Martensite and the Control of Retained Austenite

By George Vander Voort

Abstract

Formation of martensite in fine-grained steels is

probably the most common goal in heat treatment of
components. The carbon content of the parent austenite
phase determines whether lath (low-carbon) or plate
(high-carbon) martensite, or mixtures of the two will be
produced, assuming the quench rate and steel
hardenability are adequate for full hardening. Lath
martensite produces higher toughness and ductility, but
lower strengths, while plate martensite produces much
higher strength, but may be rather brittle and non-
ductile. For a given alloy content, as the carbon content
of the austenite increases, the martensite start, Ms,
temperature and the martensite finish, Mf, temperature
Figure 1: Summary of extensive as-
will be depressed which results in incomplete conversion
quenched hardness data from the
of austenite to martensite. When this happens retained literature for Fe-C alloys and steels by
austenite, which may be either extremely detrimental or Krauss [2].
desirable under certain conditions, is observed.  The amount of retained austenite present
depends upon the amount of carbon that can be dissolved in the parent austenite phase and
the magnitude of the suppression of the M s and Mf temperatures. This paper examines the
conditions under which austenite is retained and the problems associated with it presence,
with detecting it and with measuring it.

Introduction

In the early days of steel making, the heat treatment of steels was certainly an art as the
science behind what was happening was just starting to be understood by the 1930s. Prior to
the work of McQuaid and Ehn in the 1930s the carburizing of steel and its subsequent heat
treatment was very difficult as maintaining a fine grain size after carburizing was not
understood. Coarse-grained hardened carburized cases would fracture intergranularly the first
time the part was placed into service. They discovered that small additions of aluminum would
keep the grain size fine after a long exposure, generally 8 to 10 h, at the carburizing
temperature. Prior to that, coarse prior-austenite grain structures would be observed in the
carburized case that would initiate brittle intergranular fractures at minor loads. Next,
Grossman and Bain developed the theory of hardenability where the ideal critical diameter, DI,
could be calculated from steel composition and knowledge of the prior-austenite grain size.
Then, the DI could be used to estimate the as-quenched hardness profile of a uniformly
shaped bar subjected to a known quench media and quench rate.

Isothermal time-temperature-transformation diagrams

(known as IT or TTT diagrams; sometimes less
appropriately called S or C curves) were developed next
making it easier to identify diffusion-controlled
transformation structures, particularly the poorly
understood microstructures of upper and lower bainite.
But, an IT diagram, while it is helpful in understanding

Figure 2: As-quenched of brine

quenched Fe-C alloys up to nearly 2 wt.
% by Litwinchuk et al. [3].
microstructures and in developing annealing cycles, is not particularly useful for understanding
quenched and tempered microstructures. This problem was solved by developing continuous
cooling transformation, CCT, diagrams. Some years before the writer joined the
Homer Research Laboratories of Bethlehem Steel, they had developed CCT diagrams using the
arrested-Jominy bar method – a rather painful process indeed. Dilatometer-based CCT
diagrams were far easier to develop and in less time, but this equipment came later.

Development of the transmission electron microscope (TEM) utilizing the thin-foil procedure

produced a far deeper understanding of the fine details of steel microstructures because much
of the fine details of these microstructural constituents 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 important. Problems due to excessive retained austenite
had plagued the tool steel industry since the late 19th century. X-ray diffraction had been the
only practical and exact tool for the measurement of retained austenite, but XRD cannot
produce images of this, or any microstructure. LOM could not image retained austenite until it
was at least present in the 12-15% range. TEM thin foils could detect and image retained
austenite even at levels under 2% with careful use of dark field illumination, but it was not
useful for quantifying the amount present. The morphology of the martensite makes it difficult
to distinguish small particles of retained austenite within the complex plate martensite
patterns. With low-carbon lath martensite, thin films of retained austenite could be seen with
very careful TEM dark field work, but again this was very difficult work.

