Proceeding of International Conference On Research, Implementation And Education

Of Mathematics And Sciences 2015, Yogyakarta State University, 17-19 May 2015

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LINE BROADENING CORRECTION IN X-RAY DIFFRACTION ANALYSIS FOR
NANOMATERIALS CHARACTERIZATION USING CALCINED YTTRIUM
OXIDE POWDER AS A STANDARD MATERIAL
A. Indra Wulan Sari Ramadani & Suminar Pratapa*
Department of Physics, Institute of Technology Sepuluh Nopember (ITS),
Jl. Arief Rachman Hakim, Surabaya, Indonesia 60111
*Corresponding email address: [email protected]
Abstract
X-ray diffraction-line broadening correction for several instruments has been done
using annealed yttrium oxide (Y2O3) powders. This investigation was to determine the
instrumental broadening of three diffractometers, i.e. Philips X-Pert MPD in LPPM
ITS (X1), X-Pert MPD in the Department of Materials Engineering ITS (X2), and
Rigaku MiniFlex 2 in the Microstructure Laboratory of UNM Makassar (X3). The
yttrium oxide powder as the standard material was prepared by annealing the as-received
powder at 1100C for 1h. The XRD line broadening determination was performed using
Match! 2 for single line and Rietica for the Rietveld method. This investigation showed
that the XRD FWHMs of this material were minimum as compared to those of other
powders. Therefore, these broadening characteristics can be implemented in size-strain
determination including in MAUD software for each instrument. To ensure the reliability
of the implementation we measured XRD data from spinel nanomaterial samples. This
investigation confirmed that XRD data for these nanomaterials gave an average
crystallite size at above 95% similarity measured by the above three different
instruments.
Key words: XRD line broadening, yttrium oxide, nanomaterials, instrumental
broadening correction

INTRODUCTION
X - ray diffraction is one of characterization techniques are frequently used in various
research of materials engineering [1], [2]. Powder diffraction measurements with x-ray
diffractometer willl generate data in the form of a diffraction pattern that will provide an overview
of diffraction peaks at certain angles according to the characteristics of material observed. A
diffraction pattern can provide three important information i.e. position, height (intensity) and peak
shape. Information that has been obtained can be analyzed and used to identify the phase
composition, crystallite size, crystal structure, effect of strain and some other common uses that will
be very helpful in the analysis of the performance of an engineered material.
A measured diffraction profile of material symbolized as h is assumed as the convolution
product between instrumen profile g and specimen profile f [3]. Two parameters that contribute to
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A.I.W.S. Ramadani & S. Pratapa / Line Broadening Correction

ISBN 978-979-96880-8-8

the specimen profile function (f) are crystallite size and non-uniform strain. Analysis of the
crystallite size and strain effects are very important in engineering nanomaterial [4] as it relates to
the evaluation of the properties of nanomaterials that have been made such as optical, electrical, and
chemical properties[5]. There were elaborating theories for crystallite size assesment from XRD
data, where at least four aspects emerged, namely (1) the important of correction for instrument
broadening effect, (2) pattern fitting by making use of mathematical and physical models, (3) effect
of size distribution on XRD peak broadening and (4) comparability of diffraction-based crystallite
sizes to the microscopic sizes [4]. Determination of specimen profile f is done by extracting
specimen profile f from a measured diffraction profile h, called deconvolution.
2

(2 )

(1)

where denotes convolution. There are two methods of deconvolution that can be done by
conventional methods such as Fourier analysis of the diffraction peak profile or a more modern
method with a computerized system that is commonly used in this era i.e. the diffraction pattern
fitting with the peak profile function (model) [6].
Obtaining an accurate powder diffraction size-strain analysis requires some knowledge
about peak shape profiles derived from the instrument (profile g). Profile g derived from the optical
effects of diffraction and the wavelength distribution of the radiation that causes peak broadening
by the instrument, allowing the existence of differences between the characteristics of the
instrument with other. There are two ways that can be done to determine profile g, i.e. by modelling
the instrumental fundamental parameters or by measuring diffraction data using a standard
specimen. This paper focused in the second approach. A specimen could be an instrument
broadening correction when exhibits minimum measurable specimen broadening.
Development of a standard material to determine the profile of this istrument has previously
been done in some places i.e. at Curtin University which uses standard material LaB6 and MgO [7]
and ITS Surabaya uses Yttria (Y2O3) standard material [8]. This article will further report
corrections of XRD peak broadening for three instruments in three places (i.e. LPPM ITS,
Department of Materials Engineering ITS and Microstructure Laboratory of UNM Makassar).
These broadening characteristics will be imported into the software MAUD so it can be used for
more accurate nanomaterials characterization for these instruments.
METHOD
The raw materials used in this investigation were Y2O3 powders (Unical Molycorp, USA).
The yttria powder was calcined at 1100C for 1 hours with rate 10C per minute to avoid thermal
residual strain during the cooling process. XRD data were collected in several instrument to
determine the profile broadening of each instrument. Diffraction data were collected in LPPM ITS
using Philips X-Pert Bragg Brentano diffractometer with Cu tube (K = 1.5418 Angstrom)
operating at 30 kV and 40 mA. The data measured with scan speed 0,02 2/s. Diffraction data were
collected in Department of Materials Engineering ITS using Philips X-Pert Pro MPD diffractometer
with Cu tube operating with step size 0.017 2/s. At the same time, diffraction data were collected
in Microstructure Laboratory Department of Physics UNM Makassar using Rigaku MiniFlex 2
diffractometer with monochromator (activated at 26,57 2). All data measured with range 10-130
with Bragg-Brentano geometry.
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Proceeding of International Conference On Research, Implementation And Education

