You are on page 1of 86

The Role

Of Vanadium
In Microalloyed
Steels
By
Rune Lagneborg
Tadeusz Siwecki
Stanislaw Zajac
Bevis Hutchinson
Swedish Institute for Metals Research
Stockholm, Sweden

Reprinted from:
The Scandanavian Journal of Metallurgy
October 1999

THE ROLE OF VANADIUM IN MICROALLOYED STEELS

Rune Lagneborg, Tadeusz Siwecki, Stanislaw Zajac and Bevis Hutchinson
Swedish Institute for Metals Research
S-11428 Stockholm, Sweden

ABSTRACT

The overall objective of the present paper is to review the role of V in microalloyed steels
with a particular address as to how it affects microstrucural evolution and mechanical
properties. Its role in thermomechanical controlled processing (TMCP) is emphasised. The
review is largely based on work carried out at the Swedish Institute for Metals Research
(SIMR) during the last 25 years but includes also reference to other relevant, published work.

A specific aim is to demonstrate the present scientific knowledge of the subject. Therefore the
understanding and interpretation of essential phenomena related to microstructure formation
and properties are thoroughly examined, ranging from the influence of microalloying on
prevention of austenite grain growth and recrystallization, to precipitation in ferrite and its
effect on strength. Within the well-known thermodynamic database Thermocalc a special
microalloy database has been developed at SIMR, allowing reliable predictions of phase
equilibria and thermodynamic functions for phase transformations in microalloyed steels. A
comprehensive account is given of the role of V in the most important processing steps that
the microalloyed steels are subjected to, viz. TMCP, continuous casting and welding.

Compared to the other microalloying elements, Nb and Ti, V exhibits essential differences. In
particular the solubility of its carbonitrides is much larger and the solubility of its nitride is
about two orders of magnitude smaller than its carbide, contrary to Nb but similar to Ti. For
optimal alloy design and thermomechanical processing proper allowance must be made for
these differences. To reach the maximum ferrite grain refinement, ~4 µm, repeated
recrystallization in a series of rolling reductions is used in TMCP of V-microalloyed steels, so
called Recrystallization-Controlled-Rolling (RCR), as opposed to traditional controlled
rolling of Nb-steels where heavy rolling at low temperatures in the non-recrystallization
regime is the means of attaining grain refinement. RCR presents some important advantages,
in particular a more economical hot rolling practice by allowing low reheating and high
finishing temperatures.

As compared to Nb, V has certain further advantages as a microalloying element due to its
greater solubility in autstenite. The tendency for hot cracking of cast slabs is much less
pronounced and dissolution of coarse V(C,N) compounds is more easily achieved prior to hot
rolling than for the corresponding NbC.

It is demonstrated that the relatively large solubility of V(C,N) and the much lower solubility
of VN than VC makes V an eminent choice for strong and easily controllable precipitation
strengthening. A corollary of the difference in VN and VC solubilities is that N becomes an
essential microalloying element in V-steels, because it largely determines the density of

V(C,N) precipitation and thereby the degree of precipitation strengthening. Moreover, since
pure ferrite dissolves more N than C the total N-content of the steel is normally dissolved in
the ferrite before V(C,N) precipitation whereas only a fraction of the C-content, given by the
austenite/ferrite or ferrite/cementite equilibrium, is dissolved in ferrite. Hence, by precise
additions of N this circumstance facilitates the control of V(C,N) precipitation strengthening.

Recent studies at SIMR have shown that the precipitation strengthening increases
significantly with total C-content of the steel, an effect previously not recognised. Increasing
C-content delays the pearlite formation and thereby maintains for a longer time the higher
content of solute C in ferrite corresponding to the austenite/ferrite equilibrium as compared to
that of ferrite/cementite, allowing new nucleation C-rich V(C,N) to occur when most N has
been consumed.

High N-contents, >0,010%, in V-microalloyed steels are often considered to cause
unsatisfactory HAZ weldability due to solute N which has been claimed to impair toughness.
Recent studies show, however, that such sweeping statements are incorrect and that fully
satisfactory welding results can be achieved also at high N-contents by selective choice of
welding parameters. Furthermore, it has been shown that when a lowering of the impact
toughness is observed at high N-levels and high heat input it cannot be explained by solute N
but rather by changes in the HAZ microstructure.

