Acta Materialia 51 (2003) 2611–2622

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Carbon partitioning into austenite after martensite

transformation
J. Speer a,∗, D.K. Matlock a, B.C. De Cooman b, J.G. Schroth c
a
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Hill Hall 274, Golden, CO 80401, USA
b
Department of Metallurgy and Materials Science, Ghent University, BE-9052 Ghent, Belgium
c
Research and Development Center, General Motors Corporation, Warren, MI 48090, USA

Received 13 October 2002; received in revised form 23 January 2003; accepted 30 January 2003

Abstract

A model is developed to describe the endpoint of carbon partitioning between quenched martensite and retained
austenite, in the absence of carbide formation. The model assumes a stationary a/g interface, and requires a uniform
chemical potential for carbon, but not iron, in the two phases, leading to a metastable equilibrium condition identified
here as “constrained paraequilibrium” or CPE. The model is explained with example calculations showing the character-
istics of the constrained paraequilibrium condition, and applications are discussed with respect to new microstructures
and processes, including a new “quenching and partitioning,” or Q&P process, to create mixtures of carbon-depleted
martensite, and carbon-enriched retained austenite. Important new implications with respect to fundamental elements
of the bainite transformation are also discussed.
 2003 Published by Elsevier Science Ltd on behalf of Acta Materialia Inc.

1. Introduction controversial, particularly with respect to the

growth of bainite. In martensite, the displacive
Carbon partitioning between ferrite and austenite transformation (i.e. a process that involves coordi-
during high temperature diffusional transform- nated rather than diffusional movements of the iron
ations is relatively well understood. These reac- atoms) is usually believed to occur without dif-
tions are frequently referred to as reconstructive fusion of carbon or other interstitials [2], and thus
transformations, because of the short-range dif- the body-centered martensite phase can be substan-
fusional movements of iron (and substitutional) tially supersaturated with carbon. Subsequent car-
atoms that accomplish a change in crystal structure bon partitioning between martensite and any
between bcc and fcc [1]. In contrast, the details retained austenite is usually not considered,
of carbon partitioning during or after displacive or because the temperature is too low for substantial
martensitic transformations are somewhat more amounts of diffusion to occur after quenching, and
also because carbon supersaturation is usually
eliminated by competing processes, e.g. carbide
∗
Corresponding author. Fax: +1-303-273-3016. precipitation during tempering. There is, however,
E-mail address: [email protected] (J.G. Speer). evidence that carbon partitioning from martensite

1359-6454/03/$30.00  2003 Published by Elsevier Science Ltd on behalf of Acta Materialia Inc.
doi:10.1016/S1359-6454(03)00059-4
2612 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622

to (retained) austenite does occur, to thin interlath boundaries on the usual Fe-C phase diagram, and
films during cooling [3] or by isothermal holding the phase fractions may be determined from the
in a Si-containing steel after transformation [4]. lever rule. In the presence of substitutional (“X”)
Carbide-free bainite microstructures may also form alloying additions, such as in a ternary Fe-C-X sys-
by diffusionless martensitic growth, followed by, tem, long-range diffusional processes at low tem-
or along with, carbon partitioning into austenite perature are limited primarily to carbon atom
[1]. (It should be noted that the bainite transform- movements, and a “paraequilibrium” condition
ation is not universally accepted to involve a shear (following Hultgren [7,8]) is used to describe con-
mechanism, and also that it has been suggested that ditions where substitutional atoms do not partition
the term “bainite” should not be applied to carbide- between the phases during transformation, and thus
free microstructures [5]). Carbon partitioning is the Fe/X atom ratios are unchanged in the different
one means of stabilizing austenite against further phases. It should be recognized that the usual para-
transformation at lower temperatures, and is likely equilibrium condition does not have meaning in the
to be especially important in these steels containing absence of substitutional alloying additions, i.e. in
alloying additions (e.g. silicon) that suppress for- the Fe-C binary system. Thermodynamically, the
mation of iron carbides. paraequilibrium condition represents a minimum
Carbon migration after martensite transform- free energy condition, with the additional con-
ation is most often considered in the context of car- straint that the Fe/X atom ratios are unchanged. A
bide precipitation reactions during tempering. paraequilibrium transformation, such as proeutec-
Consequently, the thermodynamics of carbon par- toid ferrite precipitation from austenite at high
titioning between martensite and retained austenite undercooling, may proceed by interface migration
have not been examined completely. Thus, the involving short-range diffusion of the iron and sub-
present work is focused on developing a model to stitutional atoms to accomplish the necessary struc-
address carbon partitioning from as-quenched mar- ture change, along with long-range carbon dif-
tensite into austenite, under conditions where com- fusion to accomplish the necessary composition
peting reactions are suppressed. (Such reactions change. At paraequilibrium, the phase fractions
include cementite or transition carbide formation, and phase compositions are uniquely fixed, rep-
and decomposition of retained austenite by other resenting the minimum free energy condition in the
processes such as bainite transformation.) The absence of substitutional partitioning.
model does not address partitioning kinetics, but Under conditions where iron carbide precipi-
rather predicts the “endpoint” where partitioning is tation is suppressed, then the phase diagram is of
complete at a given partitioning temperature. The little use in predicting the metastable equilibrium
starting microstructure (i.e. initial fractions of mar- condition that applies to heating of mixtures of
tensite and retained austenite) is an input to the martensite and retained austenite at temperatures
carbon partitioning model developed below, and well below the eutectoid temperature. The meta-
may be controlled, for example, by the martensite stable equilibrium condition between martensite
transformation behavior (particularly the Ms tem- (i.e. ferrite) and austenite, identified by Hultgren
perature of the austenite in relation to the quench- [7,8], must therefore be considered. In the case of
ing temperature during heat treatment). an Fe-C binary alloy, if the minimum free energy
condition (“orthoequilibrium”) applies, then the a
and g phase fractions and compositions would
2. Thermodynamics of carbon partitioning adjust themselves until the metastable a/g orthoe-
quilibrium was achieved, where the chemical
Under equilibrium conditions, mixtures of potentials (or partial molar free energies) of each
quenched martensite plus retained austenite in component (Fe and C) would be equal in both the
binary Fe-C alloys are expected to decompose to ferrite and austenite. In the presence of slow-
ferrite and iron carbide [6]. The phase compo- diffusing substitutionals, the free energy minimiz-
sitions at equilibrium are given by the phase ation would be modified to represent a paraequilib-
 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622 2613

rium condition in which the Fe/X ratios are fixed amic condition also represents a minimum free
and the carbon potentials are equal in the phases. energy condition for the constrained system, but
In either case, it is critical to recognize that the differs from (unconstrained) orthoequilibrium,
approach to metastability (i.e. to the appropriate which also requires that the chemical potential of
minimum free energy condition) necessarily iron must be equal in both phases. Second, the
involves interface migration to adjust the phase number of iron atoms must be conserved in each
fractions appropriately. When the position of the phase during the approach to constrained paraequi-
martensite/austenite interface is effectively fixed, librium. Such a matter balance is consistent with
as we consider here when examining carbon par- the presumption of a stationary a/g interface after
titioning after martensite transformation is com- completion of martensite growth. While alloying
plete, then clearly it is not possible for the elements such as silicon are important in promot-
ferrite/austenite mixture to reach either orthoequili- ing conditions where constrained paraequilibrium
brium (in Fe-C) or paraequilibrium (in Fe-C-X), applies (i.e. where carbide formation is suppressed
and a new model is required. during tempering), the fundamentals of the con-
The metastable condition representing the com- strained parequilibrium condition apply equally
pletion of carbon partitioning between martensite well to the Fe-C binary system, which is used in
and austenite is developed below, and will be the following discussion to derive and illustrate the
referred to as “constrained paraequilibrium,” or properties of constrained paraequilibrium.
CPE. The constrained paraequilibrium condition is A schematic Gibbs molar free energy vs. com-
thus defined by complete absence of iron or substi- position diagram is shown in Fig. 1 for ferrite and
tutional atom movements, along with freedom of austenite in the iron-carbon system at a given tem-
the carbon (or interstitial) atoms to migrate as perature. The chemical potential of a component
needed. Like paraequilibrium, constrained parae- in a phase (mphase
component) is given by the tangent inter-
quilibrium presumes that only carbon atoms move cept with the respective composition axis. The
over distances greater than the unit cell dimen- common tangent construction in Fig. 1 thus illus-
sions. Unlike paraequilibrium, under constrained trates the unique orthoequilibrium condition
paraequilibrium conditions short-range move- between ferrite and austenite at this temperature,
ments of the iron and substitutionals do not occur showing the equilibrium phase compositions,
at the interface and interface migration is thus pre- XaEQ and XEQg
. The same schematic free energy vs.
cluded, hence the “constraint”. Constrained parae- composition curves for ferrite and austenite are
quilibrium also differs from paraequilibrium in that reproduced in Fig. 2, along with two arbitrarily
it applies to binary Fe-C alloys as well as higher- selected examples (I and II) satisfying the thermo-
order systems containing substitutional alloying
additions.
Constrained paraequilibrium can be readily
understood through consideration of two key con-
ditions that define its unique thermodynamic and
matter balance constraints. First, carbon diffusion
is completed under constrained paraequilibrium
conditions when the chemical potential of carbon
is equal in the ferrite and austenite phases, or equi-
valently, when the carbon activity is equal in the
two phases (with reference to a common standard
state). A similar condition has been invoked pre-
viously by Hillert and coworkers to describe a
possible local boundary condition at the a/g inter- Fig. 1. Schematic Gibbs free energy vs. composition diagram
face during bainite formation by a coupled showing the common-tangent construction representing orthoe-
diffusional/displacive process [9]. This thermodyn- quilibrium between ferrite and austenite.
2614 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622

the standard state. For the purposes here, it is con-

venient to use the data in the simplified form [12]:
⌫aC
RT ln ⫽ 76,789⫺43.8T⫺(169,105 (1)
⌫Cg
⫺120.4T)XgC
where ⌫gC and ⌫Cg represent the Henrian activity
coefficients for carbon in ferrite and austenite, T is
absolute temperature, R is the universal gas con-
stant, and XgC is the austenite composition (mole
fraction of carbon). Since the activity of carbon in
Fig. 2. Schematic Gibbs free energy vs. composition diagram each phase is given by the product of the activity
showing two possible ferrite and austenite compositions coefficient and the mole fraction of carbon, the
satisfying the CPE requirement that the chemical potential of condition whereby carbon activity is equal in the
carbon is equal in the two phases.
phases is satisfied when:
g
76,789⫺43.8T⫺(169,105⫺120.4T)XC

X ⫽ X ·e
g
C
a
C RT (2)
dynamic condition for constrained paraequilibrium
at this temperature. In each example, the tangents where XaC and XgC represent the mole fractions of
to the ferrite and austenite free energy curves inter- carbon in ferrite and austenite. The relationship in
sect the carbon axis at a single point, indicating Eq. (2) describes a locus of phase compositions at
equal carbon potentials in a and g, but the chemical any temperature; an example is shown in Fig. 3
potential of iron is clearly different in each phase, that illustrates the appropriate ferrite and austenite
indicating that orthoequilibrium is not satisfied. compositions at 400 °C. The ferrite and austenite
(The orthoequilibrium condition does represent a compositions in Fig. 3 are quite similar to previous
possible constrained paraequilibrium condition, results [9] determined using a different source of
however.) This figure shows that there is not a
unique ferrite and austenite composition that satis-
fies the general thermodynamic condition for con-
strained paraequilibrium at this temperature, but
rather there is an infinite set of possible ferrite and
austenite phase compositions. This is an important
property of constrained paraequilibrium, where the
matter balance constraint is also needed to
uniquely determine the applicable phase compo-
sitions.

