Structure–property changes during

hardening and tempering of new ultra high

strength medium carbon low alloy steel
M. R. Suresh, I. Samajdar, A. Ingle, N. B. Ballal, P. K. Rao and P. P. Sinha

not desirable, while an increase in the carbon level in con-

A medium carbon low alloy steel, electroslag ventional processing severely aVects the ductility, fracture
refined, modified AFNOR 15CDV6, has been toughness and weldability of such a class of steel.2
developed for satellite launch vehicle and Electroslag reŽ ning (ESR) processing has provided an
related applications. Conventionally processed alternative.5–8 The ESR processed, with suitable inoculation,
(without electroslag refining) mostly bainitic ascast 15CDV6 alloy showed a 40% improvement in ductility
AFNOR 15CDV6 (with 0·15 wt-% carbon and and a marginal increase in yield strength.5,7 Such impressive
~3·5 wt-% other alloying elements) has a yield gains were typically attributed to the complete elimination
strength of ~800 MPa. Electroslag refining, of inclusions above 12 mm in size.5 It was even possible to
coupled with increased carbon (0·29 wt-% carbon, double the carbon percentage (from 0·15 to 0·3 wt-%, Table 2)
but no change in percentage of other alloying and thus improve the yield strength from 800 to ~1300 MPa,
elements), increased the yield strength to about without sacriŽ cing the ductility of the original 15CDV6.6,7
1300–1400 MPa, without sacrificing ductility. The The mechanical properties and chemical compositions of
microstructure of the modified grade was AFNOR 15CDV6 and ESR modiŽ ed grades are listed in
martensitic. Martensite in the as hardened state Tables 1 and 2. The ESR modiŽ ed 15CDV6 grade is now a
was mostly in the form of laths, although ~20% promising candidate alloy in Indian satellite launch vehicles,
plate martensite was also observed. Until 150°C considered even as a replacement for the usual maraging
tempering, no noticeable loss of tetragonality was steel.
observed, while the unit cell parameter c /a ratio Research into this new class of steel, however, has been
dropped to almost 1 after 300°C tempering. The restricted to process optimisation for best combinations of
interesting observation at 150°C tempering was the yield strength and ductility.5–8 Although original AFNOR
predominant presence of fine rodlike e carbide, 15CDV6 is reported to be a bainitic grade,7 little is known
which may also explain the increased yield of the structure/microstructure of the ESR modiŽ ed grade.
strength. Tempering above 150°C converted the e The aim of the present study was to characterise the role
carbide to cementite, relatively thicker precipitates of hardening and tempering treatments on the development
of similar morphology. At higher tempering of the microstructure and mechanical properties of this new
temperatures, no evidence of spheroidisation of ultrahigh strength medium carbon low alloy steel.
cementites was noted. The highest tempering
temperatures of 500 and 600°C resulted in two
marked changes in the microstructure: the EXPERIMENTAL METHODS
appearance of M23C6 type (Cr, Fe and Mo bearing) Material and processing
carbides, and the appearance of, in some regions of
The ESR modiŽ ed grade, as used in the present study, was
the microstructure at least, a relatively ‘recovered’
made by electric arc melting followed by the secondary
lath structure. Misorientation among adjacent laths,
remelting practice of electroslag reŽ ning (ESR) of inoculated
nearly constant at 8–9° until 450°C tempering,
primary ingots.7 The basic diVerences in chemistry/constitution
increased noticeably, to 13 and 16°, after the
between the original AFNOR 15CDV6 and ESR modiŽ ed
respective tempering temperatures of 500 and
grades, as given in Table 2, can be summarised as:
600°C. I&S/1729
(i) the carbon percentage is almost double in the ESR
modiŽ ed grade
Dr Suresh ([email protected]) and Dr Sinha are with VSSC, Indian
Space Research Organisation (ISRO), Trivandrum–695022, India and (ii) the ESR modiŽ ed grade is grain reŽ ned through the
Dr Samajdar, Dr Ingle, Dr Ballal and Dr Rao are in the Department process of inoculation with niobium
of Metallurgical Engineering and Materials Science, Indian Institute (iii) a reduction in sulphur concentration and complete
of Technology (IIT) Bombay, Mumbai–400076, India. Manuscript
received 18 June 2002; accepted 1 May 2003.
elimination of inclusions (above 10–12 mm in size) is
possible in the ESR modiŽ ed grade.
© 2003 IoM Communications Ltd. Published by Maney for the The electroslag reŽ ned ingots are typically homogenised and
Institute of Materials, Minerals and Mining then subjected to thermomechanical treatments such as hot
forging and hot rolling to obtain various shapes such as
ring, bar and plate. For the present study, hot rolled plates
of 8 mm thickness were used. The plates were annealed at
INTRODUCTION 875°C before selecting coupons for carrying out heat treat-
Steel grade AFNOR 15CDV6 is a low carbon low alloy steel ment at various combinations of austenitising and tempering
of French origin.1–4 Although it has excellent properties, as temperatures. DiVerent batches of tensile coupons were
given in Table 1, for some speciŽ c applications in the Indian hardened by quenching after austenitising for 1 h at 875,
space programme (in satellite launch vehicle and related 925 and 1000°C. They were further segregated into smaller
applications) further improvement in mechanical properties, batches and tempered for 2 h at 150, 200, 300, 450, 500 and
especially the yield strength, was considered necessary.2 For 600°C. The quenching medium for hardening and tempering
cost economic reasons, an increase in alloying amount is was water.

