GRD Journals- Global Research and Development Journal for Engineering | Volume 5 | Issue 12 | November 2020

ISSN- 2455-5703

Relationship between the Diffraction Peak

Intensity and Composition in (Ti1-xWx)C
Powders
Mohsen Mhadhbi
Assistant Professor
Department of Chemical Engineering
Laboratory of Useful Materials, National Institute of Research and Physical-chemical Analysis

Abstract
In this work, nanostructured (Ti1-xWx)C (0 ≤ x ≤ 0.2) powders were synthesized through solid state mechanical alloying (MA)
process in a high-energy planetary ball mill (Fritsch Pulverisette 7) using Ti, W, and C powders mixture. Thus, MA was performed
at room temperature under argon atmosphere to avoid oxidation. The relationship between the changes in diffraction peaks intensity
and the composition of obtained powders was determined by using the structure factor calculations. However, the obtained results
were compared with the theoretical ones.
Keywords- X-Ray Diffraction, Carbide, Diffraction Peak, Composition, Nanostructure, Mechanical Alloying

I. INTRODUCTION
Titanium carbides (TiC) are a materials of great industrial importance due to its excellent properties such as good wear resistance,
high hardness, high thermal conductivity, etc. However, they possess some limitations like transverse rupture strength and low
density [1]. These special characteristics allow for various applications like high temperature structural materials, in electrical
discharge machining, and as abrasive for cutting tools and grinding wheels [2, 3]. Recently, several studies have focused on the
investigations of nanostructured titanium carbide synthesized through mechanical alloying technique [4-10].
Mechanical alloying (MA) is a simple powder processing method that is employed to fabricate alloy powders, both in
equilibrium and non-equilibrium, in the solid state. In fact, MA technique makes it possible to produce and control a refined,
homogenous, and nanostructured microstructures [11, 12]. Furthermore, MA of elemental powder mixtures, with desired
compositions, corresponding to the stoichiometry of intermetallic phases, which lead to the formation of powders with partially
ordered or disordered solid solutions [13, 14]. Hence, MA is a significant process that contains cycle of cold welding followed by
fracturing and re-welding, which cause an excellent inter-diffusion between powders particle [15, 16].
In this paper, a nanocrystalline (Ti,W)C powder was produced by MA. The morphology and microstructure of the
refractory MA powder were studied. Hence, the relationship between the diffraction peak intensities and the composition of (Ti 1-
xWx)C solid solution was also studied based on structure factor calculations from the data of X-ray diffraction.

II. EXPERIMENTAL WORK

A mixture of elemental powder Ti (< 40 μm, 99.9 %), C (5 μm, 99.9 %), and W (< 5 μm, 99.9 %) was sealed into a stainless steel
vial (45 mL in volume) with 5 stainless steel balls (15 mm in diameter and 14 g in mass) in a glove box filled with purified argon
to prevent oxidation. The ball to powder weight ratio was 70:1. The mechanical alloying (MA) procedure of 20 h was performed
at room temperature using a high-energy planetary ball mill (Fritsch Pulverisette 7). The formed powders were characterized by
X-ray diffraction using a Panalytical XPERT PRO MPD diffractometer with Cu Kα radiation. The High Score Plus program was
used in order to analyze the XRD patterns and to obtain the position, the full-width at half maximum and the intensity of various
peaks. The existing phases were determined based on the ICDD PDF2 data base. The XRD patterns were analyzed by the Fullprof
program [17] using the Rietveld method [18]. The intensity of the diffraction peaks was measured from the measured raw data by
integrating the area under the diffraction peak. The analytical functions relating the (111) and (200) diffraction peak intensities to
the solid solution composition were deduced from the structure factor calculations. Assuming that the intensity of the diffraction
peak can be determined only from the structure factor we can have a small variation that depends on other factors. In this context,
we determined the powders diffraction patterns by computer calculations taking into account other parameters, such as instrumental
broadening, strain factor.

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 Relationship between the Diffraction Peak Intensity and Composition in (Ti1-xWx)C Powders
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III. RESULTS AND DISCUSSION

A. Analytical Approach
Fig.1 shows the X-ray diffraction patterns of TiC and Ti0.8W0.2C powders MA for 20 h. As it can be seen for the case of TiC
powder (Fig. 1a) the XRD pattern consists of a new formed phase with a face center cubic NaCl type structure and correspond to
the TiC phase. Thus, the peaks are broadened due to the refinements of grains and the introduction of defects during milling. At
the same time, an additional small peak related to the Fe element as contamination resulted from the wear between the milling
media (vial and balls). For the case of Ti0.8W0.2C powder (Fig. 1b) the XRD pattern consists of broadened peaks of (Ti,W)C solid
solution, with a face center cubic NaCl type structure. In addition, a small peak related to the Fe element appeared.

