Spark Optical Emission Spectrometer

Chemical analysis and the identification of metals are used for a wide variety of
purposes. These have become necessary to control the incoming goods or to ensure
that the manufacturing process produces the product with the correct elemental
composition. It is also used in failure investigation to determine if the correct material
was chosen. Further, in cases where national / international standards are to be
adhered to, the determination of chemical composition is self-evident.

For understanding the general importance of the chemical composition in the metal
industry, one is required to know that there are thousands of metal grades already
invented and each grade has its own set of specific metallurgical properties. For
example, in steel there are already more than 3,500 steel grades known, and each
steel grade can distinguish itself from other steel grades through a different melting
point, corrosion / acid resistance, and tensile strength etc. This is why, choosing the
correct grade is absolutely imperative and using an incorrect grade can lead to
manufacturing failures with heavy damages and costs.

A chemical analysis is normally performed with a spectrometer. But a spectrometer

on its own is not enough. It is to be remembered that spectrometers need an
extensive know-how, they need high quality argon / helium to work, and that the right
surface preparation is needed for correct analysis. Every organization needs the
budget and the qualified people to integrate the spectrometer in the organization.

Optical emission spectrometry is an analytical technique, universally considered and

used to determine the chemical composition of metal and alloys. Because of its
method precision and the short analysis time, it represents a valid control system of
production in all the fields regarding metal industry in any time during production
cycle, in case, it is necessary to have a fast and accurate chemical analysis of
material.
Optical emission spectrometry is considered as one of the old optical analytical
methods. Flame was used as a light source for the optical emission spectrometry in
the beginning. In the 1950s and the early 1960s, spark (also known as arc) optical
emission spectrometry prevailed since it has better excitation capability. Of the spark
optical emission spectrometers in service today, 99 % are used for the routine
spectrochemical analysis of metals of which 80 % of them consists of alloys of iron,
aluminum, and copper. The remaining applications concern alloys of nickel, cobalt,
zinc, titanium, magnesium, and the lead /tin /solder group and 1 % consists of
refractories, precious metals, steel-making slags and geological materials.

Spectrochemical analysis is a type of chemical analysis used to determine the

arrangement of atoms and electrons within molecules of chemical compounds. It
observes the quantity of energy absorbed during changes in motion or structure. The
wavelength and intensity of electromagnetic radiation is measured to produce
quantifiable results which are primarily used for quality assessment.

Brief history

In the spectroscopic history, spark excitation was the leading technique for elemental
analysis for a long time. In 1752, Thomas Melville observed bright yellow light
emitted from a flame produced by burning a mixture of alcohol and sea salt. In 1776,
Alessandro Volta reported for the first-time, uses of sparks for chemical analysis. He
was able to identify certain gases by the colours emitted when he applied a spark to
them. In the late 18th and early 19th centuries, Fraunhofer and others compared the
spectra emitted by flames and sparks with that from the sun and planets. In 1826, W.
H. Talbot reported a series of experiments in which he observed the colouring of
flames by a variety of salts.

Nature of emission spectra was beginning to be understood in1859, when Kirchhoff

and Bunsen observed that the sharp line spectra from flames were produced by
atoms and not molecules. In the beginning of the 20th century, the sharp lines which
appeared in the light emitted from electrical arcs and sparks were a driving force for
science. During the middle of the 20h century, quantitative spark spectroscopy was
the best tool which the analysts had to probe trace concentrations for a wide range
of elements.
There are a handful of spectrometric technologies available for determining the
chemical composition of metals. The four most common used techniques in the
metal industry are (i) x-ray fluorescence (XRF) spectrometry, (ii) optical emission
spectrometry, (iii) spark optical emission spectrometry, and (iv) glow discharge
optical emission spectrometry.

