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Effect of Alloying Elements on Mechanical Properties of High P Low Alloy

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Article  in  Transactions of the Indian Institute of Metals · May 2016

DOI: 10.1007/s12666-016-0875-y

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Trans Indian Inst Met (2017) 70(1):209–216
DOI 10.1007/s12666-016-0875-y
TECHNICAL PAPER
Effect of Alloying Elements on Mechanical Properties of High P
Low Alloy Steels
Gadadhar Sahoo1 • M. Deepa1 • Balbir Singh1 • Atul Saxena1
Received: 2 November 2015 / Accepted: 14 March 2016 / Published online: 5 May 2016
 The Indian Institute of Metals - IIM 2016
Abstract Four numbers of laboratory heats containing
0.19 % P, 23–60 ppm B and varying amounts of other
elements, viz. Cr, Cu, Ni, B and Nb were made through
ingot casting route. Effects of these elements on mechan-
ical properties were studied after hot rolling the ingots in an
experimental rolling mill. Nb increased yield strength and
ultimate tensile strength considerably though its beneficial
effect on toughness was not realized in the presence of
boron. While the beneficial effect of B in the range of
23–60 ppm was not realized, the steel without B exhibited
highest toughness value. In this particular steel, the volume
fraction of {100}h001i texture component was lowest and
percentage of HAGBs was highest, both of which con-
tributed to the increase in toughness value. Further, this
steel also exhibited the distribution of highest numbers of
fine grains suitable for structural applications.
Keywords Mechanical properties 
Charpy V-notch energy  Grain size distribution 
High phosphorus steel  Fe–P–B–Nb steel  Texture
1 Introduction
A significant amount of economic loss occurs due to the
premature failure of engineering components and struc-
tures in industry and infrastructures because of degrada-
tion by corrosion. The loss due to corrosion is quite high
even in developed countries to the extent of 5 % of gross
domestic product [1]. Atmospheric corrosion is more
& Gadadhar Sahoo
gadadhar73@gmail.com
1
R&D Centre for Iron and Steel, SAIL, Ranchi 834002, India
severe in the chloride and sulphur dioxide laden envi-
ronments [2, 3]. The use of weathering steel instead of
carbon steel, having less than 3 wt% alloying elements of
Cr, Ni, Cu, and P, has been the most effective and eco-
nomical way of mitigating atmospheric corrosion [4–6].
These weather resistant steels provide optimum balance of
corrosion resistance and strength due to the presences of
various alloying elements. Because of this beneficial
property, weathering steel has been used in many struc-
tural and engineering applications.
In 1933, the first commercial weather resistant steel of
this type was introduced in the market with the trade name
of USS-CORTEN [7]. The range of chemical composition
(in wt%) of other elements in CORTEN steels are: C:
B0.12–0.16; Si: 0.25–0.75, Mn: 0.20–1.2, Cr: 0.40–1.25,
Cu: 0.25–0.55, V: 0.02–0.10, Ni: B0.65. Similar grade
steel is also produced by SAIL, India for manufacturing rail
wagons and coaches of Indian railways and for other
structural applications as well. Some of the other structural
applications include external claddings, transport tanks,
beams, angles, channels and rails etc. While addition of Cu
is crucial to improve corrosion resistance of steel, Ni is also
added to balance the hot shortness effect of Cu by
increasing solubility of Cu in austenite [8]. However,
presence of Ni makes steel costly. Therefore, possibilities
should be explored to reduce Cu content in weathering
steel by increasing other alloying element like P for which
dependence on expensive Ni will be decreased. Owing to
the catalytic effect of P in the formation of amorphous type
FeOOH compact rust layer, its concentration in weathering
steels has remained at about 0.1 wt% [9, 10]. Thus, P has
been one of the important elements in decreasing corrosion
rate of steel, especially, during long term exposure [11].
While P improves corrosion resistance as discussed
above and contributes in solid solution strengthening, it
123
210
affects the toughness of the steel due to its segregation to
grain boundaries. Therefore, P content is reduced in mod-
ern steel making process by dephosphorization or by using
high-quality iron ores containing low P content. However,
to improve the steel productivity, the development of plain
carbon steels containing a considerable amount of P has
been actively performed [12, 13]. The reduction in pro-
duction costs has been also reported by effectively using
low-quality iron ores and by omitting or shortening the
dephosphorization process. Furthermore, Shibata et al. [14]
have found that susceptibility to surface hot shortness
decreases on increasing P content up to 0.1 % in Fe-
0.1 %C-0.5 %Mn-0.5 %Cu steel. In this case, the possi-
bilities can be explored to replace or reduce judiciously the
costlier element Ni with P to even more than 0.1 %.
Simultaneously, it is required to increase toughness or
Charpy V-notch (CVN) impact energy of high P containing
steels by reducing its grain boundary segregation. Sahoo
et al. [15] have reported good strength and ductility of
steels containing P up to 0.32 wt% with proper alloy design
and controlled heat treatment. However, effect of P on
CVN impact energy has not been studied by them.
Since long, boron has been considered as a unique
alloying element in multiphase steel, since its soluble
content of 0.001–0.003 % can provide a hardenability
effect equivalent to adding approximately 0.5 % of other
elements, such as manganese, chromium or molybdenum
[16–18]. At the fully austenitized condition, boron or the
precipitation of fine Fe23(C, B)6 carbides segregate to
austenite grain boundaries and retards the transformation
from austenite to ferrite by impeding the nucleation of
ferrite, which subsequently improves the hardenability of
