ISIJ international, Vol, 38 (1 998), No. 10, pp.

1130-1 139

Strengthening Mechanismsin VanadiumMicroalloyed Steels

Intended for Long Products

S. and R. LAGNEBORG
ZAJAC.T. SIWECKl.W.B. HUTCHINSON
Swedish Institute for Metals Research, Drottning K~istinas vag 48, S-1 14 28 Stockholm, Sweden, E-mai swzc@simr.se l:

(Received on Aipril 10. 1998.• accepted in final form on May26. l998)

The present work has concentrated on the roles of vanadium, nitrogen and carbon in controlling the
microstructures and strength of steels designed for hot rolled long products. Effects of cooling rate and
additional microailoying with titanium have also been included.
The degree of precipitation strengthening of ferrite at a given vanadium content dependson the available
quantities of carbon and nitrogen. The nitrogen content of the ferrite is approximately the sameas that of
the austenite from which it forms, i.e. the total nitrogen content in steel, It was confirmed that nitrogen is
a very reliable alloying element, increasing the yield strength of V-microalioyed steels by some5MPafor
every 0.001 •/• N, essentially independent of processing conditions.
Carbon content, on the other hand, has usually been considered not relevant to precipitation strengthening
whenthe precipitation occurs in ferrite because of the very small carbon content in solution in ferrite at
equilibrium. Wedemonstrate that the effective carbon for precipitation in ferrite
maybe muchgreater than
this during the period of phase transformation, which in turn has a great effect
on precipitation strengthening.
Such behaviour is explained on the basis that the activity of carbon in ferrite is abnormally high in the
presence of under-cooled austenite and before cementite nucleation so that profuse nucleation of vanadium
is encouraged. This
carbonittide new mechanismfor precipitation is particularly significant for medium
carbon steels typically used for hot rolled bars and sections.
The total carbon content of the steel also contributes to the yield strength by increasing the volume
fraction of pearlite, It is shownthat the contribution from pearlite is stronger than generally recognised.

KEYWORDS:
V-microalloyed steels; phase transformation; stfengthening; carbo-nitrides.

for purposes of deoxidisation but

1. Introduction mayalso react together
with nitrogen as aluminium nitride. The aluminium is
The present work was carried out with the aim of normally dissolved in austenite at high temperature prior
improving the mechanical properties of hot rolled long to rolling but the nitride phase is thermodynamically
products through the control of steel chemistry and stable at lower temperatures. However, precipitation of
processing. Muchattention has previously been devoted AlN is sluggish and the particles formed relatively
to fiat products produced from microalloyed steels on coarse.3) Accordingly, AlN has little influence on the
strip and plate mills.1) Different approaches have been structures or properties of hot rolled steels although it
used successfully for flat rolled products but a common can contribute to grain refinement after normalising.
feature has been the adoption of a low carbon content Titanium forms an extremely stable nitride TiN which
( ~ 0.1 o/. C) due to the critical importance of weldabili-
ty and toughness. For long products where a high fin-
is virtually

ishing temperature is unavoidable it is, however, nor-
mal practice to utilise higher carbon contents around
0.250/. C to enhance strength and, in addition, micro-
alloying is also widely employed.
Most published literature (e.g. Ref. 2)) does not sug-
gest that differences in carbon content in the range
quoted above should affect significantly the response of
these microalloying elements in the steel. Wehave,
however, been obliged to reappraise this viewpoint in
the light of the present findings.
Four microalloying elements are widely used in various
combinations to irnprove the mechanical properties of
structural steels. Aluminium is almost universally present
restricting
insoluble in austenite and
maybe effective in
its grain growth during processing. Only
a
small titanium addition (-0.01 ~/. Ti) is required for
this purpose.4) If larger contents are present the excess
titanium can precipitate at lower temperatures as a
carbide TiC which contributes a precipitation harden-
ing effect. Niobium forms carbonitrlde phases Nb(C, N)
which are stable at low temperatures in austenite but
disso]ved at higher temperatures, for example, during
re-heating prlor to rolling. Nb(C, N) can precipitate quite
readily in austenite under deformation (strain induced
precipitation) and the particles so formed resist grain
growth and even recrystallisation of the austenite during
the intermittent deformation at lower temperatures. The
deformed austenite structure transforms to fine grained

@1998 ISIJ 1130

 ISIJ International, Vol. 38 (1 998), No, 10

ferrite
on cooling, which imparts both high strength and more prominent in Ti and Nb microalloyed steels than
toughness to such 'controlled rolled' steels.5,6)
A fur- in vanadiumsteels and it is also
moreevident with lower
ther precipitation of the remaining niobium as smaller carbon levels where the transformation temperature is

particles during cooling gives rise to additional strength- higher.

