Materials Transactions, Vol. 43, No. 3 (2002) pp.

292 to 300
Special Issue on Environmentally Benign Manufacturing and Material Processing Toward Dematerialization
c

2002
The Japan Institute of Metals

Suppression of Surface Hot Shortness due to Cu in Recycled Steels

Koji Shibata, Soek-Jong Seo 1 , Masashi Kaga 2 , Hiroshi Uchino 3 ,
Akio Sasanuma 4 , Kentaro Asakura and Chihiro Nagasaki
Department of Metallurgy, The University of Tokyo, Tokyo 113-8656, Japan
The most serious problem in the recycling of steel is the occurrence of surface hot shortness during hot deformation due to the mixing
of Cu from scrap into steels. Tin accelerates the effect of Cu. The surface hot shortness is caused by liquid embrittlement, that is, formation
of the liquid Cu-enriched phase through preferential oxidation of Fe atoms at the steel/scale interface during heating for hot deformation and
penetration of this Cu-enriched phase into the grain boundaries. Decrease in the amount of the liquid Cu-enriched phase penetrating into
grain boundaries can suppress the surface hot shortness. The amount of the liquid Cu-enriched phase penetrating into the grain boundaries
can be reduced by the suppression of oxidation, occlusion of the Cu-enriched phase into the scale, back-diffusion of Cu into the steel matrix
and suppression of penetration of the liquid Cu-enriched phase. Therefore, the effects of various elements and conditions of heating and
deformation on the surface hot shortness, oxidation, amount of the Cu-enriched phase at the interface and the penetration were examined by
tensile tests at high temperatures, thermogravimetry and optical microscopy. The conclusion can be summarized as follows. Silicon, Mn,
S (+Mn) and B reduce the susceptibility to the surface hot shortness through decreasing the amount of Cu-enriched phase at the steel/scale
interface. The effect of Si is significant. Carbon reduces the oxidation rate in LNG combustion gas. Phosphorus, Si, B and C reduce the
susceptibility to the surface hot shortness through restraining the penetration of the Cu-enriched phase into grain boundaries. Heating at higher
temperatures reduces the susceptibility mainly through a reduction in the amount of the Cu-enriched phase at the steel/scale interface, although
the loss of steels by oxidation increases. A large grain size accelerates the surface hot shortness. A small amount of H2 O in air significantly
accelerates the surface hot shortness. Effects of H2 O in heating atmosphere depend on the steel composition and more detailed research on this
is desired. Very slow deformation does not cause liquid embrittlement through dynamical re-crystallization, while at a fast deformation rate
the embrittlement is suppressed by an increase in the critical stress for the liquid embrittlement. Multiple methods using physical metallurgy
suggested by the present research for suppressing the surface hot shortness should be applied together with other methods through separation,
smelting and design of fabrication in order to promote the recycling of steels.
(Received October 22, 2001; Accepted January 7, 2002)
Keywords: oxidation, liquid embrittlement, penetration, alloy elements, impurities, temperature, atmosphere, deformation rate, grain
size, tin

1. Introduction
The amount of steel accumulation in Japan is steadily increasing year by year. As a natural result, the amount of steel
scrap, especially obsolete steel scrap, is expected to increase
at a considerable rate.1) Therefore the usage of steel scrap has
become important in steel manufacturing in Japan from the
viewpoints of resource saving and preventing environmental
problems.
In addition, the quality of the steel scrap is decreasing. That
is to say, concentrations of Cu and Sn, especially Cu, in steel
scrap are increasing.1) Copper is mainly contained in the scrap
of cars and home electronic appliances. Tin is mainly contained in the scrap of tin-coated cans. Once these elements
are mixed into steels it is difficult to remove them from the
steels in the currently used steel smelting process. Therefore
they travel between steels and scrap and accumulate in steels.
Thus they are called tramp elements.
On the other hand, Cu generally increases the strength
and corrosion resistance of steels and may decrease the environmental load during the lifecycle of steels. Copper, however, causes a serious problem during mechanical working at
high temperatures such as hot rolling and forging. Namely,
1 Graduate

Student, The University of Tokyo, Present address: Technical

Research Labs, POSCO.
2 Graduate Student, The University of Tokyo, Present address: Kimitsu
Works, Nippon Steel Corporation.
3 Graduate Student, The University of Tokyo.
4 Undergraduate Student, The University of Tokyo, Present address:
Nisshin Steel Co., Ltd.