TABLE OF CONTENTS
1. PROLOGUE ......................................................................................................................1
1.1 The discovery of vanadium and the evolution of its use..........................................1
1.2 Statistics of the use of vanadium ...............................................................................2
1.3 The development of V-microalloying for structural steels ......................................2
1.4 Scope of the present review .......................................................................................3

2. ALLOY SYSTEM AND THERMODYNAMIC BASES.................................................4
2.1 Thermodynamic considerations................................................................................5
2.2 Thermodynamic description of the Fe-V-C-N system .............................................7
2.3 The Fe-Ti-C-N system................................................................................................8
2.4 The Fe-Nb-C-N system ............................................................................................10
2.5 The Fe-Al-B-C-N system .........................................................................................11
2.6 Chemical composition of precipitated particles in multi-microalloyed steels......12
2.7 Thermodynamic Driving Force for Precipitation..................................................13
2.8 Practical consequences of different solubilities of V carbides and nitrides .........14
2.9 Summary of chapter.................................................................................................14

3. MICROALLOYING EFFECTS IN AUSTENITE........................................................15
3.1 Precipitation and dissolution of microalloy-carbonitrides in austenite................15
3.2 Grain growth inhibition and grain coarsening ......................................................19
3.3 Effects on recrystallization ......................................................................................23
3.4 Effects on the austenite-ferrite transformation......................................................24
3.5 Summary of chapter ................................................................................................25

4. PRECIPITATION IN FERRITE ...................................................................................26
4.1 Interphase precipitation ..........................................................................................27
4.2 The mechanism of interphase precipitation ...........................................................29
4.3 General precipitation...............................................................................................32
4.4 Effects of precipitation on strength ........................................................................34
4.5 Summary of chapter ................................................................................................38

5. PRINCIPLES AND PRACTICE OF THERMO-MECHANICAL CONTROLLED
PROCESSING, TMCP....................................................................................................40
5.1 General principles of recrystallization-controlled rolling, RCR, and controlled
rolling, CR, processing.............................................................................................40
5.2 Mechanical properties and microstructure of TMCP material............................41

...... HOW IS V BEST USED IN MICROALLOYED STEELS ...................3 Effect of nitrogen content ....................................................................73 REFERENCES ............6 Summary of chapter ..........46 5..........67 8..44 5...............................68 8........................................1 Austenite conditioning by thermomechanical processing ..............................................................5 Microstructure development during TMCP rolling .......................................1 Microstructural features .................................................................................52 5.........................................................................................................................................................................................................................................................................68 8........55 6..........................3 Cast structures .....................................62 7............................................................57 7.......................................................2 Precipitation strengthening .........................72 ACKNOWLEDGEMENTS ..............71 8.............................2 Ductility during casting ...........................................................................................................2 Effect of nitrogen and welding parameters on HAZ toughness of V-steels.....................4 HAZ weldability................55 6..........74 ......3 Toughness-Microstructure Relationships ........... WELDABILITY ........4 Summary of chapter ............................................................1 Structure and properties of coarsed grained HAZ..................................................65 7............................................................... 5..........................................70 8.............................................................................................54 6...........................................................61 7..............................5 Interplay between general trends in steel technology and the technology of V- microalloyed steels ...........................4 Application of TMCP practice .......................71 8...................61 7..................................................................................................................................EXECUTIVE SUMMARY...... CAST STRUCTURES..................

