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Metallurgy and processing of ultralow carbon bake

hardening steels

L. J. Baker, S. R. Daniel & J. D. Parker

To cite this article: L. J. Baker, S. R. Daniel & J. D. Parker (2002) Metallurgy and processing of
ultralow carbon bake hardening steels, Materials Science and Technology, 18:4, 355-368, DOI:
10.1179/026708302225002452

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Literature review
Metallurgy and processing of ultralow
carbon bake hardening steels
L. J. Baker, S. R. Daniel, and J. D. Parker

The development of bake hardening steels is reviewed. Classical strain aging theories still have relevance to modern
ultralow carbon chemistries, although the drastically reduced carbon contents of these steels can in uence the
kinetics observed during bake hardening. High solute carbon levels increase the bake hardening response but reduce
room temperature aging resistance, hence excess carbon levels are kept within the range 15 25 ppm. The strength
increase appears to be enhanced by a ne ferrite grain size; the published evidence is contradictory and further
research is considered necessary. Bake hardening steels can be produced from interstitial free chemistries either by
adjusting the chemistry during steelmaking to leave carbon in solution, or by annealing at high temperature to take
carbides formed during processing into solid solution. Care must be taken during coiling, annealing, and temper
rolling to ensure that suitable amounts of carbon remain in solution to produce a bake hardening product. Further
research into the in uence of processing conditions on the metallurgy of these steels is required if they are to be
successfully produced in industrial conditions. MST/5160

Dr Baker (laura.baker@corusgroup.com) was in the Engineering Doctorate Centre in Steel Technology, University of Wales
Swansea; she is now with Corus Strip UK, PO Box 10, Newport NP19 4XN, UK. Dr Daniel is with Corus Technical
Department, Llanwern Works, West Glamorgan, UK and Professor Parker is in the Department of Materials Engineering,
University of Wales Swansea, Swansea SA2 8PP, UK.
# 2002 IoM Communications Ltd.

Introduction
The threat of future legislation regarding fuel consumption
and emissions has forced the automotive industry to
develop lighter, more fuel ef cient vehicles. At the same
time, competition in the market place demands that each car
offer more than its competitor. Accessories such as air bags,
impact protection, electric windows, and air condition-
ing add considerable weight to the car and this must be
balanced by a reduction in weight of the `body in white if
fuel ef ciency is to be maintained. This weight reduction is
being achieved through close collaboration between the
automotive sector and the major steel manufacturers, with
the development of, among other measures, higher strength
steels. The superior strength of these steels allows them to be
used in thinner gauges than existing steel products, reducing
the weight of the vehicle while retaining the rigidity of the
nished component.
The development of new and existing steels is a continual
process, as better solutions are sought to the problem of
weight saving. Target properties to be met by automotive
steels in 2005, derived from an ILZRO survey,1 are given in
Table 1. Typically, thinner, stronger products are desired,
but there is often a trade-off between strength and forma-
bility, a problem that can be solved to some extent by the
use of bake hardening steels.
Bake hardening utilises the phenomenon of stain aging
to provide an increase in the yield strength of formed
components. In automotive body applications, this strength
increment is developed during the relatively low tem-
perature (150 200 C) nishing treatment required to bake
the paint coatings, during which interstitial solute atoms
migrate to the dislocations produced during pressing. Since
it requires no additional process steps, bake hardening does
not signi cantly affect production costs, and can also allow
a greater nal strength level to be achieved in higher
formability grades.
The tensile properties of bake hardening steels are
compared with those of other grades in Fig. 1 (Ref. 2),
which also indicates the direction in which properties must
develop to meet the demands of the automotive sector. Bake
hardening steels initially have a low proof stress and good
formability, making them suitable for the more complex
forming operations encountered during fabrication of outer
body parts. During forming and paint baking, the steel will
age signi cantly, resulting in the return of discontinuous
yielding accompanied by an increase in the yield strength.
Figure 2 (Ref. 3) illustrates how this strength increase com-
pares with that achieved with a formable IF steel and a high
strength rephosphorised steel. It can be seen that the use of
bake hardening steel can result in both good shape xability
and improved dent resistance in the nal component.
Since the strength increase occurs after the component
has been formed, thinner material can be used for compo-
nents such as fenders, bonnets, boot lids, and door outers,4
resulting in a weight saving of ~ 7 kg per car. Components
such as boot lids and bonnets that experience relatively
small deformations during forming bene t particularly
from the use of a bake hardening steel, as the relatively
small strength increase produced by work hardening can be
improved with a larger bake hardening increase. Resistance
to small dents caused by stones and other debris is also of
importance, with parts such as bonnets and outer door skins
being the most susceptible. Bake hardening steels can offer
superior dent resistance to both static and dynamic denting,
compared with other steel grades, because of their increased
strength after baking.5
Corrosion resistance is another important consideration
in the design of modern motor vehicles. Antiperforation

This review is a revised version of the runner-up in the 2001 MST Literature Review Prize
competition, set up to encourage the preparation of critical literature reviews by students
studying for higher degrees in the UK, and subsequently to make the best of these available to
a wider readership.

DOI 10.1179/026708302225002452 Materials Science and Technology April 2002 Vol. 18 355
356 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels

1 Elongation tensile strength relationships for various

2 Schematic illustration of bake hardening concept in
types of sheet steel2
fabrication of automotive body parts3

warranties of up to 12 years are now common and 60 80%

of the steel in an average car body will be coated to meet
these requirements.6 Table 2 summarises the coatings most
suited to particular automotive applications.7 High tem-
perature components such as exhaust systems will typically
have an aluminium type coating, whereas exposed panels
will tend to utilise the corrosion resistance of zinc. Hot
dipping treatments such as galvannealing and galvanising
are increasing in popularity over traditional electrolytic
coatings in exposed applications, owing to their lower
production costs. According to information from AISI,8 net
shipments of galvanised and galvannealed coated sheet steel
from US steel companies increased from ~ 6.5 Mt in 1991
to ~ 11 .8 Mt in 1998; during the same period, equivalent
gures were ~ 2 .0 to ~ 3. 3 Mt for electrolytic zinc coated
sheet and ~ 1.0 to ~ 1.6 Mt for other metallic coated sheet
(Zn Al, Al).
The challenge to the steelmaker is to develop alternative
products, such as bake hardening steels, which offer weight
reduction, high strength, and corrosion resistance.
DEVELOPMENT OF BAKE HARDENING STEELS
The strength increase achieved in bake hardening steels is
attributed to interstitial solute atoms (carbon and nitrogen)
migrating to and pinning dislocations. Once pinning has
occurred, an increased stress is required for further defor-
mation. This phenomenon is observed only after several
days at room temperature, but will occur in minutes at paint
baking temperatures.
Table 1 Summary of North American target properties
for 2005 for high strength light gauge sheet
steels for speci c passenger car applications1
Tensile Yield Total
Thickness, strength, strength, elongation,
Application mm MPa MPa % Coating type
The rst steels to offer bake hardenability were the rim-
ming steels. These contained large quantities of nitrogen in
solution, which, because of its high diffusion rate at room
temperature, made the strength increase dif cult to control.
Often the steel became stronger during storage, leading to
dif culties in pressing and to the formation of stretcher
strain markings. To combat this problem, the aluminium
killed steels were developed, in which nitrogen is removed
from solution by precipitation of aluminium nitride. The
carbon content of these steels was initially 40 .05%; how-
ever, with the development of vacuum degassing techno-
logies, the production of extra-low carbon (ELC) steels
containing 0.01 0 .03%C became possible (compositions
are in wt-% or wt-ppm unless otherwise indicated). The
requirement for more formable steels drove the lower car-
bon limit in steelmaking down from 200 300 ppm in 1960
to ~ 100 ppm in 1990, 9 and more recently, ultralow carbon
(ULC) steels have been developed containing 550 ppm.
Continued innovation in vacuum degassing now allows
consistent production of super-ultralow carbon (SULC)
steels containing 530 ppm carbon. Further reduction may
be possible, but will push the capabilities of vacuum degas-
sing to the limit. Furthermore, work by Hutchinson et al.1 0
has shown that reducing the total carbon content below
~ 10 ppm may actually degrade the formability of the steel
(Fig. 3).
Superformable IF steels have been developed in which the
total carbon content usually remains at ~ 30 ppm, this
carbon then being removed from solution by the addition
of carbide forming elements such as titanium and nio-
bium. These steels can be manipulated to produce a bake
hardening steel by controlling the chemistry or processing
Table 2 Automotive applications for hot dip coated
steels7
Typical application

