OPTICAL EMISSION

SPECTROSCOPY

TECHNICAL REPORT NO. 5

February 1998

Comalco Smelting
Comalco Place
12 Creek Street
Brisbane Queensland
Australia 4000
GPO Box 153
Queensland Australia 4001
Phone: (07) 3867 1711
Fax: (07) 3867 1739

Comalco Technical Report, No. 51

 CONTENTS

1. INTRODUCTION 3
2. OPERATION PRINCIPLES 3
3. CALIBRATION 4
3.1 Family of Curves Method 4
3.2 Master Curve Method 5
3.3 Drift Correction 5
3.4 Standards 5
4. SAMPLES 5
4.1 Sampling from Molten Metal 5
4.2 Preparation of Samples 6
4.3 Non-standard Samples 7
5. MEASUREMENT 7
5.1 Procedure 7
5.2 Accuracy and Precision 8
6. INSTRUMENT MAINTENANCE 8
7. TROUBLE SHOOTING 9
7.1 Bad Burn 9
7.2 Variation 9
8. GLOSSARY 10
9. REFERENCES 10

This report was prepared for Comalco Smelting by Comalco

Research & Technical Support. All enquiries should be
directed to Comalco Smeltings sales office or agents.

Comalco Smelting is a division of Comalco Aluminium Ltd.

ACN 009 679 127

2Comalco Technical Report, No. 5

 OPTICAL EMISSION
SPECTROSCOPY
ABSTRACT
Optical Emission Spectroscopy (OES) is used to
measure the composition of aluminium alloys for
control of molten metal composition. It is a rapid
test method with relative precision of 13%.
Samples are collected from the melt according to
standard ASTM E716-94 while analyses are made
according to ASTM E1251-94 by sparking of a
clean machined surface. The resulting emitted light
is measured using detectors at fixed wavelengths.
The composition of the sample is determined by
comparison of the measured intensity of each
element with that of a reference standard of known
composition.
This technical report gives a basic introduction
to Optical Emission Spectroscopy, as it is used in the
measurement of the composition of aluminium alloy
melts.
Attention to sample collection, OES calibration,
monitoring, and sample preparation are highlighted
as essential for accurate and precise measurement
of composition.
1. INTRODUCTION
Optical Emission Spectrometry (OES) is a fast,
accurate and reliable method for quantitative
analysis of metals to about 13% relative precision.
Optical emission spectroscopy methods are among
the most useful and flexible means of performing
elemental analysis of aluminium alloys [1].
Accurate analysis of metals and alloys requires
that [2]:
the melt or bulk sample is homogeneous;
samples are representative of the melt or bulk
sample; and
the metallurgical structure of the sample is similar
to that of the standards used.
The sample requirements are met by chill-cast
disk samples collected as described in ASTM E 716-
94 (or equivalents AS2612-83 or JISH 1305-1976).
For the point-to-plane method of spectrochemical
analysis [3] , samples are machined on a lathe to give
a smooth, clean surface just prior to analysis.
The sample is mounted in the spectrometer and
a spark is generated between the sample and a
tungsten electrode. Material is volatilised from the
surface of the sample resulting in emission of light.
This light is diffracted into its component
wavelengths inside the spectrometer. Fixed
detectors simultaneously measure light intensity at
wavelengths characteristic of each element.
OES requires calibration of the spectrometer
with certified chill-cast standards, which must have
the same matrix as the alloys to be tested. Therefore
quantitative OES can only be performed on chill-
cast samples collected from the melt according to
standard methods [4,5]. Other techniques, such as
Induction Coupled Plasma (ICP), can be used for
quantitative analysis of alloys in other forms, for
example billet slices, ingots, extrusions and forgings.
2. OES PRINCIPLES
The OES system consists of four main parts [6]:
sample stand;
generator;
spectrometer; and
electronics assembly.
The clean sample is mounted in the stand and a
spark is generated between the sample and a
tungsten electrode. An example of this set up is
illustrated in Figure 1. High purity argon is used as
a discharge atmosphere to prevent any interaction
between the atmosphere and the sample surface.
sample
effective
sample
discharge
spot
discharge plasma
(instantaneous
exposure)
counter
electrode
[7]
Figure 1. Sample excitation by electrical discharge .
Comalco Technical Report, No. 53
 Applied Photon,
energy, E2-E1 = hc