3. The constrained paraequilibrium condition

in Fe-C alloys

The constrained paraequilibrium condition can

be calculated for Fe-C alloys using published ther-
modynamic data, and knowledge of the as-
quenched microstructure. Carbon activities in fer-
rite and austenite have been determined by Lobo Fig. 3. Calculated locus of ferrite and austenite compositions
and Geiger [10,11], with reference to graphite as having equal carbon activities at 400 °C.
 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622 2615

free energy data [13]. In the CPE calculations partitioning) where the martensite and austenite
presented below, temperatures between 200 and have identical compositions (i.e. the same as the
600 °C are considered. The possible combinations overall carbon content of the steel, Xalloy
C ) and the
of ferrite and austenite compositions over this initial mole fractions of each phase are given by
range of temperatures are shown in Fig. 4. The fai and fgi , respectively, then the matter balance for
results in Fig. 4 are indicative of reduced carbon iron is given by:
solubility in ferrite at lower temperatures in this
fgCPE(1⫺XCg CPE) ⫽ fig(1⫺Xalloy
C ) (3)
range.
g
Calculation of the constrained paraequilibrium where fCPE and XgCCPE represent the austenite phase
condition for a particular steel requires two fraction and composition after partitioning, and we
additional inputs to address the matter balance con- recognize that the iron concentration is always
straint: 1) the total carbon concentration, and 2) the given by XFeg
= 1⫺XgC for binary alloys. It is per-
fractions of martensite and retained austenite in the haps counterintuitive that the phase fractions
as-quenched condition. The phase fractions after should change (i.e. fgCPE ⫽ fgi ) under conditions
martensite transformation are generally controlled where the a/g interface is presumed to be con-
by the degree of undercooling below the marten- strained fully, but it should be clear that movement
site-start (Ms) temperature of the austenite, accord- of carbon atoms between the phases necessarily
ing for example, to the Koistinen and Marburger involves a small adjustment in the total number of
equation [6]. The matter balance conditions atoms in each phase, and thus the mole fractions
account for changes in the phase compositions as of the phases. It also follows that the densities and
carbon partitions between the phases, and the spe- lattice parameters of the phases may be changed
cial CPE requirement that iron atoms are not trans- slightly by carbon partitioning, which could lead
ferred across the interface during partitioning, i.e. to some elastic strain considerations that are not
the number of iron atoms is conserved in each addressed here, and may be associated with some
phase. For an initial condition (prior to any carbon interesting effects that warrant investigation. The
matter balance for carbon is straightforward, wher-
eby the total carbon is given by the sum of the
amounts in each of the phases, according to:
faCPEXaCCPE ⫹ fgCPEXgCCPE ⫽ Xalloy
C (4)
The constrained paraequilibrium condition is
represented by the solution of four equations ((2),
(3), (4) above, and (5) below), in four unknowns
XaCCPE, XCg CPE, faCPE, and fgCPE, where the relationship
between the phase fractions is simply:
faCPE ⫹ fgCPE ⫽ 1 (5)
In this solution, the ferrite and austenite compo-
sitions in Eq. (2) take on their unique values,
XaCCPE and XCg CPE, representing a specific con-
strained paraequilibrium condition.
The formulation illustrated here is strictly appli-
cable to binary Fe-C alloys, but remains approxi-
mately correct for low alloy steels. Rigorous modi-
fication of the approach to account for alloying
Fig. 4. Calculated loci of ferrite and austenite compositions effects on the carbon activities would simply
having equal carbon activities at temperatures between 200 and require adjustment of the activity coefficients in
600 °C. Eq. (1) using appropriate interaction parameters for
2616 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622

the elements of interest. Dislocation trapping could compositions having different mole fractions of
influence the distribution of carbon atoms [14], martensite (or correspondingly, retained austenite)
although effects on carbon solubility of the defect prior to a hypothetical CPE partitioning treatment.
population in as-quenched martensite are not incor- As mentioned previously, such differences in mar-
porated in the treatment here. A Zener ordering tensite fraction would be expected to arise from
contribution to the carbon activity in ferrite is not quenching to different temperatures below Ms, for
required once partitioning has begun, and is thus example. Figs. 5, 6 and 7 present the calculated
not included here. Finally, the constrained parae- CPE phase compositions at temperatures between
quilibrium condition could potentially apply in 200 and 600 °C for steels containing 0.25, 0.5, and
some instances where the initial compositions of 1.0% carbon by weight, respectively. Initial mar-
the ferrite and austenite phases are not identical, tensite (mole) fractions of 25, 50, 75, and 90% are
for example after completion of bainitic ferrite shown to illustrate the results. Suppression of
growth in carbide-free bainite microstructures. A cementite formation becomes increasingly difficult
more general expression for the iron matter balance at elevated temperature, [4] and thus temperatures
then becomes: above 600 °C were not considered. Furthermore,
at elevated temperatures, the mobility of iron and
g
fCPE (1⫺XgCCPE) ⫽ fgi (1⫺XgCi) (6)
substitutionals is eventually expected to become
where XgCi represents the carbon concentration in sufficient to allow short-range lattice reconstructive
the austenite, prior to final carbon partitioning in diffusion, at which time the fundamental basis of
the presence of a fully constrained interface. constrained paraequilibrium is violated, and a tra-
ditional paraequilibrium model (or orthoequilib-
rium in binary alloys) would be more applicable.
4. Example calculations of constrained The results in Figs. 5–7 are of practical use for
paraequilibrium estimating the endpoint of carbon partitioning, but
are also useful in illustrating important character-
Determination of the CPE condition using the istics of constrained paraequilibrium. It is note-
formulation presented in Eqs. (2)–(5) requires only worthy that the CPE phase compositions are influ-
the steel composition (i.e. carbon content), and the enced by the alloy composition and the initial
initial microstructure (mole fractions of martensite phase fractions, in addition to the temperature. In
and retained austenite) to be specified. For contrast, orthoequilibrium in the Fe-C binary sys-
example, we can consider an iron-carbon alloy tem is represented by a single tie line at any tem-
containing 0.5 wt. pct. carbon, quenched to an perature, with the phase compositions independent
initial condition where 75% (molar basis) marten- of the alloy composition. (Also, the phase fractions
site is present, along with 25% retained austenite. at orthoequilibrium adjust themselves to satisfy the
At a partitioning temperature of 400 °C, the calcu- lever rule for the appropriate alloy composition and
lations yield a solution for the CPE condition rep- phase compositions given by the tie-line, whereas
resented by: the CPE phase fractions are only slightly changed
during partitioning to account for carbon atom
WaCCPE ⫽ 0.0015%, WgCCPE ⫽ 1.97%, transfer across the constrained interface.) The
results show that the CPE carbon concentration in
faCPE ⫽ 0.267, and fgCPE ⫽ 0.733
ferrite increases with increasing temperature for a
where the CPE phase compositions in this instance given initial condition, whereas the CPE carbon
(WaCCPE and WgCCPE) are reported in wt. pct. The concentration in austenite decreases slightly with
results illustrate substantial carbon partitioning increasing temperature. The relative temperature
between the phases, along with slight adjustment dependence of the austenite composition is smaller,
in the phase fractions due to carbon partitioning. because the ferrite has a greater composition
The constrained paraequilibrium phase compo- dependence of the carbon activity and quite low
sitions were calculated for a variety of Fe-C alloy calculated solute carbon levels, and the austenite
 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622 2617

Fig. 5. Constrained paraequilibrium calculations for an Fe-0.25C (wt. pct.) alloy, showing the dependence of CPE ferrite and austen-
ite compositions on temperature and initial martensite fraction (molar basis).

Fig. 6. Constrained paraequilibrium calculations for an Fe-0.5C (wt. pct.) alloy, showing the dependence of CPE ferrite and austenite
compositions on temperature and initial martensite fraction (molar basis).
2618 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622

Fig. 7. Constrained paraequilibrium calculations for an Fe-1.0C (wt. pct.) alloy, showing the dependence of CPE ferrite and austenite
compositions on temperature and initial martensite fraction (molar basis).

inherits most of the carbon in the steel at con- here (for a 1% carbon steel containing 10%
strained paraequilibrium. The CPE condition is retained austenite) are greater than 6.7 wt. pct., and
associated with phase compositions that can be therefore exceed the carbon concentration of
either carbon-rich, or carbon-depleted, relative to cementite! Consequently, it is implausible, or dif-
orthoequilibrium. When the austenite fraction is ficult, to envision conditions under which compet-
greater than would be associated with orthoequilib- ing reactions such as carbide formation could be
rium, then the CPE phase compositions have car- suppressed sufficiently to achieve constrained
bon levels less than their orthoequilibrium values; paraequilibrium in such instances. It is useful to
and at austenite fractions less than the orthoequilib- recognize that an opportunity apparently exists to
rium values, the CPE phase fractions have higher explore even greater silicon/aluminum levels than
carbon levels. For a given initial martensite frac- are typical of carbide-free bainitic steels, or to
tion, higher carbon steels have CPE phase compo- develop alternative alloying approaches to further
sitions with greater carbon levels. Interestingly, the suppress carbide precipitation, thereby enhancing
carbon levels in the retained austenite after CPE the potential for employing new microstructures
partitioning can be quite high, exceeding 2% even containing highly enriched austenite. Nonetheless,
in the lowest carbon steel considered here (0.25% the overall conclusion of this model is clear: sig-
carbon), at a retained austenite fraction of 10%. nificant carbon enrichment of retained austenite
Some caution is perhaps warranted when consider- should be possible by deliberate control of par-
ing high predicted levels of carbon enrichment in titioning after martensite transformation.
the austenite. First, it should be recognized that the
carbon activity data used for the calculations were
determined in austenite compositions well below 5. Application of CPE partitioning
1% carbon, and so extrapolation to much higher
carbon levels should be only approximate. Second, It is important to consider applications of CPE
the highest CPE austenite compositions calculated carbon partitioning and implications of the model
 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622 2619

results, although some further alloy and process levels in austenite are possible when partitioning
design considerations are also reported elsewhere occurs under CPE conditions reported above,
[15]. It is envisioned that CPE partitioning will be given suitable control of the phase fractions
most applicable for processing conditions where after quenching. The CPE model also indicates
austenite is formed at elevated temperature (either that the phase compositions after partitioning in
during full austenitization or intercritical heat a given steel are identical in martensite/austenite
treatment), followed by cooling to a temperature mixtures compared to bainite/austenite mix-
carefully selected to control the fractions of mar- tures, if the fraction of martensite is equal to the
tensite and retained austenite, and finally by a ther- fraction of bainitic ferrite.
mal treatment that accomplishes the desired extent 2. The temperature dependence of carbon enrich-
of carbon partitioning. We refer to this processing ment is different for bainitic and Q&P pro-
sequence as Q&P (quenching and partitioning), to cessing. For bainite, the extent of partitioning is
distinguish it mechanistically from conventional controlled by the temperature dependence of To,
quenching and tempering (Q&T) of martensite, rather than the CPE conditions developed
where carbide precipitation and decompositon of above.
retained austenite are typical, rather than chemical 3. The processes used to develop the phase frac-
stabilization of austenite by carbon partitioning. tions and morphologies in the final microstruc-
Steels of greatest interest for Q&P processing ture are completely separate from the carbon
will make use of controlled amounts of retained partitioning treatment, allowing complete and
austenite, and include TRIP (transformation independent control during Q&P, whereas bain-
induced plasticity) sheet steels and high-strength itic ferrite growth and carbon partitioning are
carbide-free bainitic grades [16,17]. Alloying effectively linked in the production of conven-
additions such as Si, Al or P are already present tional carbide-free bainites. Different quenched
in these steels to suppress carbide formation [4], so microstructures can also be designed prior to
major changes in alloy composition are not initially partitioning, such as lath or twinned martensite,
needed to apply the new process. The Q&P process providing additional opportunity to influence
can also be considered as a possible replacement final properties in new ways. For example, sub-
for bainitic treatment in austempered ductile iron. stantial amounts of carbon-depleted lath marten-
In each example, carbon enrichment after marten- site could be used in TRIP sheet steels to achi-
site transformation is considered to replace bainite eve higher strength levels. Somewhat elevated
formation (where carbon partitioning to austenite carbon levels in ferrite might also be achievable
is intimately coupled with ferrite growth). Decoup- by carefully controlling CPE conditions,
ling of carbon partitioning and microstructure increasing the strength of the ferritic matrix.
development (i.e. control of phase fractions and 4. Microstructure evolution occurs by an athermal
morphologies through athermal martensite mechanism in the Q&P process, whereas bain-
transformation) represents a dramatic and funda- itic transformation kinetics are thermally acti-
mental departure from conventional approaches to vated. The thermal history needed to obtain con-
microstructure control. There are widespread ventional carbide-free bainitic microstructure is
implications of this difference, including: influenced by many factors that control the TTT
or CCT kinetics, whereas the Ms and quench
1. Greater amounts of carbon enrichment in aus- temperatures largely control transformation dur-
tenite become possible when compared to con- ing Q&P [15]. During the subsequent partition-
ventional carbide-free bainites. It has been sug- ing treatment, only carbon diffusion is needed,
gested that transformation to bainite by a shear rather than carbon diffusion plus ferrite
mechanism effectively ceases when the austen- nucleation or growth. Decoupling of these pro-
ite composition is enriched to To, the compo- cesses likely leads to a different time depen-
sition where the free energies of ferrite and aus- dence of the carbon partitioning, and allows
tenite are equal. In contrast, much higher carbon greater flexibility in the intermediate tempera-
2620 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622

