Wide-Angle X-ray Diffraction (WXRD):

Chapter
9
Technique for Characterization of
Nanomaterials and Polymer
Nanocomposites
Anjali Bishnoi1, 2, Sunil Kumar1, 2, Nirav Joshi3
1
Shroff S. R. Rotary Institute of Chemical Technology, Gujarat, India; 2Indian Institute of Technology, New Delhi, India;
3
University of São Paulo, São Paulo, Brazil

CHAPTER OUTLINE
9.1 Introduction 314
9.2 Fundamentals of X-Ray Diffraction 315
9.2.1 Basics of X-rays 315
9.2.2 Generation of X-rays 315
9.2.3 Fundamentals of X-ray Diffraction 317
9.3 Principles of X-Ray Diffraction 318
9.4 Working of X-Ray Diffraction 320
9.4.1 X-ray Sources 322
9.4.2 The Specimen 322
9.4.3 X-ray Detectors 322
9.5 Applications of X-Ray Diffraction 323
9.5.1 Strengths 324
9.5.2 Limitations 325
9.6 Experimental Details 325
9.6.1 Sample Preparation and Collection 325
9.6.2 Percentage Crystallinity Determination 326
9.6.3 Crystallite Size Determination 326

Microscopy Methods in Nanomaterials Characterization. http://dx.doi.org/10.1016/B978-0-323-46141-2.00009-2

Copyright © 2017 Elsevier Inc. All rights reserved. 313
314 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

9.7 X-ray Diffraction for Nanomaterials and Polymer Nanocomposites 327

9.7.1 Wide-Angle X-ray Diffraction for Nanomaterials 327
9.7.2 Wide-Angle X-ray Diffraction Analysis for Polymer Nanocomposites 332
9.8 Summary 334
References 335

9.1 INTRODUCTION
Matter usually exists in one of the three basic states: solid, gas, or liquid; at
fixed temperature and pressure, only one of the states is typically stable for
any given material or substance. Considering the crystalline nature of any
material, all solids can be broadly classified into either amorphous or crys-
talline states. Atoms and molecules are arranged in a regular periodic
manner in all directions in crystalline solids, whereas this arrangement is
random in amorphous materials. Every crystalline substance gives a pattern
and the same substance always gives the same pattern [1]. When X-rays
interact with a crystalline substance, they are diffracted and produce a
diffraction pattern. The wide-angle X-ray diffraction (WXRD) pattern of a
pure substance is like a fingerprint of that substance. Today, more than
50,000 inorganic and around 25,000 organic single components have been
investigated, and their individual crystalline phase diffraction patterns are
collected and stored on magnetic or optical media as standards [2].
X-ray diffraction analysis has widely been employed as a characteriza-
tion technique for crystalline materials. In this method of analysis,
material under investigation diffracts X-rays in a distinctive way and
the obtained diffraction patterns contribute to various useful structural
characteristics. Position, intensity, and shape of peak is important in
defining lattice parameters, space group, chemical composition, crystal
structure, texture, qualitative and quantitative phase analyses, crystallite
size, etc. [3e6]. This technique gives information in terms of structure of
bulk, thin film crystalline, or polycrystalline materials. Various areas in
which XRD has extensively been used include nanoparticles, polymer
nanocomposites, semiconductors, the biological field (DNA, vitamins,
proteins), medicine, and many others [7e9].
Being simple, reliable, and nondestructive in nature, XRD is used more
frequently in characterization of nanomaterials and polymer nanocompo-
sites (PNCs) too. PNCs are formed by dispersion of nanofillers in the poly-
mer matrix in which the size of at least one component is in nanoscale (up to
100 nm). Nanocomposites exhibit substantial improvements in properties
such as mechanical, electrical, optical, thermal, rheological, etc. In compar-
ison to regular composites, well-dispersed nanofiller in very small quantity is
 9.2 Fundamentals of X-Ray Diffraction 315

sufficient for quality improvement of nanocomposites. Various fillers have

been utilized in the field of polymer composites, for example, nanoclays,
silica, carbon nanomaterials, nanotubes, nanofibers, etc. [10e14].
This chapter initially presents an overview of X-rays, principle, and instrumen-
tation of WXRD, its applications and limitations. Afterward, a few experi-
mental results are discussed for nanomaterials and polymer nanocomposites.

