Development of a New Etchant for Austenitic Manganese Steel

Shankha Pathak*, Abhimanyu Maharshi**

Abstract
Austenite grain size is an important parameter for the ductility of steel. The
ductility of Austenitic Manganese Steel is directly dependent on the grain size.
Therefore, it is most important to measure the grain size and to investigate the
microstructure of the steel to predict the mechanical properties of the steel.
To reveal the prior austenite grain boundaries commonly used etchants are
picric acid and 2% Nital. The main drawbacks of these etchants are the
lightly etched grain boundaries and uncertainty to reveal the twins. One of
the main objectives of the present work was to find out a viable etchant that
can efficiently reveal the grain boundaries along with the twins. The results of
the presented etchant examinations serve as an important basis for revealing
a clear picture of the austenitic grain boundaries.

Keywords: High Manganese Austenitic Steel, Grain boundary, etchant,

twins.

Introduction

High Manganese Austenitic Steel

Use of Microstructure Evolution

The original austenitic manganese steel,

containing about 1.2% C and 12% Mn, was
invented by Sir Robert Hadfield in 1882 and was
first produced by the US in 1892. The basic
condition for the chemical composition of
Austenite Manganese Steel is the ratio Mn/C=>10.
The upper borderline is normally 15% Mn, but in
practice this ratio can be increased to 20 % mostly
in thick walled castings. The main reason for using
high content of Mn is to improve the
hardenability. The steel was unique since it
exhibited high toughness, high ductility, high
work hardening ability and excellent wear
resistance. Because of its properties, it rapidly
gained acceptance as a very useful engineering
material. Hadfield`s austenitic manganese steel is
still used extensively, with minor modifications in
composition and heat treatment. Austenitic steels
with higher manganese contents (>15%) have
recently been developed for applications requiring
low magnetic permeability, low temperature
(cryogenic) strength and low temperature
toughness. It is available under the trade name
Manganal as plates, hot- rolled bars and special
shapes. At around 10% manganese content, the
steel retains in its austenite form at room

The term microstructure is used to describe the

appearance of the material on the nm-cm length
scale. It is defined as the structure of a prepared
surface or thin foil of material as revealed by a
microscope above 25 magnification.
The microstructure of a material can strongly
influence physical properties such as strength,
toughness,
ductility,
hardness,
corrosion
resistance, high/ low temperature behavior, wear
resistance which govern the application of these
materials
in
industrial
practice.
The
microstructures of natural minerals provide
information about their complex geological
history. Microstructures of a material can be
tailored to give it specific properties and it is
because of these abilities that microstructure is a
fundamental part of all materials and minerals
science.
Hence, it is clear that since microstructures
facilitate the determination of the physical
properties of a material, so, its determination is of
great importance as far as the history and the
properties of the material is concerned.

Deputy Manager, Texmaco Rail & Engg. Ltd.

BITS Pilani, K.K. Birla Goa Campus

**

Correspondence to: Mr. Shankha Pathak, Deputy Manager, Texmaco Rail &Engg. Ltd.
E- mail: dgpkid@yahoo.com

ADR Journals 2014. All Rights Reserved.

Pathak S et al.

temperature if cooled correctly. Both hardness and

ductility reach their highest points around 12%
manganese depending on other alloying elements
in steel.

the affected part or parts removed from service

before complete failure occurs.

Properties

Austenitic Manganese Steel is primarily used in

the fields of earthmoving, mining, quarrying, oil
well drilling, steelmaking, railroading and in the
manufacture of cement and clay products. It is also
used in equipments for handling and processing in
a low magnetic permeability, low temperature and
low temperature toughness conditions. Other
applications are in the field of development of
superconducting
technologies
used
in
transportation systems, nuclear fusion research
and structural materials to store and transport
liquefied gases. Mn alloy has been used in the
cement mixers, rock crushers, railway switches
and crossings, crawler treads for tractors and other
high impact and abrasive environments. It is also
used in high impact environments like inside a
shot peening machine, and earthen materials.
Other applications include fragmentizer hammers
and grates for automobile recycling and military
applications such as tank track pads