steel [19, 20]. Therefore, it is worthwhile to study the effect
of B in high phosphorus ferritic or ferrite pearlite steel,
especially for replacing phosphorus from the grain
boundary of austenite. In addition to this, Nb is one of the
most frequently added microalloying elements because of
its significant effect in retarding austenite recrystallization
[21, 22]. The pancaked austenite grain prior to transfor-
mation, which significantly increases nucleation sites due
to the strain induced precipitation of Nb(CN), transforms
into ferrite with major ferrite grain refinement [21–23].
Therefore this work aims in minimizing the detrimental
effect of phosphorus by adding suitable alloying elements
Table 1 Chemical composition of steels (in wt%)
Steels C Si Mn S P
G1 0.072 0.042 0.21 0.008 0.19
G2 0.073 0.070 0.19 0.008 0.19
G3 0.068 0.086 0.24 0.007 0.19
G4 0.072 0.086 0.21 0.007 0.19
123
Trans Indian Inst Met (2017) 70(1):209–216
like B, Nb, etc. in the presence of lower contents of C
(\0.1 %). The different techniques employed in this study
are optical microscopy, tensile test, fractography, Charpy
V-notch test, texture and grain boundary analysis by
electron back scattered diffraction (EBSD).
2 Experimental
2.1 Laboratory Heat and Hot Rolling
Four numbers of laboratory heats of low alloy steels of
25 kg each were made using a high frequency induction
melting furnace. Steel scrap of C–Mn rail steel was added
to soft iron (0.001 wt% C) to balance carbon content. In
order to obtain Cr, P, Cu and Ni in the desired ranges,
mother alloys of Fe–P, Fe–Cr along with Cu blocks and Ni
lumps were added to the liquid steel in the furnace. Alu-
minium in the form of shots and wire were used for de-
oxidation purpose. The melts were cast into
100 mm 9 100 mm square ingots, which were subse-
quently hot rolled to plates in two stages. In the first stage,
ingots were rolled into 16 mm thick plates through five
passes after soaking at 1150 C for 2.0 h. In the second
stage, once again these plates were soaked for 30 min at
1150 C and hot rolled into 5 mm thick plates. The fin-
ishing temperature was in the range of 800 to 850 C.
Chemical composition of each laboratory heat was deter-
mined using an Optical Emission Spectrometer after hot
rolling (Table 1).
2.2 Mechanical Test
Tensile test specimens were prepared as per ASTM A 370
with gauge length of 50 mm from 5 mm thick hot rolled
sheets and specimens for Charpy V-notch impact test of
dimension 55 mm 9 10 mm 9 10 mm were prepared as
per ASTM E 23-01 from 16 mm thick steel plates. Tensile
tests were performed using UTM 7200, DAK system with
cross head speed of 2 mm/min, which was equivalent to
strain rate 6.66 9 10-4 sec-1 for 50 mm gauge length and
this was as as per the requirement of static strain rate with a
screw driven machine (10-5 to 10-1s) [24]. Charpy
V-notch impact testing was carried out for all the heats at
B Cr Cu Ni Al Nb
– 0.39 0.24 0.17 0.055 –
0.006 0.43 0.23 0.163 0.02 –
0.0023 – – – 0.03 –
0.0025 – – – 0.02 0.04
Trans Indian Inst Met (2017) 70(1):209–216
three different temperatures, e.g., room temperature, 0 and
-20 C using pendulum impact tester of Tinius-Olsen
make.
2.3 Metallography
For light optical microscopy, specimens were ground suc-
cessively to 1200 grit water proof SiC paper and finally
polished using alumina suspension of particle size 1.0 lm
followed by 0.3 lm. An optical microscope (Olympus GX
71) was used for microstructural examination after etching
the specimens in 2 % Nital solution (98 % alcohol ? 2 %
nitric acid). Grain size and volume fraction of ferrite were
measured using an optical microscope (LEICA DMRME)
attached with a commercial software (Leica grain expert).
Fractured surface of tensile tested specimens was examined
using a scanning electron microscope, EVO MA 10, Carl
Zeiss for understanding the morphology and mode of
fractures in the material. For the electron back scattered
diffraction (EBSD) studies, samples were mechanically
ground along RD-ND surface using SiC paper up to 1200
grit followed by polishing using 1 lm alumina suspension
and 0.03 lm colloidal silica, respectively in an automatic
grinding cum polishing machine.
2.4 EBSD Measurement
EBSD data acquisition was performed on RD-ND plane
using a Scanning Electron Microscope (EVO MA 10, Carl
Zeiss) equipped with Oxford Instruments (OI) Nordlys
Fig. 1 Optical
photomicrograph of a G1, b G2,
c G3 and d G4 steels
211
Max fast EBSD detector. The microscope was operated
with primary electron energy of 20 keV. A step size of
0.7 lm was maintained for all the measurements per-
formed. The OI-HKL Channel 5 software was utilized to
analyze the acquired EBSD data after 90 rotation of /
(along RD). The percentage of low angle grain boundaries
(LAGBs) with misorientation angles 1–15 and high angle
grain boundaries (HAGBs) with misorientation angles
[15 were calculated after normalizing relative frequen-
cies. The percentage of (001) [011] texture was calculated
considering 15 (max) deviation.
3 Results and Discussion
3.1 Alloy Design Philosophy and Image Analysis
As provided in Table 1, the elemental compositions of all
elements in G1 and G2 steels are nearly similar except boron,
which is absent in G1 steel while G2 steel contain 60 ppm
boron. This is much above the solubility limit of B in iron. G2
steel has been planned to be used to examine the effect of B
on mechanical properties of high P steel. Both these steels
contain Cu, Cr and Ni similar to that present in weathering
steels or CORTEN steels. On the other hand, these elements
are absent in G3 and G4 steels as these steels have been
planned to be used, to study the effect of Nb alone in high P
(0.19 %) containing steel. However, the B content in these
two steels has been restricted to its solubility limit in iron
[16–18], which is 25 ppm (max). It is reported that B reduces
123
212 Trans Indian Inst Met (2017) 70(1):209–216

