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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. 2. 3.

INTRODUCTION OPERATION PRINCIPLES CALIBRATION 3.1 Family of Curves Method 3.2 Master Curve Method 3.3 Drift Correction 3.4 Standards SAMPLES 4.1 4.2 4.3 Sampling from Molten Metal Preparation of Samples Non-standard Samples

3 3 4 4 5 5 5 5 5 6 7 7 7 8 8 9 9 9 10 10

4.

5.

MEASUREMENT 5.1 Procedure 5.2 Accuracy and Precision INSTRUMENT MAINTENANCE TROUBLE SHOOTING 7.1 Bad Burn 7.2 Variation GLOSSARY REFERENCES

6. 7.

8. 9.

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
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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. 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 chillcast 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.

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 71694 (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

sample effective sample discharge spot discharge plasma (instantaneous exposure)

counter electrode

Figure 1. Sample excitation by electrical discharge

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Applied energy, E

Photon, E2-E1 = hc

E1

E2

Initial energy E1

Electron excited, energy E2

Return to initial energy 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.

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

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 signal intensities to chemical concentration for particular elements. The relationship between optical emission intensity and concentration must be established using certified standards. Normally, reference standards are certified by wet chemical methods. Comalcos Smelters and Research Centre have calibrated their OES units via either a Family of
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lens mirror primary slit

grating

Figure 3. Optical systems of a typical OES spectrometer.

Mn (wt%)

Outside calibration range Each point represents a calibration standard

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.

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.

3.4 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.

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

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

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Concentration

Master curve defined using binary standards

Alloy (working) curve defined using matrix correction standards

Binary standards High purity standard Spectral background Intensity ratio

Certified reference alloy materials

Figure 5. Relationship between master and alloy curves.

be capable of producing homogeneous chill-cast 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.

4.2 Preparation
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 Analytical Reference Materials International Inc. Aluminium Company of America Graham B. Jackson Pty. Ltd. Address PO Box 2246 Evergreen Colorado 80439 USA 600 Block Freeport Rd. New Kensington PA 15068 USA 125 Thomas St. Dandenong Vic. 3175 Australia Contact Numbers Ph: (303) 670 1300 Fax: (303) 670 1392 Ph: (412) 339 6702 Fax: (412) 339 6740 Ph: Fax: (3) (3) 9793 3322 9794 7240

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64mm

613mm

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.

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. Remelting 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 26111977 [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.

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Table 2. Example of changes in OES measured composition (wt%) due to non-standard sampling of a 6000 alloy [12] . Melt certificate 0.77 0.22 0.18 0.85 0.003 0.009 0.11 0.08 0.013 Cast billet slice 0.78 0.21 0.20 0.81 0.003 0.009 0.11 0.07 0.014 Homogenised billet slice 0.73 0.19 0.19 0.78 0.002 0.008 0.11 0.07 0.015 Extruded profile 0.73 0.19 0.19 0.78 0.002 0.008 0.11 0.07 0.015 Extrusion re-melted into chill-cast disk 0.80 0.22 0.20 0.83 0.003 0.009 0.11 0.08 0.014

Si Fe Cu Mg Zn Ni Mn Cr Ti

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]. 0.2 m Si Fe Cu Mg Mn Ti 0.44 0.16 0.03 0.50 0.03 0.014 Chill-cast Disk from Melt 3.5 m 6.8 m 0.47 0.17 0.04 0.52 0.03 0.015 0.47 0.17 0.04 0.52 0.03 0.016 0.2 m 0.41 0.15 0.03 0.51 0.03 0.015 Billet Slice Analysis 4m 0.43 0.15 0.03 0.49 0.03 0.015 7m 0.43 0.16 0.03 0.49 0.03 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.

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

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.
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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.

Table 4. OES Precision capability Element Range (wt%) 0.001 - 0.009 0.041 - 0.10 0.76 - 1.00 1.51 - 2.00 5.51 - 6.00 > 7.01

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. Tolerance ( wt%) 0.002 0.010 0.05 0.07 0.17 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.

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.

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.
Table 5. OES Precision for Some Elements in Aluminium Alloys Element Wavelength (nm) 588.995 363.545 425.435 327.396 403.076 288.158 212.415 285.213 518.362 Low Concentration (wt%) 0.0006 0.0012 0.001 0.0015 0.005 0.052 0.15 1.6
[3]

Glossary and References over page

. 3* ( wt%) 0.0003 0.0002 0.0003 0.0002 0.002 0.005 0.002 0.02 High Concentration (wt%) 0.015 0.10 0.3 4.8 1.2 11.3 1.6 3.0 3* ( wt%) 0.003 0.0007 0.003 0.11 0.03 0.16 0.07 0.08

Na Ti Cr Cu Mn Si Si Mg Mg
* standard deviation

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8.

GLOSSARY

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.

AccuracyThe closeness of the measured value to the true value. Binary AlloyAn alloy composed of two principal metallic components, for example Al-Mg. Diffraction Grating An 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. Homogeneous Substance having composition or structure. uniform

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REFERENCES
H.J. Heine, 1996Analysing Elemental Analysers, Foundry Management and Technology, October, p30. J-L. Fortier and F.M. Kimmerle, 1987 O.E.S. Quality Control of Aluminium Alloys Composition, Quality and Process Control, Light Metals, p155. 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. ASTM E 716-94 Standard Practices For Sampling Aluminium And Aluminium Alloys For Spectrochemical Analysis, (1994), Vol. 03.06. AS 2612-83, Aluminium And Aluminium Alloys Sampling And Preparation Of Solid Samples For Optical Emission Spectrometry, (1983). K. Slickers, 1983Automatic Emission Spectroscopy, ARL. Optical Emission Spectrometers Systems Description, 1982Bausch and Lomb ARL. D.E. Groteke, 1994Improving Your Spectrometric Analysis of Aluminium, Modern Casting, September, p36. J-L. Fortier and C. Tremblay, 1984 Segregation Effects in Aluminium Metal Samples, Light Metals, p1,373.

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.

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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. Spectrum The ordered arrangement of electromagnetic radiation according to wavelength.
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G. Blancfene and F. Dugain, 1986Quality Control of Spectrographic Standards for Aluminium and Aluminium Alloys, International Molten Aluminium Processing Conference, p449. P. Napolitano, Brief Description of CRCs OES Analysis, CRC:TN:96:0289. C. Taylor, 1995Internal Report, 22 November. D. Irwin, 1997Internal Report, 17 September. Japanese Industrial Standard JISH 1305 1976Method for Photoelectric Emission Spectrochemical Analysis of Aluminium and Aluminium Alloy. Japanese Industrial Standard JISZ 2611 1977General Rules for Photoelectric Emission Spectrochemical Analysis of Metal Materials.

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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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