Quick and reliable determination

of CaO, SiO
2
, Al
2
O
3
and Fe
2
O
3
in pressed limestone pellets
Introduction
Limestone is one of the major components of raw meal for cement and ceramics. The
composition of limestone has great impact on the composition of the raw meal,
consequently the process of cement production. Therefore the composition of
limestone is monitored.
This application note describes a method of analysing limestone at an elemental level
using MiniPal 2, an energy dispersive X-ray fluorescence (EDXRF) spectrometer of
PANalytical. Quick and reliable results can be obtained in just a few minutes using
this XRF method.
Samples, standards and their preparation
A set of certified limestone standards (NCS DC
from China National Analysis Center for Iron and
Steel) was used to set up the calibration. The
powders were ground for three minutes. The fine
powders were pressed into pellets at 20 tonnes for
60 seconds. No binder was necessary.
Procedure
The conditions for data acquisition are given in
Table 1. The total data acquisition time per sample
was seven minutes. The measurements were
performed in air atmosphere.
The calibration curves for determining Al
2
O
3
, SiO
2
,
CaO, and Fe
2
O
3
were set up using the regression
model of the MiniPal 2 software.
Results
Calibration
The calibration results are shown in Table 2. The
lower limit of detection (LLD) values shown in that
table are derived using the data acquisition time of
the method.
MiniPal 2: enhance your analytical power
The PANalytical cost-effective MiniPal 2 benchtop EDXRF
spectrometer is a valuable tool for stand-alone or satellite units.
Especially in those conditions where sample throughput it low
(typically 20 samples per day) and an adequate analysis is
demanded. With its portability it is also a practical choice for
sample pre-scanning or as back-up to other main-line systems. As
all our systems MiniPal 2 meets all important international
standards such as ASTM, ISO, and DIN.
The MiniPal 2 EDXRF spectrometer comes with a high-resolution
solid-state detector and a 12-position removable sample changer
with spinner enabling it to process sample batches fully
automatically, without need for operator attention. The tray can be
removed to facilitate sample loading. In order to assure optimum
analysis and measurement results, the spinner of the sample
changer rotates the sample continuously minimising the typical
error effect occuring through this heterogeneity. This is especially
important when analysing raw
material such as limestone
prepared as pressed pellets.
Element kV uA Filter Time (min)
Mg,Al, Si 4 1000 none 5
K, Ca, Fe 15 15 Al-thin 2
Table 1. Measurement conditions
Compound Concentration RMS LLD
range (%) (%)
(%)
MgO 0.29 - 3.63 0.14 0.02
Al
2
O
3
0.093 - 1.25 0.09 0.02
SiO
2
0.22 - 4.38 0.11 0.03
CaO 47.49 - 55.34 0.17 0.02
Fe
2
O
3
0.085 - 1.97 0.01 0.005
K
2
O 0.019 - 0.5 0.03 0.02
Table 2. Calibration results
Compound Average RMS
(%) (%)
MgO 1.16 0.07
SiO2 1.97 0.02
CaO 53.18 0.11
Fe2O3 0.14 0.003
Al2O3 0.36 0.02
K2O 0.08 0.01
PANalytical B.V.
P.O. Box 13, 7600 AA Almelo,
The Netherlands
Tel. +31 (0)546 534 444
Fax +31 (0)546 534 598
info@panalytical.com
www.panalytical.com
Regional sales offices
Americas
Tel. +1 508 647 1100 ; Fax +1 508 647 1115
Europe, Middle East, Africa
Tel. +31 (0)546 834 444 ; Fax +31 (0)546 834 499
Asia Pacific
Tel. +65 6741 2868 ; Fax +65 6741 2166
Equipment Configuration
MiniPal 2 compact energy dispersive X-ray fluorescence spectrometer and
controlling software.
X-ray tube: Type: low power, side window
Anode: Rh thin window
Tube settings: software controlled, max. voltage 30 kV,
max. tube power 9 W
Tube filters: five, software selectable
Detector: High resolution Si-PIN diode (< 255 eV @ 5.9 kV)
Sample changer: 12 position removable tray
Spinner: Electrical: 100 240 V, 45-65 Hz, 80 W
Radiation: Vollschutz according to Rntgenverordnung 1987
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Easy to use
User-friendly Windows-based
software makes the MiniPal 2
just about the easiest EDXRF
system in the world to
operate. No expert knowledge
is needed for routine analysis
since the software takes care
of it all. Embodies in the
software a host of innovative
features that make EDXRF
analysis a push-button
operation.
Selecting the Easy Measure
mode enables analyses to be
done in two simple steps:
Place samples in sample
changer
Press start button
View results
Its as easy as that
The RMS values represent the difference
between the given concentration and the
calculated concentration of the standards
used. The small RMS value indicates a
good calibration. As an example Figure 1
shows the calibration plot for SiO
2
.
Repeatability test
To show the repeatability of the method,
one sample was measured 400 times over
a period of four days. The average and
the standard deviations of the stability
tests are shown in Table 3.
Figure 1. Calibration plot for SiO
2
Table 3. Repeatability test results
Conclusions
The results of this analysis clearly demonstrate that the PANalytical MiniPal 2
EDXRF spectrometer is a perfect backup system for large-scale production and a
well suited stand-alone system for small-scale production to monitor the
limestone composition by accurate analysis of Al
2
O
3
, SiO
2
, CaO and Fe
2
O
3
.