ening. Niobium microalloyed steels lend themselves to Since the nitrogen contents of commercial structural
many flat rolled products where powerful mills are steels,
up to 200 ppm, are generally below the solubility
available to process the deformation hardened austenite limit in both ferrite and austenite, all the nitrogen is
but not to long products such as profiles where more available for precipitate formation, whether this occurs
complex shaping is involved which requires high finish homogeneouslyor by the inter-phase mechanism. This
rolling temperatures. Vanadiumis the most soluble of meansthat nitrogen is always present in a form where
the four elements discussed here and does not readily it
can react efficiently with microalloying elements.
precipitate in austenite.7) The nitride VN is considerably Carbon, on the other hand, is present in larger amounts
more stable than the carbide and it is probable that but has only a very restricted solubility in ferrite. Thus,
nitrogen-rich V(C,N) is the phase which occurs most while the total carbon content might be expected to have
widely. Since V(C, N) has high solubility in austenite it some effect on inter-phase precipitation (due to the
hardly affects the hot deformation process but rather content dissolved in austenite) it would not be expected
precipitates during cooling in ferrite, thereby increasing to influence homogeneousor random precipitation in
the strength level of the steel. This precipitation hard- ferrite.12) Indeed, the effect of total carbon content on
ening Is markedly enhanced with increasing nitrogen precipitation strengthening is usually considered neglig-
in the steel and so nitrogen is considered as ible in microalloyed steels. In the following sections
a beneficial we
alloying element in vanadiummicroalloyed steels. Since shall show that this assumption is not correct, at least
vanadium gives little structural refinement on its ownit in V-microalloyed steels.
Weshall also demonstrate that
is often advantageousto combineit with small titanium (about 0.010/0 Ti) in these
a small titanium additions
addition to control the austenite grain size during hot V-microalloyed steels can give rise to interactions which
rolling and thereby refine the resulting ferrite micro- are muchgreater than previously recognised. These new
structure on cooling as nitrides or carbides after hot findings are of major significance for the design of steel
roiling. chemistry intended of hot rolled long products.
A combination of different microalloy elements in the
same steel
can naturally lead to interactions since they
2. Experimental Procedure
compete for the sameInterstitial elements and mayalso
form mixed compoundswith one another. For exarnple, The was carried out on eleven V-mi-
investigation
the stable TiN phase mayincorporate significant amounts croalloyed and two (V + Ti)-microalloyed steels with
of both Nb and V and even AlN has sometimes been 0,15O.22 o/. Cand various levels of nitrogen. The chem-
detected in complex titanium nitrlde particles. Since the ical compositions and V/N ratios are given in Table
(Ti, Nb, V)N particles are rather coarse such an effect l. They were divided into 4 groups; D- (0.22010C-
reduces to someextent the contribution which the Nb O. 120/*V),
E -
(0.220/.C-0.06"/.V), G
-
(O.15"/*C~.12~/oV)
or V can be expected to make towards precipitation and H - (O.22"/oC-O, 120/0V-0.0 1"/.Ti). A11the steels were
strengthening.4'8) prepared as 2kg laboratory ingots (1 5x 120 in cross
Whenprecipitation of TiC, Nb(C, N) or V(C, N) takes section) with a cooling rate during solidification
mm
designed
place during cooling after hot rolling it may do so in to simulate commercia] continuous casting.
two different ways. Oneof these is so called inter-phase The ingots were homogenisedat 1250'C for 4h and
precipitation where nucleation occurs on the austenite- water quenched before heat treatment. Then, careful
ferrite phase boundary, producing a particle-rich sheet examination of the austenite grain size and dissolution
at the location where the boundary temporarily
is halted. of V(C, N) was performed in order to determine the heat
Thecarbonitride particles continue to grow until another treatment temperature for each steel. The criteria for the
ferrite ledge passes over them and the process is repeat- determination of the heat treatment temperature were
ed.9) This precipitation modewhich appears as rows of that the steels had the sameaustenite grain size (100 /Im)
particles in the transmission electron microscope (TEM) after austenitisation and that the temperature was such
is only possible at relatively high transformatlon tem- that all vanadium (and nitrogen) had gone into solid
peratures. A
characteristic feature is also that the
rows solution for subsequent precipitation. The actual heat
of particles that are formed in the same region on treatment temperatures that were adopted are also given
the samephase boundary all possess the sameorienta- in Table I
Specimenswere austenitised for 10 min prior
.

tion, a unique variant of the BakerNutting (B-N) ori-
entation relationship with the ferrite matrix.io) Alter-
natively, homogeneousnucleation and growth of the
carbonitrides may occur in the newly formed ferrite,
notably at lower transformation temperatures. In this
case the particles are not aligned in rows but are randomly
distributed and also are characterised by the occurrence
of different variants of the B-N orientation relation-
ship.ll) The tendency for inter-phase precipitation is
to isothenTlal transformation in salt baths maintained at
the appropriate temperature in the range 550-700'C or
to continuous cooling at 0.5, 5'C/s or 15'C to room
temperature. The holding time at the isothermal tem-
perature was 100 and 500 s followed by coollng at
5'C/s to room temperature.
After isothermal transformation or continuous cool-
ing, the ferrite grain size, the volume fraction and the
interlame]lar spacing of pearlite, precipitate morpholo-

1131 Q 1998 ISIJ

 ISIJ International, Vol, 38 (1 998). No. 10

Table 1. Chemical compositions of the investigated V and V-Ti microalloyed steels.