DOI 10.1179/030192303225004097 Ironmaking and Steelmaking 2003 Vol. 30 No. 5 379

380 Suresh et al. Hardening and tempering of ultrahigh strength medium C low alloy steel

Characterisation
Uniaxial tensile tests were carried out on 8 mm thickness
 at tensile specimens with 12·5 mm gauge width. The tensile
specimens were prepared according to ASTM standard A370,
but with a total length of 300 mm instead of the standard
length of 200 mm. The extra length was accommodated in
the grip portion. The specimens were fabricated from heat
treated plate coupons and tested in an Instron machine of
50 t capacity and at a crosshead speed of 2 mm minÕ 1. Grain
size measurements were obtained using the linear intercept
method according to ASTM standard E112.
Unit cell parameters were determined by X-ray diVraction
of electropolished bulk specimens using a Philips PW1729
diVractometer and Fe K radiation. A slow scan of 0·02° sÕ 1
was used, and measurementsa were obtained from {200}, {211}
and {220} planes. The c/a ratios were then calculated by
deconvoluting the doublets and using the procedure described
by Prokoshkin et al.9 Foils for TEM were electropolished in
a Struers Teunopol 3 twin jet polisher, using 80 : 20 methanol/
perchloric acid as electrolyte, at ­ 20°C and 10 V dc. Foils
were subsequently studied at 200 keV in a Philips CM200
TEM. Dimensional measurements were obtained using the
online interface of the CM200 series, which employs de ector
coil movements to measure distances in the microstructures.
Misorientation measurements were carried out using the
commercial package TSL–ACT. The advanced crystallo-
graphic technique (ACT) is a tool for online local orientation
measurement in the TEM. The package has been developed
and marketed by TSL–EDAX. At least 15 misorientation
measurements each from three diVerent specimens were
obtained, by means of convergent beam Kikuchi diVraction.

RESULTS
Mechanical properties
Figure 1 shows the change in yield strength (YS) (Fig. 1a),
ultimate tensile strength ( UTS) (Fig. 1b) and ductility
(as estimated by percentage elongation) (Fig. 1c) as a function
of tempering temperature for all three hardening treat-
ments. The main points concerning the relative changes in
mechanical properties, as a function of tempering temperature,
are summarised below.
1. Tempering at 150°C increased the YS, an increase of
50–100 MPa being recorded (Fig. 1a). Above 150°C tempering,
the YS was reduced.
2. Tempering reduced the UTS (Fig. 1b). The drop in UTS
at 150°C tempering was small, between 20 and 70 MPa.
Tempering above 150°C brought about a relatively sharper
drop in UTS.
3. Except for a ‘slight’ drop in ductility at about 300–450°C,
noticeable only for 875 and 1000°C hardening treatments,
the ductility change did not follow distinct pattern (other than a YS; b UTS; c elongation
a possible general trend of a shallow increase) as a function 1 Mechanical properties of electroslag refining (ESR)
of tempering temperature. The ‘slight’ drop in ductility also modified steel type AFNOR 15CDV6 after given
falls within the possible experimental scatter. hardening and various tempering treatments: variations
in yield strength (YS), ultimate tensile strength (UTS)
and percentage elongation as function of tempering
Structure and microstructure
temperature
Austenitic grain sizes measured at various austenitising
temperatures are plotted in Fig. 2. Grain sizes were nearly some regions plate martensite with internal twins was also
identical for 875 and 925°C austenitising treatments, but observed (Figs. 3 and 4). The proportion of plate martensite
almost doubled at 1000°C austenitising. Other than this was estimated to be ~20%, which did not appear to depend
diVerence in grain size, the as hardened structures in both on the austenitising treatment. The other interesting feature
cases contained mostly bcc lath martensite, although in of the as hardened structure was the ‘occasional’ presence of

Table 1 Mechanical properties* commonly reported in heat treated conditions5– 8 for AFNOR 15CDV6 steel and electroslag
refining (ESR) modified grade
Steel UTS, MPa YS, MPa Elongation, % Fracture toughness, MPa m1/2

AFNOR 15CDV6 1000 800 12 40

0·3C–CrMoV(ESR) 1300–1800 1200–1400 10 80
*UTS is ultimate tensile strength, YS is yield strength.