Cu causes many cracks to form on the steel surface during

hot workings. This phenomenon has been known as surface
hot shortness due to Cu.2) The surface hot shortness occurs
through the following mechanism. Copper tends to be enriched at the steel/scale interface by selective oxidation of Fe
atoms during the heating for hot workings. The Cu-enriched
phase usually liquefies and penetrates into austenite grain
boundaries under stress during hot rolling or forging to cause
cracks on the steel surface. Tin accelerates this deterioration
effect of Cu.3)
For this reason there are limits on the Cu and Sn contents in
each kind of steel.1) But the concentration of Cu in a certain
kind of steel scrap is now higher than the maximum tolerable
limit.1) From the viewpoint of recycling of steel, the surface
hot shortness is the most serious problem.
Several methods for suppression of the surface hot shortness can be considered. They are reduction of the amount
of Cu used in appliances such as automobiles through design
of structures and materials, reduction of the amount of Cu
in steel scrap as a raw material for steels through physical
and chemical methods of separation and reduction of the
amount of Cu in steel through smelting. It seems impossible, however, that the method will be feasible in the future.
As for the methods and , over the past ten years in Japan,
tremendous efforts have been made in order to remove Cu and
Sn from steel scrap and steels.1) In those activities, several
methods have been proposed. But it has never been clarified
whether they are applicable in the practical processes of steel
recycling.

Suppression of Surface Hot Shortness due to Cu in Recycled Steels

Table 1 Present limitations of Cu and Sn concentration in typical steels and
the aim of our research (mass%).
Steels

Cu

Sn

Sheet
(drawing)
Sheet
(commercial)
Shape
Bar

0.06 0.2

0.01 0.03

0.10 0.3

0.02 0.04

0.30 0.4
0.40 0.5

0.03 0.05
0.06 0.08

Considering the above background, the present authors

have stressed the necessity for the suppression of the surface hot shortness by physical metallurgy, namely, the method
.49) The method aims to suppress the surface hot
shortness through controlling of microstructures near the
steel/scale interface in order to reduce the amount of the liquid Cu-enriched phase penetrating into grain boundaries.
The amount of the liquid Cu-enriched phase penetrating
into grain boundaries can be reduced by suppression of oxidation, occlusion2) of the phase into scale, back-diffusion of
Cu and Sn into the steel matrix, suppression of wettability or
fluidity of the liquid phase and so on. It was expected that
these could be performed by optimization of the contents of
alloying elements and impurities, heating temperature, heating atmosphere, deformation temperature and deformation
rate. Therefore, in the present research the effects of such elements, heating and deformation conditions on the surface hot
shortness were examined in detail. The alloying elements and
impurities examined are not tramp elements from the viewpoint of steel recycling. Nickel increases the solubility of Cu
in steel and the melting point of the Cu-enriched phase. And
it has been well known that the addition of Ni is effective to
suppress the surface hot shortness.1012) But the removal of
Ni from steel in the current smelting process is very difficult.
In addition Ni is too expensive to be used in mild steels of
which the cost is required to be low. Thus, other methods for
the suppression of the shortness are desired. Table 1 shows
the present limitation of Cu and Sn concentrations in typical
steels and the aim of our research.
2. Experimental Procedures
2.1 Steels
About 40 steels were melted in vacuum furnaces and the
effects of P, Si, Mn, S, C, Ni, Sn and B were investigated.
Copper contents (mass%) in these steels were mainly 0.5%
and 0.2%Cu steels were also partially examined. Chemical compositions of some of the steels are shown in Table 2.
Steels from B1 to B4 were melted in order to examine the effects of a very low content of B, whereas Steels from CP1
to CP4 and from PC1 to PC4 were melted to determine
the effects of C and P. In the other steels, the contents of
Si, Mn, P, S, Ni, Al, Ti, B, N and O are 0.02%, 0.01%,
0.0010.002%, 0.0010.002%, 0.01%, <0.053%, <0.042%,
<0.0001%, <0.0046% and <0.0050%, respectively, when
the content is not mentioned.

