Sulphide shape In the rolling of sheet and strip in modern mills, deformation takes place mainly in

the longitudinal direction. As the extension increases, there is a deterioration in the

control transverse and through-thickness toughness parameters, attributable mainly to the
plastically deformable inclusions, such as manganese sulphides. The form of the
inclusion in the wrought product is afunction of its morphology in the cast steel and
its plasticity. The effect of composition on both factors has been investigated.
Increasing the aluminium or sulphur content of the steel promotes the formation of
Type II manganese sulphides, which are precipitated as extensive arrays of rods in
an interdendritic eutectic distribution, and which deform, as an array, to produce
highly elongat'ed stringers. l\1ildly deoxidized steels contain globular, isolated,
Type I sulphides, which do not form the particularly harmful stringers, but which
are still highly deformable. Cerium and calcium additions successfully modified the
initial morphology of the sulphide inclusions to an isolated globular form, and also
decreased their plasticity, whereas titanium additions of up to 0·12% were
ineffective in these steels at the manganese levels involved. The electron micro-
structure of deformed a-MnS, a-AI203, and Y -phase inclusions have been
investigated. Evidence of recovered substructures, recrystallization and
precipitation within manganese sulphides, and Ti3S4precipitation within V-phase
inclusions is presented. MT/488

©1979 The Metals Society. Manuscript received 1 March 1978. The original
version of this paper was presented at the conference on 'Directionality of proper-
ties in wrought products' held by The Metals Society in London on 27-28 November
1974. At the time the work was carried out the authors were with the British Steel
Corporation, Sheffield Laboratories. Dr Banks is now with the United Kingdom
T. M. Banks Atomic Energy Authority, Nuclear Power Development Laboratories, Windscale,
T. Gladman Cumbria.

In the rolling of sheet and strip in modern mills, defor-
mation takes place mainly in the longitudinal direction. As
the extension increases, there is a deterioration in the
transverse and through-thickness toughness parameters,
attributable mainly to the plastically deformable inclusions,
such as manganese sulphides.
The precipitation pattern of manganese sulphides in the
ingot has a particularly deleterious effect on the properties
of the wrought product. In the ingot the strong segregation
tendency of sulphur and the frequent distribution of
sulphides as chain-like precipitates at the primary ingot
grain boundaries cause a high local planar density of
inclusions. On rolling, inclusion clusters become displaced
and reoriented to form elongated stringers, the effect being
exacerbated by deformation of the individual inclusions.
Manganese sulphides have been classified by Sims and
Dahle,l according to their morphology in the ingot, as fol-
lows:
Type I: isolated globular sulphides which form as a
liquid phase in the liquid steel
Type II: dendritic, chain-like intergranular sulphides,
described as a cooperative eutectic2,3 or a
cooperative monotectic4,5
Type III: isolated idiomorphic sulphides which form as a
result of a divorced eutectic reaction.
The Type II morphology, which has a severe adverse effect
on ductility, is not uncommon in commercial steels and,
therefore, in recent years efforts have been made to
alleviate this problem by the addition of sulphophilic
elements. The strong sulphide formers modify the compo-
sition of the sulphide inclusions and hence their morphology
and distribution in both cast and wrought steels; they
also modify the plasticity of the sulphides during hot
deformation. These factors act in concert to reduce the
local planar density of inclusions and hence the anisotropy
of toughness parameters.
Although all the lA, I1A, IlIA, and IVA subgroup
elements constitute potential manganese sulphide modi-
fiers,6 only calcium, titanium, and Mischmetal * have been
selected for study since the application of the other elements
(with the exception of zirconium) is limited by practical
considerations. In addition, the effects of the Type II
MnS-promoting elements, aluminium, and sulphur have
been assessed.
Experimental procedures
A series of O·25C-1·2Mn, 080M40 (En8), and 606M36
(En 16M) steels were air melted in a high-frequency in-
duction furnace. The Si, Mn, S, and C levels were adjusted
by appropriate additions to the initial melt of high-purity
iron. The aluminium and, finally, the titanium, Mischmetal,
or Calsibart additions were introduced immediately before
tapping. The chemical analyses of the steels are given in
Table 1.
Each 60kg melt was cast into a cylindrical sand mould of
200mm dia., which minimized the surface area of the ingot.
The sand mould was, in turn, surrounded by a large volume
of sand. The cooling rate was measured and estimated to be
equivalent to that of an air-cooled ingot of 540 mm dia.,
i.e. a small commercial ingot. A 15 mm thick diametral sec-
tion was cut from each ingot and subjected to sulphur prin-
ting. Metallographic specimens were prepared from the
*Mischmetal is a mixture of the rare-earth elements having a typical
composition 50Ce-25La-IONd-5Pr plus the other lanthanides.
tCalsibar is the trade name of an alloy containing 15Ca-16Ba-60Si-
iAI-I Fe. The barium is added to the alloy so that it has a higher
density and a lower vapour pressure. The silicon content is usually
wholly recovered and therefore may limit the addition made to the
steel.