Spark excitation was the leading technique for elemental analysis for a long period in
the spectroscopic history. Presently, other techniques like ICP-OES (inductively
couple plasma – optical emission spectrometry), ICP-MS (inductively couple plasma
– mass spectrometry) and MIP-OES (microwave induced plasma – optical emission
spectrometry) are getting more attention because of their almost perfect analytical
performance. However, spark optical emission spectrometry still retains the super
solid sampling capability, in comparison with ICP or MIP techniques. For spark
excitation source, electrical discharge excitation sources were developed in late 19th
century. Later on, direct current, alternating current, and high voltage excitation
sources were developed in the first two decades of the 20th century.

Spark optical emission spectrometry is frequently used in metallurgical industry,

geological field and for monitoring of the environment. Numerous advances in terms
of evaluation of the instrument performance, reproducibility, limits of detection
(LODs), and linear dynamic ranges (LDR) have been done and reported. Advances
related to optimization of experimental conditions, interferences by spectrometry
molecular spectral band or by coexisting elements or background have also been
done. Improved sensitivity have been reported even for some hard-to-excite
elements such as Hf (hafnium) and W (tungsten).

A low-cost and compact spark optical emission spectrometer has been achieved by
using a hand-held spectrometer with a charge-coupled device (CCD) as a detector.

Spectroscopy and the spectrometer

Spectroscopy and spectrometer are the terms which are frequently being used when
discussing spectrochemical analysis. In simple terms, spectroscopy is the study of
energy in relation to a sample material, and a spectrometer is the instrument used
during spectrometry, the act of spectroscopy. Spectrometer is a device which
separates and analyses the individual spectral components of a physical
phenomenon to produce analytical results of interest. The spectrum, while most
naturally associated with light, can also be mass, magnetic, electron etc. leading to a
large variety of types of spectrometry, such as optical spectrometry, photoelectron
spectrometry, and mass spectrometry etc.

Spectroscopy – Spectroscopy is the study of the interaction between radiated

energy and a sample material. This interaction produces electro-magnetic waves in
the form of visible light, typically seen as sparks. Spectroscopy was introduced in the
17th century when Isaac Newton discovered that white light could be separated into
component colours using a prism, and these components could be recombined to
form white light. He realized that the prism is not what creates the colours, but it
instead works to separate colour components of white light. In the early 1800s,
Joseph von Fraunhofer performed experiments which further evolved spectroscopy
into a more precise and quantitative scientific technique. However, it was not until
the 19th century that the quantitative measurement of dispersed light was
standardized and recognized as a sound method of testing. Joseph von Fraunhofer
performed experiments with the spectrometer which led spectroscopy to become a
more precise and quantitative scientific technique.

The advantages and disadvantages of the optical emission spectroscopy are (i) fast
quantitative determination of elements (typically less than one minute), (ii) low capital
investment and operating costs, (iii) easy sample preparation, (iv) quick analysis
of carbon, nitrogen, oxygen, phosphorus, and sulphur in steel, (v) calculates carbon
content (%) of stainless steels or low alloy steels, (vi) provides input data to carbon
equivalent calculation, (vii) not completely ‘non-destructive’ (slight surface damage
can be expected), (viii) cannot test small parts, (ix) difficult to test in tightly confined
spaces, (x) needs constant calibration and maintenance, and (xi) routine third party
certification of results can be needed.

Optical emission spectroscopy can be employed on a range of materials from pure to

alloyed metals. Several industries benefit from spectrometers for process and quality
control.
Spectrometer – A spectrometer is the instrument used in spectroscopy which
produces spectral lines and measures their wavelengths and intensities. It is a
scientific device which separates particles, atoms, and molecules by their mass,
momentum, or energy. Spectrometers are integral to chemical analysis and particle
physics. There are two types of spectrometers namely (i) optical spectrometer, and
(ii) mass spectrometer.

An optical emission spectrometer, or simply ‘spectrometer’, is able to separate white

light and measure individual narrow bands of colours (spectrum). It shows the
intensity of light as a function of wavelength or frequency and the deflection is
created by refraction in a prism, or by diffraction in a diffraction grating. Optical
emission spectrometer uses the concept of optical dispersion, and since each
element in a sample leaves a unique spectral signature, spectral analysis can
determine the composition of the sample itself. Optical emission spectrometer is
common in metal production, astronomy, solar power, and semiconductor industries.