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 Suresh et al. Hardening and tempering of ultrahigh strength medium C low alloy steel 381

2 Effect of austenitising temperature on grain size

retained austenite colonies (Fig. 3). Such retained austenite

colonies, noted in only a few cases, were heavily dislocated
and rarely exceeded 100–200 nm in size. Retained austenite
colonies, although present in some specimens at up to 250°C
tempering, were not observed/noted above 250°C tempering.
Figure 5 shows the change in unit cell parameter c/a ratio,
as estimated by X-ray diVraction, as a function of tempering
temperature for both 875 and 1000°C hardening treatments.
Until 150°C tempering, no noticeable loss in tetragonality
was observed, as the c/a ratio remained nearly the same as
that of the as hardened state. Above 150°C tempering, a
rapid drop in c/a ratio as determined, and the tetragonality b
almost vanished at and above 300°C tempering, as the c/a
ratio approached unity. It is to be noted that the estimated
diVerence in the trends of c/a reduction between 875 and
1000°C hardening treatments is not signiŽ cant, as it falls
within the statistical scatter of experimental estimation.
After 150°C tempering, the most interesting feature of
the microstructure was the appearance of Ž ne rodlike pre-
cipitates (Fig 6). As identiŽ ed by electron diVraction, these
were mostly hexagonal e carbide, although in a few places
slightly thicker ( but otherwise of the same morphology)
cementite precipitates were also observed. The growth direction
of e carbide needles in the present work is similar to that
reported previously.10 Tempering above 150°C eliminated
the e carbides which were converted to the relatively thicker
(but of the same morphology)cementite precipitates. Carbides, c
M C or a complex fcc crystal structure appeared at and a bright field image; b convergent beam diffraction from martensite
23 6500°C (Fig. 7). Energy dispersive X-ray spectroscopy
above lath (a) as marked in a by white dot; c convergent beam diffraction
(EDX) identiŽ ed a strong presence of Cr, Fe and Mo in of retained austenite colony ( c) also marked in a as white cross
such carbides. An appropriate selected area diVraction pattern 3 As hardened structure after 1000°C austenitising:
for the matrix and e carbide (as shown in Fig. 6b) was easy in b, combination spot and Kikuchi makes positive
identification of phase as bcc [111], while in c (fcc [110]),
to obtain, but for thicker carbides (cementite or M C ) it schematic diagram of solution (also confirmed by
was far more diYcult. The identiŽ cation of secondary23phase,
6
diffraction at different zone axis) is included; in b, trace
in such cases, was made by convergent beam spot, the Kikuchi of Kikuchi is ‘faint’ but visible, visibility being far better
method and EDX. in negative, enabling easy identification
It is to be noted that the present study did not reveal the
presence of any other types of carbides. Until 450°C temper- (almost doubled), and the presence of high angle boundaries
ing, no change in lath morphology (or the presence of lath ( larger than 20° misorientation) was often observed. Such
interior twins) or relative misorientation among adjacent laths recovered regions, as they typically seemed to have lower
was observed (Figs. 6–8). At and above 450°C tempering, dislocation densities, were perhaps responsible for increasing
in some regions of the microstructure at least, the bcc matrix the so called relative misorientation among adjacent laths
appeared to be relatively ‘recovered’, and nearly parallel at and above 450°C (Fig. 8). The misorientation increase
lath morphology changed towards more equiaxed shapes was observed both in laths and in plates, i.e. martensite
(Fig. 7). Misorientation in such transformed laths was more with internal twins.

Table 2 Typical compositions of AFNOR 15CDV6 steel and ESR modified grade, wt-%
Steel C Si (max.) Mn P S Cr Mo Nb V Fe

AFNOR 15CDV6 0·15 0·25 0·90 0·03 0·03 1·40 0·90 … 0·25 Bal.
ESR modified 0·29 0·25 0·90 0·020 0·015 1·40 0·90 0·10 0·25 Bal.