9.2 FUNDAMENTALS OF X-RAY DIFFRACTION

9.2.1 Basics of X-rays
Electromagnetic radiation is transmitted in waves or particles at different
wavelengths and frequencies. In the electromagnetic spectrum, X-rays are
roughly classified into two types: hard X-rays and soft X-rays, between
ultraviolet rays and gamma rays. Additionally, the shorter the wavelength,
the more energetic they are, so gamma rays are somewhat more energetic
and shorter in wavelength than X-rays. Quantum electromagnetic radiation
says that energy (E) of a photon is directly proportional to its frequency
(v) multiplied by a constant factor (h).
E ¼ hv (9.1)

The constant factor is the Planck’s constant h, having a value of

6.626  1034 J s, in which v is frequency of light that is related with wave-
length l and speed of light c, so it can be rewritten as
hc
E ¼ (9.2)
l
in which the value of the speed of light is 2.99  108 m/s. It can be seen that
X-ray wavelengths range from 0.01 to 10 nm, corresponding to frequencies
in the range 3  1016 to 3  1019 Hz.

9.2.2 Generation of X-rays

X-rays are usually generated by using two different sources. The first source
is called an X-ray tube, in which electromagnetic waves are generated from
impacts of high-energy electrons with a metal target. The second is the more
advanced source of X-ray generationdthe synchrotron, in which the high-
energy electrons are confined in a storage ring [15]. The X-ray tube is
known as a laboratory or conventional X-ray source and usually has low
efficiency, and ray brightness is fundamentally limited by the thermal prop-
erties of the target material.
In the X-ray tube, a tungsten filament cathode is heated to emit electrons,
which are accelerated through a high-potential field, and finally hit the
316 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

target that emits X-rays. X-rays can be generated either by deceleration of

the electrons or through the ionization of the atoms by ejecting electrons
from the inner shells. The energy of an emitted photon depends upon the
initial and final shell positions of the electrons, and on the material used.
The X-ray spectrum, generated in a typical X-ray tube is shown in
Figs. 9.1 and 9.2 [16].
Only characteristic radiations (Ka) are used in XRD, and the rest of the
radiation is removed by filters or monochromators. These filters absorb
unwanted radiations (Kb), and allow the desired radiation to pass through.
Ka1 and Ka2 are very close in wavelength, and a weighted average of the
two is used for experimental purposes. The subject is widely studied and
well documented for particular targets and appropriate filters for them. There
are appropriate filter materials for all targets. The specific wavelengths are
characteristic of the target material (Cu, Mo, Fe, Cr, etc.). Copper is consid-
ered the most common target material for X-ray diffraction.
In the synchrotron when electrons move in a circular orbit, they accelerate
toward the center of the ring, thus emitting electromagnetic radiation. X-ray
synchrotron sources are extremely bright with minimum thermal loss and
there is no target required to cool. Importantly, the X-ray synchrotron is
easy to use and its brilliance exceeds by 10 orders of magnitude of the con-
ventional X-ray tube. The only limitation is cost; from both maintenance
and construction points of view, the X-ray synchrotron source is very
expensive and inefficient for the crystallographic laboratory. It can be

n FIGURE 9.1 The representation of a typical X-ray emission spectrum indicating only the presence of
continuous background (spectrum) and three characteristic high-intensity wavelengths: Ka1, Ka2, and
Kb.
 9.2 Fundamentals of X-Ray Diffraction 317

n FIGURE 9.2 Illustration of the atomic energy levels and emission of characteristic X-ray radiation.

seen that the spectrum consists of a wider range of wavelengths. For each
accelerating potential a continuous X-ray spectrum (also known as the white
spectrum), made up of many intense peaks with different wavelengths, is
obtained. The continuous spectrum is due to electrons losing their energy
by rapidly and unpredictably in a series of collisions with the atoms that
make up the target. Because each electron loses its energy in a different
way, a continuous spectrum of energies and X-ray wavelengths is produced,
depending on the accelerating voltage but not on the nature of the anode
material. The continuous part of the X-ray spectrum is generally not
used, unless we require a number of different wavelengths in an experiment.

9.2.3 Fundamentals of X-ray Diffraction

Diffraction is a general phenomenon of all waves that is defined as “when a
light wave passes by a corner or edge of an opening or slit they tend to bend
around that barrier, which gives geometrical shadow of the obstacle.” X-
rays and diffraction are fundamental to understanding the principle of X-
ray diffraction.
Let’s consider an individual atom. If a beam of X-rays is incident upon an
atom, the electrons of which are oscillating about their mean positions, and
when an electron decelerates (loses energy) it emits more X-rays. This
process of absorption and recreation of electromagnetic radiation is known
as scattering. By using the notation of a photon, we can say that when a
wave interacts with a point object and is scattered by that object, the result
318 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

of this interaction is a new wave, which spreads in all directions. If no

energy loss occurs, the resultant wave has the same frequency as the inci-
dent (primary) wave; this process is known as elastic. On the other hand,
inelastic scattering involves photon energy loss (photoionization). In three
dimensions, the elastically scattered wave is spherical, which can be illus-
trated in Fig. 9.3.
In constructive interference, the resultant wave is bigger than either of the
original waves, whereas in destructive interference both waves exactly
cancel one other out and no wave is left. In constructive interference,
wave amplitude increases by many orders of magnitude, which is the
keystone in the theory of diffraction.
In diffraction for crystals, the wavelength should be in the same range but at
shorter inter-atomic distances. While using electromagnetic radiation, this
condition can be fulfilled, as X-rays fall within the mentioned range of
wavelengths. X-rays scatter from electrons, and more accurately delineate
electron density and the systematically arranged crystal lattice. Thus,
when a constant wavelength is used, the differences in the diffraction pat-
terns are mainly in the intensities of the diffracted beams.

