222 / Metallographers Guide The Art of Revealing Microstructure / 223

the following etchants should work for most low-carbon and In mixing the solution, it is recommended that the nitric acid be delineated by the ferrite grain boundaries. In this microstructure, AISI/SAE 1020 steel. The packets of lath martensite in this
low-alloy steels as well as most cast irons. poured into a beaker containing the measured amount of alcohol. several cementite particles can be seen at the ferrite grain microstructure are clearly seen. The use of 2% nital is also shown
The beaker should be on a magnetic stirring device so that as the boundaries (see arrows). The cementite is difficult to see, because in the series of carbon-iron alloys in Fig. 8.10. Figure 8.10 shows
nitric acid is poured into the alcohol, it is quickly mixed into the it blends in with the grain boundaries. In the next section, it is seen packets of lath martensite in a 0.2% C-iron, and Fig. 8.10(b)
The Attack Etchants solution. that Marshalls reagent is much more effective in revealing all (0.4% C-iron) and Fig. 8. 10(c) (0.6% C-iron) show lath marten-
Major Uses. The main use for nital is to reveal ferrite grains ferrite grain boundaries and highlighting the cementite particles. site with some plate martensite (arrows). Plate martensite can be
Nital Figure 8.9 shows a 2% nital etch applied to a water-quenched seen in Fig. 8.11, which represents a 0.93% C, 14.5% Ni steel
and martensite in most carbon and low-alloy steels and cast irons.
Ingredients of 2% Nital: It is also useful in etching bainitic steels. The etchant attacks the
2 mL nitric acid (concentrated) (1 to 5% solutions can also be ferrite grains and grain boundaries to produce relief on the
used) specimen surface. Figure 8.8 shows a low-carbon sheet steel
98 mL ethyl alcohol etched in 2% nital for 30 s. Note that most of the ferrite grains are

Description. Historically, the most common etchant is a simple

solution of concentrated nitric acid in alcohol. The etchant name,
nital, is an acronym for nitric acid and alcohol. Ethyl alcohol (also
called ethanol) is preferred over methyl alcohol (methanol),
because it is less toxic. The authors prefer a mixture of 2 ml of
nitric acid in 98 mL of ethyl alcohol (2% nital). However, other
concentrations of nitric acid can be used, that is, 1 to 5% nitric
acid. A 1% solution of nital reacts slower than 2% nital. The
higher the concentration of nitric acid, the faster the etching
response. If nital is prepared with a nitric acid concentration of
over 4%, methyl alcohol should be used, because ethyl-alcohol-
based mixtures at these higher nitric acid concentrations can
become unstable. Also, these higher concentrations should not be
stored. Ethyl alcohol denatured with a small amount of methyl
alcohol is a less expensive substitute for pure ethyl alcohol (200
proof). If denatured ethyl alcohol is employed, the metallographer
must avoid denaturing agents such as benzene and aviation fuel.
These agents produce a different etching response and can usually
be detected by their odor.
Fig. 8.8 Low-carbon steel etched in 2% nital. Note grain-boundary car-
bides (arrows) are difficult to see. 1803
Table 8.1 Quick reference guide to common attack
etchants for carbon steels, low-alloy steels, and cast irons
Etchant

To reveal or enhance
General microstructure First 4% picral, then 2% nital
(unknown beforehand)
Ferrite grains and grain boundaries 2% nital or Marshalls reagent
Grain-boundary carbides 4% picral
Carbide networks 4% picral
Both ferrite grains and carbides 4% picral 1 2% nital or Marshalls
reagent
Pearlite 4% picral
Bainite 4% picral
Granular bainite (martensite-austenite 4% picral
constituent)
Martensite, as-quenched 2% nital
Martensite, tempered 4% picral 1 2% nital
Prior austenite grain boundaries Winsteards (modified) or boiling
alkaline sodium picrate
or Marshalls reagent or saturated
aqueous picric acid
General segregation 4% picral or Winsteards (modified)
reagent
Nonmetallic inclusions 4% picral
Epitaxial ferrite Marshalls reagent
Cold-worked ferrite 2 nital or Marshalls reagent

To color or darken A water-quenched AISI/SAE 1020 steel showing lath martensite. A series of water-quenched iron-carbon alloys. (a) 0.2% C-iron alloy showing lath martensite, (b) 0.4% C-iron alloy showing lath martensite and
Carbides, but not ferrite Boiling alkaline sodium picrate Fig. 8.9 Fig. 8.10
2% nital etch. 3203 a small quantity of plate martensite (see arrows), and (c) 0.6% C-iron alloy showing lath martensite with plate martensite. 2% nital etch. 5003
224 / Metallographers Guide
etched in 2% nital. The unetched constituent is retained austenite.
