Application

Note: 41301
Free Lime Determination in Clinker
ARL 9900 Series with IntelliPower
Simultaneous-Sequential XRF Spectrometer

Introduction Free lime analysis results

Key Words Calcination of cement raw A series of six clinker standards were analyzed for free
materials in the kiln lime by wet chemistry. The powders were ground for 10 s.
ARL 9900
produces a material called with two 200 mg grinding pills. They were then pressed
- 3600W
clinker. Free lime (CaO) in into pellets at 15t for 40s. and measured on the ARL 9900.
Cement clinkers has to be closely Figure 1 shows the diffractogram recorded with the
monitored to ensure the diffraction system on three different clinker pellets.
Free lime
quality of cement. Excess The two peaks assigned to C3S and CaO phases, are
Integrated XRF-XRD free lime results in resolved and not interfered by any fluorescence from the
undesirable effects such as sample. As can be seen from the peak, representing 0.5 %
X-ray
volume expansion, of free lime, the increased sensitivity of the diffraction
Fluorescence
increased setting time or system is more than adequate to monitor the free lime
reduced strength. In content even at low levels (0.1 % to 0.5 %).
addition, constant
monitoring of free lime allows the operator to determine
and maintain the optimum operating point of the kiln in Free CaO
3.0 3.3 %
order to obtain maximum reactivity and to reduce thermal 2.8
consumption. With increased reactivity, grinding of the 2.6
raw meal can also be reduced leading to further 2.4
Intensity [Kcps]

2.2
economies of energy. 2.0 1.9 %
The X-ray fluorescence technique (XRF) is used to 1.8
1.6 C 3S
perform chemical elemental analysis on cement making
1.4 0.5 %
materials. From this analysis, concentrations for the major 1.2
oxides are derived. Since mineralogical information is not 1.0
available from XRF spectra (for instance XRF gives only 0.8
the total Ca concentration in the sample including free 2.52 2.58 2.44 2.40
d Spacing [Anstrom]
CaO), wet chemical methods like titration or a separate
X-ray diffractometry (XRD) equipment are normally
Figure 1: Diffraction pattern obtained with the ARL 9900 Series in the free
required to determine the phase content in clinker or lime region for clinker samples with varying CaO concentrations
cement.
Thermo Fisher Scientific has introduced an innovative A calibration program recorded the intensities of the
instrument capable of dealing with both techniques: the characteristic diffraction peak for free lime (d=2.41) on
Thermo Scientific ARL 9900 Series with IntelliPower. the six clinker standards. The results are shown in Figure
Inside the XRF spectrometer, a diffraction system can be 2 along with the relevant parameters in Table 1. The
integrated which is capable of performing qualitative innovative diffraction system produces a sensitivity of
scans and quantitative analysis as well. The highest 600 cps/ % for free lime analysis. This is about 10 times
repeatability of angular positioning is ensured through higher than a conventional X-ray diffractometer. The
Thermo moir fringe positioning mechanism. standard error of estimate is an average of the differences
The performance of this diffraction system has been between chemical and found concentrations. It is an
improved by careful optimization of the crystal estimation of the accuracy of analysis. The value obtained
discriminator and the detector. A large gain on the (0.08 %) is well within the capability of wet chemistry.
sensitivity of the interesting phases has been obtained
which results in much better performance in term of
quantitative analysis than what is achieved with
traditionnal diffractometers.
 The short term stability was tested by measuring a In addition to these
3.5
clinker sample 11 times for 40 s. on free lime with the offices, Thermo Fisher
integrated XRD system and 40 s. on the fixed XRF 3 Scientific maintains

Free Lime Concentration [%]