E

E1 E2

Initial energy E1 Electron excited, Return to initial energy

energy E2 with emission of a photon
of wavelength

Figure 2. Schematic diagram illustrating light emission by generation of photons of characteristic wavelength.

Material is volatised from the surface of the
sample resulting in emission of light. When atoms
are excited by an external energy source, some
electrons move into higher energy levels. As these
electrons drop back to their original levels, the
atoms emit light (photons) of characteristic
wavelength. This is illustrated in Figure 2.
The spectrometer collects the light emitted from
the sample and splits it into its component
wavelengths using a diffraction grating. Fixed
detectors (photo multiplier tubes) simultaneously
measure light intensity at wavelengths
characteristic of each element. This is illustrated in
Figure 3.
Wavelengths used for OES range between 150
800 nanometres. The intensity of the signals depends
on the number of photons produced per unit time.
The spectrometer is programmed for fixed sample
types, elements and concentration ranges and only
gives results within the limits of calibration.
3. CALIBRATION
Generally, prior to performing metal analysis,
the spectrometer must be calibrated to interpret
the light spectrum emitted by the sample. This is
accomplished by inputting information relating
Curves or Master Curve method which are outlined
below. If further details are required the reader
should refer to the ASTM standard, E1251 [3] or OES
equipment suppliers.
3.1 Family of Curves Method
The Family of Curves method of calibration uses
a number of calibration standards with compositions
close to the alloy being tested. The calibration
curve is a best fit line of intensity versus the
concentration of each element in a range of
standards (Figure 4). In addition, a drift adjustment
is required which is based on a reference standard
close to the alloy of interest.
phototube sample
lens
mirror
primary slit

signal intensities to chemical concentration for

particular elements. The relationship between

optical emission intensity and concentration must
be established using certified standards. Normally, grating
reference standards are certified by wet chemical
methods.
Comalcos Smelters and Research Centre have
calibrated their OES units via either a Family of Figure 3. Optical systems of a typical OES spectrometer.