Optical emission spectrometer is user-friendly and widely accepted in the metal

manufacturing industry. Although a popular instrument, it still comes with a few
limitations including minor surface damage to the sample material and the need for
constant maintenance.

Spectrometers are frequently the instrument of choice for laboratories in the iron and
steel industry since they need only minimal intervention from the operators when
used for inspection, quality control, and alloy identification. Stationary and portable
versions are available, both with a high level of accuracy. Routine calibration and
maintenance are needed, and third-party certification of results are frequently
needed for spectrometer results to retain their validity. Spectrometers allow for metal
analysis throughout the metal life cycle from metal production to processing, as well
as at the end of its service life at the recycling plants

Optical emission spectrometers use the concept of optical dispersion. Each element
in a sample leaves a unique spectral signature, allowing spectral analysis to
decipher the composition of the sample.

Components of optical emission spectrometer

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

These excited atoms and ions in the discharge plasma create a unique emission
spectrum specific to each element. Hence, a single element generates several
characteristic emission spectral lines.

Hence, the light generated by the discharge can be said to be a collection of the
spectral lines generated by the elements 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 (e.g., photo multiplier tubes, charge coupled devices)
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.

In the broader sense, optical emission spectrometry includes, inductively coupled

plasma (ICP) optical emission spectrometry, which uses an inductively coupled
plasma as the excitation source. The terms ‘optical emission spectrometry’ and
‘photo-electric optical emission spectrometry’, however, normally refer to optical
emission spectrometry using spark discharge, direct-current arc discharge, or glow
discharge for generating the excitation discharge.Some optical emission
spectrometers feature ‘pulse distribution analysis’ (PDA) to improve the
measurement reproducibility (accuracy). This method involves statistical processing
of the spark pulse-generated emission spectra obtained from spark discharges in an
argon atmosphere. Fig 1 shows Important parts of spectrometer.
 Fig 1 Important parts of spectrometer

Sample preparation – Paper grinding is possible in most of the cases, but for lowest
carbon and oxygen levels, milling is desired. Simple and reasonable care is to be
taken during and after sample preparation, e.g., (i) the prepared surface is to be flat
in order to avoid air penetrating in the stand during the analysis, (ii) grinding paper
change is to be at well-defined time intervals, (iii) exposure of sample surface to dust
is to be avoided, and (iv) touching the prepared surface is to be avoided.

Optical emission spectrometer provides quantitative analysis using three key

components namely (i) an electrical source, (ii) an optical system, and (iii) a
computer system.

Electrical source – An electrical source is needed to excite atoms into an active

state within a metal sample. A small portion of the sample is heated to thousands of
degrees centigrade using a high voltage electrical source in the spectrometer
through an electrode. An electrical discharge is produced due to the difference in
electrical potential between the electrode and the sample metal. This electrical
discharge causes the sample metal to heat up and vapourize at the surface.

The electrode heats up the sample, exciting the atoms into an active state. This also
produces an electrical discharge, causing the sample metal to vapourize at the
surface. During this process, the activated atoms produce emission lines which are
distinct to each element. Two types of electrical discharges exist namely (i) an
electric arc, or (ii) a spark. An electric arc produces an ongoing electrical discharge,
much like lightning. An electric spark is more of an abrupt electric discharge, a brief
emission of light frequently accompanied by a sharp snapping sound. Fig 2 shows
schematic of metal surface vapourization by the electric discharge.

Fig 2 Schematic of metal surface vapourization by the electric discharge

Optical system – The optical system is composed of five main parts namely (i) the
primary slit (20 micro-metre), (ii) the grating to diffracts the light on the secondary
slits, (iii) the secondary slits to narrow down the wavelength bands, (iv) the mirrors to
reflect the light for focusing on the photo multiplier tubes, and (v) the photo
multipliers tubes. The primary lens is made of calcium fluoride (CaF2).