The mechanical properties of austenitic

manganese steel vary with both carbon and
manganese content. As carbon is increased, it
becomes increasingly difficult to retain all of the
carbon in solid solution, which may account for
reductions in tensile strength and ductility.
Manganal thrives on severe wear conditions. The
surface hardness increases with more impact and
hammering. The steel can achieve up to three
times its surface hardness during conditions of
impact without any increase in brittleness, which
is usually associated with hardness, which allows
the steel to retain its toughness. This characteristic,
known as work- hardening, plus the fact that it
remains ductile underneath, makes it the most
effective steel in combating impact and abrasion.
It has very high strength, ductility, toughness, and
excellent wear resistance in the roughest
applications. It has a low coefficient of friction
which is very important to wear resistance which
is considered to be an essential characteristic in
metal- to- metal applications. It is non- magnetic
substantially. Continuous high temperature can
embrittle it. It can be flame cut by oxy- acetylene
torch, cut by abrasive cut- off machine and electric
welded. The high hardness of face layers increases
the abrasive wear resistance but since the middle
part keeps good toughness, the steel component
supports high impact stress. It is apparently
immune to hydrogen embrittlement. There is a
gradual decrease in impact strength with
decreasing temperature. Resistance to crack
propagation is high and is associated with very
sluggish progressive failures. Because of this, any
fatigue cracks that develop might be detected, and

Phase / Compound
Ferrite
Austenite
Pearlite
Martensite
Cementite

Uses

Color of Different Phases as under

Optical Microscope
In optical microscope, different phases /
constituents are identified by the color and texture.
As the different phases of steel with specific
crystal structure corrode at different rates, the
amount of light reflected from the polished etched
surface is different and the angle of reflection
from different phases is different too. This, in turn,
creates different colors and texture, and therefore
the color and texture of different phases are
different. Typical colors / texture of different
phases revealed by 2% Nital has been tabulated
below:

Color / Texture
White
White / Yellow
Black , Lamellar
Black and white ,
Acicular
White

Table 1.Color and Texture of Different Phases after Etching with 2% Nital

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Pathak S et al.

Microstructure Preparation Process

Sawing the section to be examined
Mounting in resins (if sample is too
small)
Coarse grinding
Check Point: Grinding on progressively
finer emery paper in perpendicular to the
previous direction of polishing
Check Point: Polishing using alumina
powder or diamond paste on rotating
wheel
Etching in suitable etchant reagent
Washing in alcohol and drying
The entire microstructure preparation process can
be broadly divided into three categories:

Rough preparation.
Polishing.
Etching.

Rough Preparation
If the sample is not flat, it is necessary to remove
some material on the lathe or grinding machine
first. After it, the sample should be moved forward
and backward on the paper until the whole surface
is covered with unidirectional scratches. It is then
washed with running water to remove debris
associated with the grade of paper used. It is then
ground on the next finer paper such that the
scratches produced are at right angles to those
formed by the previous paper. This helps to easily
decide when the scratches from the coarser paper
have been completely removed. This procedure is
repeated through a range of papers. When the
specimen has been ground on the final paper, it is
generally worthwhile rotating it through and
grinding again with less pressure than before. This
technique can decrease the time required for the
next stage, which is polishing.

Polishing
Due to the very small depth of field obtained from
an optical microscope, it is essential that the
surface is optically flat, acting as a perfect mirror
which is why the specimen has to be polished.
This is done using rotating wheels covered with a
J. Adv. Res. Manu. Mat. Sci. Metall. Engi. 2015; 2(1): 1- 9.

cloth impregnated with a very fine abrasive

compound. The common compounds used are
diamond and alumina.

Etching
After examining the specimen in as polished
condition for the optimum surface quality, the
specimen should be etched with suitable etchants
to develop additional contrast to reveal the
microstructure.

Theory of Etching
Metallographic etching is the use of chemical
solutions known as etchants to create contrast
between the elements of the metal's microstructure
by selectively corroding some of those elements,
which show up as darker regions, used to highlight
features of metals at microscopic levels. This is
possible because differences in the composition,
structure or phase of a metal will create
electrochemical potentials that alter the relative
rates of corrosion when exposed to an etchant.
The features highlighted by etching include grain
boundaries, phase differences and inclusions.
Expose grain boundaries: The boundaries of
metallic grains can corrode very quickly when the
appropriate etchant is used, highlighting the edges
of the grains and making it possible to determine
their size and shape.
Highlight metallic phases: Different phases will
have different shading and texture after etching,
allowing for phase fraction estimation and
identification of undesirable phases.
Identify inclusions: Nonmetallic inclusions often
have characteristic shapes and colorations after
appropriate etching, which allows for quick size
measurement and number density estimation.
By studying the character, quantity and
distribution
of
these
different
features,
metallurgists are capable of predicting and
explaining physical properties and performance
failures of a given sample of metal.
Three main etching processes used
metallographic sample preparation are:

in

Chemical etching

Wet etching

Dry etching
Electrolytic etching
Heat tinting
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Pathak S et al.

