Applied Surface Science 318 (2014) 90–94

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Applied Surface Science

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

A mathematical method for XRD pattern interpretation in clay

containing nano composites
Kh. Khederlou a , R. Bagheri b,∗ , A. Shojaei c
a
Institute for Nanoscience and Nanotechnology, Sharif University of Technology, Tehran, Iran
b
Department of Materials Science and Engineering, Sharif University of Technology, Tehran, Iran
c
Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran

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

Article history: X-ray diffraction and rheological measurements were used to characterize nanoparticle dispersion in
Received 31 October 2013 LDPE/LLDPE/nanoclay hybrid nanocomposites. XRD patterns were interpreted with a novel distribution
Received in revised form 7 January 2014 formula and rheological measurements were used to confirm the results. Results of these two methods
Accepted 9 January 2014
indicated that increasing clay in all the prepared nanocomposites exhibited a significant improvement in
Available online 19 January 2014
filler-matrix interaction because of increasing the probability of polymer diffusion but further exfoliation
need more compatibilizing situations. It seems that this mathematical method could be used for predict-
Keywords:
ing the overall change in clay gallery d-spacing and the extent of intercalation–exfoliation of nanoclay in
XRD patterns
Rheology
these systems.
Nanoclay © 2014 Elsevier B.V. All rights reserved.
Nanocomposites

1. Introduction Montmorillonite (MMT) is the most commonly used clay in

Polymer/layered silicate (PLS) nanocomposites have become an
important area of polymer composite research. Numerous stud-
ies have demonstrated that only a few percent of layered silicate
can lead to a wide array of property enhancements, e.g. increased
stiffness and strength [1–4], enhanced gas barrier properties and
decreased flammability [5–7].
The main reason for these improved properties in nanocompos-
ites is the interfacial interaction between the matrix and layered
silicate, as opposed to conventional composites [8].
To achieve the expected improvements in properties, prepara-
tion of nanocomposites requires extensive delamination of layered
clay structure and uniform dispersion of the resulting platelets
throughout the polymer matrix [9,10]. In previous studies it has
been demonstrated that the best performances are commonly
observed for exfoliated nanocomposites [11–14].
In packaging industry, spite of importance of PE films, their uses
are restricted due to several drawbacks, including low strength
and stiffness. To overcome these drawbacks, during recent years
polyethylene compounds containing various inorganic nanofillers
such as modified clay have been made which show significant
improvement in properties at low levels of nanofiller loading
[15–17].
polymer nanocomposites and XRD and TEM are the most common
methods for measuring the extent of clay intercalation and distri-
bution in clay–polymer nanocomposites. However, among these
two methods, the XRD method is a simple accessible but quali-
tative method. On the other hand, the melt-rheological properties
are also helpful to find out the degree of polymer–filler interactions
and the role of morphology and structure in nanocomposite prop-
erties. This is because rheological material functions are strongly
influenced by the structure and the interfacial properties [18].
In this study, blends of linear low density polyethylene (LLDPE)
and low density polyethylene (LDPE), which benefit from superior
mechanical properties of LLDPE and processability of LDPE [19,20]
were used to make clay filled nanocomposites. The main objective
of this work is to quantify the XRD patterns and measure the disper-
sion state of the silicate layer in melt processed nanocomposites.
2. Experimental
2.1. Materials
The materials used in this study are described in Table 1. All
materials were dried at 80 ◦ C for 15 h before compounding.
2.2. Preparation

∗ Corresponding author. Tel.: +982166165207/+98 21 6616 5234; All materials were vacuum dried at 80 ◦ C for 15 h before use.
fax: +982166005717/+98 21 6616 5201. Melt blended composites were prepared using a SHJ-20 Nanjing
E-mail address: Rezabagh@sharif.edu (R. Bagheri). Giant co-rotating, intermeshing, twin screw extruder (L/D = 20) at

0169-4332/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2014.01.044
 Kh. Khederlou et al. / Applied Surface Science 318 (2014) 90–94 91