Ironmaking and Steelmaking 2003 Vol. 30 No. 5

382 Suresh et al. Hardening and tempering of ultrahigh strength medium C low alloy steel

4 Bright field image of as hardened structure after 875°C

austenitising: one region of twinned martensite is
marked by white cross

DISCUSSION
Technoeconomic considerations of commercial satellite launch
vehicles require high performance steels at an aVordable price.
Type AFNOR 15CDV6 steel, a low carbon low alloy steel of b
French origin,1 is often used for fabricating components for
such applications.2 The problem with conventional 15CDV6
is its relatively poor yield strength (see Table 1), considered
inadequate for some speciŽ c applications.2 The ESR modiŽ ed
15CDV6 has provided an alternative material.5–8 It is possible
to produce a cleaner steel of higher carbon percentage and
higher YS and UTS, keeping almost the same ductility as
that of the conventionally processed 15CDV6.6–8 The present
study deals with the development of mechanical properties
and structure/microstructure, as a function of hardening/
tempering treatment, in this important new class of material.
Conventional 15CDV6 is reported7 to be a bainitic grade.
As shown in the present study, the ESR modiŽ ed 15CDV6 c
is, however, martensitic. Since the presence of dislocated and
a bright field image; b diffraction pattern containing matrix (bcc lath, a)
twinned martensites has been established,9 martensites are and precipitate (hexagonal e) spots, schematic diagram of solution
generalised as laths or plates based on the notable absence is included; c relatively higher magnification (from region marked in
or presence of internal twins.11,12 The present material con- a by white cross) bright field image of precipitates
tained mostly lath martensite and ~20% plate martensite. A 6 Microstructure (TEM) of hardened and tempered
change in austenitising temperature brought about diVerences specimen: 875°C hardening followed by 150°C tempering

in the as hardened grain size (see Fig. 2), but otherwise

no marked diVerence in mechanical properties and/or
microstructure was observed.
Hardening–tempering of martensite in plain carbon and/or
alloy steels has been a subject of exhaustive research.9–18
The eVects of tempering, depending on alloy chemistry and
tempering temperature, can be generalised as: (a) a drop in
tetragonality or c/a ratio, (b) carbon segregation and carbide
precipitation/coarsening and (c) high temperature recovery
and recrystallisation of the martensitic structure.10,13,15,16 At
150°C tempering, the present observations clearly showed
strong e carbide precipitation (see Fig. 6), and almost no drop
in tetragonality (see Fig. 5). The relative strengthening, as
the yield strength increased, at 150°C can be attributed to
the observed precipitation of e carbide. A drop in tetragonality
of martensite during tempering depends on the alloying
elements present: for example, chromium, vanadium and
5 Effect of tempering temperature on overall unit cell molybdenum are expected to increase the thermal stability
parameter c/ a ratio (as estimated by X-ray diffraction) of the tetragonal lattice (even at and above 450°C), while
after 875 and 1000°C hardening treatments carbon, nickel and manganese are expected to reduce it.10,18

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 Suresh et al. Hardening and tempering of ultrahigh strength medium C low alloy steel 383

8 Effect of tempering temperature on misorientation of

neighbouring laths/plates (as estimated by TEM based
local orientation measurements) after 875 and 1000°C
hardening treatments

a
was observed, indicating no movement of grain boundaries,
either high or low angle, or no recovery/recrystallization
(see Fig. 8). The increase in relative misorientation at and
above 450°C and the observed change in lath morphology
(see Fig. 7a), on the other hand, strongly suggest the initiation
of at least recovery at these temperatures.

