FEATURE | Materials

Characterization & Testing

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Martensite and Retained Austenite

George F. Vander Voort Buehler Ltd., Lake Bluff, Ill.
Martensite development is critical to many heat-treatment processes. This paper
examines the conditions under which austenite is retained and the problems
associated with its presence, with detecting it and with measuring it.

History
Up to about 100 years ago, the heat treatment of steels was certainly an art as the
science behind what was happening was
just starting to be understood. The control of grain size in carburizing was just becoming possible by the work of McQuaid
and Ehn. They discovered that small additions of aluminum would keep the grain
size ne after a long exposure, generally
8-10 hours, at the carburizing tempera-

Hardness, Rockwell C

CCT diagrams using the arrested-Jominyture. Prior to that, coarse prior-austenite

bar method a rather painful process ingrain structures would be observed in the
deed. Dilatometer-based CCT diagrams
carburized case that would initiate brittle
were far easier to develop and in less time,
intergranular fractures at minor loads.
but this equipment came later.
Next, Grossman and Bain developed
the theory of hardenability
where the ideal critical diameter
68
(DI) could be calculated from
900
the prior-austenite grain size and
the composition. Then, the DI
65
800
could be used to estimate the
as-quenched hardness prole of
a uniformly shaped bar given a
700
60
particular strength quench.
About the same time, isother600
mal transformation (IT) diagrams
were developed, and it became
50
500
easier to identify these lesserunderstood microstructures of
Marder (27)
Hodge and Orehoski (28)
upper and lower bainite. An IT
400
40
Burns et al. (29)
diagram, while it is helpful in
Irvine et al. (30)
understanding microstructures
Kelly and Nutting (31)
300
30
and in developing annealing
Kurjumov (32)
20
Litwinchuk et al. (33)
cycles, is not particularly useful
Bain and Paxton (34)
200
10
for understanding heat-treatJaffe and Gordon (35)
0
ment structures. This problem
Materkowski (36)
100
was solved by developing con0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3
tinuous cooling transformation
Carbon, wt %
(CCT) diagrams. Shortly before
Fig.
1.
Summary
of
extensive
as-quenched
the writer joined the Homer
hardness
data
from
the
literature
for Fe-C alloys
Research Laboratories of Bethand steels by Krauss[2]
lehem Steel, they had developed
Hardness, DPH

eepending upon the carbon

ccontent of the parent austtenite phase, either lath
((low-carbon) or plate (highcarbon) martensite may form, as well as
mixtures of the two. In general, lath martensite is associated with high toughness
and ductility but low strength, while plate
martensite structures are much higher
strength but may be rather brittle and
non-ductile.
Increasing the carbon content of the
austenite also depresses the martensite
start (Ms) temperature and the martensite nish (Mf) temperature, which leads
to difculties in converting all of the austenite to martensite. When this happens,
we have retained austenite, which may be
either extremely detrimental or desirable
under certain conditions.

IndustrialHeating.com - April 2009 51

FEATURE | Materials
Characterization & Testing

1600

871
Greninger (8)
Toriano and Greninger (10)
Cohen et al (24)
Digges (25)
Greninger and Troiano (26)
Kaufman and Cohen (27)
Esser et al (28)
Bibby and Parr (29)

1400
1200
Ms Temperature, F

Hardness, Rockwell C

60

50

40

1000
800

760
649
538
427

600

316

400

204

Temperature, C

70

30
200

93
Lath

Mixed

Plate

0
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Carbon, wt %

Fig. 3. Relationship between carbon content, martensite type and Ms temperature[4]

Technological Advantages
Development of thin-foil technology for
the transmission electron microscope
(TEM) produced a far-deeper understanding of the ne details of steel microstructures because these features were well
beyond the resolution of the light optical
microscope (LOM). The development of
IT and CCT diagrams had shown that
martensite began transforming at temperatures relative to the composition of the
austenite, with its carbon content being
most critical.
Problems due to excessive retained austenite had plagued the tool-steel industry
since the late 19th century. X-ray diffraction had been the primary tool for the
study of retained austenite and certainly
for its quantication, but it could not image this microstructure. LOM could not
image retained austenite until it was at
least present in the 10-15% range. TEM
thin foils could detect and image retained
austenite even at levels somewhat under
2% with careful use of dark-eld illumination. The morphology of the martensite makes it difcult to distinguish small
particles of retained austenite within the
complex plate-martensite patterns. With
low-carbon lath martensite, thin lms of
retained austenite could be seen with very
careful TEM work, but this was very difcult work.
52 April 2009 - IndustrialHeating.com