inter granular fracture mode and also decreases ductile to
brittle transition temperature by replacing phosphorus from
the grain boundary [25].
Figure 1 shows the typical microstructure of G1, G2, G3
and G4 steels obtained using light optical microscope. All
photomicrographs consist of ferritic matrix (lighter phase)
with a small fraction of pearlite (0.28–1.14 %) at the grain
boundary region. The pearlite content varies depending on
the contents of carbon and other alloying elements
(Table 2). The grain size distribution of all steels has been
shown in Fig. 2 and the average ASTM grain size number
has been provided in Table 2. The numbers of grains dis-
tributed towards lower grain size (higher ASTM grain size
number) are maximum in case of G1 steel, which does not
contain boron. On the other hand, the distribution of grains
towards higher size (lower ASTM number) is maximum in
G2 and G3 steels. In case of the G4 steel, the distributions
of number of lower sized grains are more, especially for
Table 2 Grain size and volume fraction of experimental steels
Steels Average ASTM grain size no. Vol. fraction of pearlite (%)
G1 9.58 0.81
G2 8.50 1.16
G3 8.59 0.43
G4 8.76 0.28
ASTM grain size number 8–9 (409), 9–10 (361) and 10–11
(234), which may be due to the grain refining effect of Nb
[21–23]. Therefore, both B and Nb seem to influence grain
size of the experimental steels.
3.2 Tensile Properties and Fractography
Figure 3 shows the tensile properties, e.g., yield strength,
ultimate tensile strength and total percentage elongation at
failure (EL) obtained from the stress–strain curves of G1,
G2, G3 and G4 steels. The ultimate tensile strength (UTS)
is similar in the case of G1 and G2 steel while yield stress
(YS) and percentage elongation (EL) decreases marginally
in G2 steel. Further, G3 steel shows lowest YS and UTS
among all steels as it does not contain any alloying ele-
ments like Cu, Cr and Ni like G4 steel. On the other hand,
the highest YS and UTS of G4 steel have been attributed to
the strengthening effect of Nb (0.04 %) [21–23]. There is
not any significant variation in the percentage of elongation
among all steels. Based on these results, all the four steels
conform to the minimum required values of YS, UTS and
%EL for S235JR, S275JR, S335JR grade structural steels
of EN 10025-2: 2004 specification; where 235, 275 and
335 indicates the minimum yield strength value in MPa
[26]. The effect of B and Nb on mechanical properties will
be further understood from the CVN test.