Doors, outer Zinc (galvanised) Rocker panels, wheelhouse panels,

0.66 363 237 36
skin bumper reinforcement, oor pans,
Doors, inner cross-members, hoods, fenders, door
structure 0.64 335 201 40
outer panels, quarter panels, roofs
Hood, outer skin 0.66 359 244 36 Zinc iron Body rails, cross-members, fenders,
Hood, internal (galvannealed) doors, outer body panels, quarter
0.64 345 197 38
structure panels, hoods, oor pans, door
Trunk lid, inner panels, dash panels
outer skin 0.66 362 238 36
Aluminium Exhaust systems, chassis components
Trunk lid, Aluminium zinc Exhaust systems, air cleaner covers,
0.64 345 205 39
internal structure (~ 55Al 45Zn) brake shields, oor pan covers
Fenders, quarter Zinc aluminium Fuel tank shields, fuel oil lter shields,
panels 0.66 348 221 39
(~ 95Zn 5Al) motor housings, shock towers, deep
Floor pan 0.75 362 20 39 drawn underbody parts
Internal body Lead tin Fuel tanks, fuel lines, radiator
0.9 414 285 35
structure and heater parts, air cleaners
Roof 0.67 372 233 36 Tin Oil lter, heater components

Materials Science and Technology April 2002 Vol. 18

 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels 357
3 Effect of carbon content on formability of range of
steels,10 as characterised by through thickness/width
strain ratio during tensile deformation r
conditions to leave 15 25 ppm carbon in solution. It is
bene cial to use a SULC chemistry in the production of
these steels since smaller additions of costly titanium and
niobium are required. The improved formability of this type
of bake hardening steel has gained considerable attention
from the automotive manufacturers and its production has
now become the focus of extensive research.
Metallurgy of bake hardening steels
Essentially a high temperature strain aging process, bake
hardening is a diffusion controlled process involving the
migration of solute carbon atoms within the iron lattice.
The diffusion of these atoms will be affected by heat
treatment time and temperature and the amount of solute
present in the steel. Factors such as grain size and dis-
location density may also have an in uence. Studies on the
fundamental mechanisms of bake hardening (strain aging)
will be reviewed with an emphasis on how these may relate
to modern ULC chemistries.
MECHANISM OF BAKE HARDENING
The yield strength increase arising from bake hardening is
accompanied by the return of the yield point and yield point
elongation; there may also be a slight increase in tensile
strength and decrease in elongation. To realise this strength
increase, the following criteria must be met:1 1
(i) mobile dislocations must be present in the steel
(ii) there must be suf cient concentration of solute in
the steel to pin these dislocations
(iii) the solute must be mobile at the aging temperature
(iv) dislocation recovery must be suf ciently slow to
prevent softening.
The driving force for pinning is a reduction in lattice energy.
Both impurity atoms and dislocations induce lattice strains
in the iron matrix and these strains can be relaxed if the
interstitial atoms diffuse to the vicinity of dislocations.1 2
Early strain aging theories
For many years, the general assumption was that the
increase in strength observed was a result of strain induced
precipitation within grains, or the re-formation of grain
boundary lms that had ruptured during initial yielding.
However, this could not account for the extremely small
interstitial contents required to produce strain aging and it
was not until Cottrell and Bilby1 3 published their disloca-
tion theory in 1949 that further progress was achieved.
Cottrell and Bilby noted that the hydrostatic and shear
stresses produced when carbon is introduced to the lattice
could be reduced by atomic diffusion to edge and screw
dislocations, leading to the formation of solute `atmos-
pheres from which the dislocations must be torn before
plastic ow can occur. This leads to the characteristic upper
yield point seen in aged steels, followed by ow at a lower
yield point when new dislocations are generated and can
move under a smaller stress. It was suggested that segre-
gation would continue until a state of saturation was
reached, at which point the atmosphere could be visualised
as a central row of dislocations situated just below the
dislocation line, surrounded in the lower half-crystal by a
dilute carbon atom distribution of the Maxwell Boltzmann
type.
Cottrell and Bilby went on to calculate the rate of
formation of the atmosphere as
N (t) ~3no (p =2) 1=3 (ADt=kT ) 2=3 : : : : : : : : (1)
where N(t)/ no is the fraction of total dissolved solute
migrating to dislocations in time t (s) at absolute tem-
perature T (K), D is the carbon diffusion coef cient
(cm 2 s 1 ), A is an interaction parameter de ning the
strength of the atmosphere (Pa), L is the dislocation density
(cm 2 ), and k is Boltzmann s constant (J K 1 ).
In the derivation of this t2 /3 law, as it has become com-
monly known, it was acknowledged that as the atmosphere
builds up to equilibrium, saturation and concentration
differences would become important in modifying the ow
of the carbon atoms. However, the dif culties encountered
in modelling these effects forced the authors to assume that,
at least at the beginning of aging, the only important effect
would be the drift ow of the atoms due to interaction with
the dislocation.
Many attempts have been made to expand the relation-
ship by modelling the behaviour of the atmosphere as it
nears saturation and a comprehensive critical review of this
work was given in 1963 by Baird.1 4 1 7 Perhaps the most
important work was by Bullough and Newman, 1 8 who
analysed the kinetics of strain aging, allowing for both
drift and diffusion ow, showing that the Cottrell Bilby
relationship applied until aging was 30 40% complete; it
was concluded that in the latter stages, segregation was
retarded by back-diffusion from the core.
Importantly, Bullough and Newman calculated that
during atmosphere formation only 10% of available
solute segregated to dislocations and suggested that where
all the available solute was found to segregate, atmosphere
formation was preceded by precipitation on dislocations.
The suggestion that these precipitates would be rodlike and
stabilised by a combination of chemical binding within the
particle and elastic interaction with the stress eld of the
dislocation was later supported by the work of Nacken and
Heller.1 9
The stages of strain aging proposed by these theories have
been investigated in a number of studies and reference is
again made to Baird1 4 1 7 for a full review. Wilson and
Russell2 0 2 2 studied the in uence of strain aging on the
mechanical properties of a rimming steel strained 4% and
showed that four stages could exist during strain aging. The
rst, measurable only at subzero temperatures ( 12 C), was
attributed to the stress induced reordering of interstitial
atoms to enlarged interstices (Snoek effect2 3 ). At higher
temperatures (60 C), several distinct stages of aging were
shown2 2 to exist over times up to 10 4 min, as illustrated in
Materials Science and Technology April 2002 Vol. 18
358 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels
Increase in lower yield stress (MPa)
4 Effect of grain size on changes in mechanical proper-
ties produced by strain aging following quenching
from 200C and 4% prestrain:22 1~50, 2~195, 3~
1850 grains mm 2
Fig. 4. First, an increase in yield strength was measured,
with an accompanying increase in Luder s strain (or yield
point elongation); this was shown to follow a t2 /3 law. It was
calculated that 10% of the available solute had segregated
at the end of this stage, in accordance with the theory of
Bullough and Newman. Continued segregation caused a
further increase in yield strength, but at a much slower
rate than in the rst stage. The Lu ders strain showed no
further increase, indicating that Cottrell locking was no
longer the dominant mechanism. Instead, it was assumed
that this stage of aging was the result of the formation of
ne clusters or precipitates on the saturated dislocation
atmospheres. The nal stage of aging caused an increase in
tensile strength and a decrease in ductility, with only a small
increase in yield strength, as would be expected from matrix
precipitation hardening. Very ne precipitates were observed
in overaged specimens and it was suggested that these could
have derived from ne, closely spaced precipitates lying along
a tangled network of dislocations in the deformed grains.
These investigations led Wilson and Russell to conclude that,
once atmosphere formation has occurred, strengthening is
associated with the formation of clusters of solute atoms,
probably at close intervals along dislocations. Continued
aging is then thought to coarsen these clusters, increasing
tensile strength and eventually leading to classical precipita-
tion hardening.
Recent strain aging theories
Since the development of the early theories, strain aging, in
the form of bake hardening, has been found to be a useful
Materials Science and Technology April 2002 Vol. 18
