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Materials Letters 72 (2012) 3638

Contents lists available at SciVerse ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Sizestrain study of NiO nanoparticles by X-ray powder diffraction line broadening

N.S. Gonalves a, b,, J.A. Carvalho c, Z.M. Lima c, J.M. Sasaki a
a
b
c

Departamento de Fsica, Universidade Federal do Cear, Campus do Pici, 60440-970, Fortaleza, CE, Brazil
Instituto Federal de Educao, Cincia e Tecnologia do Cear, Campus Acara, 62580-000, Acara, CE, Brazil
Engenharia de Materiais e Cincia de Materiais, Universidade Federal do Cear, Campus do Pici, 60440-554, Fortaleza, CE, Brazil

a r t i c l e

i n f o

Article history:
Received 16 October 2011
Accepted 9 December 2011
Available online 16 December 2011
Keywords:
X-ray techniques
Nanoparticles
Microstructure

a b s t r a c t
We show that the nanoparticle sizes calculated from the X-ray powder diffraction need to be analyzed more
carefully when calculated by the Scherrer equation. When nanoparticles are not perfect crystals, microstrain
contributes to the line broadening of diffraction peaks. This additional width of the diffraction peak can introduce a
wrong estimate to the nanoparticle size. In this work, we show how to calculate directly the size and the microstrain
for NiO nanoparticles using the WilliamsonHall plotting and compare with results obtained from the Scherrer
equation. In additional to these results is that the straight line obtained in the WilliamsonHall plotting shows the
homogeneity of the nanoparticles.
Crown Copyright 2012 Published by Elsevier B.V. All rights reserved.

1. Introduction
Studies of materials in the nanoscale need characterization of
microstructure with emphasis in the particle size and microstrain.
To estimate the particle size using X-ray powder diffraction (XRPD)
measurements, the Scherrer equation is the most used method [1].
According to Azaroff, the particle size (D) can be calculated using the
Scherrer equation [2]:
D k= cos

where k is the shape coefcient for the reciprocal lattice point and shape
coefcient for crystal in the direct space [3], is the wavelength of the
incident radiation, is the full-width at half-maximum (FWHM) of the
peak and is the Bragg angle. In the Scherrer equation, the parameter
needs to be corrected to eliminate the so-called instrumental effects [4].
A classical method to make this correction uses a standard sample with
small microstrain and great particle size so that the widths of diffraction
peaks observed are only due to instrumental effects [5]. There is a simple
approach to separate contributions of sample and instrumental effects to
the peak width using Gaussian prole. Let exp be the measured width,
standard the width due to standard sample, i.e., the instrumental width,
and the corrected one. According to Cullity [6] the best expression for
this instrumental effect correction is:
q
exp 2 standard 2 :

Corresponding author at: Departamento de Fsica, Universidade Federal do Cear,

Campus do Pici, 60440-970, Fortaleza, CE, Brazil. Tel.: +55 85 88520634.
E-mail address: nizomar@sica.ufc.br (N.S. Gonalves).

The Scherrer equation gives us a rough estimate of particle size.

Despite the well-known accuracy of this method, it neglects the
importance of the microstrain, , and its effects in the powder diffraction
pattern [7].
Differentiating the Bragg equation, the microstrain, 2 d=d, can
be written as [8]
 
 
d
d
  cot yields
  tan;

d
d

where d is the d-spacing in the crystal and d is the fractional

variation of this parameter. The contribution of the microstrain to the
line broadening of the diffraction peak is [8]
4 tan:

A simple method to separate the contributions of particle size

and microstrain to the line broadening in the XRPD patterns is
the WilliamsonHall (WH) plotting [9]. This analysis supposes
that particle size (D) and microstrain () contribute to the line
broadening with Lorentzian proles described by:
D ;

where is considered as the sum of the peak width due to the

microstrain and due to particle size. WH plotting assumes that
those contributions to the peak width are convoluted in the Full
Width at Half Maximum (FWHM) of the diffraction peak. Combining
Eqs. (1), (4) and (5), the WH equation can be written as [9]

k 4
cos
sin:

0167-577X/$ see front matter. Crown Copyright 2012 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.12.046

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N.S. Gonalves et al. / Materials Letters 72 (2012) 3638

{113}

20

80

Fig. 1. X ray powder diffraction pattern of NiO.

a. To determine the microstrain () from the slope of the straight

line in the WH plotting.
b. To determine the average particle size (D) from intercept of the
straight line.
c. To calculate the line broadening due to microstrain for all the diffraction peaks: = 4 tan .
d. To separate the line width contributions due to microstrain and
due to particle size:
D  ;

where D is the line width due to particle size, is the line width
due to microstrain and is the full line width correct for instrumental effects. The plus sign is used when lattice expansion exists
and the minus sign is used when lattice compression exists.
e. To calculate the particle size using the Scherrer equation considering the corrected line width (Eq. (8)).
This WH plotting method proved that average particle size
D = 15.4 nm and microstrain is about 0.0020 to the NiO sample.
This microstrain is 20 times greater than those of Si powder (0.01%,
that is almost free of microstrain [16]). The positive signal of the
microstrain indicates a lattice expansion also observed by Maia et al.
[10]. These results suggest that NiO nanoparticles synthesized by
solgel proteic method are homogenous in size and microstrain.
As can be seen in Table 1 the average particle size obtained from
the Scherrer equation is 10 nm while the average particle size calculated using the WH plotting is 15.4 nm. Nanoparticle size estimated

0.0110

R = 0.9999

{022}

cos /

{113}

0.0105

3. Results and discussion

{222}

where u, v and w were obtained from Rietveld renement analysis

where u = 0.0186, v = 0.0244 and w = 0.0173.