With today’s knowledge we can confidently say that the observed strengthening was due to fine precipitation of V-carbonitrides during cooling or tempering. especially powder metallurgy. Sefström’s master. 1 1. confined to chemical studies of a large number of vanadium compounds. particularly when quenched and tempered. .S. The importance of V-alloying in tool steels has not diminished with time. In the U. during the first two thirds of this century. He examined the wreck and found a crankshaft made from Swedish iron that suffered less damage than expected. At that time.1 The discovery of vanadium and the evolution of its use Vanadium was discovered by the Swedish scientist and doctor Nils Gabriel Sefström in 1830. as it appears. It was only some 30 years later that vanadium was isolated as a metal due to work by the English chemist. The early use of vanadium was as a chemical compound and was based on the investigations by Sefström. Other important applications of V-alloying. Work in the first years of the century both in England and France showed that carbon steels exhibit a considerable increase in strength by V-alloying. Berzelius and Roscoe. the use of V for alloying of automotive steels had. and a special assignment was given to Professor Arnold of Sheffield College to investigate effects of V alloying in various steels. however. In order to exploit the opportunities for V as an alloying element in steel the first production unit was set up in South Wales. has made it possible to increase the hard phase content in high speed and cold work steels considerably. Sefström’s and Berzelius’ work was. an accidental beginning. After examination in his laboratories it was reported that the steel contained V. rail steels and cast iron. primarily developed. In his studies of ductile iron originating from iron ore of the Taberg mine he obtained a residue which he concluded contained a compound with a previously unknown element. in these applications the hardness of V carbide and its stability at high temperatures played an essential part. The function of vanadium salts as catalyst for many chemical reactions was discovered 1900 in Germany and has become the most important application of vanadium as a chemical. The development of new processing technologies. from high speed steels to both cold work and hot work die steels. The improved impact resistance was due to a refined grain structure resulting from grain growth inhibition by V-nitrides at the quenching or normalizing temperature. Henry Ford I watched a motor race in which a French car crashed. an understanding of the beneficial effect of V was missing. Great Britain. ~ 1910. At this point. Examples of early applications of vanadium compound are: black colouring of ink and fixing aniline black dyes for fabrics. Sir Henry Roscoe. are high temperature power plant steels. PROLOGUE 1. The usefulness of V in engineering steels was early recognised. As a result Ford gave instructions to use V-steels in critical components in Ford cars ‘in order to better resist shock and fatigue on American roads’. the famous Swedish chemist Jöns Jacob Berzelius. Hence. in recent years this has rather increased the use of V in tool steels. He announced Sefström’s discovery internationally and also initiated a large research programme on vanadium salts. took up interest in the new element. Arnold’s research together with studies in steel works in the Sheffield neighbourhood laid the foundation for a whole range of tool and die steels. At the turn of the century the technology of process metallurgy had developed such that commercial quantities of ferroalloys could be produced. vanadium. Hence.

With the broad introduction of welded structures after the Second World War strengthening of steel by increasing the carbon content became practically prohibitive in view of carbon’s detrimental effect on toughness of welded structures and on weldability. respectively. The remaining part goes to chemicals and to alloying of titanium.3 The development of V-microalloying for structural steels The development of the microalloyed structural steels and the related development of controlled rolling started in the late 1950’s.10-0.05 kg now. strip and structural sections. With time it was also recognised that strengthening by microalloy precipitation could be substituted for strengthening by carbon while weldability is improved. The development of these materials started in the 50’s and a brief historical account of this is given below. physical and high temperature mechanical and corrosive properties and are considered as a candidate in future fusion reactors. they have at present no important application as structural materials. with yield strengths ranging from 320 to 460 MPa and to be used in the as-rolled condition. 2 The most exciting and today the largest use of V is in high strength low alloy (HSLA) structural steels.010-0. 1.015% found wide use for this type of applications. Although V-base alloys have been used in nuclear breeder reactors because of their nuclear. content of C and Mn of 0. The rather constant level of steel production over the last 20 years has consequently resulted in a similar constant consumption of vanadium. However. The predominant application of vanadium is for alloying of steel and cast iron.15-0. since 1992 this level has increased to about 0.2 Statistics of the use of vanadium The world consumption of vanadium is today (1999) some 34000 tonnes per annum. World-wide about 65% of the vanadium for alloying of steel is used in microalloyed structural steels. Beside its application in alloying of steel and cast iron V is an essential alloying addition in Ti-alloys for aircraft and aerospace applications. thick walled gas pipe lines. at a level of 0. . In the 60’s and 70’s V- microalloyed steels with 0. most probably reflecting an increased use of V-microalloyed structural steels. etc.15% V and somewhat enhanced N-content 0. The steels were offered in practically all product forms. such as high speed and tools steels. Therefore the new knowledge that grain refinement can improve both these properties and at the same time enhance strength was a strong stimulus for developing new hot rolling practices and new steels. In the early 60’s Bethlehem Steel developed and marketed a series of V-N steels with max.25%. In the past normalizing heat treatment was an absolute requirement for steel plate and most structural sections used in structures for heavy-duty service. high temperature low alloy steels.04 kg per tonne steel produced. plate. a share that appears rather stable over time. 1.22% and 1. whereas the remaining 35% is used in V-alloyed steels. another name for the same group of steels and more related to their alloying is ‘microalloyed steels’. From this follows that the consumption of vanadium and the production of steel are strongly interrelated. It amounts to about 85 % of the total consumption. of which 28000 tonnes in the Western world.20% and 0.g. e.

