Optimum Microalloying of Niobium and
for Thermomechanical Processing*
By Hiroshi TAMEHIRO,** Masahiko MURATA,** Ryuichi HABU**
and Michihiko NAG UMO ***
Synopsis
For application to thermomechanical processing (TMP) with acceleated
cooling,effectof a combinedaddition of boron and a grain-refining element
such as niobium, titanium or vanadium in very low carbon steels was
studied in terms of mechanicalproperties and microstructures. It was
found that, although boron as a single addition has little effecton theprop-
erties, the combined addition of niobium and boron improvesthe strength
and toughness balance. A separate addition of boron produces coarse
Fe23(CB)s precipitates at austenite grain boundaries after rolling and
boron is consumedto invalidate the effectof r-a transformation suppres-
sion. Niobium addition to boron steel suppresses the precipitation of
Fe23(CB)s and strongly retards the r-a transformation to form a fine-
grained bainitic structure. Titanium has the same effectas that of nio-
bium, but vanadium does not. The strengthening and tougheningmecha-
nism by the combinedaddition of niobium and boron was also investigated
by examining the effectof alloying elementson the minimumrecrystalliza-
tion temperature of austenite during rolling, and r-a transformation be-
havior.
Key words: microalloying of boron; controlled-rolling; high strength
niobium-microalloyedsteel; toughness; grain-refinement; bainite structure.
I. Introduction
Since it was found that hardenability of steel is
markedly increased by microalloyed boron, the effect
of boron has been investigated and clarified by many
researchers.'-8) Boron has been widely applied to
quenched and tempered (QT) steels such as 80 kgf/
mm2 class high tensile strength steel8) and for the im-
provement of toughness in heat-affected zone.9"o)
Boron has recently been applied to controlled-rolled
(CR) steels; low-carbon bainitic steels" and ultra-
low-carbon bainitic steels for large diameter line
pipe12-15)have been developed and put into practical
use. These steels are characterized by the excellent
combination of strength, toughness and weldability at-
tained by a combined addition of niobium and boron.
In the controlled-rolling process,16-19)since slab-
reheating at high temperature is followed by rolling
in recrystallization and unrecrystallization regions of
austenite (r), ferrite (a) grains nucleate on deforma-
tion bands20) and twin boundaries21) inside r grains as
well as along elongated r grain boundaries. There-
fore the distribution of boron and the r-a transforma-
tion in CR steels may be quite different from those in
QT steels having isotropic and strain-freer grains be-
fore quenching. Boron has been studied primarily on
QT steels and, hence, only a few data are available
on the behavior and effect of boron in CR steels.22-24)
* Originally published in Tetsu-to-Hagane, 72 (1986), 458, in Japanese; formerly presented to the 110th ISIJ Meeting, October 1985,
S1393, at Niigata University in Niigata. Manuscript received on May 14, 1986; accepted in the final form on October 3, 1986.
© 1987 ISIJ
**
Kimitsu R & D Laboratory, Central R & D Bureau, Nippon Steel Corporation, Kimitsu, Kimitsu 299-11.
*** R & D Laboratories-I, Central R & D Bureau, Nippon Steel Corporation, Ida, Nakahara-ku, Kawasaki 211.
(120) Research Article
Boron in HSLA Steel
In the thermomechanical processing (TMP) with
water cooling25-29)developed as a new plate produc-
tion technology, it is possible to utilize the transforma-
tion-strengthening with bainite by accelerated cooling
which was not applicable in the conventional con-
trolled-rolling process and to utilize the precipitation-
hardening with niobium by direct quenching which
was not adoptable in the usual reheating, quenching
and tempering process. In the TMP, microalloyed
boron which suppresses the nucleation of proeutectoid
a is considered to play a very important role.
In this paper, with the aim of utilizing microalloyed
boron effectively in the TMP with accelerated cool-
ing, the effect of a combined addition of boron and a
grain-refining element such as niobium, titanium or
vanadium on the mechanical properties and micro-
structures of steel plates was examined. In addition,
the strengthening and toughening mechanism of Nb-
B steel was clarified by examining the effect of alloy-
ing elements on the minimum recrystallization tem-
perature of r, r-a transformation, distribution of boron
and others.
II. Experimental Procedure
The steels shown in Table 1 were vacuum-melted
in 150 kg heats and cast into 125 mm thick ingots. All
steels were titanium-microalloyed, low-nitrogen steels
in which nitrogen was combined stoichiometrically as
titanium nitride (TiN) to protect boron. The ingots
were controlled-rolled to 18 mm thick plates after re-
heating at 1 200°C for 1 h, and were cooled to ap-
proximately 520°C with a cooling rate of 25°C/s and
then air cooled. The rolling conditions were as fol-
lows: cumulative reduction below 930°C, 77 %; finish
rolling temperature about 800°C.
To examine the lowest recrystallization tempera-
ture of r during rolling, specimens rolled with a cu-
mulative reduction of 70 % in the recrystallization
region of r above 1000°C were subjected to 3-pass
continuous rolling with a draft of 10 % at various
temperatures between 850 and 1 000°C, and r struc-
tures were observed after water quenching. The r-a
transformation temperature was also examined by
water quenching the specimens air cooled (cooling
rate 1.5°C/s) from various temperatures after finish
rolling at 870°C.
Mechanical properties were examined by using
 Transactions ISn, Vol. 27, 1987 (121)

