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Computational Materials Science 81 (2014) 612–616

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Computational Materials Science


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

An analysis of interfacial adhesion in nanocomposites from recycled


polymers
Yasser Zare ⇑, Ali Daraei, Mostafa Vatani, Parya Aghasafari
Department of Mechanics, Tiran Branch, Islamic Azad University, Tiran, Iran

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

Article history: The present paper studies the quantitative analysis of interfacial adhesion in the nanocomposites con-
Received 18 April 2013 taining recycled polymers. The interfacial bonding is evaluated using different models for tensile proper-
Received in revised form 27 July 2013 ties of composites. A good agreement is found between the experimental results of mechanical properties
Accepted 19 August 2013
and the theoretical predictions which validate the current analysis.
Available online 19 October 2013
Many parameters such as (a) in Nicolais–Narkis, (a) in Kunori–Geil, (B) in Pukanszky model and inter-
facial strength (t) show the perfect interfacial adhesion. Moreover, the obtained values of (B) and (t) are
Keywords:
compared with other studies. The current study justifies the recycling of polymers through the incorpo-
Waste polymers
Nanocomposites
ration of nanofillers.
Interfacial adhesion Ó 2013 Elsevier B.V. All rights reserved.
Mechanical properties

1. Introduction density Polyethylene (HDPE) [17,18] and others through the addi-
tion of nanoparticles. In these works, the mechanical properties of
Nowadays, the large amounts of waste polymers threaten the nanocomposites were evaluated by experimental characterization.
people life. This problem and the other economic and petroleum The prediction and modeling of behavior have been carried out for
considerations related to polymers have increasingly motivated nanocomposites from virgin polymers, while this subject has not
the researchers to solve the problem [1,2]. Undoubtedly, the effi- been studied for nanocomposites from recycled polymers.
cient treatment of waste polymeric products is recycling and reus- The analysis of behavior provides more information without
ing. However, the major problem in this field involves the requiring to a large number of experiments. In other words, the
degradation of polymer structure in reprocessing which cause models remove any need to much cost, time and also, difficulties
much poorer properties [3]. In this regards, researchers have tried conducted to examination of properties [19–22]. Furthermore,
to introduce the best modifications that can compensate the loss of the models facilitate the development of most desirable products.
properties. As well known, the best properties of nanocomposites can be ob-
The addition of other components to the waste polymers seems tained when a perfect interfacial adhesion is provided between
to be the simplest and easiest way for reusing the recycled poly- the matrix and nanofiller [23,24]. However, whether the nanopar-
mers. The nanofillers present more excellent feature for improve- ticles can provide a good interfacial adhesion and so, an efficient
ment of all mechanical, thermal and barrier properties [4–7]. reinforcement in waste polymers or not? On the other hand,
They increase the interphase surface of the components that devel- whether the mechanical properties of nanocomposites show a
op the performances through a simply processing technology with strong interfacial bonding between the recycled matrix and nano-
low cost. It is interesting to note that the nanofillers can enhance filler phases?
the melt strength of recycled polymers while the inferior melt In this paper, much attempt is made to answer these important
strength causes an inconsistency of material after leaving the ex- questions through the quantitative analysis of interfacial adhesion
truder which makes the production of sheets or profiles, impracti- by modeling of mechanical properties.
cable [8]. Further, nanofillers increase the intrinsic viscosity of
Poly(ethylene terephthalate) (PET) which is necessary for the
reprocessing of PET wastes [9]. 2. Background
Recently, more studies have been carried out on the recycling of
polymers such as PET [8,10–12], Polypropylene (PP) [13–16], high In the condition of poor adhesion, the strength of a composite is
determined by the available effective region of load-bearing matrix
⇑ Corresponding author. Tel.: +98 21 66454514; fax: +98 21 66547514. in the absence of filler [25,26]. In this state, the interfacial layer
E-mail address: y.zare@aut.ac.ir (Y. Zare). cannot transfer stress and the tensile strength of composite