Nital will not attack austenite as it does ferrite and martensite.
Nital will not attack carbides but will enhance the interface
between the carbide and the matrix. For example, the carbides in
the air-cooled specimen of an AISI A2 tool steel in Fig. 8.12 were
not attacked by the 2% nital etch, but the carbide interfaces were
enhanced and the martensite darkened.
Fig. 8.11 Plate martensite in water-quenched 0.93% C, 14.5% Ni steel.
The unetched areas between the martensite plates are retained
austenite. 2% nital etch. 1003
Fig. 8.12 Carbides in an AISI A2 tool steel. Note the carbides are not
attacked, but their boundaries are enhanced. 2% nital etch.
10003
Marshalls Reagent
Ingredients:
Part A
5 mL sulfuric acid (concentrated)
8 g oxalic acid
100 mL water
Part B
30% solution hydrogen peroxide
Description. Marshalls reagent is a two-part etchant, with part
A consisting of 5 ml of sulfuric acid and 8 g of oxalic acid (solid
white crystals) in 100 mL of water. Part A is prepared by adding
the sulfuric acid to the water during stirring. There is a small
amount of heat generated as a result of the reaction. The oxalic
acid crystals are then added to this warm solution. Just before
using Marshalls reagent, part A is mixed with equal parts of part
B, a 30% solution of hydrogen peroxide. Normally a one to three
second immersion is adequate for proper results. Always use a
freshly mixed solution, because the etchant has a short life span.
When using Marshalls reagent, always immerse the specimen so
that the polished surface is vertical in the solution. This orienta-
tion prevents pits from forming on the surface. The etching
reaction is very effervescent. If no visible reaction occurs, a three
second etch in 2% nital is required before Marshalls reagent is
used. Sometimes, the metallographer may use a 20 second etch in
2% nital after etching in Marshalls reagent. This postetch will
increase the chemical attack and further sharpen the grain bound-
aries.
Fig. 8.13 Low-carbon steel etched in Marshalls reagent. Note the grain-
boundary Fe3C carbides (arrows) are clearly seen. Also note that
all the ferrite grain boundaries are delineated. Compare with the same steel
etched in 2% nital in Fig. 8.8. 2003
The Art of Revealing Microstructure / 225
Major Uses. Although 2% nital has been the etchant of choice Marshalls reagent has also been used to delineate epitaxial
for many decades, more recently, Marshalls reagent has been ferrite in steels that have been heat treated and cooled from the
used for low-carbon steels to sharpen the ferrite grain boundaries. two-phase ferrite plus austenite region. An example of using
Many times, 2% nital does not produce a complete ferrite Marshalls reagent for epitaxial ferrite in a low-carbon steel is
grain-boundary network, that is, gaps can be found in many of the seen in Fig. 8.18. Note the envelopes or halos around the ferrite
grain boundaries in a particular field of view (see Fig. 8.8). These grains at the prior austenite grain boundaries (see arrows). This
gaps can be a problem in measuring ferrite grain size either
manually or by image analysis. Marshalls reagent, on the other
hand, provides a complete network. Figure 8.13 shows the same
steel in Fig. 8.8 but etched with Marshalls reagent. Also, it should
be noted that the grain-boundary cementite particles (arrows) are
more clearly seen when etched with Marshalls reagent. A
higher-magnification view of this effect is seen in Fig. 8.14.
