XRF Calibration

Calibration
Dead Easy, Mate !!
Measured XRF intensity is directly
proportional to analyte concentration,
X-ray
right ?
Intensity
Oops!!

Concentration
 Calibration Strategies
• No “best” approach
– most labs have “favourite method”.
– most methods are capable of good results if
used with care.
• Method chosen must meet local criteria of:
– precision
– analysis time
– analysis cost
– contractual requirements (eg ASTM xxx
specified in contract)
 Sample Presentation
- spectrometer medium
Medium choice is part of calibration
 Sample Presentation
- spectrometer medium
XRF settings will affect intensity
 Influence of target
material

• Continuum Influence of target material of the Tube

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I ( )  KiZ   1  2 
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Parameter selection table
 Calibration
• In the real world, things are a little more
complicated and a number of corrections are
necessary before the linear relationship
between X-ray intensity and analyte
concentration can be established.
• Fortunately most corrections can be predicted
and the correction factors either measured or
calculated.
• Corrections can be either intensity or
concentration based. There are arguments for
both approaches.
Factors Effecting Calibration
• Background
– the relationship between X-ray intensity and
concentration strictly holds for pure net (ie
background corrected) intensity.
– background is matrix dependent and for some
analytes matrix variations can cause significant
variations in background (eg in coal - can get
factors of 2 or 3 variation in background as ash
level and/or composition of ash varies).
 Spectral Overlap

Peak A

Peak B

2
 Matrix Effects
• Essentially Two Components
– presence of elements giving rise to spectral
overlap at analyte peak and/or background
measurement positions.
– X-ray absorption effects
• variously termed “matrix”, “inter-element”, “a factor”
and “absorption/enhancement” effects..
 Matrix Effects
• X-ray absorption effects
– during XRF analysis all elements present in the
sample will fluoresce and produce characteristic
X-rays.
– if the energy of the characteristic X-rays from any
element is greater than the critical excitation
energy of another element, then there is the
possibility that X-ray absorption will occur.
– the absorbing element may fluoresce under such
circumstances (ie emit secondary X-rays).
Matrix - Absorption Effects
– Consider a sample containing Fe and Ca. During
XRF analysis Fe K and L X-rays will be produced.
– The energy (KeV) of the Fe Ka (6.40) and Fe Kb
(7.06) lines is greater than the Ca critical
excitation energy (4.038).
– Hence some Ca atoms may absorb some of the
Fe K X-rays and may in turn fluoresce.
– The net effect is to reduce the number of Fe K
X-rays and increase the number of Ca X-rays
reaching the detector.
 Drift Correction
• All spectrometers will show some degree of
drift with time.
• Need calibration to be time independent.
– Run a drift correction (monitor) sample(s) at
same time as initially run the calibration
samples (Day Zero)
– Run the same drift correction sample(s) at
regular intervals and calculate a drift factor.
– Adjust calibration to compensate for
instrumental drift using the drift factor.
 Drift Correction
• Can use one or more drift standards
– may not have all analytes in a single standard.
– can drift correct a single X-ray line using either
one or more standards (typically a high and a
low) standard.
• Suitable drift standards are available
commercially.
– AUSMON – CSIRO Australia
– Breitlanender
 Calibration Strategies
• Fusion methods
• Pressed powders
• Metals
• Liquids
• Loose powders
• Environmental filters
 Calibration Strategies
• Multi-Point
– Probably most widely used approach.
• “Single Point” (Norrish Approach)
– Approach used many Australian laboratories.
• Semi-Quantitative (“Standardless”)
– UniQuant
– Integral part or option of most manufacturer’s
software packages
Calibration - Multi-Point
• “Original” calibration method.
• Many “local” variations.
• Requires a series of standards of known
composition that cover the required analytical
range.
• Generally 10 or more standards used.
– depends on application, correction method, etc.
• Correlations should be avoided (eg Fe2O3
increasing in direct proportion to SiO2
decreasing).
• The one that most think is best these days
 Calibration - Multi-Point
• Relatively quick to set up new calibrations.
• Relatively easy to add additional elements.
– depends on “user friendliness” of software
package.
• Capable of very good results.
• Can use for fusions, pressed powders, metals,
liquids, etc.
 “Single” Point
(Norrish Approach)
• Based on a blank and a single synthetic multi-
element standard, plus a series of single
element/oxide beads to determine background
and spectral overlap corrections.
• Multi-element standard approximates
composition of assay samples modified to give
good measurement precision.
• Backgrounds and spectral overlaps all treated
as overlaps.
• Method used in a number of ISO and
Australian Standard X-ray methods (eg ISO Iron
Ore).
 “Single” Point
(Norrish Approach)
• Not all software supports this approach (eg
current Siemens/Bruker-AXS and ARL
software does not).
• Time consuming to set up initially.
• Difficult to add additional analytes.
• Capable of very good results.
• No more difficult to maintain than any
other calibration method.
• Applicable to fusions and possibly pressed
powders and liquids.
Calibration Standards
• Requirements for Materials Used for
Calibration Standards.
– Stable.
– Homogeneous
– Known composition and/or high purity.
– Easily weighed (eg not hygroscopic or
deliquescent).
– Preferably readily available and reasonable cost.
 Calibration Standards
• What can be used:
– Certified Reference Materials (CRM’s)
• eg NISTS, Eurostandards, SARM, BCS, etc.
– Synthetics (prepared from high purity reagents)
• typically “Specpure” grade (99.99% or better).
– Analysed samples
• eg process samples that have been analysed by a
number of techniques or laboratories.
– Mixtures of the above.
 Calibration Standards
- CRM’s
• Certified Reference Materials
– Often only certified for a few elements.
– Analyte ranges often restricted.
– Not all CRM’s are reliable.
– CRM’s for some sample types not available
• eg NZ Steel Melter Slags - high TiO2 and V2O3.
– Pre-treat according to certificate.
 Calibration Standards
- Synthetics
• Must use high purity chemicals
• worth doing spot checks - bad batches have occurred.
• Pre-treat to remove moisture and ensure
stoichiometry
o
– V2O5 105 C for 1 hour.
o
– SiO2 1000 C for 15 minutes.
– Cool quickly and weigh. Some pre-treated materials eg
Al2O3 are extremely hygroscopic.
• Can minimise weighing of small masses by making
pre-fused flux reagent mixtures.
 Calibration Standards
- Synthetics
• Advantages
– Can design calibration to cover any
compositional range for any analyte.
– Very easy to extend calibration to fit non-routine
samples.
• Disadvantages
– Time consuming to design and prepare.
– Require inventory of (expensive) pure chemicals.
Calibration Standards - Mixtures

