SURFACE AND INTERFACE ANALYSIS, VOL.

24, 375-379 (1996)

Auger Electron Spectroscopy of Boron Nitride in

Hot-rolled Graphitized Steel Sheet

Tetsuya Mega,* Ryoji Morimoto, Masahiko Morita and Jun-ichi Shimomura

Technical Research Laboratories, Kawasaki Steel Corporation, 1 Kawasaki-dori, Mizushima, Kurashiki 712, Japan

The distribution of elements in graphitized steel sheet was examined by Auger electron spectroscopy. The micro-
structure showed pronounced stringers of graphite with an area 6 pm x 15 pm parallel to the rolling direction of
the hot-rolled steel sheet after graphitization annealing at 933 K for 36 ks. Boron nitride (BN) precipitates were
rarely detected in the graphite in polished specimens, but they were found on the graphite surface in specimens
subjected to in sifu Ar+ ion sputtering. Auger electron spectroscopy colour mapping images showed stringers of BN
precipitates in the area 2 pm x 0.5 pm parallel to the rolling direction at the interior of the graphite in the steel.
The image was considered to present the Brst observation of BN precipitates in graphite. High-energy resolution
Auger spectra obtained from the area of BN precipitation coincided well with spectra of hexagonal BN (h-BN),
even in fine stmctures of B KLL and N KLL Auger transitions. It was deduced that h-BN Precipitates exist inside
the graphite and act as sites for the nucleation of graphitization. The distribution of b B N precipitation in the
graphite suggests that h-BN precipitates are formed at the unrecrystallized austenite grain boundaries during hot
rolling.

INTRODUCTION The aim of this study is to present the first observ-

Hot-rolled graphitized steel sheet has various unique
features such as hardenability and good cold-
workability, resulting from the graphitization of
cementite in hypo-eutectoid high carbon steel by
graphitization annealing. The microstructure of this
steel, composed of ferrite grains and graphite particles
with a size of a few microns, improves machinability
due to a chip-breakers effect and enhances the sliding
property due to self-lubrication by fine graphite. There-
fore, this steel has been the focus of efforts to produce
free cutting steel without P b or S and automotive
sliding members like brake discs and clutch plates in
recent years.
From the manufacturing point of view, it is very
important to maintain the hardenability of t h s steel, as
well as to promote machinability through graphi-
tization. Regarding the former, increasing the bulk con-
centration of C and adding Si improve hardenability,'
whereas, regarding the latter, the graphitization in
B-doped steel is completed more quickly than that in
steel without B because of the increase in the number of
graphite particles associated with the decrease in their
diameter.' It is believed that this acceleration of graphi-
tization by B doping comes from the following process:
hexagonal boron nitride (h-BN) precipitates by reaction
of B and N during hot rolling and it provides sites suit-
able for the nucleation of graphite in the successive
graphitization annealing because the crystal structure of
h-BN is almost identical to that of graphite. However,
no study of the existence of h-BN in graphite in hot-
rolled graphitized steel sheets has been reported to date.
ation of BN precipitation in graphite in B-added hot-
rolled graphitized steel sheet. Auger electron
spectroscopy (AES) was used to observe BN in the
graphite, as this method is not only highly sensitive to
such light elements as B, C, N and 0 on and just
beneath the surface, but also is able to detect the ele-
ments in the interior using in situ ion sputtering
equipment. From the shape of BN and graphite
obtained by the Auger electron image, the precipitation
behaviour of BN and graphite is also discussed.
EXPERIMENTAL PROCEDURES
The steel used in these experiments was melted in a
vacuum induction furnace. The chemical compositions
are shown in Table 1. The ingot was solution-treated at
1473 K and hot-rolled to a 5.7 mm thick sheet at a
finishing temperature of 1173 K, followed by furnace-
cooling to room temperature. Then graphitization
annealing was carried out at 933 K for 36 ks. A speci-
men of -5.7 mm x 10 mm x 10 mm was cut from the
sheet, mechanically polished with emery paper and
alumina paste to a mirror surface, and rinsed with
acetone and ethanol in an ultrasonic bath. In order to
identify BN precipitates from the AES peak shape, a
standard specimen for h-BN was prepared by pressing
4N grade commercially available h-BN powder into
Table 1. Chemical composition of the graphitized steel
(mass%)
C Si Mn P S Al N 8

