Session I :Ore and mineral analysis.

Benchtop
and low power XRF solutions with Thermo
Scientific ARL products from upstream to
downstream in Smelter process (raw material to
final products)
Ling Yok Ung
Application Specialist
Southeast Asia & Taiwan
Bulk Elemental Analyzer Business

The world leader in serving science

1
Nickel Mining
Thermo Fisher solutions for mining customers

https://digital.ilensys.com/ThermoFisher/MiningToolKit2.0/

Exploration Beneficiation Mining Labs Safety

Iron & steel process map & capabilities
 Nickel Production Process
RKEF Process Matte
55-65
1 %Ni 1 ARL PERFORM’X XRF 2 ARL iSpark OES
1
Saprolite Stainless Sleel
1.5-2.1% Ni 6-26% Ni

1 2
Nickel Pig
Iron (NPI)
Nickel Laterite
4-13% Ni
Ore Ore
1

1 2 Limonite MHP/MSP Nickel Battery

0.8-1.5% Ni 35-40% Ni Cathode
1 1

HPAL Process
Source:
Various sources, SSI Research.
https://en.wikipedia.org/wiki/Nickel_pig_iron#:~:text=Impurities%20are%20then%20removed%20via,to%2013%20percent%20pure%20nickel.
China Battery Materials – Daiwa Capital Markets 19 July 2022
4 https://www.aperam.com/stainless/what-is-stainless-steel/#:~:text=0.015%20to%200.10%25%20carbon%2C%2016,makes%20stainless%20steel%20more%20ductile.
Thermo Scientific ARL Product Lines and Analytical
Techniques in metallurgy

1. OES: Optical Emission Spectrometry (Elemental and Inclusion Analysis in Metals)

2. XRF: X-ray Fluorescence (Elemental analysis of all types of materials)

3. Laboratory Automation (Automated Sample Preparation and Analysis, Sample and Results
Management)
 XRF and OES
The most common elemental analysis techniques in the metals industries

XRF OES
• All types of samples  metals and slags • Conducting samples  metals
• Especially good for major alloying elements • Especially good for trace and minor alloying
elements
• Most elements
• All elements, including light ones
• Mappings, macro inclusions analysis
• Analysis of non-metallic micro-inclusions

6
Our Key Customers in the Metals Industry

Our benefits: World-class analytical technologies

and the most complete portfolio of solutions
 OES: Optical Emission
Spectrometry (Elemental Analysis
in Metals)

8
 Why using Spark OES ?

• Extremely fast and simple quantitative analysis of metallic samples

• Can determine contents of > 30 elements from ppm to % levels in < 1 minute
• Including P, S, C, N, O

• Accurate, precise, and stable

• High reliability and availability

• Low costs of ownership and easy maintenance

• High instrument availability

9
Users, uses and applications of spark OES

Users Uses
• Process control
• Metals producers
• Final product quality control
• Foundries
• Certificate of analysis
• Metals processors
• Incoming materials control
• Metals recyclers, scrap dealers
• Metal sorting
• Service laboratories
• R&D, investigation
• Universities, research centers
Applications
• Quantitative elemental analysis
• Soluble/insoluble contents
• Inclusion analysis
• Grade check
• Positive material identification (PMI)
OES Product Portfolio
Value

ARL iSpark 8860

Automated with
ARL iSpark 8860
sample manipulation
systems (SMS)
with Advanced
ARL iSpark 8860 Inclusion Analysis

ARL iSpark 8820

ARL easySpark
 ARL easySpark
Best in class benchtop metals analyzer for single and multi base applications

• Ideal for process control and quality assurance in small and mid-size
foundries, and metals processing industries

• Key features and benefits

• High-performance CCD optics
• Wide elemental coverage
• Including N in steel and Na/Li in aluminum
• Accuracy and stability
• Easy to use thanks to easyOXSAS software
• Open stand with high safety to the operator
• Low-frequency, easy maintenance, and low cost of ownership
• Full spectrum display and line library for investigation or R&D of alloys