ture process when compared to bainite. For the final austenite composition has been reported
example, alloying additions made to increase by different studies [1,21] to approximate To, and
hardenability or suppress ferrite formation dur- therefore to provide support for the displacive
ing initial cooling from the intercritical or aus- growth mechanism. The carbon concentration of
tenitizing temperature may substantially influ- bainitic ferrite is on the order of 0.03 wt. pct. [22]
ence bainitic transformation kinetics, while only or greater [23], and is believed to be influenced
slightly influencing the Q&P process through significantly by trapping of solute carbon atoms by
small effects on the Ms temperature. While not dislocations in the ferrite [24]. Most importantly,
of primary importance, it must be recognized the steel is either at constrained paraequilibrium at
that hardenability is still relevant in Q&P pro- the end of the bainite transformation, or else
cessing, influencing the response of the austen- additional carbon partitioning must occur to achi-
ite during cooling or quenching, and also the eve constrained paraequilibrium. While possible
propensity for competing microstructure [23], such partitioning after completion of the bain-
changes during carbon partitioning. ite transformation is not emphasized in the litera-
5. Carbon enrichment of austenite can be ture, and indeed the remaining carbon available for
employed in steels with microstructures that are partitioning from ferrite is rather small. Thus, it
traditionally martensitic, rather than just bain- seems reasonable to conclude that the bainite trans-
itic. For example, higher carbon austenites typi- formation may be completed under near-CPE con-
cal of moderately alloyed bearing steels or car- ditions, where the To composition represents the
burized gear steels are quenched and only CPE austenite composition.
tempered lightly, such that high hardness is pre- The ferrite and austenite compositions at the
served and significant quantities of austenite interface during transformation are also of funda-
may be retained. The austenite can provide ben- mental interest. Among the instantaneous interface
eficial properties such as pitting resistance in compositions that have been considered for
rolling contact fatigue [18], and thus alloying coupled diffusional/displacive growth of bainite
modifications with suitable partitioning treat- are paraequilibrium [20] and “local equilibrium for
ment could be used to alter the austenite stab- carbon” [9]. Both the paraequilibrium and CPE
ility, and thus the behavior in service. Similarly, condition are effectively subsets of this latter “local
in other alloys where substantial levels of sili- equilibrium” condition, which is effectively rep-
con are currently applicable, such as ductile cast resented by any of the phase compositions
irons or martensitic steels (e.g. for tempering satisfying Eq. (2) above. It is appealing to specu-
resistance in spring steels), Q&P treatments to late that the interface compositions during growth
influence the amount and character of the of bainite could perhaps be given by the particular
retained austenite may also be considered. CPE phase compositions having the austenite com-
position of To (where the appropriate free energies
Finally, it is worthwhile to consider possible are adjusted for elastic strain energy, Zener
implications of the CPE partitioning model with ordering, and dislocation/solute interactions). That
respect to bainite transformation via a coupled is, the transformation is not only completed under
diffusional/displacive [9,19,20] mechanism. In this CPE conditions, but also may proceed under near-
context, the CPE model developed here predicts CPE conditions at the interface. Under such con-
the endpoint of carbon partitioning in the presence ditions, bainite growth might be considered to
of constrained interface boundaries, rather than involve a diffusionless martensitic mechanism of
processes occurring during bainitic transformation interface migration, along with carbon diffusion-
(i.e. when the boundaries are still moving). It fol- controlled growth kinetics with essentially steady
lows that the final bainitic ferrite/retained austenite state boundary conditions that are far from
mixture in a carbide-free bainite should achieve (para)equilibrium, and yet satisfy very reasonable
constrained paraequilibrium when carbon partition- thermodynamic constraints. In this theory, growth
ing is taken to completion. In such microstructures, of a bainitic subunit is eventually inhibited both
 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622 2621

by transformation strains and by the diminishing given initial condition, whereas the carbon con-
carbon concentration gradient in the austenite. The centration in austenite decreases with increasing
transition from bainitic to martensitic transform- temperature. The CPE phase compositions can
ation is associated with the greater driving force be either carbon-rich, or carbon-depleted, rela-
and reduced carbon mobility at lower temperatures, tive to orthoequilibrium.
both which allow growth to proceed quickly 3. The austenite inherits most of the carbon in the
enough to avoid carbon buildup at the interface. steel at constrained paraequilibrium, and the
While further work is needed to establish whether retained austenite can be very enriched with car-
the kinetics and other characteristics of bainite for- bon in some instances.
mation are fully consistent with this explanation, 4. Applications of CPE partitioning may be con-
the proposed behavior provides a model for the sidered in steels where carbide formation is sup-
bainite transformation mechanism that is, at the pressed (e.g. with Si, Al, P, or even Ni
same time, both “fully” diffusional and “fully” additions). The potential for a new “quenching
martensitic. and partitioning” process, or Q&P, is proposed,
where the resulting martensite/austenite mix-
tures may be substituted for more conventional
6. Conclusions carbide-free bainitic microstructures such as
high-strength TRIP sheet steels or even aus-
Consideration of carbon partitioning from tempered ductile cast iron.
quenched martensite to retained austenite in the 5. It is suggested that constrained paraequilibrium
presence of a stationary a/g interface, under con- should also apply when partitioning is complete
ditions where carbide precipitation is precluded, after transformation to carbide-free bainite
indicates that the metastable orthoequilibrium con- microstructures. Austenite having a composition
dition (or paraequilibrium in multicomponent given by the To curve is shown to represent a
alloys) between ferrite and austenite cannot be ach- possible CPE condition, and it is speculated that
ieved. Consequently, a “constrained paraequilib- bainite growth involving a martensitic mech-
rium” or CPE model was developed here to predict anism of interface migration can occur with dif-
the endpoint of carbon partitioning in the presence fusion-controlled kinetics involving steady state
of a stationary a/g interface, i.e. applicable to the boundary conditions corresponding to CPE
carbon redistribution processes after growth of the compositions.
microstructural constituents is complete. It is
shown that the CPE condition involves special
matter balance constraints (such that the number Acknowledgements
of iron atoms is conserved in each phase during
partitioning), while satisfying the thermodynamic Two authors (Speer and Matlock) gratefully
condition where the chemical potential of carbon is acknowledge the support of the sponsors of the
equal in austenite and ferrite (i.e. carbon depleted Advanced Steel Processing and Products Research
martensite). Specific implications of the CPE Center at the Colorado School of Mines. Prof.
model results include: H.K.D.H. Bhadeshia, University of Cambridge, is
gratefully acknowledged for helpful discussions.
1. The ferrite and austenite compositions at con-
strained paraequilibrium are dependent on the
steel composition and phase fractions, in
References
addition to temperature, in contrast to orthoequi-
librium in Fe-C alloys where the tie-line is
[1] Bhadeshia HKDH. Bainite in steels. London: The Institute
dependent only on temperature. of Materials, 2001.
2. The CPE carbon concentration in ferrite [2] Bhadeshia HKDH. Carbon content of retained austenite in
increases with increasing temperature for a quenched steels. Metal Science 1983;17(March):151–2.
2622 J.G. Speer et al. / Acta Materialia 51 (2003) 2611–2622

[3] Sarikaya M, Thomas G, Steeds JW, Barnard SJ, Smith [15] Matlock DK, Bräutigam VE, Speer JG. Application of the
GDW. Solute element partitioning and austenite stabiliz- quenching and partitioning (Q&P) process to a medium-
ation in steels. In: Aaronson HI, editor. Proceedings of an carbon, high-Si microalloyed bar steel, Proceedings of
International Conference on Solid to Solid Phase Trans- THERMEC’ 2003. Uetikon-Zurich, Switzerland: Trans
formations. Warrendale, PA: The Metallurgical Society; Tech Publications, Inc.; 2003 (in press).
1982. p. 1421–5. [16] Matlock DK, Krauss G, Speer JG. Microstructures and
[4] Gallagher MF, Speer JG, Matlock DK, Fonstein NM. properties of direct-cooled forging steels. Journal of
Microstructure development in TRIP-sheet steels contain- Materials Processing Technology 2001;117:324–8.
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Working and Steel Processing Conference. Warrendale, DG, Brown P. Design of novel high strength bainitic
PA: Iron and Steel Society; 2002. p. 153–72. steels, Parts I and II. Materials Science and Technology
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Scripta Materialia 2000;43(9):831–3. [18] Roache B, Pitsko R, Chidester A, Imundo J. The effect of
[6] Krauss G. STEELS: Heat treatment and processing prin- microstructure on debris dented rolling element bearing
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[7] Hultgren A. Isothermal transformation of austenite. ASM rendale, PA: Society of Automotive Engineers, 2002.
[19] Olson GB, Bhadeshia HKDH, Cohen M. Coupled
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[8] Hultgren A. Isoterm omvandling av austenit. Jernkontorets
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Annaler 1951;135:403–94.
[20] Mujahid SA, Bhadeshia HKDH. Coupled
[9] Hillert M, Hoglund L, Agren J. Escape of carbon from
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ferrite plates in austenite. Acta Metallurgica et Materialia
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1993;41(7):1951–7.
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[10] Lobo JA, Geiger GH. Thermodynamics and solubility of [21] Matsuda H, Kitano F, Hasegawa K, Urabe T, Hosoya Y.
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Transactions A 1976;7A(September):1347–57. steel sheet. In: De Cooman BC, editor. International Con-
[11] Lobo JA, Geiger GH. Thermodynamics of carbon in aus- ference on TRIP-Aided High Strength Ferrous Alloys—
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1976;7A(September):1359–64. 2002. p. 113–9.
[12] Bhadeshia HKDH. Driving force for martensitic trans- [22] Bhadeshia HKDH, Edmonds DV. The mechanism of bain-
formation in steels. Metal Science 1981;April:175–7. ite formation in steels. Acta Metallurgica 1980;28:1265–
[13] Gustafson P. A thermodynamic evaluation of the Fe-C 73.
system. Scandanavian Journal of Metallurgy [23] Bhadeshia HKDH, Waugh AR. Bainite: An atom probe
1985;14:259–67. study of the incomplete reaction phenomenon. Acta Metal-
[14] Kalish D, Cohen M. Structural changes and strengthening lurgica 1982;30:775–84.
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Microstructural Evolution of a Low-Carbon Steel during
Application of Quenching and Partitioning Heat Treatments
after Partial Austenitization
M.J. SANTOFIMIA, L. ZHAO, and J. SIETSMA

The ‘‘quenching and partitioning’’ (Q&P) process has been studied in a low-carbon steel con-
taining 1.1 wt pct aluminum by heat treatments consisting of partial austenitization at 900 °C
and subsequent rapid cooling to a quenching temperature in the range between 125 °C and
175 °C, followed by an isothermal treatment (partitioning step) at 250 °C and 350 °C for dif-
ferent times. Characterization by means of optical and scanning electron microscopy, electron
backscattered diffraction (EBSD), magnetization measurements, and X-ray diffraction (XRD)
has shown a multiphase microstructure formed by intercritical ferrite, epitaxial ferrite, retained
austenite, bainite, and martensite after different stages of tempering. A considerable amount of
retained austenite has been obtained in the specimens partitioned at 350 °C for 100 seconds.
Experimental results have been interpreted based on concepts of the martensite tempering,
bainite transformation, and kinetics calculations of the carbon partitioning from martensite to
austenite.

