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On the influence of alloying and micro alloying on the structure and

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Proceedings of the Twenty-sixth (2016) International Ocean and Polar Engineering Conference www.isope.org
Rhodes, Greece, June 26-July 1, 2016
Copyright © 2016 by the International Society of Offshore and Polar Engineers (ISOPE)
ISBN 978-1-880653-88-3; ISSN 1098-6189

On the influence of alloying and micro alloying on the structure and characteristics of new high-strength
steels
Pavel Layus1, Victor Orlov2, Victor Malyshevsky2, Paul Kah1
1
Welding Technology Laboratory, Lappeenranta University of Technology (LUT).
Lappeenranta, South Karelia, Finland
2
Central Research Institute of Structural Materials Prometey
Saint Petersburg, Russia.

ABSTRACT microstructure; lath martensite; quenching; tempering; Arctic

This research considers ways to improve properties of F620W high-
strength steel. Economic considerations demand a reduction in alloying
elements like nickel and molybdenum, which have a strong positive
influence on steel properties. The size of austenite grain is important for
determining steels mechanical and cold-resistant properties. One
approach to form smaller austenite grain is hot plastic deformation
combined with vanadium and niobium micro-alloying. Resultant steel
has martensitic-bainitic microstructures consisting of: lath martensite;
high-temperature martensite; lath lower bainite; lath upper bainite; and
granular bainite. Niobium role is to stabilize the dislocation structure of
martensitic-bainitic steels, which increases impact toughness.
conditions.
INTRODUCTION
There is strong demand for efficient and feasible steel grades for Arctic
shipbuilding applications. Shipyards specializing in Arctic shipbuilding
are interested in the development of thick High Strength Steels (HSS)
plates of increased tensile strength, to decrease the weight and cost of
offshore structures and icebreakers. Various steel grades have been
developed for Arctic service; Fig.1 shows welded steels that have been
used in recent Arctic offshore projects and indicates the area of possible
future advances in steels development.

KEY WORDS: High-strength steels; alloying elements;

Fig. 1. Current state and area of possible future advances in low-temperature weldable steels shown in terms of plate thickness over yield strength. The
green area indicates the current level of steel development and the yellow area indicates the area in which future development might occur (Suh et al.,
2011; Hisata et al., 1999; Layus et al., 2013; Cheng, 2013).

Due to the thickness of sheet products used for shipbuilding (5-100
mm), careful selection of steel alloying elements and precise realization
of microstructural changes to improve hardening mechanisms
(Golshtein et al., 1986; Llewellyn, 2013; Gorenc et al., 2005) are the
main methods used to attain the desired strength, ductility and impact
toughness.
Complex alloying with nickel, chrome, manganese, copper and
molybdenum is usually used to achieve the required properties of hull
plates. The effect of complex alloying exceeds the influence of each
separate alloying element. Additionally, it is important to consider
bonding mechanism of alloying elements, as it is known that metallic
bonding increases resistance to brittle fracture and covalent bonding
decreases it (Golshtein et al., 1986; Weng et al., 2011; Totten, 2006).

111
INFLUENCE OF Ni, Cu, Cr AND Mo
As a rule, carbon and substitutional alloying elements, except for
nickel, increase the ductile-to-brittle transition temperature and,
conversely, grain refinement or formation of subgrain structures have
transformation diagram, nickel ensures the  transformation in the
process of quenching is according to the shear martensite mechanism.
The higher the content of nickel, the lower the critical quenching rate,
as shown in Fig. 2. Depending on the required strength and thickness of
the rolled product, the nickel content in alloyed shipbuilding steels can

however, its solvability in the -ferrum is insignificant, so its content

the effect of decreasing this temperature. Nickel is the alloying element range from 1.5 to 5.5%. Copper has a similar influence as nickel;
having the most significant influence on strength, ductility and impact
toughness. By lowering critical points and shifting the austenite should not exceed the solubility limit for a given content of nickel.
transformation curves to the right in the continuous-cooling

a c

b d
Fig. 2. Continuous-cooling transformation diagram of austenite transformation for steels of conventional composition:
a) Steels with 3% nickel (Gorynin et al., 1999a);
b) Steels with 5% nickel (Gorynin et al., 1999a);
c) Steels micro-alloyed with vanadium;
d) Steels of new compositions with low content of expensive alloying elements and micro-alloyed with niobium.

