Lab report

X-Ray Diffraction
Resolution methods (MH2000)

Experiment session: 02.02.2018

Report submitted: 12.02.2018

Cédric Terrier
Fikan Mubarok Rohimsyah
Kevin Vattappara
Konstantinos Rigas
Nate Clough
1 Cubic crystal structures (Exp. Module 1 S&GN)
Question 1: part 1. The bravais lattice can be identified by observing systematic presence or
absence of reflections in the diffraction pattern.

X- Ray difraction pattern Sample 1

250
200
150
CPS

100
50
0

120.9886129
13.26437097
16.52874193
19.7931129
23.05748387
26.32185483
29.5862258
32.85059677
36.11496773
39.3793387
42.64370967
45.90808063
49.1724516
52.43682257
55.70119353
58.9655645
62.22993547
65.49430643
68.7586774
72.02304837
75.28741933
78.5517903
81.81616127
85.08053223
88.3449032
91.60927417
94.87364513
98.1380161
101.4023871
104.666758
107.931129
111.1955
114.4598709
117.7242419

124.2529838
127.5173548
10

2θ

Figure 1. Difraction Pattern of Sample 1

To Identify bravais lattice we are following steps. We were doing this using mathematical
approach as follows :
1. Identify the x-ray pattern & peaks.
2. Determine sin2θ
3. Calculate the ratio sin2θ/sin2θmin and multiply by the appropriate integers
4. Select the result from (3) that yields h2+k2+l2 as an integer.
5. Since h, k, and l are always integers, we can obtain h2+k2+l2 values by dividing the
sin2θ values for the different XRD peaks with the minimum one in the pattern (i.e.,
the sin2θ value from the first XRD peak) and multiplying that ratio by the proper
integer (either 1, 2 or 3 we are using 1 and 3). Then yield a list of integers that
represent the various values of h2+k2+l2
6. Compare results with the sequences of h2+k2+l2 values to identify the Bravais lattice.
 By doing those steps we obtained :
Table 1. Detail value obtained for identifying bravais lattice

Peak 2ϴ ϴ sin ϴ sin2ϴ h2+k2+l2 hkl

1 38.42 19.21 0.32903147 0.10826171 1 3 3 110
2 44.68 22.34 0.38010199 0.14447752 1.33452099 4.003562975 4 111
3 65.045 32.5225 0.53763077 0.28904684 2.66988995 8.009669845 8 220
4 78.162 39.081 0.63041843 0.39742739 3.67098771 11.01296313 11 311
5 82.32 41.16 0.65816401 0.43317987 4.00122894 12.00368681 12 222
6 99.01 49.505 0.76046264 0.57830342 5.34171726 16.02515178 16 400
7 112.004 56.002 0.82905709 0.68733566 6.34883457 19.0465037 19 331
8 116.43 58.215 0.85003062 0.72255206 6.67412406 20.02237217 20 420
We identified the correct Bravais lattice by recognizing the sequence of allowed reflections
for cubic lattices (i.e., the sequence of allowed peaks written in terms of the quadratic form of
the Miller indices). We can match it into one of these following sequence :

Primitive h2+k2+l2 = 1,2,3,4,5,6,8,9,10,11,12,13,14,16…

Body-centered h2+k2+l2 = 2,4,6,8,10,12,14,16…
Face-centered h2+k2+l2 = 3,4,8,11,12,16,19,20,24,27,32…
Diamond cubic h2+k2+l2 = 3,8,11,16,19,24,27,32…

The we concluded that the bravais lattice of sample 1 is Face-centered

Part 2.

We can then calculate the lattice parameter a from relations :

λ2
𝑎2 = (ℎ2 + 𝑘 2 + 𝑙 2 )
4𝑠𝑖𝑛2 𝜃

Or

λ
𝑎= (√ℎ2 + 𝑘 2 + 𝑙 2 )
2 sin 𝜃
So, we calculated for each peak pattern and obtained

Table 2. Calculation of lattice parameter

Peak sin ϴ h2+k2+l2 a2(nm) a(nm)

1 0.32903147 3 0.16418548 0.40519807
2 0.38010199 4 0.16403936 0.40501773
3 0.53763077 8 0.16398726 0.40495341
4 0.63041843 11 0.16399222 0.40495953
5 0.65816401 12 0.16413505 0.40513584
6 0.76046264 16 0.16392779 0.40487997
7 0.82905709 19 0.16378461 0.40470311
8 0.85003062 20 0.16400202 0.40497163

