Polymer Testing 51 (2016) 69e73

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Property Modelling

Development of Halpin-Tsai model for polymer nanocomposites

assuming interphase properties and nanoller size
Yasser Zare*
Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 21 January 2016
Accepted 26 February 2016
Available online 2 March 2016

The Halpin-Tsai model for Young's modulus of composites is developed for polymer nanocomposites
reinforced with spherical nanoparticles assuming interphase properties (volume fraction, thickness and
modulus) and nanoller size. The accuracy of the developed model was evaluated by experimental data
on various samples. Moreover, the interphase properties can be calculated by comparing the experimental data with model predictions. The main effects of nanoparticle and interphase sizes, as well as
interphase modulus, on Young's modulus of nanocomposites are also described. The results show that
the developed model can accurately predict the Young's modulus of polymer particulate nanocomposites
assuming the role of the interphase. It is revealed that, disregarding the interphase or using unsuitable
values for interphase properties, leads to inappropriate estimation of Young's modulus in
nanocomposites.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Polymer nanocomposites
Young's modulus
Modeling
Interphase properties
Filler size

1. Introduction
The signicant properties of polymer nanocomposites as well as
the wide range of their applications in various technologies have
attracted much interest in scientic and industrial circles [1e6].
The nanocomposites show considerable enhancement of properties
with only a small accessible nanoller content, by using an easy
fabrication method and at low cost. The theoretical and experimental studies on different types of polymer nanocomposites
containing layered silicate (nanoclay), carbon nanotubes (CNT),
silica (SiO2), titanium dioxide (TiO2), etc. have developed highquality products for new applications or replacement of conventional products [7,8].
The improvement of mechanical properties in polymer nanocomposites is attributed to strong interfacial adhesion/interaction
between polymer matrix and nanoparticles, which suitably transfers stress from the continuous matrix to the nanoller. Also, small
nanoparticles and their good dispersion play positive roles in
behavior of polymer nanocomposites [9,10]. From a theoretical
point of view, conventional models such as Halpin-Tsai and Guth
cannot properly consider these parameters, and thus cannot give
correct calculations for mechanical properties of polymer

* No. 28, 424 Hafez Ave., Tehran, Iran.

E-mail address: y.zare@aut.ac.ir.
http://dx.doi.org/10.1016/j.polymertesting.2016.02.010
0142-9418/ 2016 Elsevier Ltd. All rights reserved.

nanocomposites [11,12]. It was shown that an interphase forms in

polymer nanocomposites due to high interfacial area and strong
interfacial interactions between polymer and nanoparticles. The
interphase as a third phase has different properties from polymer
matrix and nanoparticles phases, which signicantly affects the
properties of polymer nanocomposites.
In recent years, several theoretical investigations on interphase
properties have presented much information to attain desirable
properties in polymer nanocomposites. The interphase properties
have been studied using mechanical properties such as Young's
modulus and yield strength [13,14]. In these works, some simple
and useful models were developed, providing a practical technique
for determination of interphase properties in polymer nanocomposites. Also, the role of interfacial adhesion in behavior of
various nanocomposite systems such as shape memory polymer
nanocomposites has been discussed in previous studies [15e17],
where It was shown that interfacial/interphase characteristics play
an important role in different behaviour of polymer
nanocomposites.
The effects of volume fraction, aspect ratio and modulus of
nanoparticles on Young's modulus of polymer nanocomposites can
be evaluated by the best known Halpin-Tsai model [18]. However,
the inuence of nanoparticle size as well as interphase properties
such as thickness and modulus cannot be examined by this model,
while disregarding these parameters leads to incorrect estimation
of modulus in polymer nanocomposites.

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Y. Zare / Polymer Testing 51 (2016) 69e73

In this paper, the Halpin-Tsai model for Young's modulus of

polymer nanocomposites is developed assuming the interphase
properties such as volume fraction, thickness and modulus of
interphase and nanoparticle size. The accuracy of the developed
model is evaluated using experimental modulus values of some
reported samples from literature. Also, the interphase properties
are calculated for reported samples and the effects of material and
interphase properties on the prediction of Young's modulus are
discussed.
2. Development of Halpin-Tsai model
Halpin and Tsai [18] introduced a mathematical model for
polymer composites which has been successfully applied for
different composites in the literature. This model is represented as:

ER

1 hx4f
1  h4f

(1)

.
.