Table 1. Chemical compositions of laboratory steels. (Wt%)

Fig . 1. Effect of niobium-boron addition on the mechani- Fig. 2. Effect of titanium-boron addition on the mechani-
cal properties of plates. cal properties of plates.

full-thickness tensile and full-size 2 mm V-notch

Charpy impact specimens taken from the transverse
direction. The distribution of boron was observed
by the fission track etching (FTE) method, and the
precipitates were observed with transmission electron
microscope (TEM) and identified by electron diffrac-
tion. The r-a transformation characteristics were
studied by using a hot deformation simulator.

III. Experimental Results

1. Mechanical Properties
Figures 1 to 3 show the effect of alloy addition on
the mechanical properties of plates. For all steels,
no separation is observed on the impact fracture sur-
face and the Charpy impact energy (vE_40) is suffi-
ciently high because of the low-sulphur and carbon
contents. Boron as a single addition has no apprecia-
ble effect on the properties. The increase in tensile
strength (TS) is only 3.5 kgf/mm2 and Charpy impact
transition temperature (v Trs) is deteriorated by 10°C.
Niobium addition to base steel increases tensile
strength by about 11 kgf/mm2 without deteriorating
v Trs, as expected from previous studies.27,29) A re-
markable effect on the properties is achieved by the
combined addition of niobium and boron. Tensile
strength is increased by as much as 20 kgf/mm2, while
deterioration of v TTrsis only about l0°C. This effect
is much larger than that predicted by separate addi-
tion of niobium or boron.
Also in B steel containing titanium in stoichiometri-
cal excess of nitrogen (Ti-B steel), a remarkable in-
Fig. 3. Effect of vanadium-boron addition on the mechani-
cal properties of plates.
crease in strength can be obtained as in the case of
Nb-B steel, but low-temperature toughness is dete-
riorated by 70°C. This may be a result of smaller
contribution of titanium to grain-refinement than nio-
bium. A combined addition of vanadium and boron
is less effective in increasing strength than the com-
bined addition of boron and niobium or titanium, and
brings about deterioration of low-temperature tough-
ness : increment of tensile strength about 8 kgf/mm2
and deterioration of v Trs about 40°C. This is
caused by the small hardenability enhancement of
vanadium30) and the difficulty in practical applica-
tion of precipitation-hardening of vanadium in low
(122) Transactions ISIJ, Vol. 27, 1987
C-low N steels.
2. Microstructure
Figure 4 shows the microstructure of plates. The
microstructures of the base, B and Nb steels consist
primarily of polygonal a grain and contain small
amounts of bainite and high-carbon martensite. By
niobium addition the a grain size is reduced and the
volume fraction of bainite (bainite fraction) is in-
creased. By boron addition the bainite fraction is
also increased, but the a grain size is increased slightly
because the nucleation of a grains is suppressed by
boron.1~ The microstructure of Nb-B steel consists
of fine-grained bainite in which elongated prior r
grain boundaries can be observed. Detailed observa-
tion with TEM (Fig. 5) reveals that prior r grains
consist of bainitic laths of 0.5 to 2 sm in width
and fine high-carbon martensite of high dislocation
density at the boundaries of prior r grains and bainitic
laths. Twin boundaries are frequently observed in-
side martensite. Although the microstructure of Nb-
B steel was termed as bainite above, strictly speaking,
it should be defined as bainitic ferrite plus fine high-
carbon martensite. For convenience the microstruc-
ture consisting of bainitic ferrite plus fine high-carbon
martensite is termed low-carbon bainite in this paper.
Fig . 4.
Fig. 5. Transmission
* Grain size of Y measured after ingot-reheating
and - 0.2 in Ti-B steel.
Research Article
In contrast, bainitic structure observed in B steel is
upper bainite consisting of bainitic ferrite and cemen-
tite free of high-carbon martensite.
The microstructure of Ti or V steel is a ferrite-
bainite structure similar to that of Nb steel, though
the a grain size and the bainite fraction are different.
On the other hand, Ti-B steel has a low-carbon bainitic
structure with prior r grain boundaries as observed in
Nb-B steel. However, grain-refinement is less suffi-
cient in Ti-B steel than Nb-B steel. Coarser grains
after reheating are presumably a cause of poor grain-
refinement in Ti-B steel.* In V-B steel, the bainite
fraction is larger than that in V steel, but elongated
prior r grain boundaries are few in the microstructure.
3. RecrystallizationStop Temperatureof Austenite
Figure 6 shows the change of recrystallization stop
temperature of r during rolling with alloy addition.
The r grains of the base steel do not elongate even at
a rolling temperature of 850°C. Because of the high
r-a transformation temperature as shown in Fig. 7,
an unrecrystallization temperature range of r may
not be defined in the base steel. In alloying of a
single element, retardation of recrystallization of r is
stronger in the order of niobium, titanium and boron.
It should be noted that microalloyed boron retards
Microstructural change of plates with alloy addition.
electron micrograph showing microstructure of plates,
b efore rolling was about 3.0 (ASTM) in titanium-microalloyed steels such as Nb -B steel
 Transactions ISIJ, Vol. 27, 1987 (123)

