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-

ation of BN precipitation in graphite in B-added hot-
rolled graphitized steel sheet. Auger electron
Hot-rolled graphitized steel sheet has various unique spectroscopy (AES) was used to observe BN in the
features such as hardenability and good cold- graphite, as this method is not only highly sensitive to
workability, resulting from the graphitization of such light elements as B, C, N and 0 on and just
cementite in hypo-eutectoid high carbon steel by beneath the surface, but also is able to detect the ele-
graphitization annealing. The microstructure of this ments in the interior using in situ ion sputtering
steel, composed of ferrite grains and graphite particles equipment. From the shape of BN and graphite
with a size of a few microns, improves machinability obtained by the Auger electron image, the precipitation
due to a chip-breakers effect and enhances the sliding behaviour of BN and graphite is also discussed.
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 EXPERIMENTAL PROCEDURES
sliding members like brake discs and clutch plates in
recent years.
From the manufacturing point of view, it is very The steel used in these experiments was melted in a
important to maintain the hardenability of t h s steel, as vacuum induction furnace. The chemical compositions
well as to promote machinability through graphi- are shown in Table 1. The ingot was solution-treated at
tization. Regarding the former, increasing the bulk con- 1473 K and hot-rolled to a 5.7 mm thick sheet at a
centration of C and adding Si improve hardenability,' finishing temperature of 1173 K, followed by furnace-
whereas, regarding the latter, the graphitization in cooling to room temperature. Then graphitization
B-doped steel is completed more quickly than that in annealing was carried out at 933 K for 36 ks. A speci-
steel without B because of the increase in the number of men of -5.7 mm x 10 mm x 10 mm was cut from the
graphite particles associated with the decrease in their sheet, mechanically polished with emery paper and
diameter.' It is believed that this acceleration of graphi- alumina paste to a mirror surface, and rinsed with
tization by B doping comes from the following process: acetone and ethanol in an ultrasonic bath. In order to
hexagonal boron nitride (h-BN) precipitates by reaction identify BN precipitates from the AES peak shape, a
of B and N during hot rolling and it provides sites suit- standard specimen for h-BN was prepared by pressing
able for the nucleation of graphite in the successive 4N grade commercially available h-BN powder into
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- Table 1. Chemical composition of the graphitized steel
rolled graphitized steel sheets has been reported to date. (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 T. MEGA ET AL.

indium metal foils to ensure sufficient electrical contact gating toward the rolling direction. This indicates that
with the ground. the ferrite phase has not completely recrystallized.
Secondary electron images and Auger electron images Graphite particles are granular in the view of the T-
of elements in the graphite in the steel were observed on direction cross-section. In the view of the L-direction
two directional cross-sections denoted by the L- cross-section, however, some graphite particles are gra-
direction and the T-direction (L-direction, longitudinal nular and others are in the form of stringers parallel to
to the rolling direction; T-direction, transverse to the the rolling direction. Many of them exist in the ferrite
rolling direction) using a scanning Auger microscope grain boundaries. The interfaces between graphite par-
(PHI model-650) with an electron gun coaxial with the ticles and ferrite matrix are not flat but rather rugged.
cylindrical mirror analyser. Auger mapping was done This characteristic stringer shape seems to indicate that
at: primary electron energy of 10 keV, incident angle of some small graphite particles ranging in the rolling
30" with respect to the specimen normal, beam current direction in a small interval coalesce to form a long par-
of 20 nA, beam diameter of 0.2 pn, energy resolution of ticle elongating in the rolling direction.
0.6%, pressure in the specimen chamber of 3 x lo-* Pa, Plate 1 shows a secondary electron micrograph and
and observation area of 15 pm x 20 pm by electron an Auger electron image of graphite on the L-direction
beam scanning (magnification: x 5000). The Auger cross-section. Blue and green regions correspond to Fe
signals of Fe LMM (703 eV), C KLL (273 eV), B KLL in a ferrite grain and C in graphite, respectively. Then
(175 eV) and N KLL (382 eV) were chosen. PHI- the B and N regions were displayed in the red and green
ACCESS software was used to control the instrument regions, respectively, but these regions were observed in
and treat the AES spectra and images. In order to a cathode ray tube as the yellow region because they
reveal the BN precipitates in the graphite, Ar+ ion sput- overlapped each other. The colour image clearly shows
tering was carried out with a 3 keV primary energy, a the stringer-shaped distribution of B and N in an area
52" incident angle with respect to the specimen normal of -2 jm x 0.5 pn, parallel to the rolling direction.
and a 36 nA ion beam current (measured with a In order to investigate the chemical state of B and N
Faraday cup), with rastering over an' area of about 1 in the graphite, high-resolution Auger spectra were
mm x 1 mm to ensure uniform sputtering in the measured with an energy resolution of 0.25%, and com-
analysis chamber. The sputtering rate was estimated at pared with those associated with h-BN powder stan-
-5.3 x 1O-I' m s - l from the sputtering yield of iron. dard specimen. Figures 2(a) and 2(b) show the B and N
The microstructure of the steel was observed with a spectra of the yellow region of the Auger colour image