Of Mathematics And Sciences 2015, Yogyakarta State University, 17-19 May 2015

Diffraction data have been obtained were analyzed by using a single line method and whole
pattern using Match! program [9]. Pseudo Voigt and Voigt functions were selected as profile shape
functions to fit the peak profiles which were performed using the Fityk 0.9.1 program for single-line
[10]. The pseudo-Voigt function is simply a linear combination of Lorentzian and Gaussian
components in the ratio /(1- ), where is the pseudo-Voigt mixing parameter. This appear to
describe the symmetrical part of an X-ray diffraction peak quite well [11]. The peak shape can be
varied accross the pattern by application of the mixing parameter function [12]:
=

2 +

(2)

On the other hand, the variation of peak FWHM is defined by the Cagliotti expression [12]:
=

tan +

(3)

In this study, Rietveld analysis was done using a pseudo-Voigt function to acquire the peak
broadening parameters U, V, and W. Rietveld analysis was performed using software Rietica [12].
Rietveld refinement involved background parameters and sample displacement as global
parameters, peak profile parameters, scale factor, lattice parameters, atomic positions, thermal
factors and asymmetry effect. Rietveld refinement performed to the collected XRD patterns was
successfull indicated by Figures-of-Merit (FoMs). According to Kisi (1994), all FoMs are
acceptable if goodness-of-fit is less than 4% and Rwp less than 20% [13]. Crystallography data for
yttria, spinel and periclase were taken from ICSD Collection Code 23811 [14], 7900 [15] and 9863
[16]. Therefore, these broadening characteristics can be implemented in size-strain determination
including in MAUD [17] software for each instrument. To ensure that the characteristics of the
instrument are accurate, we measured XRD data from a tested spinel nanomaterial which was
produced using a dissolved metal method [18] and compare the anayslsis results.

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A.I.W.S. Ramadani & S. Pratapa / Line Broadening Correction

ISBN 978-979-96880-8-8

Intensity 1/2 (Counts1/2)

RESULTS AND DISCUSSION

2 Theta (Degrees)
Figure 1 XRD patterns (CuK radiation) for an yttria powder calcined at 1100C for
1 hour collected at LPPM ITS (X1), Materials Engineering ITS (X2) and UNM
Makassar (X3)

Fig. 1 shows diffraction patterns for yttria powder calcined at 1100C for 1 hour, collected
using three difractometers i.e. Philips X-Pert MPD (X1), Philips X-Pert Pro (X2) and Rigaku
Miniflex 2 (X3). It can seen that the material has sharp XRD peaks and is therefore polycrystalline.
According to the crystallography data is known that the sample consists of single phase
corresponding to the ICSD code 23811. Previously mentioned in Eq. 1 that a measurable diffraction
peak are the convolution product of those with peak broadening caused by the instrument and
specimen profiles. Contribution of instrument profile on the measured diffraction peaks will
produce systematic errors in the analysis results so that the information obtained is not accurate
therefore requires a its removal. Instead of a mathematical deconvolution, we chose to construct a g
profile from a standard material and used it as a part of the profile fitting. The calcined yttria
powder was selected as the standard material since its showed the narrowest peak width among
other candidates [8].The peak broadening effect is now assumed to only influenced by the
instrument profile. The diffraction data from the standard material were analyzed using Rietveld
and single line methods.
Table 1 shows line broadening characteristics of three diffractometer after analysis of the
XRD data from the calcined yttria as a standard materials. It shows that average FWHM of the
standard material is 0.138 2, lower than that of an MgO ceramic standard material reported
previosly, i.e. 0.167 2 [8]. These analysis results also showed differences in the peak broadening
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Proceeding of International Conference On Research, Implementation And Education