12
 ARL iSpark 8820
Ready-made high-performance solutions for iron & steel and aluminum

• Metal analyzers of the ARL iSpark family, custom designed for medium
size to large foundries, metal processors and metal producers

• Key features and benefits

• First-class PMT optics and technologies
• High performance, accuracy and stability for trace, minor and major elements
• Low Ar consumption and low operation costs
• Easy and fast maintenance
• Advanced signal acquisition and processing methods for all the channels

13
 ARL iSpark 8860
Top performance metals analyzer

• Metal analyzers of the ARL iSpark family for the most demanding steel
plants and metals producers, and all companies needing top analysis at
trace level

• Additional features and benefits versus ARL iSpark 8820

• Fully configurable single or multi base metals analyzer
• Applications in Fe, Al, Cu, Ni, Co, Ti, Pb, Sn, Ag, Au, Pd and Pt bases
• Up to 80 element channels
• Advanced ultra-fast inclusion analysis methods and inclusion analysis software tools

14
 X-Ray Fluorescence :
Elemental Analysis in Metals & Ores

15
X-ray Fluorescence Spectroscopy for Elemental Analysis

Wavelength Dispersive Integrated XRF and

XRD
XRF

Energy Dispersive
XRF
ARL PERFORM’X
High performance sequential XRF ARL 9900 Series
for advanced materials analysis Integrated XRF-XRD
For high-throughput QC/QA labs
in industries

ARL QUANT’X
Top performance
bench-top EDXRF
ARL OPTIM’X
As backup in the
metallurgy lab Economic and Convenient
WDXRF for routine analysis
What is so great about X-ray Fluorescence ?
• Precise, non-destructive multi-element analysis of conducting and non-conducting samples:
• Solids
• Liquids
• Loose powders

• Multi-element analysis:
• Beryllium to Americium
• Be to O require special conditions

• Inorganic and Organic materials

• High precision and highly reliable

• Wide dynamic range:

• sub-ppm to 100%

• Variety of sample types: bulk solids, liquids, loose powders, irregular samples, filters, thin
films - Analysis of totally unknown samples

• Powerful “standard-less” elemental analysis for totally unknown samples

• UniQuant: peak to peak standard-less analysis, best limits of detection
• QuantAS: scan based semi-quantitative analysis
Thermo Scientific WDXRF Systems

ARL PERFORM’X XRF Uniquely differentiating XRF analyzer for bulk and small samples
• Advanced and versatile sample analysis
• Closely Coupled Optics for highest performance from Boron to Uranium
• Faster analysis cycle time for high throughput lab applications at 4200W
• 1500W and 2500W versions without external water cooling
• Ability for small spot and mapping of non-homogenous or defect samples
• XY-loader for fully automated sample management
• IQ/OQ & Remote Diagnostics for easy installation and serviceability

Markets:
• Steel and super-alloys
• Slags, ferro-alloys and other raw materials
• Copper, brass and bronze
• Aluminium alloys
• Zinc and tin alloys
• Precious metals
• Petroleum/Petrochemicals
• Polymers and Chemicals
• Geochemistry
• Contract Laboratory
• Process/Manufacturing Materials Characterization
• Environmental
Thermo Scientific WDXRF and EDXRF Systems

ARL OPTIM’X XRF • Entry level, compact WDXRF instrument with a unique combination
of sequential and simultaneous devices
• Markets
• Slags, ferro-alloys and other raw materials
• Basic oxides
• Refineries
• Food and chemicals
• Back-up in large cement plants

• High performance Energy Dispersive XRF with latest SDD

technology
• Markets
• Slags and ferro-alloys as backup
• Aerosol particulate filters
• RoHS and WEEE compliancy analysis
• Forensics and trace analysis
• Petrochemical
ARL QUANT’X • Nutritional supplements
• Magnetic media and semiconductors
Thermo Scientific WDXRF Systems
ARL 9900 X-ray spectrometer
• Compact, modular XRF instrument for rapid elemental
sim/seq analysis
• Up to 32 elements analyzed within one minute
• Specific phase analysis using full integrated XRD system (Fe2+ in
sinters of Direct Reduced Iron monitoring)
• Markets
• Iron and Steel
• Aluminum and copper
• Mining and metal extraction
• Cement