0.664 1.5 0.18 0.009 0.001 0.030 0.0041 0.0016

* Author to whom correspondence should be addressed.
CCC 0142-2421/96/060375-05 Received 1 I December 1995
0 1996 by John Wiley & Sons, Ltd. Accepted 16 February 1996
376
indium metal foils to ensure sufficient electrical contact
with the ground.
Secondary electron images and Auger electron images
of elements in the graphite in the steel were observed on
two directional cross-sections denoted by the L-
direction and the T-direction (L-direction, longitudinal
to the rolling direction; T-direction, transverse to the
rolling direction) using a scanning Auger microscope
(PHI model-650) with an electron gun coaxial with the
cylindrical mirror analyser. Auger mapping was done
at: primary electron energy of 10 keV, incident angle of
30" with respect to the specimen normal, beam current
of 20 nA, beam diameter of 0.2 pn, energy resolution of
0.6%, pressure in the specimen chamber of 3 x lo-* Pa,
and observation area of 15 pm x 20 pm by electron
beam scanning (magnification: x 5000). The Auger
signals of Fe LMM (703 eV), C KLL (273 eV), B KLL
(175 eV) and N KLL (382 eV) were chosen. PHI-
ACCESS software was used to control the instrument
and treat the AES spectra and images. In order to
reveal the BN precipitates in the graphite, Ar+ ion sput-
tering was carried out with a 3 keV primary energy, a
52" incident angle with respect to the specimen normal
and a 36 nA ion beam current (measured with a
Faraday cup), with rastering over an' area of about 1
mm x 1 mm to ensure uniform sputtering in the
analysis chamber. The sputtering rate was estimated at
-5.3 x 1O-I' m s - l from the sputtering yield of iron.
The microstructure of the steel was observed with a
-
scanning electron microscope after chemical etching
with an alcoholic solution containing 3% nitric acid.
RESULTS A N D DISCUSSION
Analysis of BN
Typical secondary electron images of steels after graphi-
tization annealing observed in a L-direction and T-
direction cross-section are shown in Fig. 1. Both
microstructures showed ferrite grains with dispersed
graphite particles. The dispersed graphite was con-
firmed by the shape of the C KLL Auger spectrum.
Some ferrite grains are granular and others are elon-
Figure 1. Secondary electron images of microstructure of a graphitized steel sheet after graphitization annealing: (a) L-direction cross
section; (b) T-direction cross section.
T. MEGA ET AL.
gating toward the rolling direction. This indicates that
the ferrite phase has not completely recrystallized.
Graphite particles are granular in the view of the T-
direction cross-section. In the view of the L-direction
cross-section, however, some graphite particles are gra-
nular and others are in the form of stringers parallel to
the rolling direction. Many of them exist in the ferrite
grain boundaries. The interfaces between graphite par-
ticles and ferrite matrix are not flat but rather rugged.
This characteristic stringer shape seems to indicate that
some small graphite particles ranging in the rolling
direction in a small interval coalesce to form a long par-
ticle elongating in the rolling direction.
Plate 1 shows a secondary electron micrograph and
an Auger electron image of graphite on the L-direction
cross-section. Blue and green regions correspond to Fe
in a ferrite grain and C in graphite, respectively. Then
the B and N regions were displayed in the red and green
regions, respectively, but these regions were observed in
a cathode ray tube as the yellow region because they
overlapped each other. The colour image clearly shows
the stringer-shaped distribution of B and N in an area
of -2 jm x 0.5 pn, parallel to the rolling direction.
In order to investigate the chemical state of B and N
in the graphite, high-resolution Auger spectra were
measured with an energy resolution of 0.25%, and com-
pared with those associated with h-BN powder stan-
dard specimen. Figures 2(a) and 2(b) show the B and N
spectra of the yellow region of the Auger colour image
in Plate l(b), respectively. Figures 2(c) and 3(d) show the
B and N spectra of the h-BN powder measured under
the same conditions as those used in Figs. 2(a) and (b),
respectively. The minimum kinetic energies of the differ-
ential spectra of B KLL and N KLL for the graphite in
the steel are 175 eV and 382 eV, respectively. Each
value coincided well with those for h-BN powder, and
the Auger peak shapes of B and N were also similar to
those of the h-BN powder.
The spectrum of B shown in Fig. 2(a) was also com-
pared with that in other compounds containing B in the
steel. Cubic BN (c-BN) is known as another BN having
a different crystal structure from h-BN. The minimum
kinetic energy in the differential spectrum of B KLL for
c-BN is reported to be 172 eV, which is 3 eV smaller
than that for h-BN. The Auger peak shapes of c-BN in
the kinetic energy range 150-170 eV are quite different
 rolling direction -