Table 1 100000
Materials used in this study. DK4

Material (designation used here) Specification Supplier

80000
Low density polyethylene (LD) MFI = 2 BandareEmam
Petrochemical
Linear low density polyethylene MFI = 2.2 Tabriz
(LL) Petrochemical

Intensity (cps)
60000
Co.
Maleated polyethylene (g) MFI = 0.17 Karangin Co.
Organoclay (DK4) CECa = 110 mequive./ Zhejiang
100 g clay Fenghong Clay 40000
d(001) spacing = 3.42 nm Chemicals Co.
a
Cation exchange capacity.
20000 5%C

temperature profile of 140–160–180–190 ◦ C and at a screw speed 3%C

of 120 rpm. All composites were prepared in 2 steps by prepar-
ing LLDPE/LL-g-MA (2/3)/DK4 masterbatches at first step and then
diluting by LDPE/LL-g-MA(1/3) based on pre-determined composi-
tions.
Sample compositions are given in Table 2. In all nanocomposites,
LD/LL(+g) was fixed to be 3/1 by weight. Extruded strands were
chopped up in to pellets by a plastic granulator and dried at 80 ◦ C
for 1 h. LDPE/LL-g-MA/LDPE compounds were prepared at the same
condition as reference.
2.3. Characterization
2.3.1. X-ray diffraction
XRD patterns were obtained using a STOE-D-64295diffracto-
meter. XRD scans were performed in transmission mode using an
incident X-ray wavelength of 1.5 Å. XRD test specimens were taken
from tensile bars and all of tests were carried out in one day with
on time calibration. Reference mixtures were prepared by mix-
ing of polymer blend, compatibilizer and nanoclay with the same
composition of the corresponding melt compounded samples all in
powder form.
2.3.2. Rheology
Rheological measurements were performed at 190 ◦ C and by
means of a Physica MCR 301 Anto Paar rheometer. Rheological
parameters of the reference compounds and composites were mea-
sured using a 25 mm diameter pre-heated plate in oscillatory shear
mode (at 3% strain) and 0.8 mm gap. The temperature control was
accurate to within ±1 ◦ C.
3. Result and discussion
3.1. XRD patterns
1%C
0
1 2 3 4 5 6 7 8 9 10
2θ (degrees)
Fig. 1. XRD pattern of pristine DK4 organoclay and nanocomposites containing 3%
compatibilizer.
offer quantitative parameters based on the XRD spectrum to get
better understanding about the dispersion state.
The intercalation of the polymer chains usually increases the
interlayer spacing of the silicate gallery, leading to a shift of
the diffraction peak toward lower values of 2. According to
the 2 value of clay in the composite, one could judge about
the intercalation state of the clay in composite. However, this
procedure considers only the 2 value at the maximum peak
intensity in XRD spectrum while the role of intensity distribu-
tion is not taken into account. Therefore, according to the current
approach, two different intensity distributions with similar max-
imum intensity in XRD spectrum give the same d-spacing value
which is not reasonable. In order to offer better interpretation
about the intercalation state of clay based on the XRD spectrum,
we calculate the mean diffraction angle (2) and its correspond-
ing diffraction intensity (I) of the nanoclays basal d-spacing (0 0 1)
peak in XRD pattern according to following distribution for-
mula:
n
2i × Ii
2 = 
i=m
(1)
Ii
where m and n exhibit the characteristic peak interval where the
peak intensity becomes leveled off in both sides of the peak. Accord-
ing to 2, we can simply calculate the average d-spacing value, i.e.
d, from Bragg’s law:
n = 2d sin  (2)