A specific aim is to show the present scientific understanding of the subject. e. the many important uses of V-alloying in other steels. Around 1965 the development of controlled rolling had reached a level such that it was introduced in commercial production. though. It was found that Ti-V microalloyed steels are especially suited for this process since both these elements only retard recrystallization weakly and therefore allow repeated recrystallization during rolling. low-alloy creep resistant steels etc. that the intention is not to attempt to critically review all the available literature in the area. It should be emphasised. to microalloying effects in austenite and precipitation in ferrite and its effect on strength. ~ 1980.. thereby flattening the austenite grains gradually more with reduction and in this way the austenite was conditioned to transform to very fine-grained ferrite. are omitted. This was one of the first steels where in-line accelerated cooling was applied in a controlled manner to enhance grain refinement and strengthening by microalloy precipitation. The review is mainly based on work carried out at the Swedish Institute for Metals Research during the last 25 years but includes also reference to other relevant. In order to increase strength it was soon found advantageous to also microalloy with V.10%C. ranging from thermodynamic predictions of relevant phase equilibria in V-steels. The paper covers V-microalloyed structural steels with ferrite-pearlite microstructures having low to medium carbon contents. has been widely adopted for pipelines. it therefore requires lower rolling forces and can accordingly be practised in weaker rolling mills as well as offering superior productivity. 0. Hence. By allowing the worked austenite to recrystallize after each rolling reduction it was found possible to reach a similar grain refinement as with the former method. Therefore we have devoted the first 3 chapters following the introduction to our view as to how essential phenomena and properties of V-microalloyed steels should be understood and interpreted. By microalloying with Nb it was possible to prevent recrystallization during hot rolling.4 Scope of the present review The aim of the present paper is to review the role of V in microalloyed structural steels and our understanding of how it affects microstructure evolution and mechanical properties. developed at Jones & Laughlin around 1975 with a typical yield strength of 560 MPa. The last 3 chapters are devoted to a comprehensive account for the role of V related to the most important processing steps that microalloyed structural steels are subjected to. . This process results in higher finishing temperatures. A controlled rolling route later developed. Its role related to thermo-mechanical processing is especially addressed. published work. tool and high speed steels. thermomechanical processing.03%Nb and 0. was recrystallization-controlled-rolling.g.07%V. This type of controlled rolled Nb-V steels. with about 0. viz. continuous casting and welding. 1. 3 An early advanced V strip steel was VAN80.

Niobium nitride and carbide have relatively low solubilities and may precipitate out in the later stages of rolling. has a rather high solubility in austenite even at temperatures as low as 1050°C. inhibition of grain growth by carbo-nitride particles. ALLOY SYSTEM AND THERMODYNAMIC BASES The strengthening effect of microalloying additions may be produced by the dispersion strengthening effect of fine carbo-nitride particles or by grain refinement. In normal circumstances the solubility relationships shown in Fig. . An understanding of the role of different microalloying elements can be gained from the solubility product data summarised in Fig.e. 2. To achieve the desired metallurgical states. 2. together with a knowledge of their precipitation behaviour. particles that remain undissolved in the austenite. a detailed knowledge of the solubilities of the microalloy carbides and nitrides is required.1 represent a simplification. It is seen that TiN is extremely stable and can withstand dissolution at high temperatures during reheating prior to rolling or during welding. This is especially true for titanium and vanadium where the differences are particularly pronounced. Fig. 4 2. 2. as steel may contain more alloying elements with high affinity for carbon and nitrogen which alter the solubility of the microalloyed carbides and nitrides. To produce the very fine particles that are responsible for dispersion strengthening (i. Despite a simplification the individual solubilities of the microalloyed carbides and nitrides offer clear directions for the selection of microalloying additions for specific purposes.e. i. it is necessary that these should be freshly precipitated during or after transformation to ferrite. It is also seen that the nitrides are substantially less soluble than the corresponding carbides. or particles that will precipitate during hot rolling are required. particles that are 2-5 nm in diameter). In order to maintain a fine austenite grain size prior to transformation.1 from recent thermodynamical evaluation. or by a combination of these two effects.1 Solubilities of microalloy carbides and nitrides. Vanadium on the other hand.

