MTN 307 Materials Characterization
X-ray Diffraction Geometry
Dr. K.S. Suresh
[email protected] Diffractometer
Source
Optics
Detector
Incident Beam Part
Diffracted Beam Part
Sample
Source
Incident Beam
Optics
Diffracted Beam
Optics
Detector
X-ray generation
X-ray tube
X-rays
Be window
W cathode
Rotating anode
Electrons
Metal anode
Small angle anode
Small focal spot
Large angle anode
Large focal spot
Slits
To limit the size of beam (Divergence slits)
To alter beam profile
(Soller slit angular divergence )
Narrow slits
Lower intensity
+
Narrow peak
Mirror
focusing and remove K2
Mono-chromator
Si
remove K2
Graphite
Beam Profile
Mirror
Parallel beam
Source
Soller slit
Detector
Mirror
Sample
Para-focusing
Detector
Sample
Source
Point focus
Detector
Sample
Source
Parallel beam
Para-focusing
X-rays are aligned
X-rays are diverging
Lower intensity for bulk
samples
Higher intensity
Higher intensity for small
samples
Lower intensity
Instrumental broadening
independent of orientation
of diffraction vector with
specimen normal
Instrumental broadening
dependent of orientation of
diffraction vector with
specimen normal
Suitable for GI-XRD
Suitable for Bragg-Brentano
Texture, stress
Powder diffraction
Detectors
Single photon detector (Point or 0D)
scintillation detector NaI
proportional counter, Xenon gas
semiconductor
Position sensitive detector (Linear or 1D)
gas filled wire detectors, Xenon gas
charge coupled devices (CCD)
Area detectors (2D)
wire
CCD
3D detector
X-ray photon
Photoelectron or
Electron-hole pair
Photomultiplier tube or
amplifier
Electrical signal
NaCl crystals in a tube facing X-ray beam
Integrated intensity for a flat specimen diffractometer
Integrated intensity per unit length of diffraction line =
0 3
32
0 4
4 2
1
2
1+2 2
2
I0 intensity of incident beam
A cross sectional area of incident beam, l wavelength, r radius of
diffractometer circle
m0 permeability of free space, e charge of electron, m mass of the
electron, v volume of unit cell
F structure factor
p multiplicity factor
Bragg angle, e-2M temperature factor, m linear absorption
coefficient
Diffraction geometry
Sample
Incident Beam
Film
Lorentz-Polarization factor
Indexing the XRD patterns
FCC; wavelength=1.54056
Simple
BCC
Cubic
S1 (mm) ()() sin2 sinh22+k2+l2
(mm)
38
19.0
0.11
38
19.022.5 0.11 0.15
3
45
45
22.533.0 0.15 0.30
4
66
2+k22/
2+l22/ hLattice
22+k22+l22 Parameter, a ()
h2sin
+l22h2+ksin
66
78
78
83
33.039.0 0.30
39.041.5 0.40
83
97
97
113
21
0.055
0.11
42 0.037
63 0.038
0.038
0.75
8
0.40
11
0.45
84 0.038
5 0.036
10
0.050
0.10
41.549.5 0.45
49.556.5 0.58
12
0.58
16
0.70
6 0.038
12
8 0.036
14
0.048
0.097
113
118
118
139
56.559.0 0.70
59.069.5 0.73
19
0.73
20
0.88
9 0.037
16
100.037
18
0.046
0.081
139
168
168
69.584.9 0.88
84.9
0.99
24
0.99
27
110.037
20
0.037
0.050
0.09
0.050
0.10
0.045
0.09
0.050
0.0925
0.049
0.088
Not Constant
so it is FCC
Not
NotSimple
BCC
Cubic
Precise lattice parameter calculation
FCC; wavelength=1.54056
S1
(mm)
()
sin2
h2+k2+l2
sin2/ h2+k2+l2
Lattice Parameter, a ()
38
19.0
0.11
0.037
4.023
45
22.5
0.15
0.038
3.978
66
33.0
0.30
0.038
3.978
78
39.0
0.40
11
0.036
4.039
83
41.5
0.45
12
0.038
3.978
97
49.5
0.58
16
0.036
4.046
113
56.5
0.70
19
0.037
4.023
118
59.0
0.73
20
0.037
4.023
139
69.5
0.88
24
0.037
4.023
168
84.9
0.99
27
0.037
4.023
So it is FCC, butt different lattice
constant
Diffraction Methods
Method
Wavelength
Angle
Specimen
Laue
Variable
Fixed
Single
Crystal
Rotating
Crystal
Fixed
Variable (in Single
part)
Crystal
Powder
Fixed
Variable
Powder
Laue Method
Transmission
Zone axis
Reflection
Zone axis
crystal
crystal
Film
Incident beam
Incident beam
Film
Uses Single crystal
Uses White Radiation
Used for determining crystal orientation and quality
Rotating Crystal Method
Determination of unknown crystal structures
Powder Method
Sample
Incident Beam
Film
Useful for determining lattice parameters with high precision and for
identification of phases
Intensity (a.u.)
