Materials Characterization 56 (2006) 348 354

Selection of etching methods of primary carbides in MAR-M247

nickelbase superalloy for computer-aided quantitative metallography
Agnieszka Szczotok , Janusz Szala, Jan Cwajna, Marek Hetmaczyk
Silesian University of Technology, Department of Materials Science, Krasinskiego 8, 40-019 Katowice, Poland
Received 19 September 2005; received in revised form 22 October 2005; accepted 22 October 2005

Abstract
The usefulness of various etching methods for revealing the structure of MAR-M247 nickelbase superalloy and image
acquisition methods were analyzed from a desire to estimate primary carbides quantitatively. The analysis was carried out on
images registered using light and scanning electron microscopes. The analyzed images contained a complete range of primary
carbides occurring in the matrix and on the grain boundaries of MAR-M247 alloy.
2005 Elsevier Inc. All rights reserved.
Keywords: Carbide; Nickelbase superalloy

1. Introduction
Carbides and phase fulfill an important role in
precipitation strengthening of nickelbase superalloys.
Addition of carbon in amounts from 0.05% to 0.2%
and carbide-forming elements enables precipitation of
M23C6, MC and M6C type carbides in these alloys.
These carbides are not stable phases in the structure of
nickelbase superalloys. Under the influence of service temperature and time they may undergo transformations changing their type, size and morphology,
which affect the properties of these alloys at high
temperatures [1,2].

Corresponding author. Tel.: +48 32 603 44 67; fax: +48 32

6034400.
E-mail addresses: agnieszka.szczotok@polsl.pl (A. Szczotok),
janusz.szala@polsl.pl (J. Szala), jan.cwajna@polsl.pl (J. Cwajna),
marek.hetmanczyk@polsl.pl (M. Hetmaczyk).
1044-5803/$ - see front matter 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2005.10.011

The MC carbides are found to form script-like

structures during solidification. These structures are
composed of three distinct parts. The central cores and
elongated arms are formed of the MC carbides of (Ti,
Cr, Hf, Ta, W)C formula. The elongated script arms end
in enlarged, angular heads. The heads have (Ti, Hf,
Ta, W)C compositions and a higher hafnium content
than the cores and arms. The size of the script structures
and the ratio of head-type to core and arm-type MC
carbide have been found to be determined by solidification conditions.
The volume fraction of carbides, trapping and
growth behavior have been correlated with the growth
rate. It was found that the volume fraction of carbides
decreased at slower growth rates. This decrease was
caused by a lower solidliquid interface trapping ability
at a slower growth rate [3].
The most important part of a quantitative description
of primary carbides performed using computer-aided
methods, affecting the results obtained, is their correct

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349

electron microscopes are discussed in Ref. [8]. In the

current paper the results give a completion of those
cited.

detection. One of the factors which can influence the

detection is the etching method. Evaluation from a computer-aided quantitative metallography point-of-view of
the usefulness of etchants and observation techniques
was the aim of this study. The carbide phase occurring in the alloy MAR-M247 in the as-cast condition was revealed using bright field light microscopy
(LM) and secondary electron (SE) and back-scattered electron (BSE) techniques in a scanning electron microscope (SM) is the subject of the current
paper.

4. Results and discussion

4.1. Detection of carbides in images obtained using
light microscope
Images of structure were registered using an Olympus GX71 light microscope equipped with a DP70
colour digital camera employing various acquisition
techniques. The most satisfactory results were obtained
using a bright field technique. On the unetched metallographic specimen blocky, isolated MC type carbides
with regular shapes, MC carbides in an arrangement
termed Chinese script as well as carbides on the
grain boundaries have been found (Fig. 1a). All these
carbides show a similar grey level. A selective detection
based only on binarization is therefore impossible. Application of other criteria (for example shape or size) as
well as techniques of image acquisition also did not
give satisfactory results.
A difference in grey level between all the carbides
revealed and remaining elements of the structure visible on unetched metallographic specimens of MARM247 alloy is still sufficient for detection of these
carbides when they are treated together. In this case
multiple binarization provides good results. Images of
the etched specimens contain much more information
about their microstructure than these obtained on
unetched specimens (Fig. 1bd). These images still
are not suitable for quantitative evaluation, because
not only carbides have been revealed on these specimens, but also areas with unevenly outlined
eutectics.
Automatic procedures were tested to detect all carbides occurring on images of the structure of MARM247 alloy after etching using several etchants registered using light microscopy. Selected results of the
detection using the Met-Ilo image analysis program
[9] are given in Fig. 2.
In the case of the sample etched in a solution containing 25 ml of nitric acid, 75 ml of hydrochloric acid and
150 ml of glycerine, precipitates of the strengthening

2. Material
MAR-M247 superalloy is a polycrystalline nickel
base heat-resisting alloy (chemical composition in
Table 1). During the past two decades, this alloy
has been widely employed in fabricating advanced
turbine blades and rotating parts in the aerospace
industry because of its excellent characteristics, including good castability, strength, as well as superior
creep and hot corrosion resistance at elevated temperatures [4,5].
In particular, the carbide characteristics can play a
crucial role in determining the high-temperature properties of MAR-M247 superalloy. The behavior of a
carbide in superalloys is complex. In general, discrete
carbides precipitating at grain boundaries (GBs) can
inhibit GB sliding and improve the strength and creep
resistance of superalloys at elevated temperatures. Conversely, the coarse or script-like MC primary carbides
that exist within the grain interior or at GBs are
regarded as a major factor decreasing ductility during
creep and tensile tests. Because of the high brittleness of
MC carbides, they may act as crack initiation sites and
propagation paths [6].
3. Experimental procedure
The procedure of metallographic specimen preparation was conducted according to the recommendations of the Buehler expert system [7] for nickelbase
superalloys. Recent basic approaches to work out
etching methods enabling selection of primary carbides in images obtained using light and scanning
Table 1
Chemical composition of the nickelbase MAR-M247 alloy
Elements content [wt.%]