-
scanning electron microscope after chemical etching
with an alcoholic solution containing 3% nitric acid.
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-
RESULTS A N D DISCUSSION 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
Analysis of BN those of the h-BN powder.
The spectrum of B shown in Fig. 2(a) was also com-
Typical secondary electron images of steels after graphi- pared with that in other compounds containing B in the
tization annealing observed in a L-direction and T- steel. Cubic BN (c-BN) is known as another BN having
direction cross-section are shown in Fig. 1. Both a different crystal structure from h-BN. The minimum
microstructures showed ferrite grains with dispersed kinetic energy in the differential spectrum of B KLL for
graphite particles. The dispersed graphite was con- c-BN is reported to be 172 eV, which is 3 eV smaller
firmed by the shape of the C KLL Auger spectrum. than that for h-BN. The Auger peak shapes of c-BN in
Some ferrite grains are granular and others are elon- the kinetic energy range 150-170 eV are quite different

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.
 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 317

(b) N-KLL

?e.
~~ 0
340 370 400

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.
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

from those for h-BN,3 and do not show the fine struc- the present analysis. Therefore, the reason why h-BN is
ture of the Auger spectrum of N, as indicated by the not detected on the as-polished surface is that most of
arrows in Fig. 2(d) for that of h-BN.4 Hanke and the h-BN was covered with graphite in the as-
Muller’ have compared the B KLL spectrum of h-BN mechanically-polished specimen and it was not possible
with that of such boron compounds as pure B, B4C and to detect the h-BN existing at a position deeper than
B 2 0 3 . They found that the minimum kinetic energy in the Auger electron escape depth of a few nanometres.
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
- Precipitation of h-BN and graphite
no resemblance of Auger peak shapes with h-BN. More-
over, there was no oxygen signal, but C in the B and N Auger electron images measured in this area also
area in the graphite showed as yellow in Plate l(b). The showed the stringer-formed distribution of h-BN in an
B KLL spectrum of B 2 0 3 is quite different in shape area -2 pm x 0.5 pm parallel to the rolling direction,
from that of h-BN in the kinetic energy range 150-170 as shown in Plate l(b) and Fig. 5. This characteristic
eV, although both are similar in the kinetic energy shape of h-BN can be explained by considering the
range 170-190 eV. The minimum kinetic energy in the nucleation process of h-BN.
differential spectra of B for B203 is 3 eV lower than The ingots are subjected to solution treatment in
that of h-BN. These results lead to the conclusion that N 1473 K, hot-rolled at the finishing temperature of
the chemical state of B in the graphite is not equivalent 1173 K and cooled. During the heating process the
to that in pure B, B4C and B 2 0 3 , and the stringers ingots transform to austenite and grains are elongated
observed in the graphite shown in Plate l(b) are h-BN. by hot rolling. Some elongated austenite grains rec-
The graphite precipitates in which h-BN is observed rystallize to form granular grains, while many other
on their as-polished surfaces are very few and no h-BN grains remain in the form of elongated unrecrystallized
is observed on many graphite precipitates in the same grains even after cooling. It was reported that B segre-
specimen. Therefore, the interior of the graphite was gates at the austenite grain boundary during solution
examined by Ar + ion sputtering. Scanning electron treatment.5 As soon as the steel is hot-rolled, B segre-
micrographs of the graphite without BN on the as- gates quickly at the recrystallized grain boundaries and
polished surface after Ar’ ion sputtering for 0, 0.9, 3.6 forms a BN precipitate by reacting with some N that
and 6.96 ks are shown in Fig. 3. A white region in con- diffuses to the grain boundaries from the interior of the
trast with the surrounding graphite, indicated by the grain.6s7Therefore, in the case where recrystallized and
arrow, gradually became appreciable with increasing unrecrystallized grains coexist, h-BN can precipitate
Ar’ ion sputtering time. After sputtering for 6.96 ks, the also at the boundaries of unrecrystallized grains in a
region was clearly observed, as shown in Fig. 3(d). similar manner to those of recrystallized grains. Since
Figure 4 shows the AES spectra from the points indi- the unrecrystallized grains are coarse and elongated
cated by the arrows in Figs 3(a) and 3(d). Neither N or toward the rolling direction, BN at the grain boundary
B is observed in the as-polished specimen. However, B also precipitates in the form of stringers elongating to
and N are clearly observed in the 6.96 ks sputtered the rolling direction. During the subsequent cooling, the
specimen. No doping element (including Si, Mn and Al) 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, Some reports on graphitized steel are concerned with
stringers of h-BN precipitation exist along prior unre- the nucleation site that promotes the graphitization in
crystallized austenite grain boundaries, as shown in Fig. the steel during hot-rolling and annealing. Okamotog
5 and Plate l(b). has reported that graphite can originate in fine voids
According to Sueyoshi and Suenaga,8 graphite may formed by cracking of cementite during cold rolling in
preferentially nucleate where fine precipitates with steels containing 0.06 and 0.5 mass% C. It has been
nearly the same atomic spacing and arrangement as the proved by electron probe microanalyser that the non-
(OOO1) surface of the graphite exist. The crystal structure metallic fine inclusions, composed mainly of A120,,
of h-BN is compared with that of graphite in Table 2. SiOz or silicates, are the nucleation sites for graphite in
The atomic arrangement and spacing of h-BN are very steels containing 0.23 mass% C.8 However, experimen-
similar to those of graphite. This suggests that the h-BN tal evidence has not yet been reported to clarify h-BN
observed in Plate l(b) and Fig. 5 provides the nucle- as the nucleation site for graphite precipitation in steels
ation sites for graphitization. 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 319