ARL 9900 XRF spectrometer automated with SMS-XY or SMS-2500/SMS-3500

• Can be easily automated either with a large sample
changer ARL SMS-XY or an industrial robot ARL SMS-
2500

• With the ARL SMS-3500 series, two spectrometers

(OES and/or XRF) can be fully automated with the
same robot
 XRF Applications

21
 Mining applications

Analysis of nickel ores in air

ARL QUANT’X EDXRF 50W Benchtop

spectrometer
Pressed Pellet Sample Preparation

22
Preparation of rocks and minerals as pressed powder briquets
To prevent analytical problems due to grain size effects, it is recommended to grind to less than 50 microns

Briquet method

Crush, grind Apply pressure

and mix To standard holder
To grain Press
size <90um
5
Weigh out
Die
Protective ring

Mortar or crusher Specimen

9499D00400
 Nickel ores analysis in air
Calibration results

• 17 nickel ore certified standards were used

• Samples were pressed at 20 tons without binder
• On a borax support
• Concentration data are entered together with the intensities obtained on the various elements
• Allows to check how well the various points would align on the calibration curves.
• The results for the various elements: Mg, Al, Si, S, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu and Zn are
shown in the next slides.
• These results show that the ARL Quant’X can provide good results for most elements in mining
material without helium and without vacuum !
• Analysis in air would give significant advantages in terms of operation & maintenance of the
instrument due to the remote locations of the mines

24
Nickel ores

• Pressed pellets at 20 tons without binder

• 3 analytical conditions for 5 minutes live time
• 10 minutes total time
• Long counting time on Mg, Al, Si is required
• due to high absorption by air
MgO & SiO2 in nickel ores – pressed pellets

• ARL Quant’X EDXRF - Air environment

• Mg is absorbed 200 times in air compared to vacuum • Si is absorbed 18 times in air compared to vacuum
Ni & Co in nickel ores – pressed pellets

• ARL Quant’X EDXRF - Air environment

 Nickel ores – pressed pellets
Spectrometer precision test on same pressed pellet – 10 repeats

• ARL Quant’X EDXRF - Air environment – total counting time 10 minutes

28
 Conclusion about EDXRF analysis in air

• Analysis of nickel ores is feasible in air with an ARL Quant’X benchtop EDXRF
• Heavy absorption of Mg, Al and Si XRF signals requires at least 10 minutes total
counting time
• Can by useful for remote mines with little means
• Grinding and pressing of samples is a must
• Ensures some kind of precision and accuracy

29
 Mining applications

Analysis of iron ores and nickel ores

ARL OPTIM’X WDXRF 50W spectrometer

Fused beads sample preparation

30
ARL Optim’X WDXRF low power

UCCO technology
• 200W analytical power from 50W tube
• 500W analytical power from 200W tube
 Ni ores - Fused bead sample preparation

• ARL Optim’X
• 50W
• Total counting time: 10 minutes 40s
• Sample preparation
• Dilution 1:20
• Ammonium nitrate oxidizer

32
Preparation of Powders as Fused bead

The fusion of mineral, ceramic or raw materials

samples into an amorphous glass disk (also called
bead) allows to prevent analytical problems due to
grain size effects and mineralogical effects

Melting method

Heat for
Weigh out Cast & Cool
Melting
and mix

Flux + Specimen 1000° -1100° C

To standard holder
Glass disk
specimen
Platinum crucible Remove bubbles
9499D00500
 Ni ores – Calibration ranges and accuracy

• ARL Optim’X
• 50W
• Total counting time: 10 minutes 24s
• Sample preparation
• Dilution 1:20
• Ammonium nitrate oxidizer

• Same results can be obtained with 200W power

in 4 minutes 16s total counting time
• Same results can be obtained with ARL
PERFORM’X at 1500W in about 2 minutes
counting time