Aging time (min)
5 Effect of prestrain on increase in lower yield stress
during aging at 150C (Ref. 24)
property in automotive steels. Most of these theories were
based on work at relatively low temperatures in steels highly
saturated with both carbon and nitrogen, whereas the steels
commonly used in the automotive industry typically contain
no solute nitrogen and have total carbon contents as low
as 30 ppm. Recent work has been carried out at higher
temperatures than the classical studies, concentrating par-
ticularly on the paint curing cycle (170 C for 20 min) used
in automotive production lines.
Elsen and Hougardy2 4 in 1993 studied the aging kinetics
of a low carbon steel containing ~ 5 ppm carbon in
solution. Two distinct stages were seen in bake hardening
response during aging at temperatures between 50 and
180 C (Fig. 5). The rst stage was assumed to be the result
of long range diffusion of carbon atoms to the stress elds
around dislocations, as proposed by Cottrell and Bilby.
However, since the interaction between carbon atoms and
dislocations decreases with increasing distance, Elsen and
Hougardy suggested that the proportionality between
segregated solute atoms and mechanical properties assumed
by the Cottrell Bilby equation would be valid only at the
beginning of aging. A new relationship describing the devel-
opment of the rst step of bake hardening was developed
nc
Dr Cottrell ~Dr max,I ( t=kc ) =1+ (t=kc )nc : : : : : (2)
where Dr m a x ,I is the maximum strength increase in the rst
stage of bake hardening, t is aging time, kc is a temperature
dependent constant, and nc is a time exponent; kc was
shown to follow an Arrhenius relationship and to be depen-
dent on the dislocation density and the rate of diffusion of
carbon in a -Fe.
The maximum strength increase and time exponent were
found to be constant at all temperatures and prestrains, 2 4
implying that there is a limit to the strength increase
achieved by Cottrell atmosphere formation, regardless of
the dislocation density or aging temperature. The relation-
ship was extended to model the behaviour of the strength
increase during the second stage of aging, which was
assumed to be due to the formation of precipitates on dis-
locations.2 4 In this case, the maximum increase in strength
was found to be independent of temperature, but to decrease
with increasing prestrain, implying that precipitation is a
less effective strengthening mechanism at higher dislocation
densities. The availability of more nucleation sites on
dislocations as the density increases would lead to the
formation of smaller particles which would be expected to
increase the yield strength. The observed decrease was
attributed to the formation of coherent particles that can
more easily be cut by dislocations; decreasing particle
size would then represent less of a barrier to dislocation
movement. Elsen and Hougardy supported this theory by
 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels 359
6 Calculated26 time temperature precipitation diagram
for cementite precipitation in ferrite containing 0.045%C:
experimental points27 are for 15% carbide precipitation in
steel also containing 0.02%P and 0.35%Mn respectively
showing that the strain hardening of the steels investigated
did not differ greatly, implying that the rate of dislocation
multiplication was similar for all conditions. This relation-
ship was later con rmed by the work of Van Snick et al.2 5
The nature of the particles formed during the second
stage of bake hardening was discussed by Kozeschnik and
Buchmayr 2 6 The time temperature precipitation curves
for cementite in ferrite containing 0 .045%C were calculated
(Fig. 6) and compared with the experimental results of
Abe.2 7 The apparent discontinuities at 90 and 250 C were
attributed to the formation of low temperature carbide
(Fe 3 2 C 4 ) and e carbide (Fe2 . 4 3 . 0 C). Electron microscopy
studies2 8 3 0 had previously shown these phases to have
different structures to cementite, as well as different
nucleation and growth behaviour. Since e carbide forms
preferentially on dislocations3 1 and the times and tempera-
tures of precipitation 3 1 agree with those reported by Elsen
and Hougardy for the onset of second stage bake hard-
ening,2 4 it is likely that this particle is responsible for the
strength increase observed.
Although the stages of bake hardening and the formation
of clusters and precipitates have generally been established,
attempts to observe these particles in bake hardened steels,
principally using transmission electron microscopy (TEM),
have been unsuccessful: the particles (if in existence) have
been too ne to resolve. Rubianes and Zimmer3 2 investi-
gated the bake hardening response in a steel containing
~ 20 ppm carbon. Cementite particles were identi ed using
TEM, but no e carbide. The cementite was thought to have
precipitated during hot rolling and was not considered
responsible for any bake hardening strength increase.
Although precipitation may have occurred, it was also
possible that in steels with very low carbon contents,
precipitation would be retarded or absent and that Cottrell
locking would continue at high temperatures. No clear two
stage strengthening behaviour was observed, but the tem-
peratures used were high ( 4150 C) and the rst stage may
already have occurred. Since the effect of different levels of
prestraining was not studied, it is dif cult to say whether
Rubianes and Zimmers interpretation is correct; however,
based on the evidence presented by other authors, it is felt
that should such a study be undertaken, the continuation of
Cottrell locking at high temperatures would be ruled out.
The development of matrix precipitation hardening
during bake hardening was investigated by Okamoto
et al.3 3 In the typical bake hardening steel investigated,
although the bake hardening response was large if the
primary and secondary deformation were in the same
direction, it was found to be absent if the deformation
modes were perpendicular (Fig. 7). It was concluded that
the strength increase observed was due solely to locking
Load (kg)
Elongation at secondary deformation (%)
7 Effect of predeformation direction on bake hardening
behaviour33
of dislocations on the active slip plane and not matrix
strengthening through precipitate formation. If this is the
case, bake hardening can be absent if dislocations from
other slip planes are activated.
Work of this nature has allowed predictions to be made
regarding the stages of strain aging that will occur during
the paint baking cycles encountered industrially. Rashid3 4
showed that the aging temperatures and times commonly
used during paint baking corresponded to the end of
Cottrell locking and the beginning of precipitate formation
in the steel studied. Clearly, however, the composition of the
steel with respect to the total and solute carbon content will
greatly in uence the kinetics of aging and this can only be
used as a guide.
Very little work has been carried out on the aging
behaviour of ULC and SULC steels. Since it is these
chemistries that are under development for modern bake
hardening steels, improved knowledge of their bake hard-
ening behaviour is essential.
INFLUENCE OF SOLUTE CARBON CONTENT
The strength increase in modern bake hardening steels is
derived solely from interstitial carbon. Nitrogen is almost
always taken out of solution by additions of nitride formers
such as aluminium and titanium. Nitrogen has a faster
diffusion rate at room temperature than carbon (1 .346
10 1 6 cm 2 s 1 cf. 2 .8 610 1 7 cm2 s 1 ),3 5 which allows it to
diffuse through the ferrite matrix and pin dislocations
during storage of the steel at ambient temperatures. Room
temperature aging of this kind leads to the formation of
stretcher strain markings (Luders bands) when the steel
is pressed, resulting in an `streaky nish, which is not
acceptable for exposed automotive applications. The slower
diffusion rate of carbon allows the steel to remain at storage
temperatures for up to six months without aging. At paint
baking temperatures, however, the diffusion rate is signi-
cantly increased (2 .24610 1 2 cm 2 s 1 ), increasing the
probability of dislocation pinning.
Increasing the carbon content will increase the bake
hardening response: more solute is available to pin mobile
dislocations and the formation of clusters will occur more
rapidly. Work by Van Snick et al.2 5 showed that increasing
the carbon content from 0 to 40 ppm increased the bake
hardening response from 40 to 70 MPa; further increases in
solute carbon had no effect on the bake hardening
measured. A similar saturation effect, the level of which
increased with decreasing grain size, was observed by Hanai
et al.3 6 who attributed this to the fact that at 420 ppm
solute carbon the aging mechanism is primarily that of
precipitate formation. As the carbon content increases
so does precipitate formation, giving classical matrix
Materials Science and Technology April 2002 Vol. 18
360 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels

C(ppm)
36 ~20

34
~10

s y (kg mm_ 2 )
s y =s1 +ky d_ 1 /2
32 ~5

30

sf 2 % (kg mm_ 2 )
~5
27
sf2 % =s1 +kf d_ 1 /2
28 ~10 26
~20
25
~20

8 In uence of carbon in solution on bake hardening 8

DYS (kg mm_ 2 )

response following 2% prestrain (BH2 ) and aging sensi-
tivity of E180BH steel:32 YPE~yield point extension
hardening. This will increase the tensile strength of the
material, but have little in uence on the yield strength.
Rubianes and Zimmer3 2 categorised the effect of
increasing carbon content on bake hardening and room
temperature aging into three domains (Fig. 8). At 53 ppm
solute carbon, steels have excellent room temperature sta-
bility but show no signi cant bake hardening. The second
domain consists of steels containing 47 ppm solute car-
bon. The bake hardening response is excellent, exceeding
60 MPa: unfortunately the propensity for room tempera-
ture aging is also greatly increased in these steels. The third
domain applies to steels with carbon contents, which have
an adequate bake hardening response of 20 60 MPa but
also offer suitable resistance to room temperature aging.
Obviously, bake hardening steels should be designed to fall
in this region. It should be noted that the carbon contents
reported by Rubianes and Zimmer were measured via
internal friction methods, which do not detect carbon
lying at grain boundaries, and thus are lower than those
calculated by Van Snick et al.2 5 or Hanai et al.3 6
INFLUENCE OF FERRITE GRAIN SIZE
The literature regarding the in uence of ferrite grain size on
the bake hardening response is somewhat contradictory.
Hanai et al.3 6 studied a low carbon steel, varying the grain
size by changing the annealing conditions; decreasing the
grain size had a positive effect on the bake hardening
response (Fig. 9). It was suggested that a ne grain size
increased the strength after baking, but had no signi cant
effect on the ow stress after 2% prestrain. Bleck3 7 found a
similar response in a batch annealed bake hardening steel,
but gave no metallurgical explanation. Kinoshita and
Nishimoto 3 8 found that the bake hardening response was
lower in rephosphorised and coarse grained aluminium killed
steels than in ne grained steels. Heat treating the phospho-
rus containing steel at 550 C for 1 h increased the amount
of carbon in solution, but had only a marginal effect on the
bake hardening response. It was concluded that bake
hardening may involve a combination of carbon in solution
and carbon segregated at grain boundaries. This explana-
tion was also put forward by Meissen and Leroy3 9 and
supported by Sakata et al.,4 0 who suggested that the small
amount of solute carbon not measured by internal friction
methods had segregated to grain boundaries during cooling.
Grain boundaries offer low energy positions for solute atoms,
making them more stable and therefore unable to contri-
bute to aging at room temperature. It was postulated that at
the elevated temperatures used during paint curing opera-
tions (170 C) it would be possible for this carbon to diffuse
to the grain interiors and contribute to bake hardening.
DYS=s1 +k1 d_ 1 / 2 ~10
6
~5
4
6 8 10 12
d_ 1 /2 (mm_ 1 /2 )
9 Effect of carbon in solution and grain `diameter d on
bake hardening response D YS, ow stress after 2%
prestrain sf2% , and tensile strength after baking sy
(Ref. 36)
Van Snick et al.2 5 agreed with Obara et al.4 1 that the
in uence of grain size was due to the fact that more
cementite particles were observed in coarse grains; it was
postulated that solute carbon would move to these carbides
as well as to dislocations, resulting in less ef cient pinning.
This is a reasonable assumption for steels with relatively
high carbon contents, but not for the ULC chemistries in
which cementite is not usually present in the matrix.
In contrast to the evidence presented above, both
Pradhan4 2 and Lee and Zuidema4 3 found that bake hard-
ening response did not vary between coarse and ne grained
steels. Present knowledge on the effect of grain size is
limited and contradictory, and clearly further work is
required in this area. Further understanding of the in uence
of grain size on bake hardening would be useful to steel-
makers since it would allow bake hardening to be increased
without compromising room temperature stability.
Bake hardening steels
There are several types of bake hardening steel in
production today. Individual grades are determined by
the processing technology available and the properties
required in the nal product. These steels can be loosely
grouped into two main categories, ELC/ULC aluminium
killed steels; and IF steels.
ALUMINIUM KILLED BAKE HARDENING
STEELS
Aluminium killed steels are so called because aluminium
additions (0 .03 0 .07%) are made during secondary steel-
making to remove oxygen and nitrogen from solution.
Oxygen must be removed to prevent reaction with carbon
and consequent rimming of the steel during casting, and

