The Determination of Free Lime

with XRD and the Rietveld Method

October 16, 2019 1

XRD in Process and Quality Control

What is the Task?

• Process and Quality control in a cement plant

 Monitoring and prediction of clinker and cement quality

 Establishing of stable production conditions

The determination of free lime is one of the most important control

parameters

• „Lime“ is a mineral and therefore always „free“.

October 16, 2019 2

XRD in Process and Quality Control

The determination of free lime is traditionally performed with one of

the following methods:

• Wet chemistry

• XRD calibration

• XRD Rietveld

October 16, 2019 3

X-Ray Diffraction
Measurement
12000
10000
8000
Counts

6000
4000
2000
0

10 20 30 40 50 60
2Theta

Measurement of a clinker sample on a D4 ENDEAVOR

October 16, 2019 4
X-Ray Diffraction
Qualitative Analysis

Qualitative Analysis with DIFFRAC.EVA

October 16, 2019 5
Quantitative Phase Analysis
with TOPAS (Rietveld & FPA)

Manual sample evaluation with DIFFRAC. TOPAS in GUI mode.

October 16, 2019 6
Quantitative Phase Analysis
with TOPAS (Rietveld & FPA)

16,000 C3S_M3 52.25 %

15,000
C3S_M1 2.57 %
C2S_beta 25.92 %
14,000
C3A_cubic 2.36 %
13,000 C3A_orthorhombic 0.11 %
12,000 C4AF 14.50 %
Lime 0.38 %
11,000
Portlandite 0.01 %
10,000 Periclase 1.01 %
9,000 Quartz 0.00 %
8,000
Arcanite 0.47 %
Langbeinite 0.18 %
7,000
Aphthitalite 0.24 %
Counts

6,000 Sucrose_HKL 0.00 %

5,000

4,000

3,000

2,000

1,000

-1,000

-2,000

-3,000

-4,000

-5,000

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

Rietveld refinement with DIFFRAC.TOPAS

October 16, 2019 7
Quantitative Phase Analysis
with TOPAS (Rietveld & FPA)

16,000 C3S_M3 52.25 %

15,000
C3S_M1 2.57 %
C2S_beta 25.92 %
14,000
C3A_cubic 2.36 %
13,000 C3A_orthorhombic 0.11 %
12,000 C4AF 14.50 %
Lime 0.38 %
11,000
Portlandite 0.01 %
10,000 Periclase 1.01 %
9,000 Quartz 0.00 %
8,000
Arcanite 0.47 %
Langbeinite 0.18 %
7,000
Aphthitalite 0.24 %
Counts

6,000 Sucrose_HKL 0.00 %

5,000

4,000

3,000

2,000

1,000

-1,000

-2,000

-3,000

-4,000

-5,000

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

Rietveld refinement with DIFFRAC.TOPAS

October 16, 2019 8
Quantitative Phase Analysis
with TOPAS (Rietveld & FPA)

16,000 C3S_M3 52.25 %

15,000
C3S_M1 2.57 %
C2S_beta 25.92 %
14,000
C3A_cubic 2.36 %
13,000 C3A_orthorhombic 0.11 %
12,000 C4AF 14.50 %
Lime 0.38 %
11,000
Portlandite 0.01 %
10,000 Periclase 1.01 %
9,000 Quartz 0.00 %
8,000
Arcanite 0.47 %
Langbeinite 0.18 %
7,000
Aphthitalite 0.24 %
Counts

6,000 Sucrose_HKL 0.00 %

5,000

4,000

3,000

2,000

1,000

-1,000

-2,000

-3,000

-4,000

-5,000

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

Rietveld refinement with DIFFRAC.TOPAS

October 16, 2019 9
The next Step: Automation
with TOPASBBQ

An automated phase quantification with

TOPASBBQ is the standard procedure in
an industrial environment. No GUI.

October 16, 2019 10

Determination of Free Lime
X-Ray Diffraction with Rietveld

4.5
y = 1x - 3E-05
4.0
R² = 0.9804

3.5

3.0
Free Lime WC

2.5

2.0
N=29
1.5
Mean 0.00
1.0 SD (1ó) 0.09

0.5 Min -0.15

Max 0.21
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
fCaO-XRD

CaO XRD vs WC. Linear (CaO XRD vs WC.) Linear (1.00 Correlation)