3). and the spread between them is significant.1 Approximate expression for the solubility product As was stated above the solubility of carbides and nitrides in austenite and ferrite is usually expressed as a solubility product in terms of wt pct of microalloy element and carbon and/or nitrogen.1 where ks is the equilibrium constant. . for Nb-microalloyed steels the nitrogen was often considered to modify the effective carbon concentration as [C+12/14N] (e. 5 2. 2. in most cases greater than 150°C. log ks= log [M][X]= A-B/T. VN. The temperature dependence of the solubility product is expressed by the Arrhenius relationship in the form. (2. TiN and AlN. their composition can vary when precipitated in steels. nitrides and carbo- nitrides in austenite (see compilation in 2. 2.g. all of which have NaCl cubic crystal structure. All of these investigations expressed their results in a form of solubility products.2. The influence of carbon and nitrogen on carbo-nitride formation has been handled in different ways by different authors. For V and Zr the large difference in atomic size enables their compounds only to show limited mutual solubility.2). Therefore the individual solubility equations apply only to a particular composition investigated and are not capable of predicting the solubility at different compositions. For example.1. [M] is the dissolved microalloy (wt%). there is no mutual solubility with the carbides/nitrides of V. It is necessary to emphasise that aluminium differs from the microalloying elements V. but only the nitride.1 Thermodynamic considerations 2. It should be pointed out that the situation is even more complicated when more than one microalloy element is present and when the ratio of carbon to nitrogen is changed. the results proposed by various authors as the "best-line" relationships sometimes differ considerably. The analysis of the solubility data in terms of solubility products implicitly assumes that the activity coefficients of microalloying elements as well as carbon and nitrogen are equal to unity and the microadditons are treated as a dilute solute and any interactions between solutes in the system are neglected. 2. The carbides and nitrides are also non-stoichiometric and. where the effects of solute interactions become significant. Several authors have made efforts to establish the solubility of carbides.Zr)N. Zr and V show continuous or extended mutual solubility. However. Nb. Therefore. A and B are constants and T is absolute temperature. having a different crystal structure (hexagonal close packed). all other carbides and nitrides formed by Ti. Except for (V. NbC. An analysis of published data concerning the solubility of VC. AlN. NbN. has shown that there exist more than ten different solubility equations for each carbide/nitride. hence. [X] is the content (wt%) of nitrogen or carbon.1). The similarity of crystal structure of carbides and nitrides enables them to show mutual solubility. Nb and Ti. Fig. Nb and Ti because it does not form a carbide in steel.

1. G M = RT lna M = RT lnx M + E G M (2.2 Thermo-Calc model In order to accurately predict the austenite/ferrite carbo-nitride equilibria. 2.4) for dilute ternary solutions or a sublattice- subregular solution model proposed by Hillert and Staffanson (2.5) can be used. the Wagner formalism (2. The Wagner formalism is in fact identical to the regular solution model if the second-power terms are neglected. 2. To describe the thermodynamics of austenite. . 6 Fig. (c) TiN and (d) AlN (2. In the sublattice-subregular model proposed by Hillert and Staffansson the partial Gibbs energy of component M in each individual phase is expressed as. ferrite and the non-stoichiometric carbo-nitride phase respectively.2) where a is the activity and E G M is the excess Gibbs energy. expressions describing the chemical potentials of the transition metals and carbon and nitrogen in austenite and metal carbo-nitride are required as a function of composition and temperature.1). (b) NbC and NbN.2 Solubility data for (a) VC and VN.

