Study of Selective Etching of Carbides in Steel

G.F. Vander Voort1, E.P. Manilova2, J.R. Michael3, G.M Lucas1

1

Buehler Ltd, Lake Bluff, Illinois, 2Polzunov Central Boiler and Turbine Institute, St. Petersburg, 3Sandia National
Laboratory, Albuquerque, New Mexico

Abstract

A number of etchants have been reported in the literature to selectively outline, outline and color,
or attack specific types of carbides in steels. These etchants have been developed during the first
half of the 20th century but have not been studied since the development of modern analytical
techniques. Although they are believed to be selective, that is qualitative in nature, their value for
quantitative measurements of the carbides has not been determined. To evaluate these etchants,
eight specimens (seven different compositions) with M3C, M23C6, M7C3, M6C, M2C and MC
carbides were evaluated first by electron-backscattered diffraction (EBSD) to verify the carbides
present. The matrix of each specimen was darkened to measure the total carbide content. Then, the
various etchants were tried and the results were compared to past publication results. Quantitative
measurements were made after each etchant was used. This revealed some minor differences with
the prior literature and showed that, while useful for qualitative evaluations, they are not useful for
quantitative measurements.

Introduction

Metallographers have used certain selective etchants for years to color specific carbides as an aid to
phase identification. However, only a few of these etchants have had wide usage, e.g., alkaline
sodium picrate to color cementite. The behaviors of the others are less well known. However, even
for alkaline sodium picrate, few metallographers know that it also outlines and colors M6C
carbides. They have not been evaluated for use in quantification of these carbides.

Experimental Procedure and Results

The nominal compositions of the alloys used in this study are given in Table 1. For the white cast
iron (WCI) specimen, Table 1 gives the actual composition. The 440C martensitic stainless steel,
the M42 and the T15 high-speed steel specimens are all annealed powder metallurgy alloys with
fine carbide sizes. The other tool steels were made by ingot technology. The D3 specimen was
austenitized at 1066 C, higher than the recommended temperature, 1010 C, to dissolve all of the
small carbides, then quenched to form martensite. The W1 and the M4 specimens were spheroidize
annealed. Both spheroidize annealed and quenched and tempered specimens of M42 high-speed
steel were evaluated. The white cast iron specimen was, of course, a casting and was in the as-cast
condition.

Table 1. Nominal Composition of the Alloys Studied (Wt. %)

Grade

Mn

Si

Cr

W1
WCI
D3
T1
T15
M4
M42
440C

1.05
4.0
2.1
0.7
1.5
1.3
1.08
1.1

0.3
0.1
0.3
0.3
0.3
0.3
0.3
0.5

0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.5

0.96
12.5
4.0
4.5
4.5
3.75
17.0

Ni

Mo

18.0
12.5
5.5
1.5

1.0
4.75
4.0
1.15

Co

0.5
0.5
4.5
9.5
0.6

5.0
8.0

The specimens were prepared and analyzed using EBSD on a focused ion-beam unit. The results
are given in Table 2.

Table 2. Types and Sizes of Carbides in the Specimens

Grade M3C
W1
All
WCI All
D3
T1
T15
M4
M42
440C

M23C6

M7C3

M6C

MC

All
Small
Small
Small

Small
Large

M2C

All

Small

Large

Medium

A variety of etchants were tried to darken the matrix. Klemms I gave excellent results for the
spheroidize annealed W1 and the white cast iron (cementite and pearlite as Ledeburite) specimens.
A Beraha type solution (100 mL water, 0.6 mL HCl, 1 g K2S2O5) was used to color the ferritic
matrix of annealed T15 and M42 and to color the martensitic matrix in the M42 specimens.
Vilellas reagent was used to darken the martensite in the D3 specimen. Berahas Sulfamic acid
reagent (100 mL water, 3 g K2S2O5, 2 g Sulfamic acid and 1 g NH4FHF) was used to color the
ferritic annealed matrix of the T1 and M42 specimens. Other reagents were tried, but these yielded
the best contrast between the unaffected carbides and the colored matrix while yielding crisp grain

boundaries. The specimens were evaluated by automated image analysis to determine the volume
fraction, number per unit area and size of the carbides.
Next, the specimens were re-prepared and etched with the reagents {1-5] listed in Table 3.

Table 3. Etchants Used in the Study.

Alkaline Sodium Picrate: 100 mL water, 2 g picric acid, 25 g NaOH; use 90-100 C
Murakamis: 100 mL water, 10 g NaOH, 10 g K3Fe(CN)6; mix fresh, use at 20 C
Groesbecks: 100 mL water, 4 g NaOH, 4 g KMnO4; use at 20 C
1% CrO3: 100 mL water, 1 g CrO3; use at 2-3 V dc, 10 s
10% Ammonium Persulfate: 100 mL water, 10 g (NH4)2S2O8; use at 6 V dc, 10 s

Results of the etching experiments are shown in Table 4. These results do differ from the prior
summary of their effects [5].