0
0

0.2

0.4

0.6

0.8
1.0
Carbon, wt %

1.2

1.4

1.6

Fig. 3. Relationship between carbon content, martensite type and Ms

temperature[4]

Tool Steels
In the tool-steel industry, excessive retained austenite is universally considered
to be detrimental. Exactly what constitutes excessive is difcult to dene as not
enough data exists, and what is excessive
will vary with the grade and application.
For example, relatively low-carbon 5%-Cr
hot-work die steels such as H11 and H13
have been used for years as guage blocks.
Any dimensional change with time is to
be avoided. Consequently, these steels are
triple tempered at a relatively high temperature where retained austenite will be
converted to either fresh martensite or
bainite, and they will be tempered with
the next tempering cycle.
In other applications, any observable
(by LOM) retained austenite is highly detrimental. Service stresses will convert the
retained austenite on the rst use. As the
carbon content of the retained austenite is
high, the martensite that forms is highly
tetragonal and the resulting expansion
cracks the steel because the matrix is not
ductile enough to tolerate the expansion
stresses.
With carburized gears, on the other
hand, only a very thin layer at the surface
is carburized and may contain 20-25% retained austenite. The bulk of the gear is a
highly ductile (compared to a tool steel),
low-carbon alloy steel. Gears are usually

not impact loaded like a tool-steel die,

so the stresses are much lower and the
retained austenite usually does not transform substantially during service. If the
retained austenite did transform, the steel
around it and below it is ductile enough
to accommodate the strains without fracture. Retained austenite does become
stable with time, and some will transform
to martensite at room temperature. Samuels [1] states that up to 5% of the austenite
present after quenching and low-temperature tempering (<200C) will transform
to martensite soon after quenching or over
a period of some months.
Inuence of Carbon Content of the
Austenite
Starting in the 1930s with the development of hardenability concepts, a number
of investigators have demonstrated that
the hardness of as-quenched martensite
increases in a relatively linear fashion
from about 0.05 to 0.5 wt. % carbon. Figure 1 shows data from a number of investigators summarized by Krauss.[2] Note
that when the carbon content of the austenite is >0.8%, the as-quenched hardness drops. This is due to the presence of
retained austenite, which is much softer
than plate martensite. Litwinchuk et al.[3]
took this curve to nearly 2% carbon which
demonstrates the effect of retaining large

Fig. 4. Carbon-free martensite in 18Ni250

maraging steel (Fe<0.03% C18.5%
Ni7.5% Co4.85% Mo0.4% Ti0.1% Al)
etched with Frys reagent (1000x marker
bar is 10 m long)

Fig. 5. Low-carbon martensite in Carpenter Technologys AerMet 100 ultrahighstrength steel (Fe0.23% C13.5%
Co11.1% Ni3.1% Cr1.2% Mo) heat
treated (1093 C, AC, age at 675 C for 6 h,
AC) to coarsen the grain size and etched
with 10% sodium metabisulte (100x)

Fig. 6. High-carbon plate martensite (blue

and brown), retained austenite (white),
plus intergranular and intragranular cementite in a carburized specimen of 9310
alloy steel etched with Berahas reagent
(100 mL water, 10 g Na2S2O3 and 3 g
K2S2O5) at 1000x (marker bar is 5 m long).

amounts of retained austenite upon the

as-quenched hardness.
Figure 3, from the work of Marder and
Krauss [4], shows the relationship between
the type of martensite observed and the
carbon content and martensite-start
temperature for Fe-C alloys. Figures 4
and 5 illustrate the appearance by LOM
of carbon-free martensite in a maraging
steel and lath martensite in an ultrahighstrength, low-carbon steel (AerMet 100).
Figure 6 shows plate martensite, retained
austenite and both intergranular and
transgranular cementite in carburized
9310 alloy steel. Plate martensite frequently contains microcracks from the
impact of one plate into a previously
formed plate. These cracks can initiate
subsequent failures.
Speich and Leslie [5] showed how increasing carbon in the austenite caused
the percentage of retained austenite to
increase, the Ms to decrease and the
change in martensite type from lath to
plate. A number of studies between Payson and Savage in 1944 and Andrews in
1965 have developed empirical formulas
to calculate the Ms based on composition, not simply from the carbon content. Carbon, of course, has the largest
effect, but the inuence of alloying elements upon lowering the Ms cannot be
ignored. The Mf temperature falls with
the Ms, so the formulas predict only the
Ms temperature.