The optical system transfers the emission lines from the vapourized sample, known
as plasma, into the spectrometer. The diffraction grating in the spectrometer works to
separate the incoming light into element-specific wavelengths. The intensity of light
of each wavelength is then measured by a corresponding detector. The intensity
measured during this process is proportional to the concentration of the element in
the sample metal being tested. Since each element emits a specific set of
wavelengths based on its electronic structure, the elemental composition can be
determined by observing these wavelengths. The intensity of light of each
wavelength is measured by a corresponding detector which determines the
elemental composition. Fig 3 shows schematic of the optical system of a
spectrometer.

Fig 3 Schematic of the optical system of a spectrometer

Computer system – A computer system is needed in the spectrometer to process

the data. The measured intensities are processed through a pre-defined calibration
to produce elemental concentrations. Present day technology has advanced the user
interface to offer clear results with minimal operator intervention. The analysis time,
from the start of the analysis to the display of the result, is normally around 22 s
(seconds) to 25 s.

Principle

Spark optical emission spectrometer works on two very basic principles of physics
(Fig 4). The first is that the electrons in atoms absorb energy (get ‘excited’) and
move into higher energy states (also called orbits) when energy is applied. When this
energy source is removed, the electrons fall into the ground state and release the
absorbed energy in the form of photons. The second principle is that no two atoms of
different element can emit photons at the same wavelength. Hence, every
wavelength is unique to a single element alone. This means that once the
wavelength of the photon emitted is known, then the element, which is emitting it, is
known.

Fig 4 Principles of physics for spark spectrometer

Optical emission spectrometry is based on application of the electrical energy in the

form of spark generated by interaction of an electrode and a metal sample, whereby
the vapourized atoms are brought to a high energy state within a so-called
‘discharge plasma’. These excited atoms and ions in the discharge plasma create a
unique emission spectrum specific to each element. The radiation emitted by
element is directly fed to the spark spectrometer optics or through an optical fibre,
where it is dispersed into its spectral components. Hence, the light generated by the
discharge can be said to be a collection of the spectral lines generated by the
elements in the sample. This light is split by a diffraction grating to extract the
emission spectrum for the target elements. Fig 5 shows working principle of a
spectrometer.
 Fig 5 Working principle of a spectrometer

Excitation in spark spectrometer is produced by the energy of the electrical

discharge between the sample and the electrode. In all early instruments electrical
discharge was carried out in air but today it is carried out in an argon atmosphere.
For this type of spectrometer using electrical excitation, the sample is to be
electrically conductive. Hence, this instrumentation is very popular in the metal
industry.

Direct current arc excitation source has been used in connection with a multi-channel
spectrometer. Advantages of direct current spark are (i) simple handling, (ii) no /
minimum sample preparation, (iii) no / minimum use of special atmospheres to
achieve, (iv) complete evaporation of the analytes, (v) low contamination by the
method itself, and (vi) rapid and cost-effective qualitative method for semi
quantitative overall analysis of unknown materials.

Alternating current arc has used as excitation source and reported in 2000 by Goldik.
The arc was made from two electrodes with 10 mm gap between them. The applied
open circuit voltage was 13 kV and the closed-circuit current was 30 mA with source
temperature of 3,500 K using iron Fe (iron) spectral lines. This system has
advantage of its low acquisition and operation cost. Its atmospheric operation without
additional gas is another advantage of this new emission source.
Spark-like excitation refers to high-current discharges which come in short bursts,
similar to gun shots. Some typical electrical parameters for a ‘spark-like’ discharge,
are (i) frequency – 200 Hz (hertz) to 1,000 Hz, (ii) operating voltage – 400 V (volt) to
1,000 V, (iii) peak current – 50 A (ampere) to 150 A, and (iv) FWHM (full width at half
maximum) – 50 micro-seconds to 100 micro-seconds. Arc-like excitation refers to a
lower current, drawn-out, almost continuous discharge. Arc like discharges can be
either direct current (DC), or alternating current (AC) with a frequency like the spark-
like discharges. The DC arc is a low-current discharge of the order of perhaps 3 A to
10 A. The AC arc can provide currents as high as 20 A to 30 A with a frequency of
100 Hz to 200 Hz and a total duration for each cycle of 500 micro-seconds to 1,000
micro-seconds. Analytically, the differences between the arc and spark excitations
can be summarized as in Tab 1.