So we interpreted that the lattice parameter of sample 1 is average a in table 2 = 0.40497741

nm

Part 3
Copper Mo Kα. (λ= 0.0711 Cu Kα. (λ= 0.1542 nm) Cr Kα. (λ= 0.2291 nm)
nm)
hk d Sin(ϴ) ϴ 2 Sin(ϴ) ϴ 2 Sin(ϴ) ϴ 2
l ϴ ϴ ϴ
11 0.20871 0.17033 9.80702 0.36940 21.6791 0.54884 33.2876
0 212 031 439 835 331 21 126
11 0.19668 11.3429 0.42655 25.2491 0.63374 39.3272
1 0.18075 05 104 602 94 827 078
22 0.12780 0.27814 16.1497 0.60324 37.1023 0.89625 63.6701
0 955 823 162 13 934 54 4
31 0.10899 0.32615 19.0357 0.70736 45.0207 1.05095
1 635 771 291 313 753 261
22 0.10435 0.34066 19.9171 0.73881 47.6307 1.09768
2 606 062 274 669 133 42
40 0.09037 0.39336 23.1637 0.85311 58.5517 1.26749
0 5 1 927 203 821 654
33 0.08293 0.42865 25.3822 0.92965 68.3814 1.38122
1 379 521 465 729 549 233
42 0.08083 0.43979 26.0905 0.95380 72.5174 1.41710
0 386 096 445 825 042 421
Table 3. Diffraction change position with changing radiation source
As we can see from table above, If we increasing the λ, the diffraction position angle will be
increasing and if we increase more we get too few peaks to observe. The schematic figure to
represent the condition is presented below.

Mo Kα. (λ= 0.0711 nm)

Diffraction angle (2) →

Cu Kα. (λ= 0.1542 nm)

Cr Kα. (λ= 0.2291 nm)

Diffraction angle (2) →

Diffraction angle (2) →

Figure 2. Schematic representation examples of effect different λ to the graph

Part 4.
Based on the question, we have simple cubic structure. Simple cubic follow sequence as
follows:
h2+k2+l2 = 1,2,3,4,5,6,8,9,10,11,12,13,14,16…

From that value we can calculate d and a for each peak using Bragg’s law:

Below are the values 2ϴ obtained after calculation.

Table.4 simple cubic structure of Te-Au 2ϴ change.
a= 0.2961 nm.
Cu Kα. (λ= 0.1542 nm)

h2+k2+l2 d Sin(ϴ) ϴ 2ϴ
1 0.5922 0.26038501 15.08 30.16
2 0.41874864 0.36824001 21.6 43.2
3 0.34190683 0.45100006 26.8 53.6
4 0.2961 0.52077001 31.33 62.66
5 0.26483989 0.58223857 35.6 71.2
6 0.24176464 0.6378104 39.62 79.24
8 0.20937432 0.73648001 47.42 94.84
9 0.1974 0.78115502 51.36 102.72
10 0.18727008 0.82340968 55.42 110.84
11 0.17855502 0.86359936 59.71 119.42
12 0.17095341 0.90200012 64.42 128.84
13 0.16424673 0.93883149 69.55 139.1
14 0.15827211 0.97427148 76.95 153.9
16 0.14805 1.04154002 -
 Precise lattice parameter determination (Exp. Module 3 S&GN)
Question 2
According to module 3, there are some errors that will occur in measurements which will
affect in precision of data gained. These effect can be corrected to achieve high precision in
lattice parameter measurements by considering extrapolation function. There are two
extrapolation function that we are going to investigate
Bradley- Jay function 𝑐𝑜𝑠 2 𝜃 [1]
𝑐𝑜𝑠2 𝜃 𝑐𝑜𝑠2 𝜃
Nelson-Riley function + [2]
𝑠𝑖𝑛2 𝜃 𝜃

When the lattice parameter is plotted in these extrapolation, straight line can be drawn from
its points. Table below shows each ϴ gained from each peak and value obtained for all
function
Table 5. peaks and ϴ correspondent
Si powder
peak 2 ϴ ϴ sin ϴ sin2 ϴ cosϴ cos2 ϴ cos2ϴ/sinϴ cos2ϴ/ϴ
5 76.34 38.17 0.61799684 0.38192009 0.78618058 0.61807991 1.00013442 0.01619282
6 87.91 43.955 0.69409319 0.48176535 0.71988516 0.51823465 0.74663555 0.01179012
7 94.89 47.445 0.73662848 0.54262151 0.67629763 0.45737849 0.62090796 0.00964018
8 1 106.65 53.325 0.80203633 0.64326228 0.59727525 0.35673772 0.44478998 0.00668988
9 3 114.02 57.01 0.83876561 0.70352775 0.54449265 0.29647225 0.35346257 0.00520036
10 5 127.5 63.75 0.89687274 0.80438071 0.44228869 0.19561929 0.21811264 0.00306854
11 7 136.84 68.42 0.92990493 0.86472318 0.36779998 0.13527682 0.14547382 0.00197715