Fig. 1 compares X-ray diffraction patterns for the pristine DK4 We can also find the corresponding I by referring to the char-
and various nanocomposites containing 3% LL-g-MA with different acteristic XRD patterns. d (or even d) value provides an idea about
(1, 3 and 5 wt%) organoclay loadings. As it can be observed, it is the intercalation state, while the dispersion state is seldom inves-
difficult to compare the dispersion state of clay at various loadings tigated using the XRD spectrum. In this study we offer a simple
in compatiblized LL/LD blend by visual inspection of XRD spectra method to quantify the exfoliation state based on the XRD char-
and their characteristic peaks. In this study, it was attempted to acteristic peak. The basic idea in this approach is that the peak
intensity is dependent on the content of unexfoliated portion of
clay, because only the intercalated morphology is detectable by the
Table 2
Sample Compositions.
XRD spectroscopy.
Therefore the extent of decrease in peak intensity in melt com-
Sample Compositions pounded clay filled polymer can be directly correlated to exfoliated
abbreviation
LDPE (wt%) LLDPE (wt%) LL-g-MA (wt%) DK4 (wt%) portion of the clay in nanocomposite. In order to obtain a wise
LD/LL 75 25
result based on this approach, each nanocomposite must be com-
LD/LL/g3 75 22 3 0 pared with a reference material. The reference material in this study
LD/LL/g3/C1 74.25 21.75 3 1 was prepared by a simple mixing of polymer and clay with the
LD/LL/g3/C3 72.75 21.25 3 3 same composition of the corresponding melt compounded sam-
LD/LL/g3/C5 71.25 20.75 3 5
ple, so that the clay gallery in the reference material is the same as
92 Kh. Khederlou et al. / Applied Surface Science 318 (2014) 90–94

Table 3
Calculated parameters in XRD spectra.
  
2 I Nanocomposite I Reference mixture d dco − dcl Å R.E. (%)

DK4 powder 1.97 73,418

LD/LL/g3/C1 1.66 4,256 21,485 8.4 81
LD/LL/g3/C3 1.8 6,657 32,573 4.2 79
LD/LL/g3/C5 1.71 18,022 34,912 6.8 48

Where, dco and dcl are composite d-spacing and clay d-spacing, respectively.

original clay before compounding. According to this approach, rel-
ative exfoliation (R.E.) factor for each melt blended nanocomposite
can be calculated as follows:
 
