Chapter 1: Inorganic Analysis Reference procedure

High Precision X-Ray Fluorescence Analysis (XRF)

by Reconstitution Technique

Key words
Elemental analysis, reconstitution, precision analysis, synthetic calibration, XRF analysis

Quantities and items tested

Amounts of elements as major and minor constituents (atomic number 12 (magnesium), excluding the noble
gases and halogens) in solid materials such as metals, oxides and silicates e.g. metal alloys, ores, soils, minerals,
cements, building materials

Testing range Uncertainty of results

Mass fractions of elements from 0.1 g/kg to 800 g/kg from 5 % to 0.1 %

Fields of application
Certification of reference materials; precision analysis; e.g. of high-grade inorganic materials such as refractory
metals or special metal alloys

Methodology and instrumentation

The method of reconstitution is based on the use of synthetic calibration samples. Because of the definite
manufacturing process it is possible to use the same sample preparation procedure for both the analysis sample
and for the calibration samples, too.
The basic principle of the reconstitution is based on a pre-analysis of the analysis sample and bracketing
calibration samples an iterative assimilation of the composition of the calibration samples and the analysis
sample itself. The calibration range is therefore always adjusted to the individual case.
By the iterative adjustment of the composition of the calibration samples and the analysis sample matrix effects
and a deviation from the linear calibration function are avoidable in most cases. The trueness of the method is
controlled by the iterative principle itself.
Because of the advantages of the sample preparation procedure and the high precision XRF-analysis is the ideal
method for realizing the reconstitution principle. The method is basically usable for all analytical methods which
allow an isoformation of calibration and analysis sample, especially all methods based on solutions.
If XRF-analysis is applied the preparation of the calibration samples and the measuring sample of the material to
be investigated is realized by the fusion technique using lithium or sodium tetraborate.

Qualification and quality assurance

A high reliability of the analytical results by using the reconstitution technique is attained by the direct control of
accuracy using the iterative adjustment of calibration and analysis samples resulting in an extensive avoidance of
matrix effects.
If a reconstitution analysis is performed by XRF a number of advantages are contributing to a minimization and a
high reliability of the measuring uncertainty:
Repeated measurements with identical samples
Long range time stability of the signals
Calculable uncertainty contributions by sample preparation procedures
Optimal control of trueness
Elimination of matrix effects and optimization of calibration

Contact: Dr. Markus Ostermann Phone: +49 30 8104 1143

E-mail: markus.ostermann@bam.de Fax: +49 30 8104 1147
Division I.4: Process Analytical Technology back to Catalogue of Reference
Procedures

Date: June 2010 1(2) 104en.pdf

 Reference procedure Chapter 1: Inorganic Analysis

Further information
Basic principle of the reconstitution technique
In contrast to the conventional analytical mode (calibration for the realization of a correlation between
measuring values and amounts) the contents of elements by using the synthetic mode of reconstitution can
only be accepted as free of interferences and therefore as true, if an identity of analysis sample and the
reference sample is obtained in a sufficient way:
The composition of an unknown analysis sample is determined by synthesis of calibration samples which lead
to equal signals compared to the analysis sample.
The composition of the calibration samples is varied in an iterative way to a point where the difference among the
signals of all samples is no longer significant.

Iterative assimilation of the composition of calibration samples towards the analysis sample

Only pure substances of exactly defined stoichiometry and of well-known grade of impurities are used to prepare
the synthetic calibration samples.
Oxides, carbonates or other compounds of the relevant elements which can be produced in a suitable way with a
high grade of purity are used for this purpose. Also pure elements can be used.
The analysis sample as well as the synthetic mixtures for the calibration samples are prepared as glass fusions
(lithium or sodium tetraborate) to obtain homogeneous samples for the XRF measurements.
While preparing the borate fusions reproducible operating conditions (temperature program) have to be maintained
in order to get an optimum comparability between the calibrations samples and the analysis sample.
1150C

700C 850C

decomposition
warming up cooling down
+ 4.5 g
oxidation
Lithiumtetraborate
(Sodiumnitrate)
20C

ca. 70 30 15 15 time in minutes

Temperature program for the fusion of borate glass samples for XRF analysis

Applications
Analysis of Si-, Ca- und Al-containing alloys Analysis of copper, bronze, brass and white
alloy
Analysis of ferrous alloys and nickel alloys
Analysis of ferrochromium
Analysis of natural and technical oxides
Analysis of refractory materials (e.g. tungsten,
Analysis of cements and building materials
tantalum, niobium)

Literature
Gotthard Staats und Siegfried Noack,
Qualittssicherung in der Analytik; Die Rekonstitution Eine Methode zur Optimierung der Richtigkeit von
Analysen
Verlag Stahleisen GmbH, Dsseldorf 1996 ISBN 3-514-00581-8

Date: June 2010 2(2) 104en.pdf