Fig. 1 shows the X-ray powder diffraction pattern of the sample. The
identied phase in the pattern is cubic nickel oxide (ICDD: 47-1049)
belonging to the Fm3m space group. There exists a major quantity of
nickel oxide and a small quantity of amorphous phase peak intensity
contribution for background near 2 =20, which came from the burning
of the organic gelatin precursor [10].
The average particle size and the microstrain for the sample
were calculated using the WH plotting, showed in Fig. 2. The good
straight line in the WH plotting indicates no dispersion in particle
size and microstrain suggesting that the sample has homogeneous
particle size distribution and microstrain. This method of synthesis
yields homogeneous particles in size and microstrain.

0.0100
0.0095
0.0090

{002}

The average particle size and the microstrain were obtained as

described below. The procedure includes:

{111}

NiO was prepared [10,11] by dissolving commercial avorless

gelatin in 30 ml of distilled water, NiCl2.6H2O and NaOH in stoichiometric
quantities. The solution was stirred constantly at 40 C through 10 min
and then, dried at 100 C through 24 h. The dried gel (xerogel), with appearance of a resin, was heated up at a rate of 10 C/min and calcined at
350 C for 3 h in a rotating alumina tube furnace at 17 rpm using air atmosphere. The nal powder was washed with H2O2 and distilled water
to eliminate undesirable soluble phases.
The X-ray powder diffraction experiments were performed in a
Rigaku powder diffractometer (DMAXB) using the BraggBrentano
geometry in a continuous mode with a scan speed of 0.25/min. A
CuK radiation tube with the line focus was operated at 40 kV and
25 mA. The X-ray powder diffractions (XRPD) were taken in the
range of 2090 (2) in step sizes of 0.02. The diffracted X-ray
beam coming from the sample is focused into the detector slit with
a curved graphite monochromator. The crystalline phase was identied using the International Center for Diffraction Data (ICDD) catalog.
Rietveld renement procedures [12] were applied to diffraction patterns using the interface DBWS9807-Tools [13], as described by
Young et al. [14]. The FWHM was used to calculate the particle size
for crystallographic families. The Lorentzian function was selected to
t the peak proles of the identied crystalline phase.
To correct the line broadening for the instrumental effects we
have used the approach described before in Eq. (2), where standard
was obtained from standard LaB6 powder (SRM660-National Institute
of Standard Technology) using the Caglioti equation [15]
q
u tan2 v tan w;

60

2(degree)

2. Experimental

standard

40

{222}

{022}

Intensity (a.u)

{111}

{002}

The practical application of the WH plotting consists in the construction of a plot / cos versus sin . When the sample exhibits
homogeneous distribution of particle size and microstrain the WH
plotting has a straight line. The graph can be tted by a linear
function that provides the microstrain value from the slope and
the mean particle size from the intercept with the axis. The slope
can be positive, negative or horizontal. The positive slope indicates
a lattice expansion. The negative slope indicates a lattice compression. The horizontal slope indicates perfect crystals (particles free
of microstrain).
For this work we present the mean particles sizes for NiO calculated
from XRDP patterns by using the WH plotting method considering the
effect of microstrain and then compare with those mean particle sizes
obtained with Scherrer equation. Then we use a corrected line width in
the Scherrer equation to calculate particle size.

37

0.0085
0.0080
0.3

0.4

0.5

0.6

0.7

sin
Fig. 2. WilliamsonHall plotting to NiO (dot line is the adjusted function).

Author's personal copy

38

N.S. Gonalves et al. / Materials Letters 72 (2012) 3638

Table 1
Particle sizes calculated by Scherrer equation, Scherrer equation (corrected line width)
and WH plotting.
Crystallographic
direction

Scherrer
equation

Scherrer
equation
(corrected
line width)

WilliamsonHall plotting

{hkl}

D (nm)

{hkl}

D (nm)

D (nm)

{111}
{002}
{022}
{113}
{222}

12.2 0.2
11.8 0.2
10.8 0.2
10.3 0.2
10.1 0.2

{111}
{002}
{022}
{113}
{222}

15.3
15.3
15.4
15.4
15.4

equation to determine the particle for each crystallographic direction.

This study shows that NiO nanoparticles synthesized by the solgel
proteic method and calcined in a rotating tube furnace produce sample with homogeneous particle size and microstrain. The use of a rotating tube furnace can distribute better the energy in the calcinations
of the material to synthesize more homogeneous particles.

Acknowledgments
15.4 0.3

0.0020 0,0001

from Scherrer equation is quite different from that obtained by WH

plotting. This difference can be explained: the microstrain can induce
a greater broadening in the diffraction peak while in the Scherrer
equation, the full width of the diffraction peak is considered in the
calculation. The WH procedure presents a correction for this problem.
Finally, we have calculated the particle sizes using the corrected line
width in the Scherrer equation. This Scherrer equation only considers
the width, D , extracted from Eq. (8). With this correction, the average particle size for each crystallographic direction is about 15.4 nm,
that is the value obtained by the WH plotting.
4. Conclusion
This work demonstrates that the XRPD classical method of analysis Scherrer equation used in the characterization of crystals and,
nowadays, extended to nanomaterials can induce incorrect estimate
in the particle size. It is important to consider the WH plotting
when working with nanomaterials because that proved to be a characterization of the microstructure revealing particle size and microstrain. We suggest the use of a corrected line width in the Scherrer

The authors would like to thank Brazilian funding agencies: CNPq

and CAPES for their nancial support and the Gelita for the gelatin
used in the preparation of the samples.

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