Materials Science and Technology April 2002 Vol. 18

 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels 361
TiN (Fe 0003C 006S 003Nb 006Ti) A <1220C
B <1150C
C <930C
TiS TiS
A Ti4 S2 C2
Temperature
TiN B
TiS B
Ti4 S2 C2 TiS
TiS
TiS
TiN
Process
10 Schematic mechanism of carbosulphide and carbide
formation in titanium IF steels44
nitrogen must be removed to prevent aging of the steel at
room temperature.
The ELC steel grades typically have a carbon content of
~ 0.01%. If all this were in solution, room temperature
aging would occur very rapidly. Hence, carbon levels must
be controlled by suitable annealing practices. The ELC
steels are fairly straightforward to produce since they do not
require tight chemistry or annealing control. Care must be
taken, however, with overaging practice during annealing
to ensure an appropriate amount of carbon (15 25 ppm)
is left in solution in the nal product. These steels can
exhibit problems during galvannealing, but their main
disadvantage is low formability because of the relatively
high carbon contents.
The increased ef ciency of vacuum degassing has allowed
the more formable ULC steels to be produced, typically
containing 0 .001 0 .004%C, all of which is available for
bake hardening. Careful chemistry control during steelmak-
ing is therefore crucial to ensure suitable amounts of carbon
remain in solution in the nal product.
IF BAKE HARDENING STEELS
Like ULC steels, IF steels contain very low amounts of total
carbon ( 50. 004%). In true IF steels, all interstitial elements
are removed from solution by addition of carbide and
nitride formers such as aluminium, titanium, niobium,
and increasingly vanadium. The elimination of intersti-
tial elements during steelmaking leads to superb formability
in the nal product, making IF steels ideally suited to com-
plex modern automotive pressings. These steels do not
exhibit bake hardening since, by de nition, they have no
interstitial elements in solution. The chemistry and process-
ing of these steels, however, can be adjusted to leave
15 25 ppm carbon in solution, which, although slightly
reducing the formability, gives a propensity for bake
hardening of 30 60 MPa.
There are several types of IF steel, de ned by the com-
bination of alloying elements used, each of which can be
used as the basis for a bake hardening steel, although, as
discussed below, processing limitations make some more
favourable than others.
Titanium IF steels
In suf cient quantities and in the absence of any other
strong carbide formers, titanium can be used to form
carbides, nitrides, and sulphides (TiC, TiN, TiS, and under
certain conditions Ti4 C 2 S 2 ). For full stabilisation of the
interstitial elements, Ti must be added according to the
stoichiometric ratio 4 4
%Ti ~4( %C) + 3 :42( %N) + 1 :5( %S) : : :
MC
C
Ti4 S2 C2
11 Schematic illustration of effects of composition on
precipitation in ULC steels with given nitrogen, sul-
phur, and carbon contents: for partially stabilised
steels, white area represents solute carbon46
In true IF steels, titanium is often added in greater quan-
tities than this, to ensure complete stabilisation.
The precipitation mechanism of titanium in these steels is
summarised in Fig. 10 (Ref. 44). It is postulated that ne
titanium nitride particles formed during slab casting act as
nucleation sites for the precipitation of TiS and Ti4 C 2 S 2 .
The small amount of carbon remaining is precipitated as
TiC. During reheating of the slab, solution of carbosulphide
occurs, leaving only TiS and TiN. Cooling of the strip to
the austenite ferrite transformation temperature during
hot rolling transforms TiS to Ti4 C 2 S2 by the absorption
of titanium and carbon. This mechanism of precipitation
applies only when some titanium remains in solution: in just
stabilised or understabilised chemistries, formation of TiC
and Ti4 C 2 S2 is inhibited because of the low titanium
content. This successive precipitation of carbides and car-
bosulphides makes it dif cult to control the amount of
titanium available for carbon stabilisation and hence the
solute carbon content. However, a bake hardening product
can be produced from a titanium chemistry by inhibiting or
avoiding TiC formation, so that the total carbon content
remains in solution and is available for bake hardening.
Work by Tanioku et al.4 5 and Kojima et al.4 6 has shown
that this can be achieved by controlling total carbon
at 15 25 ppm and titanium at ~ 0 .01%. The manganese
content must be kept low (~ 0 .3%) to prevent the formation
of MnS in preference to TiS and the slab reheat temperature
must be high (~ 1200 C) to prevent the precipitation of
Ti4 C 2 S 2 . It can be seen from Fig. 11 that the amount of
carbon in solution can be adjusted by changes in com-
position.4 6 In this gure, the optimum situation is given
in (c), where titanium is tied up as TiN and TiS, with
manganese stabilising the remaining sulphur as MnS. In this
way, the total carbon content is available in solution.
Another method for producing titanium IF bake hard-
ening steels, discussed by Tsunoyama et al.,4 7 relies on
reducing the sulphur level to minimise formation of TiS.
The role of TiS as a heterogeneous nucleation site for the
precipitation of TiC can lead to the reduction in solute
carbon and hence bake hardening response. As can be seen
in Fig. 12, the aging index (the increase in yield strength
that occurs during storage at room temperature) of a
titanium only steel was increased by reducing sulphur
from 0 .008 to 0 .001%. Kawasaki et al.4 8 used a similar
philosophy, involving a decreased sulphur level (0.005%)
coupled with an increase of manganese to 1 .0%; the
formation of Ti4 C 2 S 2 was suppressed, leaving carbon in
solution and producing a bake hardening steel.
Kitamura et al.4 9 have presented a completely different
methodology for the production of titanium based bake
hardening steels. They suggested that the reduction in r
value due to solute carbon in solution through process-
: : : (3) ing can be eliminated by using a fully stabilised titanium
Materials Science and Technology April 2002 Vol. 18
362 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels
12 Effect of sulphur content on aging index (AI) in tita-
nium ELC steels:47 AI is directly related to solute
carbon content and can be used to evaluate bake
hardenability
composition. Excess carbon can then be introduced by
annealing in a carburising atmosphere. The theory suggests
that as the steel sheet absorbs carbon, the Ti/C ratio
decreases, eventually resulting in some solute carbon in
the matrix. A bake hardening response of 20 50 MPa
was achieved in this way without compromising r value
(Fig. 13). It is unlikely that this type of processing will be
widely taken up, however, as the complexity of the opera-
tion poses signi cant production challenges.
Compared with other IF compositions, the titanium
bearing steels have superior r values and elongation, with
lower yield strengths and recrystallisation temperatures.
The precipitation of the primary particles at higher tem-
peratures also makes these compositions less susceptible to
uctuations in chemistry and processing. The low recry-
stallisation temperature of these steels (700 750 C) makes
them ideally suited to the lower temperature galvannealing
lines. Unfortunately, titanium is believed5 0 ,5 1 to increase the
rate of alloying during the galvannealing process, leading
to excessive powdering of the coating during subsequent
processing. The spot weld fatigue properties of these steels
have also been shown to be poor, probably5 2 because of the
presence of large TiN particles in the microstructure.
Niobium IF steels
Niobium is a strong carbide former that can stabilise carbon
as NbC when added according to the stoichiometric ratio
(%Nb) ~7 :75( %C) : : : : : : : : : :
Nitrogen is stabilised by the addition of aluminium to form
AlN. This is more stable and therefore forms at higher
temperatures than Nb(C,N), so it can be assumed that all
niobium is available for carbide formation. The relative
simplicity of carbon stabilisation in these steels makes them
ideal for the production of bake hardening grades.
Control of solute carbon in the niobium bearing bake
hardening steels can be achieved in two ways. First, insuf-
cient niobium can be added fully to stabilise the carbon,
leaving 15 25 ppm in solution after steelmaking. This
methodology requires tight chemistry control during
steelmaking and, because of the presence of solute carbon
throughout subsequent processing, the r value can suffer.
The second method requires the full stabilisation of carbon
during steelmaking. Solute carbon is then liberated by
solution of NbC during annealing. By annealing at high
temperatures (800 850 C) and cooling at 420 K s 1 ,
15 25 ppm carbon can be retained in solution.5 3 Since
the carbon is fully stabilised until the end of annealing, r
values in steels of this type are comparable with those of
Materials Science and Technology April 2002 Vol. 18
13 Effect of processing on relationship between bake
hardenability and r for 0.003C 0.01P 0.006S 0.03Ti
steel49
traditional IF grades. High temperature annealing of this
kind can, however, lead to shape problems in the strip such
