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1.

0 Title
Phase determination of unhydrated cement using X-ray diffraction.
2.0 Abstract
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3.0 Introduction
X-ray diffraction (XRD) is used to determine the crystalline structure and lattice parameter of
materials. Using this information, it is possible to identify the material being analysed. This is
due to the fact that each metallic element in the periodic table has a unique combination of
lattice structure and parameter at room temperature (Citation needed).
There are 2 principle means of generating x-rays. The first is by firing electrons at a
target metal which will displace inner shell electrons of the metal. As the outer shell electrons
replace the lost electrons, energy is released in the form of x-rays. The second method is by
accelerating electrons using a synchrotron. As the electrons approach the speed of light, they
emit electromagnetic radiation as x-rays (Moore & Reynolds, 1997).
If a crystal substance is bombarded by x-rays of a certain wavelength, and at a
certain angle, , then the interaction between the incident x-rays and the electron density
around the atoms produces diffracted beams which yield diffraction patterns as shown in
Figure 3.1 (Mitchell, 2004).

Figure 3.1. Illustration of incident radiation diffraction by a crystal lattice (Mitchell & PerezRamirez, n.d.).

The path difference of x-rays reflected from adjacent planes is 2d(sin ) and the
constructive interference occurs when the path difference is an integer, n of the wavelength.
The resulting Equation (3.1) is known as Braggs Law and states that bombarding a crystal
lattice with x-rays of a known wavelength and at a known angle will produce diffracted x-

rays of varying intensities that represent a specific interplanar spacing in the lattice (Bragg &
Bragg, 1913).
n=2 d sin

(3.1)

Harrington (1927), Hansen (1928) and Bronmiller & Bogue (1930) were among the
pioneers of x-ray diffraction measurements of major cement phases. Ordinary Portland
cement (OPC) contains four main phases known as alite (C3S), belite (C3S), aluminate (C3A)
and aluminoferrite (C4AF). The crystallochemical characteristics of these major phases are
summarized in Table 3.1. In addition, OPC may also contain free lime (CaO), periclase
(MgO) and alkali sulfates.
Table 3.1. Salient crystallochemical characteristics of cements major phases (Chatterjee,
2006).
Name and

Proportion

composition

in clinker

Alite, C3S

50-70%

Foreign elements

Approx.

generally present impurity


Al, Fe, Mg, Cr,

level
4%

Ti, S, P, Ba, Mn,

15-30%

Al, Fe, Mg, Cr,

modifications known
3 triclinic + 3 monoclinic + 1
rhombohedral polymorphs in

Na, K
Belite, C2S

Crystallographic

temperature range 6206%

1070C
(trigonal-hexagonal), H &
L (orthorhombic),

Ti, S, P, Ba, Mn,


Na, K, V

(monoclinic) and
(orthorhombic) polymorphs
in temperature range 500-

Aluminate, C3A

5-10%

Fe, Mg, Ti, Na,

10%

K, Si

1425C
No polymorphs. Foreign
elements as solid solutions.
Only alkalis cause change in

Aluminoferrite,
C2(A,F)

5-15%

Mg, Cr, Ti, Mn,


Si,

13%

symmetry
C2F orthorhombic
(pseudotetragonal)

A unique diffraction pattern exists for each phase of cement with the intensity of each
pattern corresponding to the concentration of the phase in the mixture (Chatterjee, 2006).
Therefore, it is possible to determine the composition of any given cement clinker by
quantatively analysing its XRD pattern. However, due to complex and overlapping patterns,
peak intensity measurement and selection of standard reference materials become an issue.
Alite polymorphs most prominent in cement clinker are monoclinic and triclinic with
the rhombohedral form occurring very rarely. The rhombohedral form is characterized by a
singlet peak at 51.7 2.

4.0 Materials and Equipment


The material required for the experiment is ordinary Portland cement (OPC). The equipment
required for the experiment include the following:
XRD-6000 X-ray diffractometer
Aluminium sample holder (25 mm diameter x 1 mm depth)
Glass plate
Oven

5.0 Method
The XRD-6000 will use copper (Cu) as the target metal to generate x-rays using a voltage of
40 kV and current of 30 mA. The wavelength, of the x-rays is 1.54056 or 1.54056 nm.
6.0 Procedure
The cement was dried in an oven at 105C for at least 24 hours before the experiment to
eliminate excess moisture. A small quantity of the cement was then placed on the aluminium
sample holder. A glass plate was used to compact the cement into the sample holder to ensure
that the cement will not fall out during the experiment. The sample holder containing the
cement was transferred to the rotational sample stage RS-1001 inside the XRD-6000. The
door of the XRD-600 was ensured to be properly closed before the machine was activated.
After approximately 30 minutes, the machine outputs the results of the XRD on-screen as
well as in a file to be processed by separate software.

7.0 Results
The results of the XRD performed on the cement sample are shown in Figure 7.1. A total of
47 peaks have been registered with the strongest 3 peaks occurring at peak number 12
(32.3193), 13 (32.6996) and 17 (34.4809) with intensities of 540, 353 and 345 counts
respectively as shown in Table 7.1. Tabulated data of the 47 peaks may be found in Appendix
A.

Table 7.1. Strongest 3 peaks and intensity count.

Peak number
12
13
17

2 (Degrees)
32.3193
32.6996
34.4809

Intensity (Count)
540
353
345

900
800
700
600
500

Intensity (Counts)

400
300
200
100
0
10

20

30

40

50

60

70

80

2 (Degrees)

Figure 7.1. XRD pattern of cement sample (wavelength, = 1.54056 ).

Using the data obtained from the XRD, a graph of peaks is plotted in Figure 7.2 to remove
background and noise from the data so that clear comparisons may be made with other XRD
profiles.

600

500

400

Intensity (Counts)

300

200

100

0
10

20

30

40

50

60

70

80

2Theta (degrees)

Figure 7.2. Peak positions and intensity of the XRD profile.

8.0 Discussion
/*Coming soon*/

9.0 References
Bragg, W. H. & Bragg, W. L. (1913). The reflection of x-rays by crystals. Proceedings of the
Royal Society A: Mathematical, Physical and Engineering Sciences, 88(605), 428438.
Bronmiller, L. T. & Bogue, R. H. (1930). The X-ray method applied to a study of the
constitution of Portland cement. Journal of Research of the National Bureau of
Standards, 3(233).
Chatterjee, A. K. X-ray diffraction. In Ramachandran, V. S & Beaudoin, J. J. (Eds.),
Handbook of analytical techniques in concrete science and technology (pp. 275-332).
Delhi: Standard Publishers Disributors.
Hansen, W. C. (1928). Further studies on Portland cement compounds by the X-ray
diffraction method. Journal of the American Ceramic Society, 11(2), 68-78.
Harrington, E. A. (1927). Diffraction measurements on some of the pure components
concerned in the study of Portland cement. American Journal of Science, 13, 78.
Mitchell, B. S. (2004). An introduction to materials engineering and science: For chemical
and materials engineering. Hoboken, NJ: John Wiley & Sons.

Mitchell, S. & Perez-Ramirez, J. (n.d.). X-ray diffraction [PDF document]. Retrieved January,
29, 2016 from http://cmirt.wcupa.edu/PDFs/PXRD/00-X-Ray-Diffraction-MitchellCatalysis.pdf
Moore, D. M. & Reynolds, R. C. (1997). X-ray diffraction and the identification and analysis
of clay minerals (2nd ed.). New York: Oxford University Press.

10.0

Appendices