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FEATURE | Materials

Characterization & Testing

Revealing
Prior-Austenite Grain
Boundaries in
Heat-Treated Steels

George F. Vander Voort Consultant, Struers Inc.; Westlake, Ohio


The mechanical properties of heat-treated alloy steels are strongly in uenced by
the grain size of the parent austenite phase before quenching. But revealing the
prior-austenite grain boundaries (PGBs or PAGBs) can be quite difcult depending
upon the alloy and its microstructure.

h
here
are a number of wellestablished
(see ASTM E 112,
e
ffor example) procedures that
aare used to decorate the PGBs
during a heat-treatment cycle, e.g., the
McQuaid-Ehn carburizing test (Fig. 1)
and the oxidation test. In some mediumcarbon steels, at a specic cooling rate,
proeutectoid ferrite will precipitate at the
PGBs, while in high-carbon steels (generally hypereutectoid tool steels), proeutectoid cementite will precipitate on the
PGBs upon slow cooling from elevated
temperatures. These conditions are often
seen in as-cast or as-rolled steels, as shown

in Figures 2 and 3. But these methods


cannot be applied to determine the prioraustenite grain size of a steel part or component that has already been heat treated,
as these methods will produce a different
grain size. For this problem and this is
a common situation in failure analysis
one can only use an etching technique to
reveal the PGBs.

Fig. 1. Microstructure of 9310 alloy steel


after the McQuaid-Ehn test using alkaline
sodium picrate (90C 45 sec.) to darken
the cementite precipitated in the prioraustenite grain boundaries (magnication
bar is 100 m long)

Fig. 2. Proeutectoid ferrite precipitated in


the prior-austenite grain boundaries in an
as-cast Fe - 0.38%C - 0.26%Si - 0.79% Mn
steel (2% nital)

48 April 2010 - IndustrialHeating.com

History of Prior-Austenite Grain


Boundary Etch Development
One of the earliest etchants to have some
success at revealing PGBs in some steels
was Vilellas reagent, published in 1938.[1]

This etch has had limited success, mainly


with tool steels. Subsequently, Schrader
modied Vilellas reagent, but it also has
limited value. In 1949, Miller and Day[2]
published a 5% aqueous ferric chloride
reagent for low-carbon martensitic steels.
Aqueous ferric chloride and HCl solutions
have also been suggested. Nital, generally in concentrations of 2-10% (do not
store more than 3% HNO3 in ethanol in
a tightly closed bottle, as it can explode),
will reveal the grain boundaries in only a
few steels highly alloyed tool steels in
the as-quenched or lightly tempered condition, such as D2 and high-speed steels.

Fig. 3. Proeutectoid cementite precipitated


on the prior austenite grain boundaries
during cooling from hot rolling in this Fe 1.31% C water-hardenable tool steel. The
cementite has been darkened using alkaline sodium picrate (90C - 60 sec.), 500X.

The rst reasonably successful etchant


for PGBs was published in 1955 by Bechet
and Beaujard [3] using a saturated aqueous
picric-acid solution (as had been used in
studies of temper embrittlement) containing 0.5% of a wetting agent, Teepol
(sodium alkylsulfonate), at room temperature. This etchant has been the foundation of many subsequent modications to
improve its effectiveness.
The writer tried this etch[4] on specimens of 8620, 4140 and 5160 in the asquenched condition and after tempering
at 400, 800 and 1200F using sodium
tridecylbenzene sulfonate as the wetting
agent. It did not reveal grain boundaries
on any of the 8620 specimens. It did reveal the PGBs on as-quenched and tempered (400 and 800F) specimens of 4140
and 5160 but did not reveal them on any
specimens tempered at 1200F. Tempered
martensite and tempered bainites both
respond to this etch but only for medium
to high-carbon steels and only when tempered below ~1050F.
It is well known that saturated aqueous picric acid with a wetting agent (used
at room temperature) reveals PGBs
if phosphorus is present in the grain
boundaries, and this is easier if the specimen has been heated in the temper embrittlement range.[5] Segregation of Sn or
Sb to the PGBs, which also causes temper embrittlement, does not help reveal
the PGBs using this etch in steels free
of phosphorus.[6,7] Preece and Carter[8]
showed using TEM that there was a clear
difference in appearance between grain
boundaries that were temper embrittled
due to a high local phosphorous concentration compared to a non-embrittled
specimen with a lower local phosphorous
content, even though saturated aqueous
picric acid reveals the PGBs in both
cases and the boundaries looked similar
by light microscopy.
Studies conducted in this time period
examined the effect of a variety of wetting
agents on the etch response. Nelson[9]
conducted the most extensive comparison
using ve wetting agents, including the
most popular one, sodium tridecylbenze
sulfonate, with several different etchants