Another use for Marshalls reagent is in revealing recrystallized
grains in a partially annealed, cold worked microstructure. Figure
8.15(a) shows a small percentage of newly formed recrystallized
grains that have nucleated at prior austenite grain boundaries of a
cold-worked low-carbon steel. Figure 8.15(b) shows the same
steel after almost complete recrystallization. Note the sharpness in
the ferrite grain boundaries. The elongated unetched grains are
unrecrystallized areas (recovery has taken place but not recrystal-
lization). Figure 8.16 shows a fully cold-worked low-carbon steel
etched with Marshalls reagent. In some as-quenched low-carbon
steels, the prior austenite grain boundaries can be delineated by
Marshalls reagent. Figure 8.17 shows an example of a water-
quenched low-alloy steel etched in Marshalls reagent. Note the
sharpness of the prior austenite grain boundaries. The background
structure within the austenite grains represents packets of lath
martensite not fully resolved by this etchant. Note the small region
of ferrite that nucleated on one of the austenite grain boundaries
(center of micrograph).
Fig. 8.15 Partially annealed cold-worked low-carbon steel showing (a) a
few recrystallized grains in a cold-worked matrix and (b) an
Fig. 8.14 A higher-magnification view of the low-carbon steel in Fig. 8.14. unrecrystallized area (recovered grains) in a fully recrystallized matrix.
Note grain-boundary Fe3C carbides. Marshalls reagent. 5003 Marshalls reagent. 2503
226 / Metallographers Guide
ferrite is a result of austenite forming on the prior austenite grain
boundaries when the steel was heated into the two-phase region
just above the lower critical temperature. The ferrite in the center
of the grains never transformed to austenite. When the steel
cooled to room temperature, the austenite transformed back to
ferrite, leaving a ghostlike image shown in Fig. 8.18. Marshalls
reagent can also etch the boundaries of substructure in pure iron,
Fig. 8.16 A fully cold-worked low-carbon steel. Marshalls reagent. 1003
Fig. 8.18 A dual-phase steel showing epitaxial ferrite (new ferrite) at prior
austenite grain boundaries. The epitaxial ferrite formed when
the steel was heated into the two-phase region. Austenite formed at the grain
boundaries, and ferrite transformed epitaxially on the old ferrite upon cooling.
Marshalls reagent. 5003
as seen in Fig. 8.19. The substructure, sometimes called veining, 8 g oxalic acid
is more subtle than the darker ferrite grain boundaries. 100 mL water
Modified Marshalls Reagent Part B
30% solution hydrogen peroxide
Ingredients:
Part A
5 mL sulfuric acid (concentrated) Part C
4 drops hydrofluoric acid
Description. Marshalls reagent can be modified by adding a
few drops of hydrofluoric acid. This addition produces a more
uniform etching response. The hydrofluoric acid is added last.
When handling hydrofluoric acid, extreme care must be taken to
protect the skin from contact with the acid. Hydrofluoric acid is
extremely corrosive to human skin and can cause serious acid
burns. Latex gloves, an acid-resistant laboratory coat, and eye
protection must be worn when using hydrofluoric acid. This acid
is so corrosive that it even attacks glass. Therefore, hydrofluoric
acid is never stored in glass bottles and is never used in glass
beakers or porcelain dishes. Always use plastic containers when
mixing and using this modified Marshalls reagent. For best
results, etch while the solution is in an ultrasonic device.
Major uses. Marshalls reagent is modified with hydrofluoric
acid to enhance ferrite grain boundaries even more clearly than
those developed in the standard reagent formulation. This etchant
thus produces much sharper delineation of ferrite grain boundaries
than 2% nital in very-low-carbon steels such as interstitial-free
(IF) steels. For example, a titanium-stabilized, IF steel was etched
in 2% nital and modified Marshalls reagent in Fig. 8.20(a) and
Fig. 8.17 Water-quenched low-alloy steel showing clearly delineated
prior austenite grain boundaries. Matrix is lath martensite.
Marshalls reagent. 2003
Fig. 8.19 Pure iron showing veining (substructure) within the ferrite Fig. 8.20 Very-low carbon interstitial-free steel (a) etched in 2% nital, where only a few of the ferrite boundaries are attacked, and (b) etched in modified
grains. Marshalls reagent. 2003 Marshalls reagent, where most ferrite boundaries are delineated. 4003
The Art of Revealing Microstructure / 227
(b), respectively. The 2% nital etch in Fig. 8.20(a) shows the
ineffectiveness of this etch for very-low-carbon steels. The IF
steel etched in modified Marshalls reagent in Fig. 8.20(b) shows
almost every ferrite grain boundary delineated. This modified
form of Marshalls reagent is useful for preparing specimens for
ferrite grain size measurements using image analysis techniques.