DOI: 10.1007/s11661-008-9701-4
Ó The Minerals, Metals & Materials Society and ASM International 2008

I. INTRODUCTION (one-step treatment) or at a higher temperature (two-

step treatment), in order to transfer the carbon from the
TRANSFORMATION-INDUCED-PLASTICITY supersaturated martensite into the austenite. In this heat
(TRIP) steels are usually produced via a thermome- treatment, alloying elements such as silicon and alumi-
chanical process of intercritical annealing followed by num are also used, to avoid the carbide precipitation
rapid cooling to a bainitic transformation regime, to during the partitioning step, because carbide precipita-
obtain a microstructure of ferrite, bainite, and retained tion acts as a sink of carbon that is no longer available
austenite. During the bainitic transformation, the for- for the stabilization of the austenite. Combining this
mation of carbides is suppressed, due to the effect of heat treatment with a previous partial austenitization, a
alloying elements such as silicon and aluminum; the microstructure consisting of ferrite, carbon-depleted
austenite is thus enriched with carbon and retained at martensite, and carbon-enriched retained austenite is
room temperature. Carbon-enriched metastable retained obtained. This microstructure can lead to an interesting
austenite is considered beneficial, because the TRIP combination of mechanical properties,[3,4] from a good
phenomenon during the deformation can significantly formability, as a result of the TRIP effect from the
contribute to the formability and energy absorption of retained austenite, to a strength higher than that of
the material. conventional TRIP steels, due to the presence of
Recently, Speer et al.[1,2] proposed a novel heat- martensite instead of bainite.
treatment concept, the so-called ‘‘quenching and parti- The design of adequate Q&P heat treatments requires
tioning’’ (Q&P) process, for the development of an understanding of all the phenomena that can affect
multiphase steels with considerable retention of austen- the final microstructure of the material during this
ite in the microstructure. The Q&P process consists of a processing route. Most of the research on the Q&P
first quench (quenching step) to a temperature below the process has been focused on treatments that start with
martensite-start (Ms) temperature but above the mar- full austenitization;[5,6] the use of partial austenitization
tensite-finish (Mf) temperature, to form a mixture of has been studied less.[1] Therefore, there is insufficient
martensite and austenite, and a subsequent isothermal experimental evidence that the phenomena affect the
treatment (partitioning step) at the same temperature microstructure during the Q&P process in the case of
treatments starting with partial austenitization. In this
work, the Q&P process is studied in a low-carbon steel
M.J. SANTOFIMIA, Postdoctoral Researcher, and L. ZHAO,
Research Fellow, Department of Materials Science and Engineering,
containing 1.1 wt pct aluminum, by the application of
Delft University of Technology, are with the Materials Innovation partial austenitization followed by quenching to 125 °C,
Institute (M2i), 2628 CD Delft, The Netherlands. J. SIETSMA, 150 °C, or 175 °C and partitioning at 250 °C or 350 °C
Associate Professor, is with the Department of Materials Science and for different times. The use of a steel with a chemical
Engineering, Delft University of Technology, 2628 CD Delft, The composition similar to the typical chemistry of a
Netherlands. Contact e-mail: m.santofi[email protected]
Manuscript submitted March 26, 2008. TRIP steel will help evaluate whether such compositions
Article published online November 14, 2008 are suitable for application of the Q&P process.

46—VOLUME 40A, JANUARY 2009 METALLURGICAL AND MATERIALS TRANSACTIONS A

The resulting microstructures have been analyzed by an oxide polishing solution (OPS) suspension. The last
optical and scanning electron microscopy, magnetic specimen-preparation step was electrolytic polishing
measurements, and X-ray diffraction (XRD). The inves- with an electrolyte consisting of 78 ml perchloric acid,
tigation pays attention to the evolution of the micro- 90 ml distilled water, 730 ml ethanol, and 100 ml
structure along the whole process, but focuses on the butylglycol at 40 V for 10 seconds. The specimens were
austenite retention. analyzed by an orientation imaging microscope attached
to a Nova 600 Nanolab dual-beam focused-ion-beam
microscope (FEI Company, Hillsboro, OR) equipped
II. EXPERIMENTAL PROCEDURE with a FEG-SEM column. The analysis was performed
under the following conditions: acceleration voltage of
The chemical composition of the material used in this 20 kV, working distance of 7 mm, tilt angle of 70 deg,
work is shown in Table I. The as-received commercial and step size of 50 nm. The EBSD measurements were
material was a 1.2-mm-thick steel sheet with a multi- carried out in the cross section of the specimens, in a
phase microstructure consisting of ferrite, bainite, and plane perpendicular to the normal direction of the sheet.
retained austenite. After removing the galvanized layer, The orientation data were postprocessed with Channel 5
dilatometry specimens with dimensions of 1 9 5 9 software provided by HKL Technology (Oxford Instru-
10 mm3 were machined. Heat treatments were applied ments, Abingdon, UK).
to the specimens with a DT1000 high-resolution dila- Cubic specimens with an edge dimension of 1.0 mm for
tometer (Adamel Lhomargy SAS, Roissy en Brie, magnetic measurements were machined from dilatome-
France). The thermal schedules applied to the specimens try specimens using an electrodischarging machine. A
are displayed in Figure 1. Specimens were heated at 7307 vibrating sample magnetometer (Lake Shore Cryo-
5 °C/s, partially austenitized at 900 °C for 10 minutes, tonics, Westerville, OH), calibrated with a standard
and cooled at 100 °C/s to 125 °C, 150 °C, or 175 °C to National Institute of Standards and Technology nickel
get a partial martensitic microstructure. Specimens were specimen, was used for the experiments. With this
reheated and isothermally held at 250 °C or 350 °C equipment, magnetization curves at room temperature
(partitioning temperatures) for different times before were measured by a stepwise change in the applied
quenching to room temperature. In order to select
appropriate quenching temperatures, the Ms tempera-
ture corresponding to the remaining intercritical
austenite after the partial austenitization was measured
by dilatometry from the direct-quench treatment
(Figure 2), leading to Ms = 260 °C. The formation of
a new phase was also observed. As will be explained in
the following Section III, this new phase is identified as
epitaxial ferrite.
The specimens were ground and polished according to
the usual techniques. The etching procedure proposed
by De et al.[7] was applied to the specimens to be
observed by light optical microscopy. This etching is a
two-step procedure that consists of a first etching in a Fig. 1—Scheme of the Q&P treatments applied to the steel.
solution of 5 pct picric acid with a few drops of
hydrochloric acid (20 seconds), followed by a second
etching in 10 pct aqueous sodium metabisulfide (8 sec-
onds). Specimens were also analyzed after etching with
5 pct nital with a JEOL* JSM-6500F field-emission gun

*JEOL is a trademark of Japan Electron Optics Ltd., Tokyo.

scanning electron microscope (FEG-SEM) operating at

15 kV.
Some selected specimens were metallographically
prepared for electron backscattered diffraction (EBSD)
examination with a final polishing step of 0.5 mm, using

Table I. Chemical Composition of the Studied Steel

(Weight Percent)

C Mn Si Al P Fig. 2—Dilatometry curve corresponding to the cooling step of the

0.19 1.61 0.35 1.10 0.09 specimen obtained after direct quench at 100 °C/s from the intercriti-
cal conditions.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 40A, JANUARY 2009—47

magnetic field from 2.0 to -2.0 T. The saturation effects of substitutional elements on the lattice param-
magnetization values were obtained by fitting the eter are small compared with the influence of the carbon
approach to the saturation of the experimentally content, as can also be observed from Eq. [3]. The
obtained magnetization curve.[8] The volume fraction of results of this calculation indicate an average measure-
retained austenite in every specimen, fc, is determined by ment of the carbon content in the austenite.
comparing the saturation magnetization values obtained
both on the specimen with retained austenite, Msat(c),
and on an austenite-free specimen, Msat(f), according to
III. RESULTS
Msat ðcÞ
fc ¼ 1
b ½1 A. Optical Microscopy
Msat ðfÞ
Figure 3 shows the optical microscopy micrographs
[8] of the specimens quenched to 175 °C and partitioned at
The coefficient b is obtained via the relation 350 °C for 3 and 1000 seconds. These micrographs are
 h  used here to describe common microstructural details
Msat
b ¼ 1
fh þ fh ½2 observed for different quenching and partitioning tem-
Masat
peratures. According to the work of De et al.,[7] their
where fh is the volume fraction of cementite present in proposed etching procedure allows the identification of
the austenite-free specimen, Masat is the saturation retained austenite in TRIP and dual-phase microstruc-
magnetization of the ferrite,[9] and Mhsat is the saturation tures by the revelation of white islands clearly different
magnetization of the cementite.[10,11] The austenite-free from the ferrite phase. However, as has been analyzed in
specimen was obtained by annealing one of the austen- a previous study,[14] the distinction between martensite
ite-containing specimens at 600 °C for 1 hour. and austenite from the metallographic study using this
In order to determine the average carbon content of agent is not clear in this material. In the present case,
the austenite, XRD experiments were performed on a retained austenite and untempered martensite are
Bruker-type D8-Advance diffractometer (Bruker AXS, observed as light-colored islands in a ferritic matrix,
Karlsruhe, Germany) equipped with a Bruker VANTEC whereas tempered martensite and bainite are observed in
position sensitive detector. In the experiments, Co Ka a dark color because of the finer microstructure and, in
radiation was used; a 2h range from 30 to 135 deg, some cases, the presence of carbide precipitation.
containing the (111), (200), (220), and (311) austenite From the figures, the mixture of untempered mar-
reflections, was scanned using a step size of 0.05 deg. tensite and retained austenite is observed to be more
The austenite lattice parameter, ac, was determined from abundant in the specimen partitioned for 3 seconds than
the peak position of each austenite reflection using in the specimen partitioned for 1000 seconds. On the
Cohen’s method.[12] The carbon concentration xC of the other hand, the combination of tempered martensite and
austenite was obtained using the relation[13] bainite is more abundant in the specimen partitioned for
1000 seconds. This observation is in agreement with the
ac ¼ 0:3556 þ 0:00453xC þ 0:000095xMn þ 0:00056xAl occurrence, at longer partitioning times, of conventional
½3 martensite tempering processes such as carbide precip-
itation in martensite and decomposition of austenite
where xC, xMn, and xAl are the concentrations of into bainite. This observation is analyzed in the follow-
carbon, manganese, and aluminum, respectively, in ing Section III–B.
austenite, in weight percent. The effects of silicon and In Figures 3(a) and (b), ferrite is clearly observed as
phosphorus are not considered in Eq. [2], although the the white matrix, but a detailed observation shows very

Fig. 3—Microstructure after Q&P heat treatments with quenching at 175 °C and partitioning at 350 °C for (a) 3 s and (b) 1000 s.