Steel alloying with nickel and chrome increases hardenability, which is
very important in low carbon content (<0.10-0.13%) shipbuilding
steels. However, nickel and chrome contributes to an increase in cold
resistance it can cause tempering embrittlement. Molybdenum
primarily increases strength through its effect on precipitation
strengthening during tempering (Gorynin et al., 1999b). Molybdenum
in amounts up to 0.5% in chrome-nickel steel shifts the ferrite
precipitation area in the continuous-cooling transformation diagram to
the right and decreases the sensitivity of the steel to tempering
embrittlement.
Both chrome and molybdenum shift the ferrite precipitation area
towards lower cooling rates and decrease the intermediate
transformation temperature. They also reduce the likelihood of
formation of upper bainite in the steel structure and shift the bainitic
range in the continuous-cooling transformation diagram to the right.
Subsequent high-temperature tempering of the quenched structures
results in polygonization, dislocation annihilation and internal stress
relaxation, development of carbide forming processes, and formation of
high levels of strength and ductility (Gorynin et al., 1999b).
For economic reasons, alloying levels in modern high-strength steels
are reduced to as low as is reasonable. When reducing the alloying
levels, it must be borne in mind that the size of the austenite grain
formed is of great importance both to ensure a high level of physical
and mechanical properties and to ensure resistance to brittle and ductile