Steel C Si Mn P S Al V Ti N VN T nL]stcT]

D1 O.22 0.40 l .37 o.008 O.014 o006 0,120 oool 5 29.0 1125•C
D6 0.22 o40 1.41 o,008 0.015 o006 0,120 o0059 56 i 050'C
D12 0.21 o39 1.39 O014 0,006
o,006 0,122 ool 17 28 1170'C
D13 0.22 o39 ~.3 8 o008 O016 o006 0.119 O.0126 26 1140'C
D19 0.22 o40 l .40 o,008 O015 o.006 O.120 0.0 192 17 1160'C
D22 0.22 0.40 l .40 o008 O013 0,006 0,123 o0222 15 l 125'C
E6 0.23 o39 l .3 8 o006 O013 0,004 O.056 o0065 24 111O'C
E12 0.22 o40 l .39 o.008 0.016 o006 0.058 oall5 14 111O'C
E24 0.21 0.40 l 38 o,a08 O014 o006 0.089 o0236 lO l 125"C
G13 0.15 0.40 143 o,006 O014 o005 0,120 1
o.o 36 2.4 l 040'C
G23 0.15 o40 139 o,008 O016 o005 O.128 O.0234 1.5 1170'C
H12 0.22 o39 l 38 o,006 O013 o005 0.120 0.01 1 o0124 27 1205•C
H24 0.21 0.39 1.38 o008 O014 0,005 0,126 O014 0.0240 15 i21O'C
Other: Nb O.002, Cr OOl O, Ni OO18, M0 0.004, Cu O.008
* Stoichiometric basis

800 800

750
750
700
o o
- 650 - 700

600
650
550

500 600
o o005 ool ool 5 o02 o025 o 12 o15 O18 O21 o 24
Wtolo N wio/• C
Fig, l. Effect of nitrogen and carbon contents as wel as cooling rate on the Ar3 temperatures of the present
steels.

gies and size distribution of V(C, N) particles as well as after I

annealing at 050'C and the calculated dissolu-
yield strength of the steels were evaluated. The fer- tion temperature for V(C, N) in the respective steels. The
ritepearlite microstructures were examined by optical titanium containing steels were muchmore resistant to
microscopy after etching in nital. Lower yie]d strength grain coarsening than the corresponding V-microalloyed
wasevaluated on small compression specimens(ip5 x mm ones and showed a tendency towards mixed austenite
5 mm)machinedfrom the metallographic samples. grain structures after heat treatment. Little evident effect
Precipitate morphology and general structural effects of this was seen in the microstructures after transforma-
were studied on carbon extraction replicas and thin foils tion and it is considered that the initial treatments were
prepared from the isothermally transformed or contin- fully successful in achieving their goals of
a constant
uously cooled specimens. These were then examined in austenite grain size and full dissolution of the V(C, N)
a transmission electron microscope (TEM) JEM2000 phase.
EXoperating at 200kV. Electron diffraction and dark
field analysis
were used to identify the precipitate phases. 3.2. Transformation Behaviour
The thin foils were used mainly to study the general Transformation temperatures were determined by
structural features and extraction replicas were used to
dilatometry at three different cooling rates, O.5, 5 and
study precipitate morphology. Distributions of pre- 15'C/sec and in all cases showedthe expected reduction
cipitate sizes
were measured on micrographs by means in Ar3 with increasing cooling rate. Results which are
of an image analysing system IBAS.
summarisedin Fig. I showthat there was sometendency
for the Ar3 temperature to reduce at higher nitrogen
3. Results and Discussion
levels, especially for faster cooling rates. This
3.1. Austenite Grain Structures mayreflect
the inherent austenite stabilising effect of dissolved
The tendency for grain growth in austenite became nitrogen or, alternatively, some effect of V(C, N) pre-
less as the contents of nitrogen and vanadium in the cipitation on the kinetics of ferrite growth. There is
steeis increased.
A
full description of this behaviour is no measurable effect of the titanium additions on the
given in Ref. 13) where there shown to be good was a Ar3 temperature. However, a reduction of carbon content
correlation between the austenite grain size measured from 0.22 to O, 15o/o has a significant influence in raising