Fig. 4. Intergranular SCC cracks in 4340 alloy steel revealed by etching with saturated aqueous picric acid, plus HCl and Nacconol 90G wetting agent (80C 60 sec.), magnication bars
are 20 m long).

a)

b)

Fig. 5. Etching with 2% nital (a) reveals packets of lath martensite; etching with aqueous
saturated picric acid solution with HCl and a wetting agent at 20C (b) faintly revealed
the prior-austenite grain boundaries in SAE 723, Grade 3, Class 3 pressure vessel steel (Fe
- 0.33%C - 0.25%Mn - 0.13%Si - 3.55%Ni - 1.66%Cr - 0.48%Mo - 0.12%V). Using aqueous
saturated picric acid plus HCl and a wetting agent at 90C, however, revealed the prior-austenite grain boundaries: (c) bright-eld illumination and (d) dark-eld illumination.

including the saturated aqueous picricacid solution. Without the wetting agent
added, saturated aqueous picric acid was
an excellent general-purpose etchant
for steels, but PGBs were not revealed.
When this wetting agent was added, general-structure etching was suppressed and
PGBs were revealed. None of the other
wetting agents tried were as effective. A
number of studies on the use of wetting
agents in etchants have been reviewed.[10]
The original tridecyl version of this wetting agent has branched molecular chains,
which are difcult to manufacture and
have poor biodegradability. More recent
versions have linear chains and are biodegradable. Kilpatrick[14] evaluated the dodecyl version of this wetting agent, which
is more easily made, readily biodegradable
and works as well. Consequently, this wetting agent is the most commonly used today for revealing PGBs.

Barraclough[11] reviewed etchants tried


by 10 different authors to reveal PGBs.
He concluded that it was necessary to
temper embrittle specimens to obtain adequate grain-boundary delineation to permit measurements to be made of the grain
size. His work conrmed that picric acid
was the most suitable agent for revealing
PGBs and the solvent used was critical.
Alcohols did not work, but water or ether
gave good results. Petroleum ether is less
dangerous than ethyl ether, but both are
explosive when heated above 100C, and
static electricity can cause explosions.
Several wetting agents were tried, all
were suitable, but he preferred Teepol
(Teepol is a registered trademark of the
Shell Chemical Co. of Houston, Texas).
He found that the aqueous solution could
be used at temperatures up to 85C, but
he did not indicate if higher temperatures produced any benet or detriment.
IndustrialHeating.com - April 2010 49

FEATURE | Materials
Characterization & Testing

Barraclough used swabbing and lightly


back-polished his specimens to reduce the
etch details of the martensite within the
grains, which is now an excellent common
practice.
Brownrigg et al.[12] followed up on this
study with a slight modication that they
stated allowed them to bring out PGBs for
as-quenched steels from 0.03-0.8% C with
bainitic structures. They used a solution of
100 mL saturated aqueous picric acid, plus
2 mL Teepol plus 6 drops of HCl. After
mixing, they ltered out the excess picric
acid, which they stated reduces staining
of the specimen surface. They immersed
specimens at room temperature for 4-10
minutes. They demonstrated that PGBs
could be revealed in low-carbon (0.04%),
as-rolled bainitic structures that were not
recrystallized after hot rolling.
Bodnar et al.[13] studied development
of PGBs in CrMoV rotor steels using 13
different etchants. The saturated, aqueous picric-acid etchant produced better
results than most but was still inadequate.
Tempering specimens in the embrittlement range did not help because the phosphorous content was too low. Addition of
a small amount (3-5 drops per 50 mL of
etchant) of HCl to the etchant produced
markedly better results. They etched for
5-8 minutes with the beaker placed in an
ultrasonic cleaner for agitation (the water
level in the ultrasonic cleaner must be
lower than the etchant level in the beaker,

Fig. 7. Prior-austenite grain boundaries revealed in fully martensitic Modied 4330V


alloy steel with only 0.005%P (Fe - 0.29%C
- 0.39%Mn - 3.54%Ni - 1.69%Cr - 0.54%Mo
- 0.11%V (1110F temper) using aqueous
saturated picric acid plus HCl and a wetting
agent at 90C for 60 seconds.