Modified Marshalls reagent can also be used to delineate the
pearlite colony boundaries of a fully pearlitic steel. An example is
seen in Fig. 8.21 where the colony boundaries of fully pearlitic
AISI/SAE 1080 steel are outlined using the modified Marshalls
reagent.
From the previous examples, it can clearly be seen that
Marshalls reagent and modified Marshalls reagent are extremely
useful in microstructural development. The authors are using
these reagents for most applications where 2% nital was once
employed.
Picral
4% Picral
Ingredients:
4 g picric acid
96 mL ethyl alcohol
5 drops zephiran chloride (wetting agent)
Description. Picral is an etchant that contains picric acid
(2,4,6-trinitrophenol) dissolved in alcohol. The name picral is an
acronym for picric acid and alcohol. As with nital, ethyl alcohol
is preferred over methyl alcohol for toxicity reasons. As with nital
228 / Metallographers Guide
discussed previously, if denatured ethyl alcohol is used, it is
important to avoid benzene and aviation fuel as denaturing
additives. Methyl alcohol is an acceptable additive.
This etchant is called 4% picral even though the picric acid is
not in liquid form and 4 g of solid picral only approximates 4 mL
of liquid. The solution should be mixed while being magnetically
stirred. The picric acid crystals are added during the stirring
action. It must be remembered that the yellow picric acid crystals
are explosive, and as a precaution, they are always kept moist (dry
crystals of picric acid should never be touched or handled by the
metallographer). Caution should be taken when handling and
storing picric acid. Some laboratories do not allow the use of
picric acid for safety reasons. This is very unfortunate for the
metallographers in those laboratories, because if properly
handled, picric acid can be used safely.
One feature of picric acid is unusual in that the more it is used
to etch specimens, the stronger the etching reaction. Upon use, the
solution will become darker in color. For its very first use, the
metallographer does not know how long to leave the specimen in
the solution, because it is unpredictable. However, with more use,
the etching time becomes more predictable.
Metallographic Tip: In order to have a predictable
etching time when using 4% picral, place a piece of
steel (about 30 g [1 oz]) in the solution before using.
The steel will darken the solution by producing iron
ions. The release of these ions will heighten the
reaction for etching metallographic specimens.
When rinsing the specimen after etching in 4% picral, it is ad-
visable to rinse in water to remove the bulk of the etchant, then
Fig. 8.21 Pearlite colonies are outlined in an AISI/SAE 1080 steel using
modified Marshalls reagent. 2003
The Art of Revealing Microstructure / 229
immerse the specimen in a beaker of alcohol, followed by flushing Description. A few drops of hydrochloric acid added to picral Saturated Aqueous Picric Acid
the surface with a stream of alcohol from a squeeze bottle. Because provide more effective etching response.
picric acid is almost insoluble in water, the alcohol immersion and Major Uses. Picral plus hydrochloric acid is used to sharpen Ingredients:
flush is necessary to remove all the final traces of the etchant from features in low-alloy steels containing moderate to high amounts 10 g picric acid
the specimen. If the specimen contains pores or cracks, it is advis- of chromium. The enhanced picral reagent sharpens grains and 100 mL water
able to immerse the specimen in a beaker of alcohol and agitate the carbides. 1 g sodium tridecylbenzene sulfanate (wetting agent)
beaker, using an ultrasonic cleaning device. One problem with pi-
cral is its ability to stain yellow almost anything it touches, particu- Description. Water is used instead of alcohol as the solvent of
larly the skin and clothing. To prevent staining, do not allow the the picric acid. However, only about 1% picric acid will dissolve
solution to splash or come into contact with your fingers (latex rub-
ber gloves should be used) or clothing.
For best results, a few drops (approximately five) of a wetting
agent called zephiran chloride (a 17% solution) in 100 mL, when
added to 4% picral, will enhance the contrast between constituents
and will increase etching speed. A 17% solution of zephiran
chloride can be found in most drug stores. A wetting agent is a
surface-active agent or surfactant that modifies the surface energy
between the solid specimen surface and the liquid etchant.