Metals Technology March 1979 81

 82 Banks and Gladman Sulphide shape control

Table 1 Analysis of experimental steels, wt-%

Steel AI N
number C Si Mn 5 Sol. Insol. As AIN Sol. Insol. Ti Ca C(: 0

1 0·25 0·42 1·16 0·008 < 0·002 0·004 0·0076 0·010 0·002 0·0117
2 0·24 0·33 1·18 0·008 0·033 0·011 0·0067 0·009 0·002 0·0047
3 0·26 0·38 1·19 0·007 0·101 0·011 0·0079 0·008 0·003 0·0047
4 0·26 0·26 1·14 0·021 0·002 0·001 0·0010 0·011 0·003 0·0102
5 0·24 0·22 1·12 0·021 0·025 0·012 0·0118 0·011 0·003 0·0053
6 0·25 0·25 1·20 0·051 0·004 <0·001 0·0010 0·011 0·003 0·0072
7 0·25 0·24 1·14 0·050 0·031 0·012 0'0096 0·011 0·003 0·0049
8 0·245 0·19 1·11 0·051 0·116 0·012 0·0104 0·010 0·003 .. .. 0·0037
9 0·25 0·18 1·18 0·009 <0·002 <0·001 0·0017 0·006 0·003 0·05 NA 0·0098
10 0·25 0·22 1·18 0·012 <0·002 <0·001 0·0010 0·002 0·005 0·10 NA 0·0115
11 0·255 0·22 1·17 0·007 0·027 0·011 0·0012 0·002 0·007 0·065 NA NA
12 0·26 0·16 1·18 0·010 0·013 0·020 0·0006 0·002 0·008 0·09 NA 0·0069
13 0·25 0·15 1·17 0·010 0·003 <0·001 0·0015 0·008 0·001 <0·02 0·048 0·0070
14 0·25 0·30 1·17 0·011 0·004 <0·001 0·0015 0·007 0·001 <0·02 0·088 0·0110
15 0·26 0·23 1·18 0·009 0·035 <0·001 0·0062 0·008 0·001 <0·02 0·050 0·0096
16 0·26 0·24 1·15 0·009 0·035 <0·001 0·0087 0·008 0·001 <0·02 0·075 0·0070
17 0·12 0·09 0·72 0·026 NA NA 0·0010 0·009 0·003 0·06 NA 0·0232
18 0·21 0·16 1·08 0·025 NA NA 0·0029 0·005 0·006 0·08 NA 0·0133
19 0·25 0·23 1·18 0·026 0·027 0·013 0·0006 0·002 0·009 0·075 NA 0·0056
20 0·25 0·27 1·14 0·026 0·022 0·015 0·004 0·002 0·011 0·12 NA 0·0090
21 0·26 0·23 1·14 0·027 NA NA 0·0046 0·010 0·001 0·003 0·039 0·114
22 0·255 0·185 1·23 0·025 NA NA 0·0040 0·013 0·001 0·004 0·102 0·0175
23 0·26 0·18 1·21 0·025 0·039 0·001 0·0037 0·010 0·001 0·002 0·065 0·0078
24 0·25 0·19 1·15 0·026 0·032 < 0·001 0·0114 0·010 0·001 0·002 .. 0·078 0·0088
25 0·37 0·65 0·84 0·011 0·032 0·005 0·0073 NA NA 0·002 0·0076
26 0·36 0·30 0·78 0·013 0·030 0·013 0·0062 NA NA 0·001 0·0067
27 0·37 0·24 0·82 0·029 0·022 0·010 0·0071 NA NA NA 0·0051
28 0·40 0·68 0·76 0·029 0·021 0·005 0·0093 NA NA 0·003 0·0059
29 0·40 0·38 0·82 0·034 0·023 0·010 0·0096 NA NA 0·002 0·0065
30 0·34 0·30 1·38 0·198 NA NA 0·0010 0·007 0·001 <0·001 0·0092
31 0·34 1·02 1·36 0·176 NA NA 0·0006 0·009 0·002 0·015 0·0090

columnar and equiaxed zones of each section. Charpy- The inclusions in selected steels were examined by
impact specimens were manufactured with their longitudinal electron probe microanalysis, or by X-ray diffraction of
axes normal to the direction of columnar grain growth, and powder residues extracted in a 5% solution of bromine in
tested at 150°C. Two sections were cut from the remainder methanol. Carbon-extraction replicas, prepared in the
of each ingot and rolled either from 1200°C in a falling usual manner, from selected rolled steels, were examined by
temperature regime or at 900°C by reheating after each high-voltage electron microscopy.
pass, to a 4: 1 reduction. The x-z plane was prepared for
metallographic examination.
Various methods of assessing the inclusion plasticity Results
have been cited in the literature.7-9 In accordance with
other recently published work,10 the definition due to
Malkiewicz and Rudnik 9 has been utilized in the present EFFECTS OF COMPOSITION ON INCLUSION
investigation. The plasticity ratio v is defined by CONSTITUTION AND MORPHOLOGY
210gA Selected inclusions were examined in the as-cast or as-rolled
v=-- conditions by electron probe microanalysis, and typical
310gh analyses are given in Table 2. The morphological classi-
where A=a/b and h=Fo/F1; a and b are the major and fication of Sims and Dahle1 applies, strictly, to manganese
minor axes, respectively, of the ellipsoidally deformed sulphides, but it is also commonly used to describe other
inclusion, and Fo and F1 are the initial and final cross- sulphide species. In this paper, classification will be based
sectional areas of the steel. The advantages of this expres- solely on form.
sion are: the value of the plasticity ratio for zero-inclusion In unmodified steels the sulphide is always (Mn, Fe)S,
deformation is always zero, the terms 10gAand logh are provided the Mn/S ratio is greater than 5. The iron content
both measures of true strain, the distribution of 10gA could not be determined accurately owing to the thickness
values is normal enabling statistical analyses to be per- of the inclusion relative to the depth of penetration of the
formed, and also bimodality may be more easily identified.
The mean projected length and mean projected width,
measured on the x-z face, may be computed using the Quan-
timet or, alternatively, the aspect ratio of each inclusion Table 2 Electron probe microanalysis of selected in-
measured manually. However, the QTM is not able to differ- clusions
entiate between cerium oxides, sulphides, and oxysulphides
Analysis, %
so that the possibility of a bimodal distribution could not Steel Inclusion type Fe MnS AI Ti Ca Si02 AI203 Ti203 MnO
be tested. Also, the value of mean 10gAis not equal to the
value of log (mean A),particularly in the situation where the 4 Type I MnS 60 28 15 ..
range of A-values is large. The length and width of about 4 Silicate 33 1 1 .. .. .. 21 17 27
6 Type II MnS 57 32 16 .. 3
250 inclusions, therefore, were measured manually. Oxides 8 Type II MnS 47 36 19 .. ..
were included in the aspect-ratio measurements since it is 8 Alumina 78 .. .. 22 ..
18 Oxide 29 2 .. .. .. 2 60
believed that oxides and sulphides will both form voids by 19 Type II MnS 55 30 17 .. ..
interface decohesion at very low strains, and hence con- 19 Oxide 33 1 .. .. .. .. 70 15
tribute to the fracture process in a like manner.
28 Type II MnS 6 59 31 6 ..