@1998 ISIJ 1132

 ISIJ International,
Fig. 2. Optical micrographs after diffei'ent
isothermal t]~ansformation at (d)
the transformation temperature as it would be expected
from the phase diagram.
A small influence of nitrogen content was seen during
isothermal phase transformatlon in the range 550 to
700'C. Raising the nitrogen level from 0.001 to 0.02010
accelerated all stages of the transformation, reducing the
times by about 40 o/o. Such an effect is at odds wlth the
results of the continuous cooling behaviour and, although
small, seemsto be consistent with earlier work on lower
carbon structural steels.14)
Additional isothermal transformation experiments
were carried out on selected steels using heat treatments
in a salt bath at 650'C after austenitisation, then followed
by water quenching. Metallographic examination of these
specimens was carried out to determine the amounts of
ferrite, pearlite and untransformed austenite which were
present as a function of the holding time. These results
showed that the time for the on-set of pearlite trans-
formation in the 0.22 o/o Csteel wasabout 3times greater
than for the O, 15o/o Csteel.
3.3. Microstructures
Optlcal micrographs of the final structures are pre-
sented in Fig. 2
for the steel D22 whlch was essentlally
typical of all the steels with the higher carbon level
(-0.220/0 C), irrespective of vanadium or titanium
content. Figures 2(a)2(c) demonstrate the effect of the
Vol. 38 (1998), No. 10
constant cooling rates (a) 0.5*C/s, (b) 5*C/s and (c) 15'C/s, and after
650'C, (e) 600"C and (O 550'C.
different cooling rates. At the lowest rate of 0.5'C/s the
structure consists of pro-eutectoid ferrite delineating the
prior 'austenite grain boundarles together with pearlite.
At 5'C/s the grain boundary ferrite is thinner while the
majority of the structure consists of upper bainite or
interlocklng Widmanstatten ferrite in finely dispersed
pearlite. For the fastest coollng rate of 15'C/s there is
still
a very thin skeleton of ferrite at the prior austenite
boundaries but most of the structure consists of lower
balnite with somepresence of martensite.
Figures 2(d)-2(f) show structures of the isothermal-
ly transformed steels. At 650'C this consists of pro-
eutectoid ferrite and pearlite, resembling quite closely
that of the slowly cooled steel (Fig. 2(a)). The amount
of primary ferrite decreases on transformation at lower
temperatures and a Widmanstatten morphology becomes
predominant at 550'C. The remaining constituent is,
however, pearlite in all cases.
There was little visible difference between the mi-
crostructures of the titanium-containing steels and those
microalloyed wlth v'anadium alone. The lower carbon
steels contained, as expected, Iess pearlite and showed
less tendency to formation of Widmanstzitten
or bainitic
structures.
Measurementswere madeof the volume fractions of
different phases as wel] as the ferrite grain size and pear]ite
inter]amellar spacing. With increasing cooling rate or
1133 O 1998 ISIJ
 ISIJ Internationai, Vol. 38 (1998), No. 10

lowering of the isothermal transformation temperature
there was a tendency for the volume fraction of pearlite
to becomegreater and for the Interlamellar spacing to
decrease. The morphology of the pearlite varied con-
siderably, even within one and the samespecimen. Some
regions showed classical lamellae whereas in others
the cementite was discontinuous or even spheroidised.
Twoexamples are shownby TEMmicrographs
foils in Fig. The tendency for discontinuous pearlite
3.
structures becameenhanced at lower temperatures and
higher cooling rates.
Precipitate morphology wasexaminedin
steels using both foils and carbon replicas
Vanadium-rich particles, presumably nitrides or carboni-
trides, were always visible in the ferrite. This was true
for polygonal ferrite as well as pearlitic ferrite. Some
examples of the precipitate distributions are shown in
Fig.4. For the heat treatment conditions which have
been described above there was no tendency for pre-
cipitate
row formation. For all conditions relevant to
the present discussion the precipitates were randomly
distributed, either nucleated homogeneously in the
of thin matrix (Fig. 4(b)) or on dislocations in the acicu]ar ferrite
structures (Fig. 4(c)). The fact that these particles had
formed in the ferrite after transformation and not on the
inter-phase boundary during transformation was evident
several of the both from their randomdispersion andfrom the existence
in the TEM. locally of several different variants of the B-Norientation
relationship. This is an important distinction as will be
discussed below.
Detailed measurementsof particle sizes were made
using extraction replicas on steels having different
nitrogen contents after isothermal transformation at
650'C. For steel having 0.0050/0 nitrogen the particles
were relatively sparse with an average diameter of - nm. 6
They becamesmaller and more dense with increasing
nitrogen content, having a size of only
- 3nm in the
0.022 o/o N
steel.

3.4. Yield Stresses

Yield stresses for the different steels and conditions
investigated here are summarisedin Fig. 5where results
of continuous cooling treatments are shownin (a) to (c)
and isothermal treatments in (d) to (f). There is a striking
similarity between
these figures where strength in
all

as a functlon of nitrogen content in the steels.

plotted
Whenthe steels are separated into the four classes
according to carbon, vanadium and titanium content
there is in each case a fairly uniform gradient cor-
responding to -5MPaper 0.001 o/o N. This is clear
confirmation of the preference for vanadium to form
nitrldes or nitrogen-rich carbonitrides. As the nitrogen
content is increased the chemical driving force for
Fig. 3. Transmission electron micrographs showing different
precipitation
is Increased and the particles becomefiner
pearlite structures In continuously cooled samples of and more numerous, thereby increasing the yield stress.
steel D13, The samephenomenonhas been recognised previously

