•ABRAM L. BODIBA, EZEKIEL D. DIKIO, MICHAEL HORSFALL
• TEST & MEASUREMENT 2016 CONFERENCE & WORKSHOP • 26 - 28 SEPTEMBER 2016
ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE ON X-RAY FLUORESCENCE
Introduction
Sampling process
Sample preparation
Instrumentation
Calibration
Results
Conclusion
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 2
•CONTENTS
•Manganese is the 12th most abundant
element.
•Manganese plays an important role in
Steel production
Battery production
Dietary additives
Chemical production
Aluminum beverages cans
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 3
•INTRODUCTION
SLIDE 4
•INTRODUCTION
The manganese deposit
in the Kalahari basin is
the biggest mineral
deposit in the world
known to man
The Kalahari situated
60km northwest of
Kuruman in the Northern
Cape Province of South
Africa
Kalahari basin Contains
around 90% of the
world’s manganese ore
reserves
Manganese mining is one of the major
activities taking place within the
Kalahari region.
The lower grade mines are open pit
and high grade mines are underground
A rapid grade analysis is required to
make decision for ore selective mining,
stockpiling, and Rail loading
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 5
•INTRODUCTION
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 6
•SAMPLING
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 7
•SAMPLING
•It is well known that sampling and sample preparation are
the source of errors on XRF analysis
•The errors occur during
Sampling
Sample reduction
Sample mixing
Sample division
Sample preparartion
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 8
•SAMPLING
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 9
•SAMPLE PREPARATION
•All samples were prepared under controlled conditions,
including
The pulverizing
Pulverizing mass and time,
pelletizing pressure and holding time
The samples were pulverized to 100% passing 75 μm
sieves.
•40 samples were collected to be used as secondary
reference standard
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 10
•SAMPLE PREPARATION
Press pellet must comply with some physical conditions:
Must have a flat surface for analysis
Must be homogenous.
Must be stable under vacuum
Must be infinitely thick for the x-ray wavelength to be measured.
Must have a consistent thickness.
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 11
•SAMPLE PREPARATION
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 12
•CALIBRATION STANDARD
Name %Mn %Fe %CaO %MgO %SiO2 %Al2O3 %P
BLANK 0.000 0.000 0.000 0.000 0.000 0.000 0.000
ES 5 38.400 5.500 13.938 3.873 4.645 0.230 0.023
ES 4 33.700 4.300 14.921 3.964 5.635 0.236 0.023
ES 33 30.667 4.300 15.239 6.714 4.666 0.296 0.023
ES 32 17.050 6.800 15.750 4.035 4.520 0.246 0.021
ES 31 12.548 7.700 24.657 3.718 6.717 0.291 0.023
ES 30 7.431 10.500 19.769 8.650 4.750 0.351 0.027
ES 3 34.000 4.500 14.541 3.392 4.084 0.272 0.020
ES 29 8.679 8.300 15.695 3.542 2.617 0.285 0.024
ES 28 37.300 4.300 12.301 3.535 4.959 0.262 0.067
ES 20 32.100 4.400 14.628 3.688 4.695 0.252 0.071
ES 19 6.000 12.000 14.979 9.863 3.662 0.261 0.052
ES 15 35.800 6.500 10.366 4.155 3.024 0.540 0.103
ES 13 36.700 10.100 14.669 3.873 4.914 0.268 0.029
ES 10 24.615 8.900 17.438 4.158 5.404 0.250 0.060
EL 9 38.100 4.300 14.537 2.989 4.560 0.174 0.018
EL 8 38.000 4.000 14.655 3.574 4.458 0.186 0.020
EL 6 38.900 2.900 14.938 2.823 3.326 0.181 0.019
Name %Mn %Fe %CaO %MgO %SiO2 %Al2O3 %P
EL 3 38.900 3.900 14.232 3.257 1.246 0.190 0.020
EL 23 37.800 4.400 13.198 3.969 4.526 0.282 0.020
EL 22 37.100 4.000 14.411 4.133 4.696 0.230 0.021
EL 2 40.800 3.800 8.919 1.795 5.678 0.215 0.020
EL 19 35.200 4.200 20.901 3.722 8.532 0.265 0.092
EL 18 36.600 4.000 14.968 5.292 4.508 0.264 0.046
EL 17 21.882 4.500 17.816 4.007 4.776 0.296 0.069
EL 16 26.538 5.200 14.851 3.510 4.738 0.286 0.075
EL 15 20.300 5.300 14.296 4.333 2.388 0.196 0.087
EL 14 39.300 4.400 14.550 5.866 4.540 0.247 0.051
EL 13 38.500 4.400 14.285 3.653 4.562 0.260 0.039
EL 11 38.100 4.600 13.254 2.333 4.724 0.216 0.084
EL 1 39.4 4.1 13.542 4.367 7.894 0.842 0.022
RR1 39.4 4.21 13.24 3.11 4.65 0.22 0.02