I Nanocomposite
Relative exfoliation (R.E.) = 100 × 1 −
I Reference
Eq. (3) quantifies the exfoliation state of clay (if any) in the
nanocomposites based on peak intensity depression. Therefore, we
believe that this parameter (R.E.) along with 2 (or d) can provide
more information and quantitative measure to evaluate the dis-
persion state (both intercalation and exfoliation state) in a wise
manner.
According to Table 3, 2 and I are the lowest at 1 wt% clay
loading which can be correspondent with the better intercalation
of DK4 at this clay loading. Additionally, the higher R.E. value is
relevant to this composition (1 wt% clay loading). Beyond 1 wt%
clay loading, 2 and I increase while R.E. value decreases suggest-
ing the loss in the nanoscale dispersion of clay at higher loading.
This could be attributed to the lack of sufficient compatibilizer
at higher clay loading to breaking the clay bundles and inter-
calation/exfoliation of clay gallery. It is also observed that the
change in d spacing (d) in nanocomposite containing 5 wt% organ-
oclay is more than that of 3 wt% while its R.E. value significantly
lower.
This result could be originated from the fact that in LD/LL/g3/C5,
compatibilizer enhances the interaction of clay and polymer matrix
resulting in more diffusion of polymer in clay gallery but is insuffi-
cient for breaking the bundles and exfoliating silicate platelet. Fig. 2
shows a schematic view of these XRD patterns interpretation.
Reference Mixture
70000
Nanocomposite
60000
Relative intensity
3.2. Rheological behavior
3.2.1. Oscillating and steady measurements
Rheological characteristics of nanocomposites prepared in this
study were determined to get deep insight into the dispersion state
(3) of clay in the matrix and compare the results with XRD data men-
mixture
  above. Fig. 3 shows logarithmic plots of complex viscosity
tioned
(∗ ) versus angular frequency (ω) as well as steady state shear vis-
cosity () versus shear rate () at 190 ◦ C. Several trends in this figure
could be addressed. It is seen that both blend and corresponding
nanocomposites exhibit shear thinning behavior, however at fre-
quencies higher than 1 rad s−1 such behavior is more extensive. It
is also inferred that the incorporation of compatibilizer enhances
both shear viscosity and complex viscosity of LL/LD blend at low
frequencies (below 1 rad s−1 ) and low shear rates (less than 0.1 s−1 )
which is attributable to the improvement of interfacial interaction
between LL and LD components in presence of compatibilizer.
As shown in Fig. 3, it is deduced that both complex viscosity
and steady state shear viscosity of nanocomposites increase con-
siderably by incorporation of clay, however, the extent of increment
depends on the clay loadings. Accordingly, both viscosities increase
monotonically up to 3 wt%, then, they show a decrease at 5 wt% clay
loading compared to nanocomposite containing 3 wt% clay. Such
enhancement at low clay loading (up to 3 wt%) can be attributed
to the nanoscale dispersion (intercalation/exfoliation) of clay in
compatibilized LD/LL. This behavior is almost consistent with the
XRD spectra and the relevant parameters presented in Table 3. As
the nanoscale dispersion of 1 and 3 wt% loading of clay (based on
parameters d and R.E. as presented in Table 3) is almost similar, the
higher viscosity of 3 wt% loaded nanocomposite compared to that
of 1 wt% loaded nanocomposite can be ascribed to its higher con-
tent of clay. The loss in viscosities of LD/LL nanocomposites at 5 wt%
clay loading can be attributed to the loss in the dispersion state of
clay at such clay concentration which is consistent with XRD data
DK4 mentioned above.
The role of clay on the rheological behavior of compatiblized
LD/LL can be best illustrated using the simple power low model.
Accordingly * –ω curves of both compatiblized blend and the
corresponding nanocomposites in the low frequency region, i.e.
<1 rad s−1 , were fitted by power-law model to determine the shear

50000
thinning exponent. For the frequency sweep data, the power-law
expression is written as
40000
LD/LL/g3/C5
LD/LL/g3/C3 ∗ = kωn (4)
30000
where *
is the dynamic viscosity, k is a sample specific pre-
LD/LL/g3/C1 exponential factor, ω is the oscillation frequency in the frequency
20000
sweep test and n is the shear thinning exponent. k and n can be
directly calculated from the logarithmic plot of complex viscosity
10000
(* ) versus frequency (ω) as [21]:

0 log (∗ ) = log k + n log ω (5)

1.65 1.70 1.75 1.80 1.85 1.90 1.95 2.00
The n values of the samples in low frequency region, i.e.
Relative <1 rad s−1 are listed in Table 4.
Table 4 exhibits that n slope increases by incorporation of clay
Fig. 2. Parameters introduced in this study for comparing reference mixtures and
clay powder (I) and corresponding nanocomposites (I, 2) in XRD characteristic
which can be attributed to the Nano scale dispersion of clay in the
peaks. composite.
 Kh. Khederlou et al. / Applied Surface Science 318 (2014) 90–94 93

(a)

10000
10000

8000

η*(pa.s)
(pa.s)

6000
*

1000 0%C
1%C
3%C
5%C
LD/LL 4000
1
ω (rad/s)
0.01 0.1 1 10 100 1000

ω (rad/s)

(b)

10000
8000

6000
η (pa.s)
η (pa.s)

0%C
1000
1%C
3%C
5%C
LD/LL 4000
0.02 0.04
º
γ (1/s)
1E-3 0.01 0.1 1 10
º
γ (1/s)
 
logarithmic plots of (a) complex viscosity ∗ versus angular frequency (ω) and (b) steady state shear viscosity () versus shear rate ( 0 ) at 190 ◦ C for 75/25 blend of
Fig. 3.
LDPE/LLDPE, compatibilized blend and corresponding nanocomposites with 3 wt% compatibilizer and 1, 3 and 5 wt% clay.