48—VOLUME 40A, JANUARY 2009 METALLURGICAL AND MATERIALS TRANSACTIONS A

fine boundaries separating ferrite areas inside the same 100 seconds. A comparison of these figures shows that
well-defined ferrite grain. The ferritic areas that are there has not been any substantial tempering of the
closer to the austenite/martensite grains correspond to martensitic microstructure during partitioning at 250 °C
ferrite that has grown from the ferrite present after the for less than 100 seconds. However, carbide precipita-
intercritical treatment during the first cooling (the so- tion is observed in specimens partitioned for 1000 sec-
called epitaxial ferrite[15,16]). A detailed characterization onds at this temperature, as shown in Figure 5(c) and
of the epitaxial ferrite formed during cooling in this (d) for the specimen quenched at 125 °C.
material can be found elsewhere.[14] Moreover, more The characteristic tempering phenomena occurring in
details of the formation of epitaxial ferrite in this the martensite at 350 °C are different from those
material will be presented in the following Section III–B, occurring at 250 °C. In addition, the carbon partitioning
III–C. from martensite to austenite is faster at 350 °C than at
Optical microscopy observations give indications 250 °C. These changes in the kinetics of the processes
about the microstructure present in the specimens for should be reflected in the characteristics of the micro-
every Q&P condition. However, they do not provide structure of the specimens partitioned at 350 °C. In this
microstructural details smaller than a few microns; vein, Figure 6(a) shows the microstructure of the
therefore, scanning electron microscopy has been used specimen quenched at 125 °C and partitioned at
for these purposes. 350 °C for 10 seconds, in which blocks of tempered
and untempered martensite in a ferrite matrix are
observed. One of the blocks of tempered martensite is
B. Scanning Electron Microscopy
enlarged in Figure 6(b), showing carbide precipitation.
Epitaxial ferrite can also be distinguished by scanning These two figures provide evidence that 10 seconds of
electron microscopy. As an example, Figure 4 shows the partitioning at 350 °C is enough time to start the
microstructure of the specimen quenched at 125 °C and tempering of the microstructure. Similar behavior has
tempered at 350 °C for 10 seconds, as observed by been observed after quenching at 150 °C and 175 °C.
FEG-SEM. Epitaxial ferrite is clearly distinguished After partitioning for 1000 seconds at 350 °C, bainite
from intercritical ferrite because of a different topogra- has been observed in all the specimens. The resulting
phy. This means that intercritical and epitaxial ferrite bainitic microstructure, shown in Figure 7, is formed by
have a different response to the 5 pct nital etching. bainitic ferrite plates separated by films of retained
These differences are due to a distinct composition of austenite or martensite formed during the final quench.
substitutional alloying elements in each type of ferrite, Figure 7(a) displays the microstructure of the specimen
because epitaxial ferrite has grown during rapid cooling quenched to 150 °C and partitioned at 350 °C for
under paraequilibrium conditions with the austen- 1000 seconds, showing a high fraction of bainite.
ite,[15,17] whereas the partitioning of alloying elements Figure 7(b) contains an enlarged micrograph of the
was possible to a certain extent during the intercritical square area drawn in Figure 7(a), showing details of
annealing. the decomposition of residual austenite in bainite.
From scanning electron microscopy observations, no Figures 7(c) and (d) show the presence of bainite in
substantial differences have been detected in the micro- the specimens quenched to 125 °C and 175 °C, respec-
structures observed after partitioning at 250 °C for tively, and partitioned at 350 °C for 1000 seconds. In all
every quenching temperature. In particular, Figures 5(a) the observed cases, bainitic ferrite plates are free of
and (b) show the microstructures of the specimens internal cementite particles, which is characteristic of
quenched at 125 °C and partitioned at 250 °C for 3 and upper bainite.

Fig. 4—(a) and (b) FEG-SEM micrographs of a specimen quenched to 125 °C and partitioned at 350 °C for 10 s. The square in (a) is enlarged
in (b). (EF is epitaxial ferrite, IF is intercritical ferrite, TM is tempered martensite, and RA/UM is retained austenite or untempered martensite).

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 40A, JANUARY 2009—49

Fig. 5—FEG-SEM micrographs of specimens quenched to 125 °C and partitioned at 250 °C for (a) 3 s, (b) 100 s, and (c) and (d) 1000 s. The
square in (c) is enlarged in (d), showing a block of tempered martensite containing carbide precipitation.

Fig. 6—(a) and (b) FEG-SEM micrographs of a specimen quenched to 125 °C and partitioned at 350 °C for 10 s. The square in (a) is enlarged
in (b), showing a block of tempered martensite containing carbide precipitation.

C. Electron Backscattered Diffraction Figure 8(a) shows a scanning electron microscopy

In order to support some of the microstructural image of the EBSD scan displayed in Figure 8(b) of the
features mentioned, an EBSD analysis was performed specimen quenched to 150 °C and partitioned at 350 °C
on the specimens quenched to 150 °C and partitioned at for 10 seconds. In particular, Figure 8(b) is a combined
350 °C for 10 and 1000 seconds. band-contrast (BC) map and color-coded phase map, in

50—VOLUME 40A, JANUARY 2009 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 7—FEG-SEM micrographs of specimens partitioned at 350 °C for 1000 s: (a) microstructure of specimen quenched at 150 °C, (b) detail of
bainite corresponding to the square drawn in (a), (c) bainite in specimen quenched at 125 °C, and (d) bainite in specimen quenched at 175 °C.
(UB is upper bainite, TM is tempered martensite, and RA/UM is retained austenite or untempered martensite).

which blue corresponds to bcc lattice, red corresponds to grains analyzed does not show significant changes when
fcc lattice, and darker areas correspond to a very low BC, the boundaries between intercritical and epitaxial ferrite
most probably indicating martensite. Retained austenite are reached. This observation confirms the formation of
is observed with an equiaxed morphology and is situated epitaxial ferrite by the growth of the intercritical ferrite
very close to martensite, near the ferrite boundaries. in the absence of nucleation.
A similar combination of figures is shown in Figure 9,
for the specimen quenched to 150 °C and partitioned at
D. XRD and Magnetic Measurements
350 °C for 1000 seconds. In this case, austenite is
observed with a filmy morphology and surrounded by One of the desired goals in the Q&P process is
ferrite. This microstructure resembles, in morphology obtaining multiphase microstructures with an adequate
and size, the one presented in Figure 7 and identified as volume fraction and adequate carbon enrichment of the
bainite. This austenite morphology was not observed retained austenite. Therefore, the characterization of the
after partitioning for 10 seconds and reinforces the retained austenite in volume fraction and carbon con-
microstructural interpretation done in previous Section tent is of pre-eminent importance in this investigation.
III–A, III–B. Figures 11(a) and (b) show the volume fraction of
The arrows in Figure 9(a) indicate the presence of retained austenite (measured by the magnetization
epitaxial ferrite. Figure 10(a) shows a combined BC and method) and its carbon content (from XRD) in the
orientation image map of the microstructure analyzed in specimens thermally treated with a partitioning temper-
Figure 9. It is clear that epitaxial ferrite shares the grain ature of 250 °C. The horizontal solid line represents the
orientation with the surrounding ferrite. Moreover, the corresponding measurements in the specimen directly
point-to-origin misorientation profile along the black quenched. The volume fraction of retained austenite for
straight line shown in Figure 10(a) was analyzed, with all the quenching temperatures and partitioning times is
point 1 being the origin of the analysis. The resulting rather close to the one measured in the specimen directly
misorientation profile is shown in Figure 10(b). The quenched, leading to values between 0.03 and 0.06.
misorientation between the two neighboring ferrite Carbon content measurements are also close to the

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 40A, JANUARY 2009—51

Fig. 8—EBSD analysis of the sample quenched to 150 °C and partitioned at 350 °C for 10 s: (a) secondary electron image of the scan analysis;
and (b) combined BC map and color-coded phase map corresponding to the scan shown in (a), in which blue corresponds to bcc lattice, red cor-
responds to fcc lattice, and darker areas correspond to a very low BC, most probably indicating martensite.

Fig. 9—EBSD analysis of the sample quenched to 150 °C and partitioned at 350 °C for 1000 s: (a) secondary electron image of the scan analy-
sis; and (b) combined BC map and color-coded phase map corresponding to the scan shown in (a), in which blue corresponds to bcc lattice, red
corresponds to fcc lattice, and darker areas correspond to a very low BC, most probably indicating martensite.

value obtained in the direct-quenched specimen and are The same measurements corresponding to the speci-
approximately constant along the partitioning times, mens treated with a partitioning temperature of 350 °C
with a slight tendency to decrease in the case of are presented in Figures 11(c) and (d). In this case, some
partitioning for 1000 seconds. common tendencies are observed for every quenching

52—VOLUME 40A, JANUARY 2009 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 10—(a) Combined BC and orientation image map of the microstructure analyzed in Fig. 9 and (b) misorientation measured with respect to
the first point along the line shown in (a).

Fig. 11—(a) Volume fraction and (b) carbon content of retained austenite, for Q&P heat treatments with partitioning at 250 °C; (c) volume frac-
tion of retained austenite; and (d) carbon content for partitioning at 350 °C. The horizontal solid line represents the corresponding measurement
in the direct-quenched specimen; shaded areas represent the estimated error of this measurement.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 40A, JANUARY 2009—53

temperature studied: (1) after the partitioning for 3 and remains untransformed. After the second quench, the
10 seconds, the volume fraction of austenite and the surrounding austenite is either transformed to (untem-
carbon content are similar to the specimen directly pered) martensite or retained, in both cases showing a
quenched, with a slight decrease in volume fraction at smooth surface by scanning microscopy.
10 seconds, in comparison to the result at 3 seconds; (2) A consequence of this morphology is that the initial
there is a substantial increase in the volume fraction of carbon content in the martensite and austenite before
austenite after partitioning for 100 seconds, without the partitioning step is not equal; it is higher in the
changes in the carbon content; and (3) at 1000 seconds of austenite than in the martensite. Therefore, the end of
partitioning, there is a decrease in the volume fraction of the carbon partitioning from martensite to austenite
austenite, with an obvious increase in its carbon content. during the partitioning step will be reached at an earlier
stage than is the case when the carbon content is the
same in both phases. Moreover, this additional carbon
IV. DISCUSSION enrichment of the austenite is favorable for stabilizing
this phase.
A. Cooling from Intercritical Region However, an excess of epitaxial ferrite would reduce
The calculation of the amount of ferrite remaining the amount of martensite formed at the quenching
after the partial austenitization at 900 °C using MTDA- temperature to levels that could not be interesting in
TA (National Physical Laboratory, Teddington, UK) terms of the strength of the steel. Therefore, it is
leads to a volume fraction equal to 0.34. However, the important to control the formation of epitaxial ferrite
amount of ferrite found experimentally was 0.74 ± 0.05, during the quenching step, in order to ensure an
which is almost two times greater than the amount adequate volume fraction of austenite before the for-
expected from this calculation. This important discrep- mation of martensite.
ancy originates from the formation of epitaxial ferrite. The quenching temperature determines the amount of
The formation of epitaxial ferrite during the cooling martensite and austenite prior to the partitioning step.
step of the heat treatments has important implications in Since the experimental Ms temperature is known, the
the subsequent microstructure before the partitioning amount of martensite formed after quenching to tem-
step. As schematically represented in Figure 12, epi- peratures of 125 °C and 175 °C is estimated by using the
taxial ferrite formation introduces carbon gradients in Koistinen and Marburger equation.[18] Table II shows
the remaining austenite during the first cooling step, the calculated volume fractions of the phases. These
leading to more carbon enrichment close to the austenite estimations show that the volume fraction of austenite
boundaries and less carbon in areas well inside the
austenite grains. As a result, martensite formed at the Table II. Estimation of Martensite and Austenite Volume
quenching temperature will be more likely formed inside Fractions at Every Quenching Temperature
the austenite grains, leaving the austenite that is closer
to the boundaries untransformed. This morphology can Quenching Volume Fraction Volume Fraction
be observed in Figure 5(d), in which the martensite that Temperature (°C) of Martensite of Austenite
looks tempered is situated in the center of the former
125 0.20 0.06
austenite grain. This martensite is formed during the
150 0.18 0.08
first quench of the Q&P process and tempered during 175 0.16 0.10
the partitioning step, while the surrounding austenite

Fig. 12—Scheme of morphology and carbon profiles during different stages of the Q&P process. (A is austenite, IF is intercritical ferrite, EF is
epitaxial ferrite, and M is martensite.)