Chemical Etching
This typically involves immersing the sample in
an etchant or swabbing the surface with an
etchant. The etchant selectively corrodes
microstructural features. Immersion time or
etching time is highly dependent on the system.
The selection of the optimum etchant is also very
important in sample production. Deeper etches are
preferred for low magnification examinations,
while shallow etches are preferred for higher
magnification etches. Based on the reagents used
and the techniques used, chemical etching is
divided into wet etching and dry etching.

 Wet Etching
Wet etching is the use of chemical solution to
dissolve a material when immersed in it. A wet
etching process involves multiple chemical
reactions that consume the original reactants
and produce new reactants. The wet etch
process can be described by three basic steps.
(1) Diffusion of the liquid etchant to the
structure that is to be removed. (2) The reaction
between the liquid etchant and the material
being etched away. A reduction- oxidation
(redox) reaction usually occurs. This reaction
entails the oxidation of the material then
dissolving the oxidized material. (3) Diffusion
of the byproducts in the reaction from the
reacted surface. This is a simple technology
which requires only a container with a liquid
solution that will dissolve the material in
question. It will give good results if a
combination of etchant and mask material can
be found to suit our application. But
unfortunately, there are complications since
usually a suitable mask that does not dissolve
or at least etches much slower than the material
to be patterned, needs to be found out. Wet
etching works very well for etching thin films
on substrates, and can also be used to etch the
substrate itself. The problem with substrate
etching is that isotropic processes will cause
undercutting of the mask layer by the same
distance as the etch depth. Anisotropic
processes allow the etching to stop on certain
crystal planes in the substrate, but still results
in a loss of space, since these planes cannot be
vertical to the surface when etching holes or
cavities. To get rid of this limitation, dry
etching must be considered.

 Dry Etching
In dry etching, plasmas or etchant gases
remove the substrate material. The reaction that
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takes place can be done utilizing high kinetic

energy of particle beams, chemical reaction or
a combination of both. Based on this, there are
three main types of dry etching:

I.

Physical Dry Etching

Physical dry etching requires high energy

kinetic energy (ion, electron, or photon) beams
to etch off the substrate atoms. When the high
energy particles knock out the atoms from the
substrate surface, the material evaporates after
leaving the substrate. There is no chemical
reaction taking place and therefore only the
material that is unmasked will be removed.

II.

Chemical Dry Etching

Chemical dry etching or vapor phase etching

does not use liquid chemicals or etchants. This
process involves a chemical reaction between
etchant gases to attack the substrate surface.
The chemical dry etching process is usually
isotropic and exhibits high sensitivity.
Anisotropic dry etching has the ability to etch
with finer resolution and higher aspect ratio
than isotropic etching. Due to the directional
nature of dry etching, undercutting can be
avoided.

III.

Reactive Ion Etching

Reactive ion etching (RIE) uses both physical

and chemical mechanisms to achieve high
levels of resolution. The process is one of the
most diverse and most widely used in industry
and research. Since the process combines both
physical and chemical interactions, the process
is much faster. The high energy collision from
the ionization helps to dissociate the etchant
molecules into more reactive species. In the
RIE- process, cations are produced from
reactive gases which are accelerated with high
energy to the substrate and chemically react
with it.

Electrolytic Etching
Electrolytic etching involves the use of the anodic
compartment as the specimen to be etched and the
cathodic compartment as a material that is
conductive but highly insoluble in the electrolyte
used. Typical examples of the materials that are
generally used as the cathode are platinum and
graphite. Most electrolytic etching processes use
direct current electrolysis. Since, oxidation occurs
at the anode, therefore, specimen to be etched gets
oxidized in the process.

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Pathak S et al.

Heat Tinting
Heat tinting, sometimes called thermal etching, is
the process of oxidizing a sample in a furnace.
Due to difference in oxidation rates of different
parts of the sample surface, various structures are
revealed.

