Spark Optical Emission Spectroscopy

Analytical Workshop 2012

Dr Heath Bagshaw CMA, Trinity College Dublin

Why Use Spark OES Analysis?

Quick, reliable and reproducible analysis technique Can analyse wide range of elements Usually used for metals\alloy analysis, such as :Steel, cast iron and high alloyed steels Non-ferrous metals and their alloys AI: wrought alloys, casting alloys, etc. Cu: bronze, brass, cupronickel, etc. Mg, Zn alloys, solders Nitrogen in steel P in aluminium Ultra low carbon analysis Elements such as Se, La, Te, etc. Good limit of detection for most materials - generally less then 50 ppm although 10 ppm detection limits are typical. Higher resolution spectrometers (using PMTs) have limits of detection of <10ppm with 1ppm typical, detection of O and N possible. Analytical Workshop 2012

Colours - Flame Testing

When an element is burned it burns with a distinct colour Strontium Potassium

Barium

These colours are due to the emission spectrum of the element.

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Basic Theory

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More Basic Theory

The emitted radiation\light is split using a prism or diffraction grating to produce a spectrum.

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Basics cont
modern equipment uses a slightly different set up:-

A diffraction grating is used to produce the spectrum and mirrors focus the radiation onto detectors. Analytical Workshop 2012

Emission Spectra
In the case of optical emission spectroscopy the EM radiation is in the visible\optical region of the EMS which we see as different colours depending on the wavelength\energy of the emitted photon.

The energy of a photon and its wavelength are related by the following equation:-

E = hc
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where h is Planck's constant (6.626 10-34 joules) and c is the speed of light (2.998 108 m/s).

Examples of Emission Spectra

Emission spectrum of H

Emission spectrum of Fe

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The System
Sample sparked to produce a burn Polychromatic light Emitted Light

CCD measures the light intensity at each wavelength

Diffraction Grating, Produces a dispersion spectrum

Computer
Calculation of results Comparison to Standards Data output and storage

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The Spectrometer (Schematic)

The diffraction grating Is like a concave mirror with lines ruled on it. Modern Gratings have up to 4000 rules/mm. Entrance Slit

130 800 nm Grating The incoming light is reflected and diffracted, producing the spectrum

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The Spectrometer (Real)

Entrance Slit

130 800 nm

The CCD chips simultaneously detect all incident light and determine the intensity of each wavelength. Analytical Workshop 2012

The Sample
Generally speaking the sample is metallic, flat and freshly ground. The sample is clamped in place and sparked to generate a spectrum this leaves burn marks on the sample:-

Burn marks

Sample

If the sample does not burn correctly spurious results can be produced. Poor burning can be caused by poor grinding and rough\uneven surfaces.

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Analysis
The Intensity of an emission line (colour) is proportional to concentration allows measurement of how much of each element is present. A number of standards are run first to set up a calibration curve, these take into account any matrix matching difficulties (i.e. overlap of elements in some materials). Take the example of Fe Requires six standards to correctly calibrate the instrument for Fe analysis.

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Analysis Continued
Once calibration is completed numerous samples can be analysed. The sample is simply clamped into place, sparked and a spectrum collected. The spectrometer collects the intensity of light at all wavelengths and compares this to the values for the calibration standard. This gives an accurate value of the elements present in the sample. Multiple sparks are collected until concordant results are obtained within an acceptable standard deviation. Further samples of the same alloy type can then be analysed. Different alloys require re-calibration before analysis can occur.

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System Types
Spark Optical Emission Spectrometers come in all shapes and sizes for a multitude of uses. Foundry\steel making applications usually floor standing to analyse composition of metals during production quality control. Portable units often used in manufacturing plants to assess metal composition. Portable units to analyse large immovable materials Hand held units to assist in scrap sorting The smaller the unit the less accuracy In the measurements so convenience over quality still useful as analysis can be Performed anywhere.