9.3 PRINCIPLES OF X-RAY DIFFRACTION

Once X-rays and diffraction became deeply understood, crystal state and
crystal lattice became key parameters. Every crystalline material is made
up of a periodic arrangement of atoms. There may be many ways of inter-
action of X-rays when they come into contact with crystalline material.
Elastic or inelastic scattering by electrons of material keeping scattering
by nucleus as virtually negligible. When the energy of an incoming and
an outgoing photon is the same, it is called elastic scattering or Thompson
scattering. Emitted radiation undergoes constructive or destructive

n FIGURE 9.3 Elastic scattering by the spherical wave.

 9.3 Principles of X-Ray Diffraction 319

n FIGURE 9.4 Geometrical illustration of Braggs’ law.

interference. Diffraction peaks for constructive interference are collected and

analyzed. Constructive interference obeys Bragg’s law, whereas destructive
interference does not. The process is schematically shown in Fig. 9.4.
The sample is exposed to an X-ray beam of wavelength (l) at an angle q
with the tangential surface. This expression is written mathematically in
the form of Bragg’s law, which can be shown as:
2dSin q ¼ nl (9.3)

in which n is an integer, l is the wavelength of the radiation, d is the spacing

between atomic planes, and q is the angle between the radiation and the
atomic planes (Bragg angle). Rewriting Bragg’s law, we get
nl
Sin q ¼ (9.4)
2d
Two methods of XRD are common in practice: one is the Laue method, in
which q is kept constant and l is varied; the second is the powder diffrac-
tion method, in which l remains constant and q is varied. In both cases, the
intensity of the diffracted X-ray beam against diffraction angle 2q is
measured, which gives the diffraction pattern of the material. For crystalline
materials, the XRD pattern shows sharp maxima (peaks) at respective
diffraction angles, whereas, for amorphous solids, such peaks are absent
and a broad maximum (hump) appears.
The different crystallographic planes in a crystal are characterized by Miller
indices (hkl). They are the three integral numbers that are related to the
reciprocal values of the intersection of a given plane with the
320 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

crystallographic unit-cell axes. The diffraction pattern results in a series of

spots when the material irradiated is a single crystal. These diffraction spots
transform into circles when the material is in a polycrystalline state.
Because polymers are neither fully crystalline nor fully amorphous, the
crystallinity is expressed in terms of a degree of crystallinity, which is a
measure of the extent to which the material is crystalline. The total intensity
is divided into two parts, intensity of the diffracted beam from the crystal-
line part (Ic) and intensity of the diffracted beam from the amorphous part
(Ia). The degree of crystallinity (Q) is determined by using the following
expression:
Ic
Q ¼ (9.5)
ðIc þ Ia Þ

The knowledge and understanding of the degree of crystallinity in polymers

are vital for predicting the properties and determining the application poten-
tial in various fields.

9.4 WORKING OF X-RAY DIFFRACTION

In this section, we are providing some general experimental background to
the X-ray diffraction technique. Each instrument has its unique features, and
an X-ray diffractometer has the following three major components:
n X-ray source
n Specimen
n X-ray detector
All three components lie on the circumference of a circle called the focusing
circle. The angle between the plane of specimen and source is the Bragg
angle (q). The angle between the projection of source and detector is 2q
(Fig. 9.4) [17].
The 2q measurement range depends on the crystal structure of the material
and the time to obtain diffraction pattern. Generally, for an unknown spec-
imen ranges of angles are large because the reflection positions are not
known. The radius of the diffractometer is fixed. The diffractometer circle
is referred to as a goniometer circle. The goniometer is the component in
which the specimen holder takes place in the X-ray diffractometer. It has
arms to which the X-ray source and the detector are mounted. This central
part of the diffractometer is used to move the X-ray source, the sample, and
the detector relative to each other in a very precise manner. Two types of
goniometer are generally available: q/q goniometers, in which the sample
has a fixed position as shown in Fig. 9.5A, while the X-ray source and
 9.4 Working of X-Ray Diffraction 321

n FIGURE 9.5 (A, B) Features of X-ray diffraction spectroscopy.

detector move; and q/2q goniometers, in which the X-ray source has a fixed
position and the sample as well as the detector move per Fig. 9.5B. The
whole instrument can be illustrated as shown in Fig. 9.6. In most powder dif-
fractometers, the goniometer is vertically mounted, but in other setups it is
mounted horizontally specifically to study thin films. As we have discussed
X-ray sources in Section 9.2, we will give a brief idea about specimen and
detectors that are generally used in diffractometers.

n FIGURE 9.6 X-ray diffractometer illustration.

