New Products and Applications in XRF, XRD, OES and Automation ...

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The world leader in serving science

D. Bonvin – J.M. Böhlen – R. Yellepeddi – P. LembergeThermo Fisher Scientific

1024 Ecublens

Switzerland

SASP Frühjahrstagung – Villars s/Glâne - April 2016

New Products and Applications in

XRF, XRD, OES and Automation

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Thermo Fisher Scientific (Ecublens) SARL SwitzerlandFactory of OES, X-Ray and Automation products

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Combined OES, X-Ray and automation experience

• 80+ years of OES experience

• 60+ years of X-ray experience

• 30+ years of automation experience

OES:Optical Emission Spectrometry for metals and alloysXRF: X-ray Fluorescence for Elemental Analysis of materialsXRD: X-ray Diffraction for Phase or Mineral Analysis of materials

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H

Na

Li

K

Rb

Cs

Fr

Mg

Be

Ca

Sr

Ba

Ra

Sc

Y

La

Ac

Ti

Zr

Hf

V

Nb

Ta

Cr

Mo

W

Mn

Tc

Re

Fe

Ru

Os

Co

Rh

Ir

Ni

Pt

Cu

Ag

Au

Zn

Cd

Hg

Al

B

Ga

In

Tl

Si

C

Ge

Sn

Pb

P

N

As

Sb

Bi

S

O

Se

Te

Po

Cl

F

Br

I

At

He

Ar

Ne

Kr

Xe

Rn

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Th Pa U Pu Am Cm Bk Cf Es Fm Md No LwNp

Not measurable Rare gasesUnstable elements

Standard elements Ultra light elements not measurable by some techniques

Pd

The Periodic Table – our common language

Elemental Analysis - What is it?

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Detection limits and dynamic range comparison

ICP-MS

ICP-AES

GFAAS

AAS

1 ppq 1 ppt 1 ppb 1 ppm 1,000 ppm 100%

X-ray Fluorescence

Arc-Spark OES

TRACE BULK

Liquids

Solids

Combustion : TOC; TN; TS, TOX


Optical Emission Spectrometers

Applications and products

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Spark-OES - instrument operational diagram

Spark

source

&

stand

Ele

ctr

on

ics

Co

mp

ute

r

Optics and detection

(1) Preparation

(2) Ablation,

excitation &

light emission

(3) Light separation

(4) Light detection

(4) Signal

acquisition

(Instrument control)

(5) Data

processing

(Instrument control)

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Iron & Steel

40-50%

Aluminum

15-25%

Copper

10-12%

Zinc

8-10%

Nickel5%

Lead and others

(Co, Mg, Sn, Ti,

precious metals

ARL 3460 ARL 4460

Fast multibase spectrometers

• Up to 60 elements analysed simultaneously in <30s

• Capability for determination of micro-inclusions

Optical Emission: Elemental analysis of solid metals

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• Bench-top system

• unique multi-grating/CCD optical system

• high spectral resolution and enhanced

analytical performances

Elemental Analyses (solid metals):Optical Emission Spectrometers - new generation

• Iron

• Aluminum

• Copper

• Zinc

• Nickel

• Lead

ARL iSpark series ARL easySpark

• Combines photomultipliers with CCD

(charge-coupled device) for speed and

flexibility


X-ray Fluorescence techniques and their applications for materials analysis

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X-rays: what are they ?

Radio waves - Ultra-short

Waves (1km to 1cm)

Radar and microwaves

Infra-red

Visible

(0.8 to 0.4 µµµµm)

Ultra-violet X-rays

10 -9 to 10-12 m

Gamma rays

• Photons with a wavelength comprised between 10 -9 to 10 -12 m

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XRF is used for the elemental analysis of a variety of materials

Oils

Metals, Slags

Ores and raw materials

Chemicals

Food productsGlass

Polymers

Ceramics

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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:

• Be - F to U

• 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

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Polymer or

Fused Glass BeadBulk Sample

(Metal, Glass or

Pressed Powder)

Conventional Solid Samples

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N Kαααα1,2

1.16 %

4.88 %

blank

Analysis of various elements in plants by XRF

• Typical samples: tobacco leaves, tomato, lettuce, wheat, etc.

• Freeze dried and pressed

• Typical elements

• Ca, Mg, S, K, Na , Cl, P, Fe, Sn, Mn + Nitrogen

• High powersequential XRF

• 4200W

• 50 micronsBe window

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Loose Powder, Paste or Drillings

Liquids

Cassette (sample holder)

Stretched filmPP or mylar

Plastic cell

Other Sample Types

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Thin Layers

Thin layers on a substrate

• Multilayer mono-element

Dust on a filter

• Monolayer multi-element

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• A fixed volume of air is pumped through a filter

• Particles present in air are collected on the filter

• The filter is then analyzed.