7 The real crystalline structure of nitrides and carbides is expressed in the form of two sublattices. This is mainly due to the quite narrow austenite single phase region in the experimental temperature range. Fe4N(γ´) and so-called sigma phase (σ). the properties of elements and phases are described by the mathematical representation of their thermodynamic properties and the phase equilibria and complete phase diagrams are calculated by minimising the Gibbs energy.2x10-5 T (2.12) and ferrite (2. one for the substitutional elements and one for the interstitial elements. Considerable experimental uncertainty still remains which makes some difficulty in the accurate determination of the interaction parameters. 2. an interstitial solution cannot extend beyond the composition where all the interstitial sites are occupied. LFe . graphite and metastable phase cementite.12500/T + 6.11) for liquid phase and fcc. V3C2 carbide. The VN phase has a NaCl type of structure. VN). which comprises the thermochemical parameters for multi- component systems of HSLA steels. in the form -(7645. The solubility of VC carbide in the Fe-V-C system has been studied rather extensively (2. 2. Interactions between different atoms in higher-order systems are described by the mixing parameters. austenite) from Fe-poor fcc phase (i. The carbon atoms are randomly distributed in the interstitial sublattice at high temperatures. liquid.2 Thermodynamic description of the Fe-V-C-N system 2.63 – 0.5 + 2. In the Thermo-Calc approach (2. This model is now successfully utilised to calculate the volume fraction and compositions of particles at different temperatures as well as the driving force for precipitation.e. Both V2C and VC carbides have appreciable ranges of homogeneity due to the carbon deficit (2.9).056lnT + 4.e.3) and ferrite.7). V2C1-x carbide. Fig.11).V :C . 2. in austenite.6).2.069T)[1+(yFe-yV)] (2. In addition to these phases. VC1-x carbide. Since this phase is isomorphous with austenite from a crystallographic point of view. which can be described as fcc V with all the interstitial sites filled with N.7600/T – 10. To take fcc V-N as an example. liquid (L). Several reports were presented previously on the equilibrium nitrogen solubility and nitride formation in austenite (2. Most of the interstitial sites are usually vacant and vacancies (Va) must thus be treated as an additional element. The following equations were obtained. The analysis of the alloy systems of microalloyed steels described below was made with the aid of the Thermo-Calc model. the solubility of VN in austenite is described by a miscibility gap which separates the Fe-rich fcc phase (i.4) .8lnT + 7. vanadium mononitride (VN)). Using these parameters it was possible to estimate the solubility product of VN in austenite and ferrite. two fcc phases (austenite (γ). sigma (σ) phase. which may be regarded as a V1Va1 to a compound V1N1. log (wt%V)(wt%N)= .7x10-6 T (2. N2 gas is involved in some equilibria.1 The Fe-V-C Ternary System In the Fe-V-C ternary system the following phases have been considered (including a vanadium-rich eutectic). The database can also be used to calculate metastable equilibria since the data can be extrapolated from the regions where the phases involved are stable. vanadium dinitride (V2N)). austenite. log (wt%V)(wt%N)= .3 (2. The experimental iso- fcc carbon activity data in austenite were described by the ternary interaction parameter.10).2.34 + 1. the model of the solution extends from pure V. The ternary interaction parameters LFe.2 The Fe-V-N Ternary System The Fe-V-N ternary system consists of two bcc phases (ferrite (α) V(b-V)).8). ferrite.13). A general Thermo-Calc database for the thermodynamic properties of microalloyed steels has recently been developed at the SIMR (2. two hcp phases (iron nitride (ε).V:C were evaluated by Ohtani and Hillert (2. In principle.

