Quantitative Phase Analysis

The Basics of X-Ray Diffraction

 XRF & XRD
Elements & Phases
1400 1500
1300

Elements
1200
1100
1000
900
800
700
600

XRD
500
KCps
400
300
200

22000
100

Mineral Phases
30 40 50

18000
20
10

16000
0

14000
56 54 52 50 40 30 20 10 9 8 7 6 5 4 3 2 1 0,5

KeV

12000
Counts
10000
8000

XRF
6000
4000
2000
0

20 30 40 50 60 70
2Theta (Coupled TwoTheta/Theta) WL=1.54060
XRF & XRD
Different Methods

XRF XRD

• Elements only • Phases / Minerals

• Atom Number • Crystal Structure

• Single Peaks • Multiple Peaks

• Net Intensity (Height or • Profile Fitting (Area and

Area) Shape of Peaks)

• Absolute Intensities • Relative Intensities

• Calibration • No Calibration
• Standards • No Standards
• Drift Correction • No Drift Correction
Elements & Phases

• Phase:
A physically distinctive form of matter, such as a solid, liquid, gas or
plasma. A phase of matter is characterized by having relatively uniform
chemical and physical properties.

H20

gaseous liquid solid

Elements & Phases

• Phase:
A physically distinctive form of matter, such as a solid, liquid, gas or
plasma. A phase of matter is characterized by having relatively uniform
chemical and physical properties.

solid solid solid

Elements & Phases

• Phase:
A physically distinctive form of matter, such as a solid, liquid, gas or
plasma. A phase of matter is characterized by having relatively uniform
chemical and physical properties.

solid solid solid

Different Phases:
Different XRD Patterns

Black: Diamond
Red: Graphite
Blue: C60 Fullerene

Ideal calculated diffraction patterns from the 3 phases mentioned above

Unit Cell and Crystal Structure
Unit Cell

• Crystalline materials show a 3-

dimensional periodic structure

• An ideal crystal is formed by unit

cells of the same size and shape,
consisting of atoms arranged in
an identical manner

• The size and shape of the unit cell

are described by the lattice
parameters, which are the length
of the edges and the angles
between them
 Unit Cell and Crystal Structure
Unit Cell

Z
• Crystalline materials show a 3-
dimensional periodic structure

• An ideal crystal is formed by unit

cells of the same size and shape,
c
consisting of atoms arranged in
an identical manner

α – The size and shape of the unit cell

β are described by the lattice
b
parameters, which are the length
γ Y
a of the edges (a, b, c) and the
angles between them (α, β, γ).

X
Unit Cell and Crystal Structure
Crystal Lattice

d2

d1
The Bragg-Brentano Diffractometer
Geometry
The Bragg-Brentano Diffractometer
Geometry

X-ray Detector
tube

q q 2q
Sample
W. H. Bragg and W. L. Bragg
Diffraction Relation

n  2d sin q
Powder Diffraction

Incident Diffracted
beam beam
Relation between
Angle and Peak Position
Intensity (counts)

2q 2q 2q
X-Ray Diffraction
Identificaton of Minerals

C 3A
C3A cubic C3A orthorhombic
X-Ray Diffraction
Identification of Minerals

34000
6000

32000
30000
5000

28000
30000

26000
4000

24000
22000
Counts

20000
3000

Counts

18000
16000
2000

14000
20000
Counts

12000
10000
1000

8000
6000
0

19 19.2 19.4 19.6 19.8 20 20.2 20.4 20.6 20.8 21 21.2 21.4 21.6 21.8 22 22.2

4000
2Theta

2000
10000

0
32.7 32.8 32.9 33 33.1 33.2 33.3 33.4 33.5
2Theta
0

10 20 30 40 50 60
2Theta

C3A cubic C3A orthorhombic

X-Ray Diffraction
The Theory

Perfect diffractometer Perfect sample

 Easy to extract peak-

2θ positions and integrated areas
X-Ray Diffraction
The Reality

Almost perfect Real sample

84
diffractometer
82
80
78
76
74
72
70
68
66
64
62
60
58
56
54
52
50
48
46
44
42
40
38
36
34
32
30
28
26
24
22
20
18

