industrial minerals â€“ how onsite x-ray analysis saves money

Industrial Minerals –How Onsite X-ray Analysis Saves Money

Welcome

Alexander SeyfarthXRF Product Manager

Today’s Topics:What you will learn:

How XRD and XRF increase production quality and quantity while reducing analysis time and costThe differences between X-ray and other analytical methods to help you make informed decisions about the best approach for process controlCase studies demonstrating the practical use of XRD and XRF

Introduction – What to analyze for?Elemental Analysis with XRFPhase Analysis with XRDCombined XRD-XRF for Cost-Effective Onsite AnalysisSummaryQ&A

Holger CordesSenior Applications Scientist XRD

Arkady BumanXRF Business Development Manager

Introduction

Industrial Minerals… what are we talking about?

Industrial minerals are geological materials, which are widely used as raw material and additive in a wide range of industrial applications and processes:• Ceramics • Glass• Construction• Paints• Chemicals• Plastics• Paper• Electronics

Industrial MineralsMaterials

Typical Industrial Minerals are Limestone SandKaolinBentoniteSilicaBariteGypsumTalc

At the end of the process powerful analytical tools are required to allow a close control of the mining process and to establish an accurate quality control.

Dolomite, "Grube Clara", Oberwolfach, Black Forest

Industrial MineralsAnalysis of Materials

Today the challenge is to establish an analytical procedure in the process which is flexible to meet changing qualityrequirements and to ensure shortest time to results.

The Analysis adds VALUE and establishes the suitability of a product to be used in specific applications

Each application defines the final quality criteria regarding elemental and phase composition, impurities, grain size…

For example:Sand for Glass Industry (Fe content)Kaolin for Paper Industry (Fe content, mineral composition)Kyanite for Refractories (mineral composition, Al/Si and Fe)Clay as filler for Polymers (mineral type and composition)

Industrial MineralsWhat to analyze for?

Chemical Composition• ELEMENTAL concentrations • Which elements are present?• How much is there (weight %)?

Mineral (Crystalline) Phase Composition• MINERAL analysis or phase analysis• What minerals are present?• How much of each?• Physical properties such as crystallite size, strain, texture• Glass or amorphous content

Methods for Elemental Analysis

Inorganic elemental analysis can be accomplished by a number of methods, including:• Optical spectroscopy

o probes the outer electronic structure of atoms – Flame atomic absorption – Graphite furnace atomic absorption – Optical emission e.g. ICP OES

• X-ray fluorescence spectroscopyo probes the inner electronic structure of atoms

Please use your mouse to answer the question on the right of your screen:

What methods or techniques are you currently using for the analysis of your materials? (Check all that apply.)

Titration (e.g. Mg, Ca)ICP (Multielement)AAS (Multielement) XRF Spectroscopy (EDXRF or WDXRF)Gravimetric Determinations (e.g. SiO2)XRD Powder Diffraction Microscopy on thin sectionsMicroscopy on grain mounts Electron microscopy & microanalysis

Audience Poll

Elemental Analysis with XRF

Arkady Buman

Elemental Analysis Using Electromagnetic Radiation: X-rays

Emission of characteristic X-rays• XRF - X-ray Fluorescence

Analysis

Transitions of electrons between inner shells of the atomEnergy of characteristic X-rays independent of chemical bindingSolid and liquid samples can be measured directly (NO digestion needed!)

X-ray Fluorescence AnalysisEnergy-dispersive XRF (EDXRF)

The detector is used to record both

the energy E and the number N

of X-ray photons

Sample

X-ray Fluorescence Analysis Wavelength-dispersive XRF (WDXRF)

An analyzer crystal separates the various wavelengths λ (energies)

The detector records only the number N of X-ray photons at a given wavelength (energy)

Sample

Industrial MineralsEasy, Fast and Safe Sample Preparation

Loose powder the quick and simple preparation method(30 s) The loose powder of the minerals are just poured in a cup

and measured directly

Pressed pellet widely used preparation method for process control(5 min) The powder is pressed to form a stable pellet for better

accuracy and precision

Fused bead most accurate and precise method(10 min) The material is ignited with Li-Borate flux in a furnace to

form a stable glass bead. Matrix influences are reduced.