Of Mathematics And Sciences 2015, Yogyakarta State University, 17-19 May 2015

Table 1 Line broadening characteristics for each instruments estimated by

Rietveld refinement using MAUD

Gaussian
Value

Caglioti Value

Average
Instruments
FWHM
(2)

X1

0.138

0.007

-0.005

0.02

0.5

0.005

X2

0.146

0.043

-0.175

0.24

0.3

0.005

X3

0.130

0.030

-0.030

0.03

0.6

0.001

Figure 2. XRD full patterns (CuK radiation) for the tested nanomaterial collected at
LPPM ITS (X1), Materials Engineering ITS (X2) and UNM Makassar (X3)

characteristics in each instrument. These differences come from the optical effects of diffractometer
and the wavelength distribution of radiation, leading to the necessity of instrument characterization
prior to the use of line broadening information for microstructural analysis. It further causes the
possibility of differences in the line broadening characteristics of each instrument.
Table 1 shows the line broadening characteristics of each instrument estimated by Rietveld
refinement using MAUD, where Cagliotti value 0, 1 & 2 are the parameters U, V & W in the
Cagliotti expression shown in Eq. 3. On the other hand, Gaussian value in table 1 refers to mixing
parameter shown in the Eq. 2. Gaussian parameter values in Table 1 indicate that instrument X3 has
a broader peak characters than the other two instruments. Similarly, Fig.2 shows the diffraction

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A.I.W.S. Ramadani & S. Pratapa / Line Broadening Correction

ISBN 978-979-96880-8-8

Table 2. Estimated crystallite size and non-uniform

microstrain for the spinel tested material performed using
MAUD software [17]. Estimated standard deviations for the
least significant digit are given in the parantheses.

Instruments

Crystallite Size
(nm)

Strain (10-4)

X1

11(1)

1.7 (0)

X2

10(1)

1.0 (0)

X3

10 (1)

1.6 (0)

pattern of the tested nanomaterial measured using three instruments. It appears that the diffraction
pattern produced by instrument X3 has a broader peak and also a considerable background as
compared to the other instrument.
The line broadening characteristics for each instrument was then introduced to MAUD
software [17] for estimating the crystallite size and microstrain. Reliability test was performed to
ensure that the instrument characterization was correct and the analysis results were accurate. As
shown in Fig.2, the tested material is composed of two phases, namely spinel MgAl2O4 (according
to ICSD code 7900) and periclase (ICSD code 9863) with phase content of, respectively, 58.6(2)
and 41.4 (1) wt%.
The crystallite size estimation and the non-uniform strain of the spinel in the tested
materials obtained from the instruments are shown in Table 2. The size-strain analyses were done
after eliminating the instrument profile that has been imported into MAUD. By doing so, the peak
broadening of the sample is only affected by the specimen profile. In principle, relation between the
diffraction peak broadening (B) with crystallite size (D) is described by the Scherrers equation [19]

(2)

where is the wavelength of the radiation used in and 2 is the Bragg angle. Note, however, that
the peak broadening in Eq.(2) should be (a) instrumentally corrected and (b) free from strain effects.
Data in Table 2 shows that the estimated average crystallite size from the instruments are in
about 95% agreement. This indicates that the peak broadening characteristics of each instrument
which has been introduced to MAUD are reliable. Table 2 also presents the non-uniform strain
values for the tested material which maybe resulted from the sample processing. These values,
however, are minute and quite similar, emphasizing that the instrument profile corrections are
satisfactory.

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Proceeding of International Conference On Research, Implementation And Education

Of Mathematics And Sciences 2015, Yogyakarta State University, 17-19 May 2015

CONCLUSIONS
It can be concluded from this study that:
1. The average XRD FWHMs from yttria powders calcined at temperatures 1100C lower
than that of the MgO standard ceramic material. This result accentuates that the powder has
fulfilled the requirement for its use as a standard material for XRD line broadening
correction.
2. Each XRD instrument used in this study exhibits a specific line broadening characteristics
but further analysis to the tested material shows that the estimated crystallite size and nonuniform microstrain are very similar at a value of approximately 10 nm and of around a
diminutive value of 1,310-4 respectively
ACKNOWLEDGEMENTS
Gratitude are to the Ministry of Education and Culture of the Republic of Indonesia who has
provided support to the first author through a tuition fee for her master degree through BPPDN
Calon Dosen Scheme 2013-2015.
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