293

2.2 Tensile tests at elevated temperature and evaluation

of susceptibility to the surface hot shortness
Round bar specimens were machined from hot rolled
plates. Length and diameter of the reduced region were
6.0 103 m and 3.0 102 m, respectively. Tensile tests
were carried out mainly at the strain rate of 2.8 102 s1
after heating the specimen at 1373 K or 1473 K for 1800 s in
oxidizing atmospheres. Similar tensile tests were also performed after heating in Ar gas. Susceptibility to the surface
hot shortness was evaluated from values of the parameters calculated from the maximum load and total elongation using the
following equations:
E p (%) = (PAr P)/PAr 100

(1)

E p (%) = (PAr P  )/PAr 100

(2)

E e (%) = (Ar )/Ar 100

(3)

where PAr and P are the maximum load in Ar gas and in oxidizing atmospheres, respectively. P  is the corrected value
of the maximum load considering the reduction in the specimen diameter by oxidation. Ar and are total elongation in
Ar gas and in oxidizing atmospheres, respectively. Our previous research4) revealed that these parameters represented the
susceptibility to the surface hot shortness very well. These parameters show larger values as the maximum depth of surface
cracks increases.
Two kinds of oxidizing atmospheres were used: ambient air
and a controlled atmosphere of 74%N2 16%H2 O8%CO2
2%O2 . The composition of the latter atmosphere is similar to
that of the combustion gas of LNG.
2.3 Observation of oxidation rate by thermo-gravimetry
A weight increase by oxidation of the steel was measured
using a thermobalance in air and in the LNG combustion gas
during heating at 0.33 K/s and holding at 1373 K for 1800 s.
The specimen was a cylinder of 5.0 103 m diameter and
3.0 103 m height.
2.4 Optical microscopy
Specimens of 101010(103 m)3 size were polished
mechanically and heated in air or in the LNG combustion gas.
After air-cooling from 1373 K or 1473 K they were mounted
in epoxy resin and were polished mechanically for optical microscopy.
2.5 Tensile tests using specimens implanted with a rod of
Cu or Cu alloy
In order to examine the effects of various elements in steels
or the Cu-enriched phase on the penetration of the liquid Cuenriched phase into grain boundaries, tensile tests were carried out in Ar gas after heating at 1373 K for 1800 s using
round bar specimens implanted with a rod of tough-pitch Cu
or Cu alloy in the hollow of 4.0 103 m diameter along the
tensile axis. Length and diameter of the reduced region of the
specimen were 1.0 102 m and 2.02 m, respectively.

294

K. Shibata et al.
Table 2 Chemical composition of the steels used to examine the effects of B, C and P (mass%).

Steels

Si

Mn

Cu

Al

Ti

B1
B2
B3
B4
CP1
CP2
CP3
CP4
PC1
PC2
PC3

0.100
0.100
0.099
0.098
0.001
0.098
0.470
0.001
0.46
0.48
0.10

<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.020
0.020
0.015

0.50
0.51
0.51
0.51
0.16
0.16
0.16
0.16
0.48
0.49
0.49

0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.100
0.001
0.019
0.020

0.002
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001

0.48
0.48
0.49
0.48
0.21
0.21
0.22
0.20
0.49
0.50
0.49

0.037
0.051
0.053
0.053
0.040
0.040
0.048
0.044
0.010
0.028
0.019

0.041
0.041
0.042
0.042
0.040
0.043
0.039
0.043
0.001
0.001
0.001

< 1
7
28
48
< 1
< 1
< 1
< 1
< 1
< 1
< 1

13
9
11
14
11
14
8
8
12
30
6

20
20
20
20
30
30
40
30
30
10
40

(B, N, O: ppm)

40

60
50

1373K
30

: 1373K
: 1473K

40
20

30
20

10

10
0

0.2

0.4

0.6

0.8

Fig. 1 Effect of Si and P on E p of 0.1%C0.5%Mn0.5%Cu steels heated

at 1373 K in air. Compositions of other elements are as low as those of
Steel B1 shown in Table 2.