3.2.2. Viscoelastic behavior
Fig. 4 exhibits the dynamic storage (G ) and loss moduli (G ) of
LD/LL blend and corresponding nanocomposites. These parameters
can be used to illustrate the viscoelastic behavior and morphologi-
cal characteristics of blend and the corresponding nanocomposites.
The terminal zone slope of log G’ and G versus logω for LD/LL
blend and Nanocomposites in low frequency region, i.e. <0.1 rad s−1
are presented in Table 5.
These values for LD/LL blend were found to be 1.19 and 0.82,
respectively. These slopes show deviation with respect to theoret-
ical relaxation exponents, i.e. G ∼ ω2 and G ∼ ω, which may be
attributed to the polydispersity of polymer.
The terminal slopes for nanocomposite containing 1%C were
found to be 1.13 and 0.81 which do not exhibit considerable dif-
ference compared to that of LD/LL blend. This can be explained
by the fact that the nanocomposites show liquid-like behavior,

Table 4
Shear thinning exponent of samples. Table 5
Terminal slopes of log G and G versus logω for samples.
Samples n
Samples G G
LD/LL −0.185
LD/LL/g3 −0.194 LD/LL 1.19 0.82
LD/LL/g3/C1 −0.202 LD/LL/g3/C1 1.13 0.81
LD/LL/g3/C3 −0.222 LD/LL/g3/C3 1.10 0.80
LD/LL/g3/C5 −0.199 LD/LL/g3/C5 1.07 0.79
94 Kh. Khederlou et al. / Applied Surface Science 318 (2014) 90–94
100000
10000
G', G'' (Pa)
1000
2 G''(LL+LD/3%g/1%C)
100
1 G''(LL+LD/3%g/5%C)
0.1 1 10
ω (rad/s)
Fig. 4. Logarithmic plots of shear storage modulus (G ) and loss modulus (G ) versus ␻ at 190 ◦ C for 75/25 blend of LDPE/LLDPE and other nanocomposites with 3%
compatibilizer and 1%, 3% and 5% clay.
similar to the LD/LL blend. It is believed that the silicate layer load-
ing leads to a significant change in terminal behavior whenever
very large amount of layered silicate is loaded into the polymer
matrix resulting in nanoparticle network structure in the molten
state [18].
It is observed that the terminal zone slope of nanocomposites
decreases slightly by increasing the clay content. Such behavior is
more likely attributed to the confinement of polymer chain within
the clay gallery in intercalated structure. This explanation is con-
sistent with XRD data that the exfoliation is limited at higher clay
loading and the dominant morphology would be the intercalated
structure.
4. Conclusion
The Rheological measurement shows that the proposed math-
ematical method’s results for interpretation of XRD patterns
are in a good agreement with several polymer nanocomposites
properties. Overall, XRD patterns and rheological measurements
indicated that increasing clay in all the prepared nanocom-
posites, exhibited a significant improvement in filler–matrix
interaction because of increasing the probability of polymer
diffusion but further exfoliation need more compatibilizing situ-
ations.
References
[1] A. Usuki, A. Koiwai, Y. Kojima, M. Kawasumi, A. Okada, T. Kurauchi, Interaction
of nylon 6-clay surface and mechanical properties of nylon 6-clay hybrid, J.
Appl. Polym. Sci. 55 (1995) 119–123.
[2] L. Liu, Z. Qi, X. Zhu, Studies on nylon 6/clay nanocomposites by melt-
intercalation process, J. Appl. Polym. Sci. 71 (1999) 1133–1138.