Analytical PerformanceAdvantages Using XRF for Industrial Minerals

XRF as the analytical tool for process and quality control for industrial minerals provides:

qualitative and quantitative analysis fast and easy sample preparationelements from Be to U in all kind of sampleseven light elements, like B, C, N, O and Fstandardless calibration for all materialslinear concentration range from ppm to 100%highest accuracy and reproducibility up to 0.05% (rel.) typical detection limits (LLD): ~ 1 to 10 ppm

The main requirements for the industrial mineral business are easily met by XRF, like:

shortest time to result for a close monitoring of the mining processthe simple and fast sample preparation procedure, the high analytical flexibility and ease of use

Quartz Sand Analysis

Quartz sand value is a function of its iron content

The less iron. the higher the achievable price (e.g. play sand to glass sand)

Other elements can be important as well (Na2O, K2O, CaO) as they are used to asses the phase content of Feldspar in a sand.

Fast Determination of Fe in Sand

Fine ground powder to ensure homogeneous sample from grab composite (e.g. silo), or direct sand if grain size of sand is around 70 microns

Loose powder or pellet preparation

Accuracy achievable is limited by reference material and repeatability of preparation (e.g. fineness of material)

100 sec measurement at a count rate of > 100 000 yields an accuracy of Fe +/- 6 ppm

Precision is limited by preparation but 10 ppm is readily achievable on a pellet

XRF for Flexible and Fast Multielement Analysis of Industrial Minerals

A typical application for industrial minerals is the determination of the elemental composition of the product for the major and minor concentration level. For specific products, also, elements at the trace level must be analyzed.

The analysis of the Feldspar composition is a representative example for such an analytical job.

The Feldspar samples in this case are prepared as pressed pellets to meet the requirements for higher accuracy and better precision.

Industrial MineralsElemental Analysis of FeldsparNa,K (AlSi3O8) to Ca2 (AlSi3O8)

Feldspar is used in porcelain, ceramic and glass production. It is often used to reduce the melting temperature of quartz and to control the viscosity of molten glass.

Analytical Task:Process control to sort the material from the quarry and quality control of the raw products for the ceramics industry

Determine the concentrations of Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, Fe2O3, Rb, Sr, Zr, and Ba in a range of major, minor and trace concentration levels

Date: 01-11-19 Na2O MgO Al2O3 SiO2 P2O5 K2O CaO TiO2 Fe2O3 Rb Sr Zr Ba

Average(%) 6.93 0.14 16.14 73.37 0.11 1.67 0.95 0.07 0.17 0.00 0.03 0.02 0.02

STD Dev.(%) 0.010 0.002 0.02 0.03 0.001 0.002 0.0010 0.0009 0.0004 0.00008 0.00008 0.00017 0.0008

STD Dev. Rel.(% 0.1 1.2 0.1 0.0 1.2 0.1 0.1 1.2 0.2 1.6 0.3 0.9 5.2


Average(%) 6.92 0.14 16.12 73.23 0.13 1.67 0.95 0.07 0.17 0.00 0.03 0.02 0.02

STD Dev.(%) 0.010 0.003 0.01 0.04 0.002 0.002 0.0017 0.0007 0.0003 0.00007 0.00009 0.00012 0.0005

STD Dev. Rel.(% 0.1 2.1 0.1 0.1 1.4 0.1 0.2 1.0 0.2 1.5 0.3 0.6 3.6


Average(%) 6.92 0.14 16.13 73.26 0.13 1.67 0.95 0.07 0.17 0.00 0.03 0.02 0.02

STD Dev.(%) 0.014 0.003 0.01 0.04 0.002 0.002 0.0017 0.0008 0.0004 0.00004 0.00011 0.00015 0.0008

STD Dev. Rel.(% 0.2 1.8 0.1 0.1 1.4 0.1 0.2 1.1 0.2 0.8 0.4 0.8 5.6

Total of three days

Average(%) 6.92 0.14 16.13 73.29 0.12 1.67 0.95 0.07 0.17 0.00 0.03 0.02 0.02

STD Dev.(%) 0.012 0.003 0.02 0.07 0.004 0.002 0.0017 0.0008 0.0004 0.00007 0.00010 0.00015 0.0007

STD Dev. Rel.(% 0.2 1.9 0.1 0.1 3.3 0.1 0.2 1.1 0.2 1.3 0.4 0.7 4.7

Industrial MineralsElemental Analysis of Feldspar K(AlSi3O8)

Unrivalled analytical performance with WDXRF!