Fig. 6. Change of recrystallization stop temperature of

austenite during rolling with alloy addition. Fig . 7. Change of r-a transformation temperature of plates
with alloy addition.

the recrystallization of r during rolling, and that the

recrystallization stop temperature is 870°C. Although
the mechanism of the retardation of recrystallization
by boron has not been fully understood,31) a proba-
bility is the retardation of recovery due to the strong
interaction between boron atoms and lattice defects
such as dislocations and vacancies.')
The combined addition of boron and niobium or
titanium raises the recrystallization stop temperature
of 7 more than the separate addition, because niobium
or titanium addition to B steel may increase the
amount of solute boron as will be described in Sec.
111.5. The combined addition of vanadium and
boron brings no effect over the separate addition of
boron. The higher recrystallization stop temperature
of r in Nb-B steel than in Ti-B steel is advantageous
for refinement of r structure in controlled-rolling.

4. Characteristicsof r-a Transformation

Figure 7 shows the change of r-a transformation
temperature with alloy addition. The addition of
boron to the base steel lowers the transformation tem-
perature about 40°C. The addition of niobium or Fig. 8. Number of polygonal ferrite particles per unit area
titanium lowers the transformation temperature 20°C, as a function of time at 600°C.
though it refines the r structure to a great extent.
This is a result of hardenability enhancement due to
niobium or titanium dissolved during reheating.27,29)
The combined addition of boron and niobium or tita-
nium markedly lowers the transformation tempera-
ture. The transformation temperature of Nb-B steel
is about 670°C, which is 150°C lower than that of
the base steel. Consequently, in Nb-B and Ti-B
steels, bainitic transformation occurs without forma-
tion of polygonal a grains at r grain boundaries.
Figures 8 and 9 show the nucleation and growth
rate of a grains at r grain boundaries during isothermal
transformation without hot deformation. In austeni-
tizing at 1 200°C for 1 h, niobium is completely dis-
solved. Compared with the base steel, Nb steel is
characterized by a longer incubation time and slower
growth rate of a grains.32) As a result, a grains in Nb Fig . 9. Diameter of largest polygonal ferrite particles as a
steel are smallest. In comparison with the base steel, function of time at 600°C.
(124) Transactions ISIJ, Vol. 27, 1987