Metals Technology March 1979

 Banks and Gladman Sulphide shape control 83

a b

c d
a steel 1, 0·008%5; b steel 6, 0·051 %5 ; c steel 4, 0·003%AI ; d steel 5, 0·037%AI
1 Optical micrographs of sulphide in cast steel, showing effects of sulphur and aluminium xSOO

electron beam. However, although it is known that up to observation has been made by the authors; (cf steels 4, 6,
60% of the manganese may be replaced by iron, a value of and 8, Table 2). Globular, relatively isolated duplex silicate-
5 % would be more typical. 11 sulphide inclusions are frequently observed in silicon-killed
Increasing the sulphur l~~velcan lead to a replacement of steels, whereas in aluminium-treated steels alumina
Type I with Type II manganese sulphide (Fig.1a and b). galaxies are observed, often in association with Type II
The sulphur level at which this occurs depends on the sulphides. The concomitant reduction in oxygen levels is
carbon, oxygen, silicon, and manganese contents.12 The the cause of the replacement of Type I by Type II sulphides, 2
Type II sulphides formed as a result of increasing the which form by a cooperative mechanism at columnar
sulphur level (rather than by adding aluminium) have very grain boundaries (cf Fig.Ie and d). In the absence of
pronounced rod-like structures. A possible explanation for aluminium, isolated globular Type I sulphides are ob-
the effect of sulphur or, more precisely, S/O ratio is that the served to form loose networks in the interdendritic regions
first formed liquid-oxide phase takes the sulphide into owing to sulphur segregation. In modified steels, prior
solution and, subsequently, on cooling, precipitates it at deoxidation with aluminium is essential to avoid the
the globular oxide/metal interface. Increasing the sulphur occurance of gross oxide stringers.
level (or reducing the oxide content) to a level which In the present work titanium additions of up to 0'12%
exceeds the solubility causes the sulphide to be nucleated result in the formation of (Mn,Ti)S inclusions containing
directly. up to 3~!c> titanium. The oxide phase in non-aluminium-
Published work 13 has shown that although aluminium is treated titanium-modified steels is Tb03 containing small
effective in modifying the sulphide morphology it has a amounts of alumina. In aluminium-treated steels, the
negligible effect on sulphide composition. A similar oxide phase is alumina containing up to 22% Th03, in

Metals Technology March 1979

84 Banks and Gladman Sulphide shape control

sulphides take the Type II morphology, the networks of

which are more extensive than those resulting from alu-
minium alone (Fig.2a).
Electron probe microanalysis of inclusions in Misch-
metal-treated steels is complicated because of the number
of metals present, their physical similarity (causing the
masking of X-ray emission lines), the difficulty of providing
stable standards, and the duplex nature of the inclusions.
Accordingly, the electron probe microanalyses were
supplemented by X-ray analyses of powder residues
extracted using a 5% solution of bromine in methanol.
The relative amounts of the identified phases are given in
Table 3.
It is evident that at low cerium levels the rare earth (RE)
AI03 phase is formed, and at higher cerium levels RE202S
becomes the major phase present. Manganese sulphides
remain in the steel at Ce/S ratios of less than about 3. The
RExSy phases (RES, RE2S3, RE3S4, etc.) were not observed.
These inclusion phases are in accordance with those noted
a
by Wilson and Wells. 14In addition, Wilson et al.I5 utilized
the available standard free-energy data for various RE
compounds, and predicted that RE202S would form before
RExSy phases. The REAI03 and RE202S phases form as
globular duplex isolated (Type I) inclusions (e.g. steel 22,
Fig.2b). The Mischmetal additions were sufficient to
eliminate the Type II morphology in all except steel 21
(0·039Ce-0·027S). Clustering of inclusions may occur at
high oxygen or sulphur levels.
Modification of manganese sulphides with calcium (as a
1 or 0'4% addition of Calsibar) causes the formation of
(Mn,Ca)S containing about 6% calcium in solution.
Calcium aluminates were observed frequently in the centre
of the calcium-substituted manganese sulphide inclusions.
Calcium sulphide was not observed. Although a 0'4%
addition of Calis bar at the 0·01 % sulphur level was
sufficient to convert the manganese sulphides from the
Type II to Type III morphology (Fig.2c), a 1% addition
was required for the higher sulphur levels.
b

CHARPY DUCTILE SHELF ENERGY VALUES

Quantitative metallography can provide a measure of
average inclusion spacing, provided that the inclusions are
randomly distributed. The importance of Charpy ductile
shelf energy is that it can provide a measure of the degree of
inclusion clustering in the cast steel. As clusters of in-
clusions are retained in an exacerbated form in the wrought
product, this information is vital to an understanding of the
origins of directionality.
The ductile fracture surfaces were examined by scanning
electron microscopy (Fig.3), which showed that voids were
nucleated by large inclusions. It is axiomatic, therefore,
that the inclusion distribution and morphology largely
determine the ductile shelf energy. The steel composition
may control the inclusion microstructure in two ways, i.e.

Table 3 Electron probe and X-ray analyses of in-

c
clusions in M ischmetal-treated steels
a steel 18, O'08%Ti; b steel 22, 0·1 02%Ce; c steel 26, 0·001 %Ca
2 Optical micrographs of sulphide inclusions in cast Steel Steel Inclusion
number S, % AI,% Ce,% REAI03 RE202S MnS
steel showing effects of titanium, cerium, and
calcium x 450 13 0·010 0·004 0·048 Medium Medium
15 0·009 0·036 0·050 Large Small
21 0·027 0·004 0·039 Small to Small to Small to
accordance with the relative free energies of formation of medium medium medium
22 0.025 0·004 0·102 .. Very large ..
the oxides of titanium and aluminium. Titanium nitride 23 0·025 0·040 0·065 Small to Small to Small to
inclusions, recognizable by their typical cubic yellow ap- medium medium medium
24 0·026 0·032 0·078 Large
pearance, were distributed uniformly through the steel. The

Metals Technology March 1979

 Banks and Gladman Sulphide shape control 85

a b

c d

e
a steel 4, Type I MnS, x550; b steel 22, RE-metal-modified sulphides, x500; c steel 8, Type II MnS, x550; d steel 18, Type II MnS in titanium-bearing
steels, x 510; e steel 30, Type II MnS, x 500; f steel 31 , calcium-modified sulphides, x 520
3 Scanning electron micrographs of fracture surface of cast steel

Metals Technology March 1979

86 Banks and Gladman Sulphide shape control

110
J S7 %
(a)
(j) 0·01 0·025 0'18
~100 rollQd at 900°C 0 • •
w rollQd at 1200°C 0 • A
~
(j) 1-5

••
90
u
~
°
lD
(\J 80
I
• o

1-0
6 -;
'-' 0 ------ I •0
-0---0__ 0
0::: 70
>- 0
~
U
° 60
• \l\l
t:05
u
i=
U ----_
0 0 ---

0 (j)
lD <!