Table 4. Results of the Etching Experiments

Etchant

M3C

M23C6

M7C3

M6C

MC

M2C

Alk.Na Pic.

Colors

NA

NA

Colors

NA

NA

Murakami

NA

Faint

Out/Col

Out/Col

NA

Outlined

Groesbeck

NA

NA

Faint

Out/Col

NA

Outlined

1% CrO3

NA

Outlined

Out/Col

NA

Colors

Attacks

10% AP

Outlined

Attacks

Outlined

Outlined

Attacked

Attacked

NA no affect

Out/Col outlined and colored

Some examples of the results of the etching experiments are given; space restrictions, however,
limit this to a few examples. Figure 1 shows the microstructure of spheroidize annealed W1
specimen etched a) with Klemms I to darken the ferrite and b) with alkaline sodium picrate to

Figure 1. Cementite in spheroidize annealed W1 tool steel etched with: a) Klemms I to color the
ferrite and with b) alkaline sodium picrate, 60 s at 90 C, to color the cementite.

Figure 2. M7C3 carbides in D3 tool steel after hardening etched with a) Vilellas reagent to darken
the matrix, b) Murakamis, 10 s at 20 C, c) CrO3, 3 V dc, 10 s, and d) ammonium persulfate, 6 V
dc, 10 s.

e
Figure 3. MC (large) and M6C (small) carbides in annealed M4 high-speed steel etched with a)
Berahas to darken the ferritic matrix, b) alkaline sodium picrate, 120 s, 90 C, c) Murakamis, 20 s,
20 C, d) Groesbecks, 5 s, 20 C, and with e) 1% CrO3, 3 V dc, 10 s, to attack the MC. Alkaline
sodium picrate, Murakamis and Groesbecks reagents all color or attack the M6C carbides.

color the cementite. Electrolytic ammonium persulfate started to etch the matrix even before the
current was turned on. It outlined the cementite. Results for the white cast iron specimen were
similar. Figure 2 shows the microstructure of the D3 specimen etched with a) Vilellas reagent,
with b) Murakamis reagent to outline color the M7C3 carbide and c) electrolytic 10% ammonium
persulfate, which outlined the M7C3 carbide, but did not color it, and etched the martensite while
revealing the prior-austenite grain boundaries. Figure 3 shows the microstructure of the annealed
M4 high speed steel specimen etched with a) Berahas reagent to color the ferritic matrix, with b)
alkaline sodium picrate to color the M6C carbides and outline the large MC carbides, with c)
Murakamis reagent, which heavily attacked the M6C carbides but had no affect on the MC
carbides, with d) Groesbecks reagent, which acted similarly, but did not attack the M6C as heavily,
and e) with electrolytic CrO3, which attacked the MC. Note that Murakamis, Groesbecks and the
1% CrO3 reagent all appear to reveal many small carbides in the matrix, but this appears to be an
artifact.
But, in general, most of the etchants produced higher volume fractions and greater numbers of
particles than were obtained when the matrix was etched. In a few cases, the results were close, as
was the case for the M7C3 carbides in the D3 specimen etched with Murakamis and Groesbecks
reagents compared to the measurement made when the matrix was darkened. But, this was the
exception rather than the rule.

Conclusions

The experiment showed that the reagents do have reasonable selectivity and can be used to identify
carbides when sophisticated electron instruments are not available. The results frequently agreed
with the literature, but differences were observed. Alkaline sodium picrate colored the M3C and
M6C carbides, and nothing else, as claimed. For example, Murakamis used at room temperature
outlined and colored M7C3 carbides in D3 rather than attacking them and attacked the M23C6
carbides in 440C, instead of faintly revealing them. Groesbecks reagent did not attack the Cr23C6
carbides, and did not reveal them. It faintly revealed the M7C3 carbides and it outlined the M2C
carbides rather than attacking them. Electrolytic CrO3 outlined M7C3 carbide, as stated, but did not
attack them, as claimed. It did not outline M2C carbides, but attacked them. Electrolytic 10%
ammonium persulfate has not been studied in the past as to its selectivity. It has mainly been used
to color M23C6 carbide in sensitized austenitic stainless steels. In this study, it outlined M3C, M6C
and M7C3 carbides, and attacked M23C6, M2C and MC carbides. In general, they are not satisfactory
for quantitative metallographic measurements as bias was obtained in the volume fractions, number
of particles per unit area and their size.

Literature

[1] R.F. Campbell, et al., Trans. Am. Inst. Mining, Metallurgical Eng., 1960, p. 723-732.
[2] T. Nishizawa, Scand. J. Metallurgy, 1972, p. 41-48.
[3] F. Maratray and R. Usseglio-Nanot, Factors Affecting the Structure of Chromium and
Chromium-Molybdenum White Irons, Climax Molybdenum SA, Paris, p. 27.
[4] L.R. Woodyatt, G. Krauss, Met. Trans., 1979, p. 1893-1900.
[5] G.F. Vander Voort, Metallography: Principles and Practice, ASM International, Materials Park,
Ohio, 1999, p. 223-224.