channels. The results are summarized in Table 2 where 2.5 a network of represen-
XRF results on major oxide are also included for 2
tative organizations
comparison. They show the fine repeatability of the throughout the world.
1.5
system: ~1 % relative standard deviation. This is
1
approximately 10 times better than what is achievable by
wet chemistry. 0.5
Finally, a long term stability test was also performed 0
1 1.5 2 2.5 3 3.5
over 50 hours. Excellent results were obtained with sigma Peak Intensity [Kcps] Africa-Other
values well within statistics (1.8 % free lime 0.02 %). +27 11 570 1840
Figure 2: Calibration curve of free lime in clinker using the ARL 9900 Series. Australia
+61 3 9757 4300
Conclusion
SAMPLE -CONCENTRATION- Austria
By using the diffraction system integrated into the ARL DIFFERENCE NAME Kcps NOM. % CALD% +43 1 333 50 34 0
9900, free lime in clinker can be quantified with high ABSOL. % Belgium
sensitivity, reliability and excellent stability. +32 53 73 42 41
Clinker 1 1.54 0.80 0.93 0.13
Canada
Limestone additions to cement which are becoming Clinker 2 1.30 0.53 0.53 0.00 +1 800 530 8447
increasingly important in Europe following recent Clinker 3 2.98 3.30 3.32 0.02 China
regulations, can also be monitored using this integrated Clinker 4 1.62 1.10 1.07 -0.03 +86 10 8419 3588
Denmark
XRF-XRD instrument, as well as other clinker phases like Clinker 5 2.09 1.90 7.84 -0.06 +45 70 23 62 60
C3S, C2S, C3A or C4AF. Clinker 6 1.41 0.77 0.71 -0.06 Europe-Other
The advantages of this combined system are obvious: Standard error of estimate 0.08 % +43 1 333 50 34 0
Finland / Norway /
XRF and XRD can be performed on the same sample BEC 1.636 % Sweden
and under identical conditions thus cutting down all Q (sensitivity) 600 cps/ % +46 8 556 468 00
extra costs for additional hardware and ensuring more Limit of Detection 156 ppm France
+33 1 60 92 48 00
reliable and stable total analysis.
Table 1: Regression results on free lime Germany
XRF performance is not affected by the addition of this +49 6103 408 1014
diffraction system. India
+91 22 6742 9434
Software and data treatment methods are common to CONCENTRATIONS [%] Italy
XRF and XRD measurements. XRD XRF +39 02 950 591
A rapid and flexible system can be configured based on FREE Japan
RUN LIME CaO SiO2 Al2O3 Fe2O3 MgO K2O Na2O SO3 +81 45 453 9100
fixed XRF channels for simultaneous analysis of all
1 0.67 65.54 21.42 5.59 3.97 1.55 0.68 0.58 1.01 Latin America
cement oxides, the diffraction system which has the +1 561 688 8700
capability of measuring free lime (CaO) and calcite 2 0.68 65.52 21.41 5.59 3.96 1.55 0.68 0.58 1.00 Middle East
(CaCO3) phases, our Moir fringe goniometer for a 3 0.67 65.52 21.41 5.59 3.96 1.55 0.68 0.58 1.00 +43 1 333 50 34 0
sequential XRF analysis on any of 83 elements of the 4 0.66 65.50 21.40 5.58 3.96 1.55 0.68 0.58 1.00 Netherlands
+31 76 579 55 55
periodic table and back-up of the fixed channels. 5 0.67 65.50 21.39 5.58 3.96 1.55 0.68 0.58 1.00
New Zealand
The combination of XRF and XRD in the same 6 0.66 65.52 21.41 5.58 3.96 1.55 0.68 0.58 1.01 +64 9 980 6700
instrument can now provide complete quality control of 7 0.66 65.52 21.41 5.59 3.96 1.54 0.68 0.58 1.00 Russia/CIS
+43 1 333 50 34 0
clinker and cement. Separate instruments or methods are 8 0.67 65.51 21.41 5.58 3.96 1.55 0.68 0.58 1.00
South Africa
no longer required resulting in significant savings from 9 0.67 65.51 21.41 5.59 3.96 1.55 0.68 0.58 1.00 +27 11 570 1840
increased operator efficiency and lower maintenance and 10 0.65 65.50 21.39 5.59 3.96 1.55 0.68 0.58 1.00 Spain
+34 914 845 965
running costs. Average 0.67 65.51 21.41 5.59 3.96 1.55 0.68 0.579 1.00
Switzerland
More than 200 ARL 9900 Series are in operation St Dev 0.007 0.014 0.011 0.009 0.004 0.003 0.001 0.002 0.001 +41 21 694 71 11
around the world. RSD 1.04 0.02 0.05 0.16 0.10 0.18 0.09 0.27 0.08 UK
+44 1442 233555
Table 2: Typical reproducibility (10 runs) of free lime analysis in clinker. USA
Included is also the usual XRF analysis. Total counting time: 80 s. +1 800 532 4752

www.thermoscientific.com Thermo Fisher Scientific (Ecublens)

SARL, Switzerland is ISO certified.
2011 Thermo Fisher Scientific Inc. All rights reserved. All trademarks are the property of Thermo Fisher Scientific Inc. and its subsidiaries.
Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details.
AN41301_E 04/11C

Part of Thermo Fisher Scientific