Fig. 1: X-ray diffraction patterns of (a) TiC and (b) Ti0.8W0.2C powders MA for 20 h

In this study, we suppose that the change in intensity of the diffraction peaks is a function of the structure factor alone, the
intensity of the two main peaks of TiC powder can be written as follows:

F(111)  4( fT i  f C ) (1)

F( 200)  4( f 'Ti  f 'C ) (2)

In the case of (Ti1-xWx)C powders, the intensity of the diffraction peaks increase. This is explained by the fact that W has
more electrons than Ti and consequently the atomic scattering factor of Ti is smaller than that of W (as given in Table 1). So, we
used new analytical functions [19] to determine the atomic scattering factors for the different elements (Ti, C, and W).
Table 1: Calculated scattering factors for the different elements
f(Ti) f(C) f(W)
(111) peak 17.140 3.686 62.652
(200) peak 14.433 3.581 60.798
In the case where tungsten replaces titanium, the mole fraction is x, the above structure factors will be:
F(111) = 4[(1 - x) f Ti + x f W - f C ]
(3)
F( 200) = 4[(1 - x) f '´Ti + x f ' W - f 'C ]
(4)
However, as shown in Fig. 1, there is a difference between the intensities of the (111) and (200) peaks due to the different X-ray
scattering factors of Ti and W.
The general equation relating the absolute intensity of (111) peak with the scattering factors of Ti, W, and C is defined as:
2
I (111)  C111 F(111)
(5)

Substitution of Equation (3) into Equation (5) we find:

I (111)  C111 ( f T i  f C )  ( f W  f Ti ) x  (6)

2

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 Relationship between the Diffraction Peak Intensity and Composition in (Ti1-xWx)C Powders
(GRDJE/ Volume 5 / Issue 12 / 002)

The equation relating the absolute intensity of (200) peak with the scattering factors of Ti, W, and C is defined as:
2
I ( 200)  C 200 F( 200)
(7)
Substitution of Equation (4) into Equation (7) we find:
I ( 200)  C111 ( f 'T i  f 'C )  ( f 'W  f 'Ti ) x 
2
(8)
where C111 and C200 are constants obtained from the intensities of (111) and (200) peaks of pure TiC having a known structure.
However, the peak (111) of pure TiC is more intense than the peak (200) (see Fig. 1).
In fact, the absolute intensities are normalized by the highest intensity peak. We multiply by 100 to calculate the intensity of each
second main peak as following:
I W(111)
I (111)  100 
I W( 200)
(9)
W
I ( 200)
I ( 200)  100 
I W(111)
(10)
Substitution of both Equations (6) and (8) into Equations (9) and (10) we obtain:
 ( f W  f Ti ) x  ( f Ti  f C ) 
2
C
I (111)  100  111  
C 200  ( f 'W  f 'Ti ) x  ( f 'Ti  f 'C )  (11)
2
C111  ( f 'W  f 'Ti ) x  ( f 'Ti  f 'C ) 
I ( 200)  100   
C 200  ( f W  f Ti ) x  ( f Ti  f C )  (12)

B. Comparison with Experimental Results

During the fitting, only the C111/C200 ratio was adjusted because the slope was invariant. Fig. 2 shows the relative intensity of (111)
and (200) diffraction peaks as a function of the composition (comparison between experimental and theoretical results). As it can
be seen from the figure, for the experimental the C111/C200 ratio is equal to 0.612 while for the case of theoretical the C111/C200 ratio
is equal to 0.526. This explains that there is no dependency between the experimental results and XRD measurements conditions.
Further, the intensity values depend on several factors such as the step, the scan speed, and the scan mode. Unlike the intensity
ratio which does not depend on these factors. Hence, we can mention that all of these obtained results are related to the carbon
stoichiometry of the studied carbide (Ti1-xWx)C.

Fig. 2: Variation of the relative intensity of (111) and (200) diffraction peaks as a function of the composition

IV. CONCLUSIONS
In this paper, the relationship between the diffraction peak intensities and the composition of (Ti1-xWx)C solid solution was studied
based on structure factor calculations from the data of X-ray diffraction. Furthermore, the experimental results are in agreement
with theoretical calculations. This approach can be used to study the composition of the (Ti1-xWx)C solid solution.

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 Relationship between the Diffraction Peak Intensity and Composition in (Ti1-xWx)C Powders
(GRDJE/ Volume 5 / Issue 12 / 002)

ACKNOWLEDGMENT
Author would like to acknowledge the support of Global Research and Development Journals.