EL 5 42.059 4.5 13.206 2.862 6.352 0.172 0.023
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 13
•CALIBRATION STANDARD
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 14
•CALIBRATION
Calibration range
Name Low Max
%Mn 0.00 43.025
%Fe 0.00 12.000
%CaO 0.00 24.657
%MgO 0.00 9.863
%SiO2 0.00 8.532
%Al2O3 0.00 0.842
%P 0.00 0.103
Typical Low grade Manganese
Name Typical value
%Mn 37.000
%Fe 4.000
%CaO 14.000
%MgO 3.000
%SiO2 4.000
%Al2O3 0.200
%P 0.020
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 15
•LOWER GRADE MINERALOGICAL
COMPOSITION OF KALAHARI BASIN Kalahari low grade manganese
Mineral Compositions
Braunite Mn2Mn6SiO12
Kutnohorite Ca(Mn,Mg,Fe++)(CO3)
2
Calcite CaCO3
Hausmannite Mn3O4
Hematite Fe2O3
Bixbyite (Mn,Fe)2O3
Manganite MnO(OH)
Braunite 2 Ca(Mn,Fe)14SiO24
Position [°2θ] (Copper (Cu))
10 20 30 40 50 60 70
Counts
1000
2000
3000
Thorn Inifinity_FY_14_A
Peak List
Bixbyite C; Mn2 O3
Hematite; Fe2 O3
Hausmannite; Mn3 O4
Manganite; Mn O ( O H )
Braunite-1Q; Mn +2 Mn6 +3 Si O12
Braunite-2Q; Ca Mn11.6 Fe2.4 Si O24
Kutnohorite, magnesian; C2 Ca1 Fe0.13 Mg0.23 Mn0.64 O6
Calcite, syn; Ca ( C O3 )
Position [°2θ] (Copper (Cu))
10 20 30 40 50 60 70
Counts
1000
2000
3000
Lab_Std 2_FY_14
Peak List
Bixbyite C; Mn2 O3
Hematite; Fe2 O3
Hausmannite; Mn3 O4
Manganite; Mn O ( O H )
Braunite-1Q; Mn +2 Mn6 +3 Si O12
Braunite-2Q; Ca Mn11.6 Fe2.4 Si O24
Kutnohorite, magnesian; C2 Ca1 Fe0.13 Mg0.23 Mn0.64 O6
Calcite, syn; Ca ( C O3 )
Position [°2θ] (Copper (Cu))
10 20 30 40 50 60 70
Counts
1000
2000
3000
Tripple Star_FY_14_B
Peak List
Bixbyite C; Mn2 O3
Hematite; Fe2 O3
Hausmannite; Mn3 O4
Manganite; Mn O ( O H )
Braunite-1Q; Mn +2 Mn6 +3 Si O12
Braunite-2Q; Ca Mn11.6 Fe2.4 Si O24
Kutnohorite, magnesian; C2 Ca1 Fe0.13 Mg0.23 Mn0.64 O6
Calcite, syn; Ca ( C O3 )
North mine
Central mine
South mine
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 16
•INSTRUMENTATION
XRF generally consist of four basic
components:
• An excitation source - X-ray tube
• A sample
• A detector
• A data collection and analyzing
system.
ElementMono/
GonioCollimator Crystal Detector
Counting
Time (s)Filter
Mn Mono 0.25 LiF200 ExKrBe 30 on
Fe Mono 0.25 LiF200 Sc 30 on
Ca Mono 0.60 LiF200 ExArBe 30 None
Mg Mono 0.60 AX03 FPC 30 None
Si Mono 0.60 PET FPC 30 None
Al Mono 0.60 PET FPC 30 None
P Mono 0.60 Ge111 ExNeBe 30 None
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 17
•INSTRUMENTATION SETUP
• Thermo Fischer scientific advance 9900 series
• QXAS program
• 3.6 kW Rh X-ray tube
• Monochrometer (fixed channel)
• The current 50mA
• Voltage 50kV
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 18
•CALIBRATION LINES
Mn
• A total of four standards were removed from
the calibration as outlier.
• four standards had high percentage
differences.
• Three standards were also removed to
improve the correlation on the graph
• The correlation coefficient is 0.9995 which
indicates a good correlation between the given
concentrations and intensities
Fe
• A total of 36 standards was used, no standard
were removed from the calibration as outlier.
• Six standards were removed to improve the
correlation on the graph.
• The correlation coefficient is 0.9995 which
indicates a good correlation between the given
concentrations and intensities
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 19
•CALIBRATION LINES
CaO
• A total of ten standards were removed from
the calibration as outlier
• The standards had high percentage
differences.
• One standard was also removed to improve
the correlation
• The correlation coefficient is 0.9996 which
indicates a good correlation between the
given concentrations and intensities
SiO2
• Four standards were removed to improve the
correlation on the graph
• The correlation coefficient is 0.9993 which
indicates a good correlation between the
given concentrations and intensities
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 20
•CALIBRATION LINE CONT.
Al2O3
• A total of 36 standards was used, no standard
were removed from the calibration as outlier
• Sixteen standards were removed to improve
the correlation on the graph.