0927-0256/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.commatsci.2013.08.041
Y. Zare et al. / Computational Materials Science 81 (2014) 612–616 613

depends on the effective load bearing cross-section area portion (B) parameter is related to the load carried by the dispersed
(1  W) as: phase depending on the interaction which can be applied as a
quantitative measurement of filler–matrix adhesion. The (B)
rc ¼ rm ð1  wÞ ð1Þ
parameter is shown as:
where (rm) and (rc) are the tensile strength of the matrix and com-  
ri
posite, respectively. If (W) is assumed as a power law function of B ¼ ð1 þ AqlÞ ln ð13Þ
volume fraction of filler (/), Eq. (1) can be presented as: rm
where (A) is the specific surface area of filler (contact surface), (q) is
rc ¼ rm ð1  a/b Þ ð2Þ
density of filler, while (l) and (ri) are the thickness and strength of
where (/) is the volume fraction of the filler and (a) and (b) depend the interphase, respectively. The Pukanszky model can be reformu-
on the filler–matrix interaction and the shape and arrangement of lated as:
particles.
rc 1 þ 2:5/
Based on Eq. (2), Nicolais and Narkis [26,27] suggested a model ln rReduced ¼ ln ¼ B/ ð14Þ
for tensile strength of composites reinforced with spherical parti- rm 1  /
cles as: According to Eq. (14), when a linear correlation is observed be-
2=3 tween the reduced tensile strength (ln rReduced) and the volume
rc ¼ rm ð1  a/ Þ ð3Þ
fraction of filler (/), the model is valid.
In the case of good adhesion, the interfacial layer can transfer a Sato and Furukawa [35,36] also suggested a model for tensile
small portion of stress while the deformation of matrix is very modulus of composites containing an adhesion parameter (f) as:
small. In this case, the tensile strength includes a contribution of " ! #
both matrix and filler properties. Therefore, the value of parameter 0:5/2=3 /2=3 wf
E ¼ Em 1þ ð1  wfÞ  ð15Þ
(a) in Nicolais–Narkis model becomes smaller than 1.21 which 1  /1=3 ð1  /1=3 Þ/
shows the stronger adhesion.
  !
Kunori and Geil [28] related the tensile strength of composites / 1 þ /1=3  /2=3
with (a) parameter, which is a stress concentration factor as: w¼ ð16Þ
3 1  /1=3 þ /2=3
rR ¼ expða/Þ ð4Þ
The (f) parameter of 1 shows the poor adhesion, while f = 0 indi-
where (rR) is the relative tensile strength as (rc/rm). The higher val- cates to the perfect adhesion.
ues of (a) indicates to a greater stress concentration.
In the case of good interfacial adhesion, Piggott and Leidner [29]
3. Results and discussion
introduced an empirical model including a coefficient of particle–
matrix adhesion (a), as:
The tensile strength and modulus of nanocomposites containing
rc ¼ K rm  a/ ð5Þ various nanofillers such as layered silicate, CaCO3, carbon nanotube
The effect of interfacial interaction and filler properties on the (CNT) and different waste matrices such as PET, PP and HDPE were
tensile strength of composites [30] can be presented as: provided from the literature. Table 1 shows the studied nanocom-
  posites and the attributed references in which all experimental
at data and other details were given. Accordingly, I refrain from the
rR ¼ 1 þ 1 / ð6Þ
rm further discussion of the details.
Table 1 illustrates the calculated parameters from models for
where (a) is the aspect ratio of filler and (t) is the interfacial stress
different nanocomposites. The (a) parameter from Nicolais–Narkis
transfer parameter. (a) can be calculated from the developed Hal-
model is obtained from the linear plotting of experimental tensile
pin–Tsai model for randomly 3 dimensional (3D) platelet fillers
strength against (/2/3). As observed in Table 1, the value of (a) for
[31,32] as:
PP/CaCO3 nanocomposite is 0.59. It is lower than 1.21 demonstrat-
E ¼ 0:49 E1 þ 0:51 E2 ð7Þ ing the good interfacial adhesion between recycled PP and CaCO3
  nanofiller.
1 þ gn/ The calculated (a) parameter from Kunori–Geil model (Eq. (4))
E1 ¼ Em ð8Þ
1  g/ is also observed in Table 1. The higher values of (a) which shows
  the greater stress concentration are obtained in samples No. 7
1 þ 2g/ and No. 8. Other (a) values are much smaller than zero presenting
E2 ¼ Em ð9Þ
1  g/ a perfect interfacial adhesion.
Further, the same trend of previous calculations is observed by
g ¼ ðEf =Em  1Þ=ðEf =Em þ nÞ ð10Þ Piggott–Leidner model (Eq. (5)), where the lowest (a) parameter,
indicating to the best interfacial adhesion is obtained for samples
n ¼ 2a ð11Þ
where (E1) and (E2) are the tensile moduli of the composite in the Table 1
longitudinal and transverse directions, respectively. (Em) and (Ef) The calculated interfacial parameters from different models.
are the tensile modulus of matrix and filler, respectively. No. Sample a (Eq. (3)) a (Eq. (4)) a (Eq. (5)) B (Eq. (12)) Refs.
Pukanszky developed a model based on the spontaneous forma-
1 PET/clay – 17.63 23.28 21.45 [10]
tion of interphase in composites assuming the variation of tensile
2 PET/clay – 4.75 6.83 8.48 [11]
strength as a function of composition [33,34]. The Pukanszky mod- 3 PET/clay – 3.27 3.8 6.9 [12]
el can be presented as: 4 PP/clay – 10.77 15.67 15.6 [15]
5 PP/clay – 1.49 1.52 4.91 [13]
1/ 6 PP/CNT – 4.35 7.13 9.3 [14]
rc ¼ rm expðB/Þ ð12Þ
1 þ 2:5/ 7 PP/CaCO3 0.59 1.52 1.48 1.74 [16]
8 HDPE/clay – 1.61 1.61 1.76 [18]
614 Y. Zare et al. / Computational Materials Science 81 (2014) 612–616