CONCLUSIONS
1. Unlike the conventionallyprocessed steel grade 15CDV6,
which is reported to be bainitic, the structure of the ESR
modiŽ ed 15CDV6 is martensitic, with mostly lath martensite,
although ~20% plate martentsite was also observed. The
as hardened grain size nearly doubled between 875/925 and
1000°C austenitising, but otherwise the microstructures were
similar.
2. The estimated c/a ratio did not change noticeably at
150°C tempering. A strong drop in c/a ratio was noted
above 150°C, and a near complete loss of tetragonality was
observed at and above 300°C.
3. At 150°C tempering, signiŽ cant e carbide (rodlike and
Ž ne) precipitation was observed. The e carbide precipitation
b possibly explains a relative increase in yield strength at 150°C
a bright field image; b diffraction pattern corresponding to matrix tempering. Above 150°C tempering, e carbide was replaced
bcc lath, schematic diagram of spot indexing is included by cementite of similar morphology. At and above 500°C
7 Microstructure (TEM) of hardened and tempered tempering, M C precipitates were observed. All the carbides
specimen: 875°C hardening followed by 600°C tempering; contained Cr,23Fe6 and Mo.
relatively well ‘recovered’ laths (marked by white
4. Misorientation among adjacent laths did not change
cross in a) and carbides of M23 C6 type (marked by
white dot in a) were often observed at this condition until 450°C tempering; the average misorientation value was
8–9°. At and above 450°C tempering, in some regions of
the microstructure laths appeared to be ‘recovered’, and a
The present observation of the sharp drop in c/a ratio marked increase in misorientation was observed in both
at 150–300°C tempering and the near complete loss of laths and plates.
tetragonality at and above 300°C may be explained by the
strong presence of carbon and manganese. The sequence of
carbide precipitation, as observed in the present study, was: ACKNOWLEDGEMENTS
e carbide Þ cementite Þ M C . It should be noted that in The authors would like to acknowledge the use of the RSIC
all the carbides, chromium and23 6molybdenum as well as iron (IIT Bombay) TEM facility and the mechanical testing facility
were observed by EDX, although exact quantiŽ cation is of the Materials Characterisation Division of VSSC. Two of
questionable in the Ž ne structures of e carbide and cementite. the authors (MRS and PPS) are grateful to the Director of
Although vanadium is expected to be a strong carbide former,10 VSSC for granting permission to publish the present study.
no evidence of VC or V C was observed in the present Partial Ž nancial support from the Department of Science
heat treatment schedule. It 4 seems
3 that at and above 500°C, and Technology (DST) is also acknowledged.
only M C forms, and secondary hardening eVects on the
23 6 properties, through alloy carbide formation, is
mechanical REFERENCES
not re ected even at 600°C tempering (see Fig. 1). 1. ‘French norms for steel products (AFNOR–BNS)’, Vol. 1, Spec.
The other interesting issue in tempering is the high temper- no. A35–55A, Paris, France, 1978, 299.
ature recovery and recrystallisation.14,17 With the present 2. m. s. n. balasubramanian: ISRO–SLV(E) Mission, ‘15CDV6
combination of grade and heat treatment, until 450°C no steel for rocketry’, Internal technical report, VSSC, Trivandrum,
signiŽ cant increase in misorientation among adjacent laths India, 1978.

Ironmaking and Steelmaking 2003 Vol. 30 No. 5

384 Suresh et al. Hardening and tempering of ultrahigh strength medium C low alloy steel

3. k. sreekumar, m. s. p. murty, a. natarajan and p. p. sinha: 10. r. honeycombe and h. k. d. h. bhadeshia: ‘Steels microstructures
T rans. Indian Inst. Met., 1982, 35, 349. and properties’; 2nd edn, 171; 1995 London, Edward Arnold.
4. m. s. p. murty, b. r. ghosh and p. p. sinha: T rans. Indian Inst. 11. r. a. grange, c. r. hribal and l. f. porter: Metall. T rans. A,
Met., 1982, 35, 33. 1977, 8A, 1775.
5. m. chaterjee, m. s. n. balasubramanian, k. m. gupt and 12. l. j. habraken and m. econopoulos: Proc. Symp. on ‘Trans-
p. k. rao: Ironmaking Steelmaking, 1990, 17, 38. formation and hardenability in steels’, Ann Arbor, MI, USA,
6. g. m. padki, m. s. n. balasubramanian, k. m. gupt and p. k. rao: 1967, Climax Molybdenum Co., 88.
Ironmaking Steelmaking, 1983, 10, 180. 13. p. m. kelly and j. nutting: J. Iron Steel Inst., 1961, 197, 199.
7. m. chaterjee: PhD thesis, Department of Metallurgical Engineer- 14. g. r. speich and w. c. leslie: Metall. T rans., 1972, 3, 1043.
ing, IIT Bombay, India, 1989. 15. y. h. tan, d. c. zeng, x. c. dong, y. h. he and s. q. hu: Metall.
8. m. chaterjee, m. s. n. balasubramanian, k. m. gupt and T rans. A, 1992, 23A, 1413.
p. k. rao: Ironmaking Steelmaking, 1994, 21, 399. 16. g. r. speich: T rans. AIME, 1969, 245, 2553.
9. s. d. prokoshkin, l. m. kaputkina, m. l. bernshteyn and 17. d. huang and g. thomas: Metall. T rans., 1971, 2, 1587.
v. y. mozzhukhin: Phys. Met. Metall., 1983, 55, (6), 99. 18. g. v. kurdjumov: J. Iron Steel Inst., 1960, 195, 26.

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