Scope of Present Innovation

To reveal the austenite grain boundaries,
commonly used etchants are picric acid and 2%
Nital. Austenite grain size is an important
parameter for the ductility of steel. The
ductility of Austenitic Manganese Steel is
directly dependent on the grain size. Therefore,
it is most important to measure the grain size
and to investigate the microstructure of the
steel to predict its mechanical properties.
The main drawbacks of these etchants are the
lightly etched grain boundaries and uncertainty
to reveal the twins. One of the main objectives
of the present work was to find out a viable
etchant that can efficiently reveal the grain
boundaries along with the twins. The results of
the presented etchant examinations serve as an

important basis for revealing a clear picture of

the austenitic grain boundaries.

Experimental Procedure & Results

For carrying out this experiment, following
equipments are used: optical microscope (Carl
Zeiss, Germany) with 1000X magnification,
polishing machine, image analysis software.
Sample was collected from cast, heat treated
high manganese austenitic railway crossing.
The chemistry of the steel is as follows:
%Carbon-1.15, %Manganese-12.45, %Silicon0.38, %Sulphur-0.008, %Phosphorus-0.045.
1. Reagent: 3gm Ammonium persulfate+ 1g
silver nitrate+ 3-4 ml H3PO4 + 50ml H2O
H3PO4 (P+5) is a good oxidizing agent. Since its
oxidizing character is less as compared to sulfuric
acid or hydrochloric acid, so the oxidizing time
will be high. To fasten the reaction, catalyst like
silver nitrate is used. H2O acts as the wetting
agent.
Etching time: 10-15 sec.

Figure 1.Magnification: 100X

Figure 2.Magnification: 500X
Lightly etched grain boundaries observed in fig.1 and fig.2

2. Reagent: Ammonium persulfate 5gm +5ml

HNO3+ 50ml H2O+Heat 50-70oC.
Ammonium persulfate and nitric acid both are
very strong oxidizing agents. Ammonium
persulfate is soluble in nitric acid and acts as a
stabilizer for nitric acid and also increases its

J. Adv. Res. Manu. Mat. Sci. Metall. Engi. 2015; 2(1): 1- 9.

oxidizing character. Since ammonium persulfate is

most soluble in H2O, so, H2O acts as the wetting
agent. Heat is provided in order to fasten the rate
of the reaction.
Etching time: 5-10 sec.

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Pathak S et al.

Figure 3.Magnification: 100X

Figure 4.Magnification: 500X
Moderately etched grain boundaries without twins are observed in both the magnifications

3. Reagent: Ammonium persulfate 5gm + 1-2 gm

KMnO4 + 50 ml H2O.
KMnO4+Fe+2Mn+2 + Fe+3.
Hence, we can see that KMnO4 (Mn+7) is a good

oxidizing agent. So, KMnO4 as well as ammonium

persulfate act as oxidizing agents. H2O acts as a
wetting agent.
Etching time: 5 sec.

Figure 5.Magnification: 100X

Figure 6.Magnification: 500X
Moderately etched grain boundaries without twins are observed in both the magnifications

4. Reagent: 5gm Ammonium persulfate + 1-2 gm

KMnO4+5ml HCl+50ml H2O+Heat 50-70oC
2KMnO4+16HCl2KCl+2MnCl2+8H2O+5Cl2
From the above reaction, it can be inferred that Cl2
is released during the course of the reaction.
Chlorine has the highest electron affinity and the

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fourth highest electro negativity of all the reactive

elements. For this reason, chlorine is a
strong agent. Ammonium persulfate also acts as an
oxidizing agent. H2O acts as a wetting agent. Heat
is applied in order to speed up the reaction.

Etching time: 3-5 sec.

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Pathak S et al.

Figure 7.Magnification: 100X

Figure 8.Magnification: 500X
Deeply etched grain boundaries with twins are observed

5. Reagent: 5gm Ammonium persulfate + 1-2 gm

KMnO4+ 3-4ml conc. H2SO4 + 50ml H2O.
6 KMnO4 + 9 conc.H2SO4 6 MnSO4 + 3 K2SO4
+ 9 H2O + 5 O3

sulfuric acid should not be added too much as it

may lead to the production of Mn2O7 which is
explosive. Hence, both ammonium persulfate and
ozone act as oxidizing agents. H2O acts as a
wetting agent.