• In some instances, there may not be suitable

CRM’s to cover the required concentration or
analyte range. Can overcome by using:
– mixtures of CRM’s
– mixtures of CRM’s and pure chemicals
 Calibration
• It is good laboratory practice to prepare at
least some of the calibration standards in
duplicate.
– Easier to identify if a “bad” calibration point is due
to a preparation error or matrix / spectral overlap
problem.
– Improves precision of calibration.
Calibration - Pressed Powders
• CRM’s or well analysed samples are best
approach.
– minimises matrix, grinding and mineralogical
effects.
• Can use mixtures of pure chemicals and/or
CRM’s and pure chemicals, but can have
problems with particle size and other
mineralogical effects.
• Must control particle size of calibration
standards and assay samples.
– Particle size control is absolutely critical for
powder XRF analysis.
 Calibration Standards
- Metals
• Only approach available is CRM’s or analysed
samples of similar matrix.
• Sometimes metallurgical history (presumably
related to grain size) can effect calibration.
 Calibration Standards
– Loose Powders
• Use same approach as for pressed powders
 Calibration Standards
- Liquids
• Multi-point using standard solutions.
• CRM’s and analysed samples
– (eg oils, hydraulic fluids)
• Standard addition
 Calibration Standards
- Environmental Filters

• Make up standard filters by depositing an

aliquot of solution onto a filter and allowing to
dry.
– Multi-point using standard solutions.
– Standard addition
• Depositing known mass of pure chemicals as
“dusts” onto filters.
– Requires special apparatus and careful validation.
 Matrix Correction
• Can minimise matrix effects by closely matching
calibration standards and assay sample matrices.
• Except in rare cases corrections will still be
required.
• Various correction models available:
– Lachance-Traill
– Rasberry-Heinrich
– Norrish and Hutton
– etc
 Calibration Summary

• Background correct
• Spectral overlap correct
• Matrix correct
– the process is normally iterative
– start with an approximate composition
– correct and obtain a better approximation to the
composition.
– repeat until convergence (usually only a couple of
iterations).
Calibration Summary

• Calibration lines should ideally be linear.

• Deviations from linearity may be due to:
– errors in detector dead time correction.
– small errors in the alpha factor determinations.
– alpha factor(s) not constant over entire calibration
range.
• models using higher order terms (eg b and  terms) seek to
theoretically allow for this non-linearity.
• some software packages calculate fundamental alphas for
each sample using the composition of the sample at each
iteration stage (so called “variable alphas”).
 Calibration Summary

• ALWAYS validate calibration using CRM’s, cross

analysis with other laboratories or other
techniques.
• Beware of relying just on good correlation
coefficients, figures of merit, etc for the
calibration curve.
– easy to get an r2 goodness of fit index of 0.99998
but the results may be rubbish.
 Calibration Summary
• Always back-up calibration data
– Include day one drift correction data.
– Hard copy and electronic
– Ensure calibration data is date stamped
• Allows easy recovery in the event of a problem.
• Requirement of most quality accreditation systems (eg
ISO17025).
• Also back up instrument configuration and
alignment data
– Allows recovery in the event of a system failure.
– Assists engineer during servicing of the instrument.

Link to a good example of how to create a good calibration