After getting the value of ϴ we can calculate respective d and a for each ϴ obtained from Cu
Kα. (λ= 0.1542 nm)
Table 6. d and a obtained from ϴ calculation
peak sin ϴ 2d d hkl a
5 0.61799684 0.24951584 0.12475792 12 0.43217411
6 0.69409319 0.22216037 0.11108019 16 0.44432074
7 0.73662848 0.20933212 0.10466606 19 0.45622878
8 1 0.80203633 0.19226062 0.09613031 20 0.42990781
9 3 0.83876561 0.18384159 0.09192079 24 0.45031808
10 5 0.89687274 0.17193075 0.08596537 27 0.44668918
11 7 0.92990493 0.1658234 0.0829117 32 0.46901941

From those value above, we will draw graph from each function according to Bradley-Jay
and Nelson-Riley function
 Table 7. Bradley-Jay variable function
a Cos2 ϴ
0.43217411 0.61807991
0.44432074 0.51823465
0.45622878 0.45737849
0.42990781 0.35673772
0.45031808 0.29647225
0.44668918 0.19561929
0.46901941 0.13527682

Bradley-Jay extrapolation
0.48
lattice parameter (a)

0.47
0.46
0.45
0.44 y = -0.0461x + 0.4639
0.43 R² = 0.352
0.42
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Cos2 ϴ

Figure 3 Bradley-Jay extrapolation

Table 7. Nelson-Riley variable function

𝑐𝑜𝑠 2 𝜃 𝑐𝑜𝑠 2 𝜃
a +
𝑠𝑖𝑛2 𝜃 𝜃
0.43217411 1.01632724
0.44432074 0.75842566
0.45622878 0.63054815
0.42990781 0.45147986
0.45031808 0.35866292
0.44668918 0.22118118
0.46901941 0.14745097
 Nelson-Riley extrapolation
0.48
lattice parameter (a)

0.47
0.46
0.45
0.44 y = -0.0252x + 0.4598
0.43 R² = 0.331
0.42
0 0.2 0.4 0.6 0.8 1 1.2
(〖𝑐𝑜𝑠〗^2 𝜃)/(〖𝑠𝑖𝑛〗^2 𝜃)+(〖𝑐𝑜𝑠〗^2 𝜃)/𝜃

Figure 3 Nelson-Riley extrapolation extrapolation

By plotting each value we can draw straight line and get gradient function. By extrapolating
with Bradley-Jay extrapolation function we obtained value for a = 0,4639 and with Nelson-
Riley extrapolation we obtained value for a= 0,4598. As we can see, the closest value for lattice
parameter compared to average value from Bragg’s law calculation is from Nelson-Riley
equation. It is prove that Nelson-Riley Extrapolation has more precision compared to Bradley-
Jay extrapolation and It is suitable for this sample.
Question 3:
3.1)
In a single-phase region, a change in composition generally produces a change in
lattice parameter and, therefore, a shift in the position of the diffraction peaks of that
phase. In a two-phase region there is no change in the lattice parameters so no change
in the position of diffraction peaks. However, there is a difference in the intensity of the
reflection peaks.
Three different regions are present on the phase diagram: Two single phase regions
(𝛼, 𝛽) and one 2-phase region (𝛼+𝛽). In the 𝛼 phase, atoms B are dissolved in the
matrix and occupy interstitial sites. It results in a distortion of the lattice and the lattice
parameter increases.Taking into consideration Bragg’s law, 2dsin=n, for the same
wavelength, the angle 𝜃 decreases when the interplanar distance increases. As a
result, the peaks present on the XRD pattern are shifted to lower values if the
concentration of solute elements increases.

In a 2-phase region, the concentration of solute elements within the same phase
doesn’t change while varying the global concentrations. Therefore, there is no peak
shift. An XRD pattern of a 2-phase region presents both peaks from the lattice A and
B whereas in a single phase region only peaks from one phase are present.

The XRD patterns of the different mixture of Erythtritol (Er) and Xylitol (Xy) is used to
determine the phase diagram Er-Xy. Between 10% and 95% of Xy, all the patterns
show peaks from both pure Er and pure Xy. Therefore, the 2-phase region is between
these two concentrations. The peak shifts are hard to notice but one can be visible
between pure Xy and 90% Xy at 2𝜃 equal to 33.

3.2)
In the case of Aluminum and Titanium, the components have a different crystal
structure with the following lattice parameters:

aAl= 0.4049 nm aTi= 0.2951 nm cTi= 0.4683 nm

In the framework of Vegard’s law, both components, Al and Ti, in their pure form,
should have the same crystal structure. We may assume that Vegard's law is obeyed
and that Titanium has a hypothetical fcc structure. At this point we should convert the
lattice parameters of hcp to fcc using the geometrical relationship between the cells
cTi= aTi(2/3) hence, in fcc aTi= 0.4056 nm

Following the assumptions made before, the crystal lattice constant of our alloy, Ti-
Al, and the concentrations of these elements, present a linear relation at constant
temperature.