Precision and accuracy:

XRF – Flexible, Multielement Analysis of Industrial Minerals

The example of the routine Feldsparanalysis shows that XRF achieves:

highest precision down to 0.05%unrivalled long term stability reliable trace analysis

XRF allows close monitoring of mining processes and of the product quality.

Applying WDXRF immediately pays for itself by ensuring optimal product quality.

XRF – Fast Multielement Analysis of Industrial Minerals

If the application is process control and high sample throughput is required - the same analytical results as with a sequential WDXRF instrument –S8 TIGER can be achieved much faster with the new simultaneous WDXRF spectrometer– S8 LION

The Fastest Multielement Analysis: Simultanteous WDXRF

The S8 LION(((

WDXRF spectrometer

Fast• Simultaneous

Reliable• Reliability by design• German engineering

Dedicated• Cement• Minerals & Mining

Smallest footprint• less than 1.2 m2

S8 LION(((

Spectrometer Setup

Experience and Skill of Laboratory Employees

To run an application successfully is just half of the job. The most important part starts by implementing the procedure in daily routine.

Easy and failsafe operation becomes important if more employees with less experience work with the instrument.

Using a standalone unit with TOUCHCONTROL™ interface will make it happen!

Experience and Skill of Laboratory Employees

New developments for the S2 RANGER, S8 TIGER and S8 LION with the unique Touch ‘n Analyze concept and TouchControl allow intuitive operation with less training and greatly reduced operator error.

Since ready-made solutions don’t require daily calibrations and quality check procedures are factory installed, start-up of reliable daily routine is seamless.

XRF – Flexible, Fast Multielement Analysis of Industrial Minerals

Similar applications :Andalusite, KyaniteSilica sands, optical silica, beach sandsUlexite, Colemanite (Boron)Borax (Boron, Sodium)Salt(s)Clays, KaoliniteLimestone, DolomiteTitanium

Tools can range from handheld to floor standing…

XRF for Industrial MineralsFit for Purpose

S2 RANGER

S8 TIGER S8 LIONS4 PIONEER

Phase Analysis with XRD

Holger Cordes

X-ray Diffraction. . . Why “Phase” Matters

TiO2 as reported on a chemical analysis can appear as different minerals: rutile, anatase, …

Copyright © Fabre MineralsComments: Acicular, golden yellow crystals of rutile epitaxially overgrown on black crystals of hematiteLocation: Novo Horizonte, Bahia Brazil.Scale: 4 x 3.5 x 3 cm.

Copyright © Fabre MineralsComments: anatase with calciteLocation: Hardangervidda, Norway, (1999).Scale: 1.5 x 3 cm.

http://www.fabreminerals.com/

http://www.fabreminerals.com/

X-ray Diffraction. . . Why “Phase” Matters

The atomic (chemical) composition is obtained from XRFThe same atoms may arrange in different geometries orcrystal structures

the resulting natural materials are called minerals or phasesThe crystal structure determines the physical properties of a material. Therefore, minerals with the same/similar chemistry may differ in:• Hardness• Color or spectral absorption of light• Durability or wear resistance• Solubility• Cleavability, grindability• many more …

Knowing the phases has immediate financial impact: • The economic value of a material• Costs of mining, transport, processability• Properties of a final product

What is X-ray Diffraction?The Mineral “Fingerprint”

Anatase Rutile

The interaction of X-rays with mineral phasesyields typical patternsThese patterns are the “fingerprints“ of the mineralphases present in a sampleThis fingerprint is used to identify and quantifythe mineral phases

What is X-ray Diffractionand How Does It Work?

The x-ray wavelength is of the same order as the distances in the crystal lattice

For each possible d-spacing(distance between parallel sets of planes with atoms in a crystal lattice), a peak is observed at a distinct angle 2Θ.

The atoms and their positions in the unit cell determine the peak intensities.