322 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

9.4.1 X-ray Sources

Production of X-rays has been described in Section 9.2; a high-voltage
electron beam is directed to a metal target inside an X-ray tube under
high vacuum. In this case, both voltage and current are variables and espe-
cially suitable operating voltages depend on the target metal, e.g., copper
25e40 kV, molybdenum 50e55 kV, iron 25e30 kV, and chromium
25 kV. Among all, copper is the most frequently used target, and typical
operating conditions are 40 kV and 30 mA. As described earlier, radiation
penetration occurs when sufficiently energetic incident X-rays knockout
electrons from the K-shell of the atom, the atom that enters an excited state.
The atom returns to ground state by filling the holes in the K-shell with the
emission of X-rays. This emission of radiation is the fluorescent radiation,
which radiates in all directions with the same wavelength. If the specimen
element has a lower atomic number than the target metal, the X-rays will be
absorbed, which results in a decrease in the intensity of the diffracted beam
and an increase in background noise due to the large amount of fluorescent
radiation. So to avoid fluorescence radiation from specimens and from other
transition elements, try to use lower ionization energy than
K-shell electrons. Copper is most frequently used because of its average
wavelength and high intensity.

9.4.2 The Specimen

Another important component in a typical X-ray diffractometer is the spec-
imen on which the thin layer of crystalline powder is spread. It should be a
nondiffracting and amorphous material to avoid interference when exposed
to the X-ray beam, such as a glass microscope slide. The quantity of powder
used for each experiment is a few milligrams and before mounting it on the
medium, grind the sample to a fine powder, typically in a fluid to minimize
inducing extra strain (surface energy) that can offset peak positions and to
randomize orientation. Care must be taken to create a flat upper surface and
to achieve a random distribution of lattice orientations unless creating an
oriented spray. Most of the powdered specimen is flat (see Fig. 9.6), so to
increase or decrease the intensity the specimen can be moved horizontally
by various angles.

9.4.3 X-ray Detectors

Several types of detectors are available for detection of the diffracted beam
intensity, mainly proportional, scintillation, and solid state. It is important to
be familiar with the manual of the instrument to select which detector is
suitable for the apparatus. Particularly for powder work, the proportional
 9.5 Applications of X-Ray Diffraction 323

detector is often used. The scintillation detector is common but, in recent

diffractometers, it is not used frequently. The solid-state detector has
many advantages but because of high cost, it is not used very often. Gener-
ally, the working principle of the detectors is based on the conversion of X-
ray photons into another signal, which can be analyzed.
Several technologies are available for the detectors. Gas detectors are based on
the ionization of a gas by the incoming X-ray photons that generate voltage
pulses. Solid detectors use the phenomenon of fluorescence of special materials
and which can be converted into either voltage pulses or visible light that
further is recorded by a charge-coupled device (CCD) camera.
Semiconductor technologies are also used widely for the detection of
X-rays. These detectors can be classified into three categories: Zero-
dimensional detectors (point detectors), one-dimensional detectors
[position-sensitive detectors (PSD)], or two-dimensional detectors (plane
or curved plates).

9.5 APPLICATIONS OF X-RAY DIFFRACTION

WXRD has various applications in different fields such as chemistry,
material science, geology, environmental science, medicine, etc. WXRD
has been utilized to characterize almost all types of organic and inorganic
materials (polymers, drugs, minerals, zeolites, catalysts, metals, and
ceramics) irrespective of their physical states (loose powders, thin films,
polycrystalline, and bulk materials). This method has widely been used
for quantitative analysis, phase identification, and for determination of
structure imperfections. One may get complete structural information
of material by the proper use of this technique. The broad application
of powder XRD is summarized as shown in Fig. 9.7. Applications of
XRD can be expressed as follows:
n Typical characterization of variety of crystalline materials
n Determination of unit-cell dimensions
n Crystal structures
n Purity analysis of crystalline samples
n Mineral identification
n Quantitative analysis of minerals
n Characterization of thin film samples
n Textural characterization
n Determination of lattice mismatch
n Determining of dislocation density
n Statistical study of the relative orientations of the individual crystals
324 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

n FIGURE 9.7 Applications of WXRD.