4Comalco Technical Report, No. 5


Outside calibration
Mn
(wt%) range
Each point
represents a
calibration
standard
Intensity
Figure 4. Example of a calibration curve for Family of Curves
method.
This method of calibration is suited to analysis of
relatively few alloys of similar composition. An
analytical curve is required for each element based
on 520 standards covering a limited concentration
range. Providing the standards are available, the
Family of Curves method can be used for in-house
calibration of a spectrometer.
3.2 Master Curve Method
The Master Curve method of calibration assumes
that there is a relationship between the shape of the
master curve and the alloy (working) curve for each
element in a given alloy matrix. There may be a
change in the background, but no change to the
shape of the curve. Binary standards containing
only the element of interest in a pure aluminium
base are used to establish the master curve and
then a number of certified reference alloys
(commercially available) are used to define the
alloy (working) curve for a given alloy type. This is
illustrated in Figure 5.
Master Curve calibrations are generally set up by
the equipment suppliers or an OES consultant using
certified binary reference standards. Fifty or more
binary standards are normally required to cover
the entire concentration range for common
aluminium alloy types. Up to four certified reference
standards of similar composition to the alloy of
interest are then used to adjust for the alloy matrix.
These standards can also be used to correct for
instrument drift.
Setting up a calibration curve for copper (Cu) in
6063, for example, requires 36 Al-Cu binary
standards to produce the Master Curve ranging
from 0.0001 to 6 wt% Cu which covers the range for
most aluminium alloys. Three certified 6063
standards are used to adjust for matrix effects and
establish the alloy working curve from 0.001 to 0.09
wt% Cu. These standards are also used for drift
correction.
3.3 Drift Correction
Drift correction may be required due to changes
in the optics, the excitation source, processing
electronics and even ambient room temperature or
humidity [8]. These changes can cause drifts in the
intensity ratios from those recorded during the
initial calibration. If a drift correction is not made,
errors will occur and false concentration readings
will result.
The drift may be corrected using a two-point
standardisation procedure. Standards are measured
at high and low concentrations for the elements of
interest, and adjustments are made. For the Master
Curve method of calibration, matrix correction
standards can also be used as drift correction
standards.
3.4 Standards
Standards should be selected to cover the
concentration ranges of all elements for which the
spectrometer is capable. The standards should also
match the alloy type being evaluated.
Certified standards can be obtained from a
number of sources, as shown in Table 1.
4. SAMPLES
The point-to-plane method is dependent on the
matrix and metallurgical structure of the samples.
Hence, the samples must be carefully collected to
ensure compatibility with the certified standards.
This involves collection of chill-cast disk samples.
However, segregation profiles can also exist in
chill-cast samples [9,10], and thus the conditions of
sample collection, as well as the surface preparation
must be controlled.
4.1 Sampling from Molten Metal
Sample collection for OES analysis should be
performed according to standard ASTM E716-94
(equivalents AS 2612-83 [5] or JISH 1305-1976 [14]).
Different moulds may be used to collect
representative samples of the melt, but these must
Comalco Technical Report, No. 55
 Master curve - Alloy (working) curve -
Concentration defined using defined using matrix
binary standards correction standards

Binary
standards

High purity
standard

Spectral Intensity ratio

background

Certified reference
alloy materials

Figure 5. Relationship between master and alloy curves.

be capable of producing homogeneous chill-cast 4.2 Preparation

disks having smooth surfaces free of surface pockets
and porosity. One type of chill cast disk is shown in
Figure 6.
The molten metal from which the sample is
collected must be well above the liquidus (melting)
temperature. Dross must also be removed from the
surface of the melt prior to sampling. A ladle is
preheated and then dipped into the metal and
stirred below the surface before quickly
withdrawing. The disk mould is carefully filled at
an even rate allowing air to escape. The metal must
freeze without disturbance. The initial cast disk is
used for preheating the mould and should be
discarded. An additional sample is collected for the
analysis disk. Collecting an additional sample may
not be required if the mould is already hot.
Surface preparation is critical, and particular
care is required in sample preparation to ensure a
clean flat surface is presented for OES measurement.
The sprue of the chill-cast disk is removed, and
the bottom surface is machined using a lathe or
milling machine to a specified depth (1422% of
disk thickness) below the original surface, according
to ASTM E716-94. This depth is important since it
corresponds to the composition that best represents
the average composition of the whole disk [9].
The surface finish should be smooth, with only
fine tool marks, and should be the same as the
reference sample. Ethanol or isopropanol, may be
used as the machining lubricant to avoid
contamination of the surface.

Table 1. Some suppliers of OES Chill-cast Reference Standards.

Company Address Contact Numbers

Analytical Reference PO Box 2246 Ph: (303) 670 1300
Materials International Inc. Evergreen Colorado 80439 USA Fax: (303) 670 1392

Aluminium Company 600 Block Freeport Rd. Ph: (412) 339 6702
of America New Kensington PA 15068 USA Fax: (412) 339 6740
Graham B. Jackson 125 Thomas St. Ph: (3) 9793 3322
Pty. Ltd. Dandenong Vic. 3175 Australia Fax: (3) 9794 7240