1000
a 150
800 877 b 142
128
100 120
600
Count

109
Count

648 653 102

400
50
49 53
200 315
19 8
242
21 63 0
0 4-5 5-6 6-7 7-8 8-9 9-10 10-11 11-12 12- 13
6-7 7-8 8-9 9-10 10-11 11-12 12- 13
ASTM Grain Size Number
ASTM Grain Size Number

300 500

250
c 400
d
257 409
244
200 222 361
300
Count
Count

150 287
200 234
100 118
93 100
50
8 41 58 6 18 100 28
0 0
4-5 5-6 6-7 7-8 8-9 9-10 10-11 11-12 12- 13 5-6 6-7 7-8 8-9 9-10 10-11 11-12
ASTM Grain Size Number ASTM Grain Size Number

Fig. 2 Grain size distribution of experimental steel a G1, b G2, c G3 and d G4

123
Trans Indian Inst Met (2017) 70(1):209–216 213

600 70 the dimple depends on the stress state [28], the deeper and
YS 60
larger size of the dimples are possibly due to the marked
550
UTS EL work hardening effect of phosphorus as phosphorus con-
50
centration is quite high (0.19 %) in these investigated steels
Strength (MPa)

500 than that of conventional steels [29, 30].

40

EL (%)
450 30
20
400
10
350 0 steel. This may be attributed to the excess boron above the
G1 G2 G3 G4
Steel
Fig. 3 As rolled steels showing YS, UTS, and % elongation at room
temperature testing condition
Figure 4 shows the fractured surface of specimens after
fracture during tensile test under RT. All the SEM frac-
tographs exhibit primarily ductile dimple ruptures. The
dimples are conical equiaxed, along with some elliptical &
elongated cup and cone depressions, which is generally
expected for ductile specimens that fail under uniaxial
tension [27]. These types of fractures occur due to the
formation of microvoids during tension at second phase
particles and inclusions, which subsequently grow and
coalesce due to fracture of the ligaments between micro-
voids. Whether elliptical or conical, some of the dimples
are larger and deeper in all cases. While the morphology of
3.3 CVN Impact Toughness
As shown in Table 3, there is a significant drop in Charpy
V-notch (CVN) energy of G2–G4 steels from that of G1
solubility limit of 10–30 ppm in iron [16–18]. The excess
boron may have formed larger precipitates of Fe23(C, B)6
carbides and facilitated grain boundary decohesion. Hong
et al. [31] have studied the effect of B (10–20 ppm) on
CVN energy of Fe-0.15 %C-0.2 %Si-1.5 %Mn-1.5 %Cr
steel containing 0.02 and 0.05 % P. They found that CVN
energy at RT is highest when steels contain 10 ppm B
while CVN energy decreases when B concentration
increases to 20 ppm or when no B is present in the steel.
The severe segregation of B at grain boundaries occurs and
forms boro-carbide precipitates when an excess amount of
B is added into the steels, which can act as intergranular
crack initiation sites during the Charpy impact test [32, 33].
Therefore, solubility limit of boron may exceede in G2–G4
steels and hence, addition of B does not help in improving
CVN energy. Furthermore, grain size plays an important
role in increasing strength and toughness. From the grain
size distribution data of all steels (Fig. 2), it is noticed that

Fig. 4 Fractographs of a G1,

b G2, c G3 and d G4 steels

123
214 Trans Indian Inst Met (2017) 70(1):209–216

Table 3 Average Charpy V-notch energy in Joule with standard deviation at different temperature
Steels Energy at RT (20 C) Energy at 0 C Energy at -10 C Energy at -20 C

G1 53 ± 2.0 8.0 ± 3.8 7.5 ± 1.0 7.4 ± 0.5

G2a 10.3 ± 1.8 – – –
G3 12.0 ± 3.4 5.6 ± 2.1 5.0 ± 0.5 5.0 ± 0.8
G4a 7.2 ± 1.5 – – –
a
Impact test was not carried out below RT as CVN energy at RT was already very low for these steels

Fig. 5 Distributions of grain b 0.06

boundary misorientation of the
a 0.06

experimental steel a G1, b G2,

c G3, and d G4
0.04

Number fraction
0.04
Number fraction

0.02 0.02

0.00 0.00
10 20 30 40 50 60 10 20 30 40 50 60

Misorientation Anlge (degree) Misorientation Anlge (degree)

c 0.06
d 0.06

0.04

Number fraction
0.04
Number fraction

0.02 0.02

0.00
0.00
10 20 30 40 50 60
10 20 30 40 50 60
Misorientation Anlge (degree)
Misorientation Anlge (degree)