112
fracture. To this end, hot plastic deformation combined with micro-
alloying with vanadium and niobium is used (Lagneborg et al., 2001;
Shanmugam et al., 2005; Kostryzhev et al., 2013)..
PECULIARITIES OF STEEL MICROSTRUCTURE
In sheet product manufacturing, quenching of high-strength heat-
hardenable steels can be carried out either with separate furnace heating
or with direct quenching. In the quenching process, martensitic-bainitic
structures consisting of the following structural constituents are formed:
lath martensite (Fig. 3 ); high-temperature martensite (martensite of
self-tempering) (Fig. 3b); lath lower bainite (Fig. 3c); and granular
bainite (Fig. 3d).
Fragments (laths) grouped in relatively large clusters within prior
austenite grains. Each martensite lath is a result of homogeneous shear.
As a rule, lath are parallel to each other inside the clusters and divided
by small-angle boundaries, i.e. weakly misoriented relatively to each
a c
b d
Fig. 3. Typical structural constituents in high-strength low alloyed steel:
a) Lath martensite;
b) High-temperature martensite (self-tempering martensite);
c) Lower bainite;
d) Granular bainite.
Increase in sheet thickness affects the heat transfer in a way that is
equivalent to a decrease in the cooling rate, which in the case of low
levels of alloying elements increases the possibility of the appearance
of bainite in the steel structure. Bainitic structure is formed in the
intermediate temperature range when sufficient diffusibility of carbon
113
other. Misorientation of fragments located in different clusters can
reach 90°. Martensitic lath formed at high temperatures are filled with
dislocations with a concentration of =1013-1014 m-2 (Malyshevsky et
al., 2014). At the boundaries of martensitic lath there are thin (10-20
nm) retained austenite layers.
High-temperature martensite presents non-fragmented irregular-shaped
areas with the same dislocation concentrations located both inside
grains and near the boundaries of prior austenite grains and adjacent to
lath martensite clusters. Dispersed particles oriented in three
crystallographic equivalent directions and mating to the crystalline
lattice of 3 cemented carbide are located uniformly throughout the
extent of the high-temperature martensite. The presence of these
subsequent cooling in the -phase. This process, which is possible
carbides shows that the processes of self-tempering are taking place in
directly during quenching, is typical for steels with the martensite-start
temperature ( S) significantly higher than the ambient temperature.
is provided but the  transformation is realized according to the
shear (diffusionless) mechanism, and the structure contains two phases
different morphological variations of the -phase. In typical lower and
with different carbon content. The carbon-depleted phase consists of
upper bainite formed during isothermal holding, the carbon-enriched
phase is embodied by particles of cementite that are equally spaced
inside the ferritic plates or at their boundaries. Under conditions of
continuous cooling, more complex bainitic structures are formed
containing a carbon-enriched fraction not only in the form of carbides
but also in the form of austenite and/or martensite. With bainitic
structures of this type, the shape, sizes and character of the distribution
of the carbon-enriched phase depend both on the cooling rate and the
Lath lower bainite is an area of the irregular-shaped -phase with high
chemical composition of the steel.
dislocations concentration, which is shown in Fig. 3c. Carbide phase
dispersed particles of cementite type oriented strictly parallel to each
 60° with the long axis of the -crystals are located in the areas of
other and elongated along a direction which often forms an angle of
lower bainite. In each crystal of lower bainite the cementite
precipitation-plates have only one orientation.
Granular carbideless bainite is usually exists in the form of large
irregular-shaped weakly fragmented areas with high dislocations
concentrations. Isolated dislocation martensite areas or retained
austenite areas are located within these areas. There are no regular
carbide precipitations, only isolated large particles. The absence of
regular carbide precipitations is because the austenite that is a part of
the -phase in the process of transformation. This -phase is formed in
carbideless bainite is an efficient stock of carbon, which is forced out of
diffusion over large distances is possible. In these conditions, the -
the upper temperature range of bainitic transformation, i.e. when carbon
phase (often called bainitic ferrite) and carbon-enriched austenite are
formed; on subsequent cooling, the carbon-enriched austenite
transforms to dislocation martensite or lower bainite or remains
unchanged in the form of retained austenite.
In martensitic and bainitic crystals of structural steels, dislocations of
different nature are often found: dislocations, which were involved in
the martensitic-bainitic transformation; dislocations inherent to
martensite and bainite from austenite and a product of stress relaxation
in the austenite in the transformation process; and dislocations
occurring as a result of mutual deformation of adjacent martensite and
bainite ranges (self-accomodation).
After previous plastic deformation in austenitic condition at relatively
large size of lath bainite cluster (for example, 40-60 micron for
austenite grain of 160 micron) each cluster contains a large number of
blocks. Significant numbers of boundaries between such blocks are
large-angle, whereas boundaries between adjacent clusters are not
large-angle. The ratio of structural elements with boundaries of one or
another type, which depends on the pattern of the plastic deformation in
After tempering, a uniform finely dispersed mixture of the -phase and
the austenite, defines the steel properties.
carbide is formed as a result of decomposition of the martensitic-
bainitic structure. Carbon-enriched areas which consist of retained
austenite or bainite decompose with precipitation of round carbides. At
the same time, polygonization (dislocations randomly arranged inside
the grain that collect forming a wall) and annihilation (decrease of
dislocation concentration as a result of mutual elimination of
dislocations) take place, which results in release of lattice distortion,
internal stress relaxation and softening.
Depending on the type of structure formed in the quenching process,
the carbide-forming process during tempering exhibits particular
characteristics. Carbide formation in lath martensite of secondary
hardening of steels undergoes a number of stages, which are
temperature-dependent, and are examined in detail in (Sakganik et al.,
2009). The most important finding is that at a tempering temperature of
500-550° the formation of carbide of 3 type is completely
suppressed, and dispersed (~30-40 nm) particles of special carbides of
( r, )7 3- type, and later VC are precipitated on
dislocations, fix them and stabilize the dislocation structure. Further
increase of tempering temperature to 600-650° results in coagulation
114
of the special carbides, as a result of which dislocation nodes are
released and dislocation polygonization occurs. Nickel enhances these
carbide-forming processes, and chrome, molybdenum and vanadium
inhibit carbide coagulation. At higher tempering temperatures, special
carbides are arranged mainly at the boundaries of lath and blocks.
In lower bainite tempering of heat-hardenable steels there are no
significant changes in the structure; the major part of the carbon atoms
are bonded into cementite carbides. During the tempering process,
small particles of cementites are dissolved and large r, Mn, Mo-
alloyed cementite particles (Semicheva et al., 2005) are grown. In high-
temperature tempering, special carbides are formed in rather small
amounts.
In tempering of carbideless bainite, no carbides precipitate in bainitic
ferrite areas. Carbon-enriched retained austenite areas, which depend
on the alloying and tempering temperature, can be transformed during
the high temperature tempering into a ferritic-carbide mixture. At lower
tempering temperatures, bainite and high-carbon martensite are formed,
which during repeated higher-temperature tempering can form large
amounts of laminar cementite particles. Bainite and martensite are
formed in retained austenite areas at tempering temperature below
500° .
CASE STUDY
Based on the above recommendations, chemical composition of F620W
steel alloying was changed from alloying with V to alloying with Nb,
as indicated in Table 1.
Table 1. Chemical composition of conventional and improved F620W
steel.
Steel grade C Mn Si Cu+Ni Mo+Cr Nb V
F620W with 0.08- 0.3- 0.17- 2.2- 0.55- - 0.01-
V 0.10 0.6 0.37 2.9 1.05 0.03
F620W with 0.08- 0.3- 0.17- 2.2- 0.55- 0.01- -
Nb 0.10 0.6 0.37 2.9 1.05 0.03
In the proposed high-strength steel F620W with Nb, the finely
dispersed carbonitrides of niobium that precipitate during hot rolling
stabilize the dislocation structure of the martensitic-bainitic steel,
resulting in additional hardening. Consequently, the increased
tempering resistance of the deformed and quenched steel allows an
increase in the tempering temperature, i.e. contributes to an increase in
steels impact toughness.
Fig. 4. Stress-strain diagrams of F620W steels with V and Nb at
dynamic crystallization temperate of 1050°C.
The formation of carbide caused by additives of chrome, molybdenum,
niobium (Fig. 5) and vanadium significantly reduce the speed of
softening during the tempering.
 a b c d
Fig. 5. Microstructure of high-strength steel:
a) Carbide particles of conventional high-strength steel in light-field image;
b) Carbide particles of conventional high-strength steel in dark-field image;
c) Carbide particles of new high-strength steel in light-field image;
d) Carbide particles of new high-strength steel in dark-field image.