6Comalco Technical Report, No. 5


Measurement region
Figure 6. Example of chill-cast mould and disk sample with measurement region shaded on the schematic diagram.
Measurements can be performed around the disk,
except at the edge (5 mm) and in the centre (up to
12 mm radius) to avoid possible segregation. This is
illustrated in Figure 6. The unknown sample and
the cross-check reference samples should be
prepared by the same method.
4.3 Non-standard Samples
The correct samples for composition analysis by
OES are chill-cast disks collected from the melt and
measured according to the relevant standards [3-5].
Measurements on billet slices or wrought product
samples are only approximate since alloy
calibrations are based on chill-cast disk reference
samples. This inaccuracy is due to matrix effects
caused by the differences in the metallurgical
structures of the standards and samples. If analyses
are required on cast billet, ingot or wrought samples,
they should be re-melted and sampled according to
the ASTM E716 [4,5]. However, great care is required
to avoid losses of volatile elements (such as
magnesium, Mg). Care must also be taken to avoid
contamination during re-melting.
64mm 613mm
Previous work by Comalco has illustrated the
effect of non-standard samples, as shown in Tables
2 and 3. Measurements on billet slices and extrusion
profiles generally gave lower values compared to
the analysis in the original melt certificate. Re-
melting of an extruded profile and casting of a
standard chill-cast disk resulted in an analysis
similar to that obtained from the original chill-cast
disk from the melt.
5. MEASUREMENT
5.1 Procedure
The analysis of aluminium alloys is performed
according to standard ASTM E 1251 (JIS 2611-
1977 [15]). Prior to conducting measurements, the
OES must be calibrated, and corrected for any drift,
as discussed in Section 3.
The machined chill-cast disk sample is sparked
two to four times in the measurement region
shown in Figure 6. Excessive variation in the
composition from repeated sparks (or burns) is
normally a sign of a problem in the sample or its
preparation.
Comalco Technical Report, No. 57
Table 2. Example of changes in OES measured composition (wt%) due to non-standard sampling of a 6000 alloy [12] .
Melt Cast billet Homogenised Extruded Extrusion re-melted
certificate slice billet slice profile into chill-cast disk
Si 0.77 0.78 0.73 0.73 0.80
Fe 0.22 0.21 0.19 0.19 0.22
Cu 0.18 0.20 0.19 0.19 0.20
Mg 0.85 0.81 0.78 0.78 0.83
Zn 0.003 0.003 0.002 0.002 0.003
Ni 0.009 0.009 0.008 0.008 0.009
Mn 0.11 0.11 0.11 0.11 0.11
Cr 0.08 0.07 0.07 0.07 0.08
Ti 0.013 0.014 0.015 0.015 0.014

Table 3. Example of differences in OES measured composition (wt%) for chill-cast disk sample compared to billet slice (6063 alloy)
measured along the log length [13].
Chill-cast Disk from Melt Billet Slice Analysis
0.2 m 3.5 m 6.8 m 0.2 m 4m 7m
Si 0.44 0.47 0.47 0.41 0.43 0.43
Fe 0.16 0.17 0.17 0.15 0.15 0.16
Cu 0.03 0.04 0.04 0.03 0.03 0.03
Mg 0.50 0.52 0.52 0.51 0.49 0.49
Mn 0.03 0.03 0.03 0.03 0.03 0.03
Ti 0.014 0.015 0.016 0.015 0.015 0.016