Major Uses. Picral is used for steels containing pearlite,
bainite, tempered martensite, cementite, and other carbides. It is
particularly useful for heat treated carbon and low-alloy steels and
tool steels. As opposed to nital that attacks ferrite grains and grain
boundaries, picral attacks interfaces between ferrite and carbides
and is not sensitive to pearlite colony orientation. An example of
the use of picral is shown in Fig. 8.22, which represents a
water-hardenable tool steel (grade W1) in the normalized condi-
tion. Figure 8.22(a) shows the W1 tool steel etched in 2% nital. As
can be seen, many of the pearlite colonies are not delineated and
appear as grayish patches. In Fig. 8.22(b), where the same steel is
etched in 4% picral, most of the pearlite colonies are etched, and
the dispersion of rounded carbides is more evident. Picral is not
sensitive to orientation of the pearlite constituents and will etch Fig. 8.23 Carbides in a low-carbon steel. 4% picral. 15003
evenly, whereas nital is very sensitive to orientation and will
attack the microstructure unevenly. An example of picral attacking
the interfaces of carbide particles is seen in Fig. 8.23 and 8.24.
This specimen in Fig. 8.23 shows carbides clearly delineated by
the 4% picral etch. Figure 8.24 shows carbides (arrows) formed
from a carbon stain on the surface of a batched-annealed low-
carbon steel sheet. The carbides prevented uniform phosphating of
the surface.
Variations of Picral
There are a number of important etchants that are variations of
the standard 4% picric formula. Some of these variations employ
water instead of alcohol, and others are used hot instead of at
room temperature.
Picral Plus Hydrochloric Acid
Ingredients:
4 g picric acid
96 mL ethyl alcohol Fig. 8.22 A normalized water-hardenable AISI W1 tool steel (1.03% C)
etched in (a) 2% nital, where some of the pearlite colonies Fig. 8.24 Surface carbides resulting from a carbon stain on the sheet
5 drops hydrochloric acid appear as grayish patches, and (b) 4% picral, where the pearlite colonies are surface of a batch-annealed low-carbon steel (see arrows). 4%
5 drops zephiran chloride etched and the carbides more clearly delineated. 10003 picral plus zephiran chloride. 10003
230 / Metallographers Guide
in water at room temperature. By mixing 10 g of picric acid
crystals in 100 mL of water, only a portion of the crystals will
dissolve upon stirring. After stirring, the saturated liquid should be
decanted from the undissolved crystals. In order to produce
etching uniformity and reproducable speed, 1 g of sodium
tridecylbenzene sulfanate should be added as a wetting agent to
100 ml of solution. Note that zephiran chloride, which is used in
4% picral, is not added as a wetting agent. Zephiran chloride,
which works well in an alcohol-based solution, does not work
well in a water-based solution. Also, sodium tridecylbenzene
sulfanate works well in water-based solutions but not in alcohol-
based solutions.
Major Uses. To reveal prior austenite grain boundaries in a
fully martensitic microstructure, saturated aqueous picric acid is
normally employed. Often, the metallographer is asked to mea-
sure prior austenite grain size, because it is a very important
metallographic feature that relates to mechanical properties and in
determining proper heat treatment. Etching results and etching
time can be improved by etching the specimen with the aid of an
ultrasonic cleaning device. For steels containing over 1% Si, a
small amount of ethylenediamine tetraacetic acid (EDTA) can be
added to prevent staining.
Vilellas Reagent
Ingredients:
1 g picric acid
5 mL hydrochloric acid (concentrated)
100 mL ethyl alcohol
Description. It consists of 5 mL of hydrochloric acid mixed
with 1 g of picric acid and 100 ml of alcohol (ethyl alcohol
Fig. 8.25 The tempered martensitic microstructure in the heat-affected zone of a welded ASME SA 213 T-23 steel showing (a) prior austenite grain boundaries
and (b) the grain boundaries decorated with carbides. Vilellas reagent. 4003 and 15003, respectively
preferred). The picric acid is first added to the alcohol while
stirring is taking place. The picric acid crystals are then dissolved
in the solution with continuous stirring action. The hydrochloric
acid is added last.
