XRF 1045

Cement Analysis by the Pressed Powder

Method on Benchtop WDXRF Supermini200
According to ASTM C114-11

Benchtop wavelength dispersive

Portland cement cement
X-ray fluorescence spectrometer
Portland cement
Supermini200
hydraulic cement
pressed powder method
pressed pellets
benchtop
ASTM C114

Bert23-www.aerosolplanet.com

Introduction samples. Complete two rounds of tests on different

Cement is one of the most important materials for days repeating all steps of sample preparation. Cal-
construction. Many kinds of hydraulic cements, in- culate the differences between values and averages
cluding Portland cement, with various physical proper- of the values from the two rounds of tests.
ties are produced by changing the composition of · When seven CRMs are used in the qualification pro-
clinker minerals; therefore, it is important to control the cedures, at least six of the seven differences between
chemical composition of cement products and interim duplicates obtained of any single analytes shall not
products. exceed the limits shown in Table 1 and the remaining
ASTM C114-11 covers chemical analysis of hydraulic differences by no more than twice that value.
cement. In this standard, procedures of wet chemical · For each analyte and each CRM, the average ob-
analysis are mainly described and X-ray fluorescence tained shall be compared to the certified concentra-
(XRF) spectrometry is mentioned as an example of tions. When seven CRMs are used in the qualification
“Rapid Test Methods”. In practice, XRF spectrometry procedure, at least six of the seven averages for each
has been used for chemical composition analysis of analytes shall not differ from the certified concentra-
cement owing to its simple sample preparation and tions by more than the value shown in Table 1, and
high precision. the remaining average by more than twice that value.
This application note demonstrates quantitative analy-
sis for Portland cement by the pressed powder method The maximum permissible variations in analysis results
according to ASTM C114-11 on Rigaku Supermini200, defined in ASTM C114-11 are listed in Table 1.
a benchtop sequential wavelength dispersive XRF ASTM C114-11 directs that acceptable reference ce-
spectrometer. ments are NIST CRMs, or other reference cements
traceable to the NIST CRMs.
ASTM C114-11 and calibration standards In this application note, seven NIST CRM’s
The standard ASTM C114-11 has the following de- (SRM1881a, 1884a, 1885a, 1886a, 1887a, 1888a and
scriptions about “Rapid Test Method”: 1889a) were used for calibration and a qualification
· Using the test method chosen, make single determi- test.
nations for each analyte under consideration on at
least seven CRM (Certified Reference Material)

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 XRF 1045

Table 1 Maximum permissible variation (unit: mass%)