 Complex Patterns
16
14
12
10
8
6
2θ
4
2
0
20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39
Deconvolution / Convolution Methods
Basic Principle

Y(2q)  (W x G) x S
Well known approach latest since Klug & Alexander, 1954
The Fundamental Parameters Approach
Line Profile Generation

Y(2q)  (W x Geq x GAx) x Si x Pi x Ui + Bkg

Fundamental Parameters
Approach Both
Empirical Approach

W = Emission Profile
Geq = Instrument Convolutions in the Horizontal Plane
GAx = Instrument Convolutions in the Axial Plane
Si = Sample Convolutions
Pi = Micro-Structure Effects
Ui = Any User-Supplied Convolutions
Bkg = Background
Convolution Synthesis of Line Profiles

W G

Y(2q)  (W x G) x S

S
 Information in a Diffractogram

Peak positions (d-spacings):

dimension of the elementary cell

• Lattice parameters Peak intensities: content of the elementary cell

• Space group • Crystal structure

• Quantitative analysis (scaling factor)

Profile width and shape

• Instrument contributions
• Microstructure (Size, strain,...)

Background
• Scattering from sample environment (air, sample holder, ...)
• Incohorent scattering
• Amorphous phase amounts
 The Result of the Measurement:
A Diffractogram
12000
10000
8000
Counts

6000
4000
2000
0

10 20 30 40 50 60
2Theta

5min measurement of a slag cement sample on a D8 ENDEAVOR

 Quantification with XRD
QPA methods available in TOPAS

• Traditional Rietveld method

• Internal standard method

• External standard method (O'Connor & Raven, 1988)

• Degree of crystallinity method (DOC)

• Partially or not known crystal structures (PONKCS) method

(Scarlett & Madsen, 2006)

• Pattern scaling (Chipera & Bish, 2002)

• Calibration method
QPA methods in TOPAS
Traditional Rietveld method

Y(2q)  (W x G) x S
• In a Rietveld refinement, we build a model for both the
diffractometer and the sample
• We can calculate the diffraction pattern of our model.
• And we can adjust our model with different refineable parameters.

• The procedure used is called a least-squares refinement.

• The smaller the difference, the better (=closer to the real sample)
is our model for the sample.

S   wi  yi ( obs)  yi ( calc) 
2
 min
i
QPA methods in TOPAS
Traditional Rietveld method

9,500
9,000
8,500
8,000
7,500
7,000
6,500
6,000
5,500
5,000
Counts

4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64
2Th Degrees

The blue curve represents the measurement data, whereas the red curve is the
calculated diagram. The difference between both is given in grey.
QPA methods in TOPAS
Traditional Rietveld method

• Uses the Hill and Howard (1987) relationship

to calculate weight fractions Wa

𝑆𝑎 𝑍𝑀𝑉 𝑎
𝑊𝑎 =
σ𝑛𝑗=1 𝑆𝑗 𝑍𝑀𝑉 𝑗

(where:
Sa scale factor phase A;
ZM mass of unit cell contents;
V unit cell volume;
n number of phases)

• Important: Rietveld QPA delivers only

relative phase amounts!
X-Ray Powder Diffraction
in a Cement Plant

10000
9000
8000
7000
6000
Counts
5000
4000
3000
2000
1000

Measurement
0

10 20 30 40 50 60
2Theta (Coupled TwoTheta/Theta) WL=1.54060

Data Evaluation

Process Control
&
Quality Control
 The Result of the Measurement:
A Diffractogram
12000
10000
8000
Counts

6000
4000
2000
0

10 20 30 40 50 60
2Theta

5min measurement of a slag cement sample on a D8 ENDEAVOR

Quantitative Phase Analysis
with TOPAS

Manual sample evaluation with DIFFRAC.TOPAS in GUI mode.

The next Step: Automation
with TOPASBBQ

An automated phase quantification with

TOPASBBQ is the standard procedure in an
industrial environment. No GUI!
The next Step: Automation
Push Button Solutions
The next Step: Automation
Results Manager
 Innovation with Integrity

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