OES -Optical Emission Spectroscopy, or OES, is a well trusted and widely used analytical technique used to determine the

elemental composition of a broad range of metals.

The type of samples which can be tested using OES include samples from the melt in primary and secondary metal production, and in
the metals processing industries, tubes, bolts, rods, wires, plates and many more.
The part of the electromagnetic spectrum which is used by OES includes the visible spectrum and part of the ultraviolet spectrum. In
terms of wavelength, that’s from 130 nanometers up to around 800 nanometers.

OES can analyze a wide range of elements from Lithium to Uranium in solid metal examples covering a wide concentration range,
giving very high accuracy, high precision and low detection limits.

The elements and concentrations that OES analyzers can determine depend on the material being tested and the type of analyzer
used.

How does Optical Emission Spectroscopy work?

All OES analyzers contain three major components, the first is an electrical source to excite atoms within a metallic sample so that they
emit characteristic light, or optical emission, lines – requires a small part of the sample to be heated to thousands of degrees Celsius.
This is done using an electrical high voltage source in the spectrometer via an electrode. The difference in electrical potential between
the sample and electrode produces an electrical discharge, this discharge passes through the sample, heating and vaporizing the
material at the surface and exciting the atoms of the material, which then emits the element-characteristic emission lines.

Two forms of electrical discharge can be generated, either an arc which is an on/off event similar to a lightning strike, or a spark – a
series of multi-discharge events where the voltage of the electrode is switched on and off. These two modes of operation are used
depending on the element measured and the accuracy required.

The second component is an optical system. The light, the multiple optical emission lines from the vaporized sample known as a plasma
pass into the spectrometer. A diffraction grading in the spectrometer separates the incoming light into element-specific wavelengths and
a corresponding detector measures the intensity of light for each wavelength. The intensity measured is proportional to the
concentration offset element in the sample.

The third component is a computer system. The computer system acquires the measured intensities and processes this data via a
predefined calibration to produce elemental concentrations. The user interface ensures minimal operator intervention with results clearly
displayed which can be printed or stored for future reference.

So how do we generate element-specific optical emission lines from a metallic sample?

When the energy of an electrical discharge interacts with an atom, some of the electrons in the atom’s outer shells are ejected. Outer-
shell electrons are less tightly bound to the nucleus of the atom because they are further away from the nucleus and so require less
input energy to be ejected. The ejected electrons create a vacancy making the atom unstable.

To restore stability, electrons from higher orbits further away from the nucleus drop down to fill the vacancy. The excess energy
released as the electrons move between the two energy levels or shells is emitted in the form of element-specific light or optical
emission.

Every element emits a series of spectral lines corresponding to the different electron transitions between the different energy levels or
shells. Each transition produces a specific optical emission line with a fixed wavelength or energy of radiation.

For a typical metallic sample containing iron, manganese, chromium, nickel, vanadium, etc., each element emits many wavelengths,
leading to a line-rich spectrum. For example, iron emits just over 8000 different wavelengths so choosing the optimum emission line for
a given element in a sample is important.

The characteristic light emitted by the atoms in the sample is transferred to the optical system where it is split into its spectral
wavelengths by the high-tech grading, the grading contains up to 3600 grooves per millimeter.

Next the individual spectral line peak signals are collected by detectors and processed to generate a spectrum showing the light
intensity peaks versus their wavelengths. This means that OES provides qualitative information about the sample measured, however,
OES is also a quantitative technique.

The peak wavelength identifies the element, and its peak area or intensity gives an indication of its quantity in the sample. The analyzer
then uses this information to calculate the sample’s elemental composition based on a calibration with certified reference material. The
whole process, from pressing a start button or a trigger to getting the analysis results, can be as quick as 3 seconds or it can take up to
30 seconds for a full accurate quantitative analysis, it all depends on the analyzer used, the range of elements measured and the
concentrations of those elements.

Compared to other analytical techniques, OES has many advantages: it’s fast and relatively easy to use, it measures a wide range of
elements and concentrations in many different types of materials, including important elements such as carbon, sulfur, phosphorous,
boron and nitrogen. It’s extremely accurate when measuring low levels of trace and tramp elements, and it’s fairly low-cost compared to
other techniques.
For trace analysis of metals OES is the preferred method, OES is also currently the only method which can analyze carbon and nitrogen
on site, out of the laboratory.

SThe Reasons of Using Argon Gas

1. Below are the reasons of using high purity argon as the shielding :
2. Argon is an inert gas and won’t react with the elements in the alloy during the sparking period.
3. Isolate the atmosphere by flushing the surface so that the spectrometer won’t detect the elements in the atmosphere.
4. Spectrometer can detect the element, which has its characteristic peak below the wavelength 200nm correctly.
5. In the composition of alloy, the element Argon is not ignored.
6. Price of Argon is relatively inexpensive, typically, the price of inter gases from cheapest one to most expensive one:
Argon <Helium < Neon < Krypton or Xenon
The Awavelength range covered in oes is from 130-800nmrgon our OEAAS products

Argon is important in OES spectrometers analysing light elements like carbon, sulphur, phosphorous
& nitrogen. These elements are below 200nm in wavelength & Ar allows the optics of the
spectrometerto see from 200 & below. Issues from Ar cause a no. Of problems for a spectrometer,
most importantly the false rejection of a material that is otherwise good.

Common issues associated with the Ar system are:----

Argon quality: OES spectrometer users assume Ar is Ar but, there are different grades of Ar. 4.8 Ar
is 99.998 % pure while 5.0 is 99.999 % pure. The slight jump in the purity is the result of a no. Of
factors all of which contribute to 5.0 grade Ar.