9.5.1 Strengths
n Ease of availability of instrument
n Simplified data interpretation
n Versatile technique for identification of an unknown mineral
n Often provides unambiguous mineral determination
n Minimal sample preparation
n Reliable and fast technique for both known and unknown crystalline
samples
n Nondestructive technique
n Mixed phases can also be analyzed
n Easy and simple sample preparation
n Easy interpretation of data as these units are widely available
 9.6 Experimental Details 325

9.5.2 Limitations
n Chances for misinterpretations are high, if sample is not homogeneous
or single phase.
n Standard reference file of inorganic compounds is required.
n Characterization of amorphous materials is not possible by WXRD.
n Lack of depth-profile information.
n Indexing of patterns for nonisometric crystal systems is quite
complicated.
n For single-phase material, detection limit is 5% by weight.
n For mixed materials, detection limit is w2% of sample.
n Chances of peak overlay exist.

9.6 EXPERIMENTAL DETAILS

9.6.1 Sample Preparation and Collection
Proper sample preparation is one of the most important steps in the analysis
of powder samples by X-ray diffraction. It is difficult to overemphasize the
attention to proper sample preparation, especially because it is always under
the complete control of the operator carrying out the experiment. Poorly pre-
pared samples will inevitably result in unusable experimental data, which will
require additional effort to repeat everything from the beginning, thus wasting
both time and resources. On the other hand, high-quality sample preparation
for powder diffraction may take longer, but this is time well spent.
To determine an unknown substance requires three important things, i.e., the
material, an instrument for grinding, and a sample holder. Obtain few milli-
grams or grams of the substance as pure as possible. The second step is to
grind the substance into fine powder, typically in a fluid to minimize
inducing extra strain (surface energy) that can offset peak positions and to
randomize orientation. The third step is to place the fine powder into the
sample holder or onto the sample surface by sprinkling on the double sticky
tape, smearing uniformly onto the specimen, or packing into specimen hold-
er. Sample preparation includes not only the right sample treatments to
remove undesirable substances, but also appropriate techniques to obtain
desirable crystallite size, orientation, thickness, etc. It is noted that sample
properties also influence the quality of a powder pattern by either reducing
or distorting intensities.
Now, during the data collection, the intensity of diffracted X-rays is contin-
uously recorded as the sample and detector rotate through their respective
angles. A peak in intensity occurs when the material contains lattice planes
with d-spacing appropriate to diffract X-rays at that value of q. Although
326 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

each peak consists of two separate reflections (Ka1 and Ka2), at small values
of 2q the peak locations overlap with Ka2 appearing as a hump on the side of
Ka1. Greater separation occurs at higher values of q. Typically, these
combined peaks are treated as one. The 2l position of the diffraction peak
is typically measured as the center of the peak at 80% peak height. Addition-
ally, results or X-ray diffraction plot is presented as peak position at 2q and
X-ray counts (intensity) in the form of an xey plot. Determination of the
unknown substance is only possible by knowing the d-spacing of each
peak, which is obtained by the Bragg equation for the appropriate value of
l. Once all d-spacing is determined, automated search/match routines
compare the d-spacing of the unknown to those of known materials. Because
each mineral has a unique set of d-spacing, matching the d-spacing provides
an identification of the unknown sample. It is important to compare this
d-spacing for hundreds of thousands of inorganic compounds, which are
available from the International Center for Diffraction Data as the Powder
Diffraction File (PDF). Commonly, this information is an integral portion
of the software that comes with the instrumentation.

9.6.2 Percentage Crystallinity Determination

Values of peak positions, full width at half maximum (FWHM), and areas
are determined from the XRD, which is used subsequently for the calculation
of the fraction of the crystalline material. The following is the equation used
for calculating percentage crystallinity:
 
sum of all A0p s
Crystallinity ¼
AT

Amorphous contents ¼ 1  ðcrystallinityÞ (9.6)

in which AT is the total area of the diffraction pattern (including peaks and
amorphous background but subtracted from the sample-holder background),
and AP is area of the amorphous diffraction part.

9.6.3 Crystallite Size Determination

Crystallite size generally corresponds to the coherent volume in the material
for the respective diffraction peak. Sometimes, it also corresponds to the size
of the grains of a powder sample, or thickness of polycrystalline thin film or
bulk material. The Scherrer’s equation is used for determination of size of
particles of crystals in the form of powder, which can be represented as
follows:
ks l
L ¼ (9.7)
ðcos qÞs
 9.7 X-ray Diffraction for Nanomaterials and Polymer Nanocomposites 327

in which, L is the mean size of the ordered (crystalline) domains, ks is a

shape factor constant in the range 0.8e1.2 (typically equal to 0.9), l is the
X-ray wavelength, s is peak width at FWHM, q is the Bragg angle.