~ 50
• 'Y
ttJ
~ 0
>-

• •
<.9
0::: 40 TYPQ II
W
Z sulphidQS
W \l
I-
U
<!
30
0 basQ
• •
Q..

2 20 • basQ + Al
0 basQ + CQ
>-
Q..
0::: 10
• basQ + CQ + Al
'V basQ + Ti 0·5
<!
I
• basQ + Ti + Al --g--------------e
u
o 5 10 15 20 25 30 35 o
AREA FRACTION (SULPHIDE + OXIDE) IN
COLUMNAR ZONE, x 104
4 Charpy ductile shelf energy as function of inclusion 6 Effects of titanium and calcium on inclusion
area fraction plasticity ratio

the sulphur content which largely determines the volume
fraction of inclusions present in the steel, and the alu-
minium, sulphur, titanium, cerium, and calcium contents
which determine the morphology and distribution and
hence planar density of the sulphide inclusions.
0-4
stQQI 1
0·3
0·2
The relationship between shelf energy and the area
fraction of (sulphide+oxide) inclusions in the columnar
zone of the O·25%C steels is shown in Fig.4. Although
increasing the volume fraction reduces the impact energy,
the data points fall into two regimes, the upper containing
the base (low-sulphur) steels (Fig.3a) and the cerium-
treated steels (Fig.3b), which exhibit well dispersed in-
clusions, and the lower containing the base (high-sulphur)
stQQI 8
(with AL)
S7 %

0·1 001 0025

stQQls rollQd from 900°C 0 •
o stQQls rollQd from 1200°C 0 •
0·8
stQQI 20 stQQI 22
1-4 g calculatQd V
G07 (with Ti) (with MischmQtal)
~0·6
~ 1·2 •
0·0086%
60.5 " .•.. 02 as REAL03
w >- ""
t: lO
8:0A u ~
I- 0
wO·3
> ~ 0-8 0
~0·2 ..J
<{ Q..

~ 0·1 0·6
w
0::: 0
0-4
0·3
>
~ 0·4
..J
•
w 0·025°10 S as
0·2 0::: 0.2 RE202S
0·1
o 0
-0-4 0 0-40'8 1-2 1·6 2·0 -04 0 040·8 l2 1·6 2·02-4
LOG A

5 Histograms showing effect of aluminium, titanium

M ischmetal, and calcium on aspect ratio in steel~
rolled from 1200°C 7

Metals Technology March 1979


a b
a and b steel 1, initially containing Type I sulphides x 500; c steel 6, initially containing Type II sulphides, x 500; d steel 30, showing inclusion
stringer x 100
8 Optical micrographs of sulphide inclusions in rolled steel
steels (Fig.3c) and the titanium-treated steels (Fig.3d),
which exhibit extensive networks of Type II morphology
sulphides. One of the cerium-treated steels (21) contained a
proportion of Type II rnanganese sulphides which were
instrumental in reducing the impact-energy value. The
salient feature of Fig.4, therefore, is that the upper regime
contains only isolated sulphides, whereas the lower regime
contains Type II morphology sulphides. Similarly, a 1%
addition of Calsibar to 080M40 and 606M36 steels (27, 28,
30, and 31) modifies the sulphide morphology from Type II
to Type III (Fig.3e and f) and in both cases results in an
approximately 50% increase in shelf energy. The Charpy
ductile shelf energy, therefore, provides a technique for
ranking the degree of indusion clustering in the cast steel,
and emphasizes the extent to which clustering may be
present before rolling.
INCLUSION PLASTICITY
The importance of inclusion plasticity ratio (or index of
Banks and Gladman Sulphide shape control 87
deformability) lies in the fact that it gives a direct indication
of the hot-deformation behaviour of the inclusion in its
steel environment. It is possible, therefore, to connect
metallographic studies of the deformation of individual
inclusions with the subsequent mechanical behaviour of the
aggregate of steel and inclusion population. In addition, it
provides a measure of the tendency of both individual
inclusions and clusters of inclusions to form elongated
stringers.
Histograms illustrating the distribution of inclusion
aspect ratios for a number of steels, selected to show the
effects of aluminium, titanium, cerium, and calcium, are
presented in Fig.5. Steel 1 contains a proportion of silicate
inclusions which are generally assumed to be more plastic
than sulphides at elevated temperatures.16 The high mean
logarithm of aspect ratio (indicated by the dashed line) of
steel 1 relative to steel 8 after rolling from 1200°C is in
agreement with this assumption. The addition of up to
0·12% titanium (steel 20) has no significant effect on the
Metals Technology March 1979
88 Banks and Gladman Sulphide shape control

a steel 20, 0'12%Ti; b steel 24, 0'078%Ce; c steel 28, 0'003%Ca; d steel 30, O%Ca; e steel 31 , 0'015%Ca
9 Optical micrographs of sulphide inclusions in rolled steel, showing effects of titanium, cerium, and calcium
x500