Si1 Si2 Si3 Si4 Si5 Si6

Fig. 2 Effect of Si and Ni on E p of 0.1%C0.5%Mn0.5%Cu steels heated

in air. Compositions of Si and Ni are shown in the figure. Compositions
of other elements are as low as those of Steel B1 shown in Table 2.

3. Results
3.1 Effects of Si and P on the susceptibility to the surface
hot shortness
In Fig. 1, the effects of Si and P on E p of 0.1%C0.5%Mn
0.5%Cu steels heated in air are shown. The susceptibility decreases as the content of Si increases. Steels of a very low
content of P revealed higher susceptibility. The existence of
about 200 ppm P in steel decreases the susceptibility. However the addition of more P does not decrease the susceptibility much further.
Figure 2 shows effects of Si and Ni on E p of 0.1%C
0.5%Mn0.5%Cu steels heated in air. Addition of 0.5%Ni
significantly decreases the susceptibility: this content of Ni
is almost the same as that of Cu. Steels containing 0.4%Si
reveal similar susceptibility by the addition of only 0.26%Ni.
By adding Ni with Si, a smaller Ni addition can be used to
reduce the susceptibility to the levels obtained by a single,
larger addition of Ni.
3.2 Effects of B on the susceptibility to the surface hot
shortness
Figure 3 shows the effects of B on the susceptibility parameters of 0.1%C0.5%Mn0.5%Cu steels heated at 1373 K in
the LNG combustion gas. Addition of 7 ppm B decreases the
susceptibility to the surface hot shortness. But the effect is
reduced by a further addition of boron. Figure 4 exhibits ef-

Fig. 3 Effect of B on E p , E p and E e of 0.1%C0.5%Mn0.5%Cu steels

heated at 1373 K in LNG combustion gas. B1: 1 ppm > B, B2: 7 ppm B,
B3: 28 ppm B, B4: 42 ppm B.

fects of B on the susceptibility parameters of the same steels

heated at 1473 K in the LNG combustion gas. Comparing
with the results at 1373 K, the effects of B on the susceptibility parameters are not obvious. Remarkably high values of E e
at 1473 K are attributed to the very large values of Ar at this
temperature.
3.3 Effects of Mn and S on the susceptibility to the surface hot shortness
Figure 5 shows the effects of Mn and S on E e and E e of
0.5%C0.5%Cu steels heated at 1373 K in air. The addi-

Suppression of Surface Hot Shortness due to Cu in Recycled Steels

60

80
70

295

1473K

60

40

50

30

40

20

30

10

20

B1

1373K

50

B2

B3

B4

Fig. 4 Effect of B on E p , E p and E e of 0.1%C0.5%Mn0.5%Cu steels

heated at 1473 K in LNG combustion gas. B1: 1 ppm > B, B2: 7 ppm B,
B3: 28 ppm B, B4: 42 ppm B.

CP1

CP2

CP3

CP4

Fig. 6 Effect of C and P on E p of 0.16%Mn0.2%Cu steels heated in LNG

combustion gas.

0.6

30
1373K

: Ep
: Ep'

0.5
0.4

20
0.3
0.2

10
0.1
0

S1

S2

S3

0.2

0.4

0.8

S4

Fig. 5 Effect of Mn and S on E p and E p of 0.1%C0.5%Cu steels heated at

1373 K in air. Compositions of Mn and S are shown in the figure. Compositions of other elements are as low as those of Steel B1 shown in Table 2.

Fig. 7 Effects of Si and P on the oxidation rate of 0.1%C0.5%Mn0.5%Cu

steels heated at 1373 K in air. Steels are the same as those used for Fig. 1.

0.6

tions of S and Mn decrease E e and E e , although the effects

are small. The decrease in E e and E e by single addition of
0.02%S is relatively large. But this is attributed to the decrease in PAr due to hot shortness by the formation of liquid
FeS.

0.5

3.4 Effects of C and P on the susceptibility to the surface

hot shortness
Figure 6 shows the effects of C and P on E e of 0.16%Mn
0.2%Cu steels listed in Table 2 heated at 1373 K in the LNG
combustion gas. Ultralow C steel exhibits large susceptibility to the surface hot shortness. Addition of 0.1%C reduces
the susceptibility. The steel containing 0.5%C shows slightly
smaller E p than that of the 0.1%C steel. Addition of 0.1%P
to the ultralow carbon steel reduces the susceptibility to the
level of that of the 0.1%C steel.