B steel has a longer incubation time and an identical grains, compared with the base and B steels.31~ At
rate of nucleation and growth. The resultant a higher and lower cooling rates, the transformation
grains in B steel are largest because a grains continue curve of Nb steel and those of the base and B steels are
to grow after start of transformation. This effect of reversed. This is caused by an extensive refinement
boron has been confirmed by many researchers.' of r structure in Nb steel and hence the small depen-
The combined addition of niobium and boron has a dence of the transformation temperature on cooling
further effect of suppressing the r-a transformation, rate. For Nb-B steel, the transformation curve re-
resulting in different transformation characteristics mains on the low-temperature and long-time side,
from a separate addition of niobium or boron. In even with hot deformation. It should be noted that,
Nb-B steel, no polygonal a grains nucleate at r grain although the r structure, in Nb-B steel is refined as in
boundaries and after a long incubation time the Nb steel, the transformation curve of Nb-B steel is
bainitic transformation takes place, and hence prior r hardly affected by deformation. Consequently, a fine-
grain boundaries are preserved in the resultant mi- grained, low-carbon bainitic structure is achieved by
crostructure. accelerated cooling.
Figure 10 shows a continuous cooling transforma-
tion (CCT) diagram accompanying hot deformation 5. Distribution of Boron
performed by a hot deformation simulator. With ap- Figure 11 shows the distribution of boron in plates
plication of simulated hot rolling, the transformation revealed by the FTE method. In contrast to QT
curve is shifted to the high-temperature and short-time steels, clear segregation of boron at prior r grain
side. This tendency is strongest in Nb steel, because boundaries cannot be observed in TMP steels. From
the r structure in Nb steel is highly refined by rolling the distribution of boron, elongated prior r grain
to provide a larger number of nucleation sites of a boundaries can be faintly recognized.* The elonga-

Fig. 10.
CCT diagram performed by a hot deformation
simulator.

Fig. 11.
Distribution of boron in plates
revealed by FTE method.

* When a large reduction is accumulated in the unrecrystallization region of r

, it is very difficult to distinguish r grain boundaries from
deformation bands or twin boundaries inside r grains. So these boundaries may be described as Y grain boundaries.