50 April 2010 - IndustrialHeating.com

a)

b)

Fig. 6. Prior-austenite grain boundaries are not revealed in martensitic A-350 (LF3) alloy
steel (Fe - 0.07%C - 0.74%Mn - 3.66%Ni - 0.2%Cr - 0.07%Mo (1350F temper) using nital (a)
but are revealed using aqueous saturated picric acid plus HCl and a wetting agent at 90C 2 minutes (b, as etched).

or the beaker will ip over). This was followed by light repolishing to remove some
of the etch detail within the grains. Other
etchants for revealing PGBs have been
developed; reference [4] lists 28 reagents
published prior to 1984 for this purpose.
Experimental Procedure
Before specimens can be etched, they must
be properly prepared to a very high quality level. The rst and most critical step is
sectioning, which must be conducted to
induce minimal damage. Use abrasive cutoff machines (avoid torch cutting, shearing, band saws or power hack saws as they
induce far too much damage) with a blade/
wheel designed for metallography and for
steels of the hardness level being prepared.
Generally, mounting is performed but
may not be necessary if the structure at the
edges of the sample is not important (as in

a)

a specimen cut from the interior of a part).


Commence grinding with SiC paper, using as ne a grit size as possible. As a rule,
start grinding with 120-grit SiC for steels
60 HRC; start with 180-grit SiC for steels
between 35 and 60 HRC; and start with
220- to 240-grit SiC for steels <35 HRC.
Next, polish the specimens using at,
low-resilience cloths, such as DP/MD-Plan
or DP/MD-Pan with 9-m diamond, using
a load of 25-30 N per specimen, 150 rpm,
for at least 5 minutes. Next, polish with
DP/MD-DAC, DP/MD-DUR or DP/MDSAT cloths with 3-m diamond, same load
and rpm, for 5 minutes. For martensitic
and bainitic steels that are to be etched to
reveal prior-austenite grain boundaries, a
1-m step is not necessary. The nal step
would be to use either a synthetic neoprene cloth (such as DP/MD-Chem) or a
napped or ocked cloth (such as DP/MD-

b)

Fig. 8. Prior-austenite grain boundaries revealed in 8620 alloy steel using aqueous saturated picric acid plus HCl and a wetting agent at 80-90C, 60 seconds; specimen as-quenched
(a) and after tempering at 400F (b). Prior-austenite grain boundaries revealed in 8620
alloy steel using aqueous saturated picric acid plus HCl and a wetting agent at 80-90C, 60
seconds; after an 800F (c) and a 1200F (d) temper.

Floc or DP/MD-Nap) using either colloidal


silica (such as OP-S) or a neutral alumina
suspension (such as OP-AN). Polishing is
usually conducted at 120-150 rpm, same
load, from 1-3 minutes.
A good practice is to lightly etch the
specimens after the last step with a general-purpose reagent, such as 2% nital, to
see what the structure actually is and how
well prepared the specimens are before
proceeding to use the saturated aqueous
picric-acid etch. After examination, repeat the last step for at least 1 minute to
remove this etch. Cleaning after each step
is important to prevent contamination of
the next step and poor results.
The writer has been using saturated
aqueous picric acid plus a wetting agent
and a small HCl addition (when steels
have more than about 1% Cr) for some
time but formerly at room temperature.
The specimen would be placed polished
face vertical in a beaker with at least 100
mL of the etchant in an ultrasonic cleaner
(the water level in the ultrasonic cleaner
should not be higher than the etchant
level in the beaker or it will ip over).
The timer would be set for 7 minutes with
etching at room temperature.
Results with 8620, 4140 and 5160 were
described above (without the HCl addition). Light back-polishing was always
done to try and improve the visibility of
the grain boundaries. As sodium tridecylbenzene sulfonate became difcult to
obtain, the writer switched to the dodecyl
version with no apparent difference.
Results
Several broken, heat-treated, 4340-alloysteel nut inserts from the riser of an oil
rig were examined. To determine if the
crack patterns were intergranular, specimens were etched in the saturated aqueous picric-acid ltered solution with HCl
using Nacconol 90G as the wetting agent
(Nacconal is a registered trademark of the
Stepan Company of Northeld, Ill.). This
is described as sodium alkyl benzene sulfonate. On the MSDS sheet, the composition is given as 90-93% sodium dodecylbenzen sulfonate, 5% sodium sulfate, 1%
sodium chloride and 1.5% water. HCl was

a)

b)

c)

d)

Fig. 9. Prior-austenite grain boundaries revealed in fully martensitic 4140 alloy steel using
aqueous saturated picric acid plus HCl and a wetting agent at 80-90C; specimen in the
as-quenched condition (a) and after a 400F (b) temper. Prior-austenite grain boundaries
revealed in fully martensitic 4140 alloy steel using aqueous saturated picric acid plus HCl
and a wetting agent at 80-90C; after an 800F (c) and a 1200F (d) temper.