0.1

4. Discussion
4.1 Effects of elements on oxidation rate
Figure 7 shows the effects of Si and P on the oxidation
rate of 0.1%C0.5%Mn0.5%Cu steels heated at 1373 K in
air. Single addition of Si does not change the oxidation rate,
although the susceptibility to the surface hot shortness decreases with an increase in Si content (Fig. 1). A single addi-

: 1373K
: 1473K

0.4 <1ppm

7ppm

28ppm

42ppm

0.3
0.2

B1

B2

B3

B4

Fig. 8 Effect of B on the decrease in diameter of the tensile specimen of

0.1%C0.5%Mn0.5%Cu steels during heating in LNG combustion gas.

tion of P increases oxidation rate, although a single addition

of P decreases the susceptibility to the surface hot shortness
(Fig. 1). Co-addition of Si and P decreases oxidation rate, and
the susceptibility to the surface hot shortness is decreased by
co-addition of Si and P (Fig. 1). Namely, the susceptibility
to the surface hot shortness can be hardly explained solely by
the effects of Si and P on oxidation rate.
Figure 8 exhibits the effects of B on the decrease in the diameter of the tensile specimen by oxidation during heating in
the LNG combustion gas. Comparing with the results shown
in Fig. 3, the effect of B on the susceptibility to the surface

296

K. Shibata et al.

Si

Si

Fig. 9 Effect of Si on Cu-enriched phase at the steel/scale interface of 0.1%C0.5%Mn0.02%P0.5%Cu steels heated at 1373 K in air.
Arrows indicate Cu-enriched phase (1: Cu-enriched phase occluded into scale, 2: Cu-enriched phase partially occluded into scale).

Cu

Cu
Cu

Fig. 10 Effect of P on Cu-enriched phase at the steel/scale interface of 0.1%C0.5%Mn0.02%Si0.5%Cu steels heated at 1373 K in
air. Steels are the same as those used for Fig. 1. (a) 0.002%P, (b) 0.02%P, (c) 0.1%P.

hot shortness cannot be explained by the effect of B on the

oxidation rate.
In the previous study,8) the present authors measured an
increase in the specimen weight during heating in air and the
LNG combustion gas and revealed that the effects of C and
P on the susceptibility cannot be explained by the effects of
such elements on oxidation rate.
4.2 Effects of elements on microstructure near steel/scale
interface
Figure 9 shows the effect of Si on the Cu-enriched phase
near the steel/scale interface of 0.1%C0.5%Mn0.02%P
0.5%Cu steels heated at 1373 K in air. It is revealed that
some Cu-enriched phases are occluded into the scale and the
amount of the Cu-enriched phase at the steel/scale interface
is reduced in the steel containing 0.4%Si. Such reduction of
the amount of the Cu-enriched phase contributes to the decrease in the susceptibility to the surface hot shortness. The
occlusion of the Cu-enriched phase is caused by the internal
oxidation of Si as mentioned by Nicholson and Murrary.2) But
the details of the effect of Si remain unknown.
Figure 10 shows the effects of P on the Cu-enriched phase
near the steel/scale interface of 0.1%C0.5%Mn0.5%Cu
steels heated at 1373 K in air. With an increase in P content the amount of the Cu-enriched phase increases, although
the susceptibility to the surface hot shortness is decreased.
Therefore the decrease in the susceptibility to the surface hot
shortness by the P addition cannot be explained by the effect
of P on the amount of the Cu-enriched phase at the steel/scale