Metals Technology March 1979

 Banks and Gladman Sulphide shape control 89

mean logarithm of aspect ratio, although there is an in-

crease in the proportion of undeformed oxide inclusions. 0·25°/oC stQQls 080M40 stQQls 606M36stQQIs
The addition of Mischmetal (steel 22) effects a dramatic o TYPQ I MnS 'V TYPQ IT MnS ~ TypQ IT MnS
reduction in inclusion plasticity, the aspect ratio being x TyP<2 IT MnS ~ Type I MnS +Ca A TYPQ I MnS+Ca
reduced to almost unity. Calcium effects a modest reduction o TypQ II MnS+Ti
in inclusion plasticity, the mean logarithm of aspect ratio
being reduced from 0·89 to 0'38, in steels 27 and 28 rolled TYPQ I MnS
from 1200°C. The variation of inclusion-relative plasticity
1-4
with % titanium, the ratio of % ca1cium/<j6sulphur, and ~/o
cerium are shown in Figs.6 and 7, in confirmation of T/cY~DQIT Mnj TYPQ II MnS +Ti
these observations. o
Micrographs selected to emphasize the salient features i= 1-2 o
<{
are presented in Figs.8 and 9. Type I MnS inclusions 0:::
deformed either to ellipsoids (Fig.8a) or to a more complex
shape, such as the silicate-containing inclusion of Fig.8b.
Deformation of Type II sulphide inclusions causes both the
>-
~ lO
U
i=
(/)
jxxlJ.

V
o
o
elongation of the individual sulphide branches and the JOB
reorientation of the complete colonies, with their con- Q..
o
stituent branches, into the rolling plane. The deformed and z
o o TYPQ IMnS + Ca
reoriented Type II sulphides appear in optical micrographs ~0·6 o
as stringers contained within a ferrite envelope (Fig.8c and L
d). Rolled titanium-modified steels contained extensively
deformed sulphide inclusions, but the globular brown Ti203 0-4
particles and angular yellow Ti(C,N) particles remained
undeformed (Fig.9a). The cerium (or rare earth) oxides
and oxysulphides remain essentially spherical after rolling 0·2
(Fig.9b). The sulphides in the Calsibar-treated 080M40
steels were only slightly elongated, and frequently con-
tained dark-grey globular calcium aluminate particles
o
3·0 4·0 5·0
(Fig.9c). The addition of calcium to 606M36 steels favour- MEAN MAXIMUM CHORD WIDTH, I-lm
ably modified the sulphide distribution, but the plasticity
10 Effect of initial inclusion size on plasticity ratio
was not significantly changed (Figs.9d and e).
Large variations in plasticity ratios between the material
rolled from 1200°C and that rolled at 900°C were not ob- with increasing temperature. 10There are no published data
served, although the mean value increased from 0·72 to on the variation of relative plasticity of Type II MnS with
0·79. One explanation of this is that the finish-rolling tem- temperature.
peratures were not too dissimilar; or it may be a conse- Although there are few quantitative data on the effect of
quence of the Type II sulphide morphology in 18 of the 31 inclusion size on plasticity ratio, it is accepted that small
steels examined. Work cited in the literature has shown particles deform less readily than large ones, and generally
Type I MnS inclusions to have maximum relative plas- only start to deform at low temperatures and large re-
ticityat 1100°,17 750°,18 or 900°C,10and the relative plas- ductions. This effect has been ascribed by Kiessling16
ticity of Type III MnS inclusions to decrease continuously to the forces at the metal/inclusion interface. In Fig.l0 the

a b
a at 900°C, x 80 000; b from 1 200°C, x 75 000
11 Electron micrographs of manganese sulphides after rolling

Metals Technology March 1979

90 Banks and Gladman Sulphide shape control

plasticity ratios have been assessed in terms of inclusion

size in the equiaxed zone of the cast ingot. Despite the
presence of some scatter, owing to variations in inclusion
chemistry, it is clear that the plasticity ratio is strongly
dependent on inclusion size. In addition, the effects of
inclusion type and composition on plasticity are greatly
clarified. Type II manganese sulphides are shown to be
more plastic at a given size than Type I manganese
sulphides. This may be owing to a number of reasons, such
as: the higher oxygen content of Type I sulphides; the
possibility that the size of a Type II inclusion is more
appropriately described by the size of the entire colony
rather than the size of its constituent branches; or the
effect of the reorientation of the branches giving rise to an
apparent rather than a real elongation. The effect of the
deformation of the Type II rods is small, however, com-
pared to the effect of the redistribution of the entire
eutectic colony. It is also shown that, for a given size,
titanium and calcium additions reduce inclusion plasticity,
and although there is some scatter in the titanium-modified
steels, the plasticity-ratio values form a smooth curve as a
function of inclusion size, and are independent of sulphur
level. The effect of Calsibar additions in 606M36 steels is to
increase the inclusion size, with a concomitant decrease in
plasticity and, therefore, only minor changes in overall
plasticity ratios.

INCLUSION SEGREGATION
The spatial distribution of sulphide and oxide inclusions
within the ingot naturally is also of importance in relation
to the local planar density of inclusions. A decrease of
about 25% in the average volume fraction of non-refractory
sulphide inclusions in the equiaxed zone relative to the
columnar zone was observed, together with a correspond-
ing decrease in sulphide size. This is in accordance with the
normal segregation pattern in the lower region of kiIled-
steel ingots. However, the size of the ingot was such that
the equiaxed zone was not sufficiently large to cause segre-
gation of oxides and refractory sulphides, although this is a
cause for concern in commercial ingots.19

TRANSMISSION ELECTRON MICROSCOPY

OF DEFORMED INCLUSIONS
Currently, considerable research effort is being directed
towards measurement of the in situ deformation of in-
clusions. However, very little is known about their internal
structure and other factors which control their hot deform-
ability. For this reason the electron microstructure of
inclusions has been investigated. The inclusions were
extracted on to carbon replicas and examined by trans-
mission electron microscopy at an accelerating voltage of
IMV.
Figure 11a reveals the structure of a MnS inclusion
deformed at 900°C in steel 7 showing a partially recovered
dislocation structure, whereas Fig.llb reveals a fully
recovered dislocation structure in an inclusion in the same
steel, after rolling from 1200°C. The inclusions were
confirmed as MnS by selected-area electron diffraction.
Thus, the deformation mechanism of MnS inclusions under
a transmission micrograph of FeS in M nS, x 72 000; b selected-area
hot-rolling conditions is very similar to that of austenite, as diffraction pattern, (110) zone a-MnS; c transmission micrograph of
would be expected since it has the fcc sodium chloride oxides in M nS, x 28 800
structure and a melting point close to that of steel. Some 12 Electron micrographs of manganese sulphides con-
dislocation arrays intersected the surface of the inclusion, taining second-phase particles
where thermal grooving had taken place. The thermal
grooving would assist in the process of fragmentation
under conditions of low-temperature deformation. contrast may be seen (arrowed) in Fig.12a, and the
Occasionally, unusual features were observed within associated diffraction pattern, from a (110) zone of a- MnS
MnS inclusions. Faint, but numerous, areas of fringe (Fig.12b), exhibits streaking in <111> directions. This