To ensure that the OES instrument is delivering
accurate results, certified reference standards
(similar alloy to that being tested) are routinely
cross-checked. These standards are measured prior
to the unknown alloy analysis. The cross check
results should be recorded and monitored.
Appropriate action is required if the precision falls
outside acceptable criteria, as discussed below.
Accurate results can only be assured by tracing
calibrations to primary standards/methods, and if
outside established control chart limits, by applying
a drift correction. The cross-check analysis should
be repeated after making the drift correction.
5.2 Accuracy and Precision
Accuracy is the closeness of the measured value
to the real value, while precision is a measure of
repeatability. The accuracy and precision of the
spectrochemical measurement are a function of
concentration and may deteriorate at low levels of
elements.
The accuracy of spectrochemical measurements
is assessed by determining the deviation from a
reported elemental concentration for an accepted
reference standard.
OES may be used for quantitative elemental
analysis of metals to about 13% relative precision.
The general precision of OES testing is given in
Table 4, while Table 5 shows the precision for
particular elements in the range of interest for
aluminium alloys [3].
The 3 sigma values define the 99.73% confidence
limits (or the range which covers 99.73% of results).
6. INSTRUMENT MAINTENANCE
The cleaning and general maintenance
procedures used by Comalco (on an ARL 3560 OES)
are given below as a guide [11]. The instrument
instruction manual should be referred to for specific
maintenance and cleaning practices.
The sample stand, table, glass bowl and o-rings
should be cleaned with tissue paper before each
analysis. Thorough cleaning of the sample stand is
also required after a number of samples have been
analysed (up to about 30), or when changing alloys.
Solvent should not be used to clean the table cavity
and stand, but ethanol can be used to clean the glass
bowl and the electrode tip.
When deposits form on the electrode, it should be
cleaned and and sharpened as required. A wire
brush can be used for cleaning of the electrode tip
prior to sample analysis, although care must be
taken to avoid contamination.

8Comalco Technical Report, No. 5

 [8]
Table 4. OES Precision capability .

Element Range Tolerance

(wt%) ( wt%)
0.001 - 0.009 0.002
0.041 - 0.10 0.010
0.76 - 1.00 0.05
1.51 - 2.00 0.07
5.51 - 6.00 0.17
> 7.01 3%

Typically the lens should be cleaned every three

months while replacement of the filter which collects
metal concentrates is generally required on a
monthly basis.
Check the argon supply frequently. Also regularly
check the oil level in the vacuum pump and replace
the oil every six months.
Preventative maintenance of the OES instrument
should be performed (by the equipment supplier or
agent) on a six-monthly basis.
7. TROUBLE SHOOTING
7.1 Bad Burn
A bad burn is usually due to an air leak between
the sample and the top of the excitation chamber.
This may be caused by a crack in the sample, or
samples which have not been machined flat.
A bad burn has shallow pitting in the centre area
of the spark, and is surrounded by a white/brown/
silver ring. If the aluminium intensity is measured,
the value will be low in the case of a bad burn, and
the results should be rejected. In contrast, a good
burn, shown in Figure 7, features a deeply pitted
area in the centre of the spark, and is surrounded by
a black ring.
Figure 7. Photograph illustrating good burns on a chillcast
disk sample.
7.2 Variation
Variation in results may be due to a number of
possible causes. These include:
incorrectly collected chill-cast disk which contains
inclusions or porosity, or a chill-cast disk collected
from a melt with low metal temperature;
inhomogeneous sample, or incorrect machined
depth;
contamination during sample machining and
preparation;
drift correction not performed; and
contamination of OES instrument.
Discrepancies may also arise between sites or
instruments due to the use of different standards,
or use of the wrong standards.
Glossary and References over page

[3]
Table 5. OES Precision for Some Elements in Aluminium Alloys .

Element Wavelength Low 3* High 3*

(nm) Concentration ( wt%) Concentration ( wt%)
(wt%) (wt%)

Na 588.995 0.0006 0.0003 0.015 0.003

Ti 363.545 0.10 0.0007
Cr 425.435 0.0012 0.0002 0.3 0.003
Cu 327.396 0.001 0.0003 4.8 0.11
Mn 403.076 0.0015 0.0002
Si 288.158 0.005 0.002 1.2 0.03
Si 212.415 0.052 0.005 11.3 0.16
Mg 285.213 0.15 0.002 1.6 0.07
Mg 518.362 1.6 0.02 3.0 0.08
* standard deviation