interface.
Figure 11 exhibits effects of B on the microstructure near
the steel/scale interface of 0.1%C0.5%Mn0.5%Cu steels
(Table 2) heated at 1373 K in the LNG combustion gas. The
amount of the Cu-enriched phase is reduced a little by the addition of 7 ppm boron. Further addition of boron causes grain
boundary oxidation.
It was also revealed that the addition of 0.02%S reduced
the amount of the Cu-enriched phase at the steel/scale interface 0.1%C0.5%Mn0.5%Cu steels. And the addition of
0.5%Mn reduced the amount of the Cu-enriched phase, although the effect was smaller than that of S.
4.3 Effects of elements on penetration of liquid Cu into
austenite grain boundaries
Figure 12 shows the effects of Si and P on stress-strain
curves of Cu implanted specimens of 0.1%C0.5%Mn
0.5%Cu steels. The stress decreases markedly at the critical
point. It is thought that penetration of Cu into grain boundaries occurs rapidly and causes brittle fracture at the critical
point. The strain at the critical point is increased by the addition of Si and P. Phosphorus increases the stress at the critical point. From these results, it is known that Si and P in
steels restrain the penetration of the Cu-enriched phase into
grain boundaries. Generally, the following equilibrium equation holds for the penetration of a liquid phase into a grain
boundary at the surface.
2SL cos(/2) = b

(4)

Suppression of Surface Hot Shortness due to Cu in Recycled Steels

<1ppm

7ppm

28ppm

42ppm
Fig. 11

16
14
12
10
8
6
4
2
0

Effect of B on microstructure of the steel/scale interface of the steels heated at 1373 K.

1373K
BASE

0.05

0.1

297

0.15

0.2

0.25

0.3

Fig. 12 Effects of Si and P on the stress-strain curves of Cu implanted specimens of 0.1%C0.5%Mn0.5%Cu steels heated at 1373 K. Steels are the
same as those used for Fig. 1.

where SL is solid/liquid interface energy, b is boundary energy of solid and is dihedral angle. The rate of penetration
of Cu is very slow when tensile stress does not exist.13) But
under tensile stress, the penetration proceeds at a much higher
rate. McLean14) proposed the following critical condition that
the stress starts crack propagation by liquid embrittlement.
3 b
2SL b

(5)

where is applied stress and b is atomic diameter. If P segregates along the grain boundary and decreases the grain boundary energy, the critical stress is expected to increase. This effect of P is contributable to the effect of P that restrains the

surface hot shortness. However, the reason for the effect of Si

suppressing the penetration of liquid Cu has remained unclarified.
In practice, the Cu-enriched phase is conceived to contain
Si together with Fe, P, O and other elements. Therefore, in the
future more detailed experiments should be performed in order to clarify the effects of elements in the Cu-enriched phase
on the penetration of the liquid Cu-enriched phase.
Imai et al.3) reported that the concentration ratio of Sn to
Cu in the Cu-enriched phase is nearly the same as the concentration ratio of Sn to Cu in steels. In order to clarify the
effect of the dissolution of Sn in the Cu-enriched phase, the
present authors performed tensile tests using specimens implanted with a rod of CuSn alloys having various Sn contents. The result is shown in Fig. 13. Dissolution of Sn into
Cu suppresses the penetration. From this result, it is known
that the effects of the dissolution of elements into the Cuenriched phase on the penetration cannot be neglected.
Figure 14 shows the effect of B on the penetration. As the
content of B increases, the penetration is suppressed. Subsequent to the experimental results mentioned above, it has
been clarified that B tends to enhance grain boundary oxidation, whereas B reduces the amount of the Cu-enriched phase
at the steel/scale interface and the penetration. Therefore, the
most beneficial effect of boron on the suppression of the surface hot shortness is observed upon the addition of 7 ppm.
The present authors observed the segregation of B along
austenite grain boundaries in the previous study7) using the
alpha particle track etching method (auto-radiography using B10) ) for the specimens of Steels B2, B3 and B4 waterquenched from 1373 K. Therefore, the suppression of the pen-

298

K. Shibata et al.

20

heating procedures is desired.

Temperature : 1373K-4 -1
Strain rate : 8.3 10 s

10

Cu

0
0

0.05

0.1

0.15

0.2

Fig. 13 Effect of Sn content in Cu-enriched phase on the stress-strain

curves of specimens of a 0.1%C0.5%Mn0.5%Cu steel implanted with
a rod of CuSn alloy.