[3] T. Lan, T.J. Pinnavaia, J. Chem. Mater. 6 (1994) 2216–2219.
[4] Z. Wang, T.J. Pinnavaia, J. Chem. Mater. 10 (1998) 3769–3771.
140000
120000
100000
80000
G', G'' (Pa)
G' (LL+LD)
G'(LL+LD/3%g/1%C) 60000
G'(LL+LD/3%g/3%C)
G'(LL+LD/3%g/5%C)
G'' (LL+LD)
40000
G''(LL+LD/3%g/3%C)
100
ω (rad/s)
100
[5] P.B. Messersmith, E.P. Giannelis, Synthesis and barrier properties of poly(␧-
caprolactone)-layered silicate nanocomposites, J. Appl. Polym. Sci. 33 (1995)
1047–1057.
[6] K. Yano, A. Usuki, A. Okada, T. Kurauchi, O. Kamigaito, Synthesis and properties
of polyimide–clay hybrid, J. Appl. Polym. Sci. 31 (1993) 2493–2498.
[7] S. Bourbigot, S. Duquesne, Fire retardant polymers: recent developments and
opportunities, J. Math. Chem. 17 (2007) 2283–2300.
[8] C.H. Hong, Y.B. Lee, J.W. Bae, J.Y. Jho, B.U. Nam, T.W. Hwang, J. Ind. Eng. Chem.
11 (2005) 76.
[9] T.G. Gopakumar, J.A. Lee, M. Kontopoulou, J.S. Parent, Influence of clay exfoli-
ation on the physical properties of monmorillonite/polyethylene composites
polymer, Ploymer 43 (2002) 548–5491.
[10] K. Chrissopoulu, I. Altintzi, S.H. Anastasiadis, E.P. Giannelis, M. Pitsikalis, N.
Hadjichristidis, Controlling the miscibility of polyethylene/layered silicate
nanocomposites by altering the polymer/surface interactions, Polymer 46
(2005) 12440–12451.
[11] S. Arunvisut, S. Phummanee, A. Somwangthanaroj, Effect of clay on mechanical
and gas barrier properties of blown film LDPE/clay nanocomposites, J. Appl.
Polym. Sci. 106 (2007) 2210.
[12] M. Osman, V. Mittal, U. Suter, Poly(propylene)-layered silicate nanocompos-
ites: gas permeation properties and clay exfoliation, Macromol. Chem. Phys.
208 (2007) 68.
[13] K. Yano, A. Usuki, A. Okada, Synthesis and properties of polyimide–clay hybrid
films, J. Polym. Sci., Part. A: Polym. Chem. 35 (1997) 2289.
[14] R. Kuroda, T. Ogawa, T. Sakaya, Gas barrier resin composition and process for
producing the same, in: U.S. Pat, 5,854,326, 1998.
[15] C. Zhao, H. Qin, F. Gong, M. Feng, S. Zhang, M. Yang, Mechanical, thermal and
flammability properties of polyethylene/clay nanocomposites, Polym. Degrad.
Stab. 87 (2005) 183–189.
[16] A. Durmus, A. Kasgoz, C.W. Mascosko, Linear low density polyethylene
(lldpe)/clay nanocomposites, Part I: Structural characterization and quantifying
clay dispersion by melt rheology, Polymer 48 (2007) 4492–4502.
[17] K.H. Wang, M.H. Choi, C.M. Koo, M.Z. Xu, I.J. Chung, M.C. Jang, Morphology and
physical properties of polyethylene/silicate nanocomposites prepared by melt
intercalation, J. Polym. Sci., Part B: Polym. Phys. 40 (2002) 1454–1463.
[18] S. Sinha Ray, Rheology of polymer/layered silicate nanocomposites, J. Ind. Eng.
Chem. 12 (2006) 811–842.
[19] M. Yamaguchi, S. Abe, Mechanical, thermal and flammability properties of
polyethylene/clay nanocomposites, Appl. Polym. Sci. 74 (1999) 3135–3159.
[20] J. Lu, H.J. Sue, Morphology and mechanical properties of blown films of low
density polyethylene/linear low density polyethylene blend, J. Polym. Sci., Part
B: Polym. Phys. 40 (2002) 507–518.
[21] R. Krisnhamoorti, E.P. Giannelis, Macromolecules 30 (1997) 4097.