.
Ef Em x
h Ef Em  1

(2)

x 2l=d

(3)

where ER is relative modulus as Ec/Em, Ec and Em are the

Young's modulus of composite and matrix, respectively. Also, 4f,
Ef, l and d are volume fraction, modulus, length and diameter
of nanoparticles, respectively. x 2 is considered for spherical
nanoparticles in this article.
However, this model under predicts the modulus of polymer
nanocomposites in most cases, as mentioned before. The volume
fraction of interphase (4i) for nanocomposites containing spherical
nanoparticles can be calculated by:

"
4i

R Ri
R

3

 1 4f

(4)

where R and Ri are radius of nanoparticles and interphase

thickness, respectively. If Ri 0, 4i 0, which indicates the absence
of interphase in polymer nanocomposites.
By addition of interphase effects to Halpin-Tsai model, it is
developed for spherical nanoparticles contained nanocomposites
to:


ER

1 2hf 4f 2hi

RRi
R


1  hf 4 f  hi

RRi
R

3

3


 1 4f


 1 4f

(5)

.
.
.

hf Ef Em  1
Ef Em 2

(6)

hi Ei =Em  1=Ei =Em 2

(7)

where Ei is Young's modulus of interphase.

3. Results and discussion
In this section, the correctness of the developed model is
examined using experimental data of samples in reported valid
literature. Also, the developed model is applied to calculate the
interphase properties by experimental modulus. Subsequently, the
effects of interphase properties on predicted modulus are
explained.

Table 1 shows some reported samples chosen from literature

and their characteristics. The experimental moduli of reported
samples are tted to the developed model to calculate the thickness
and modulus of interphase. The modulus of interphase (Ei) varies
from the modulus of polymer matrix (Em) to modulus of nanoller
(Ef), i.e. Em < Ei < Ef. Several Ei are chosen from this range and
various Ri are obtained by comparing the developed model to
experimental data. Finally, an average Ri is applied to the developed model and an exact Ei is calculated for any sample. The
calculations of interphase properties are shown in Table 1. The
highest Ri is obtained for No. 2 sample as 40 nm, and the smallest
one is calculated as 1 nm for No. 5 sample. The Ri data are higher
than R values in some samples, but also Ri < R in others.
In addition, the highest and the smallest Ei are obtained as 6
and 1.7 GPa for No. 1 and No. 6 samples, respectively. The range of
Ei is smaller than those of Ef in the present samples. However,
the values of Ri and Ei are logically expressed in the correct
ranges for polymer nanocomposites. Accordingly, the developed
model can accurately predict interphase properties by Young's
modulus of polymer nanocomposites.
Fig. 1 shows the experimental data and the predicted results by
the model for No. 2 and 6 samples. As shown, good agreement is
achieved between experimental and theoretical data by suitable
interphase properties, which conrms the prediction capability of
the developed model for Young's modulus of polymer particulate
nanocomposites. However, disregarding the interphase (Ri 0) or
improper values for interphase properties, undoubtedly results in
incorrect estimation of modulus for the reported samples,
demonstrating the main effects of interphase characteristics for
prediction of nanocomposite behavior.
Fig. 2 displays the calculated 4i at different mass concentrations of nanoparticles (Eq. (4)) for No. 3 and 4 samples using R
and Ri values reported in Table 1. It is found that 4i is larger than
4f in these samples at different nanoller contents. Accordingly,
interphase as a third phase between polymer matrix and nanoparticles occupies a signicant volume fraction in polymer nanocomposites and plays a main role in their properties.
Fig. 3 shows the effects of R and Ri on 4i according to Eq.
(4) (4f 0.02). It is observed that the smallest 4i data are found by
low Ri and high R. However, 4i has a higher level at smaller R
and higher Ri. The highest 4i, which results in the best Young's
modulus, is achieved by the smallest nanoparticles and the thickest
interphase. Accordingly, small nanoparticles and large interphase
thickness have positive effects on Young's modulus of polymer
particulate nanocomposites. The developed model also shows the
detrimental effect of aggregated/agglomerated nanoparticles (high
R) on 4i, which nally reduces the Young's modulus of polymer
nanocomposites, independent of the signicance of Ri. Therefore,
preventing some undesirable occurrences, such as the aggregation/
agglomeration of nanoparticles and the poor interfacial adhesion/
interactions, should be carefully considered in the fabrication
process of polymer nanocomposites [25,26].
Fig. 4 illustrates the inuences of Ri and Ei on Young's
modulus of polymer nanocomposites by developed the model at
4f 0.02, R 20 nm, Em 2 GPa and Ef 60 GPa. The Young's
modulus depends to both Ri and Ei levels at small Ei, but it
only relates to Ri level at higher Ei. The smallest ER is found at
the lowest Ri, while the largest ER is obtained at the greatest
levels of both Ri and Ei. In fact, the high ranges of Ri and Ei
have positive effects on the nal ER of polymer nanocomposites,
but a small Ri is enough to get a poor ER. Therefore, the properties of interphase signicantly affect the modulus of polymer
nanocomposites. According to the developed model, providing a
thick and strong interphase in polymer nanocomposites produces a
largely improved modulus. Some techniques, such as the