54—VOLUME 40A, JANUARY 2009 METALLURGICAL AND MATERIALS TRANSACTIONS A

available for further carbon partitioning is limited to martensite to austenite is in an advanced stage after
values lower than 0.10 in the case of quenching to isothermal treatment for 100 seconds, whereas the
175 °C, and lower yet for quenching at 150 °C and completion of the process, including the homogeniza-
125 °C, as a consequence of the formation of epitaxial tion of carbon in the austenite, takes place after
ferrite during cooling. 1000 seconds. Partitioning during 3 or 10 seconds is
not long enough to get considerable carbon enrichment
of the austenite and, consequently, not long enough to
B. Partitioning at 250 °C
further stabilize this phase. Therefore, the modeling
In a previous study,[19] the present authors have results can justify that the carbon content and volume
simulated the kinetics of carbon partitioning from fraction of austenite after 3 and 10 seconds of parti-
martensite to austenite based on the constrained carbon tioning are similar to those obtained on the specimen
equilibrium assumptions,[20,21] considering the alloy directly quenched; this is also true for the increase in the
studied in this work. These calculations have been used volume fraction observed after 100 seconds of parti-
here to make an interpretation of the experimental tioning. Moreover, the initial stages of the carbon
results observed for different partitioning temperatures partitioning process, from the relatively carbon-rich
and times. In particular, calculations corresponding to martensite to austenite, generate steep carbon gradients
the case of quenching at 125 °C and 175 °C and in the austenite close to the austenite/martensite inter-
partitioning at 250 °C showed that the completion of face, which can be interpreted as creating possible sites
the carbon partitioning and the homogenization of for the formation of carbides. This consideration
carbon in the austenite are reached after partitioning for explains the carbide precipitation in the martensite
approximately 105 seconds. Therefore, after partitioning observed close to the ferrite boundary in the specimen
times of 3, 10, and 100 seconds, the carbon diffusion is quenched at 125 °C and partitioned 350 °C for 10 sec-
not substantial enough to get an additional carbon onds (Figure 4(b)).
enrichment and, consequently, a volume fraction in- After 1000 seconds of partitioning, all the specimens
crease in the retained austenite, which is in agreement show a decrease in the volume fraction of austenite and
with the experimental results. Given that, experimen- a significant increase in the carbon content of the
tally, the volume fraction and carbon content of the retained austenite. The reason for this behavior is the
retained austenite is similar to those obtained in the observed decomposition of the austenite in bainite
specimen directly quenched, the carbon enrichment of (Figure 5). Bainite formation takes place through the
the austenite due to the formation of epitaxial ferrite is successive nucleation and diffusionless growth of bain-
probably the process responsible for the austenite itic ferrite plates that soon afterward partition the excess
retention in these specimens. of carbon to the surrounding austenite. The growth of
As is shown in Figure 5, carbide precipitation was each bainitic ferrite plate continues until it is stifled by
observed in specimens partitioned for 1000 seconds at the strength of the residual austenite.[22,23] Cementite
250 °C. This carbide precipitation is detrimental to the could then precipitate from the enriched austenite
microstructural characteristics of the material, because it between the bainitic ferrite plates. However, given that
reduces the amount of carbon to be partitioned to the the steel is alloyed with a considerable amount of
austenite. Carbide precipitation explains the absence of aluminum, carbide precipitation between the bainitic
carbon enrichment (and the constant volume fraction) of ferrite plates is likely to be inhibited. Therefore, the
the austenite in specimens partitioned for 1000 seconds. carbon that is rejected from the bainitic ferrite enriches
In particular, this carbide precipitation is probably the residual austenite, leading to an additional carbon
responsible for the decrease in the carbon content in enrichment of this phase that explains the obvious
the austenite in specimens quenched at 125 °C and increase in the carbon content experimentally deter-
150 °C after 1000 seconds of partitioning (Figure 11(b)). mined after partitioning for 1000 seconds. Moreover,
As has been shown in Table II, different quenching this process involves a reduction in the volume fraction
temperatures lead to slightly different amounts of of austenite, because part of the austenite transforms to
austenite available for carbon partitioning during the bainitic ferrite plates.
partitioning step. However, apart from small differences To understand the formation of bainite at this
in the carbon content of the retained austenite, which temperature, the bainite start (Bs) temperature corre-
are not significant if the error bars are taken into sponding to the residual austenite just before the
account, no significant differences have been observed martensitic transformation (taking into account the
between the resulting microstructures formed under formation of epitaxial ferrite) has been calculated using
different quenching temperatures. the procedure proposed by Bhadeshia,[24,25] which
includes the effects of C, Si, Al, and Mn. This
calculation results in Bs = 360 °C, which means that
C. Partitioning at 350 °C
a partitioning temperature of 350 °C is inside the
During partitioning at 350 °C, the volume fraction temperature range of the bainite formation and that,
and carbon content in the austenite show complex therefore, its formation would be possible during the
variations (Figures 11(c) and (d)) that are independent partitioning step, if the conditions for nucleation are
of the quenching temperature used. The calculations of favorable.
carbon partitioning kinetics at 350 °C presented in The thermodynamic method developed by Bhadeshia[26]
Reference 19 showed that carbon partitioning from for the calculation of bainite incubation times, which is

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 40A, JANUARY 2009—55

based on Russell’s method,[27] has been used for the formation of epitaxial ferrite takes place in a higher
estimation of the incubation times for bainite at 250 °C temperature range, which leads to a higher presence of
and 350 °C, considering the chemical composition of the this phase and a significant effect on the final micro-
austenite just before the martensitic transformation. structure.
Following this method, the incubation time for the
formation of bainite is given by
tðDGm Þp Q0 V. CONCLUSIONS
ln ¼ þC ½4
Tz RT The Q&P process has been studied in a low-carbon
steel containing 1.1 wt pct aluminum. The main results
where t is the incubation time; T is the temperature; R is are presented in the following points.
the gas constant; DGm is the available driving force for
nucleation, calculated as a function of the activity of 1. Epitaxial ferrite forms during the first cooling of
carbon in ferrite and austenite; and C, p, and z are the specimens, at a cooling rate of 100 °C/s. The
constants. Appropriated values for C, p, and z can be epitaxial ferrite introduces carbon-content gradients
found in Reference 26. According to this calculation, the in the remaining austenite before the formation of
incubation time for bainite at 250 °C is 1330 seconds, martensite, leading to higher carbon content in the
which explains the absence of bainite in the specimens areas closer to the borders of the austenite grains.
partitioned at this temperature (250 °C is a temperature Therefore, martensite is formed within the grain
below Ms, but bainite has been shown to form isother- during the quenching step, leaving untransformed
mally at temperatures below Ms[28]). On the other hand, the austenite closer to the grain boundaries.
the calculated incubation time for bainite at 350 °C is 2. It is experimentally observed that partitioning at
only 20 seconds. This nucleation time reasonably agrees 250 °C does not lead to an efficient carbon enrich-
with the observation of a significant nucleation and ment of the austenite. This might be due to the slow
growth of bainite in the specimen partitioned for partitioning kinetics and to the possibility of the
1000 seconds; this is in comparison with the specimen formation of carbides.
partitioned for 100 seconds, in which bainite was not 3. The occurrence of carbide precipitation during the
observed. partitioning step at 350 °C starts to be observed on
During partitioning at 350 °C, the overall microstruc- samples isothermally treated for 10 seconds, but the
ture evolution has been similar for every quenching kinetics of carbon partitioning is a dominant pro-
temperature used, as is observed for partitioning at cess at 100 seconds of partitioning time, leading to
250 °C. Therefore, this indicates that, although the a considerable increase in the austenite volume frac-
austenite available for the partitioning step is slightly tion, to levels of approximately 0.08.
different for every quenching temperature, variations of 4. At 1000 seconds of partitioning at 350 °C, the
approximately 50 °C in the quenching temperature do decomposition of the austenite to upper bainite
not significantly affect the final microstructure. leads not only to an obvious increase in the carbon
content of the austenite but also to a decrease in
the volume fraction, to values approximately 0.03.
D. Additional Comments 5. The microstructure evolution during the partition-
The application of Q&P heat treatments with partial ing step has been observed to be independent of the
austenitization has led to a microstructure formed by a quenching temperature used, indicating that,
large amount of ferrite (0.74), which limits the effective- although the austenite available for the partitioning
ness of this process in producing a novel microstructure. step is slightly different for every quenching temper-
The microstructures after these heat treatments have ature, variations of approximately 50 °C in the
also shown martensite, retained austenite, and, in some quenching temperature do not significantly affect
cases, bainite. Carbide precipitation has been observed the final microstructure in the cases analyzed in this
after partitioning for 1000 seconds at 250 °C and for study.
10 seconds at 350 °C. In general, the degree to which
these processes overlap with the carbon partitioning
from the martensite to the austenite, the key to the Q&P ACKNOWLEDGMENTS
process, is considerable.
For the reasons stated earlier, the application of The authors thank Dr. Carlos Garcı́a de Andrés for
Q&P heat treatments to typical TRIP chemistries seems providing the dilatometry facilities at the National
difficult, because these chemical compositions are Centre for Metallurgical Research (CENIM-CSIC) in
optimized for the promotion of bainite formation. This Madrid, Spain, and acknowledge Mr. Orlando Garcia-
bainite, in TRIP steels, is formed by an isothermal Leon and Dr. Roumen Petrov for their assistance and
treatment at a relatively high temperature; it is under- for the provision of the EBSD facilities at the Univer-
standable, then, that the formation of epitaxial ferrite sity of Ghent, Belgium. The authors also thank
does not overly affect the resulting microstructure. Drs. Dave Hanlon and Theo Kop (Corus RD&T,
However, in the case of the Q&P process, the material IJmuiden, The Netherlands) for fruitful discussions,
is first cooled to a temperature below the martens- and acknowledge the support Corus RD&T provided
itic start temperature. Therefore, in this case, the for this project.

56—VOLUME 40A, JANUARY 2009 METALLURGICAL AND MATERIALS TRANSACTIONS A

 OPEN ACCESS 11. F.C. Schwerer, C.E. Spangler, and J.F. Delly, Jr.: Acta Metall.,
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This article is distributed under the terms of the 12. B.D. Cullity: Elements of X-Ray Diffraction, Addison-Wesley,
Creative Commons Attribution Noncommercial Li- Reading, MA, 1978, pp. 359–67.
13. N.H. van Dijk, A.M. Butt, L. Zhao, J. Sietsma, S.E. Offerman,
cense which permits any noncommercial use, distribu- J.P. Wright, and S. van der Zwaag: Acta Mater., 2005, vol. 53, pp.
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original author(s) and source are credited. 14. M.J. Santofimia, L. Zhao, R. Petrov, and J. Sietsma: Mater.
Charact., 2008, doi:10.1016/j.matchar.2008.04.004.
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1. J.G. Speer, A.M. Streicher, D.K. Matlock, F.C. Rizzo, and G. 17. G. Ghosh and G.B. Olson: Metall. Mater. Trans. A, 2001, vol.
Krauss: in Austenite Formation and Decomposition, E.B. Damm and 32A, pp. 455–66.
M. Merwin, eds., TMS/ISS, Warrendale, PA, 2003, pp. 505–22. 18. D.P. Koistinen and R.E. Marburger: Acta Metall., 1959, vol. 7,
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Res., 2005, vol. 8, pp. 417–23. 19. M.J. Santofimia, L. Zhao, and J. Sietsma: Proc. 2nd Int. Conf.
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Opin. Solid State Mater. Sci., 2004, vol. 8, pp. 219–37. ing, Graz, Austria, Andreas Ludwig, ed., ASMET, The Austrian
4. D.V. Edmonds, K. He, F.C. Rizzo, A.M.S. Clarke, D.K. Matlock, Society for Metallurgy and Materials, 2007, pp. 368–73.
and J.G. Speer: 1st Int. Conf. Super High Strength Steels, Asso- 20. J.G. Speer, D.K. Matlock, B.C. De Cooman, and J.G. Schroth:
ciazione Italiana Di Metallurgica, Rome, Italy, 2005, pp. 1–20. Acta Mater., 2003, vol. 51, pp. 2611–22.
5. D.K. Matlock, V.E. Bräutigam, and J.G. Speer: Mater. Sci. 21. J.G. Speer, D.K. Matlock, B.C. De Cooman, and J.G. Schroth:
Forum, 2003, vols. 426–432, pp. 1089–94. Scripta Mater., 2005, vol. 52, pp. 83–85.
6. D.V. Edmonds, K. He, M.K. Miller, F.C. Rizzo, A. Clarke, D.K. 22. H.K.D.H. Bhadeshia and J.W. Christian: Metall. Trans. A, 1990,
Matlock, and J.G. Speer: Mater. Sci. Forum, 2007, vols. 539–543, vol. 21A, pp. 767–97.
pp. 4819–25. 23. S.B. Singh and H.K.D.H. Bhadeshia: Mater. Sci. Eng., 1996, vol.
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2003, pp. 27–30. 24. H.K.D.H. Bhadeshia: Met. Sci., 1981, vol. 15, pp. 178–80.
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Amsterdam, 1983, pp. 2558–60. 27. K.C. Russell: Acta Metall., 1969, vol. 17, pp. 1123–31.
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Materials Research, Vol. 8, No. 4, 417-423, 2005 © 2005

The “Quenching and Partitioning” Process: Background and Recent Progress

John G. Speera, Fernando C. Rizzo Assunçãob*, David K. Matlocka, David V. Edmondsc

Advanced Steel Processing and Products Research Center,

a

Colorado School of Mines, Golden, CO 80401, USA

b
Department of Materials Science and Metallurgy,
Pontifícia Universidad Católica, 22453-900 Rio de Janeiro - RJ, Brazil
c
School of Process, Environmental and Materials Engineering, University of Leeds,
Leeds LS2 9JT, United Kingdom

Received: July 19, 2004; Revised: April 8, 2005

A new process concept, “quenching and partitioning” (Q&P) has been proposed recently for creating
steel microstructures with retained austenite. The process involves quenching austenite below the martensite-
start temperature, followed by a partitioning treatment to enrich the remaining austenite with carbon, thereby
stabilizing it to room temperature. The process concept is reviewed here, along with the thermodynamic basis
for the partitioning treatment, and a model for designing some of the relevant processing temperatures. These
concepts are applied to silicon-containing steels that are currently being examined for low-carbon TRIP sheet
steel applications, and medium-carbon bar steel applications, along with a silicon-containing ductile cast iron.
Highlights of recent experimental studies on these materials are also presented, that indicate unique and attractive
microstructure/property combinations may be obtained via Q&P. This work is being carried out through a
collaborative arrangement sponsored by the NSF in the USA, CNPq in Brazil, and the EPSRC in the United
Kingdom.