Metals Technology March 1979


a x 50 000; b x 12 000
13 Transmission electron micrographs of alumina inclusions after rolling from 1200°C
suggests that small coherent FeS precipitates have been
formed within the MnS inclusion, since the solubility of
FeS in MnS may be as much as 60% at I180°C but
decreases rapidly with falling temperature,20 and Widman-
sHitten precipitation of FeS in artificial FeS-MnS alloys
has been observed.21 In addition, Kiessling22 has noted
that the corrosion behaviour of inclusions is related to
their conductivity, which, in turn, is related to their FeS
content, such that there is a conductivity minimum for
small FeS contents. The decomposition of a supersaturated
alloy with the formation of coherent particles, such as
those observed, may be expected to give rise to a classical
resistivity maximum 23such as that reported by Kiessling.
It has also been suggested that oxide particles may be
present in MnS inclusions, and, although no selected-area
diffraction evidence has been obtained, the appearance of
the microstructure shown in Fig.12c (small second-phase
particles inhibiting subgrain growth) is consistent with this
suggestion. The inclusions shown in Fig.12 were from the
same steel as those shown in Fig.II. Some diffraction
patterns could be analysed only by including forbidden
reflections which could not be caused by double diffraction.
It is postulated, therefore, that the MnS contains transition
metals in ordered solid solution, or that vacancies induced
to compensate for the consequent change in valency of the
metal ions are themselves ordered.
The electron microstructure of alumina inclusions
(Fig.13) is entirely consistent with their known refractory
properties. The alumina inclusion, from steel 7, exhibits an
occasional low-angle boundary but little evidence of
significant dislocation mobility. At low magnification it can
be seen that the particle fractured in a brittle manner into
hard angular fragments (Fig. I3b).
The electron microstructure of inclusions in an experi-
mental HSLA steel is shown in Fig.14. This steel, from a
different source, is not included in Table 1, but contained a
higher level of titanium (0·23%) than the other steels
studied by the authors. Figure I4a shows arrays of
featureless precipitates within the inclusions and smaller
particles which have apparently precipitated on dislocation
arrays revealed by slip traces. Figure I4b shows an unusual
Banks and Gladman Sulphide shape .control 91
dislocation reaction (arrow A) and some particles exhibit-
ing Moire fringe contrast (arrow B). It is germane to
emphasize that the micrographs in Figs.II-14 represent
the structure within extracted inclusions. Figure I4c may be
analysed as a (00·1) zone of Y-phase (Ti(C,N)S). The
second-phase particles have little effect on matrix (Le.
strain-field) contrast, structure-factor contrast, or orient-
ation contrast, which suggests that precipitate and matrix
are almost identical in structure and lattice parameter.
Y-phase,24 TiS2, and ThS425 are hexagonal phases having
similar lattice parameters. Their crystal data are given in
Table 4.
ThS4 may be regarded as TiS2 with sulphur atoms re-
moved from alternate basal planes, and Y-phase as TiS2
with carbon or nitrogen replacing sulphur atoms. Although
a more accurate electron-diffraction examination is neces-
sary to identify the inclusions and internal precipitates
conclusively, it is suggested that the precipitation of
vacancies, or the incorporation of carbon or nitrogen on
cooling TiS2 inclusions could give rise to the observed
two-phase structure, with little structure-factor and strain-
field contrast (Fig. 14). The Moire pattern (arrow B) in
Fig.14b has a spacing of ~2·4nm. The operating re-
flection is the (11·0) reflection which has d spacings of
0·171 nm for ThS4 and 0·1603nm for Y-phase. The Moire
spacing D for parallel superimposed lattices of spacings
dl and d2, given by D=d1d2/(dl-d2), is calculated to be
2·55 nm, in excellent agreement with the measured value,
which tends to confirm that the inclusions in this steel are
Y-phase containing ThS4.
Discussion
The role of non-metallic inclusions as nucleating sites for
void formation in the ductile fracture of steels has become
well established.26 Elongation of the inclusions leads to
poor ductility in the situation where the inclusions are
stressed normal to their longitudinal direction,27 and
Metals Technology March 1979
92 Banks ,!nd Gladman Sulphide shape control

Table 4 Crystal parameters of second-phase in-

clusions

Phase a,nm c,nm System

TiS2 0·3412 0,5695 Hexagonal

Y-phase (Ti(C, N) S) 0·3206 1·1190 Hexagonal
Ti3S. 0·3430 1·1440 Hexagonal
TiS2 (2 unit cells) 0·3412 1·1390 Hexagonal

dispersed deformed Type I and Type III MnS inclusions.