Tab 1 Analytical comparison of arc and spark excitation

Arc Spark
Parameter Unit
discharge discharge

Precision % RSD
(comparison (relative
1–5 0.3 – 1
of standard
repeatability) deviation)

LOD (limits ppm (parts per

1 – 10 10 – 100
of detection) million)

The precision numbers listed in Tab 1 are at concentrations well above the limit of
detection. The primary function of the excitation source is to generate spark-like or
arc-like electrical discharges. These discharges vapourize sample material and
produce excitation of the electrons of the atoms for the measurement of spectral line
light intensities.

Yamamoto and Takimoto invented a device composed of a sample holder having a

through hole, a spark electrode, and an inert gas inlet tube, suited for use in the
measurement of oxygen in a metal sample, wherein the size, i.e., the diameter, of
the metal sample was appropriately selected so that the electric spark was
generated from the whole discharged area to eliminate the influence of element
segregation in the sample. The analytical precision was improved by using an
optimized threshold value obtained by measuring the relationship between the
maximum analytical precision and spectral intensity of matrix element. The elemental
detection was performed by measuring the spectral ratio of the analyte element to
the matrix element within the threshold range.

A typical spark stand (electrode and sample geometry) diagram is shown in Fig 1. It
shows the conventional ‘point-to-plane’ configuration (electrode to sample). The
electrode typically is made of tungsten, although graphite electrodes have been used
in the past with non-ferrous materials. The spark stand in modern instrumentation is
flushed with argon to prevent oxidation effects and allow transmission of UV
(ultraviolet) wavelengths absorbed by oxygen.

The voltage in the circuit is normally between around 400 V and 1,000 V which is not
enough to cross the 3 mm to 4 mm spark gap, a much higher voltage, on the order of
10,000 V, is needed, which is provided by an ignitor circuit. In present day spark
excitation sources, the discharge is unidirectional, from the electrode to the sample.
The switch is opened and closed electronically many times per second. This is
referred to as the ‘frequency’ of the discharge. In ‘spark gap’ temperature of 5,000 K
to 15,000 K is generated. It is in this region where analytical processes important for
spectrochemical analysis occur.

The detectors like charge coupled devices or photo multiplier tubes, which are the
most suitable line for the application, are then used to measure the range of
wavelengths emitted by each element. The concentration of the element in the
sample is directly proportional to the radiation intensity, which is calculated internally
from a stored set of calibration curves and can be shown directly as percent
concentration. Fig 6 shows structure of optical emission spectrometers
 Fig 6 Structure of optical emission spectrometers

High energy pre-spark – The excitation source has another very important function.
It is to homogenize the sample surface in preparation for the actual measurement of
light intensities. The homogenization is achieved by first subjecting the sample
surface to a HEPS (high energy pre spark). The action of HEPS is comparable to
that of a remelt furnace, i.e., on subjecting the sample surface to the electrical
discharge the sample is effectively ‘re-melted’. This technique is important in
removing any effects of the metallurgical history or structure of the sample (for
example, cast versus wrought, heat treatment, and so forth).

Typical pre-spark currents can be from around 120 A to 150 A with durations from
around 10 s to 20 s. Depending upon the electrical parameters used, the crater
produced in the sample surface during the high-energy pre-spark is around 10 mm in
diameter with a maximum depth (penetration at the centre) on the order of 50 micro-
metre.

The sample is ready after the pre-spark period for the actual measurement or
integration of the light intensity signals. This technique is used primarily when very
small quantities of elements present in sample are to be detected. The excitation is
carried out by spark-like discharge for around a 5 s time period. The complete
source cycle during the sparking of a sample is (i) HEPS (homogenization) – 10 s,
(ii) spark (measurement) – 5 s and (iii) arc (measurement) – 5 s.