Maximum difference Maximum difference of
Analyte between duplicates the average of duplicates
from the certificate values
SiO2 0.16 ±0.2
Al2O3 0.20 ±0.2
Fe2O3 0.10 ±0.10
CaO 0.20 ±0.3
MgO 0.16 ±0.2
SO3 0.10 ±0.1
Na2O 0.03 ±0.05
K2O 0.03 ±0.05
TiO2 0.02 ±0.03 Without n-hexane With n-hexane
(dry grinding) (wet grinding)
P2O5 0.03 ±0.03
Figure 1 Comparison of the condition in
ZnO 0.03 ±0.03 the container after pulverizing
Mn2O3 0.03 ±0.03
Cl 0.003 N/A
Measurements were performed in vacuum on the Su-
permini200 with a 200 W Pd target X-ray tube for the
Instrument components listed in Table 1. Measurement condition
The Supermini200, a benchtop sequential wavelength is shown in Table 2.
dispersive X-ray fluorescence (WDXRF) spectrometer,
is designed to minimize the peripherals in installation Table 2 Measurement condition
such as cooling water, power supply, installation area, X-ray tube Pd target, 200 W end-window type
etc. The Supermini200 has good sensitivity for the light Tube condition 50 kV and 4.0 mA
elements such as Na, Mg, P and Cl, relative to EDXRF Analysis area 30 mm in diameter
systems, and does not show any spectral overlap Path atmosphere Vacuum
between typical analytes for cement raw meal, owing Element Si Al Fe Ca Mg S Na
to high spectral resolution of the WD optics. Line Kα Kα Kα Kα Kα Kα Kα
The Supermini200 is equipped with an air-cooled 200 Primary filter Out Out Out Out Out Out Out
W X-ray tube and up to three analyzing crystals, in Crystal PET PET LiF PET RX25 PET RX25
which elements from fluorine to uranium can be Detector PC PC SC PC PC PC PC
analyzed. Counting time (s) 40 40 20 40 60 40 60
The Supermini200 has the same base software as the Element K Ti P Zn Mn Cl
ZSX Primus series have and, therefore, the software is Line Kα Kα Kα Kα Kα Kα
user-friendly and flexible. Primary filter Al Out Out Out Out Out
Crystal PET LiF PET LiF LiF PET
Sample preparation Detector PC SC PC SC SC PC
The sample preparation for X-ray fluorescence analy- Counting time (s) 40 20 40 60 60 60
sis is easier than other analytical methods in general. Note) LiF: LiF(200), PC: F-PC
It is important to obtain fine grain size for samples
when grinding in order to reduce the influence of grain Calibration
size on analyzed results. In view of processing many The results obtained in the calibration curves are
samples continuously, the cleaning of grinding con- shown in Table 1 and Fig. 2.
tainers to avoid contamination from prior samples A matrix correction method is applied to the calibra-
should be able to be performed in a simple manner. tions. The symbol ○ shows the data point before the
When grinding cement samples, the samples can stick correction and the symbol ♦ shows the data after cor-
to the inner wall of the container, which causes a rection in the calibration charts.
problem in cleaning. In order to avoid the problem, The accuracy of calibration is calculated by the fol-
n-hexane was added as a grinding agent to prevent the lowing formula,
samples from sticking to the wall of the tungsten car-
∑ (C ) 2
bide container (the wet grinding method; see Fig. 1). i − Ĉ i
A binder was mixed with the ground cement powder Accuracy = i

n−2
samples (the ratio of sample to binder was 10 to 1).
Ci : calculated value of standard sample
Four grams of the mixture was pressed into an alumi-
num ring (inner diameter, 32 mm) at 150 kN. Ĉ i : reference value of standard sample
n : number of standard samples.
Measurement

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 XRF 1045

SiO2 Al2O3 Fe2O3 CaO

Intensity
Intensity
Intensity

Intensity

Std. value (mass%) Std. value (mass%) Std. value (mass%) Std. value (mass%)
(1) SiO2 calibration curve (2) Al2O3 calibration curve (3) Fe2O3 calibration curve (4) CaO calibration curve

MgO SO3 Na2O K2O

Intensity
Intensity
Intensity

Intensity
Std. value (mass%) Std. value (mass%) Std. value (mass%) Std. value (mass%)
(5) MgO calibration curve (6) SO3 calibration curve (7) Na2O calibration curve (8) K2O calibration curve

TiO2 P2O5 ZnO Mn2O3

Intensity

Intensity

Intensity

Intensity

Std. value (mass%) Std. value (mass%) Std. value (mass%) Std. value (mass%)
(9) TiO2 calibration curve (10) P2O5 calibration curve (11) ZnO calibration curve (12) Mn2O3 calibration curve

Cl Table 3 Calibration results (unit: mass%)

Analyte Calibration range Accuracy

SiO2 18.637 – 22.38 0.15

Intensity

Al2O3 3.875 – 7.06 0.096

Fe2O3 0.152 – 3.09 0.024
CaO 57.58 – 67.87 0.11
MgO 0.814 – 4.475 0.057
SO3 2.086 – 4.622 0.049
Na2O 0.021 – 1.068 0.0055
K2O 0.093 – 1.228 0.0027
Std. value (mass%)
TiO2 0.084 – 0.366 0.0022
(13) Cl calibration curve
P2O5 0.022 – 0.306 0.0014
Figure 2 Calibration curves of Portland cement ZnO 0.001 – 0.107 0.0009
Mn2O3 0.007 – 0.259 0.0029
Cl 0.0019 – 0.013 0.0007