a
b no increase in the aspect ratio of individual inclusion
c electron microscopical examination of an experimental
a transmission micrcgraph, x 72 000; b transmission micrograph,
x 180000; C selected-area diffraction pattern, (00'1) zone Y-phase
14 Electron micrographs of V-phase inclusions in ex-
perimental titanium-modified HSLA steel
Baker and Charles28 have established a quantitative re-
lationship between through-thickness COD (z-y testpieces)
and the inclusion length per unit area, projected in the
short-transverse direction P for steels containing randomly
Baker and Charles28 proposed that COD is dependent on
the inclusion separation in the fracture plane, and derived a
relationship between inclusion separation and the pro-
jection parameter P; P, in turn, was shown to be related
to the inclusion volume fraction, aspect ratio, and length.
In most commercial steels, however, the inclusion separ-
ation is controlled by local variations in volume fraction,
owing to Type II sulphide formation, and to segregation in
the ingot, and these factors are not readily quantifiable. 29
The factors which control the local interinclusion
spacing in the wrought product have their origins in the
characteristics of the inclusions in the ingot. It is only
possible, therefore, to ameliorate the directionality in the
wrought product by control of the ingot structure. The
sulphophilic elements act to modify the sulphide mor-
phology, and hence spacing, in the cast steel, and also the
composition, and hence the plasticity, of the sulphide during
hot deformation. An increase in the free energy of sulphide
formation, which implies an increase in sulphide melting
point, favours both modification processes. Figure 15 illus-
trates the correlation between initial-distribution modi-
fication and plasticity modification for the titanium- and
RE-metal-treated steels, showing how both modification
processes are effected concomitantly.
The effects of sulphur and aluminium may be deduced
from steels 1-8. There is a marked increase in the area
fraction of inclusions with increasing sulphur content, but
sections. In the absence of aluminium, sulphur may pro-
mote the formation of Type II MnS inclusions. Therefore,
the effect of sulphur on directionality is achieved through
an increase in the size and number of Type II MnS
inclusions, rather than by modification of the inclusion
plasticity ratios. Nevertheless, at a constant size of section
Type II sulphides are more plastic than Type I, although in
practice the effect of the whole Type II array is dominant.
The addition of aluminium similarly has no effect on
inclusion plasticity ratios, but ensures the formation of
Type II sulphides. Proper deoxidation with aluminium
before modification by titanium, cerium, or calcium is
essential if clusters of refractory oxides are to be avoided.
Titanium additions of less than 0·12% were not observed
to exert any great influence on sulphide morphology in
either the cast or rolled conditions (Fig.6). The reduction in
plasticity ratios at the 0·01%)Slevel is apparently a result of
the smaller size of the sulphides, as shown in Fig.l0. An
HSLA steel containing 0·23% Ti (Fig.14) indicated that the
sulphides had been modified to the non-plastic Y-phase.
German30 and Japanese31 work has suggested that modifi-
cation of sulphides occurs at titanium levels of about
0·15% dependent upon the Mn content. Up to 0·02~1aTi
forms Ti203, up to 0·03~) Ti forms TiN, and approximately
0'03% Ti is required to form the Y-phase, leaving about
0·07% Ti in solution at steelmaking temperatures but
available for dispersion strengthening at lower tempera-
tures.

Metals Technology March 1979

 Banks and Gladman Sulphide shape control 93

S, °/0 fortuitous, although commercial steels have oxygen con-

0·01 0-025 tents reasonably constant at about 30ppm. However, this
optimum ratio would yield cerium contents of 0'02 and
CC2-modifiC2d StC2C2ls 0
rollC2d from 1200°<: • 0·050/0'at the 0·01 and 0'0250/0S levels, respectively, which
CC2-modifiC2d stC2C2ls 0 are approximately half those required to reduce the
110 rollC2d from 900°(:
plasticity ratio to zero, according to either the experimental
Ti-modifiC2d StC2C2ls !::. data or the calculated curve (Fig.7). Allowing for the
rollC2d from 1200°C
")100 Ti -modifiC2d StC2C2ls 'V
o higher oxygen contents in the experimental steels, this
rollC2d from 900°C 00 00 suggests that either (a) the improvement in transverse
C:;j ductility is largely a result of the modification in the ingot
~ 90
I/)
of Type II to globular sulphides (which, according to the
• I present work, occurs close to the optimum eelS ratio of
~t) I.
<{CU about 2), although modification of inclusion plasticity is also
I Y 80 of importance, or (b), the higher oxygen levels have severely
If)~
inhibited the formation of the preferred CexSy.15
~o Additions of calcium successfully modified the sulphides
i= ~ 70 in the cast and the rolled steel (Figs.2 and 9) although the
zO
-lD effect was not as marked as with RE-metal treatment.
LL~ Steel 31 contained modified sulphides in the ingot, but
O~ 60 there was no measurable improvement in plasticity ratio
z>. (Fig.6). However, the sulphides in this steel were relatively
0E> • !::.. 'iJ
-C:;j
'V ~
large (45~~ > 4fLm) and would deform to a greater degree,
~ ~ 50 owing to the greater force on the metal/inclusion interface.
u .
LL~ On the other hand, steels 25 and 26 contained initially small
-a.
o E 40 ," , (6 and 20% > 4fLm, respectively) modified sulphides
0.-
2>.
Q.
L
, which would deform to a lesser degree. Calcium, therefore,
is reasonably effective in reducing inclusion plasticity but,
as shown in Fig.l 0, causes the formation of larger sulphides.
~ 30
~ Significant reductions in directionality may be conferred by
as little as 20 ppm of calcium as (Mn, Ca)S.
20
1-2 lO 0·8 0·6
MODIFICATION OF PLASTICITY,
mC2an log A for 4: 1 rolling dirC2ction Conclusions
15 Correlation between initial shape modification and
plasticity modification for titanium and RE-metal- 1. The anisotropy of tensile ductility, Charpy impact
inoculated steels energy, and COD in the wrought product may be reduced
by controlling the distribution and shape of sulphide in-
clusions. Elimination of Type II sulphides from the ingot
The effect of the RE metals on inclusion morphology is prevents the formation of elongated clusters of inclusions,
very marked. In the fully modified condition the as-cast and certain sulphophilic elements reduce the inherent
sulphides and oxysulphides are present as isolated, duplex, plasticity of the inclusions. Both of these factors are impor-
globular inclusions. These inclusions resist deformation tant in controlling the anisotropy of properties in wrought
under hot-rolling conditions, although at high-inclusion steels.
volume fractions, clusters may be displaced to form 2. Sulphur, aluminium, and additions of up to 0·12%
stringers. titanium promote the formation of Type II manganese
The plasticity ratios of the Mischmetal-treated steels are sulphides which deform as an array to produce highly
shown as a function of cerium content in Fig. 7. The calcu- elongated clusters of inclusions within ferrite envelopes.
lated variation of plasticity ratio with cerium content is It should be noted that non-deformable refractory oxide
also shown, and forms an upper bound to the experimental clusters may give a similar effect. The addition of calcium
results. The calculation was based on the assumption that: or rare earths caused the formation of a more favourable
(i) Mischmetal contains 50~1a cerium, the balance con- sulphide dispersion in the cast steel.
taining the other chemically similar rare earths 3. Titanium additions of about 0'15~ ~, dependent upon
(ii) RE compounds do not deform (v=O) the manganese content, are required to produce sulphide
(iii) the free energy of formation of the RE oxides shape control. Rare-earth metal additions equivalent to a
(REAI03) is greater than that of the oxysulphides Ce/S ratio of 2 prevent the formation of Type II sulphides
(RE202S). and minimize the anisotropy of tensile ductility, although
The theoretical curve is in good agreement with the in the present work larger Ce contents were required to
experimental data at the 0·01~/~S level, but overestimates eliminate inclusion plasticity completely. Calcium as a 1 or
the RE metal required at the 0'025%S level. This may 0'4~6 Calsibar addition eliminates the formation of Type II
result from the substitution of the RE metals in MnS, so sulphides, but is less effective than rare-earth metal
reducing the plasticity ratio, or by the formation of RExSy treatment in reducing sulphide plasticity ratios. Both
phases (e.g. Ce2S3), which would increase the slope of the titanium and calcium reduce the plasticity but increase the
curve. size of sulphide inclusions leading to only minor changes in
It has been noted in the literature32,33 that the optimum plasticity ratios.
Ce/S ratio for transverse-ductility values is between 1·5 and 4. The electron microstructures of deformed a-MnS,
2·2 when the cerium is added as Mischmetal. In view of the a-Ah03, and Y-phase inclusions have been investigated.
free energy of formation of cerium oxides this is clearly Evidence of recovered substructures, recrystallization, and