Fig. 4. Transmission electron micrographs of precipitates in isothermally transformed samples (a)

(b) D6 650'C, (c) D13_ 650'C and (d) D22 650'C.
steel
D13700'C,

C 1998 ISIJ 1134

 ISIJ Internationa]. Vol. 38 (1998), No. 10

700 725
(a)
Continuous cooling 0.5'C/s
700
lsothermal tra nsformation (d)

650
-
600'C!500s
~
:~ ~
~!
675
600 650
u, U'
-

u) CO
UJ UJ
625
a(
h
co
C]
550
~
U)
600 -

500 O
d JJ
575

>-
450 -
1::b'22c-~.12V
l~- o,22c-o 06v l !
U
> 550 - -1- O22C-O12V
i~ O22C-O06V
400
-~-
~~
o,i 5c-o i 2v
o22c-o 12v+Ti
525
-h 12V
O.15C-O
_-Q-022C-O.i2V+1LJTi =
-
500 -

o 0,005 0,01 ooi5 o02 0,025 o o005 o ol oOi5 o02 o,025

800
(b) 700 -
Continuous cooling 5'C/s (e)
675 lsothermal transformation
650'C/500s
~
E
750
~
E
650
625
U' 700
C,;
U) -
U) 600
UJ
a,: O( 575
h
,,) 650 -
h
U) 550
O Q
J
J 525

> 600 ;:
500 =1- O22C-O1~V
-
1~i' J 2~c-5,1
2v l~ O22C-O06V
L~_=_
-~- o22c-o 06v :
475 -O- O22C-O12V+T'
550 -~ __'_____~
o 15c-0'1 2v 450 -~ 5C-O12V
0.1

o o005 OO1 OO15 o02 o025 o o005 OO1 0.01 5 o02 o025
Wto/. N WtQ/o N
1200 (c) Isothermal transformation
0.0130/0 N 72o (D
lioo ^
O.2201DC-O120loV-N
~
.

E 1 ooo ~
E
700

680
g, 900 C,'
U) CO 660
UJ
Q: 800 O( 640
h
U, 700
~
U,
O 620
-

J Q
J
UJ 600
Hlh O22C-O12V UJ 600 H~HO022'/•N
>,
500 ~r 15C-O12V --] l
O22C-0,06V i > ~r0'013D/QN
H~0
-O- O,22C-Oi2V+Ti
580 -h0'0120/0N
HF0'O0150/0N
400 560
-

- =--
o 10 i5 500 550 600 650 700 750

COOLING
RATE, 'Cls Transformatron Temperature, 'C
Fig. 5. Yield stresses as function of nitrogen content after continuous cooling at (a) 0.5'C/s, (b) 5'C/s, (c)
a range
of cooling rates and after isothermal transformation at (d) 600'C, (e) 650'C and (D a range of different
temperatures.

in lower carbon structural steels.14)
Reduction of the vanadium content from 0,12 to
0.06 o/o brings about a decrease of
- 70 MPain the yield
stress. Such an effect is to be expected as the amountof
the strengthening phase V(C, N) is necessarily decreased.
More surprising are the markeddecreases in
occasioned by the reduction in carbon level from O.22
to 0.15 "/o as well as by the presence of so little as 0.01 ol*
titanium. The actual decrements in yield stress lie in the
range 75 to 100 MPafor the isothermal treatments and
rather more for the continuously cooled samples. When
the yield stress data for the isothermally transformed
steels are plotted against the transformation temperature
as in Fig. 5(f) there is seen to be a maximum in the
vicinity of 600'C for both the carbon contents investi-
gated. The loss of strength above 600'C
may be a
combination of the coarser ferrite and smaller fraction
of pearlite as well as a larger particle size for the
vanadium-containing precipitates. Below 600'C, the fall
must be attributed to incomplete precipitation as more
of the vanadium is retained in solid solution due to its
low diffusivity at these temperatures.
The effect of cooling rate on strength is of especial
yield stress interest as improved properties
maybe achieved without
the addition of extra alloying elements in
an economical
wayby accelerated cooling. Yield stresses plotted against
cooling rate in Fig. 5(c) show an almost linear rela-
tionship having a slope of approximately 25 MPa/'C/sec
which is about double that observed in lower carbon
plate steels previously.14) The
more powerful effect of
cooling rate in the present case
maybe in part due to
finer scale precipitation of V(C, N) and in part a result
of increased hardenability of the matrix. For example,
the strong influence of carbon content at the highest
cooling rate of 15'C/s is probably mainly due to the oc-
currence of hard phases such as bainite and martensite.