9.7 X-RAY DIFFRACTION FOR NANOMATERIALS

AND POLYMER NANOCOMPOSITES
9.7.1 Wide-Angle X-ray Diffraction for
Nanomaterials
In recent years, nanomaterials has become a core area of research because of
its tremendous advantages and applications. There are various techniques
for measuring and characterizing nanoparticles. There is not one method
that is best suitable for characterization of nanoparticles but rather choose
the method with fewer time constraints and lower cost of analysis. A
straightforward technique may simply detect the presence of nanoparticles;
others may give the quantity, the size distribution, or the surface area of the
nanoparticles. XRD has great potential to analyze nanomaterials because
the width and shape of reflections yield information on the substructure
of the nanomaterials. Microstructure of nanomaterials is an obvious choice
for powder diffraction techniques because of simple processing, easy use,
and the importance of getting clear information about its crystallite size,
microstrain of the lattice, dislocation structures, etc. In the study of nanoma-
terials, the crystallite size is usually the sole factor of interest. In a powder
diffraction pattern, broadening of reflections contains much information like
crystallite strain, shape, and stacking faults, which are often not considered.
Numbers of different nanocrystalline powders were analyzed for size char-
acteristics using a number of different techniques. They include commercial
ZnO [18], TiO2 [19], NiO [20], SnO2 [21], and some titanates like BaTiO3
[22,23] and PbTiO3 [24], as well as some polymer composites by using
different nanofillers. The most common polymers used for polymer nano-
composites are epoxy [8], polytetrafluoroethylene [25], polypropylene
[26], polycarbonate [27], polyvinyl butyral [28,29], poly (methacrylic
acid) [30], polyurea [31], etc. Control of crystallinity in nanoparticles holds
the key to optimizing their functionality. It has been shown that modification
of crystallinity can lead to dramatic changes in nanoparticle properties.
There are different techniques to prepare these nanomaterials like solegel
[32], hydrothermal [33], solvothermal [34], Pechini process [35], carbother-
mal [36], and many more for their electrical, chemical, and mechanical prop-
erties. Each technique has its own advantages and disadvantages. Importantly,
varying different reaction parameters like reaction time, temperature, concen-
tration, pH, crystallite size, and shape changes, can be confirmed by X-ray
328 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

diffraction and also by other techniques. Nanoparticles with controlled crystal-

line and amorphous characteristics are desirable in many applications.
Through this investigation, we synthesized some common semiconducting
oxides as well as ceramic oxide to understand the importance of X-ray
diffraction for nanomaterials.
Fig. 9.8 shows the XRD pattern of BaTiO3 powder, which is prepared by
hydrothermal technique [37]. X-ray diffraction was performed on a Bruker
AXS D8 Advance X-ray diffractometer using Ni-filtered Cu-Ka radiation.
Normal XRD scans with step resolution of 0.02 degrees with a time step
of 0.5 s were used. To ensure stability of the measurements with respect
to change in resolution in angular coordinates and time, measurements
were repeated with angular step size (in 2q) of 0.05 degrees with a time
step of 2 s. The Cu-Ka2 diffraction signal was removed by a standard strip-
ping procedure to obtain the correct lattice parameters and grain size. Based
on the XRD pattern shown in the figure, BaTiO3 exhibits a phase having a
cell parameter of 4.03 Å and space group Pm-3m (221). This cubic phase of
BaTiO3 phase is as per the standard XRD. The average crystallite size is
w33 nm, which is measured by Scherrer’s equation.
Further modification of barium titanate by rare earth dopants like lanthanum
and by magnesium, enhance the dielectric properties of nanomaterials.

JCPDS:01-074-1968
(110)
Intensity (a.u.)

(211)
(200)

(220)
(100)

(111)

(311)
(201)

(310)

20 30 40 50 60 70 80
2θ (deg.)
n FIGURE 9.8 XRD pattern of barium titanate powder.
 9.7 X-ray Diffraction for Nanomaterials and Polymer Nanocomposites 329

0.2% La-Doped
0.6% La-Doped
0.8% La-Doped
1% La-Doped
Intensity (a.u.)

Δ Δ Δ

Δ The BaLa2Ti2O8 Phase

Δ

10 20 30 40 50 60 70 80
2θ (deg.)
n FIGURE 9.9 XRD of La-doped barium titanate.

0.2% Mg-Doped
0.6% Mg-Doped
0.8% Mg-Doped
1% Mg-Doped

Δ The Ba2MgCl6 Phase

Intensity (a.u.)

Δ Δ

Δ
Δ

10 20 30 40 50 60 70 80
2θ (deg.)
n FIGURE 9.10 XRD of Mg-doped barium titanate.

