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Information
Correction functions
Divergence slit
.
Background Determination
Iterative approximation
By peak search
Manual
Background Determination
Iterative approximation
By peak search
Manual
Background Determination
Iterative approximation
By peak search
Manual
Pattern Treatments
Data reduction functions
Background determination
Peak search
Profile fitting
K2 stripping
Smoothing
Correction functions
Divergence slit
.
Edit data
Basic XRD Course
10
11
12
Pattern Treatments
Data reduction functions
Background determination
Peak search
Profile fitting
K2 stripping
Correction functions
Divergence slit
.
Edit data
13
Profile fitting
Counts
6000
6000
4000
4000
2000
2000
0
43.50
44
44.50
Position [2Theta] (Copper (Cu))
45
43.50
44
44.50
Position [2Theta] (Copper (Cu))
45
14
Pattern Treatments
Data reduction functions
Background determination
Peak search
Profile fitting
K2 stripping
Correction functions
Divergence slit
.
Edit data
Basic XRD Course
15
K2 Stripping - Purpose
To remove the K2 contribution from a scan
To improve resolution
16
K2 Stripping - Algorithm
Assume that the shape
and width of the K1
and K2 peak are the
same
Use the known
wavelengths to
calculate the K2
position from the K1
position
Rachinger method
Basic XRD Course
17
K2 Stripping - Example
18
Pattern Treatments
Data reduction functions
Background determination
Peak search
Profile fitting
K2 stripping
Correction functions
Divergence slit
.
Edit data
Basic XRD Course
19
20
21
22
80
Peak list
60
40
20
20
40
60
80
100
120
140
160
180
200
100
Probability curve
of peak & profile
data
80
60
40
20
20
40
60
80
100
120
140
160
180
200
23
80
60
Low probability
40
20
20
40
60
80
100
120
140
160
180
200
20
40
60
80
100
120
140
160
180
200
100
80
High probability
60
40
20
24
Semi-quantitative Analysis
Estimates the mass fractions of the identified
phases
All phases must have been identified
Amorphous material is not taken into account
25
26
Pattern Treatment
27
Phase identification
28
Phase Identification
29
Phase Identification
30
10
Rietveld
Introduction to Rietveld refinement
31
Rietveld Refinement
Devised by Hugo Rietveld, 1969
Originally for Neutron diffraction
Whole pattern structure refinement
No crystallographic information is lost
32
Rietveld refinement
33
11
Standardless
Quantitative
analysis
Crystal Structure
Refinement
34
Minimisation of differences
The term that is minimised is Sy
S y = wi ( y i y ci )
35
single line
methods
Whole pattern
method
36
12
Data collection
High resolution
High Intensity (> 10 000 counts)
Large 2 range (5-100)
At least 5-10 steps across FWHM
Avoid preferred orientation
Particle size 1-10m
37
Particle size
38
Calculated intensity
y ci = s L K FK (2 i 2 K )PK A + y bi
2
S = Scale factor
K represents the Miller indices
LK= Lorenz polarisation and multiplicity factors
is the reflection profile function
PK is the preferred orientation function
A is the absorption factor
FK is the structure factor of the Kth Bragg reflection
Ybi is the background intensity of the ith step
39
13
Refinement Parameters
1. Global Parameters
Background
Zero shift
Specimen displacement
40
Refinement Parameters
2. Phase Related
Parameters
41
Manual Background
Background is set at
the beginning of the
refinement.
Straight line is drawn
between set points.
Linear Interpolation
42
14
Refined background
Polynomial
Chebyshev
Shifted Chebyshev
Amorphous sinc function
Damped amorphous sinc function
Refined Background
I = A + B + C2 + D3 + E4..
1st coefficient (A) is referred to as the
flat background parameter
A
2
44
Refined Background
I = A + B + C2 + D3 + E4..
1st coefficient (A) is referred to as the
flat background parameter
A, B
2
Basic XRD Course
45
15
Refined Background
I = A + B + C2 + D3 + E4..
1st coefficient (A) is referred to as the
flat background parameter
A, B, C
2
46
Manual Vs Refined
Manual
Time consuming
Can miss weak reflections
Handles difficult backgrounds
Refined
Can be automated
Adjustable throughout refinement
47
Space Group
Determines the symmetry of the structure
Fixed at the start of the refinement
230 Space Groups
NaCl Fm3m
Rutile P 42/mnm
Gypsum C 2/c
48
16
Indexing
Fitting peak list to unit cell dimensions
Try different programs and compare results
49
Cell Refinement
50
Atomic Positions
Each atom in the structure
must have its atomic
coordinates recorded.
E.g.
Special positions
(0, 0, 0)
(, , 0)
(, , 0.492)
(0.2346, 0.987, 0.456)
51
17
Preferred orientation
Results from crystallites lining up with each other.
May results from crystal growth mechanism or special
cleavage planes.
Use back-loading techniques and spin sample.