• Different types of filters are commonly used:

• Teflon, polycarbonate, quartz

Preparation of Air Filter Samples for XRF analysis

To pumping device Aspiration of ambient air

Filter or film

To standard holder for XRF analysis

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• High sensitivity for trace analysis

• Exclusive detector

• New unique SDD1000 detector

• breaks the 1 nanogram/cm2 detection limitbarrier (air filters)

• Fastest pulse processing electronics

• Excellent sample-handling flexibility

• Large samples up to 30cm x 40cm x 5cm

• 10 pos or 20 pos magazine

• Down to 1mm spot analysis

• CCD camera for sample positioning

• Wintrace software under Windows ® 7

• Advanced analytical algorithms

• Simple, robust and easily transportable

Thermo EDXRF Spectrometer

ARL QUANT’X

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EDXRF applications

Environmental Analysis

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Sewage Sludge: Background

• Sludge is a byproduct of the waste water treatment process.

• contains valuable organic matter and is rich in nutrients such as nitrogen and

phosphorous.

• But may concentrate heavy metals and non-biodegradable organic compounds as

well as potentially pathogenic organisms.

• Analysis of sludge helps decide if it must be disposed of due to high heavy metal content or if it can be sold as fertilizer.

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Sewage Sludge: Classical Analysis by ICP-AES

Reflux digestion during 1h

&

Cooling down (approx. 1h)

Filtration over a paper filter

+ 10ml conc. HNO3

Analysis by ICP (approx. 1h)

5g of dried sludge (granules) as

powder / 100ml H2O

Recalculate conc. (dry matter)Final results

3 hours

Source: Services Industriels de Genève (SIG)

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Sewage Sludge: Alternative Analysis by EDXRF

About 20 g of dried sludge

(granules)

Grinding of granules and

pelletizing (approx. 15

min)

Analysis by ED-XRF

(approx. 10 min) Final results

30 minutes

Source: Services Industriels de Genève (SIG)

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Sewage Sludge: UniQuant FP Analysis in Practice

• Analysis of 3 certified reference material

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ARL QUANT’X

Selected Applications

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A variety of possible applications (I)

• Mining

• Feldspar analysis

• Uranium ore analysis

• Magnesium oxide ore analysis

• Environmental Applications

• Analysis of sewage sludge

• Analysis of waste (plastics, used oil, ash, contaminated soil)

• Analysis of air filters

• Analysis of waste for incineration

• Analysis of gemstones, minerals and pearls

• gemology

• Analysis of gold and precious metals

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A variety of possible applications (II)

• Analysis of coatings and paints

• Petro-chemical Industry

• Analysis of Re, Pt and Pd in catalysts

• Heavy metals in waste oil

• Light to heavy elements in polymers

• Nuclear Power Industry

• Analysis of corrosion residues in water collected on filters (cooling circuit)

• Determination of U in HF (U recovery)

• Cement

• Backup for cement analysis or when WD-XRF is too expensive

• Analysis of alternative fuels

• Pharmaceutical components

• Heavy metals in Active Pharmaceuticals Ingredients (API)


Small Spot Analysis Resultswith ARL PERFORM’X

WDXRF

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Small Spot Analysis by WDXRF

• Recent advances in hardware and software permit narrow spot analysis of specimens down to 0.5 mm

• We use on-board camera to select the point(s) that we want to measure on the specimen

• Even a full quantification of the chosen spot for 75 elements is possible when combined with UniQuant standard-less analysis

Focused analysis on any visible grain of this Granite allows a specificelemental determination

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Small Spot Analysis

• Spot location selected with on-board camera

• Sample positioned by movements of slide and rotation

• Analysis always focused at the center of the X-ray beam

• Opens up the capability to analyze non-homogeneous samples

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UniQuant Analysis of Contamination at 29 mm

• Glass sample shows a shiny spot

• Traditional UniQuant analysis only provides the global composition over a diameter of 29mm

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UniQuant Analysis of Contamination at 29 mm


• Traditional UniQuant analysis only provides the global composition over a diameter of 29mm

Oxide/

Element

Conc.

%

StdErr %

SiO2 69.77 0.23

Na2O 12.16 0.16

CaO 7.57 0.13

MgO 3.54 0.09

Al2O3 1.09 0.05

K2O 0.330 0.016

SO3 0.215 0.011

Fe2O3 0.200 0.010

TiO2 0.0704 0.0035

BaO 0.0239 0.0052

Cl 0.0228 0.0011

CuO 0.0175 0.0009

MnO 0.0118 0.0007

ZrO2 0.0091 0.0005

P 0.0073 0.0006

Cr2O3 0.0069 0.0006

SrO 0.0066 0.0003

SnO2 0.0018 0.0009

ZnO 0.0016 0.0004

StdErr = error due to counting statistics

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UniQuant analysis at 0.5 mm


• SiO2 is found because the 0.5mm spot is larger than the metallic inclusion and the goniometer sees the glass matrix as well.