Figs. 9.9 and 9.10 show the XRD pattern of lanthanum- and magnesium-
doped barium titanate. The WXRD peaks of the doped material varying
different percentages of rare earth elements are compared with the WXRD
graph of barium titanate powder, which will confirm the presence of doping
330 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

in the material [2]. The inclusion of the peak in the WXRD spectra reveals
the presence of the rare earth element in the powder. The average crystallite
size is in the range 35e40 nm for all the Mg-doped barium titanate samples.
In addition, a new phase showing stoichiometric of BaLa2Ti2O8 is observed
in La-doped barium titanate. The diffraction peaks from BaLa2TiO8 are
labeled in Fig. 9.9 with the symbol “D.” And, similarly, new phase
Ba2MgCl6 is observed in Mg-doped barium titanate. The second phase
corresponds to ion substitution with barium titanate [38].
Figs. 9.11 and 9.12 show the XRD pattern of pure NiCo2O4 and NiO nano-
materials, which were prepared by the urea-assisted coprecipitation method.
The crystal phase and purity of the prepared NiO and NiCo2O4 samples were
identified by X-ray powder diffraction (XRD), CuKa1 radiation
(K ¼ 1.5406 Å, Rigaku Rotaflex RU-200B) in the 2q range from 10 to
90 C with a step of 0.02 at a scanning speed of 2 degrees/min. The XRD
pattern of NiCo2O4 nanowires obtained after an annealing for 2 h at
450 C is shown in Fig. 9.11. All diffraction peaks were indexed as a cubic
structure of NiCo2O4 with an F*3 (202) space group (JCPDS file No.
20-0781) at 2q values of 18.9, 31.1, 36.6, 38.4, 44.6, 55.4, 59.02, 64.9,
73.8, and 76.9 corresponding to the (111), (220), (311), (222), (400),
(422), (511), (440), (620), and (533) crystal planes, respectively. Addition-
ally, a structural and morphological analysis of calcined samples of NiO

n FIGURE 9.11 XRD pattern of NiCo2O4 annealed at 450 C for 2 h under ambient atmosphere.
 9.7 X-ray Diffraction for Nanomaterials and Polymer Nanocomposites 331

n FIGURE 9.12 X-ray diffraction pattern of NiO sample annealed at 400 C.

microspheres was carried out. Fig. 9.12 shows the crystal phase of NiO
samples prepared at 400 C for 2 h in air atmosphere. All diffraction peaks
at 37.38, 43.28, 62.78, 75.59, and 79.5 are perfectly indexed to (111),
(200), (220), (311), and (221) crystal planes of cubic NiO phase (JCPDS
47-1049), respectively, indicating that crystalline NiO formed after heat
treatment. The more intense peak located at 2q ¼ 43.3 degrees indicates
that crystal growth dominated through the (200) plane, which corresponds
to the interplanar spacing d200 ¼ 0.2 nm. The average crystallite size of
the obtained NiO samples were calculated from the major diffraction peak
(200) using Scherrer’s equation, in which, K is the Scherrer’s coefficient
equal to 0.89, b is the FWHM, l is the wavelength of the X-rays
(1.5406 Å), and q is the Bragg diffraction angle of the XRD peak. The
obtained average crystallite size is 45 nm.
XRD measurements were also carried out on the powder sample of halloy-
site nanotubes (HNTs) and are shown in Fig. 9.13. The measurements were
conducted on an X-pert PRO model-PW 3040-60 (Netherlands), X-ray
diffractometer of PAN analytical using Ni filtered Cu Ka radiation of
1.54. XRD patterns of HNTs exhibit characteristic peaks at 2q of 12.18,
20.07, and 24.78 degrees accordance with the crystal plane (001), (110),
and (200) with the d-spacing values of 0.73, 0.44, and 0.36 nm, respectively.
This HNT basal reflection shows its tubular morphology with a small crystal
size of 27.11 nm determined from the Scherrer relation [39]. Due to this first
332 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

n FIGURE 9.13 X-ray diffractograms HNTs (intensity vs. 2q).

peak, HNTs used in this study are classified as (7 Å) halloysite with a dehy-
drated formation [40,41].

9.7.2 Wide-Angle X-ray Diffraction Analysis for

Polymer Nanocomposites
Nanocomposite is the system in which at least one of the components of the
system exists with a dimension less than 100 nm. Polychlorinated naphtha-
lenes (PCNs) ensuring combination of stiffness and toughness properties
have allured materials scientists due to their outstanding optical, electrical,
and mechanical properties. In such nanocomposites, fibers (surface area to
volume ratio A/V [ 1, e.g., halloysite nanotubes, carbon nanotubes), plate-
lets (surface area to volume ratio A/V  1, e.g., nanoclay), and other nanofil-
lers are good choices as reinforcing fillers. Toyota Central Research Group has
developed nanoclay exfoliated PA-6, which showed significant increase in the
heat distortion temperature (HDT) and accompanied hardness [42]. Due to the
unique properties of nanofillers in terms of their morphology, nanoscale diam-
eter, high aspect ratio (length-to-diameter ratio, l/d), and compatible chemistry
on external and internal surfaces of nanofillers, these remain attractive and
preferable as reinforcement for various PCNs. The improved mechanical
properties for such nanocomposites are because the applied load is efficiently
transferred from matrix to the nanofillers [43,44]. The WXRD is one of the
most common and useful techniques to understand the effect of nanofillers
 9.7 X-ray Diffraction for Nanomaterials and Polymer Nanocomposites 333