1373K
10

0
0

B4

B2
B1

Fig. 14 Effect of B on the stress-elongation curves of Cu implanted specimens of the steels shown in Table 2. B1: 1 ppm > B, B2: 27 ppm B, B4:
42 ppm B.

etration by B is attributable to the segregation of B along grain

boundaries by an equilibrium segregation mechanism. However, B tends to segregate along grain boundaries by a nonequilibrium mechanism even during fast cooling. Therefore,
segregation of B along grain boundaries should be observed
using specimens cooled at a much higher rate. In addition, the
effects of dissolution of B in the Cu-enriched phase should
also be examined.
4.4 Effects of heating temperature
Comparing Fig. 3 and Fig. 4, E p and E p at 1473 K are
found to be maller than those at 1373 K. As for E e the effect of heating temperature is opposite and the reason for
this has been mentioned before (3.2). It has been generally
observed that the surface hot shortness tends to occur most
severely around 1373 K.2, 5, 12) The reasons for this result are
conceived to be as follows. At higher temperatures, internal
oxidation and grain boundary oxidation tend to occur and occlusion of the Cu-enriched phase into scale are accelerated.2)
In addition, back-diffusion of Cu occurs from the steel/scale
interface into the steel matrix.12) On the other hand, heating
at a higher temperature enhances oxidation and increases the
loss of steels as shown in Fig. 8. Therefore optimization of

4.5 Effects of austenite grain size

Heating at a higher temperature results in coarser grains.
Therefore, the effects of austenite grain size on loadelongation curves were examined using 0.11%C0.52%Mn
0.50%Cu steel heated at higher temperatures in Ar gas before
performing the tensile test at 1373 K. And it was observed
the surface hot shortness was enhanced in the specimens having larger grain size. Therefore, in the event of the restraining effect of heating at higher temperatures on the surface hot
shortness, the suppression effects of the occlusion of the Cuenriched phase and back-diffusion of Cu into the steel matrix
are larger than the acceleration effects of coarser grains on the
surface hot shortness. In addition, it was clarified that the effect of elements on austenite grain size was negligibly small
in the present research.
4.6 Effects of atmosphere of heating furnace and deformation rate
In the present research, two oxidizing atmospheres were
used: air and the LNG combustion gas. In the latter atmosphere, the concentration of H2 O was higher than that in the
former.
Maeda and Sato15) reported that H2 O in heating atmosphere
changed the microstructure of the scale: H2 O formed many
voids in layers parallel to the steel/scale interface in the scale.
Such a change in the microstructure of the scale is expected
to affect the oxidation rate and therefore the surface hot shortness. Hence, the susceptibility parameters were compared between specimens of 0.5%Mn0.5%Cu steels shown in Table 2
heated in air and in the LNG combustion gas. The results are
shown in Fig. 15. In this figure, the effect of the atmosphere
is very small. On the other hand, Fig. 16 shows the effects
of atmosphere on the load-elongation curves of a 0.5%C
0.5%Mn0.5%Cu steel heated in various atmospheres. Comparing the curves heated in air and in dry air, the effect of
a small amount of H2 O is remarkably large. Nicholson and
Murrary2) reported the effect of H2 O on the surface hot shortness depending on oxygen content.
Uchino et al.8) showed that the oxidation rate of a 0.1%C
0.02%P steel is much higher in LNG combustion gas than in
air, whereas the oxidation rate of a 0.5%C0.02%P steel is
similar in both atmospheres and the oxidation rate of 0.5%C
0.001%P steel is a little slower in LNG than in air. Therefore,
effects of atmosphere depend on the chemical composition of
steel. Details of the effects of atmosphere should be clarified
in the future.
On the other hand, Seo et al.5) found that the susceptibility to the surface hot shortness depended on the strain rate
and showed the maximum at around 1 101 s1 . Figure 17
shows the effect of strain rate on stress-strain curves of specimens implanted with a Cu20%Sn rod into 0.1%C0.5%Mn
0.5%Cu steel. It is revealed that the penetration of the Cuenriched phase shows strain rate dependency. Therefore it is
known that the penetration does not occur only through the
static conditions such as shown by eq. (5) but also through
dynamical conditions of which the details remain unknown.
Figure 17 shows that liquid embrittlement does not occur at
the very low strain rate. Sasanuma et al.16) showed that the

Suppression of Surface Hot Shortness due to Cu in Recycled Steels

80

80

: Ep
: Ep'

70

in air

60

60

50

50

40

40

30

30

20

PC1

Fig. 15

PC2

20

PC3

1373K
800
Ar gas
600
dry air
air

200
0

LNG combustion gas

20

40

60

80

100 120 140

Fig. 16 Effects of heating atmosphere on the load-elongation curve of a

0.5%C0.5%Mn0.5%Cu steel.