1135 C 1998 ISIJ

 ISIJ International, Vol. 38 (1 998), No. 10

1ooo 300
@Gladman
et al (normalized) 16) (a) Isothermal Transformation
900 OGladman
et al (1 100'C) (16) 280
650'C!500s
800
AKouwenhoven(1 7) 260
.Zajac et al (15) and present results

~ .\ \O
i20/0V-O 013010N
:~
Q;
700

600
o
~D
"~i$\ ~
~
240

220
Q)
UJ AA A d~l
\1F
' \~\. :2 200
O( 500 '
Q(
H
,,)
400
" ' I~
~
900
",'
~ AA~ 180
JO A A~A
'
E3
d~ 160
LU 300 O IH0.22C-O i2V
> C-Mnsteels A i~- 0.22C-O 06V
140 -•- O22C-O
15C-O12V
200 A
120 -O- O 12V+Ti
1oo O O005 OO1 OO15 O02 O025
o wiolo N
o 02 04 06 08 1
Fig. 7. Deducedvalues ofprecipitation strengthening in steels

~
~
500

450
(b) isothermally transformed at 650'C.

Rep=fp {1 78+3.8(Sp)~~5}

~
O
400
sp
(
Re=, f.(a + d~ l/2) + I -, f.)(b + S, 1/2) + Si + N+ p+ ARp

~
350

300
-
E-**
i50nm
250nm Re=./~ {66 + 51('/* Mn)+ 12, I (d.) ~ 0.5}
- 350nm
-

O 250 + (I -,f.){ 150 + 3.4 (Sp) ~ 0.5} + 73(o/oSi)

O
~:a'

UJ
200 + 425("/oN)0.5 + ARp
O,
,: 150 Here, ARp is the contribution due to precipitation
strengthening which is to be determlned from the ex-
~ a,
1oo
Gladmanet al. (16) ~~*
--~_ \ perimentally measured yield stresses together with
C 50 Rep= I -(f*) I /3]{1 78+3. 8(Sp)~~'2}
O f values of ferrite grain size, d., pearlite fraction, (1 -.f.)
CO o and pearlite interlamellar spacing, Sp. According to the
o2 04 0~ 08 1
above expression an increase in carbon content from O. 15
FERRITE,f*
to 0.220/0 raises the yield stress by some65MPa when
Fig. 6. Experimental data (a) and models for pearlite con- only the contributlon from pearlite Is considered.
tribution to yield strength (b).
Flgure 5 shows that generally similar behaviour was
found for all the conditions studied but for simpiicity of
3.5. Analysis of Strengthening Mechanisms analysis we shall restrict ourseives here to the 650'C
A when considering the strength of
usual practice isothermal data where the microstructures clearly con-
structural steels is to express the yield stress by a series slsted of equi-axed ferrite and pearlite nodules. Values
of terms representing (i) the iron matrix, (ii) solid solution of the precipitation strengthening ARp deduced using
effects, (iii) grain size, (iv) precipitation hardening and the above expression are plotted as function of nitrogen
in
somecases also content (2). For low carbon
(v) pearlite content in Fig. 7.
structural contribution due to pearlite is small
steels the Each of the four classes of steel chemistry shows a
and is frequently ignored. For higher carbon levels this similar dependence of precipitation strengthening on
is not
so and Gladmanet al.16) have analysed in detail nitrogen content. This agrees with the increasing density
the behaviour of steels containing ~0.40/. (~~55"/o C of precipitates that was observed in the and con- TEM
They firms the importance of the vanadium-nitrogen affinity
pearlite). obtained the best weighted meanof the
strengths of ferrite and pearlite as: for strengthening by second phase particles. The effect
of vanadium content (0.120.06 o/*) is qualitatively in
Re* =,f~/3Re.+(1 -fl/3)Rep
-p agreement with expectations but the effect of carbon
wheref* is the volume fraction of ferrite and Re*, Rep content (O.22-0. 15 o/.) remains to be explained.
are yield stress of ferrite and pearlite respectively. If it is assumed to begin with that the ferrite is

The present steels lie outside the range of Gladmanet strengthened by homogeneouslyprecipitated vanadium
al.'s study but rather higher in carbon content than for nitride then the driving force for nucleation which will
most previous studies. An examination of published data dictate the profusion of particles should be given ap-
for ferrite-pearlite steelsl6,17) Ied to the conclusion that proximately by the product of concentrations of and V
the most reasonable description of the contributions of Nin the steels. Onthis basis, the deduced precipitation
pearlite and ferrite to yield stress wasas a simple weighted strengthening contributions have been plotted against
mean, Fig. 6. Based on this assumption and using data the product (V x N) in Fig. 8. It is
seen that the steels
from published literature the yield stress could be having different vanadium levels have movedcloser to
expressed as: one another than in the previous figures but still do not
coincide. Also, extrapolation towards very low values of
the product (V x N) Ieaves a significant value of ARpin
all cases. These observations
can be taken to imply that

C 1998 ISIJ 1136

 ISIJ International, Vol. 38 (1998), No. 10

325 Table 2. Average nano-hardness values for ferrite grains

'-.-I-
O22C-O.12V after isothermal transformation at 650'C.
300 Oi 5C-Oi2V
la- 06V 0.22C-O
*-~ O22C-O12V~Ti
O.22C-O
275 - ,~> - i2V~Ti
•