F620W steel plates of 50 mm thickness were produced. Mechanical
properties were measured by static tension tests of cylindrical samples
and full thickness tests and the average tensile and yield strength are
760 MPa and 700 MPa respectively. Test specimens were prepared
according to standard GOST 1497-84: Specimen type 3 4. Fig. 6
depicts the specimen preparation and Fig. 9b shows chart of yield
strength in dependence to tempering temperature.
Fig. 8. Drawing of Charpy V-notch impact test specimen, sizes are
given in mm (ISO 148-1; EN 10045-1).
Quenching-induced changes in the mechanical properties of low-
alloyed high-strength steels compared with conventional high-strength
steels are shown in Fig. 9.

Fig. 6. Drawing of static tension test specimen, sizes are given in mm

(GOST 1497-84).

Cold-resistance properties can be measured by conducting Charpy

impact tests, according to EN 10045-1. The requirements for this grade
of steel is 80 J at -60°C. Fig. 7. shows the specimen drawing and Fig. 9
c and d presents Charpy impact test results for F620W steel alloyed
with Nb and V.

115
 a b

c d
Fig. 9. Quenching-induced change in mechanical properties:
a) Strength characteristics during tempering of steel of conventional chemical composition;
b) Strength characteristics during direct quenching of new steel with the reduced amount of alloying elements;
c) Impact strength characteristics during tempering of steel of conventional chemical composition;
d) Impact strength characteristics during direct quenching of new steel with the reduced amount of alloying elements.