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 XRF 1045

Qualification test for ASTM C114-11 the Table 4 comparing with the values of ASTM C114
Quantitative analyses have been carried out for the requirement.
seven NIST SRM’s of Portland cement using the cali- The results prove that the analysis method demon-
bration curves obtained above. The results are listed in strated in this application note meets the requirements
described in ASTM C114-11.
Table 4 Qualification rest results (unit: mass%)
Difference of the average
Difference between
duplicates
of duplicate from Repeatability test
Analyte the certificate values To demonstrate the stability of the instrument, the du-
Limit Maximum Limit Maximum
(ASTM) difference (ASTM) difference
plicated pressed pellets of NIST SRM 1889a were
SiO2 0.16 0.08 0.2 0.2
measured 10 times consecutively. The test results are
Al2O3 0.20 0.03 0.2 0.1
listed in Table 5. The results show the good measuring
Fe2O3 0.10 0.01 0.10 0.04
precisions.
CaO 0.20 0.12 0.3 0.2
In comparison with the values of the limits defined in
MgO 0.16 0.03 0.2 0.1
ASTM C114-11 shown in Table 4, the standard devia-
SO3 0.10 0.06 0.1 0.1
tions of the repeatability test obtained meet or exceed
Na2O 0.03 0.005 0.05 0.01
the ASTM C114 limits. The results demonstrate that
K2O 0.03 0.01 0.05 0.01
the performance of the Supermini200 meets or ex-
TiO2 0.02 0.003 0.03 0.004
ceeds the precision requirements for hydraulic cement
P2O5 0.03 0.003 0.03 0.003
analysis as stated in ASTM C114-11.
ZnO 0.03 0.001 0.03 0.002
Mn2O3 0.03 0.002 0.03 0.002
Conclusion
Cl 0.003 0.001 N/A 0.001
The qualification test for ASTM C114-11 demonstrated
that the test results on the Supermini200 using pressed
Table 5 Repeatability test results (unit: mass%) powder briquettes of wet-ground samples meet the
Results of 10-time consecutive measurements requirements for analysis of hydraulic cement defined
Certified
Analyte value
1st pressed pellet 2nd pressed pellet in ASTM C114-11.
(SRM1889a) Average
Standard
Average
Standard The precision obtained by the repeatability test is much
deviation deviation
better than the defined values required in ASTM
SiO2 20.66 20.714 0.032 20.700 0.017
C114-11.
Al2O3 3.89 3.857 0.007 3.851 0.010
The Supermini200 is a wavelength-dispersive
Fe2O3 1.937 1.915 0.005 1.917 0.008
benchtop X-ray fluorescence spectrometer equipped
CaO 65.34 65.349 0.031 65.388 0.026
with a newly developed high-power air-cooled X-ray
MgO 0.814 0.882 0.005 0.879 0.004
tube that does not require cooling water. The
SO3 2.69 2.671 0.004 2.695 0.005
spectrometer configuration results in high sensitivity,
Na2O 0.195 0.194 0.006 0.193 0.005
relative to benchtop energy-dispersive XRF
K2O 0.605 0.607 0.004 0.606 0.004
spectrometers, for light elements such as Na or Mg, as
TiO2 0.227 0.227 0.005 0.226 0.007
well as heavy elements.
P2O5 0.11 0.111 0.001 0.112 0.001
ZnO 0.0048 0.0050 0.0000 0.0047 0.0005
Reference
Mn2O3 0.2588 0.2590 0.0018 0.2607 0.0018
ASTM C114-11 Standard Test Methods for Chemical
Cl 0.0019 0.0018 0.0004 0.0015 0.0005
Analysis of Hydraulic Cement

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