Major Uses. Another etchant that delineates prior austenite
grain boundaries in a martensitic quenched and tempered steel is
Vilellas reagent. The etchant works best when the martensite is
tempered between 300 and 500 C (570 and 930 F). Figure
8.25(a) shows prior austenite grain boundaries in a welded
heat-affected zone of American Society of Mechanical Engineers
(ASME) T-23 steel. The martensite was tempered at 700 C (1300
F). Figure 8.25(b) shows that the austenite grain boundaries are
decorated with carbides from the tempering process. These
carbides at the boundaries are the reason the prior austenitic
boundaries can be seen. A similar example is shown in Fig. 8.26,
which shows prior austenitic grain boundaries in a quenched and
tempered 0.23% C, 3.4% Ni, 1.7% Cr, 0.5% Mo steel. The steel
was subject to surface oxidation, which penetrated the austenite
grain boundaries. Vilellas reagent is also useful in etching
martensitic stainless steels and tool steels. This etchant can also be
applied to any ferrite-carbide microstructure. Figure 8.27 shows
an AISI D2 tool steel etched in Vilellas reagent. Note the
sharpness of the carbide particles and grain-boundary carbide
networks in this microstructure.
Boiling Alkaline Sodium Picrate
Ingredients:
2 g picric acid
25 g sodium hydroxide
100 mL water
Description. Sodium hydroxide (NaOH) dissolved in 100 mL
of distilled water provides an alkaline pH to alter the acid pH of
the picric acid. First, the sodium hydroxide is added to the water
while being stirred. The ensuing exothermic reaction produces
enough heat to dissolve most of the picric acid, which is added
next with continuous stirring. The warming of the mixture assists
4% picral. In the darkening of a carbide phase such as cementite,
Fig. 8.26 Quenched and tempered 0.23% C, 3.4% Ni, 1.7% Cr, 0.5% Mo
steel showing oxidation penetrating the austenitic grain bound-
aries. The austenite grain boundaries are also delineated, because they are
decorated with carbides. Vilellas reagent. 5003
Fig. 8.27 An AISI D2 tool steel showing large eutectic carbides and small
carbides in a martensitic matrix. Vilellas reagent. 5003
The Art of Revealing Microstructure / 231
the dissolution of the picric acid crystals. Before etching, the
solution is heated to boiling and held for five to ten minutes. The
specimen is immersed into the boiling solution.
Major Uses. This etchant is useful in darkening cementite.
Figure 8.1(b) shows an example of using the boiling alkaline
sodium picrate etchant for darkening the cementite constituent in
an AISI/SAE 1040 steel. Figure 8.1(a) is the same steel etched in
the metallographer has a tool to identify carbide phases in a mixed
microstructure. The previously discussed etchants are all used for
chemical attack of the constituents in a microstructure. Because
none of these etchants darken a constituent, it is sometimes
difficult to distinguish between small regions of retained austenite,
ferrite, and cementite. With boiling sodium picrate, the cementite
is easily distinguishable. Boiling alkaline sodium picrate can be
used to enhance prior austenitic grain boundaries. However, as
seen in Fig. 8.28(a) and (b), the technique requires addditional
etching in nital and picral. The as-quenched 0.5% Mo-B steel was
etched for ten minutes in boiling alkaline sodium picrate, followed
by etching for ten seconds in 2% nital and 20 seconds in 4% picral
with hydrochloric acid. After etching, the specimen was lightly
wiped on a dry polishing cloth (rayon type).
Winsteards Reagent
Ingredients:
Part A:
2 g picric acid
10 mL ethyl alcohol
Part B:
200 mL water
5 mL sodium tridecylbenzene sulfanate (40% solution)
Ingredients: (modification)
Part A:
2 g picric acid
10 mL ethyl alcohol
Part B:
200 mL water
5 mL sodium tridecylbenzene sulfanate (40% solution)
5 drops hydrochloric acid
Description. This water-based reagent is mixed in two parts,
because picric acid is very difficult to dissolve in water. The picric
acid/alcohol solution is prepared first. This solution is then added
to the water, and sodium tridecylbenzene sulfanate is added as a
wetting agent. For effective etching, this reagent is used hot,
between 60 and 70 C (140 and 160 F). Modified Winsteards
reagent contains the addition of five drops of hydrochloric acid.