θλ

sin2 ⋅⋅

=nd

Powder Diffraction Basics:Sample properties

Diffraction of an ideal powder

Diffraction of a small number of crystallites ("spotiness effect")

Diffraction of textured materials

Sample preparation requirements

Powder preparation• Reduce particle size with mortar and pestle (or automatic mill) to

grain sizes smaller than 10 μm to increase the number of crystallites, and avoid spotiness and microabsorption effects

• Coarse grinding increases preferred orientation and microabsorption effects and leads to errors

• The sample surface in the holder should be flat and smooth.

Identical sample preparation for XRF and XRD is possible, but needs to be tested.

Low Background

Filter papers Clays Automation Cavities Preferred

orientation

Kind of information obtained from a powder diffraction pattern

Peak positions Intensities

Peak shape Scaling factorsIntensities

Phase Identification:The Search/Match Program EVA + ICDD

ICDD database over 200.000 entris

Stick patterns serve as “fingerprints” for mineral phases in a phase mixture

Scaling the relative intensities allows semi-quantitative analysis(RIR- method)

00-007-0239 (I) - Brucite, syn - Mg(OH)2 - I/Ic PDF 1.6 - S-Q 8.6 %00-041-1475 (*) - Aragonite - CaCO3 - I/Ic PDF 1. - S-Q 17.1 %00-005-0586 (*) - Calcite, syn - CaCO3 - I/Ic PDF 2. - S-Q 74.2 %File: m1.RAW

Lin (

Counts

)

0

5000

10000

2-Theta - Scale

16 20 30 40 50

Quantitative Mineral Analysis Using X-ray Diffraction

Standard-based methodsConventional method (DQuant): Calibration curve with standards required, mostly used for quality control, accurate but problematic with peak overlap between phasesReference intensity ratio method: Quick semi-quantitative method for many minerals using the I/Icor values from the ICDD database (can be done in EVA program)Full pattern analysis: Scaling of full patterns of standard minerals, very consistent sample preparation and standard minerals necessary

Standardless methodsRietveld analysis with TOPAS: standard-less, peak overlap between phases can be resolved, all crystal structures have to be known

Please use your mouse to answer the question on the right of your screen:

Which method do you prefer for quantitative phase analysis? Choose one:

Conventional standard-based quantificationReference-Intensity ratio methodFull pattern scaling based on reference scans of pure phasesStandardless Rietveld analysis because of peak overlap or because standards are not available

Audience Poll

Conventional Standard-based Analysis: Example - Lime

Free lime determinationCalibration based on chemical analysis Concentration range: 0.3 - 3%Accuracy: 0.1%

Basic Principles of the Rietveld Method

The Rietveld method is a full-profile approach to quantitative phase analysis using powder diffraction dataThe Rietveld method generates a calculated diffraction pattern that is compared with the observed dataLeast-squares procedures are used to minimize the difference between the complete observed and calculated diffraction patterns. The following parameters are simultaneously refined:

• Structural parameters of each phase (lattice parameters, atomic coordinates, site occupancies). These are normally obtained from a database or the literature (e.g. ICSD database, www.crystallography.net, etc.)

• Various experimental parameters affecting the pattern (displacement correction, peak shape, background, etc.)

The Rietveld method is standardlessThe Rietveld method can be used to characterize several phases simultaneously

TOPAS Software for Rietveld RefinementUser Interface

Parameter window with instrument and structure information for each phase

wt.% for each phase

Measured curveCalculated curveDifference curve

Quantification of Phases with Complex Structures and Peak Overlap –K-Feldspar (NBS 70a Standard)

Perthite (According to NBS certificate 10 to 15% Albite + Microcline)

Mineral Quantification Example: Sample from a cinder cone in the Haleakala Crater Valley, Maui

Common problem: Not every minor phase can be identified; amorphous or nano-crystalline phases may be present. Mostly Iron Oxide and Sulfate minerals, some minor phases could not be identified.