I"II ll Steel Colo Vo/e No/o Average nano-hardness, Standard error

GPa (~)
~
E
250
I/1 D6
D22
o22 O.12 o005 3.750 0.083

225
0.22 0,12 0.022 4.250 O,
142
CL
Q(
l//~ /
l" ~~
A5 0,lO 0.129 0.005 2785 0,073
200 / A25 OlO
//
0.130 0.025 3.629 0,054

/ /
175 /
lr~*
800
150
750
125 *

O OOOI O002 O003 700

co

VXN :D

~650
UJ
Fig. 8. Deduced values of precipitation
strengthening for u
UJI
isothermally transformed (650'C) steels plotted against 600
ac
:)
the product of their vanadium and nitrogen contents. H 550
Data points joined by arrows indicate the effect of a:
UJ
vanadium being partially combined in TiN. I~
500
'
ferrite +
~
LU
•-
' : austenite
H 450 ferrite +
cementite :
not only nitrogen but also carbon is involved in the
precipitation 400
process.
It is
not a p,'iol'i evident whether the precipitations 350
consist of two species. VN
and VC, or whether they are
carbonitrides V(C, N) where the composition depends
the respective contents of the interstitials
on
A O 5
WEIGHT
1O
CARBON
_PERCENT ,
15,
E-3
20 25 30 35

in ferrite. On Fig. 9. So]vus lines for carbon in ferrite calculated using

balance and in the absence of chemical analyses of the Thermo-Calc for equilibrium with cementite as well as
particles austenite.
we believe the latter
description is the more
probable. All the present steels are hyperstoichiometric
with respect to vanadium and would be capable of grains. Sampleswere selected having four combinations of
forming sole]y the more stable due to the high VN nitrogen and carbon levels, isothermally transformed
diffusivity of nitrogen. If separate VCprecipitates were at 650'C. Between20 and 50 ferrite grains were measured
to form they would be expected to grow at almost the in each case and the results
are given in Table 2.
samerate as VN
particles, Iimited by the rate of diffu- The values in Table 2 show that the strength of the
sion of vanadium. (At these temperatures in ferrite the ferrite does depend on the carbon level of the steel as
equilibrium solubilities of vanadium are muchless than well as the nitrogen level, which therefore confirms that
the total contents in both cases). Any differences in the the precipitation strengthening is indeed dependent
upon
dispersion of particles must be associated with their the total carbon content.
nucleation frequencies. It VC
maybe possible that the At first sight there is no evident reason why the total
phase nucleates separately but more slowly than VN. carbon content should affect the precipitation of vana-
However, this seemsunlikely since the level of vanadium dium carbonitride since the solubility and activity of
in solid solution would be reduced by the carbon in ferrite is defined by the iron-carbon equi-
more rapid
nitride precipitation which would further reduce the librium in the two-phase structure. However, during
already weak driving force for carbide formation. Our transformation on cooling the equilibrium phases change
tentative conclusion is therefore that the strengthening from being ferrite + austenite to being ferrite + cementite
phase is V(C* Nl_*) for which the exact composition and there is a substantial change in the carbon solubility
as well as the scale of dispersion is dependent on the in ferrite. Figure 9
shows the two solubility limits for
combined activities of both nitrogen and carbon in the carbon in ferrite calculated using the Thermo-Calc pro-
newly transformed ferrite. cedure.18) At 600'C, for example, the solubility of
Figure 8
also confirms that the precipitation strength- carbon in metastable equilibrium with austenite is five
ening contribution is significantly reduced in the O. 15"/o C times greater than the true solubility in equilibrium with
steels as compared with those containing the higher cementite. Thus, during the initial stages of transforma-
carbon level, O.22 o/*. There seems to be no indication tion the activity of carbon in ferrite is very large and
in the literature that the total carbon content of the profuse nucleation of V(C,N) will be favoured. The
steel will affect the precipitation strengthening in ferrite, carbon activity wlll remain unchangedeven if V(C, N) is
espccially when this occurs homogeneouslyafter trans- being formed since the diffusion rate is very high and
formation. Therefore, in order to check that the pres- austenite provides an inexhaustible store. In practice the
ent findings were not the result of an incorrect evalu- metastable c(-y equilibrium solubilities
ation of the effect of the pearlite content,
may not be so
somefurther large as shown in Fig. 9 since diffusion of carbon in
measurementswere made using a nano-hardness inden- austenite occurs awayfrom the interface tending to lower
tor which cou]d be localised purely within the ferrite the concentration there. This will be accentuated if the

1137 C 1998 ISIJ

 ISIJ International, Vol. 38 (1 998). No. 10

1 steels may, according to the previous experimental

austenite
results,14) combine also vanadium up to (Ti0.7V0.3)N at
the solution temperature of 1
- 200'C, thereby reducing
z
the amounts of nitrogen and vanadium which are ava-
o
ao
ol ~r
-O-
fcc-O 22%C
fco-O Io/oC
=
' ilable for precipitation strengthening subsequently. In
a(
'1:
l
l~
[ l:~1!
i_:~
bcc-O 220/0C
J
i9( C
bcc- o~i~L:~
Fig. 8
the effect of this loss of available and N
is
V
o ,~ -
shownby newdata points joined by arrows to the original
ones. The newpositions are closer to those of the Ti-free
~~.'