Metals Technology March 197,.;

94 Banks and Gladman Sulphide shape control
precipitation within manganese sulphides and of TisS4 pre-
cipitation within the Y-phase has been presented.
Acknowledgments
The authors would like to thank Dr K. J. Irvine, Manager
of the Sheffield Laboratories, British Steel Corporation, for
permission to publish this paper.
References
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2. L. K. BIGELOW and M. C. FLEMINGS: Report CR-7Q-13, Army
Materials and Mechanics Research Center, 1970.
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Fifth Harold Moore Lecture
Can a simple heat treatment
Walter S. Owen
The Fifth Harold Moore Lecture will be delivered at 18.00
on Tuesday, 22 May 1979, at the Metropole Hotel,
National Exhibition Centre, Birmingham, by WaIter S.
Owen, Head of the Department of Materials Science and
Engineering, Massachusetts Institute of Technology, Cam-
bridge, Mass., USA.
Laws passed and regulations approved by the Congress of
the United States in recent years require new automobiles
in the USA to conform to standards of NOx emission,
impact resistance, and fuel consumption by 1982 which will
test to the limit the technological and manufacturing
resourcefulness of the American automobile industry. To
meet the new standards and, at the same time, to maintain
the low price and feeling of big-car luxury traditionally
associated with the Detroit product, radical changes will
have to be made in the materials used. Changes in engine
design and a reduction in the size of the automobiles alone
Metals Technology March 1979
13. P. P. MOHLA and J. BEECH: Br. Foundryman, 1968,453.
14. w. G. WILSON and R. G. WELLS: Met. Progr., 1973,103,75.
15. w. G. WILSON, D. A. R. KAY., and A. VAHED: J. Met., 1974,26,15.
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1968, London, The Iron and Steel Institute.
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705.
19. I. G. DAVIES, M. RANDLE and R. WIDDOWSON: Met. Technol., 1974,
1,241.
20. R. KIESSLING and N. LANGE: 'Non-metallic inclusions in steel',
Part II, 128; 1966, London, The Iron and Steel Institute.
21. Ibid., 109.
22. R. KIESSLING: 'Sulfide inclusions in steel', 442; 1974, New York,
American Society for Metals.
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176.
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of electron diffraction patterns'; 1971, London, Hilger.
25. A. TAYLOR and B. J. KAGLE: 'Crystallographic data on metal and
alloy structures'; 1962, New York, Dover Publications.
26. T. GLADMAN, B. HOLMES, and I. D. MCIVOR: 'The effect of second-
phase particles on the mechanical properties of steel', 68; 1971,
London, The Iron and Steel Institute.
27. M. WAHLSTER, H. HEIMBACH, and K. FORCH: Stahl Eisen, 1969,89,
1037.
28. T. J. BAKER and J. A. CHARLES: 'The effect of second-phase
particles on the mechanical properties of steel', 79; 1971,
London, The Iron and Steel Institute.
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American Society for Metals.
30. F. HEISTERKAMP and L. MEYER: Thyssen Forsch., 1971, 3,44.
31. H. GONDA, Y. TANI, T. YAMAGUCHI, I. KOZASU, J. NOSE, and Y.
IKEGAMI: Nippon Kokan Tech. Rep. (Overseas), 1973,9.
32. J. H. LITTLE and W. J. M. HENDERSON: 'The effect of second-phase
particles on the mechanical properties of steel', 182; 1971,
London, The Iron and Steel Institute.
33. J. L. MIHELICH, J. R. BELL, and M. KORCHYNSKY: J. Iron SteeIInst.,
1971,209,469.
save Detroit?
will be insufficient. The manufacturers would like to
continue to make cars out of steel, because steel is the
cheapest acceptable material for many components. But
steel can retain its position in the automobile market only
if it can be made much stronger (thus reducing the section
thickness and weight) without impairing its ductility,
formability, weldability, and low cost.
New steels for automobiles have been developed from
the laboratory to full-scale production with astonishing
speed in the last three years. The most promising of the new
steels - 'dual-phase steels' - have more than twice the
strength of traditional automobile sheet and can be formed
using existing presses and dies. An essential step in the
processing of this remarkable class of new steels is a
simple, but unconventional, heat treatment. The history,
physical metallurgy, application, and future development
of dual-phase steels will be reviewed and discussed.