Observe symmetry related peaks all high / low in intensity
52
Gaussian (G)
Lorentzian (L)
Voight
Pseudo-Voight
Mixture of Gaussian and Lorentzian
pV = L+(1-)G
Pearson VII
Mod-TCH pV
Basic XRD Course
53
Scale Factor
Simple scalar variable
Leads to quantification.
54
18
Peak Width
Full Width Half Maximum (FWHM)
FWHM is dependent on
Cagliotti function
H2 = U tan2 + V tan + W
Often sufficient just to refine W
55
56
Temperature Factors
Thermal vibration of the atoms
Can be model Isotropic or Anisotropic
Labelled U or B
No vibration
With vibration
57
19
SOF
58
Ca4AF
4CaO.Al2O3.Fe2O3
Iron and Aluminium share the same site
Fe3+ Al3+
Need to link the occupancy together
59
200
100
0
15
20
25
Position [2Theta]
60
20
Peak Asymmetry
Refinement Strategy
Start with few parameters
Increase number as refinement proceeds
62
63
21
64
65
66
22
Potential problems
Needs structure data
Incorrect solutions can look good
Can be numerically unstable
67
Unstable Refinements
Use variable limits
Compatible with automation
68
Mixture3
Eskolaite 16.3 %
Fluorite 44.0 %
Calcite 39.8 %
10000
5000
0
20
30
40
50
Position [2Theta]
60
70
69
23
15000
10000
5000
0
25
30
35
Position [2Theta]
70
Cell Parameters
Counts
15000
Mixture3
Eskolaite 17.5 %
Fluorite 58.6 %
Calcite 23.8 %
10000
5000
0
20
25
30
35
Position [2Theta]
71
Mixture3
Eskolaite 17.4 %
Fluorite 59.4 %
Calcite 23.2 %
10000
5000
0
20
25
30
35
Position [2Theta]
72
24
Peak width, W
Counts
15000
Mixture3
Eskolaite 17.6 %
Fluorite 59.7 %
Calcite 22.7 %
10000
5000
0
20
25
30
35
Position [2Theta]
73
Amorphous Quantification(1)
Analyzing an amorphous material using the
Rietveld calculations in HighScore Plus
1.
74
Amorphous Quantification(2)
This example shows how to determine the amorphous
content of a sample with a Rietveld refinement by
addition of a crystalline standard phase.
Amorphous compound(s) are invisible for the Rietveld
method. Only crystalline phases are taken into account
and their sum is normalized to 100%. The amount of the
crystalline phases is overestimated in case amorphous
material is present too.
75
25
Amorphous Quantification(3)
76
Amorphous Quantification(4)
77
Amorphous Quantification(5)
Counts
Silicon 32.1 %
Quartz 67.9 %
20000
10000
0
20
30
40
Position [2Theta]
6000
4000
2000
0
-2000
-4000
-6000
78
26
Amorphous Quantification(6)
79
80
81
27
Experimental
Correction and
normalization
Fourier transformation
Nanocomposite
Nanosized pores
84
28
10
10
10
10
Nano TiO2
Background
sample
background
Sample
background-subtracted
Background-corr.
0.03
-1
23
0.02
DV(R)
65
6
0.01
2 Theta [deg]
0
10
20
30
40
50
60
70
80
90 100
R []
SAXS, Nanoparticles
85
Residual Stress
Intensity (counts)
4000
3000
2000
1000
0
61.5
62.0
62.5
63.0
63.5
64.0
64.5
65.0
65.5
2Theta ()
86
Texture
Texture of rolled Copper
Measure the change in
intensity of one hkl at
different sample tilts
ODF project:
C:\...tical\X'Pert Texture\Cu111.rw 1
Pole figure: 111 Raw
43.2800
2Theta:
Inte nsities :
Psi Phi
Intensity
Min
65.0 92.5
4942.090
Max
25.0 87.5
103941.760
2D
Dim ension:
Schmidt
Projection:
Linear
Scale:
X'Pert
Color m ap:
10
Contours:
Intensity
Color
1
13942.060
3
31942.000
5
49941.940
7
67941.880
10
94941.790
ODF project:
C:\...tical\X'Pert Texture\Cu220.rw 1
Pole figure: 220 Raw
74.1200
2Theta:
Inte nsities :
Psi
Phi
Intensity
Min
75.0 267.5
2809.000
Max
20.0 182.5
30032.890
2D
Dim ension:
Schmidt
Projection:
Linear
Scale:
X'Pert
Color m ap:
10
Contours:
Intensity
Color
1
5283.899
3
10233.697
5
15183.495
7
20133.294
10
27557.991
87
29
002
Phi 0.00
Psi 0.00
X 0.00
Y 0.00
Z 9.195
Omega
1.0
POM RSM
3.1
5.9
0.6
10.9
0.4
20.4
38.1
0.2
71.0
-0.0
132.6
-0.2
247.5
-0.4
461.9
-0.6
862.2
-0.8
1609.3
-1.0
002.xrdml
1.7
0.8
3003.9
-1.0
-0.5
0.0
0.5
1.0
Omega/2Theta
5606.8
10465.3
88
Rocking Curves
89
Reflectivity
90
30