as heat buckling.5 3 Some continuous annealing lines can
operate at these high temperatures, but they are beyond the
limits of conventional hot dip galvanising lines. Steelmakers
must therefore assess their own production capabilities
before deciding on a suitable processing route for the
niobium IF based bake hardening steels.
The niobium steels have higher recrystallisation tem-
perature (750 800 C) than titanium compositions. This is
attributed to the low temperature formation of niobium
carbides, producing ne particles that readily retard grain
boundary movement during annealing.5 4 Galvannealing
properties are superior to the titanium grades, but the high
recrystallisation temperature makes them unsuitable for
many galvannealing lines.
Niobium titanium IF steels
By combining titanium and niobium to stabilise carbon and
nitrogen, a steel can be produced with an excellent com-
bination of properties.5 5 For full stabilisation, titanium and
niobium must be added according to
( %Nb){7 :75 ( %Ti){3 :42( %N) {1 :5(%S)=4 ~0 (5)
By reducing the sulphur level and increasing manganese, the
formation of TiS can be suppressed, leaving all titanium
available for nitrogen stabilisation. The precipitation of
Ti4 C 2 S 2 can also be suppressed in this way, so carbon
is controlled by niobium alone. As with the Nb only
compositions, carbon content can be controlled either by
: (4) understoichiometric addition of niobium, or by high tem-
perature annealing and controlled cooling, depending on
the capabilities of individual steelmakers. These steels
have been widely researched and are the choice of many
manufacturers. Not only do they have a good balance of
mechanical properties, they also offer good coating cha-
racteristics without the need for the high recrystallisation
temperatures necessary for the niobium only steels.
Vanadium IF steels
The use of vanadium as a stabilising element in IF steels is a
more recent development. Vanadium can be substituted for
niobium and titanium to form both carbides and nitrides.
The stoichiometric ratio is 5 7
( %V) ~4 :24( %C)+ 3 :64( %N) : : : : : : : : (6)
Vanadium is only a moderate carbide former and it is likely
that higher concentrations will be required for full stabi-
lisation. For this reason, V Ti combinations are common,
where titanium is added in suf cient quantities to stabilise
nitrogen, leaving vanadium available to form VC.
 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels 363
14 Equilibrium carbon solubility in pure and alloyed
ferrites57
Vanadium containing steels have lower recrystallisation
temperatures than other IF compositions. The recrystal-
lisation temperature of a 0 .0041C 0.0025N 0 .041V steel
was found by Engl and Gerber5 6 to be ~ 700 C, compared
with 700 800 C for a similar niobium or titanium stabilised
steel. Because vanadium carbide is much less thermo-
dynamically stable than TiC or NbC, signi cantly higher
solubility can be achieved during annealing.
Taylor and Speer5 7 studied various Ti V alloying com-
binations, where titanium was added in suf cient quantities
to stabilise nitrogen as TiN and vanadium was added to
form VC. The relative solubility of carbon in iron in the
presence of titanium, niobium, and vanadium is shown
in Fig. 14. At annealing temperatures of 750 C, 20 ppm
carbon can be dissolved with additions of vanadium,
whereas in the presence of titanium and niobium only
1 2 ppm would be liberated at this temperature.
Interestingly, it was also reported5 7 that higher solute
carbon contents could be tolerated in V Ti bake hardening
steels before room temperature aging occurred (40 50 ppm
cf. 535 ppm in titanium IF steels). It was suggested that,
owing to its strong af nity for any carbon in solution,
vanadium may exert a kinetic effect on aging. Hence on
solution of vanadium carbides during annealing, the
mobility of the carbon is restricted by the presence of the
vanadium and room temperature aging occurs more slowly
than in steels stabilised by niobium and titanium. Further
work on the in uence of vanadium on the kinetics of aging
was considered necessary to clarify this phenomenon.
Although many strategies are used in the production of
IF bake hardening steels, the combination of composition
and processing route chosen will depend largely on the
capabilities of individual steelmakers. To date, however,
Ti Nb combinations have received the greatest attention
because of their enhanced properties and relative ease of
manufacture.
Processing bake hardening IF steels
The most important process areas for producing bake
hardening steels are steelmaking, coiling, annealing, and
temper rolling. In other areas, the processing conditions will
be similar to that for a standard IF steel. The processing
route from iron ore to coated steel strip is complex,5 8
involving many stages. The speci c challenges during steel-
making having been discussed above, the rolling and
annealing practices will now be described.
15 Effect of slab reheating temperature (SRT) on solu-
tion of precipitates in niobium and titanium IF
steels59
HOT ROLLING
During hot rolling, the steel is at temperatures from
~ 700 C to 1250 C. It is during this process that many
precipitates form and the microstructure is controlled.
Control and understanding of the hot strip mill is crucial in
the production of IF steels.
Slab reheating
Solution of precipitates, formed during the solidi cation of
the slab, occurs when the slab is preheated before hot
rolling. Temperatures used can range from 1000 to 1250 C
and are important in determining the hot band grain size
and texture. Nitrogen is removed from solution by the
formation of either TiN or AlN. In titanium bearing steels,
TiN is formed at high temperatures and does not dissolve
during slab reheating. In niobium steels, however, AlN
dissolves and reprecipitation occurs during hot rolling and
high temperature coiling. Ohashi et al.5 9 showed the effect
of increasing reheat temperature on the solution of pre-
cipitates in stabilised IF steels (Fig. 15). At higher tem-
peratures (1250 C), there is complete solution of NbC and
partial solution of MnS and TiN. The compositions used
for bake hardening steels result in low solution tempera-
tures for sulphides: in titanium steels all sulphides are
dissolved after 1 h at 1250 C (Ref. 60) and there is partial
solution at 1150 C. Solution of precipitates during slab
reheating makes the bake hardening steels more susceptible
to temperature variations in downstream processing where
reprecipitation must occur, and therefore lower slab reheat
temperatures are desirable.
Finishing temperature
Hot roll nishing must be completed above the Ar 3
temperature to ensure recrystallisation occurs through the
strip. Temperatures should not greatly exceed this value
since higher temperatures can lead to hot band grain
growth, which in turn causes poor texture development and
hence poor r value in the nal product. Because of the ULC
Materials Science and Technology April 2002 Vol. 18
364 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels
16 Effect of coiling temperature after hot rolling on yield
point elongation60
content of these steels, Ar3 is higher than in other steels,
usually in the range 890 930 C.
Runout table practice
Various cooling regimes can be employed on the runout
table. It has been reported by Tanaka et al.6 1 that in IF
steels, rapid cooling of the strip soon after the nal nishing
stand can decrease the hot band grain size. This will lead to
improved r value in the nal product and is a practice widely
taken up by steel manufacturers.
Coiling temperature
Coiling temperature has an in uence on the quantity and
size of precipitates, lower coiling temperatures resulting in
ner carbide and nitride precipitates and therefore higher
levels of carbon and nitrogen in solution. At high coiling
temperatures (~ 750 C), carbon and nitrogen precipitation
is completed and coarse precipitates are formed during slow
cooling, producing favourable textures for deep drawing
on annealing. In contrast, precipitation is not completed
during coiling at low temperatures and further particles can
form during annealing which then interfere with recrystal-
lisation and reduce r value. Lips et al.6 0 observed that in
fully stabilised bake hardening steels, carbide precipitation
was completed after coiling at 720 C, but that some carbon
remained in solution after coiling at 650 and 580 C, leading
to the yield point elongations shown in Fig. 16. The under-
stabilised steels still showed a high yield point elongation
after coiling at 720 C, but since insuf cient stabilising
elements were present for complete carbide formation, this
is to be expected.
Steels that are stabilised with titanium have been shown5 3
to be robust to variation in coiling conditions. This is
attributed to the formation during steelmaking of coarse
TiN precipitates that are stable at the temperatures com-
monly used during coiling (650 750 C). However, Hoggan
and Sung6 2 showed that increasing the coiling temperature
of titanium bearing bake hardening steels with high levels
of carbon in solution from 650 to 720 C was undesirable,
resulting in a lower proof stress, tensile stress, and bake