Quantitative Rietveld AnalysisAbsolute and Standardless

Absolute method for direct and highly accurate quantitative phase analysis of mineral mixtures, if the crystal structures are knownStandardless method for determination of phase amounts, lattice parameters, crystallite size and much moreIndependent of equipment and sample properties such as tube aging, solid solution effects, and preferred orientationIntrinsic handling of solid solution and preferred orientation effectsOperator-independentCan be operated without human interaction (TOPAS BBQ)

Automation of Quantitative TOPAS Analysis

For repetetive analysis of similar samples, Rietveld analysis can be completely automated with the TOPAS interface hidden from the operator (TOPAS BBQ)If combined with a postion sensitive detector, cement or mineral analysis, including quantification, can be performed in 2 to 5 minutes Customizable text file as output

Bruker AXS XRD InstrumentsThe New D8 ADVANCE

Largest portfolio of dedicated optics and detectorsTrue plug & play functionality, fully automatic component recognition and configuration

• Sample changers• Low / high temperatures• Hot humidity• Transmission, reflection• …

Alignment-free switch of configurations – whatever your sample, whatever your application

Versatile research instrument

Bruker AXS XRD InstrumentsD4 ENDEAVOR

D4 ENDEAVORQuality control instrumentCompact designlarge sample changercomplete automation option

Bruker AXS XRD InstrumentsThe D2 PHASER

D2 PHASERPortable desktop instrumentResearch, Quality controlNo installation, no alignmentNo external cooling neededFastest on the market with LYNXEYE detector

26/05/2009Bruker Confidential49

The D2 PHASERGo onsite and save money

No installation, No alignment, No instrument configurationSave consumablesDon’t send samples – Send data, save time and money


The D2 PHASER What Can Be Done With It?

Qualitative Phase Analysis (Phase ID)Quantitative Phase AnalysisCrystallite Size & Microstrain AnalysisStructure Determination and Refinement


The D2 PHASER - Phase IDGeological Sample / Construction Material

Major phase: GypsumMinors: Quartz

ChloriteDolomiteMuscovite

Scan parameters:• 3-60 ° 2Theta• Step size 0.02°• 1 sec/step• total 50 min

20 µg


The D2 PHASER - Phase Quantification Calibration Based: Respirable Silica

ApplicationSilica dust is cancerogene and needs to be monitored.NIOSH 7500 norm20 – 2000 µg, LOD 5 µgMeasurement of the 100% quartz peakFilter paper sample holder

Instrument setupLYNXEYESoller 4°Divergence 1mm

Scan parameters26.1-27.1° 2θStep size 0.01°

>30 µg 1 sec/step - total 5 min<30 µg 5 sec/step - total 25 min

Red curve6 µg


The D2 PHASER - Phase Quantification Respirable Silica - DQUANT

Std.Dev.: 1.4 µg

Smalest value: 6 ±0.9 µg

Zero offset 1.8 µg(norm ±5 µg)


The D2 PHASER - Phase QuantificationTiO2 Rutile/Anatase - TOPAS

White Pigments – detection of detrimental modificationsRequest > 0.5 % Rutile

< 2% 1 sec/step- total 50 min> 2% 0.2 sec/step - total 10 min


The D2 PHASER - Phase Quantification Fluorescent Material

No Fe-discrimination

with Fe-discrimination

• Same concentrations• Improved statistical

confidence measure

With discrimination:


The D2 PHASER: Phase QuantificationVDZ Round Robin 2005 Cement Clinker - TOPAS

2Th Degrees656055504540353025201510

Cou

nts

9,0008,5008,0007,5007,0006,5006,0005,5005,0004,5004,0003,5003,0002,5002,0001,5001,000

5000

-500-1,000-1,500-2,000-2,500

C3S monoclinic (NISHI) 71.55 %C2S beta (MUMME) 8.07 %C3A cubic 2.07 %C3A Na orthorhombic 5.20 %C2Fe2-xAlxO5 (Colville) 10.30 %Lime 0.82 %Periclase 0.61 %Arcanite K2SO4 0.77 %Portlandite 0.61 %

Scan parameters:• 10-65 ° 2θ• Step size 0.02°• 0.5 sec/step - total 25 min

Instrument setup:• LYNXEYE• Soller 2.5°• Divergence 1mm

phase mean esdResults VDZ Round Robin

Excellent agreement (±1 wt.%)between TOPAS quantitative analysis and reference data

Summary

XRF for elemental analysis • Wide range of elements: from Boron

(B) to Uranium (U)• Excellent repeatability

XRD for phase analysis• Phase identification • Phase quantification

Combined techniques • Easy and economic sample

preparation• Fast results• Readily automated • Easy to use, even by inexperienced

operators

Analysis on the same sample!

Any Questions?

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click Send.

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industrial minerals â€“ how onsite x-ray analysis saves money

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