mechanical and morphological properties of poly-
propylene and high density polyethylene matrix composites reinforced with
surface modified nano sized TiO2 particles, World Acad. Sci. Eng. Technol. 70
(2010) 289e294.
[29] T.P. Selvin, J. Kuruvilla, Mechanical properties of titanium dioxide filled
Polystyrene microcomposites, Mater. Lett. 58 (2004) 281e289.
[30] L. Huang, R.R. Zhan, Y. Lu, Mechanical properties and crystallization behavior
of polypropylene/nano-SiO2 composites, J. Reinf. Plast. Compos. 25 (2006)
1001e1012.
[31] C. Youxinga, W. Zhangpingb, J. Yujie, Modified polypropylene filled with
nano-Al2O3, Adv. Mater. Res. 174 (2011) 494e497.
[32] L. Li, Q. Dou, Effect of malonic acid treatment on crystal structure, melting
behavior, morphology, and mechanical properties of isotactic polypropylene/
nano-CaCO3 composites, J. Macromol. Sci. B 50 (2011) 831e845.
[33] J.L. Deng, Introduction to grey system, J. Grey Syst. UK 1 (1989) 1e24.
[34] S. Daneshpayeh, F.A. Ghasemi, I. Ghasemi, M. Ayaz, Predicting of mechanical
properties of PP/LLDPE/TiO2 nanocomposites by response surface methodol-
ogy, Compos. Part B Eng. 84 (2016) 109e120.
[35] M. Ayaz, D.M. Khaki, N.B.M. Arab, Improvement of grain size and dome height
of microalloyed steels using Taguchi method based on grey relational grade in
controlled rolling, J. Iron Steel Res. Int. 20 (2013) 115e123.