hardening response. This was accompanied by an increase
in r9 0 and in total elongation. An increase in hot band grain
size at high coiling temperature was suggested as the
probable cause.
In niobium bearing bake hardening steels, coiling tem-
perature can have a signi cant effect on the nal properties,
since the ne, dense AlN precipitates formed can retard
recrystallisation and inhibit grain growth, leading to poor r
values. These steels must be coiled at higher temperatures to
promote the precipitation of coarse AlN particles and allow
Materials Science and Technology April 2002 Vol. 18
17 Effect of coiling temperature after hot rolling on
aging index (AI) of titanium niobium IF steels63
the formation of favourable recrystallisation textures during
annealing. The use of high coiling temperatures is proble-
matic, however, because it can lead to increased micro-
structural variation through the coil and the formation of
extensive scale. Also, complete precipitation of NbC during
coiling will give less carbon in solution and a lower bake
hardening response.
Hwang et al.6 3 found that increasing the coiling tem-
perature of a dual stabilised bake hardening steel, with an
Nb/C ratio of 0 .55, from 560 to 700 C produced a signi-
cant increase in r value (from 1 .5 to 2 .0). This increase was
explained by differences in precipitate dispersion in the fully
and understabilised steels: it was suggested that increasing
the coiling temperature increases the size and reduces the
density of precipitates. Fine precipitates suppress the devel-
opment of favourable deep drawing textures during anneal-
ing, explaining the increase in r value. This hypothesis is
supported by the fact that the amount of solute carbon in
the steel was signi cantly reduced by coiling at higher
temperature, as demonstrated by a decrease in the aging
index (Fig. 17) 6 3 and a reduction in the height of the Snoek
peak. However, since the niobium content of the steel was
insuf cient to stabilise all the carbon present, it was pos-
tulated that the formation of an Nb C complex may
be responsible for the lack of carbon in solution. The
formation of such a complex would restrict the movement
of solute carbon, accounting for the absence of any
measured aging index or Snoek peak. The strong negative
interaction energy between niobium and carbon indicates
that a complex of this type could form in suitable con-
ditions.6 4 The grain structure of this steel was found to be
elongated, in contrast to the equiaxed grains observed in the
fully stabilised steel. It was suggested that this could be due
to precipitation of the Nb C complex on grain and sub-
grain boundaries during annealing, retarding the nucleation
and growth of new grains and enhancing favourable {111}
textures, in a similar manner to AlN precipitates in a batch
annealed steel.
The precipitate morphology after coiling will have an
in uence on the annealed steel properties. Van Snick et al.6 5
studied three Ti Nb bake hardening steels and showed that
after a high coiling temperature of 720 C, larger NbC
precipitates were formed and little carbon remained in
solution. At low coiling temperature (620 C), very ne
(~ 3 nm) precipitates were found, which were attributed to
the lower diffusion rates of niobium and carbon at this
temperature. However, since this steel will be supersaturated
with carbon after hot rolling, NbC will precipitate during
annealing instead of going into solution as would be expected
after coiling at high temperature. This could lead to a lower
 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels 365
Ti Nb TiNb
r value
Cold reduction (%)
18 Effect of cold reduction on r for titanium, titanium
niobium, and niobium IF steels66
bake hardening response in the nal product if the interaction
of these two processes is not taken into account.
COLD ROLLING
Cold rolling plays a vital part in the formation of favourable
textures for deep drawing during annealing, but has little
effect on other properties. The variation of r value with cold
reduction in the three common IF steel types is shown in
Fig. 18 (Ref. 66); Ti Nb steels show the highest r value for
equivalent cold reduction because the precipitates formed
during hot rolling and coiling are not large enough to
compromise the r value during annealing. A reduction of
90% produces the highest r value in all the steels, but these
reductions are rarely achieved in practice, 80% being
more common. The data shown represent fully stabilised
chemistries and it should be noted that the presence of
solute carbon in understabilised bake hardening steels will
adversely affect the nal r value.
ANNEALING
Batch annealing is rarely used in the production of IF based
bake hardening steels as cooling rates are slow and there is
a risk of carbide formation. It is far more common for
continuous annealing or galvannealing lines to be used, in
which control of heating and cooling rate is easier.
As described above, annealing plays a crucial role in the
development of bake hardening in the fully stabilised
chemistries. A signi cant amount of work has been carried
out on the effect of varying annealing conditions on the
nal bake hardening response. The majority of these studies
have concentrated on the niobium bearing steels, as these
chemistries are most likely to bene t from high tempera-
ture annealing due to the solution of NbC. Sakata et al.4 0
showed that in a titanium only stabilised steel containing no
excess titanium, increasing the soaking temperature from
800 to 900 C increased the bake hardening response from
510 to ~ 40 MPa. However, the nal bake hardening
response was lower than that of an equivalent niobium
stabilised steel. Annealing temperatures of ~ 900 C are
rarely reached in commercial annealing lines, and it is
unusual to use a fully stabilised titanium chemistry as the
basis for a bake hardening steel.
The dissociation of NbC through high temperature
annealing is an important consideration in the production
of bake hardening steels. The effect of increasing soak
temperature on this solution appears to be dependent on the
Nb/C ratio. Sakata et al. showed that control of Nb/C at
0 .7 2.0 led to an increase in bake hardening response of
30 50 MPa on increasing the soak temperature from 750
to 950 C. This was supported by Lips et al.6 0 Itami et al.,6 7
however, found that increasing soak temperature to 900 C
had no signi cant in uence on the nal bake hardening
19 In uence of cooling rate on bake hardening response
of titanium niobium IF steels60
response in understabilised steels and was signi cant only
when Nb/C was ~ 2 .1. In contrast, Hwang et al.6 3 found no
in uence of increasing soak temperature on fully stabilised
Ti Nb steels, but observed an increase from 40 to 50 MPa
in steel with an Nb/C ratio of 0.55. The differences may be
attributed to the coiling history of the steels and certainly
the steel studied may have formed the Nb C complex
discussed above. It has been suggested that a low coiling
temperature in niobium bearing steels may lead to further
NbC precipitation during the heating stage of annealing;
evidence for this has been provided by Van Snick et al., 6 5
who found that increasing the soak temperature from 820 to
850 C did not prevent the formation of elongated ferrite
grains. This grain morphology is determined by the dis-
tribution of precipitates in the hot band, as described by
Wilshynsky; 6 8 thus, if NbC is formed during hot rolling by
use of a high coiling temperature, equiaxed grains are
formed during annealing. If, however, NbC precipitation
is delayed by using a low coiling temperature, NbC will
precipitate during heating before annealing. These particles
will form on the elongated side of the grain after cold
rolling, impeding equiaxed grain growth, so that blocky
ferrite grains develop. Furthermore, TEM investigations by
Van Snick et al.6 5 showed that the small (3 nm) precipitates
found at grain boundaries after low temperature coiling had
grown to 10 15 nm after annealing and matrix precipitates
that were not visible after coiling had grown to 5 10 nm
after annealing, suggesting that further NbC precipitation
had occurred, reducing the bake hardening response.
The in uence of cooling rate on the retention of carbon
in solution after NbC solution has been investigated by a
number of researchers.4 0 ,6 0 It can be seen from Fig. 19
(Ref. 60) that a cooling rate of at least 20 K s 1 after
annealing at 900 C for 60 s is necessary to achieve an
adequate bake hardening response in a fully stabilised Ti
Nb steel after full solution of carbides. Cooling rate had no
in uence on the understabilised chemistry (Nb/C ~0 .25),
since carbide solution had not occurred. Since the annealing
temperature in this investigation was certainly high enough,
it would suggest that an Nb/C ratio of 0 .25 is too low for
carbide solution. It would seem that a minimum Nb/C ratio
of ~ 0.3 is required before any carbon can be liberated by
high temperature annealing.
The effect of holding temperature in the galvannealing
line on bake hardening was studied by Satoh et al.6 9 The
steel was annealed at 870 C and rapidly cooled to retain
carbon in solution. A considerable drop in bake hardening