REFERENCES
[1] J. Kübarsepp, H. Reshetnyak, H. Annuka, “Characterization of the serviceability of steel-bonded hard metals”, International Journal of Refractory Metals and
Hard Materials, Vol. 12, Issue 6, 1993, pp. 341-348.
[2] A. Rajabi, M.J. Ghazali, A.R. Daud, “Review on Chemical Composition, Microstructure and Sintering Temperature Modifications on Mechanical Properties
of TiC-based Cermet”, Materials and Design, Vol. 67, Issue 15, 2015, pp. 95-106.
[3] H. Xiong, Z. Li, K. Zhou, “TiC whisker reinforced ultra-fine TiC-based cermets: microstructure and mechanical properties”, Ceramics. International, Vol.
42, Issue 6, 2016, pp. 6858-6867.
[4] X. Cui, Y. Wang, L. Wang, L. Cui, M. Qi, “Synthesis of nanometer-sized TiC and SiC from petroleum coke by reactive milling”, Petroleum Science and
Technology, Vol. 19, 2001, pp. 971-978.
[5] W. Tang, Z. Zheng, W. Wu, J. Lü, J. Liu, J. Wang, “Structural evolutions of mechanically alloyed and heat treated Ti50C50 and Ti33B67 powders”, Materials
Chemistry and Physics, Vol. 99, 2006, pp. 144-149.
[6] D. Chaira, S. Sangal, B.K. Mishra, “Efficient Synthesis and Characterization of Nanostructured TiC Powder by Reaction Milling”, Transactions of the Indian
Institute of Metals, Vol. 64, Issue 6, 2011, pp. 549-554.
[7] H. Jia, Z. Zhang, Z. Qi, G. Liu, X. Bian, “Formation of nanocrystalline TiC from titanium and different carbon sources by mechanical alloying”, Journal of
Alloys and Compounds, Vol. 472, Issues 1-2, 2009, pp. 97-103.
[8] L.L. Ye, M.X. Quan, “Synthesis of nanocrystalline TiC powders by mechanical alloying”, Nanostructured Materials, Vol. 5, Issue 1, 1995, pp. 25-31.
[9] M. Razavi, M.R. Rahimipour, A.H.R. Zamani, “Synthesis of nanocrystalline TiC powder from impure Ti chips via mechanical alloying”, Journal of Alloys
and Compounds, Vol. 436, Issues 1-2, 2006, pp. 142-145.
[10] M.B. Rahaei, R. Yazdani rad, A. Kazemzadeh, T. Ebadzadeh, “Mechanochemical synthesis of nano TiC powder by mechanical milling of titanium and
graphite powders”, Powder Technology, Vol. 217, 2012, pp. 369-376.
[11] C. Suryanarayana, N. Al-Aqeeli, “Mechanically alloyed nanocomposites”, Progress in Materials Science, Vol. 58, Issue 4, 2013, pp. 383-502.
[12] H. Yu, Y. Sun, L.X. Hu, Z.P. Wang, H.P. Zhou, “Microstructure and properties of mechanically milled AZ61 powders dispersed with submicron/nanometer
Ti particulates”, Materials Characterization, Vol. 127, 2017, pp. 272-278.
[13] C. Suryanarayana, “Mechanical alloying and milling”, Progress in Materials Science, Vol. 46, Issues 1-2, 2001, pp. 1-184.
[14] M. Krasnowski, T. Kulik, “Nanocrystalline and amorphous Al-Fe alloys containing 60-85% of Al synthesised by mechanical alloying and phase
transformations induced by heating of milling products”, Materials Chemistry and Physics, Vol. 116, Issues 2-3, 2009, pp. 631-637.
[15] M. Pilar, J. Sunol, J. Bonastre, L. Escoda, “Influence of process control agents in the development of a metastable Fe-Zr based alloy”, Journal of Non-
Crystalline Solids, Vol. 353, Issues 8-10, 2007, pp. 848-850.
[16] L. Lu, Y. Zhang, “Influence of process control agent on interdiffusion between Al and mg during mechanical alloying”, Journal of Alloys and Compounds,
Vol. 290, Issues 1-2, 1999, pp. 279-283.
[17] J. Rodríguez-Carvajal, “An introduction to the program FullProf”. Laboratoire Léon Brillouin, 2001.
[18] HM. Rietveld, “A profile refinement method for nuclear and magnetic structures”. Journal of Applied Crystallography, Vol. 2, 1969, pp.65-71.
[19] D. Waasmaier, A. Kirfel, “New analytical scattering-factor functions for free atoms and ions”. Acta Crystallographica Section A, Vol. 51, 1995, pp.416-431.

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