Additional cold-resistant tests which were performed are Nil-Ductility
transition temperature test and Crack Tip Opening Displacement test.
Steels ductile-brittle transition temperature is the temperature at which
the fracture energy passes below a certain value. The temperature
above which steel fracture in a ductile mode and below which it is
brittle is known as the Nil-Ductility Transition (NDT) temperature. The
nil ductility temperature is a critical because as steel is cooled below
that temperature, it has a greater tendency to fracture on impact load. In
this study NDT test was carried out on a vertical drop-testing machine
K90 with an impact energy of 1350 Joules, as specified in RMRS rules
(Russian Maritime Register of Shipping, 2012) and ASTM E-208
standard. Fig. 10 shows specimen drawing and the results of the NDT
test. NDT tests results is the highest temperature, at which at least one
specimen is fractured.
The Crack Tip Opening Displacement test (CTOD) evaluates the
resistance of steel to crack propagation. CTOD tests were carried out by
RMRS rules (Russian Maritime Register of Shipping, 2012) and BS
7448 P.1. Fatigue growth cracking was measured by Schenck PEZ-
4371 machine with 250 kN load at a frequency of 5-8 Hz. Fig. 11
illustrates the full thickness CTOD specimen drawing and the test
results. CTOD testing process starts with cooling down the specimen to
a few degrees below the testing temperature, e.g. if the intended testing
temperature is -60°C, the specimen is cooled down to about -62°C. The
next step is the specimen assembly, placing it into the testing machine
and thermo gauges installation. Gauges are used for precise temperature
control during testing. The test starts when the temperature of the
specimen becomes equal to the intended test temperature. During the
test, the obtained data is collected and recoded. The recoded data
includes load, opening displacements, time and traverse displacement.

a b
Fig. 11. Drawing of CTOD specimen, sizes are given in mm (BS 7448-
a b 1:1991).
Fig. 10. Drawing of NDT specimen, sized are given in mm (ASTM
E208).