Research Article

tion of 1 grains is pronounced in Nb-B and Ti-B steels,
while the elongation in B and V-B steels is slight. It
is noted that, in B and V-B steels, boron is found in
agglomeration like precipitates. Since the agglome-
rated boron is not observed in the specimen water
quenched immediately after reheating, it is considered
that precipitation proceeds during temperature drop
of the plate during and after rolling.
Figure 12 is a transmission electron micrograph of
typical precipitates in B steel, identified as Fe23(CB)6,
TiN and MnS by electron diffraction. The agglom-
erated boron, determined as iron-borocarbide Fe23-
(CB)6, is characterized by continuous precipitation
at r grain boundaries. It is known in QT steels that
the precipitation of coarse Fe23(CB)6 decreases the
amount of boron to retard r-a transformation,32,33)
therefore high strength cannot be obtained by the
separate addition of boron. On the other hand,
Fe23(CB)6is not observed in Nb-B and Ti-B steels.
Thus, the microalloying of carbide formers such as
niobium and titanium in extra low-carbon B steel
suppresses the precipitation of Fe23(CB)6 and manifests
the effect of boron on suppressing r-a transformation.
Iv. Discussion
1. Effect of CombinedAddition of Niobium and Boron
The separate addition of niobium or boron sup-
presses the nucleation of a grains at prior r grain
boundaries, and niobium also inhibits the growth of a
grains. However, a sufficient reduction is applied in
the unrecrystallization region of r, the effect of nio-
bium on r-a transformation suppression is markedly
Fig. 12.
Transmission electron micrograph
of precipitates in steel B plates.
*
In B steel rolled at a low-temperature, e.g.,
boundaries.
Transactions ISIJ, Vol. 27, 1987 (125)
reduced by refinement and deformation of 1 structures.
This tendency is weaker in B steel, compared with
Nb steel, since the minimum recrystallization tem-
perature is higher and the refining effect of r struc-
tures is weaker. When B steel is controlled-rolled,
Fe23(CB)6of about 0.5 µm in size continuously pre-
cipitates at elongated r grain boundaries.* It is well
known that the precipitation of coarse Fe23(CB)6 re-
markably reduces the effect of boron suppressing r-a
transformation due to lack of segregated boron at r
grain boundaries or due to nucleation of a grains on
Fe23(CB)6,32,33)In Nb-B steel, the precipitation of
Fe23(CB)6 is not observed, and boron is homoge-
neously distributed. Rolling in the unrecrystalliza-
tion region of r nucleates a grains not only at
elongated r grain boundaries but also at deformation
bands inside r grains. Boron in Nb-B steel segregates
at all a nucleation sites and strongly suppresses the
nucleation of a.
Since the precipitation of Fe23(CB)6insider grains
is not observed in B steel, it is not induced by rolling
deformation but is brought by segregation of boron
at r grain boundaries. Whether or not the rolling
reduction accelerates the precipitation of Fe23(CB)6
is not apparent because recrystallized r grain bound-
aries are newly formed after each pass at high tem-
peratures, i.e., although the distance between boron
and r grain boundaries is shortened by recrystalliza-
tion of r, r grain boundaries also move by recrystalli-
zation. The addition of niobium to B steel, however,
evidently suppresses the precipitation of Fe23(CB)6at
r grain boundaries, and ensures the segregation of bo-
ron at all possible nucleation sites of a and conse-
700°C, the precipitation of Fe23(CB)s is observed inside r grams as well as at r grain
Research Article
(126) Transactions ISIJ, Vol. 27, 1987

quently increases the hardenability of B steel. In a taking the low-temperature toughness into considera-
very low carbon steel, strain induced precipitation of tion. This value is two or three times that for QT
niobium carbide (NbC) eliminates carbon required steels.
for the precipitation of Fe23(CB)6i actually, this effect An optimum niobium content does not mean the
is smaller in higher carbon content.34) The strong total content but the content dissolved in r. As seen
effect of niobium on retarded recrystallization of 1 dur- in Fig. 14, the bainite fraction becomes 100 % at
ing rolling is also considered to contribute to suppress- 0.014 % Nb and the strength reaches a maximum
ing the precipitation of Fe23(CB)6, because boron above 0.02 % Nb. Since the amount of niobium dis-
atoms are trapped at lattice defects introduced by solved during reheating is much larger than 0.02 %
rolling in the unrecrystallization region of r. in view of the solubility product, some amount of nio-
Suppression of r-a transformation by the combined bium dissolved in r may precipitate during rolling to
addition of niobium and boron may be a consequence contribute to refinement of r structures by inhibiting
of the stabilization of r and the retardation of carbon
diffusion by solute niobium. As is apparent from the
experimental results of isothermal transformation
(Figs. 8 and 9), the retardation of carbon diffusion by
solute niobium is stronger than that by solute boron.
According to the measurement of carbon diffusion
coefficient in r by Funakoshi et al.,35) diffusion of
carbon in 0.5 % Mo, 0.05 % Nb, and 0.1 % Ti
steels tends to be accelerated at about 1 200°C, af-
fected little at about 1050°C, and suppressed below
900°C. The suppression of carbon diffusion below
900°C is stronger for niobium and titanium than for
molybdenum. The stabilization of 1 and the retarda-
tion of carbon diffusion by solute niobium is considered
to contribute to suppressing the precipitation of
Fe23(CB)6.
The strengthening mechanism by the combined ad-
dition of niobium and boron originates in enhance-
ment of the precipitation-hardening by NbC due to
accelerated cooling after rolling in addition to the
transformation-strengthening. 27,36)Accelerated cool-
ing at a suitable rate after rolling produces fine dis-
Fig. 13. Effect of boron content on the mechanical prop-
persion of NbC in a matrix to maximize the precipi- erties of plates. Base composition is 0.029%C-
tation-hardening.
1.49%Mn-0.047 %Nb-0.020%Ti-0.0020%N.
2. OptimumContentsof Boron and Niobium
The optimum range of the content of solute boron
to obtain maximum hardenability is 3 to 5 ppm in
QT steels.8'37) Since the optimum content of solute
boron depends on the amount of boron segregated at
a nucleation sites such as r grain boundaries, it may
be larger in TMP steels with abundant a nucleation
sites than in QT steels.
Figure 13 shows the effect of boron content on the
mechanical properties of plates. In these steels, ni-
trogen is combined with titanium, so that microalloy-
ed boron may be retained in solution after repeating
prior to rolling. The strength is raised with increase
in boron content as a result of the increasing bainite
fraction and the tensile strength reaches a maximum
at a boron content above 0.002 %. Low-tempera-
ture toughness deteriorates abruptly above 0.001 %.
Prior r grain boundaries are revealed clearer in the
optical microstructure with increasing boron content,
presumably because of increase in the amount of bo-
ron segregated at r grain boundaries. Precipitation
of coarse Fe23(CB)6 is observed with an addition of
about 0.003 % B, which is therefore the highest con- Fig. 14. Effect of niobium content on the mechanical prop-
tent for effective strengthening. As a result, the op- erties of plates. Base composition is 0.029%C-
timum boron content in TMP steels is about 0.001 %, 1.51%Mn-0.020%Ti-0.0012%B-0.0020%N.
 Transactions ISIJ, Vol. 27, 1987 (127)