In the tool steel industry, excessive retained austenite is universally considered to be highly

detrimental and is the cause of many service failures. Exactly what constitutes as being
“excessive” is difficult to define as what is found to be excessive will vary with the grade and
application. Relatively low-carbon (for tool steels) 5% Cr hot work die steels such as H11 and
H13 have been used for years as guage blocks. Any dimensional change with time must 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 (>12-15%) retained
austenite using the light microscopeis
highly detrimental. Service stresses
(strain rates can be very high) will Figure 3: Graph by Marder and Krauss showing the
convert the retained austenite, even if it relationship between carbon content, martensite type and
has become stabilized with time, on the Ms temperature [4].
first service impact load. Because the carbon content of the retained austenite is high, the
martensite that forms is highly tetragonal (high c/a lattice ratio) and the resulting expansion
cracks the steel as the matrix is not ductile enough to tolerate the expansion stresses. On the
other hand, with carburized gears, 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 (certainly when
compared to a hardened tool steel) low-carbon alloy steel. Gears are usually not impact
loaded like a tool steel die, so the service 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 the case 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 (<200 C) will transform to martensite soon
after quenching or over a period of some months.

Influence of Carbon Content of the Austenite

With the development of hardenability concepts, a

number of investigators 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
Figure 10: Influence of carbon content of the
austenite on the percentages of lath (or plate) softer than plate martensite. Litwinchuk et al. [3]
martensite, Ms temperature and percentage of expanded the study of the hardness of as-
retained austenite [5]. quenched steels to a bulk carbon content of nearly
2% which demonstrates the effect of retaining very large 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 to 9 illustrate the appearance by LOM of
martensite in steels with increasing carbon content. Figures 4 and 5 show 8115 and 1524 alloy
steels after water quenching from 1700°F. They illustrate fully lath martensite matrix structures.
Figure 6 shows 1541 which is mostly lath martensite but does have some plate martensite
present. Note that as the carbon content of the alloy increases towards the eutectoid carbon
content, the correct austenitizing temperature decreases so that it does not greatly exceed the
AC3 temperature. Figure 7 shows 10B62, a boron-treated carbon steel (B is used to increase
hardenability). It was reportedly austenitized at 1525°F, but the mostly plate martensite
structure looks too coarse for that temperature. Compare the apparent coarseness of the
structure of the 10B62 to the 1541. Figure 8 shows over-austenitized 1095 carbon steel,
austenitized at 1650°F, which dissolved all of the cementite, coarsened the prior-austenite
grains and resulted in visible retained austenite. Compare Figure 8 to Figure 7 and to Figure
9. Figure 9 is a W1 water-hardened tool steel at 1.05% C.  Note that the martensite, which is
all plate, is much finer in appearance and that there is considerable un-dissolved cementite
present. Figures 1 and 2 illustrate the detrimental effect of dissolving too much carbon in the
austenite, but they only reveal its affect on hardness, not on the retained austenite content
and potential service failures.

Figure 4: As-quenched lath Figure 5: As-quenched lath Figure 6: As-quenched lath

martensite in 8115 alloy martensite in 1524 alloy steel
and plate martensite in 1541
steel(0.13/0.18% C) (0.19/0.25% C) austenitized
alloy steel (0.36/0.44% C)
austenitized at 1700°F and at 1700°F and water
austenitized at 1600°F and
water quenched.  There are a quenched.  A slight amount
water quenched.  The
few patches of ferrite present. of grain boundary ferrite is
specimen was etched with
The specimen was etched present. The specimen was
nital and the image is at
with nital and the image is at etched with nital and the
1000X (magnification bar is
1000X (magnification bar is image is at 1000X
10 μm).
10 μm). (magnification bar is 10 μm).
Plate martensite frequently contains micro-cracks 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, as well as decrease the M s and change the martensite type from lath to plate, Figure
10. A number of studies between Payson and Savage in 1944 and Andrews in 1965 have
developed empirical formulas to calculate the M s based upon composition, not simply from
the carbon content. Carbon, of course, has the largest effect, but the influence of alloying
elements upon lowering the Ms cannot be ignored. The Mf temperature falls with the M s, 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 case, 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 un-etched austenite using nital. 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 three times, the most recently using railroad cone bearings of carburized
8720 alloy steel. Unfortunately, no details of how these bearings were processed and then
prepared for metallography are known. But, at some earlier time, they were analyzed by x-
ray diffraction. Three pieces claimed to contain 25.4, 19.7 and 16.2% retained austenite were
given to the writer who mounted them in a low-temperature 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 – but the image analysis results were very low
compared to the x-ray diffraction results. Of course, it is possible that some of the retained
austenite had isothermally 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 7: As-quenched plate and Figure 8: As-quenched plate Figure 9: As-quenched plate
lath martensite in 10B62 alloy steel martensite and small white angular martensite and un-dissolved
(0.54/0.67% C) austenitized at patches of retained austenite in cementite (small white globular
1525°F and water quenched. The 1095 alloy steel (0.90/1.03% C) particles) in W1 carbon tool steel
structure appears to be coarser than austenitized at 1650°F (dissolves (1.05% C) correctly austenized at
what should be obtained with a all cementite suppressing the Ms 1475°F and brine quenched.  Note
1525°F austenitize.  The specimen and Mf resulting in visible retained that no retained austenite is visible
was etched with nital and the austenite and some grain growth) and the grain structure is fine as
image is at 1000X (magnification and water quenched.  The can be inferred from the finer plate
bar is 10 μm). specimen was etched with nital and martensite compared to that in Fig.
the image is at 1000X 8.  The specimen was etched with
(magnification bar is 10 μm). nital and the image is at 1000X
(magnification bar is 10 μm).