The most important part of the protocol is excitation of the sample. The sample is
excited on a sample stand by using an electronic device which provides high voltage
spark.  A low voltage arc between the surface of the sample under test and a counter
electrode is used to analyze the sample. A classical source is of the RLC (resistor,
inductor, and capacitor) circuit discharge type and its frequency can rise up to 400
Hz. A spark is generated by applying high voltage to the sample and the emitted light
is used to determine the concentrations of the element within the sample.

The purpose of sample slide helps in placing the sample in a reproducible way
relative to the optical device in the spectrometer. The argon is circulated in the
enclosure of the sample stand at a rate of 0.2 litres per minute (l/m) to 0.5 l/min
which increases automatically during sparking. A water circuit is used to cool the
table. The process involves production of two sparks, one is of high voltage while
other is of low voltage. The high-energy spark prepares (melt and homogenize) the
sample surface and then the light emitted from lower energy spark is measured. The
shutter is of the instrument unit opens during the measuring phase by an
electromagnetic valve.

The optical dispersion system of the spectrometer is placed in a mechanical housing.

To avoid any deformation in the spectrometer by dilatation, it is placed in a thermo-
controlled (at 38 deg C +/- 0.1 deg C) insulated cabinet called oven. The light path is
around 2 m (metre) long. As air absorbs ultraviolet light, it is necessary to put the
spectrometer under vacuum to avoid this effect.

As regards detection system, photo multiplier tube is most commonly used as the
detector for direct-reading optical emission spectrometer. However, this system has
limitations of single channel and bulkiness. With the fast development in detectors,
other detectors like semi-conductor, solid-state detectors including the charge-
coupled device, photo-diode-array detector (PAD), and charge-injection device (CID)
are used in spark optical emission spectrometer.

In its broadest definition, a charge-coupled device image sensor is an analogue

integrated circuit which converts an optical image into an electronic output. As with
several semi-conductor components, the evolution of charge-coupled device from a
laboratory concept has been extremely rapid, boosted by their potential for a wide
range of applications in both consumer products and sophisticated professional
equipment. Today, this advanced technology is used in the spectrometers. In the
present-day optical emission spectrometers, charge-coupled device has the
equivalent of 8,044 detectors of 7 micrometres by 7 micrometres. Because of this, all
the wavelengths (from 170 nanometres to 410 nanometres) necessary for multi-
element, multi-base analysis are available without the need for additional hardware.
Their integrated nature provides their best-known features, namely unlimited lifetime
and miniaturization. To these can be added some more specific characteristics,
including image analysis in discrete elements (pixels) with exact field registration.
Each spectrum is stored, and a retrospective analysis for ‘extra’ elements is possible
without the need to spark the sample another time.

Solid-state detectors have an advantage of multi-channel detection for simultaneous

multi-element measurements. Whereas charge-coupled device detectors have made
possible to detect elements simultaneously in polymer materials within 5 s, the use
of miniaturized   spectrometer led to a possible portable spark optical emission
spectrometer instrument. But quick quantitative analysis of 1.8 (Zn) mg/g (milli grams
per gram) to 9.3 (Mg) mg/g direct solid sampling has been made possible by LODs
(limits of detection).

Coates and co-workers proposed an on-site analyzer for analyzing lubricant oils and
functional fluids. The optical emission spectrometer analyzed light captured from a
spark emission stand through which the fluid sample has flown. Diagnostic text for
an operator is generated by an expert which operates system according to a set of
rules based on the information collected from the optical emission spectrometer and
other measurement devices about the fluid sample. The size, weight, and cost of
instrument has reduced and made it suitable for on-site analysis.

Charge injection device, a solid-state detector similar to charge coupled device, has
also been used in optical analytical instrumentation. It has same main advantages as
the charge coupled device. The entire spectral range has been recorded with the use
of a direct current arc spectrometer using echelle grating and a charge injection
device camera as a detector. Simultaneous precision in measurement can be
achieved in any particular emission line. The technique has been applied for the
determination of molybdenum in tungsten compounds.