in the polymer structure. With the help of XRD diffractograms, % crystal-

linity, nucleating effect of nanofillers, degree of dispersion of nanofillers in
polymer matrix, crystallite size, etc. can be analyzed.
The PA-612 and HNT were predried to remove the moisture by keeping
them in a vacuum oven at 80 C for 12 h and 4 h, respectively. The melt
mixing of PA-612 and HNT was carried out in a corotating twin-screw
extruder (Model Steer Omega-20, L/D ¼ 40) at a screw speed of 200 rpm.
The continuous strands thus obtained were cooled in water and chopped
in a granulator followed by vacuum drying at 80 C for 24 h. These granules
were injection molded on an L&T Demag machine (Model PFY 40-LNC4P)
to obtain test specimens for WXRD tests. WXRD measurements were car-
ried out on the injection-molded specimen of virgin PA-612, PA-612/
HNT-filled nanocomposites to characterize any structural changes (crystal-
line organization) in terms of peak intensity, crystallinity, and shift in the
crystalline peaks corresponding to different planes as a function of compo-
sition ratio of nanocomposites.
The WXRD results for the pure HNTs and the PA-612/HNT nanocomposite
are shown in Fig. 9.14. The diffractograms of halloysite show characteristic
peaks at 2q ¼ 12.18 degrees of HNTs (0.72 nm) basal spacing for the (001)
peak, which is related to the dehydrated form of HNT. In contrast, for
PA-612, the two characteristic peaks of matrix occurred around
2q ¼ 20.04 degrees that correspond to the (110) plane, and peaks at
2q ¼ 23.38 degrees that correspond to (110), respectively. The new peaks
that appear at 2q ¼ 12.11 degrees in the nanocomposites are characteristic
peaks of HNTs. The characteristic peak at 2q ¼ 12.18 degrees of HNTs in
both the investigated nanocomposites is shifted to a lower 2q value as
compared to that of the pure HNT. The lower value of 2q and increasing of
the basal spacing of the HNTs may be attributed to the intercalation between
the HNTs and the PA-612 matrix. The nanocomposites, however, revealed an
intense peak at 2q y 20 degrees indicating the noninterference of HNT with
the a-crystalline phase, whereas the appearance of a broad peak accompanied
by bimodal splitting of the peak at 2q y 23e24 degrees indicates the effective
interference of HNT with the b-crystalline phase of polyamide.
Further, the WXRD patterns exhibit two distinct crystalline peaks attributed
to the semicrystalline nature of the PA-612. The peak position, d-spacing,
FWHM, crystallite size, and % crystallinity of the neat PA-612 and its nano-
composites are listed in Table 9.1. The % crystallinity of the PA-612
increased with HNT content increases, also an increase of the HNT loading.
The stronger diffraction intensity of the PA-612/HNTs nanocomposites at
2q ¼ 12.19 degrees implied higher crystallinity of the nanocomposites than
334 CHAPTER 9 Wide-Angle X-ray Diffraction (WXRD)

n FIGURE 9.14 X-ray diffractograms of PA-612/HNTs nanocomposites (intensity vs. 2q).

Table 9.1 D-spacing, Crystallite Size, and % Crystallinity From XRD Analysis of PA-612/HNT
Nanocomposite
HNT Contents (%) Peak Pos. (2q degree) FWHM (2q degree) d-Spacing (Å) d (nm) Crystallinity (%)

0 20.07 0.60 4.43 14.11 25.12

23.38 1.20 3.80
5 20.01 0.54 4.43 15.68 28.21
23.23 1.08 3.81
24.62 0.48 3.61
10 20.07 0.48 4.42 17.64 29.87
23.19 0.60 3.78
24.67 0.48 3.61

the matrix. This behavior could be due to the interaction between the HNTs
and matrix contributing to the change in the structure of PA-612 matrix. The
crystallite size of PA-612 is also increased when HNT loading increases.

n 9.8 SUMMARY
In this chapter we have elaborated all aspects related to WXRD. Funda-
mentals, principle, and operation have been discussed extensively. For
easy understanding of technique, a few experimental results have also
 References 335

been incorporated. Examples included in this chapter are taken on the basis
of recent research trends.

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