Figure 11 shows the microstructure of the cone bearing that was reported to contain 25.4%
retained austenite etched with 4% nital plus 1% zephiran chloride which gave better results
than 2% nital. 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 2% nital and two other
etchants tried). 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 similar experiments previously.

Figure 12 shows an extreme example of over-austenitization where a large amount of carbide

was dissolved in D3 tool steel (Fe - 2.0 to 2.35 % C – 11.0 to 13.5 % Cr) which prevented any
martensite to form upon quenching. When the retained austenite level is rather high, tint
etchants will color the austenite. In this case, annealing twins can be seen in the austenitic
matrix.

Ads by SpeedCheckerAd Options

Figure 11: Surface of a carburized 8720 alloy steel Figure 12: Type D3 tool steel grossly over-
railroad cone bearing etched with nital plus 1% austenitized at 2200°F dissolving most of
zephiran chloride. Image analysis yielded 13.3% Cr23C6carbide and some of the Cr7C3 primary carbide
retained austenite vs 25.4% by XRD (1000X). (the white globular particles still present). The matrix
is all retained austenite, colored by the tint etch used
(Beraha’s sulfamic acid #4, viewed with polarized
light and sensitive tint).  Note that annealing twins
can be seen in the matrix and oxidation is present in
some of the austenite grain boundaries (500X).

Conclusions
Martensite is the most important constituent produced by heat treatments designed to
produce ideal mechanical properties. Isothermal treatments may sometimes be used to
produce lower bainite microstructures which do yield excellent properties while being immune
to certain embrittlement problems, such as temper martensite embrittlement, that
detrimentally affect tempered martensitic steels. But, hardenability issues limit the ability to
use this technology more widely.

The appearance of martensite does vary with the amount of carbon dissolved in the austenite.
Examples of lath martensite, lath and plate martensite, plate and lath martensite and plate
martensite and retained austenite or plate martensite and cementite microstructures were
illustrated.  Examples of excessive retained austenite were illustrated.  It is the writer’s
experience, based upon three experiments using specimens with different austenite contents
determined by x-ray diffraction, that retained austenite in steels cannot be observed with the
light microscope until the amount is in the range of about 12 to 15%. Retained austenite
above this level has only been shown to be helpful to service performance when it is present in
the carburized cases of gear teeth. In tool steels, most of which are through hardened,
unstable retained austenite leads to a short service life and fracture.

References:

1. L.E. Samuels, Light Microscopy of Carbon Steels, ASM International, Materials Park, OH,
1999, p. 273.
2. G. Krauss, “Martensitic Transformation, Structure and Properties in Hardenable Steels, in
Hardenability Concepts with Applications to Steel, D.V. Doane and J.S. Kirkaldy, eds., AIME,
Warrendale, PA, 1978, pp. 229-248.
3. A. Litwinchuk et al., J. Material Science, Vol. 11, 1976, p. 1200.
4. G. Krauss, Principles of Heat Treatment of Steel, ASM, Metals Park, OH, 1980, p. 52.
5. G.R. Speich and W.C. Leslie, Met. Trans., Vol. 3, 1972, p. 1043.
6. G.F. Vander Voort, Metallography: Principles and Practice, McGraw-Hill Book Co., NY, 1984;
ASM International, Materials Park, OH, 1999.

George Vander Voort has a background in physical, process and mechanical metallurgy and
has been performing metallographic studies for 47 years. He is a long-time member of ASTM
Committee E-4 on metallography and has published extensively in metallography and failure
analysis. He regularly teaches MEI courses for ASM International and is now doing webinars.
He is a consultant for Struers Inc. and will be teaching courses soon for them. He can be
reached at 1-847-623-7648, EMAIL: georgevandervoort@yahoo.com and through his web
site: www.georgevandervoort.com