• Analysis of the inclusion tells us it is a copper-tin alloy

Element Shiny

Spot

%

Glass

Surface

%

Al 0.74 0.50

Cu 24.34 0.02

Fe 1.57 0.16

Sn 1.19 0.50

SiO2 34.84 70.46

Spot analyses (all values in %)


Elemental Mapping Results with ARL PERFORM’X

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Surface Mapping Analysis – ARL PERFORM’X

• Hardware and sofware advances also permit X-ray mapping capability

• Spot by spot acquisition over a selected surface

• Cartography down to 0.5 mm spots

• Resolution down to 0.1mm steps

• Allows construction of detailed composite maps of elements

• Identification and characterization of elemental impurities, inclusions or gradients

Mapping of an area of a rock

determines distribution of elements

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Feldspar Mapping

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Feldspar

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• XRF can be used in a many different applications

• Standard-less analysis is one of the most important recent innovation in XRF• has made XRF very popular and truly universal analysis method for totally

unknown samples of different shapes and nature

• in central labs, R&D centers and contract labs

• ED-XRF solves analytical problems in environmental analysis and investigative work

• WD-XRF is chosen for all process control with best performance on light elements (F to Cl) and highest precision for minor and major elements• Small spot analysis and mapping open the capabilities towards non-

homogeneous samples

Conclusion

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Laboratory Automation Solutions

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Automation Product portfolio

ARMS

ARL SMS-3500• ARL 4460

• ARL FAA

• ARL 9900 XRF


• ARL 4460

• ARL FAA

• ARL 9900

ARL SMS-Advantage• ARL 3460 Advantage

ARL SMS-XY• ARL 9900

• ARL Advant’X

ARL SMS-Omega• ARL Optim’X

ARL QuantoShelter• ARL SMS-Omega

ARL SMS-XY

• ARL SMS-2500


• ARL 9900 XRF

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Complete Workflow Solution with Lab automation

Milling

Machine with

direct robot

access

Milling

Machine with

direct robot

access

ARL 4460 Metals

Analyzers

New ARL SMS-3500

Electronics cabinet

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Haas Mini Mill milling machine with ARL PrepControl

• Direct milling machine access for production samples and standards

Ultra fast loading / unloading : 8 seconds

� Also available for the Herzog HS-FF and HS-FF2000 milling machines

The Haas Mini MillSample loading & unloading by

the SMS-2500 robot

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Total Lab Automation Solution in a Steel Plant

POSCO (Korea)


Simultaneous X-ray DiffractionPrinciples and Applications

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Why X-ray Diffraction ?

• XRD measurement gives information about the 3-D arrangement of atom (or molecules) in a crystalline solid. {> 90% of solids are crystalline}

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Why X-ray Diffraction ?

• XRD measurement gives information about the 3-D arrangement of atom (or molecules) in a crystalline solid. {> 90% of solids are crystalline}

• For example, knowing that a solid is made of Carbon doesn’t tell you

whether it is

• Graphite or

• Diamond

• or a mixture of the two.

• The structural arrangement of the carbon atoms is what determines the material properties (& what you measure via XRD).

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Simultaneous X-ray Diffraction

A unique detection mode

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Curved detector principleThe EQUINOX diffractometers use the curved detector

principle, namely real time acquisition across a wide

acquisition range.

• no motorization required: neither on sample nor on

detector incidence

• Simultaneous acquisition mode: for a fix θ sample

incidence you can see all diffraction peaks on 2θ on the

detector.

Simultaneous X-ray DiffractionA unique detection mode

sample

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EQUINOX 1000

Bench-top X-ray Diffractometer

• Ultra-fast unique Equinox curved detector

• measures all diffraction peaks simultaneously

• also called PSD for position sensitive detector

NEW offer on XRD: EQUINOX 1000

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EQUINOX detector

ZnO10 sec acquisitionEQ100 CPS 180 Detector X-Ray tube Copper

Simultaneous acquisition of all diffraction angles

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Conclusion

• There are many applications for X-ray diffraction

• Both research and industry benefit from the capability to distinguish between phases or compounds

• New XRD systems can acquire a full spectrum simultaneously

• Fast acquisition of data

• Acquisition of data until the desired phase is detected

• Rietveld analysis allows standard-less phase quantification

• No need to run standard samples similar to the unknown material

• Equinox 100 and 1000 are bench-top and can be easily installed in every laboratory

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Thermo Scientific XRF and XRD Product Portfolio:Strong and complementary technologies

EDXRF Powder XRDWDXRF Integrated XRF and XRD

Portable Niton

XRF: Elemental analysis

ARL QUANT’X-

Top performance EDXRF

ARL OPTIM’X: Surprising

performance in WDXRF

ARL 9900 Series

Integrated XRF-XRDARL X’TRA: High

performance Powder XRD

ARL PERFORM’X

High Performance

sequential XRF

XRD: Analysis ofStructure-crystallography

Phase or compound

Equinox 100 & 1000

Benchtop XRD

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Thank you for your attention !

Merci de votre attention !

Danke für ihre Aufmerksamkeit !

New Products and Applications in XRF, XRD, OES and Automation ...

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