As in the unmodified solution, effective etching is achieved if this
reagent is used hot, between 60 and 70 C (140 and 160 F ). In
232 / Metallographers Guide
using Winsteards reagent, if the unmodified solution does not
work, try etching in a beaker placed in an ultrasonic cleaning
device. If it still does not work, try using the modified version
with five drops of hydrochloric acid.
Major Uses. Winsteards reagent is used to delineate prior
austenite grain boundaries, as shown in Fig. 8.29 and 8.30. Figure
8.29 represents a quenched and tempered MIL-S-23194 compo-
Fig. 8.28 Prior austenite grain boundaries in a quenched 0.5% Mo-B
steel. (a) 2003 and (b) 5003. Boiling alkaline sodium picrate
etch followed by 10 seconds in 2% nital etch and 20 seconds in 4% picral
etch
sition F low-alloy steel etched for 1.5 minutes in modified
Winsteards reagent. The solution was heated to 65 C (130 F).
The prior austenite grain boundaries in this quenched and tem-
pered low-alloy plate are clearly seen. A similar example of
etching in modified Winsteards reagent is shown in Fig. 8.30 for
a water-quenched 0.27% C, 1.0% Mn, 1.02% Cr, 0.27% Mo steel.
In this case, the solution was heated to 70 C (160 F).
Fig. 8.29 Prior austenite grain boundaries in a quenched and tempered
MIL-S-23194 composition F-steel forging. Modified Winsteards
etch. 5003
Fig. 8.30 A water-quenched 0.27% C, 1.0% Mn, 1.02% Cr, 0.27% Mo
steel showing prior austenite grain boundaries. The dark bands
are due to segregation in the bar. Modified Winsteards etch. 2503
The Art of Revealing Microstructure / 233
4% Picral and 2% Nital Basic Tint Etchants for Carbon and Low-Alloy
Steels and Cast Irons
Description. For etching specimens with ferrite plus pearlite
microstructures, 4% picral (aged) and 2% nital can be mixed Some metallographic reagents react with the surface of the
together in equal parts. In some cases, the specimen is used as a constituents in the microstructure to form what appear as films or
two-step etching procedure by first etching in 4% picral followed tints. These reagents are grouped as tint etchants (Table 8.2). The
by 2% nital. After step one, rinse in water and alcohol immedi- surface is not physically altered, such as the attack etchants
ately. After etching, the specimen should be rinsed in water and
alcohol and dried in a warm air blast.
Major Uses. For ferrite-pearlite steels and ferritic steels con-
taining carbides, a combination etch using mixed 4% picral and
2% nital will delineate the boundaries between the carbides and
ferrite and the ferrite grain boundaries. Figure 8.31 shows the
results of the combination picral/nital etch used on an annealed
and air-cooled bar of AISI/SAE 1018 steel. The ferrite grain
boundaries are clearly shown, along with the regions of pearlite.
A similar but coarser microstructure can be seen in an AISI/SAE
1018 steel bar in the cold-finished (cold worked at the surface)
condition in Fig. 8.32. Note in this case, the ferrite grains are
slightly elongated. It is interesting that the steel in Fig. 8.31 had
a notch toughness absorbed energy value (Charpy test) of 156 J
(115 ft lbf), whereas the steel in Fig. 8.32 had a notch toughness
absorbed energy value of only 9 J (7 ft lbf). The lower value is
due to the cold work in the latter steel bar.
An example of using the two-step procedure is shown in Fig.