added in the amount of 6 drops per 100 mL


of the saturated aqueous picric-acid solution (1-500 mL). After this was mixed, the
excess picric acid was removed by ltering.
Etching was conducted at room temperature for 7 minutes using the ultrasonic
cleaner for agitation. However, the results
were marginal. Hence, the writer heated
the solution to 80-90C (below the boiling
point to retard evaporation). Specimens
were swab etched for 2 minutes and then
back-polished. Results were exceptionally
good, as shown in Figure 4, revealing an
almost fully intergranular crack path from
stress-corrosion cracking (bulk hardness
was well above the safe limit for highstrength steel in salt water).
In a study of SAE 723 Grade-3 Class-3
pressure-vessel steel forgings, it was necessary to reveal the prior-austenite grain
structure. A previous investigator had
etched the specimens with 2% nital and
claimed it revealed a very coarse prioraustenite grain size. As nital will only
reveal the lath martensite and give a contrast etch to the lath packets, the writer
used the saturated aqueous picric-acid

etchant, plus HCl and Nacconol 90G as


the wetting agent. Figure 5a shows an example of the structure etched with nital,
revealing a coarse lath packet size. First,
the saturated picric-acid etch was used at
room temperature, but the results (Figure
5b) were inadequate. The specimen was
re-polished and etched at 90C, and the
results were much better (Figure 5c) as
there was much less structure etching.
Dark-eld illumination may be used effectively to reveal the boundaries with
strong contrast (Figure 5d).
The value of back-polishing after etching is illustrated in Figure 6, which shows
a specimen of A-350 (LF3) high-alloy steel
(Fe-0.07%C-0.74%Mn-3.66%Ni-0.2%Cr0.07%Mo). Note the very low carbon
content, which usually makes the task impossible. Also, the phosphorous content
was only 0.008%, and it was tempered at
1350F.
These three factors, very low carbon and
phosphorus and very high tempering temperature, would normally make it impossible to reveal the PGBs. But, as shown in
Figure 6, it was possible with the etchant
IndustrialHeating.com - April 2010 51

FEATURE | Materials
Characterization & Testing

heated. This gure also demonstrates the


benet of careful light back-polishing after
etching to remove extraneous etch detail
within the grains and make the boundaries more visible. A specimen from a forging of modied 4330V with only 0.005%
phosphorus that was tempered at 1110F
was also successfully etched (Fig. 7). With
this low P content and high tempering
temperature, other etchant variations
would not reveal the PGBs.
For this study, the writer re-prepared the
previously mentioned 8620 and 4140 specimens that were in the as-quenched and
quenched-and-tempered (400, 800 and
1200F) conditions. They had been etched
with the saturated aqueous picric-acid reagent without the HCl addition at room
temperature. This time, HCl was added
and etching was done at 80-90C for 60120 seconds. Figure 8 shows the four fully
martensitic 8620-alloy-steel specimens in
the as-quenched and quenched-and-tempered conditions, while Figure 9 shows the
four fully martensitic 4140-alloy-steel
specimens in the same heat-treated conditions. In all cases, the prior-austenite grain
boundaries are visible.
Four specimens of 4340-alloy steel were
isothermally transformed to lower bainite
and then tempered at 300, 500, 700 and
900F. They were etched with the heated
saturated aqueous picric-acid reagent containing HCl and Nacconol 90G wetting
agent. Figure 10 shows the specimens tem-

a)

b)

Figure 10: Prior-austenite grain boundaries in 4340 alloy steel isothermally transformed to
lower bainite using aqueous saturated picric acid plus HCl and a wetting agent after tempering at 300F (a) and 500F (b). These specimens were back polished after etching.

pered at 300 and 500F that were carefully


back-polished after etching. Results were
similar for the two tempered at 700 and
900F.
Conclusions
Revealing prior-austenite grain boundaries
has been one of the most difcult and frustrating tasks assigned to the metallography/
materialography laboratory. The most successful etch had been saturated aqueous
picric acid containing a wetting agent, usually sodium dodecylbenzene sulfonate, at
room temperature for periods of 4-20 minutes. However, this etch was unable to reveal PGBs in martensitic or bainitic steels
with carbon contents below ~0.3% or with
phosphorus contents below ~0.010%, even
when subjected to step-embrittlement cycles or for steels tempered above ~1050F.

However, if a small amount of HCl is


added and the etchant is used at ~80-90C
(results were good at 70C when tried on
one specimen), these limitations are overcome. Filtering the solution before use
does help reduce staining/pitting attack.
Careful, low-pressure back-polishing on
a stationary cloth using OP-AN alumina
slurry is very effective at reducing extraneous etch detail within the grains and
enhancing grain-boundary visibility.
Acknowledgement
The writer is grateful to Michael He and
the staff at Scot Forge (Spring Grove, Ill.),
for the use of their equipment and for supplying some of the forged specimens tested
in this program. IH
References (available online)

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