40

4.2

-1 -1

10 s

8.3

1373K

10-2 s-1

30
4.2

PC2

PC3

-4 -1

10 s

10

0.2

schematically. Silicon, Mn, S (+Mn), C and B reduce the

susceptibility to the surface hot shortness. Heating low carbon steels in low H2 O atmosphere and heating at a higher
temperature also restrain the shortness. Very slow deformation suppresses the surface hot shortness, although the product efficiency decreases. Very fast deformation seems to be
feasible for the suppression of the surface hot shortness under
the precise control of each reduction. Fine grain size reduces
the depth of the penetration of the Cu-enriched phase and restrains the surface hot shortness.
Indeed the effect of each of the above methods is not so
large, but the multiple usage of these methods is conceived
to be feasible. In order to promote recycling of steels, such
methods using physical metallurgy should be applied together
with other methods using separation, smelting and design of
fabrication. Of course the methods employing physical metallurgy should not deteriorate other properties of steels and
should not increase the environmental loading. Therefore optimization is desired in controlling chemical compositions of
steels and conditions of heating and deformation.
5. Conclusion

8.3

0.1

PC1

in LNG

-3 -1

10 s

20

0
0

: Ep
: Ep'

Comparison of E p and E p of 0.5%Mn0.5%Cu steels heated in air and in LNG combustion gas.

1000

400

70

299

0.3

0.4

0.5

Fig. 17 Effect of strain rate on the stress-strain curve of a 0.1%C

0.5%Mn0.5%Cu steel implanted with a rod of Cu20%Sn alloy.

reason is attributed to dynamic re-crystallization which suppressed the stress at low levels. At a high strain rate, the critical stress for liquid embrittlement increases. From these results it is speculated that plastic deformation plays an important role in the occurrence of liquid embrittlement.
4.7 Feasibility of the suppression of surface hot shortness using physical metallurgy
The present research revealed that there are many methods using physical metallurgy for restraining the surface hot
shortness due to Cu. In Fig. 18, such methods are shown

Experimental results can be summarized as follows.

(1) Silicon, Mn, S (+Mn) and B reduce the susceptibility to the surface hot shortness through decreasing the amount
of the Cu-enriched phase at the steel/scale interface. Significant occlusion of the Cu-enriched phase into the scale was observed in steels containing Si. Carbon decreases the amount
of the Cu-enriched phase through reducing the oxidation rate
in the LNG combustion gas.
(2) Phosphorus, Si, B and C reduce the susceptibility to
the surface hot shortness through restraining the penetration
of the Cu-enriched phase into grain boundaries.
(3) Heating at higher temperatures reduces the susceptibility, although the loss of steels by oxidation increases.
(4) Larger grain size accelerates the surface hot shortness.
(5) A small amount of H2 O in air accelerates significantly
the surface hot shortness. Effects of H2 O in heating atmosphere depend on steel composition and more detailed research is desired.
(6) Very slow deformation does not cause the embrittlement due to the liquid Cu-enriched phase, because the stress
level is decreased by dynamic re-crystallization of steels. At

300

K. Shibata et al.

Fig. 18 Schematic draw of physico-metallurgical methods for suppression of the surface hot shortness due to Cu.

a fast deformation rate the embrittlement is suppressed by an

increase in the critical stress for the liquid embrittlement.
(7) Multiple methods employing physical metallurgy
suggested by the present authors for suppressing the surface
hot shortness should be applied together with other methods
through separation, smelting and design of fabrication in order to promote recycling of steels.
Acknowledgements
The authors are grateful to all co-researchers and to
Nippon Steel Corporation, Kawasaki Steel Corporation and
Sumitomo Metals Co. Ltd. for steel melting. This research
was financially supported by the Special Coordination of
Japan Ministry of Education, Culture, Sports, Science and
Technology.
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