Ozone is an excellent oxidizing agent. Conc.

Etching time: 5 sec.

Figure 9.Magnification: 100X

Figure 10.Magnification: 500X
Moderately etched grain boundaries without twins observed

6. Reagent: 5gm Ammonium persulfate + 10ml

H2O2+ 5ml HCl +50ml H2O
H2O2 (aq.) + HCl (aq.)  H2O + HOCl (aq.)
HOCl (aq.) + HCl (aq.)  Cl2 + H2O
Some oxygen is also produced from the ordinary

J. Adv. Res. Manu. Mat. Sci. Metall. Engi. 2015; 2(1): 1- 9.

decomposition
of
hydrogen
peroxide:
2H2O2 2H2O + O2. So, as a whole, both oxygen
and chlorine which are very good oxidizing agents
for iron are released during the course of the
reaction. H2O acts as a wetting agent.
Etching time: 5-10 sec.

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Pathak S et al.

Figure 11.Magnification: 100X

Figure 12.Magnification: 500X
Austenitic grain boundaries revealed but very lightly etched

7. Reagent: 5gm Ammonium persulfate + 50ml

H2O +1-2 gm KMnO4+ 10ml H2O2+ 5ml HCl.
In this reagent, the sequence followed is H2O
followed by KMnO4 followed by H2O2. After
mixing, HCl is added and finally ammonium
persulfate is added.

KOH+HCIKCL+H2O
MnO2 + 4 HClMnCl2 + 2 H2O + Cl2 (Good
oxidizing agent)

2KMnO4 + H2O22KOH + MnO2 +O2 (good

oxidizing agent)

So, both oxygen and chlorine which are good

oxidizing agents are released. The unused KMnO4
can contribute as an extra oxidizing agent.
Ammonium persulfate acts as an oxidizing agent.
H2O act as a wetting agent.

After HCl is added,

Etching time: 3-5 sec.

Figure 13.Magnification: 100X

Figure 14.Magnification: 500X
Lightly etched Austenitic grain boundary observed

8. Conventional Reagent: 2 ml Nitric Acid + 98

ml Ethyl Alcohol.

Etching time: 20-35 sec.

Here polished surface is etched with the solution

for a few seconds to a few minutes.

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Pathak S et al.

Figure 15.Magnification: 100X

Figure 16.Magnification: 500X.
Lightly etched Austenitic grain boundary without twins observed

Conclusion
By studying and comparing all the micrographs, it
is evident that reagent 3 and reagent 4 revealed
high manganese austenitic steel microstructure
most prominently. However, with reagent 4, grain
Conventional
Low clarity
Very uncertain for High
Manganese austenitic
steel
Lightly etched grain
boundary
Twins may be / may not
be detected
High etching time
Less rate of corrosion

boundaries along with TWINS have been

observed with considerable clarity. Therefore,
reagent 4 which is a solution of ammonium
persulfate, KMnO4, HCl and H2O is found to be
the most efficient etchant among all the reagents.
New Etchant
Better Clarity
Almost Nil

Deeply etched grain

boundary
Clear twins can be
detected
Less etching time
Very high rate of
corrosion

Table 2.A tabular comparison of conventional etchant vs. new etchant

References
1. Nayak AP, Logeeswaran VJ, Islam MS.
University of California, Davis. California.
2. Vander Voort GF. ASM Handbook
Metallography and Microstructure. Volume
9:493512.
3. Grajcar A, Krukiewicz W, Koodziej S.
Corrosion behaviour of plastically deformed
high-Mn austenitic steels. JAMME Nov
2010; 43(1): 228- 35.
4. Walker P, Tarn WH. Handbook of Metal

J. Adv. Res. Manu. Mat. Sci. Metall. Engi. 2015; 2(1): 1- 9.

Etchants.
5. Reiter J, Bernhard C, Presslinger H.
Austenite grain size in the continuous casting
process: Metallographic methods and
evaluation. Material Characterization Jun
2008; 59(6): 737- 46.
6. Mukhopadhyay SM. Sample preparation for
Microscopic
and
spectroscopic
characterization of solid surface and films.
Department of Mechanical and Materials
Engineering, Wright State University,
Dayton, Ohio.

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