observed with holding temperatures of 700 800 C was
attributed to the formation of NbC. A slight decrease was
also seen at 300 C, owing to Fe 3 C precipitation. Holding
within the normal range (400 600 C), however, had no
Materials Science and Technology April 2002 Vol. 18
366 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels
Bake hardening (MPa)
Temper rolling reduction (%)
20 Effect of temper rolling on bake hardening response
of ZSTE180BH steel in as temper rolled (BH0) and
temper rolled and 2% prestrained (BH2 ) conditions71
in uence on the nal bake hardening properties, making
these steels suitable for both continuous annealing and
galvannealing.
The solution and reprecipitation of niobium carbides
during annealing is clearly dependent on a number of fac-
tors including composition and coiling history and further
research will be necessary before a de nitive understanding
and adequate process control can be achieved.
TEMPER ROLLING
Lee and Zuidema4 3 showed that increasing the temper
rolling extension of aluminium killed batch annealed steel
from 1 to 5% decreased the bake hardening increment from
60 to 45 MPa and suggested that this was a result of stress
relaxation in the strain elds of dislocations during paint
baking. This is in agreement with work by Low and
Gensamer,7 0 who separated the stress relaxation component
from the total strain aging in a low (0 .01%) carbon deep
drawing steel, showing that the change in yield strength
of the material reached a maximum at 10% strain, decreas-
ing at higher strains. In contrast, the stress relaxation
component increased monotonically as the initial strain was
increased. Thus, the yield strength increase is independent
of prestrain; however, since stress relaxation increases with
increasing initial strain, the apparent increase reduces in
magnitude. If this interpretation is correct, temper rolling
should produce a larger decrease in bake hardening than
tensile strain, since the inhomogeneous strain imparted
may produce local strains far higher than the macroscopic
temper mill extension applied. In these areas the stress
relaxation would be high and hence the bake hardening
reduced.
Bleck et al.7 1 found that in a hot dip galvanised IF type
bake hardening steel the strength increase after a 2%
prestrain (BH 2 ) remained essentially constant once the
temper mill extension had reached 0. 5% (Fig. 20). In con-
trast, the bake hardening response in the as temper rolled
material (BH 0 ) was found to decrease with temper mill
extensions 41. 5%. Although this was attributed to the
increase in yield strength after these strains, it may also be
affected by the differences in dislocation density of the as
temper rolled and prestrained material.
Temper rolling is the nal step in steel processing and is
particularly important for bake hardening steels. Not only is
the shape of the strip controlled, but temper rolling is essen-
tial in the production of a steel that will not age at room
temperature. When carbon is in solution, the yielding beha-
viour of the steel is discontinuous, i.e. a sharp yield point
accompanied by a yield point extension will be seen on the
stress strain curve. Successive microyielding leads to the
formation of Luders bands, which manifest as stretcher strain
Materials Science and Technology April 2002 Vol. 18
markings in pressed sheets. These markings, once formed,
cannot be disguised by painting or other surface treatments
and are highly undesirable in exposed applications. Temper
rolling can prevent discontinuous yielding by imparting a
small strain in the strip. The yield point elongation is exceeded
by this strain and further yielding is continuous. Over time,
interstitial elements will diffuse to the mobile dislocations
produced during temper rolling and the yield point will
reappear. Non-aging steel, considered to be stable at room
temperature for three months, can be achieved by temper
rolling a bake hardening steel in the range 0.8 1.4%. Temper
rolling extension is believed to retard aging at low tempera-
tures because the characteristic `herringbone distribution of
dislocations generated when the steel is rolled prevents the
formation of Cottrell atmospheres.
The mechanisms behind the in uence of temper rolling on
bake hardening remain unclear and further research in this
area is necessary.
Conclusions
The extensive ongoing research into all aspects of bake
hardening steels indicates their importance to the auto-
motive industry.
For the most part, the classical strain aging theories of the
1940s and 1950s remain applicable. Bake hardening is
universally agreed to be a result of the formation of Cottrell
atmospheres during heat treatment of the steel. Classical
studies demonstrated the existence of a second stage during
strain aging, which is attributed to the formation of
precipitates on the saturated atmospheres. However, in
the context of current steels having reduced carbon con-
tents, the existence of a precipitation stage during bake
hardening has been questioned. Some researchers have
observed a two stage strength increase during bake harden-
ing, but no precipitates have been observed. Furthermore,
work has concentrated mainly on ELC steels, with little
research on the IF type ULC steels commonly produced for
the automotive market. Clearly, more research is required
to elucidate the mechanisms responsible for bake harden-
ing in these modern chemistries if a consistent product is
to be produced.
Other metallurgical factors such as the in uence of solute
carbon content and the in uence of ferrite grain size on
bake hardening have also been widely researched, although
again this has been mainly con ned to ELC steels with little
work on IF type ULC steels. It is now generally accepted
that solute carbon should be controlled to 15 25 ppm to
produce a bake hardening response of 30 60 MPa. Lower
solute carbon contents will not produce adequate bake
hardening, whereas increasing the solute level will lead to
problems in the room temperature aging properties of the
steel.
The in uence of ferrite grain size is still the source of
debate. Many studies have indicated that a ne grain size
improves the bake hardening properties. However, a sig-
ni cant number of researchers have found grain size to have
no in uence. If ferrite grain size does in uence bake
hardening, this would be a valuable route to increase the
bake hardening response without compromising room
temperature aging properties. More research in this area
is obviously necessary.
Of the bake hardening steels in production, IF based
chemistries are receiving most attention because of their
increased formability. These steels can contain titanium and
niobium to control solute carbon and nitrogen contents and
may be fully or understabilised. Vanadium containing steels
are also being used and show good potential for increased
bake hardening performance. The in uence of vanadium on
carbon mobility is unclear and more research is required
 Baker et al. Metallurgy and processing of ultralow carbon bake hardening steels 367
before it can be used in the widespread manufacture of these
steels.
Whichever alloying combinations are chosen, careful
control of additions during steelmaking is required to
ensure a controlled amount of carbon remains in solution in
the nal product. Slab reheating causes the solution of all
niobium precipitates and some titanium precipitates; care
must then be taken during downstream processing to ensure
that reprecipitation occurs at the correct time. High hot
rolling nishing temperatures are required to ensure rolling
above the Ar3 temperature to prevent strained ferritic
rolling. Coiling has an important effect on the annealed
properties of the steel and must be controlled, especially in
the niobium bearing steels. Coiling at too high a tem-
perature will lead to the formation of coarse NbC, leaving
little carbon in solution for bake hardening: low coiling
temperatures may lead to supersaturation of the steel lattice
and the precipitation of NbC during annealing. Annealing
itself can be vital, particularly when fully stabilised chemis-
tries are used. With the right coiling history, producing ne
NbC particles, high temperature annealing can be used to
dissociate NbC and retain suf cient carbon in solution to
produce bake hardening. The solution of precipitates is
dependent on many factors including composition and
coiling temperature, and further research is necessary to
clarify these interactions.
The nal processing stage, temper rolling, is critical in
ensuring that the steel does not age at room temperature.
The reasons behind the inhibition of strain aging by temper
rolling are not entirely understood, but it is thought that
the inhomogeneous strain patterns produced in the mater-
ial prevent the formation of Cottrell atmospheres. Bake
hardening has been shown to decrease with increased
temper rolling, although this effect appears to be dependent
on the particular bake hardening test used. Better under-
standing of the effect of temper rolling on bake hardening in
IF chemistries, which has not been widely studied, would
clearly also be bene cial.
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