Keywords: carbon partitioning, retained austenite, martensite

1. Introduction 2. Background and Q&P Fundamentals

High strength ferrous alloys containing significant fractions of 2.1. Carbon partitioning concept
retained austenite have been developed in recent years, and have
important commercial applications. In sheet steels, for example, Carbon partitioning between martensite and retained austenite
carbon-enriched metastable retained austenite is considered beneficial is usually ignored in quenched steels, because the temperature is
because the TRIP phenomenon during deformation can contribute normally too low for substantial amounts of carbon diffusion to occur
to formability and energy absorption. In gear and bearing surfaces, after quenching, and because carbon supersaturation in martensite is
austenite is considered to provide damage tolerance in rolling/sliding ordinarily eliminated by a different mechanism, viz. carbide precipita-
contact fatigue applications. In thicker section structural applica- tion during tempering. Consequently, while carbon-enriched retained
tions, retained austenite may provide enhanced resistance to fracture. austenite has been identified in martensitic steels for some time2,
Similarly, austempered ductile cast iron materials develop favorable the thermodynamics of carbon partitioning between martensite and
property combinations through a microstructure of fine ferrite plates retained austenite has been scarcely considered. Recently, a model
in combination with carbon-rich retained austenite. has been developed to address carbon partitioning from as-quenched
Steels with substantial amounts of carbon-enriched retained martensite into austenite, under conditions where competing reac-
austenite are typically produced by transforming at low tempera- tions such as bainite, cementite or transition carbide precipitation are
tures, leading to a microstructure containing “carbide-free bainite” suppressed1. The model predicts the “endpoint” of partitioning, when
that consists of bainitic ferrite laths with interlath retained austenite. martensite (i.e. ferrite) is in metastable equilibrium with austenite.
Alloying additions such as Si or Al are made to suppress cementite Metastable equilibrium between austenite and ferrite is not a new
precipitation that usually accompanies bainite formation. Recently, concept3, and equilibrium (e.g. orthoequilibrium) and paraequilibrium
an alternative processing concept, “quenching and partitioning (or concepts are well understood at sub-critical temperatures for condi-
Q&P), has been developed for the production of austenite-contain- tions where partitioning of slow-moving substitutional elements is ei-
ing steels, based on a new understanding of carbon partitioning ther complete or absent, respectively. It must be recognized, however,
hypothesized between martensite and retained austenite1. This paper that transformations occurring under equilibrium or paraequilibrium
reviews the fundamental elements of the process concept, and recent necessarily involve interface migration and thus require short range
experimental investigations to examine the Q&P processing response movements of iron and substitutional atoms, even when long-range
of two commercial Si-containing steels and a commercial Si-contain- substitutional diffusion is precluded as in the paraequilibrium case.
ing ductile cast iron. When the position of the martensite/austenite interface is effectively
*e-mail: [email protected]
418 Speer et al. Materials Research

a
constrained, as we consider to apply for carbon partitioning between f CPE xCaCPE + f CPE
g
xCgCPE = xCalloy (3)
martensite and retained austenite at relatively low temperatures, then
and the relationship between the phase fractions of α and γ is sim-
even short-range diffusional movements of iron and substitutionals
ply:
are precluded, and it is not possible for a ferrite/austenite mixture
to reach equilibrium in the Fe-C system (or paraequilibrium in a
f CPE g
+ f CPE =1 (4)
multicomponent alloy systems). The metastable α/γ equilibrium in
Example CPE calculations have been reported previously , where 1
the case of an immobile or constrained interface, is therefore termed
it was shown that most of the carbon in the steel is expected to parti-
“constrained paraequilibrium” or CPE. Paraequilibrium and CPE
tion to the austenite, and quite high levels of carbon enrichment are
derive fundamentally from the immobility of iron and substitutionals
possible. The dependence of the metastable CPE condition on alloy
in comparison to carbon and other interstitials. Consequently, these
carbon content, temperature, and the as-quenched austenite and
two conditions are considered by the authors to be closely related,
martensite phase fractions was also illustrated. While the detailed
although this view is not held universally4 and remains the subject
calculations are not difficult, it was found that the austenite composi-
of discussion5.
tion at constrained paraequilibrium can be closely approximated by
Constrained paraequilibrium is essentially defined by one thermo-
assuming that virtually all of the carbon in the martensite partitions to
dynamic requirement, and one key matter balance constraint. First,
the austenite, and then applying the appropriate carbon matter balance
carbon diffusion is completed under constrained paraequilibrium
based on the amount of retained austenite present after quenching9.
conditions when the chemical potential of carbon is equal in the fer-
The results of the constrained paraequilibrium model suggested a
rite and austenite. Ignoring effects of alloying on carbon activity, this
new process, whereby austenite is formed at high temperature (either
requirement may be represented using results of Lobo and Geiger6,7
by full austenitization or intercritical heat treatment), followed by
for the Fe-C binary system as follows:
cooling to a temperature carefully selected (between Ms and Mf) to
76, 789 - 43.8T - (169, 105 - 120.4T) xCc (1) control the fractions of martensite and retained austenite, and finally
xCc = xCa $ e
RT by a thermal treatment that accomplishes the desired carbon partition-
a g
where x and x represent the mole fractions of carbon in ferrite and
C C ing to enrich the austenite with carbon and stabilize some (or all) of
austenite. The relevant thermodynamics are embedded in Equation 1. it to room temperature. This process sequence and the corresponding
This thermodynamic condition may be understood by comparing microstructural changes are illustrated schematically in Figure 2 10.
the schematic Gibbs molar free energy vs. composition diagram in The process assumes that carbon supersaturation is relieved by dif-
Figure 1a representing metastable equilibrium in the Fe-C system, fusion into retained austenite, and is referred to as quenching and
with constrained paraequilibrium in Figure 1b.
In (ortho) equilibrium, or paraequilibrium in higher order alloys,
a g
there are unique ferrite and austenite compositions (xEQ and xEQ )
satisfying the common tangent construction whereby the chemical
potentials of both carbon and iron are equal in both phases (mCa = mCg
and mFE
a
= mFE
g
). (In paraequilibrium, the same construction would apply G
if the vertical axis at the composition of pure iron were replaced by
the appropriate composition in multicomponent space representing ' A MA#  MG#
the relative fractions of iron and substitutional elements in the alloy).
In constrained paraequilibrium, the thermodynamic condition that
the chemical potential of carbon is equal in both phases requires MA&E  MG&E
only that the tangents to the ferrite and austenite free energy curves
must intersect the carbon axis at a single point. This condition can
be satisfied by an infinite set of phase compositions8, and examples XA%1 XG%1
of two such conditions are given in Figure 1b, one which is associ- &E #
ated with phase compositions (xCaP-EII and xCgP-EII) having a higher carbon (a)
concentration than the equilibrium phase compositions, and one as-
sociated with phase compostions (xCaP-EI and xCgP-EI ) having lower carbon
levels than equilibrium. The actual CPE phase compositions must
also satisfy the unique matter balance constraint associated with
the stationary α/γ interface. This second constraint requires that the G
number of iron (and substitutional) atoms is conserved in each phase
M#A ))  M#G ))
during carbon partitioning. Mathematically, this matter balance for '
iron may be represented by: A
g
f CPE (1 – xCgCPE ) = f ig (1 – xCalloy) (2)
where x is the overall carbon content of the steel (in atom fraction,
alloy
C
recognizing also that in Fe-C binary alloys, 1 – xC = xFE ), f ig is the M#A )  M#G )
g
mole fraction of retained austenite before partitioning begins, and f CPE
and xCgCPE represent the austenite amount and carbon concentration, X#A0%) X#A0%)) X#G 0%
) X#G 0%
))
&E #
respectively, at constrained paraequilibrium when carbon partition-
ing is complete. (A small change in austenite fraction is consistent (b)
with transfer of carbon atoms across the interface). Constrained Figure 1. Schematic molar Gibbs free energy vs. composition diagrams il-
paraequilibrium is achieved when Equations 1-2 above, and Equa- lustrating metastable equilibrium at a particular temperature between ferrite
tions 3-4 below are satisfied, where the mass balance for carbon is and austenite in the Fe-C binary system. a) equilibrium (EQ), and b) two
represented by: possible constrained paraequilibrium conditions (I and II).
Vol. 8, No 4, 2005 The “Quenching and Partitioning” Process: Background and Recent Progress 419

partitioning, or Q&P, to distinguish it mechanistically from conven- are usually not considered detrimental, whereas cementite can be of
tional quenching and tempering (Q&T) of martensite, where carbide more concern. Thus, the greater emphasis has been on understanding
precipitation and decomposition of retained austenite (to ferrite plus when transition carbides are replaced by cementite formation16,17, rath-
cementite) are typical. The example in Figure 2 indicates an initial er than on the initiation of transition carbide precipitation. For Q&P
full austenitization step, although intercritical annealing is also en- processing, however, any transition carbide precipitation diminishes
visioned for formable sheet products containing an equiaxed ferrite the potential for carbon enrichment of austenite, and it is necessary
component in the microstructure. During intercritical annealing, a to develop a better understanding of the onset of transition carbide
smaller initial fraction of austenite would be present with a higher formation, including composition and processing effects9,18.
initial carbon content. Precipitation of transition carbides within retained austenite
The quenching and partitioning heat treatment was envisioned during martensite tempering has not been documented. Since the
to have application to high-strength austenite containing TRIP sheet chemical potential of carbon is much higher in as-quenched martensite
steel products, replacing an isothermal bainitic heat treatment of than in the retained austenite, it is reasonable to conclude that carbide
low-carbon steels containing substantial additions of Si, Al, or P to nucleation would be more likely in bcc ferrite than in austenite9,19.
suppress carbide formation. Some suggested advantages of Q&P The α/γ interface is also a favored site for carbide formation. In the
include the potential for greater carbon enrichment of austenite, Q&P process, high carbon supersaturation of the martensite prior
decoupling of the (bainitic) ferrite growth kinetics from the carbon to partitioning could conceivably drive transition carbide formation
partitioning process, and increasing strength via formation of sub- to a greater extent than would be possible during bainite growth at
stantial quantities of lath martensite in the microstructure. Other the same temperature if bainitic ferrite grows with a much lower
opportunities were identified to employ retained austenite through carbon content than the austenite. (In this context, it should be noted
Q&P processing of higher strength bar steels or even austempered that the carbon supersaturation of bainitic ferrite during growth
ductile cast iron. Finally, it was suggested that a specific CPE phase remains a subject of controversy). In any event, the extent to which
composition (where the austenite composition approximates To) carbide formation is suppressed will be a critical factor influencing
might even represent a viable steady state boundary condition at the the microstructures that are achievable using the Q&P process, and
α/γ interface during bainitic ferrite growth, providing a model for further studies are needed to establish more clearly the influences of
the bainite transformation mechanism that is both “fully” diffusional alloying and processing on the carbide precipitation behavior and
and “fully” martensitic1. kinetics in these steels.
2.2. Importance of suppressing carbide precipitation 2.3. Process design (selection of quenching temperature)
The absence of carbide formation is a fundamental element A methodology for designing the quench temperature to achieve
of the constrained paraequilibrium model, since the existence of the maximum possible retained austenite fraction after Q&P process-
metastable equilibrium between ferrite and austenite is precluded if ing, was developed in a recent publication9. The model ignores
the more stable ferrite plus iron carbide equilibrium can be achieved. partitioning kinetics, and assumes that all of the carbon partitions
Any carbide formation effectively “consumes” carbon, since these from martensite to austenite, and that carbide precipitation is avoided
carbon atoms are no longer available to enrich the austenite. Thus, completely. The model results are shown in Figure 3, for a 0.19%C,
it is necessary to understand and control carbide precipitation proc-
esses that may occur during any partitioning treatments associated 
with the Q&P process.
It is well known that cementite formation can be eliminated or -INITIAL QUENCH
suppressed through additions of silicon11,12, and also that aluminum GINITIAL QUENCH
and even phosphorus can produce a similar effect13. Such elements 
thus play a critical enabling role in the Q&P process. It is also well
known in the martensite tempering literature that silicon suppresses
cementite formation, or delays the transition from early-stage tem- 
0HASE &RACTION

pering (where ε or η carbides are present), to later-stage tempering

(where θ-Fe3C is present)14-16. In martensite, fine transition carbides
-FINAL QUENCH