Comalco Technical Report, No. 59

8. GLOSSARY
AccuracyThe closeness of the measured value to
the true value.
Binary AlloyAn alloy composed of two principal
metallic components, for example Al-Mg.
Diffraction GratingAn optical device which
consists of an assembly of narrow slits or
grooves which produce a large number of
light beams of different wavelengths.
ExcitationThe addition of energy to a particle or
substance at ground state to produce an
excited state.
HomogeneousSubstance having uniform
composition or structure.
Induction Coupled Plasma analysis (ICP)A wet
chemical analysis technique where a liquid
sample is drawn up into a nebulizer, atomised
in a stream of argon, and vented into an
induced argon plasma. Sample atoms are
excited, and the emitted light intensity at
each wavelength is measured.
PhotonA massless particle carrying energy.
Point-To-Plane MethodA self-initiating oscillatory
capacitor discharge or triggered capacitor
discharge is produced between a prepared
flat surface of the sample and the tip of a
shaped graphite electrode.
Quantitative AnalysisAnalysis to determine the
elemental composition of the sample.
Relative PrecisionA measure of reproducibility
expressed as a percentage of the concentration
of the element being measured.
SegregationNon-uniform distribution of alloying
elements or phases resulting in localised
concentrations.
SparkA short duration electric discharge causing
volatilisation of material accompanied by
emission of light.
SpectrometerA spectroscope calibrated for the
measurement of light of specific wavelengths.
SpectrumThe ordered arrangement of
electromagnetic radiation according to
wavelength.
10Comalco Technical Report, No. 5
SprueAn opening through which molten metal is
poured into a mould.
VolatiliseConversion of a substance from a liquid
or solid state to a gaseous or vapour state.
WavelengthThe distance between two points
having the same phase in two consecutive
cycles of a periodic wave.
Wrought AlloyAn alloy that is mechanically
worked after casting.
9. REFERENCES
(1) H.J. Heine, 1996Analysing Elemental
Analysers, Foundry Management and
Technology, October, p30.
(2) J-L. Fortier and F.M. Kimmerle, 1987 O.E.S.
Quality Control of Aluminium Alloys
Composition, Quality and Process Control,
Light Metals, p155.
(3) ASTM E 1251-94, Standard Test Method For
Optical Emission Spectrometric Analysis Of
Aluminium And Aluminium Alloys By The
Argon Atmosphere, Point-To-Plane, Unipolar
Self-Initiating Capacitor Discharge, (1994),
Vol 03.06.
(4) ASTM E 716-94 Standard Practices For
Sampling Aluminium And Aluminium Alloys
For Spectrochemical Analysis, (1994), Vol.
03.06.
(5) AS 2612-83, Aluminium And Aluminium
Alloys Sampling And Preparation Of Solid
Samples For Optical Emission Spectrometry,
(1983).
(6) K. Slickers, 1983Automatic Emission
Spectroscopy, ARL.
(7) Optical Emission Spectrometers Systems
Description, 1982Bausch and Lomb ARL.
(8) D.E. Groteke, 1994Improving Your
Spectrometric Analysis of Aluminium,
Modern Casting, September, p36.
(9) J-L. Fortier and C. Tremblay, 1984
Segregation Effects in Aluminium Metal
Samples, Light Metals, p1,373.
(10) G. Blancfene and F. Dugain, 1986Quality
Control of Spectrographic Standards for
Aluminium and Aluminium Alloys,
International Molten Aluminium Processing
Conference, p449.

(11) P. Napolitano, Brief Description of CRCs

OES Analysis, CRC:TN:96:0289.

(12) C. Taylor, 1995Internal Report, 22

November.

(13) D. Irwin, 1997Internal Report, 17

September.

(14) Japanese Industrial Standard JISH 1305

1976Method for Photoelectric Emission
Spectrochemical Analysis of Aluminium and
Aluminium Alloy.

(15) Japanese Industrial Standard JISZ 2611

1977General Rules for Photoelectric
Emission Spectrochemical Analysis of Metal
Materials.

IMPORTANT DISCLAIMER
This brochure was prepared with no
particular reader in mind and therefore,
although we believe that the information
herein is accurate and reliable, no warranty
of accuracy, reliability or completeness is
given and (except insofar as liability under
any statute cannot be excluded). No
responsibility arising in any other way for
errors or omissions or negligence is accepted
by the company or any director, employee, or
agent of the company.

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