• The correlation coefficient is 0.9960 which
indicates a good correlation between the given
concentrations and intensities
MgO
• Eight standards were also removed to
improve the correlation on the graph
• The correlation coefficient is 0.9991 which
indicates a good correlation between the
given concentrations and intensities
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 21
•CALIBRATION LINE CONT.
30 Yes
Inc.
2
[kcps]
40 66 20 150 2 20 66.16
Threshold Window Start End Inc. Global
ø29 mm Yes Norm
Energy Profile data
PHD Param [Step] Count.Time [s] Count Rate
Ca_m LiF200 ExArBe 80 None
mA PBF/
PBD
Mask Rotatio
n
AGC Type
Energy Profile Parameters
Element/Line Gonio Crystal Detector Collimato
r
kV
Energy Profile
Instrument: ARL 9900
File Information
P
• A total of 36 standards were used,
• five standards were removed from the
calibration as outlier.
• Five standards were removed to improve
the correlation on the graph.
• The correlation coefficient is 0.9980 which
indicates a good correlation between the
given concentrations and intensities
R2 SEE LOD Samples
Mn 0.9995 0.2916 0.001 29
Fe 0.9995 0.0606 0.00121 30
CaO 0.9996 0.0943 - 25
MgO 0.9991 0.0550 0.00418 32
SiO2 0.9993 0.0507 - 28
Al2O3 0.9960 0.0106 - 20
P 0.9980 0.0012 0.0008 26
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 22
•CALIBRATION SUMMARY
Name %Mn %Fe %CaO %SiO2 %MgO %Al2O3 %P
Sarm 138 37.230 5.792 13.230 6.309 3.839 0.197 0.019
Amis 407 36.210 4.160 15.680 5.610 3.220 0.291 0.019
SARM 17 38.661 4.311 14.415 4.637 3.183 0.221 0.019
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 23
•CRM
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 24
•EVALUATION (SARM 138)
Sarm 138 Sarm 138 CRM value
Element Results True value SD Absolute variance % Recovery
%Mn 37.230 37.500 ± 0.64 0.27 99.3%
%Fe 5.792 5.740 ± 0.11 0.05 100.9%
%CaO 13.230 13.010 ± 0.30 0.22 101.7%
%SiO2 6.309 6.060 ± 0.22 0.25 104.1%
%MgO 3.839 3.810 ± 0.08 0.03 100.8%
%Al2O3 0.197 0.198 ± 0.01 0.00 99.5%
%P 0.019 0.018 ± 0.02 0.00 108.6%
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 25
•EVALUATION (AMIS 407)
Amis 407 Amis 407 CRM Value Absolute variance % Recovery
%Mn 36.210 36.25± 0.57 0.04 99.9%
%Fe 4.160 4.22± 0.13 0.06 98.6%
%CaO 15.680 15.81± 0.48 0.13 99.2%
%SiO25.610 5.51± 0.16 0.10 101.8%
%MgO 3.220 3.17± 0.10 0.05 101.6%
%Al2O30.291 0.29± 0.03 0.00 100.3%
%P 0.019 0.02± 0.01 0.00 108.8%
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 26
•EVALUATION (SARM 17)
SARM 17 SARM 17 CRM value Absolute variance % Recovery
%Mn 38.661 38.810 ± 0.300 0.15 99.6%
%Fe 4.311 4.270 ± 0.090 0.04 101.0%
%CaO 14.415 14.400 ± 0.900 0.02 100.1%
%SiO2 4.637 4.690 ± 0.240 0.05 98.9%
%MgO 3.183 3.030 ± 0.180 0.15 105.0%
%Al2O3 0.221 0.240 ± 0.120 0.02 92.1%
%P 0.019 0.018 ± 0.015 0.00 103.3%
Low grade
PP
Consensus
true value
Consensus
Standard
deviation
Relative
percentage
difference
Z-score
%Mn 33.700 33.765 0.143 0.065 -0.456
%Fe 5.260 5.300 0.051 0.040 -0.785
%SiO2 5.410 5.400 0.116 -0.010 0.086
%CaO 18.760 18.280 0.595 -0.481 0.808
%MgO 2.970 2.960 0.094 -0.010 0.106
%Al2O3 0.210 0.219 0.037 0.009 -0.228
%P 0.022 0.019 0.001 -0.003 2.167
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 27
•INTER-LABORATORY COMPARISON
Kalahari Manganese Round Robin Scheme
Advantage of press pellets techniques
•Ease of preparation
•Offer quick turnaround time
•Low cost
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 28
•CONCLUSION
•The results showed good agreement with the certified
value of the CRM’s.
•Inter-laboratory comparison was satisfactory.
•Matrix matching press pellets provide a fast and simple
analysis method.
•Acceptable accuracy level for production
26 SEP 2016ACCURACY EVALUATION OF MATRIX MATCHING CALIBRATION OF MANGANESE ORE
ON XRFSLIDE 29
•CONCLUSION
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