new products and applications in xrf, xrd, oes and automation
TRANSCRIPT
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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
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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
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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)
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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
• Glass sample shows a shiny spot
• 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
• Glass sample shows a shiny spot
• 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 %)
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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 SMS-2000• ARL 3460
• 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 SMS-2500• ARL 4460
• 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)
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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 !