~ 0,01
ferrite
stee]s but there is still
a large discrepancy. Thus, the effect
of titanium cannot be adequately explained by the
presence of (Ti, V)N precipitation. Observations during
oool -
isothermal treatments showedthat the rate of transfor-
O 20 40 60 80
mation was faster in the Ti-containing steels than similar
'/Q Transformed ferrite steels without titanium. This
mayhave been due to the
Fig, lO. Values ofcarbon contents in ferrite and austenite for somewhatduplex nature of the austenite grain structure
two different steel compositions calculated using and/or the tendency for the transformation products to
Thermo-Calc on the assumption that both phases nucleate heterogeneously on large titanium-containing
are homogeneous,
particles. A more rapid transformation will provide less
tirne forV(C,N) to precipitate the
presence of
in
interface migration is hindered by someeffect such as supersaturated carbon in the ferrite in the
manner
solute drag of substitutional elements. In the extreme discussed above, and accordingly a smaller degree of
case where boundary mobility is
very low and full precipitation strengthening. However, this explanation
equllibration of carbon can take place both in ferrite may be regarded as rather speculative and it is not cer-
and austenite the new metastable carbon levels can be tain that the effect of titanium on yield stress can be
calculated with the aid of Thermo-Calc (activities of understood at present. The present steels were, as
carbon in ferrite and austenite are equal). Figure 10 shows explained above, treated to contain constant austenite
such calculation for two different carbon contents and grain sizes. Under industrial hot rolling conditions the
demonstrates that the level of carbon dissolved In ferrite Ti-alloyed steels should maintain finer austenite grain
which governs the nucleation of V(C,N) is indeed a structures due to the pinning effect of TiN particles on
function of the total carbon content. In reality the carbon grain boundaries. Such an effect should compensateto
content in ferrite should lie somewherebetween these someextent for the loss of precipitation strengthening
values and the limit given in Fig. 9 (i.e. -0.024"/. at C and also makea useful contribution towards improving
650'C) depending on phase boundary mobility. the toughness. However, the present results are supported
The above situation continues until pearlite is nu- by experience of full-scale production which show that
cleated at which point a new equilibrium with a re- strength is often reduced when titanium additions are
duced carbon activity is established. So fast is the dif- madeto vanadiummicroalloyed steels in hot rolled long
fusion of carbon in ferrite that the transition can take products. 19)
place in less than one second for typical microstructures.
The great reduction in carbon activity at this stage is 4. Conclusions
likely to virtually eliminate further nucleation of V(C, N)
although some continued growth of existing particles The present study on a range of V-C-N-(Ti) alloyed
maybe expected. steels has examined the transformation behaviour and
As the total carbon level of the steel increases, the strengthening mechanisms after cooling in various
kinetics of the y-oc phase transformation are progres- mannersfrom austenitising temperatures where the ini-
sively retarded since
more time is required for diffusion tial structures
were nearly constant. The steel composi-
of carbon in the shrinking austenite. This was confirmed tions were chosen so as to be relevant to hot rolled
in the present steels from microstructures of samples structural long products.
quenchedafter different holding times at 650'C. Not only A major strengthening effect, varying between 100-
is the carbon activity in ferrite higher but also the period 300MPa, is due to the homogeneousprecipitation in
of tirne during which the ferrite is supersaturated with ferrite of vanadium-containing particles. These are
carbon is prolonged, so allowing more nucleation of probably carbonitrldes V(C, N).
V(C, N) particles and accordingly a more dense pre- The degree of precipitation strengthening at a given
cipitation. In these ways the positive influence of total vanadiumcontent dependson the available quantities of
carbon content on the precipitation strengthening con- carbon and nitrogen. The nitrogen content of the ferrite
tribution can be understood. is approximately the
sameas that of the austenite from
Figures 5and 7also demonstrate a reduction in yield which it forms, being closely related to the total nitro-
stress and precipitation strengthening when a small gen content in steel. Nitrogen is an important alloy ele-
addition (0.01 "/.) of titanium is made. It is well known ment in these vanadium steels and typically produces
that titanium forms nitrides TiN at high temperature an increase in yield stress of about 5MPafor each
which due to their large size produce almost no hardening 0.001 o/o N, essentia]ly independent of processing condi-
effect. Furthermore, such particies in VTi microalloyed tions and carbon contents. It affects the transformation

O 1998 ISIJ 1138

 ISIJ International. Vol. 38 (1 998), No. 10

kinetics to only a small extent. REFERENCES

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1139 O 1998 ISIJ