8.33. In this case, a water-quenched and tempered AISI/SAE 1020
steel was etched to bring up the carbides (4% picral) and the
residual martensite lath boundaries (2% nital). A free-machining
AISI/SAE 1213 steel bar was etched in 4% picral followed by 2%
nital, as seen in Fig. 8.34. In this microstructure, there is ferrite
plus pearlite banding, manganese sulfide inclusions, and a ferritic Fig. 8.32 Cold-finished AISI/SAE 1018 steel showing ferrite plus pearlite
microstructure. Equal parts 4% picral (aged) mixed with 2%
matrix. The two-part etch reveals all constituents. nital etch. 2003
Fig. 8.31 Air-cooled AISI/SAE 1018 steel showing a ferrite plus pearlite Fig. 8.33 Water-quenched and tempered AISI/SAE 1020 steel showing
microstructure. Equal parts 4% picral (aged) mixed with 2% fine carbides and residual laths of martensite. 4% picral fol-
nital etch. 2003 lowed by 2% nital etch. 5003
234 / Metallographers Guide

extremely important and must be properly prepared in order to

ensure a uniform and effective chemical deposit. The chemically
deposited film is very fragile and requires a different etching
procedure. It is recommended that the following set of simple
rules be followed for proper tint etching:
Fig. 8.34 Free-machining AISI/SAE 1213 steel bar showing ferrite plus
pearlite banding, manganese sulfide inclusions, and a ferrite
matrix. 4% picral followed by 2% nital etch. 3203
containing acids, but result in a chemically deposited film on the
surface. They are very useful in distinguishing martensite in a
mixed microstructure. They are also important in color metallog-
raphy. The common tint etchants are aqueous solutions of sodium
or potassium metabisulfite and/or sodium thiosulfate. It is the
metabisulfite (S2O522) and the thiosulfate (S2O322) ions that are
the active ingredients in the etchant. In aqueous or acidic
solutions, the metabisulfite and thiosulfate ions decompose into
sulfur dioxide, hydrogen sulfide, sulfur, and hydrogen. The
presence of sulfur and the sulfur compounds provides the sulfur
(S22) ion that creates a sulfide film on the steel surface.
General Procedure in Using Tint Etchants
Tint etchants are very different than the attack etchants de-
scribed previously. The surface condition of the specimen is
Rule 1: Always use a freshly mixed solution. Generally, tint
etchants are not stored for future use.
Rule 2: Always use a freshly polished surface. If no reaction is
occurring on the specimen surface or if the reaction is spotty,
the specimen may have been in the air too long, and a passive
film has formed on the surface. To recover the surface, the
specimen should be lightly pre-etched in 2% nital. After the
pre-etch, immerse the specimen in water and then into the tint
etching solution. Do not dry the specimen surface before
immersion into the tint etch solution.
Rule 3: When etching, always watch the surface of the
specimen. It is important to obtain the proper color from tint
etchant. Knowing the proper color comes with experience.
Rule 4: Do not agitate the specimen in the tint etching solution.
Movement of the specimen can disturb the fragile chemically
deposited surface film.
Rule 5: Do not swab the surface of the specimen while etching.
Swabbing will damage and physically remove the chemically
deposited surface film.
Rule 6: If the specimen surface is underetched (undertinted),
the metallographer must start over. Never put the specimen
back into the solution without repolishing the surface. A quick
repolish (less than ten seconds) with 0.3 m aluminum oxide
(alumina) is all that is necessary. Remember, this is a thin
surface stain and it is not formed by chemical attack, as in the
case of most etchants.
Rule 7: Never flush the specimen surface with a stream of
water from the tap. Rinse the specimen by gentle immersion in
a beaker of water.
Rule 8: Gently rinse the water from the specimen surface with
a minimal amount of alcohol. Too much alcohol can change
the characteristics of the stain.
Rule 9: Never wipe the specimen dry. Gently blow dry the
surface of the specimen.
Rule 10: Always use distilled water with the pH adjusted to 2
to 4. Water above a pH level of 7 will not work.

Table 8.2 Quick reference guide to common tint etchants The Common Tint Etchants
for carbon steels, low-alloy steels, and cast irons
Etchant
Sodium Metabisulfite
To reveal or enhance
Bainite 15% sodium metabisulfite Ingredients:
Granular bainite (martensite-austenite 15% sodium metabisulfite 8 to 20 g sodium metabisulfite
constituent)
Martensite, as-quenched 15% sodium metabisulfite Dilute in 100 mL water
Retained austenite 15% sodium metabisulfite
Description. This is a general-purpose tint etchant. Sodium
To color or darken
Ferrite grains Berahas reagent or Klemms reagent metabisulfite dissolves easily in water. A range of the amount of
Ferrite, but not carbides Berahas reagent sodium metabisulfite is given, depending on the desired staining
Martensite (ferrite and retained 15% sodium metabisulfite response. The greater the amount of sodium metabisulfite, the
austenite not attacked)
darker the stain on the specimen surface. Before using this