Plate 1. Scanning electron micrograph (a) and Auger images of B and N (yellow), C (green) and Fe (blue) for the graphite precipitation (b) of the L-direction cross-section in the
graphitized steel sheet after graphitization annealing. The B and N regions were displayed in red and green, respectively, but these regions were observed in a cathode ray tube as
the yellow region because they overlapped each other.
 BN IN HOT-ROLLED GRAPHITIZED STEEL
(b) N-KLL
?e.
~~ 0
340 370
m
i50 Kinetic
(C) B-KLL
190
170Enorgy (cv)
Figure 2. High-resolution Auger spectra of (a) 6 KLL and (b) N
KLL from the yellow region in the graphite precipitate shown in
Plate 1 and those of (c) 6 KLL and (d) N KLL in a standard h-BN
powder specimen.
from those for h-BN,3 and do not show the fine struc-
ture of the Auger spectrum of N, as indicated by the
arrows in Fig. 2(d) for that of h-BN.4 Hanke and
Muller’ have compared the B KLL spectrum of h-BN
with that of such boron compounds as pure B, B4C and
B 2 0 3 . They found that the minimum kinetic energy in
the differential spectra of B KLL for pure B and B4C
are 184.8 eV and 184.3 eV, respectively, which are 10
eV larger than that for h-BN (175 ev), and that there is
no resemblance of Auger peak shapes with h-BN. More-
over, there was no oxygen signal, but C in the B and N
area in the graphite showed as yellow in Plate l(b). The
B KLL spectrum of B 2 0 3 is quite different in shape
from that of h-BN in the kinetic energy range 150-170
eV, although both are similar in the kinetic energy
range 170-190 eV. The minimum kinetic energy in the
differential spectra of B for B203 is 3 eV lower than
that of h-BN. These results lead to the conclusion that
the chemical state of B in the graphite is not equivalent
to that in pure B, B4C and B 2 0 3 , and the stringers
observed in the graphite shown in Plate l(b) are h-BN.
The graphite precipitates in which h-BN is observed
on their as-polished surfaces are very few and no h-BN
is observed on many graphite precipitates in the same
specimen. Therefore, the interior of the graphite was
examined by Ar + ion sputtering. Scanning electron
micrographs of the graphite without BN on the as-
polished surface after Ar’ ion sputtering for 0, 0.9, 3.6
and 6.96 ks are shown in Fig. 3. A white region in con-
trast with the surrounding graphite, indicated by the
arrow, gradually became appreciable with increasing
Ar’ ion sputtering time. After sputtering for 6.96 ks, the
region was clearly observed, as shown in Fig. 3(d).
Figure 4 shows the AES spectra from the points indi-
cated by the arrows in Figs 3(a) and 3(d). Neither N or
B is observed in the as-polished specimen. However, B
and N are clearly observed in the 6.96 ks sputtered
specimen. No doping element (including Si, Mn and Al)
317
400
Figure 3. Change in scanning electron images of the graphite
precipitate during sputtering in the L-direction cross-section of
graphitized steel sheet after graphitization annealing. Sputtering
time: (a) as-polished; (b) 0.9 ks; (c) 3.36 ks; (d) 6.96 ks.
except for C in the graphite precipitates is detected in
the present analysis. Therefore, the reason why h-BN is
not detected on the as-polished surface is that most of
the h-BN was covered with graphite in the as-
mechanically-polished specimen and it was not possible
to detect the h-BN existing at a position deeper than
the Auger electron escape depth of a few nanometres.
- Precipitation of h-BN and graphite
Auger electron images measured in this area also
showed the stringer-formed distribution of h-BN in an
area -2 pm x 0.5 pm parallel to the rolling direction,
as shown in Plate l(b) and Fig. 5. This characteristic
shape of h-BN can be explained by considering the
nucleation process of h-BN.
The ingots are subjected to solution treatment in
N 1473 K, hot-rolled at the finishing temperature of
1173 K and cooled. During the heating process the
ingots transform to austenite and grains are elongated
by hot rolling. Some elongated austenite grains rec-
rystallize to form granular grains, while many other
grains remain in the form of elongated unrecrystallized
grains even after cooling. It was reported that B segre-
gates at the austenite grain boundary during solution
treatment.5 As soon as the steel is hot-rolled, B segre-
gates quickly at the recrystallized grain boundaries and
forms a BN precipitate by reacting with some N that
diffuses to the grain boundaries from the interior of the
grain.6s7Therefore, in the case where recrystallized and
unrecrystallized grains coexist, h-BN can precipitate
also at the boundaries of unrecrystallized grains in a
similar manner to those of recrystallized grains. Since
the unrecrystallized grains are coarse and elongated
toward the rolling direction, BN at the grain boundary
also precipitates in the form of stringers elongating to
the rolling direction. During the subsequent cooling, the
matrix transforms to ferrite and pearlite phases while
378 T. MEGA ET AL.
x 104