recrystallization of r,31~ When niobium is mainly become longer. A 0.007 % Nb addition to B steel
utilized for transformation-strengthening, the effect of doubles the time to 50 % transformation, and a
a large amount of niobium addition becomes small. 0.043 % Nb addition prolongs it by about twenty
Although the precipitation-hardening effect per unit times.
amount of niobium is remarkably increased,27,36~the Figure 17 shows the distribution of boron in speci-
quantity of niobium precipitated in a decreases due mens isothermally transformed at 700°C for 1 000 s.
to the lowering of r-a transformation temperature and In Nb-free steel, agglomerated boron identified as
the accelerated cooling. Fe23(CB)6 by electron diffraction is observed both at
As shown in Fig. 15, the microstructure of plates r grain boundaries and inside r grains, and segrega-
becomes of uniform low-carbon bainite above 0.014 tion of boron cannot be observed at r grain bound-
% Nb. The bainitic structure becomes finer and the aries. The addition of niobium reduces the precipi-
low-temperature toughness improves with increasing tation of Fe23(CB)6 both at r grain boundaries and
niobium content above 0.014 %. A banded struc- insider grains, and produces a clear segregation of
ture of polygonal a and low-carbon bainite is formed boron at r grain boundaries. At a niobium content
at a niobium content of 0.007 %, due to the lack of above 0.026 %, a clear segregation of boron can be
solute niobium. In this case, the distribution of bo- observed at r grain boundaries, though the precipi-
ron also has a banded structure as shown in Fig. 15; tation of Fe23(CB)6 remains insider grains. There-
boron is uniformly distributed in the area considered
as low-carbon bainite, while it is agglomerated in the
area of polygonal a. In both Nb-free and 0.007 % Nb
steels, boron is in agglomeration inside r grains as well
as at r grain boundaries.
Sekine and Maruyama20> reported that precipita-
tion of about 0.02 % Nb is required for suppressing
the recrystallization of r at 1000°C. This require-
ment is considered to vary depending on the chemi-
cal composition and processing variables. If about
0.02 % Nb is precipitated during rolling, solute nio-
bium in the present 0.021 % Nb steel almost complete-
ly precipitates during rolling, resulting in the lack of
niobium dissolved in r before r-a transformation.
Thus it may be impossible to obtain the remarkable
effect of the combined addition of niobium and bo-
ron.
Figure 16 shows the variations of isothermal trans-
formation curves at 700°C with niobium content.
The experimental conditions are given in the figure.
With increasing niobium content, the incubation time Fig. 15. Changes of microstructure and distribution of bo-

for nucleation of a grains and the transformation time ron in plates with niobium content.