Y. Zare / Polymer Testing 51 (2016) 69e73

71

Table 1
The interphase properties of reported samples by developed model.
No.

Sample [Ref.]

R (nm)

df (g/cm3)

Em (GPa)

Ef (GPa)

Ri (nm) Eq. (5)

Ei (GPa) Eq. (7)

1
2
3
4
5
6

PEEKa/SiO2 [19]
PEEK/Al2O3 [20]
PPb/CaCO3 [21]
PSc/SiO2 [22]
Epoxy/Al2O3 [23]
PP/SiO2 [24]

6.5
15
22
8
17
6

2.2
4
2.7
2.2
4
2.2

4.6
3.9
1.75
3.12
3.15
1.46

80
370
26
80
370
80

16.5
40
25
20
1
2.2

6
4.3
4
3.6
3.2
1.7

a
b
c

poly (ether ether ketone).

polypropylene.
polystyrene.

Fig. 1. The experiment results and the predictions of the developed model for a) No. 2 and b) No. 6 samples.

Fig. 2. 4i at different weight percentage of nanoparticles for a) No. 3 and b) No. 4 samples according to Eq. (4).

Fig. 3. The effects of R and Ri on the interphase volume fraction according to Eq. (4) at 4f 0.02.

72

Y. Zare / Polymer Testing 51 (2016) 69e73

Fig. 4. The inuences of Ri and Ei on ER by the developed model at 4f 0.02, R 20 nm, Em 2 GPa and Ef 60 GPa.

Fig. 5. ER as a function of R and Ef according to the developed model at 4f 0.02, Em 2 GPa, Ri 20 nm and Ei 40 GPa.

application of compatibilizer, coupling agent, treatment of nanoparticles, etc., can considerably improve the properties of interphase in polymer nanocomposites [27,28].
Fig. 5 also depicts ER as a function of R and Ef according to
the developed model at 4f 0.02, Em 2 GPa, Ri 20 nm and
Ei 40 GPa. As observed, ER does not depend to Ef in this
condition. It only relates to nanoparticle size, where it increases
with decreasing particle size. At Ri 20 nm, only nanoparticles
smaller than 20 nm can cause greatly improved ER. Therefore, the
encouraging role of small nanoparticles as well as the detrimental
effect of aggregated/agglomerated nanoparticles on ER is shown
in this illustration.

4. Conclusions
The Halpin-Tsai model for Young's modulus of polymer particulate nanocomposites was developed assuming interphase properties and particle size. The calculations demonstrated good
agreement with experimental results for several reported samples.
Also, the ndings showed that the developed model can accurately
predict the interphase properties by Young's modulus using a
simple and easy method. It was established that disregarding
interphase (Ri 0) or improper values of interphase properties
results in inappropriate estimation of modulus in reported samples.
It was found that 4i is much larger than 4f at different
nanoller contents, which indicated that interphase occupies a
signicant volume fraction in polymer nanocomposites and plays a
main role in their properties. Also, the smallest nanoparticles and

the thickest interphase created the highest 4i, which led to the
best Young's modulus in polymer nanocomposites. According to
predictions of the developed model, Young's modulus depended on
Ri and Ei levels at small Ei, but it only related to Ri level at
higher Ei.
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