MAR-M247

Cr

Ni

Co

Mo

Ta

Ti

Al

Fe

Others

8.25

59.0

10.0

0.7

10.0

3.0

1.0

4.5

b0.5

0.15

0.015 B, 0.05 Zr, 1.5 Hf

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Fig. 1. Primary carbides visible on specimens from MAR-M247 alloy: a) unetched; b) etched (electrolytic etching: 10% H3PO4; 3 V); c) etched (100
ml HNO3 and 1 ml HF); d) etched (50 ml of lactic acid, 30 ml of nitric acid, 2 ml HF). Light microscope, bright field.

Fig. 2. Initial images of carbides (a, c) of specimen etched in 50 ml of nitric acid (65%) and 50 ml of icy acetic acid solution and images with detected
carbide phase (b, d).

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351

Fig. 3. SE images of carbide phase revealed on an unetched specimen of MAR-M247 alloy.

phase were poorly etched when compared with the

carbide phase (Fig. 2a). However, it is not a serious
limitation because the grey level of both phases is
different.
On the images of the structure etched in 50 ml of
nitric acid (65%) and 50 ml of icy acetic acid solution,
as in Fig. 2a, script and blocky carbides are visible (Fig.
2c). The results obtained after automatic detection are
better for the etchant containing icy acetic acid.
4.2. Selective evaluation of carbides using scanning
microscopy methods
The morphology and chemical composition of the
carbide phase occurring in the primary structure of

MAR-M247 alloy were evaluated using a scanning

electron microscope (Hitachi S-4200) equipped with
an X-ray spectrometer (VOYAGER 3500).
On the secondary electron (SE) images the same
types of carbides are visible (Fig. 3), which were observed using the light microscope. Lace occurring on
the boundaries of carbides is a characteristic feature of
most particles observed.
Back-scattered electron (BSE) images make it possible to differentiate better the grey levels of primary
carbides and the matrix, which is essential for automatic
detection (Fig. 4).
As a result of etching the alloy MAR-M247 in the ascast state several types of primary MC carbides (HfC,
(Ta,W,Ti,Hf)C of various carbide-forming element

Fig. 4. SE and BSE images of the same area of an unetched specimen of MAR-M247 alloy.

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Fig. 5. SE images of MAR-M247 specimens etched in four different reagents: m (electrolytic etching: 50 ml of lactic acid, 30 ml of nitric acid, 2 ml
HF; 2V); l (electrolytic etching: 2 g CrO3, 100 ml of water; 3V); g (10 g CuSO4, 50 ml H2O, 50 ml C2H5OH, 50 ml HCl); and o (95 ml HCl, 2 ml
HNO3, 3 ml H2O2).

contents, (Hf,Ta)C) and secondary solid solutions of

primary MC carbides with various contents of carbideforming elements have been revealed (Fig. 5).
Moreover, the occurrence of tungsten-rich M6C carbides and M23C6 type carbides containing mainly chromium has been established.
A trial of primary carbide selective detection on
images registered using a scanning electron microscope was carried out on the unetched specimens and
also on samples etched in reagents b (electrolytic
etching: 10% H3PO4; 3V dc), d (50 ml of lactic
acid, 30 ml of nitric acid, 2 ml HF) and i (4 g
CuSO4, 20 ml HCl, 20 ml of water). Before binarization, initial images were smoothed using a mean
filter. In the case of using b and d etchants the
primary carbides (Fig. 6b, f) were detected on the

BSE images (Fig. 6a, e), because on the SE images

(Fig. 6c, g) differentiation of grey level between
carbides and the metallic matrix was too small;
which makes binarization difficult (Fig. 6b, d). This
problem does not occur on the unetched specimens
and those etched in i etchant for which the BSE as
well as the SE images enable correct detection of the
carbide phase.
An additional advantage of using i etchant is the
possibility of the automatic binarization of carbide
phases on images etched in this etchant using a
maximum variation method without the necessity of
an operator participation in this process. Trials of
automatic detection of all the carbides occurring on
images registered with a scanning electron microscope and present in the structure of MAR-M247

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353

Fig. 6. Detection of carbides on SE images (c, g) and BSE images (a, e) presenting the structure of MAR-M247 alloy after etching in d
etchant.

alloy after etching in etchant d were performed. The

selected results of the detection of carbides performed using the Met-Ilo program are presented in
Fig. 6.

5. Conclusions
In the structure of the MAR-M247 alloy in the ascast state several types of primary MC carbide as well

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A. Szczotok et al. / Materials Characterization 56 (2006) 348354

as M6C and M23C6 carbides occur. They often form

clusters containing carbides of various chemical compositions, but of very similar grey level, which does not
enable their computer-aided selective quantitative evaluation. Tests of the selective detection of primary carbides does not succeed on images registered using the
various light microscope techniques, because differentiation of grey level between the carbide phase and the
matrix of the alloy on the unetched and etched samples
using various etchants specimen is not sufficient.
The research described here indicates that detection
of the carbides occurring in the as-cast MAR-M247
alloy should be carried out on images of unetched
samples using scanning as well as light microscope
methods. Depending on the research method used for
carbide phase evaluation the most advantageous results
of specimen etching are the result of the action of a
variety of etchants.
Acknowledgements
Scientific work funded by the Scientific Research
Committee in the years 20032005 as a research project
No. 6 T08 2003C/06083.
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