No. 1 and No. 4. Also, the specimens No. 7 and No. 8 show the Table 2
worst (a) values. The obtained parameters by models.

The high specific surface area of silicate layers can significantly No. Sample a (Eq. (11)) t (Eq. (6)) f (Eq. (15)) Refs.
increase the interfacial interactions between polymer and filler 1 PET/clay 10 58.3 2.5 [10]
phases, attributed to many factors such as constituent types of sys- 2 PET/clay 140 3.6 18 [11]
tem, degree of dispersion, interactions between particles and poly- 3 PET/clay 22 8.2 4 [12]
mer and particle–particle interactions [37,38]. The negligible effect
of CaCO3 content on the tensile modulus and strength of PP/CaCO3
sample (No. 7) was reported [16]. Also, the impact strength of sam- observed in Table 2. The most value of (t) is obtained for sample
ples decreases by incorporation of CaCO3 nanoparticles, despite the No. 1 equivalent to 58.3 MPa, as expected according to the ob-
toughening effect of CaCO3 nanoparticles. The lower level of inter- tained parameters from other models.
facial adhesion can be related to the poor dispersion of CaCO3 Based on the literature results, the composites having only
nanofiller, even with stearic acid treatment. The weak dispersion weak Van der Waals interactions between matrix and filler show
may be induced by the low viscosity of recycled PP together with relatively low (t) values [39]. Frankland et al. computed the (t)
the large contents of aggregates in the higher content of CaCO3 for weakly interacted PE–CNT about 2.7 MPa, while the interfacial
(20 wt%). strength (t) between 30 and 110 MPa have been found for cross-
Moreover, the sample No. 8 does not show any improvement in linked PE–CNT nanocomposites [40]. Also, Durmus et al. obtained
the tensile strength of recycled HDPE/clay nanocomposite (except the (t) value of 5 MPa for linear low density Polyethylene
in 1 wt% of nanoclay content), even in the presence of maleated PE (LLDPE)/clay nanocomposite [38]. As a result, the interfacial
and the well exfoliated clay platelets [18]. The authors attributed strength parameter (t) for the present nanocomposites verifies
the slight enforcement of clay to the possible existence of other fill- the strong bonding between recycled polymers and nanofillers.
ers and additives in the recycled HDPE. The values of (B) coefficient from Pukanszky model (Eq. (12))
The experimental results of tensile strength are also success- are obtained through the linear plot of ln (reduced tensile strength)
fully fitted to Eq. (6). From the slope of plotted lines, the values against nanofiller content (/), as shown in Table 1. The minimum
of (at) are obtained. The aspect ratios of nanofillers (a) have not (B) value of 1.74 and maximum 21.45 are calculated for the current
been exactly characterized by the authors; therefore, they can be nanocomposites. They can be considered as good results, compared
approximately obtained by the developed Halpin–Tsai model mod- with (B) values obtained for other systems, ranging from negative
el (Eqs. (7)–(11)). Fig. 1 illustrates the calculation of (a) from devel- values up to about 20 as a maximum level reported by Szazdi et al.
oped Halpin–Tsai model model for samples that their tensile [41,42]. The results particularly agree with the further parameters
modulus was reported and the obtained values of (a) are shown obtained by other studied models. Demjen et al. [34] found the
in Table 2. Consequently, the calculated interfacial strength (t) is maximum (B) of 2.45 for composites containing different amounts