116
CONCLUSIONS
The most commonly used alloying elements in high-strength steels are
nickel, copper, chromium and molybdenum. Nickel has the greatest
effect on strength, ductility and impact toughness. Its effects are
shifting the austenite transformation curves in the continuous-cooling
transformation diagram to the right. However, use of a high nickel
percentage is not economically feasible. Copper has a similar effect, but
due to its low solvability in steel, it is used in lesser amounts comparing
to nickel. Chrome and molybdenum shift the ferrite precipitation area
into the range of lower cooling rates and decrease the intermediate
transformation temperature. They also reduce the likelihood of
formation of upper bainite in the steel structure and shift the bainitic
range in the continuous-cooling transformation diagram to the right.
In sheet product manufacturing, quenching of high-strength heat-
hardenable steels can be done both with separate furnace heating and
with direct quenching. A martensitic-bainitic structure consisting of the
following structural constituents is formed: lath martensite; high-
temperature martensite (martensite of self-tempering); lath lower
bainite; lath upper bainite; and granular bainite. With a tempering
temperature of 500-550° the formation of carbide of 3 type is
completely suppressed, and dispersed (~30-40 nm) particles of special
carbides of ( r, )7 3- type, and later VC are precipitated
on dislocations and stabilize the dislocation structure. Further increase
of tempering temperature up to 600-650° results in coagulation of
special carbides, thereby releasing the dislocation nodes. Nickel
improves processes of carbide forming, and chrome, molybdenum and
vanadium inhibit carbide coagulation. At higher tempering
temperatures, the special carbides are arranged mainly at the boundaries
of lath and blocks.
The increased tempering resistance of deformed and quenched steel
allows an increase in tempering temperature, i.e. contributes to an
increase in impact toughness. The carbide formation caused by
additives of chrome, molybdenum, niobium, and vanadium
significantly reduce softening during tempering. Thus, in spite of the
low alloying levels in the proposed high strength steels, indirectly
estimated by the carbon equivalent value, it is possible to attain higher
strength without degradation of resistance to brittle fracture.
ACKNOWLEDGEMENTS
This research was carried out in the Welding Technology Laboratory of
Lappeenranta University of Technology (LUT) and was supported by
the Finnish Funding Agency for Technology and Innovation (TEKES)
as a part of TutLi-project: “Neural-Network-Controlled Self Regulating
Welding System”.
REFERENCES
ASTM E208. Standard Test Method for Conducting Drop-Weight Test
to Determine Nil-Ductility Transition Temperature of Ferritic
Steels.
BS 7448-1:1991. Fracture mechanics toughness tests. Method for
determination of KIc, critical CTOD and critical J values of
metallic materials.
Cheng, YF (2013). Stress Corrosion Cracking of Pipelines, John Wiley
& Sons, 210-275.
117
View publication stats
EN 10045-1 Charpy impact test on metallic materials. Test method (V-
and U-notches).
Golshtein, MI, Litvinov, VS, Bronfin, BM (1986). Metallophysics of
high-strength alloys, Metallurgy, 194-298 (in Russian).
Gorenc, BE, Tinyou, R, Syam, A (2005). Steel Designers' Handbook,
UNSW Press, 225-357.
Gorynin, IV, Rybin, VV, Malyshevsky, VA, Legostaev, YL,
Semicheva, TG (1999). “Main aspects of development and use of
high-strength structural steel,” Material science issues, 3(20), 7-21
(in Russian).
Gorynin, IV, Rybin, VV, Malyshevsky, VA, Semicheva, TG,
Sherokhina, LG (1999). “Transformation of dislocation martensite
in the process of tempering of secondary hardened steel,” MiTOM,
9, 13-32 (in Russian).
GOST 1497-84. Metals. Methods of tension test.
Hisata, M, Miyake, T, Kawabata, F. (1999). Kawasaki steel: “420 MPa
Yield Strength Steel Plate with Superior Fracture Toughness for
Arctic Offshore Structures,” Technical report no. 40, 56–62.
ISO 148-1 Metallic materials - Charpy pendulum impact test - Part 1:
Test method.
Kostryzhev, AG, Alshahrani, AA, Zhu, C, Ringer, SP and Pereloma,
EV (2013). “Effect of deformation temperature on niobium
clustering, precipitation and austenite recrystallisation in a Nb-Ti
microalloyed steel,” Mater Sci and Eng A: Structural Mater:
Properties, Microstructure and Processing, 581, 16-25.
Lagneborg, R, Sivetsky, T, Zayats, S, Hutchinson, B (2001). Role of
vanadium in micro-alloy steels, State Science Center Ural Institute
of Metals of Russian Federation, 71-99 (in Russian).
Layus, P, Kah, P, Martikainen, J, Pirinen, M, Khlushova, E, Ilyin, A
(2013). ”European and Russian Metals for Arctic Offshore
Structures,” Proc 23rd Int Offshore and Polar Eng Conf,
Anchorage, ISOPE, 4, 242–249.
Llewellyn, DT (2013). Steels: Metallurgy and Applications, Elsevier,
248-301.
Malyshevsky, VA, Orlov, VV, Khlusova EI (2014). Materials science
basis of thermomechanical processing of modern low-carbon steels
used for shipbuilding and main gas and oil pipelines, The Prometey
Central Research Institute of Structural Materials, 87-150.
Russian Maritime Register of Shipping, Rules for the Classification,
Construction and Equipment of Mobile Offshore Platforms, 2012.
Sakganik, VM, Shmakov, AV, Popov, VV (2009). “Efficient modes of
controlled rolling on the 5000 mill for round billet with low
temperature,” Steel, 10, 47-50 (in Russian).
Semicheva, TG, Sherokhina, LG, Khlusova, EI (2005). ”Processes of
carbide forming and embrittlement in the process of tempering of
ship steel,” Material science issues, 2 (42), 69-78 (in Russian).
Shanmugam, S, Tanniru, M, Misra, RDK, Panda D, Jansto, S (2005).
“Precipitation in V bearing microalloyed steel containing low
concentrations of Ti and Nb,” Mater Sci Technol, 21 (8), 883-892.
Suh, I-S, Kim, S-H, Park, Y-H, Kim, WG, Lee, C-S and Lee, J-K
(2011). “Development of SMYS 345/420 MPa Steel Plates for
Arctic Offshore Structures,” Proc 21st Int Offshore and Polar Eng
Conf, Maui, Hawaii, ISOPE, 4, 388–392.
Totten, GE (2006). Steel Heat Treatment: Metallurgy and
Technologies, CRC Press, 654-815.
Weng, Y, Dong, H, Gan, Y (2011). Advanced Steels: The Recent
Scenario in Steel Science and Technology, Springer Science &
Business Media, 315-405.