Fig. 16.
Isothermal transformation curves at
700°C for various niobium contents.
(128) Transactions ISIJ, Vol. 27, 1987
fore, the addition of niobium to B steel also suppresses
the precipitation of Fe23(CB)6 during isothermal
transformation and manifests the effect of boron on
r-a transformation suppression, as in the case of TMP.
The precipitation of Fe23(CB)6is suppressed by nio-
bium addition, because the precipitation of NbC dur-
ing isothermal transformation and the retardation of
carbon diffusion rate by niobium dissolved in r limit
supply of carbon for precipitation. The rolling reduc-
tion, however, is considered to decrease the enhance-
ment of r-a transformation suppression by increasing
niobium content, due to strain induced precipitation
of NbC during rolling.31~ Accordingly, the mini-
mum niobium content is 0.02 % for strength and
0.04 % for low-temperature toughness requirement.
It should be noted that the optimum boron and nio-
bium contents depend on the base chemical composi-
tion and processing variables.
V. Conclusions
A combined addition of boron and a grain-refining
element such as niobium, titanium or vanadium in
very low carbon steels was studied in terms of the
mechanical properties and microstructures. In ad-
dition, the strengthening and toughening mechanism
by the combined addition of niobium and boron was
clarified by examining the minimum recrystallization
temperature of r, and r-a transformation behavior.
The following conclusions were obtained.
(1) A good strength and toughness balance is
achieved by a combined addition of niobium and bo-
ron. A separate addition of boron or a combined ad-
dition of vanadium and boron to a low-carbon steel
has no appreciable effect on the mechanical proper-
ties. Although a combined addition of titanium and
boron increases strength as in the case of the com-
Fig. 17. Distribution of boron
bined addition of niobium and boron, low-tempera-
ture toughness is remarkably deteriorated.
(2) The combined addition of niobium and bo-
ron strongly suppresses the r-a transformation and
produces a fine-grained bainitic structure consisting
of bainitic ferrite and fine high-carbon martensite in
which elongated prior r grain boundaries can be ob-
served.
(3) Boron like niobium and titanium retards the
recrystallization of r during hot rolling. The com-
bined addition of boron and niobium or titanium,
however, elevated the minimum recrystallization tem-
perature more than the separate addition of niobium,
titanium, or boron.
(4) Precipitation of Fe23(CB)6 is observed at r
grain boundaries by the FTE method in B and V-B
steels. Niobium or titanium addition to B steel sup-
presses the precipitation of Fe23(CB)6 and protects
boron for retardation of r-a transformation. In Nb-
B and Ti-B steels, boron atoms segregate at lattice
defects such as deformation bands introduced by roll-
ing as well as at unrecrystallized r grain boundaries.
This distribution of boron strongly suppresses the r-a
transformation of steel.
(5) The marked suppression of r-a transformation
by the combined addition of boron and niobium or
titanium is caused by the stabilization of r and the
lowering of carbon diffusion rate by solute niobium
or titanium, in addition to the enhanced r-a transfor-
mation suppressing effect of boron resulting from the
inhibition of precipitation of Fe23(CB)6. Precipita-
tion of Fe23(CB)6 is suppressed because, in a very
low carbon steel, strain induced precipitation of NbC
or TiC limits supply of carbon required for the pre-
cipitation of Fe23(CB)6.
in specimens isothermally transformed at 700°C for 1 000 s.
 Transactions ISIJ, Vol. 27, 1987 (129)

Acknowledgement 16) K. J. Irvine, T. G. Gladmann, J. Orr and F. B. Pickering:

The authors wish to thank Dr. H. Sekine, R & D JISI, 207 (1970), 717.
17) T. Tanaka, N. Tabata, T. Hatomura and C. Shiga: Micro
Laboratories-I, Nippon Steel Corporation, for his
Alloying 75, Union Carbide, Washington D.C., Oct., 1975.
useful discussion and advice.
18) I. Kozasu, C. Ouchi, T. Sampei and T. Okita: Micro
Alloying 75, Union Carbide, Washington D.C., Oct., 1975.
19) M. Fukuda, T. Hashimoto and K. Kunishige: Micro
REFERENCES Alloying 75, Union Carbide, Washington D.C., Oct., 1975.
1) Boron in Steel, ed, by S. K. Banerji and J. E. Morral, 20) H. Sekine and T. Maruyama : Tetsu-to-Hagane, 58 (1972),
RIME, Warrendale (1979). 1424.
2) R. A. Grange and J. B. Michell: Trans. ASM, 53 (1956), 21) H. Inagaki : Trans. ISIJ, 23 (1983), 1059.
157. 22) Y. E. Smith and C. A. Siebert: Met. Trans., 2 (1971),
3) B. M. Kapadia, R. M., Brown and W. J. Murphy: Trans. 1711.
TMS-AIME, 242 (1968), 1689. 23) B. Serin, Y. Desalos, Ph. Maintrepierre and J. Rofesvernis :
4) M. Ueno and T. Inoue: Trans. ISIJ, 13 (1973), 210. Mem. Sci. Rev. Met., 75 (1978), 355.
5) G. F. Melloy, P. R. Slimon and P. P. Podgursky: Met. 24) S. Watanabe, H. Ohtani and T. Kunitake: Tetsu-to-Hagane,
Trans., 4 (1973), 2279. 62 (1976), 1842.
6) A. Brown, J. D. Garnish and R.W.K. Honeycombe: Met., 25) D. M. Fegreds: Met. Tech., 4 (1977), 417.
Sci., 8 (1974), 317. 26) E. A. Almond, R. S. Michell and R. S. Irani: Met. Tech.,
7) Y. Yamanaka and Y. Ohmori: Trans. ISIJ, 1'1 (1977), 6 (1979), 205.
92; 18 (1978), 404. 27) C. Ouchi, T. Okita and S. Yamamoto : Tetsu-to-Hagane,
8) R. Habu, M. Miyata, S. Sekino and S. Goda : Trans. ISIJ 67 (1981), 969.
18 (1978), 492. 28) K. Bessyo, H. Yoshinaga, S. Watanabe, M. Nakamura and
9) T. Funakoshi, T. Tanaka, S. Ueda, M. Ishikawa, N. S. Suzuki : Tetsu-to-Hagane, 70 (1984), 1407.
Koshizuka and K. Kobayashi : Tetsu-to-Hagane, 63 (1977), 29) H. Tamehiro, N. Yamada and H. Matsuda : Trans. ISIJ,
303. 25 (1985), 54.
10) H. Ohtani, S. Watanabe, Y. Kawaguchi and Y. Yama- 30) F. Schmidt: Thesis to Claustahl Tech., Hochshule, (1968).
guchi: Tetsu-to-Hagane, 64 (1978), 2205. 31) C. Ouchi : Tetsu-to-Hagane, 70 (1984), 2081.
11) K. Terasawa, H. Higashiyama and S. Sekino : Toward 32) Y. Ohmori : Trans. ISIJ, 11 (1971), 339.
Improved Ductility and Toughness, Climax Molybdenum, 33) Ph. Maintrepierre, D. Thivellier and R. Tricot: Met.
Kyoto, (1971), 103. Trans., 6A (1975), 287.
12) A. Massip and L. Meyer: Stahl u. Eisen, 98 (1978), 989. 34) H. Tamehiro, M. Murata, R. Habu and M. Nagumo :
13) H. Nakasugi, H. Matsuda and H. Tamehiro: Alloys for Trans. ISIJ, 27 (1987), 130.
the 80's, Climax Molybdenum, Ann Arbor, June 1980. 35) Funakoshi et al. (referred in T. Tanaka and T. Enami :
14) K. Matsumoto, T. Taira, K. Ume, T. Hyodo, K. Tsukada Tetsu-to-Hagane, 58 (1972), 1775.)
and K. Arikata : Tetsu-to-Hagane, 69 (1983), 51350; Trans. 36) H. Sekine, T. Maruyama, S. Sekiguchi and T. Ohno :
ISIJ, 24 (1984), B92. Tetsu-to-Hagane, 56 (1970), 569.
15) T. Hashimoto, H. Ohtani, M. Nakanishi, Y. Komizo and 37) C. R. Simcoe, A. R. Elsea and G. K. Manning: Trans.
Y. Fujishiro: Tetsu-to-Hagane, 69 (1983), A309. AIME, 203 (1955), 193.