Analysis of Single Phase
2()
d ()
(I/I1)*100
27.42
3.25
10
31.70
2.82
100
45.54
1.99
60
53.55
1.71
56.40
1.63
30
65.70
1.42
20
76.08
1.25
30
84.11
1.15
30
89.94
1.09
I1: Intensity of the strongest peak
Procedure
Note first three strongest peaks at d1, d2, and d3
In the present case: d1: 2.82; d2: 1.99 and d3: 1.63
Search JCPDS manual to find the d group belonging to the strongest
line: between 2.84-2.80
There are 17 substances with approximately similar d2 but only 4 have
d1: 2.82
Out of these, only NaCl has d3: 1.63
It is NaClHurrah
Specimen and Intensities
Substance
File Number
2.829 1.999 2.26x 1.619 1.519 1.499 3.578 2.668
(ErSe)2Q
19-443
2.82x 1.996 1.632 3.261 1.261 1.151 1.411 0.891
NaCl
5-628
2.824 1.994 1.54x 1.204 1.194 2.443 5.622 4.892
(NH4)2WO2Cl4
22-65
2.82x 1.998 1.263 1.632 1.152 0.941 0.891 1.411
(BePd)2C
18-225
Presence of Multiple phases
d ()
I/I
0.98
5
7
4
1
More Complex
Remaining
Pattern of Cu2O
3.01 Lines 5
Several permutations combinations possible
2.47 I/I1
72
d
d ()
I/I1
e.g. d1; d2; and d3, the first three strongest lines show()
2.13
28
Observed
Normalized
3.020
9
several alternatives
2.09 *
100
3.01
5
7
2.465
100
Then take any of the two lines together
and match
1.80 *
52
72 1.50
100
20
It turns out that 1st and 3rd strongest lies
to Cu2.47
2.135belong
37Pattern
for Cu
9
and then all other peaks for Cu can be1.743
separated
out I/I1
28 1.29
39
1 d () 2.13
18
Now separate the remaining lines and normalize
the1.50100 20 1.28 * 28
2.088
1.510
27
1.22
4
intensities
1.808
46
9 1.08
13
20
1.287
171.278 1.29
*
20
Look for first three lines and it turns out that the
36
4 1.04 *
17
1.233
4 1.09 1.22
phase is Cu2O
If more phases, more pain to solve
1.0674
0.9795
1.0436 0.98
5
2
0.9038
3
4 0.8293
9
0.8083
0.91
0.83
0.81
*
*
8
10
Diffraction from a variety of materials
(From Elements of X-ray
Diffraction, B.D. Cullity,
Addison Wesley)
Lattice Strain
do
No Strain
Uniform Strain
d strain
Non-uniform Strain
Broadeing b 2 2
d
tan
d
Residual Stress
Hull Failure of MSC Carla container vessel
Failed on 24 November 1997, while travelling from La Harve, France to Boston, USA.
Built in 1972 in
Lanskrona,
Sweden
Residual Stress
The stress resident inside a component or
structure after all applied forces have been
removed
Residual stresses are generated, after plastic
deformation that is caused by applied
mechanical loads, thermal loads or phase
changes. Mechanical and thermal processes
applied to a component during service may also
alter its residual stress state.
Types of residual stress
From theory of elasticity
For Isotropic material
For isotropic elastic solids
When s33 = 0,