Detecting Retained Austenite

Over the years, the writer has tried many
etchants, plus tint etchants, in an effort to
try to preferentially color retained austenite.
In almost all cases, these efforts have failed.
Many years ago, an investigator published
a short paper claiming that the addition of
1% zephiran chloride a wetting agent frequently added to 4% picral to increase the
speed of etching[6] would reveal retained
austenite by creating a strong contrast
between the dark martensite and the unetched austenite. This author claimed to be
able to see and measure, by point counting,
retained austenite down to ~2% in steels.
The writer has tried to duplicate this
experiment using railroad cone bearings of
carburized 8720 alloy steel. Unfortunately,
details of how these bearings were processed
and then prepared for metallography were
unknown. But at some earlier time they
were analyzed by X-ray diffraction (XRD).
Three pieces claimed to contain 25.4, 19.7
and 16.2% retained austenite were given
to the writer, who mounted them in a lowtemperature-curing epoxy compound and
ground and polished them. Nital plus zephiran chloride did reveal the retained austenite much better than nital without the
addition, and higher amounts of retained
austenite were recorded when zephirian
chloride was added. The image-analysis
results, however, were very low compared
to the XRD results. Of course, it is possible
that some of the retained austenite had iso-

thermally transformed between the time

when the XRD work was done and when
the image analysis work was done a time
that may have been a few years.
Figure 8 shows the microstructure of
the cone bearing that was reported to
contain 25.4% retained austenite etched
with 4% nital plus 1% zephiran chloride.
The image, by eye, does not appear to be
one-fourth retained austenite, and image
analysis measured only 13.3% with this
etch (and less with other etchants). The
specimen with 19.7% retained austenite
was measured as 8.5% by image analysis
with this etch, and the specimen with
16.2% retained austenite was measured
as only 1.2% retained austenite by image
analysis with this etch. In general, this
is the type of difference that the writer
has always seen when doing such experiments previously.
A new technique utilizing the scanning electron microscope (SEM) has been
developed. Called electron backscatter
diffraction (EBSD), it has the ability to
map microstructures according to crystalstructure differences. The writer has tried
recently (about ve years after the imageanalysis work was done) to determine the
percent retained austenite of the 25.4%
specimen by EBSD.
Some authors have claimed that EBSD
can detect and measure retained austenite down to ~2% and get data that agrees
with XRD data. The specimen with 25.4%
IndustrialHeating.com - April 2009 53

500
100

300

75

100
Relative
volume PCT
lath martensite

50

40
Volume PCT
retained

25
0

20
0

0.4

0.8

1.2

Ms Temperature, C

700

Ms Temperature

Volume PCT

Relative volume % lath martensite

FEATURE | Materials
Characterization & Testing

1.6

Carbon, wt %

Fig. 7. Inuence of carbon content of the austenite on the percentages of lath (or plate) martensite, Ms temperature and percentage of
retained austenite[5]

Fig. 8. Surface of a carburized 8720 alloy-steel railroad-cone bearing etched with nital plus 1% zephiran chloride. Image analysis
yielded 13.3% retained austenite vs 25.4% by XRD (1000x).

retained austenite was re-prepared metallographically using the

best procedures for EBSD and analyzed by Stefan Zaefferer of the
Max Planck Institute for Steel Research in Dsseldorf, Germany.
EBSD showed only about 5% retained austenite in this specimen.

Examination of the mapped pixels around the patches of retained

austenite revealed that there were many that appeared black on
an index of quality map, indicating that they were not producing
an indexable diffraction pattern. It is possible that these pixels
were from austenite that had transformed to fresh martensite. But
even if these pixels were added to the pixels that were from FCC
austenite, the percentage would still be much less than 25.4%.

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Future Work
Working with a carburized specimen presents difculties due
to the variation in carbon and microstructure in the case. The
writer is planning additional EBSD work with Dr. Zaefferer using 1.25-inch-diameter bars (to avoid mounting and conductivity
problems) of O1 and 52100 alloy steels, high-carbon steels with
enough hardenability to be through-hardened and with enough
carbon and alloy content to produce >10% retained austenite.
As their alloy content is not high, carbide interference peaks and
texture problems by XRD should be minimal. Transverse and longitudinal specimens will be prepared and tested by XRD, then by
LOM and EBSD. These tests will be performed quickly, and other
labs will participate to evaluate the reproducibility of the data.
Some experiments will be run at a later date to access the inuence of time since heat treatment upon the data. IH
References (available online)
For more information: Contact George F. Vander Voort, director, Research & Technology, Buehler Ltd., 41 Waukegan Road, Lake Bluff, IL
60044; tel: 847-295-4590; e-mail: George.VanderVoort@buehler.com;
web: www.buehler.com
Additional related information may be found by searching for
these (and other) key words/terms via BNP Media SEARCH at www.
industrialheating.com: lath martensite, plate martensite, austenite, intergranular fracture, Mf temperature, Ms temperature, isothermal transformation