100 200 300 400 500

Kinetic Energy (eW
Figure 4. Auger spectra of the BN nucleus of the graphite precipitate (a) before and (b) after 3 keV Ar+ ion sputtering for 6.96 ks in the
graphitized steel sheet after graphitization annealing.

the h-BN precipitates do not change. Therefore,
stringers of h-BN precipitation exist along prior unre-
crystallized austenite grain boundaries, as shown in Fig.
5 and Plate l(b).
According to Sueyoshi and Suenaga,8 graphite may
preferentially nucleate where fine precipitates with
nearly the same atomic spacing and arrangement as the
(OOO1) surface of the graphite exist. The crystal structure
of h-BN is compared with that of graphite in Table 2.
The atomic arrangement and spacing of h-BN are very
similar to those of graphite. This suggests that the h-BN
observed in Plate l(b) and Fig. 5 provides the nucle-
ation sites for graphitization.
Some reports on graphitized steel are concerned with
the nucleation site that promotes the graphitization in
the steel during hot-rolling and annealing. Okamotog
has reported that graphite can originate in fine voids
formed by cracking of cementite during cold rolling in
steels containing 0.06 and 0.5 mass% C. It has been
proved by electron probe microanalyser that the non-
metallic fine inclusions, composed mainly of A120,,
SiOz or silicates, are the nucleation sites for graphite in
steels containing 0.23 mass% C.8 However, experimen-
tal evidence has not yet been reported to clarify h-BN
as the nucleation site for graphite precipitation in steels
containing B. The present paper is, therefore, considered

Figure 5. Auger images of Fe, B, C and N for the precipitation of graphite of the L-direction cross-section after 3 keV Ar' ion sputtering for
6.96 ks in the graphitized steel sheet after graphitization annealing.
 BN IN HOT-ROLLED GRAPHITIZED STEEL
Table 2. Crystal structure of h-BN and graphite
Crystal system Space group
h-BN Hexagonal P63/mmc
Graphite Hexagonal P63/mmc
a JCPDS: Joint Committee on Powder Diffraction Standards.
to be a new demonstration that h-BN precipitation
exists in graphite as a nucleation site and promotes
graphitization in B-doped graphitized steel sheet.
During the graphitization annealing, graphite precipi-
tates grow and their shape is affected by their growing
process. The characteristic stringer-shaped graphite par-
ticles are explained as follows. During graphitization
annealing, graphite precipitates in contact with h-BN in
prior austenite grain boundaries. In the boundary of
unrecrystallized grain, some h-BN particles lie in the
rolling direction at a short intervals. Therefore, graphite
particles formed at such h-BN particles grow, contact
each other and finally coalesce to form a larger particle
with a rugged surface elongating toward the rolling
direction.
CONCLUSION
The distribution of elements in graphite in hot-rolled
graphitized steel sheet was investigated by AES. The fol-
lowing results were obtained:
REFERENCES
1. S. Yamamoto, Y. Kawano and Y. Murakami, Bull. Jpn. Inst.
Met. 11,903 (1972).
2. Y. Kawabata, M. Morita, F. Togashi and T. Higashino, CAMP-
ISlJ 3,754 (1990).
3. G. Hanke, M. Kramer and K. Muller, Mater. Sci. Forum 54/55,
207 (1 990).
4. R. Trehan, Y. Lifshitz and J. W. Rabalais, J . Vac. Sci. Technol.
8,4026 (1990).
319
e(nm) O m ) JCPDS no.'
0.250 44 0.66 562 32-0421
0.24704 0.672 44 41 -1 478
(1) The formation of stringers of h-BN precipitates in
the graphite elongated in the rolling direction was
clearly revealed by the Auger mappings and high-
resolution Auger spectra,
(2) The h-BN precipitates exist inside the graphite.
Most h-BN precipitates are not detected in the as-
mechanically-polished specimen surface, but were
revealed on the sputtered surface by Ar' ion in the
analysis chamber.
(3) It is inferred that the h-BN exists in the graphite as
nucleation sites of the graphite and thus promotes
further graphitization in the B-doped graphitized
steel sheet.
(4) The shape of the h-BN particle in the graphite sug-
gests that the h-BN precipitates at the unre-
crystallized austenite grain boundaries during hot
rolling.
(5) The characteristic shape of graphite particles sug-
gests that the graphite precipitates in contact with
h-BN particles which lie in the rolling direction at
small intervals, grow, contact each other and finally
coalesce to form a larger particle.
5. G. Hanke and K. Muller, J. Vac. Sci. Technol. A2,964 (1984).
6. S. Watanbe, H. Ohtani and T. Kunitake, Tetsu-to-Hagane 62,
1842 (1976).
7. X. L. He, Y. Y. Chu and J. J. Jonas, Acta. Metall. 37, 147
(1989).
8. H. Sueyoshi and K. Suenaga, J. Jpn. Inst. Met. 42,676 (1978).
9. A. Okamoto, Metall. Trans. 20A, 1917 (1989).