The optical emission spectrometers can be factory calibrated for iron and steel
utilizing a very sophisticated multi-variable regression tool which corrects for matrix
effects as well as spectral interferences. The tool provides an immediate ‘turnkey’
system which gives the user the highest accuracy possible. The calibrations are
available for the different qualities. For each quality, the supplier use certified
material as standard samples and setting-up samples are delivered with the
instrument to maintain the accuracy of the calibration.

In a spark optical emission spectrometer, the principles outlined above are leveraged
to analyze metallic samples to assess exactly which elements are present in it, and
in what proportion. The output of the optical emission spectrometer is a detailed
assessment of the elemental composition of the sample in weight percentages.

Test procedure

First up, there is a need to ‘spark’ the sample. Hence, the sample is first prepared,
i.e., one face of the sample is made absolutely uniform, clean, flat and as free from
surface flaws as possible. Suitable methods of sample preparation are to be used for
this. The prepared sample is then placed on the sample stand. The sample stand
has a hole in it which the sample must cover. Below this, there is an electrode at a
fixed distance from the sample’s exposed surface. This entire spark enclosure is
filled with argon when analysis is to be done. Then, a high current is applied to the
sample.

The extremely high levels of direct current create a plasma in the argon-purged
atmosphere of the spark chamber, and a rapid series of high-energy sparks is hence
created between the electrode and the sample. Application of these sparks causes a
part of the sample to vapourize. The vapourized atoms in the plasma absorb energy
and their electrons move to higher energy-states with each spark. With each
removal, the electrons move back into ground state and emit photons. Given the
large number of elements simultaneously emitting photons, a composite emission is
generated. This composite light is made to fall upon a diffraction grating. The
diffraction grating separates each individual wavelength and creates a spectrum
inside what is called the ‘optical chamber’.

The spectrum can now clearly be analyzed. The basis for analysis is of course,
simplicity itself. The wavelengths which characterize each element are known.
Further, the stronger the intensity of the emission at an element’s wavelength, the
higher is its concentration. A database containing the concentration levels that
different intensity values correspond to for each wavelength of interest is available
which simply look up the emission intensity against this database and say with
conviction what the concentration of individual elements is.

New developments

The first instruments (very early) had to work without photo-emitters. The earliest
procedures hence had to rely on more mundane analog methods. As per these
procedures, a photographic plate is simply placed, upon which the diffracted
spectrum would fall. This plate was then developed and studied to arrive at the
required results.

In the 1930s however, there emerged the photo multiplier tube, a vacuum tube which
emits electrons when light is incident upon it. Spectrometers hence rapidly moved to
using photo multiplier tubes. A photo multiplier tube was hence placed inside the
optical chamber in precise position for each wavelength which the user wished to
analyze. Along with this, there was also a computer connected to the spectrometer.
The computer stored the database against which the photo multiplier tubes’ outputs
were compared to arrive at the elemental composition needed. This automated the
process and not only made it far more rapid and convenient, but also far more
accurate and error-free.

This worked very well for decades, but, as the technology moved on, photo multiplier
tubes clearly had a number of drawbacks. Photo multiplier tubes have medium high
resolution, and very high focal length. Further, they were very large and expensive.
Flexibility was absent, once manufactured, there was no possibility of any
modification. It did not have any ability at all to modify. Even a single element
increase meant a new optical emission spectrometer. Cost and tedium were very
high. Detectors, cards etc. were extremely expensive. Regular profiling was needed.
It had vacuum which was required to be maintained. This led to the fading away of
photo multiplier tubes and increase in the popularity of charge-coupled devices and
complementary metal oxide semi-conductor (CMOS) detectors. Fig 7 shows
developments in optical emission spectrometers.
 Fig 7 Developments in optical emission spectrometers

The introduction of charge-coupled device and now complementary metal-oxide

semiconductor (CMOS) detectors solved literally every issue which the photo
multiplier tube devices posed and also offered several more upsides to spectrometer
makers and users. Just a few of these are (i) unmatched flexibility since every
wavelength is captured and so can be analyzed, (ii) no limitation of space as charge
coupled devices are small, (iii) instruments became smaller and less expensive since
high-resolution grating and charge coupled devices result in shorter focal lengths,
(iv) fewer detectors mean fewer cards and lower cost with low tedium and low
running costs, (vi) no need for profiling etc. since all this is automated, and (vii) no
vacuum and efficient electronic which results in lower running costs.