34
 NiO and Fe2O3 calibration curves – fused beads

• ARL Optim’X at 50W

NiO calibration graph Fe2O3 calibration graph

35
Iron Ore Analysis Using WDXRF
• Measurement conditions for 12 elements
• 7.6 minutes total measurement time : Al, Ca, Cr, Fe, K, Mg, Mn, Si, Ti, P, S, and V
• Using the 50 W ARL OPTIM’X Spectrometer, data was collected at condition of 30 kV and 1.67 mA, taking 36
seconds of analysis time for each element (with the exception of Mg, which required 60 seconds)
• Other elements can be added if required
• Calibration was performed using 7 iron ore certified reference materials (CRMs). Samples were fused into
beads, without ignition, with a sample to flux ratio of 1:10. Ammonium nitrate oxidizer was added to the fusion
mix.
Conclusion

• ARL Optim’X at 50W can analyze Ni ores as fused beads in about 10 minutes

• The 200W version would permit to reach the same precision in 4 minutes counting time

• An ARL Perform’X 2500W provides twice better precision in the same 4 minutes

• As a goniometer is used both in ARL Optim’X and in ARL Perform’X the counting times can be
chosen independantly for each element/oxide depending on the precision required

• For the best performance, higher power XRF spectrometer can be chosen
• Simultaneous- sequential XRF to ensure best analysis speed and high analytical flexibility
 Mining applications

ARL 9900 high power WDXRF spectrometer

38
ARL 9900 Simultaneous/Sequential XRF

• Compact, modular XRF instrument for rapid

elemental simultaneous/sequential analysis

• Power versions
• 1500W – 2500W – 4200W

• Various possible configurations

• Up to 32 fixed channels
• Up to 24 fixed channels with one goniometer

ARL 9900 XRF Series

 Fast XRF analysis

XRF XRF
XRF
X-RayXRF
XRF
XRF
Goniometer Tube XRF
XRF
XRF
Fixed
Fixedchannel
Fixedchannel
Fixedchannel
channel
Fixed channel
Fixed XRF
XRF
channel
Sequential Elemental
Elemental
Elemental
Elemental
Elemental
Fixed
analysis
analysis
analysis
Fixed
analysis XRF
channel
XRF
analysis channel
elemental Elemental
Information
Information on
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thethe
Information
elements
ononFixed
Elemental XRF
analysis
onFixed
inElemental
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on
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analysis channel
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XRF
in Fixed channel
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in
Fixed
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sample
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sample in
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Fixed Elemental
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channel
Information
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channel
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sample
elements
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onin
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• Fast XRF analysis with fixed channels Sample the elements
the in
sample
the sample
the sample
• Each one is dedicated for one element
• Flexibility of analysis of 84 elements with the goniometer
• Analysis concurrently with fixed channels analysis

40
 Calibration for Iron ores
Element Min Max
ISO 9516 Fe (%) 52,46 71,51
SiO2 (%) 0,02 10,89
Al2O3 (%) 0,077 5,137
• Reference calibration for iron ores TiO2 (%) 0,002 10,210
• According to ISO 9516-1 2003 - Standard method Mn (%) 0,048 2,593
CaO (%) 0,014 9,510
for XRF analysis of iron ores P (%) 0,005 1,610
• Preparation as fused beads S (%) 0,002 1,081
MgO (%) 0,005 1,491
• 11:1 dilution K2O (%) 0,003 0,160
• Lithium tetraborate- Lithium metaborate mixture Na2O (%) 0,008 0,150
V (%) 0,002 0,437
Cr (%) 0,001 0,268
Co (%) 0,001 0,015
Ni (%) 0,002 0,154
Cu (%) 0,001 0,009
Zn (%) 0,001 0,028
As (%) 0,002 0,039
Sr (%) 0,003 0,007
Zr (%) 0,002 0,008
Ba (%) 0,004 0,340
Pb (%) 0,002 0,056