Fig. 1. The calculations of aspect ratio (a) from developed Halpin–Tsai model model for (a) No. 1, (b) No. 2 and (c) No. 3 samples.
Y. Zare et al. / Computational Materials Science 81 (2014) 612–616 615

Fig. 2. The prediction of tensile modulus by Sato–Furukawa model at different adhesion parameter (f) for (a) No. 1, (b) No. 2 and (c) No. 3 samples.

of CaCO3 micro-particles treated with different silane coupling and the most suitable (f) values are presented in Table 2. As indi-
agents and stearic acid. These findings confirm that the nanofillers cated, (f) values of 1 and 0 represents the poor and perfect adhe-
introduce a better interfacial interaction to the recycled polymers sion, respectively. However, all reported values of (f) in Table 2
compared to the treated micro-particles to the neat polymers. are lower than zero and the negative (f) parameter has not been
In addition, Szazdi et al. [42] stated that the usual techniques investigated in the previous studies on the nano- and micro-com-
such as X-ray diffraction (XRD) and transmission electron micros- posites. As observed in Fig. 2, the higher level of (f) parameter in-
copy (TEM) do not present any reliable information about the de- duces smaller values of tensile modulus. In other word, the best
gree of exfoliation. They also indicated that the nanocomposites modulus is achieved by inferior (f) values. As a result, the calcu-
which do not exhibit any silicate reflection in XRD scans, may have lated (f) data indicates that the little content of nanofillers provide
very poor mechanical properties that shows a small degree of exfo- a significantly improved tensile modulus in the nanocomposites
liation. They have quantitatively estimated the extent of exfolia- from recycled polymers. The nanofillers can produce much interfa-
tion by (B) values assuming the specific surface area of silicate cial interactions with matrices and the best modulus and strength
layers of 750 m2 g1 and (B) value of 195 for possibly perfect exfo- is introduced by perfect interfacial adhesion between nanoparti-
liation. Their analysis indicated that the extent of exfoliation is ex- cles and recycled matrices. In conclusion, the negative values of
tremely small in most nanocomposites, maximum 10% in the best (f) show much interfacial bonding between polymer and nanofiller
case. According to these criteria, the most level of exfoliation in the phases for the studied samples.
present samples is estimated as 11% for sample No. 1 (B = 21.45).
However, the morphological analysis showed the most exfoliated
clay layers in the matrix [10]. First of all, the nanoparticles may 4. Conclusion
have much lower surface area than 750 m2 g1 (assumed by Szazdi
et al.). Therefore, a (B) value lower than 195 is expected for evalu- This paper aimed to study the interfacial adhesion in the vari-
ation of full exfoliation, according to Eq. (13). Also, it is believed ous nanocomposites containing recycled polymers. The analysis
that other factors such as modification of crystalline structure of interfacial adhesion in the recycled polymer nanocomposites
due to nucleation promotion of nanofillers [5], interaction and was carried out using the various models for tensile strength and
interfacial adhesion between matrix and filler phases [43], chemi- modulus of composites. The different types of waste polymers such
cal reactions [44] and so on can affect the mechanical properties of as PET, PP, HDPE containing nanoclay, CaCO3 and CNT were chosen
nanocomposites, in spite of Szazdi et al. approach correlating the for evaluation. A good agreement was found between the experi-
less improved mechanical properties to the slighter level of exfoli- mental data and the models.
ation of nanoclay [42]. Many interfacial parameters from Nicolais–Narkis, Kunori–Geil,
Fig. 2 shows the prediction of tensile modulus by Sato–Furuka- Piggott–Leidner, Pukanszky and Sato–Furukawa models proved the
wa model (Eqs. (15) and (16)) at different adhesion parameter (f) perfect interfacial bonding between the nanofillers and recycled
616 Y. Zare et al. / Computational Materials Science 81 (2014) 612–616

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