Hence, spectrometers rapidly shifted towards using these devices and today, the
modern optical emission spectrometer exclusively comprises of optics with these
devices. Present day spectrometers are of two types. Type A use single / fewer (2 to
3) charge coupled devices / complementary metal oxide semi-conductor detectors
closer to the grating. These spectrometers have lower resolution, low focal length,
very compact, and very economical. Type B use several charge-coupled devices /
complementary metal oxide semi-conductor detectors (5 to 20+) further away from
grating. These spectrometers have very high resolution, medium focal length,
compact compared to spectrometer with photo multiplier tube, and economical
compared to spectrometer with photo multiplier tube.
While modern optical emission spectrometer design focuses exclusively on charge
coupled device / complementary metal oxide semi-conductor detectors, there remain
some legacy instrument models which still feature photo multiplier tube detectors.
Just as when the shift to DSLRs (digital single lens reflex) began, it did not
immediately see all analog SLRs (single lens reflex) immediately withdrawn, so too,
while the fall in photo multiplier tube optical emission spectrometer’s market share
has been precipitous, there are still a handful of models with this technology which
remain in the market.

Application

Optical emission spectrometer is capable of solid sampling. It is widely applied for

the analysis of a broad range of samples. It is applied for the analysis of steel,
metals and alloys, geological samples, biological samples, environmental samples,
and other kinds of samples and special techniques. It has a very high up-time,
delivers dependable performance. The optical emission spectrometer offers rapid
elemental analysis of solid metal samples, making it indispensable for quality control
in iron and steel plants and aluminum metallurgy processes.

The spark optical emission spectrometer is able to determine all the elements
necessary in the present and future applications, in all possible qualities of iron and
steel such as white or grey cast iron, alloyed cast iron, low alloy steel and high alloy
steel. It is the answer to the analytical needs, whether for incoming goods control,
metal sorting, process quality control, final product quality control, certification or
investigation.

In case of sampling, it is used to analyze the inclusions of micro impurities and the
macro components. It is used to analyze the standard reference materials and real
steel samples. It is also used in the analysis of non-metal elements (e.g., carbon,
nitrogen, sulphur, phosphorus, oxygen, silicon, and boron) in steel samples.
Quantitative or qualitative analysis of nitrogen in steel is also determined through this
technique.

Considerable progress has been made in the analysis of low concentration carbon,
nitrogen, and oxygen in steels by optical emission spectrometry. The concentration
of these elements, as well as those of phosphorus, sulphur, and hydrogen is to be
reduced to obtain so-called ‘clean steels’, or controlled, as they have, individually or
together, dramatic effects on steel properties, such as strength, formability,
toughness, weldability, fatigue resistance, etc. The constant amelioration of steel
cleanness being necessary to produce always improved and more competitive steel
products, there is a demand for quantitative analysis at lower and lower levels. The
new performance obtained with the latest models of optical emission spectrometer
fulfills the latest analytical requirements of steel producers regarding carbon,
nitrogen, and oxygen.

In case of metals and alloys, the technique is used (i) for the analysis of impurity of
elements in metals or alloy, (ii) for the analysis of primary and commercial-purity of
aluminum, (iii) for the analysis of molybdenum powder in chromium, iron, and nickel,
(iv) for the analysis of oxygen in copper, and (v) for the detection of gases in titanium
and for the detection of impurities (iron, silicon, copper, manganese, aluminum, and
nickel) in pure magnesium.

In case of geological and related samples, the technique is used for the
simultaneous determination of gold, platinum, palladium, rhodium, iridium, and
ruthenium in geological samples and for the analysis of rock, ores and minerals.

In case of biological samples, direct analysis of micro-volume of biological samples

like liver, heart, brain, kidney, bone, serum, and muscles of white albino rats has
been reported by this method.

In case of environmental and waste samples, the technique is used for the analysis
of chromium in air and micro quantities of elements in waste samples.