41
General oxide calibration – raw materials
Elements Range (%) Typical SEE (%)

Ignited Samples Ignited Samples

Na2O 0.4-10.4 0.1
MgO 0.2-97.3 0.22
Al2O3 0.2-89.2 0.16
SiO2 0.3-99.7 0.23
P2O5 • Wide ranges can be covered completely
0.06-40.0 0.11
using a preparation technique as fused
SO3 0.05-2.92-46.2 0.05 beads (using dilution 12 with Li
K2O 0.03-15.4 0.03 tetraborate flux or Li tetraborate + Li
CaO 0.03-94.4 0.32 metaborate)
TiO2 0.02-3.8 0.03 • Better accuracy by
Cr2O3 • Reducing mineralogical effects
0.02-17.4 0.03
MnO • Eliminating inhomogeneous samples
0.02-8.0 0.01
• Matrix normalization
Fe2O3 0.03-94 0.15
 Minerals, Refractories and Ceramics
Ceramin calibration

• Wide ranges can be covered completely using a preparation

technique as fused beads (using dilution 12 with Li tetraborate
flux or Li tetraborate + Li metaborate)
• Better accuracy by
• Reducing mineralogical effects
• Eliminating inhomogeneous samples
• Matrix normalization
• 24 elements/oxides including several traces.
• covers minerals like clay, dolomite, limestone, bentonite, marl,
sand, laterite, feldspar, bauxite, magnesite, firebrick, silica brick,
sillimanite, rocks, slags, cement, zircon ores, rutile, illmenite and
ceramics.

43
 Standardless Analysis:
UniQuant

44
 What is UniQuant?

• Original and most powerful standard-less

XRF program
• Most advanced and powerful Fundamental
Parameters algorithms
• Standard-less analysis package for semi-
quantitative to quantitative analysis
• Fully pre-calibrated and factory installed
What‘s in the box?
• SUS samples to maintain the calibration
• 9 CAL samples as setting up samples (SUS) + 1
teflon sample
• Available for all ARL XRF spectrometers • 1 dongle
• ‘Uniquantometers’ • Software delivered with OXSAS or Wintrace on
USB flash drive

45
Why Use UniQuant®?
CONVENTIONAL METHOD
1. Sample 2. Search & buy 3. Measure 4. Analyze unknown 5. Quantitative
& Preparation matching Standards + sample prepared results
Standards Calibrate

UniQuant® METHOD
1. Sample
& prepared or
2. Search & buy 3. Measure 2. Analyze unknown 3. Quantitative
not
matching Standards + sample prepared results
Standards Calibrate or not
 How does UniQuant work?
The measurement

• UniQuant does not work on a fine step scan of

the entire spectrum
• UniQuant measures peak-to-peak

Peak to peak analysis permits:

 Lower limits of detection – measurement time
spent collecting relevant signal
 Selective counting time, per element
 Use of sample spinning
 In case of small samples
 In case of inhomogeneous samples

47
 How does UniQuant work?
Validation
Comparison of reference values and UniQuant results
• CDA 922 Copper alloy
• RENE 41 Nickel Alloy
• SS484 tool steel (solid and drillings)
• S1 basic slag
• Nim G Granite (majors)
• Nim G Granite (traces)
• Environmental sample
• Polyproylene
• Hast X (Nickel alloy)
• Steel A286
• Cement NIST 1885
• Flint Clay NIST 97b
• BCS 380 aluminum alloy drillings
• BCS 364 leaded bronze drillings

26
 Automated laboratories
Automated cabins

49
Full automation for pressed pellets (e.g., slags and ores)
• Samples are milled and pressed automatically in a steel ring
• Usually, 40mm or 51.5mm steel rings
• Sample travels on transport belt to the XY loader of ARL 9900

Courtesy Sococim
Automation Product Portfolio

• Automation of OES and XRF spectrometers

• Up to two sample-preparation machines
• Single source including the Thermo Scientific robot
• Markets
• Primary metals producers
• Fabricated metals products
• Industrial equipment, transportation
• Service labs, QA/QC, production control
SMS-2500
Conclusion

• Mining applications can be addressed by different types of XRF spectrometers depending on the
requirements
• EDXRF system without helium nor vacuum can satisfy the needs in very remote locations
• Low power WDXRF shows excellent accuracy on fused beads
• Precision and speed of analysis can be increased by using a higher power XRF spectrometer

• Modern XRF spectrometers can be fully automated to allow unattended operation 24/7
 Thank you
53