Glycol Titration Method: CaO + Ca(OH)2

October 16, 2019 11

Determination of Free Lime
X-Ray Diffraction with Rietveld

4.5
y = 0.9997x + 0.0015
4.0
R² = 0.9924

3.5

3.0
Free Lime WC

2.5

2.0
N= 3 x 8
1.5
Mean 0.00
1.0 SD (1ó) 0.09

0.5 Min -0.11

Max 0.11
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Free Lime XRD

CaO XRD vs WC Linear (CaO XRD vs WC) Linear (1.00 Correlation)

Ethanol Titration Method: CaO only

СПАССКЦЕМЕНТ
October 16, 2019 12
Determination of Free Lime
X-Ray Diffraction with Rietveld

4
y = 1.0429x - 0.0111
R² = 0.966
3.5

2.5
Free Lime WC

1.5 N= 135
Mean 0.00
1
SD (1ó) 0.10

0.5 Min -0.39

Max 0.27
0
0 0.5 1 1.5 2 2.5 3 3.5 4
Free Lime XRD

CaO XRD vs WC Linear (CaO XRD vs WC) Linear (1.00 Correlation)

Ethanol Titration Method: CaO only

October 16, 2019 13

Determination of Free Lime
Problems with Wet Chemistry

Wet Chemistry XRD

1900
1800

1.06 0.36
1700

1.06 0.71
1600

1.06 1.44
1500

Lime
1400

5.0
4.5
1300

4.0
1200

Free Lime WC
Counts

3.5
1100

3.0
1000

2.5
2.0
900

1.5
800

1.0
700

0.5
600

0.0
0.0 1.0 2.0 3.0 4.0 5.0
500

Free Lime XRD

400

36 37 38 39 40
Ca XRD vs WC Linear (1.00 Correlation)
2Theta (Coupled TwoTheta/Theta) WL=1.54060

October 16, 2019 14

Typical Standard Deviation for WC
CCRL Round Robin

Number of Average SD SD Average SD SD

Test Samples Year
Laboratories Value absolute relative Value absolute relative
CCRL Samples 155, 156 2005 182 1.86 0.43 23.20 1.23 0.27 22.30
CCRL Samples 159, 160 2006 170 1.07 0.20 18.90 1.14 0.21 18.30
CCRL Samples 161, 162 2006 179 1.41 0.30 21.40 0.53 0.19 36.50
CCRL Samples 163, 164 2007 188 0.63 0.18 27.80 0.61 0.18 30.60
CCRL Samples 165, 166 2007 184 0.77 0.18 23.60 0.97 0.22 23.10
CCRL Samples 167, 168 2008 197 0.43 0.23 54.30 0.70 0.24 34.30
CCRL Samples 169, 170 2008 179 1.36 0.32 23.60 1.36 0.32 23.50
CCRL Samples 161, 172 2009 182 0.88 0.20 23.40 1.04 0.22 20.80
CCRL Samples 173, 174 2009 184 1.65 0.34 20.40 1.04 0.21 20.20
CCRL Samples 175, 176 2010 182 0.93 0.23 24.50 0.49 0.21 42.80
CCRL Samples 177, 178 2010 166 0.59 0.18 29.80 1.26 0.25 20.10
CCRL Samples 179, 180 2011 177 0.72 0.19 26.00 0.52 0.22 42.00
CCRL Samples 181, 182 2011 174 0.82 0.20 24.00 0.94 0.21 23.00
CCRL Samples 183, 184 2012 174 0.82 0.20 24.00 0.72 0.18 25.00
CCRL Samples 185, 186 2012 172 1.25 0.23 19.00 0.88 0.17 20.00
CCRL Samples 187, 188 2013 170 1.42 0.26 18.00 0.45 0.18 39.00
CCRL Samples 189, 190 2013 172 1.00 0.22 22.00 0.98 0.21 22.00

Average values 178 0.96 0.23 26.10 0.87 0.22 27.26

October 16, 2019 15

Determination of Free Lime
X-Ray Diffraction and Calibration
9000

2100
2000
Lime

1900
1800
8000

1700
1600
1500
7000

1400
Counts

1300
1200
6000

1100
1000
900
Counts

5000

800
700
600
4000

36 37 38 39
2Theta (Coupled TwoTheta/Theta) WL=1.54060
3000
2000
1000
0

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

October 16, 2019 16

Determination of Free Lime
Problems with Calibration

Lime

C2S beta / Belite CaO / Lime

October 16, 2019 17

Turn Key XRD Cement Package

October 16, 2019 18

X-Ray Diffraction
Automation with TOPAS BBQ

What are the requirements on a control tool?

 Accurate
 Precise
 Fast
 Examination of representative sample
 Minimum of user interaction and / or
influence
 No expert knowledge required

October 16, 2019 19

 Innovation with Integrity

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