In order to determine the solid solubility of Ti in Al by x-ray diffraction we should, at

first, create a master plot. The x-ray diffraction patterns of fine powders of our
compounds are taken using Cu Ka radiation. Then the patterns of several mixtures
of our compounds in different compositions are obtained after appropriate heat
treatment. Then we index all the diffraction patterns and calculate the lattice
parameters which, then, are plotted against the amount of Ti. As a result, a relation
between the lattice parameters and the solute content is extracted. In such a way, a
master plot is obtained. By investigating more samples and creating the master plot
in that way, we may take more accurate results

We plot the lattice parameters of the two components versus the composition and
join the lattice parameters of the two components. Then we record the x-ray
diffraction pattern of our alloy, Ti-Al. We index the diffraction patterns and calculate
the lattice parameters. Then, using the master plot that we created before, we
estimate the solid solubility of Ti in Al.
Question 4:
The Powder Diffraction File (PDF) is extremely useful for crystalline structure data. It
is a collection of x-ray diffraction patterns and lattice parameters that can be used to
help determine phases from their crystalline structure. Another useful tool is the
Hanawalt Search Method. This method consists of a numerical index manual listing
compounds in the order of decreasing d spacings.
Figure 1: Solid Sample graph of 2 theta values obtained using XRD

Using the Powder Diffraction Files and Hanawalt search method it was found that the
above sample was made up one phase: Austenite. See table 1 for the 2 theta
values and corresponding d spacing values that matched our graph.

Figure 2: Powder Sample graph of 2 theta values using XRD

Using the Powder Diffraction Files and Hanawalt search method again, it was found
that the above sample was made up of both ZnO and MgO. The specific points
associated with each substance are indicated on Figure 2. See Table 1 for the 2
theta values and corresponding d spacing values that match the phases found in the
graph above.

Table 1

One of the reasons it can be harder to determine the phases in a solid sample is that
when performing XRD on a solid sample the x-rays only penetrate the top layer
whereas with a powder sample the x-rays go through the bulk of the powder and
diffract in different directions. This obtains more data and makes it easier to find
different phases within the sample where it may be harder to find them with a solid
sample that penetrates less far.

Question 5:
The direct comparison method is a useful tool to measure the phase proportions of
powder containing several phases. First, an XRD pattern is performed. The peaks are
identified to the different phases. By making the ratio if the intensities, one can find the
ratio of the phase proportions using the following formula:

Where 𝛼 and 𝛽 refer to the two phases present in the mixture and R is a constant
depending on the phase, 𝜃 and the miller indices hkl. The equation to find its value is
given below:
The XRD pattern shows two kinds of peaks with different intensities. Using the method
described in the question 1, the analysis of the ratio sin12sin22 results in a FCC
lattice for the weak-intensity peaks (2=50.83; 59.37; 88.93; 110.45) and a BCC lattice
for the bigger peaks (2=52.29; 77.09; 99.48; 123.57). As austenite has a FCC lattice,
the weak-intensity peaks correspond to the retained 𝛾-phase.

Calculation of R:

The analysis of the intensity ratio is performed with the two first peaks at 2=50.83
and2=52.29. The hkl indices correspond respectively to 111 for the FCC lattice and
110 for the BCC one. From the appendix 6, it leads to a multiplicity of 8 for 111 and 12
for 110 in a cubic system.

The value of F is given by:

F2=16f2 for unmixed hkl in a FCC structure
F2=4f2 for an even hkl in a BCC structure
Where f is the atomic scattering factor of iron. From appendix 3, the f value of iron with
sin=2.78 nm-1gives 17.47. The wavelength of Cu K𝛼 is used and a linear regression
between 2 and 3 is performed to find the exact value of f.

The last parameter is the volume of the unit cell. In a cubic system, a2=d2(h2+k2+l2).
Using the Bragg’s law with the the wavelength of Cu K𝛼, it gives:

The lattice parameter are a=0.311 nm for austenite and a=0.247 nm for the BCC
lattice. As both lattice are cubic, v=a3.

Using all these parameters, the ratio of the R values of the FCC and the BCC lattice
are found. The exponential part is deleted as it is the same for both R.

Calculation of the concentrations:

The integration of the area of the peaks without the background noise gives a

where 𝛼 refers to austenite and 𝛽 to the BCC lattice.

Therefore, the ratio of the composition is found:

Finally, the proportion of each phase can be found using

Consequently, there is 1.18% of retained austenite and 98.82% of the BCC

structure.