Table 2. Crystal structure of h-BN and graphite

Crystal system Space group e(nm) O m ) JCPDS no.'

h-BN Hexagonal P63/mmc 0.250 44 0.66 562 32-0421

Graphite Hexagonal P63/mmc 0.24704 0.672 44 41 -1 478
a JCPDS: Joint Committee on Powder Diffraction Standards.

to be a new demonstration that h-BN precipitation (1) The formation of stringers of h-BN precipitates in
exists in graphite as a nucleation site and promotes the graphite elongated in the rolling direction was
graphitization in B-doped graphitized steel sheet. clearly revealed by the Auger mappings and high-
During the graphitization annealing, graphite precipi- resolution Auger spectra,
tates grow and their shape is affected by their growing (2) The h-BN precipitates exist inside the graphite.
process. The characteristic stringer-shaped graphite par- Most h-BN precipitates are not detected in the as-
ticles are explained as follows. During graphitization mechanically-polished specimen surface, but were
annealing, graphite precipitates in contact with h-BN in revealed on the sputtered surface by Ar' ion in the
prior austenite grain boundaries. In the boundary of analysis chamber.
unrecrystallized grain, some h-BN particles lie in the (3) It is inferred that the h-BN exists in the graphite as
rolling direction at a short intervals. Therefore, graphite nucleation sites of the graphite and thus promotes
particles formed at such h-BN particles grow, contact further graphitization in the B-doped graphitized
each other and finally coalesce to form a larger particle steel sheet.
with a rugged surface elongating toward the rolling (4) The shape of the h-BN particle in the graphite sug-
direction. gests that the h-BN precipitates at the unre-
crystallized austenite grain boundaries during hot
rolling.
CONCLUSION (5) The characteristic shape of graphite particles sug-
gests that the graphite precipitates in contact with
The distribution of elements in graphite in hot-rolled h-BN particles which lie in the rolling direction at
graphitized steel sheet was investigated by AES. The fol- small intervals, grow, contact each other and finally
lowing results were obtained: coalesce to form a larger particle.

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