#G  #I #G  #I #G  #I
G
#M  #I #M  #I
G 
G
G
!C G GFINAL
G
G
4EMPERATURE

G 
G
    
-3 04 1UENCH 4EMPERATURE —#
14 G
G Figure 3. Predicted Q&P microstructure components for experimental steel
-& containing 50% intercritical ferrite, vs. quench temperature, assuming full
4IME G partitioning prior to final quenching to room temperature. The final austenite
fraction at room temperature is given by the solid bold line. Dashed lines
Figure 2. Schematic illustration of the Q&P process for producing of austen- represent the austenite and martensite (M) present at the initial quench
ite-containing microstructures. Ci, Cγ, Cm represent the carbon concentrations temperature, and the additional martensite formed during the final quench to
in the initial alloy, austenite, and martensite, respectively. QT and PT are the room temperature. For this example, Minitial quench+ Mfinal quench+ γfinal = 0.5, and
quenching and partitioning temperatures10. the intercritical ferrite fraction is 0.5.
420 Speer et al. Materials Research

1.96%Al, 1.46%Mn, 0.02%Si (by weight) TRIP sheet steel composi- ranging between 150 and 210 °C, and equilibrated for 120 seconds
tion, assuming that intercritical annealing was conducted to achieve before partitioning at temperatures between 250 and 500 °C in mol-
a microstructure containing 50% austenite and 50% ferrite prior to ten salt for times ranging between 10 and 3600 seconds, and finally,
quenching. In this figure, the final austenite fraction after partitioning quenched to room temperature. The quenching temperatures were
and cooling to room temperature is plotted (bold solid line) vs. the designed using the methodology described above.
quenching temperature prior to partitioning. The austenite and mar- The results showed that substantial levels of retained austenite
tensite fractions at the quench temperature are also plotted, along with could be achieved by Q&P processing of the 9260 alloy, approaching
the fraction of “fresh” martensite that forms during final cooling. 30% by volume. The relationship between the amount of retained
The model first estimates the fractions of austenite and martensite austenite and the quench temperature is reproduced here in Figure 4,
at the quench temperature (QT in Figure 1) based on the undercool- for conditions involving a 10 seconds partitioning treatment at
ing below Ms, according, for example, to the Koistinen-Marburger14 500 °C. The figure shows that the amount of austenite measured by
relationship: X-ray diffraction was in qualitative agreement with model calcula-
tions, although the measured austenite fractions were lower than the
fm = 1 – e – 1.1x10-2(Ms – QT) (5)
maximum amounts predicted.
where fm is the fraction of austenite that transforms to martensite Partitioning at lower temperature (250 °C) led to partition-
upon quenching to a temperature QT below the Ms temperature, and ing treatment times that would be more appropriate for industrial
Ms for the applicable austenite composition can be estimated from processing of bulk specimens (e.g. 45 to 60 minutes), whereas much
published correlations. (For processing where intercritical annealing shorter times were associated with the maximum austenite fractions
is conducted rather than full austenitization, the initial carbon con- at higher temperature (e.g. 10 seconds at 400 °C). Some encouraging
centration of the austenite is controlled by the intercritical annealing property results were noted in this study, such as hardness levels in
temperature, and may be estimated by assuming that nearly all of excess of HRC58 in combination with austenite fractions approaching
the carbon in the steel is contained in the austenite, since the carbon 10%. In contrast, substantial austenite levels were not achievable by
solubility in ferrite is very low). After completion of (full) partition- conventional quenching and tempering, and lower hardnesses were
ing between martensite and austenite subsequent to quenching, the associated with bainitic processing (austempering). The combination
carbon concentration in the remaining austenite may be estimated, of high hardness along with a significant retained austenite fraction is
and the final phase fractions may be predicted after final cooling, considered to be of possible interest for gear or bearing applications,
again applying the Koistinen and Marburger relationship to the where “damage tolerance” under pitting or contact fatigue conditions
carbon-enriched austenite. is enhanced by austenite that is present in the microstructure21.
The model results indicate an “optimum” quenching temperature Microstructure characterization is currently underway, and
that yields a maximum amount of retained austenite. Above the peak Figure 5 shows an example resulting from quenching to 190 °C,
temperature, substantial austenite fractions remain after the initial and holding in the bath for 120 seconds. Transmission electron
quenching step, but the austenite stability is too low during final microscopy (TEM) shows the martensite substructure in bright field
quenching, and increasing amounts of fresh (Mfinal quench) martensite (Figure 5a), along with finely dispersed retained austenite in dark
are found at higher quench temperatures, reducing the final austenite field (light regions in Figure 5b). This heat-treatment condition is
fraction at room temperature. Below the peak temperature too much associated with much more retained austenite (> 6%) than is obtained
austenite is consumed during the initial quench prior to carbon par- by quenching directly to room temperature (< 2%), illustrating that
titioning, and the carbon content of the retained austenite is greater partitioning has already begun during the 120 seconds equilibration
than needed for stabilization at room temperature. The peak is found at the quench temperature (190 °C)20.
at the particular quench temperature where martensite formation is
just precluded during the final quench, whereby the austenite has 
an Ms temperature of room temperature after full partitioning. This
methodology provides guidance for experimental processing design, #ALCULATED -AXIMUN
and allows the effects of changes in a variety of processing variables OF 2ETAINED !USTENITE
to be explored and predicted. Partitioning kinetics are not predicted in 
this simple model, however, and development of a more sophisticated
!USTENITE 6OLUME &RACTION

model will require further understanding of the length-scale of the

microstructure over which partitioning occurs, and the kinetics of
carbide precipitation processes that may occur. 

3. Highlights of Recent Progress 0ARTITIONING 4EMPERATURE  —#

(OLDING 4IME  SECONDS
3.1. Medium-carbon bar steels 
Initial investigation of the Q&P processing concept verified the
presence of significant amounts of carbon enriched austenite in a
0.35%C, 1.3%Mn, 0.74%Si (wt. pct.) microalloyed bar steel, despite

the apparent formation of some transition carbides during the parti-
tioning treatment10. More recently, the Q&P processing response of
a 0.6%C, 2%Si (grade 9260) steel was examined by Gerdemann, and     
compared to the results of conventional austempering or quenching 1UENCH 4EMPERATURE —#
(to room temperature) and tempering20. Wafers (28.5 mm in diameter Figure 4. Final volume fraction of retained austenite depending on the quench
by 2.5 mm thick) were austenitized in molten salt for 15 minutes at temperature at a partitioning temperature of 500 °C, and calculated austenite
900 °C, quenched into a molten tin-bismuth bath at temperatures volume fraction over this quench temperature range20.
Vol. 8, No 4, 2005 The “Quenching and Partitioning” Process: Background and Recent Progress 421

3.2. TRIP sheet steels conducted using a 0.19%C, 1.63%Si, 1.59%Mn TRIP sheet steel18.
Transformation response and mechanical behavior are both being
High strength sheet steels containing significant fractions of assessed, and initial results have been very encouraging. Variations
retained austenite have been developed in recent years, and are the in quenching temperature were examined, along with selected vari-
subject of growing commercial interest23,24. Carbon-enriched meta­ ations in partitioning time and temperature, using either “1-step” or
stable retained austenite is considered beneficial because the TRIP “2-step” Q&P processing. In 1-step processing, partitioning is carried
phenomenon during deformation can contribute to formability and out at the quenching temperature, while 2-step processing involves
energy absorbtion. These steels are typically produced by intercritical reheating to a selected partitioning temperature that differs from the
annealing followed by austempering, with additions of Si, Al, or P quench temperature.
to suppress carbide formation that usually accompanies the bainite New microstructures that extend the strength levels of current
transformation. Initial studies on the Q&P processing response9 TRIP steels resulted from Q&P processing, as shown in the results of
of TRIP sheet steel showed that substantial amounts of austenite Figure 6, comparing the measured strength and formability (ductility)
could be obtained via Q&P processing, with measured retained combinations with current “state-of-the-art” sheet grades including
austenite fractions similar to the predicted maximum of 15% in this dual-phase (ferrite-martensite), austempered TRIP (bainite), and
0.19%C, 1.96%Al, 1.46%Mn steel. Because of concerns related to martensitic steels. (The data used in this figure are discussed further in
uncertainty in the effects of aluminum on the Ms temperature, and reference18.) Much additional opportunity remains to explore available
overlapping of the carbon partitioning and bainite transformation property combinations, and optimize retained austenite fractions and
mechanisms owing to accelerated austenite decomposition kinetics austenite stability, as well as to understand the operative fundamental
associated with aluminum additions, more recent studies have been mechanisms and explore industrial processing capabilities. Scanning
electron microscopy, as illustrated in the example of Figure 7, shows
the presence of intercritical ferrite (dark featureless areas), along with
a mixture of martensite and fine retained austenite. The fine sub-
structure in the Q&P heat treated condition is apparently responsible
for the elevated strength levels and distinguishes the resulting Q&P
microstructure from bainite produced by conventional austempering
at the same temperature as partitioning is accomplished in Q&P18.
3.3. Austempered ductile cast iron
Austempered ductile iron (ADI) contains substantial levels of
silicon, and is usually processed by heating into the austenite-plus-
graphite phase field, followed by austempering at a lower temperature
to transform the austenite to “ausferrite,” which is essentially bainitic
ferrite with carbon-enriched retained austenite. This microstructure
provides ADI with high strength in combination with ductility and
toughness that is sufficient for many applications. Because of the
high-silicon levels and the importance of retained austenite, Q&P was
considered to offer a potential heat treating alternative for ADI, and a
team of 4th year undergraduate students at Colorado School of Mines
(a)

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(b)    
Figure 5. TEM bright field (a) and (002)γ dark field (b) images showing 5LTIMATE 4ENSILE 3TRENGTH -0A
martensite and retained austenite in 9260 alloy quenched to 190 °C and Figure 6. Total elongation vs. ultimate tensile strength for TRIP, Dual phase
equilibrated for 120 seconds before final cooling to room temperature22. (DP), martensitic (M), and Q&P sheet steel products18.
422 Speer et al. Materials Research

using high-resolution TEM techniques. Initial results have already

confirmed the presence of ε-carbide in the 9260 bar steel after quench-
ing to 150 °C and partitioning for 3600 seconds at 250 °C22. Clearly,
substantial work remains to understand the fundamental transforma-
tion characteristics of these alloys during Q&P processing, and to
optimize the chemical compositions, microstructures and properties,
although the results to date are of great encouragement.

Acknowledgments
The authors acknowledge the support of the Advanced Steel
Processing and Products Research Center, a National Science
Foundation Industry/University Cooperative Research Center at
the Colorado School of Mines, and the Inter-American Materials
Collaboration Program. Funding is acknowledged from NSF award
0303510 (USA), CNPq (Brazil), and EPSRC (United Kingdom).
POSCO, Ispat-Inland Steel Company, MACSTEEL, North Star Steel,
Applied Process, Inc., and Farrar Corporation are acknowledged for
Figure 7. Microstructure of Si-TRIP sheet steel containing 8.4% austenite, providing experimental materials.
processed by intercritical annealing (75% γ + 25% α) followed by quenching
to 200 °C and partitioning at 400 °C for 10 seconds. Etched in 2% nital.
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has recently examined the response of a commercial 3.7%C, 2.5%Si, tioning into austenite after martensite transformation. Acta Materialia.
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