Grade 4.8 Ar goes by the trade name zero while 5.0 Ar goes by the name ultra high purity-UHP.

Pressure: The amount of pressure within an Ar bottle is important for maintaining proper opwration.
When the pressure reaches 500 psi, it is time to place an order for a new bottle, when the pressure
reaches 300 psi, it is time to disconnect the bottle & connect to the new bottle. 300 psi is considered
empty as any low pressure will cause the Argon to ripple through the line instead of flowing & any
co2 or h2o trapped at the bottom of the cylinder will move with the Ar.

Flushing the system:

45 mins- 1 hour is the recommended duration for the Ar to flush through the system to remove
particles & atmospheric gases out of the system. Testing of samples after 10-20 mins. will give
incorrect readings

Summary: Ar grade, pressure & flushing duration play important roles in the spectrometer for the
analysis of low levels of analysis.If any one of the above parameters are not met, then the
operational performance of the spectrometer will fail.

What is the electromagnetic spectrum?

The electromagnetic spectrum consists of all the different wavelengths of electromagnetic radiation, including light, radio waves, and X-rays. We name regions of
the spectrum rather arbitrarily, but the names give us a general sense of the energy of the radiation; for example, ultraviolet light has shorter wavelengths than
radio light. The only region in the entire electromagnetic spectrum that our eyes are sensitive to is the visible region.
 Gamma rays have the shortest wavelengths, < 0.01 nanometers (about the size of an atomic nucleus). This is the highest frequency and most energetic region of
the electromagnetic spectrum. Gamma rays can result from nuclear reactions and from processes taking place in objects such as pulsars, quasars, and black
holes.
X-rays range in wavelength from 0.01 – 10 nm (about the size of an atom). They are generated, for example, by super-heated gas from exploding stars and
quasars, where temperatures are near a million to ten million degrees.
Ultraviolet radiation has wavelengths of 10 – 310 nm (about the size of a virus). Young, hot stars produce a lot of ultraviolet light and bathe interstellar space with
this energetic light.
Visible light covers the range of wavelengths from 400 – 700 nm (from the size of a molecule to a protozoan). Our sun emits the most of its radiation in the visible
range, which our eyes perceive as the colors of the rainbow. Our eyes are sensitive only to this small portion of the electromagnetic spectrum.
Infrared wavelengths span from 710 nm – 1 millimeter (from the width of a pinpoint to the size of small plant seeds). At a temperature of 37 degrees C, our
bodies give off infrared wavelengths with a peak intensity near 900 nm.
Radio waves are longer than 1 mm. Since these are the longest waves, they have the lowest energy and are associated with the lowest temperatures. Radio
wavelengths are found everywhere: in the background radiation of the universe, in interstellar clouds, and in the cool remnants of supernova explosions, to name a
few. Radio stations use radio wavelengths of electromagnetic radiation to send signals that our radios then translate into sound. Radio stations transmit
electromagnetic radiation, not sound. The radio station encodes a pattern on the electromagnetic radiation it transmits, and then our radios receive the
electromagnetic radiation, decode the pattern and translate the pattern into sound.

RELATION BETWEEN LIGHT & ENERGY & wavelength

E= hν (pronounced as “new”)

=hc/λ, where
c = speed of light = 3 x 108 m/sec
λ = wavelength
ν = frequency

E is energy, νν is frequency( actually it is a Greek letter called nu, it is not v) and h is Plank's constant (h=6.626×10^-34 J s).
This equation is in accordance with the Plank's Quantum Theory. It shows that energy of a quantum of radiation varies directly with its frequency.

The wavelength range covered in oes is 130-800nm that covers the visible range i.e.
from 400-700 & 100-400 nm is the uv range
Principle of Optical Emission Spectrometry

Optical emission spectrometry involves applying electrical energy in the form of spark generated between an electrode and a metal sample,
whereby the vaporized atoms are brought to a high energy state within a so -called “discharge plasma”.

Spectral lines
These excited atoms and ions in the discharge plasma create a unique emission spectrum
Therefore, the light generated by the discharge can be said to be a collection of the spectral lines generated by the element s in the sample. This
light is split by a diffraction grating to extract the emission spectrum for the target elements. The intensity of each emission spectrum depends on
the concentration of the element in the sample. Detectors (photomultiplier tubes) measure the presence or absence or presence of the spectrum
extracted for each element and the intensity of the spectrum to perform qualitative and quantitative analysis of the elements.

The intensity is generated in the output as counts

The element intensity is directly proportional to the concentration of the element.

Standardization- also called as drift correction or recalibration is done using only one standard, namely intelligent calibration logic or ical & is done for
CCD based spectrometers where the drift in the intensity is adjusted with that of the original.

CCD- A Charge Coupled Device (CCD) is a highly sensitive photon detector. The
CCD is divided up into a large number of light-sensitive small areas (known as
pixels) which can be used to build up an image of the scene of interest. A photon
of light which falls within the area defined by one of the pixels will be converted
into one (or more) electrons and the number of electrons collected will be directly
proportional to the intensity of the scene at each pixel. When the CCD is clocked
out, the number of electrons in each pixel are measured and the scene can be
reconstructed.

An actual CCD will consist of a large number of pixels (i.e, potential wells),
arranged horizontally in rows and vertically in columns. The number of rows and
columns defines the CCD size, typical sizes are 1024 pixels high by 1024 pixels
wide. The resolution of the CCD is defined by the size of the pixels, also by their
separation (the pixel pitch). In most astronomical CCDs the pixels are touching
each other and so the CCD resolution will be defined by the pixel size, typically
10-20µm. Thus, a 1024x1024 sized CCD would have a physical area image size of
about 10mm x 10mm.