G1 steel consists of more fine grains in comparison to other
steels, which can be the reason of its showing maximum
toughness. From application point, only G1 steel conforms
the minimum requirement of 27 J at 20 C for S235JR,
S275JR, S335JR grade structural steels in EN 10025-2:
2004 specification [26].
3.4 Grain Boundaries Misorientation and Texture
The difference in CVN energy of the experimental steels
will be further understood in this section through electron
back scattered diffraction (EBSD) studies. Figure 5 shows
the distributions of grain boundary misorientation of the
experimental steels G1–G4. The fractions of low angle
grain boundaries (LAGBs) of G1–G4 steels calculated
from Fig. 5 are 43.5, 68.5, 49.6 and 48.5 %, respectively
and those of high angle grain boundaries (HAGBs) are
56.6, 31.5, 50.4 and 51.7 %, respectively. The ratio of
HAGBs to LAGBs of G1–G4 steels are 1.3, 0.5, 1.0 and
1.1, respectively. Both the ratio of HAGBs to LAGBs and
the fraction of the HAGBs are highest in case of G1 steel,
which may have led to the best toughness (53 J at 20 C)
of this steel. Generally, the transition temperature
decreases with an increase in the number of high-angle
boundaries of 15 or higher [34–37]. However, more
pronounced effect of HAGBs in deflecting the cleavage
crack propagation direction and helping in decreasing
transition temperature has been reported at low tempera-
tures, especially sub zero temperatures [35–37]. As all the
experimental steels have low CVN toughness at zero or
sub-zero temperature, the significant variation of HAGBs
has not been noticed. In view of this, texture study may
provide some insight about the variation in toughness of
investigated steels.
Ray and Jonas [38] have reviewed that a minor com-
ponent of the transformation texture viz. {100}(011)
component has often been responsible for property deteri-
oration and associated delamination process. A lateral split

123
Trans Indian Inst Met (2017) 70(1):209–216
Fig. 6 High angle grain boundary maps showing {100} h011i texture component in experimental steel a G1, b G2, c G3 and d G4
of through thickness embrittlement occurs on the fractured
surfaces of Charpy impact specimens, which is mainly due
to the presence of ferrite grains containing the {100} (uvw)
type texture [39]. More recently, the {001}h110i texture
has been reported as detrimental for the CVN toughness
value of 1009 line pipe steel [39]. The volume fraction of
this texture component is negligible in G1 steel (0.67 %)
while it is much higher for G2 (2.64 %), G3 (10.4 %) and
G4 (4.83 %) steels. The {100}h011i texture component
maps of G1–G4 steel are shown in Fig. 6. Further, the
volume fraction of (100)||ND fiber is found to be lowest for
G1 steel (2.5 %) while it is much higher for G2 (18.6 %),
G3 (8.7 %) and G4 (7.2 %) steels. Therefore, probably the
215
excess boron in G2, G3 and G4 steels have resulted in
deleterious ferrite grains with {100}(011) and (100)||ND
texture. On the other hand, the volume fraction of these
components is minimum in G1 steel resulting in maximum
toughness.
4 Conclusions
• Four numbers of steels containing high P, small amount
of B, Nb and other alloying elements were studied.
• The grain size distribution of G1 steel exhibited the
presence of fine grains while that of G2, G3 and G4
123
216
steel containing B exhibited the presence of relatively
coarse grains. Among the B added steels, the grain size
was relatively finer in the case of G4 steel due to the
presence of Nb.
• While YS was nearly 350 MPa or more for all steels
and UTS was more than 475 MPa, Nb increased YS
and UTS significantly. Fractured surface of all steels
exhibited dimple rupture type failure, which was a
characterstic of ductile fracture.
• Charpy V-notch (CVN) energy at RT was significantly
lower (\12 J) for G2, G3 and G4 steels while the G1
steel without containing B exhibited significantly
higher CVN energy (53 J).
• The highest toughness of G1 steel was attributed to its
lowest volume fraction of {100}h001i texture compo-
nent, highest percentage of HAGBs and fine grain
grains.
• Addition of Nb (0.04 %) did not improve CVN energy
when B was present in excess of 23 ppm.
Acknowledgments Authors are thankful to the management of
RDCIS, SAIL, Ranchi for the support provided to carry out this work
and permitting for the publication.
Compliance with Ethical Standards
Conflict of interest None.
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