Fig.3 Solubility and composition of V(C. until practically all the nitrogen is consumed. When the nitrogen is about to be exhausted there is a gradual transition to form mixed carbo- nitrides. If larger contents are present the excess titanium can precipitate at lower temperatures as carbide TiC which contributes a precipitation hardening effect. Also shown in this figure is the mole fraction of nitrogen in carbo-nitrides at various temperatures for various nitrogen contents from hyperstoichiometric levels to zero.N) in V-microalloyed steels Thermo-Calc calculations of precipitation of V(C. 2. Also shown in this figure is the mole fraction of nitrogen in carbo-nitrides at various temperatures and for various nitrogen contents from hyperstoichiometric levels to zero. suggesting that vanadium carbide will be completely dissolved even at low austenitising temperatures. 2.4(b). 2. Only a small titanium addition (~ 0. until practically all the nitrogen is consumed.01%Ti) is required for this purpose. nitrogen and vanadium interaction with other elements present in steels have been taken from the SSOL and TCFE Thermo-Calc databases (2. A significant feature of the solubility of vanadium carbide in austenite is that it is considerably higher than those of the other microalloy carbides and nitrides. This shows that the solubilities of titanium nitride and titanium carbide are significantly different and the precipitates formed in the austenite are almost pure nitrides.5. For V-microalloyed steels the effect of manganese on the activity of V is especially important. It is worth noting that in the Ti-steel . Nitrogen rich vanadium carbonitrides may precipitate during or subsequent to the γ-α transformation. Titanium forms an extremely stable nitride TiN that is virtually insoluble in austenite and may be effective in restricting its grain growth during processing and welding. Mn is known to increase the activity coefficient of V and at the same time decrease the activity coefficient of C. is shown in Fig.7). Precipitation during the transformation is a result of the solubility drop of the vanadium carbo-nitrides associated with the transformation from austenite to ferrite at a given temperature. 8 Fig. 2. 2. This shows that vanadium starts to precipitate in austenite as almost pure nitride.2.4. For these calculations the parameters for the carbon.3 The Fe-V-N ternary system at 800°C. 2.N) in steels microalloyed with vanadium is shown in Fig.3 The Fe-Ti-C-N system The calculated precipitation of TiN and TiC in steels microalloyed with titanium.

2.6. 2. 2.10% V steels at various nitrogen contents. nitrogen rich carbonitrides and carbides in 0. . nitrogen rich carbonitrides and carbides in 0. 9 containing 0. When the nitrogen is about to be exhausted there is a gradual transition to form mixed carbo-nitrides. Therefore for proper calculation of the precipitation of microalloyed carbides and nitrides the effect of all elements present in the steel must be considered.01%Ti or less for controlling austenite grain size there is usually sufficient nitrogen to combine all Ti as TiN.4 Example showing the precipitation of nitrides. Titanium exerts a strong affinity not only for carbon and nitrogen but also to other elements such as oxygen and sulphur. 2. It is also clear from this figure that the formation of Ti-sulphides or carbosulphides will decrease the amount of Ti available for TiN and TiC.14). In Ti-microalloyed low-carbon steels the carbosulphide Ti4C2S2 or sulphide TiS may form which remain undeformed during hot rolling (2. Fig.01%Ti steels at various nitrogen contents. Fig. Ti4C2S2.5 Calculated precipitation of nitrides.5 (b). Fig. is more stable than MnS and the formation of MnS is restrained by the addition of Ti to the steels. According to Fig.

The deformed austenite structure transforms to fine grained ferrite on cooling.15). for realistic contents of carbon and nitrogen in steel. 2. Hence. 10 Fig. 2. mixed carbo-nitrides form at all nitrogen contents.7 where the difference in solubility between the nitride and the carbide is relatively small. which imparts both high strength and toughness to such ‘controlled rolled’ steels. relatively pure nitrides cannot form at all.N) is stable at low temperatures in austenite but dissolves at higher temperatures. during re-heating prior to rolling. .7 Example showing the precipitation of Nb carbonitrides in 0.03% Nb steels at various nitrogen contents.4 The Fe-Nb-C-N system For Nb-steel. 2.N) can precipitate quite readily in austenite under deformation (strain induced precipitation) and the particles so formed resist grain growth and even recrystallization of the austenite during the intermittent deformation at lower temperatures. Nb(C. for example. Fig. 2.6 Calculated precipitation of MnS. A further precipitation of the remaining niobium as smaller particles during cooling gives rise to additional strengthening. Ti4C2S2 and TiN in low manganese steel. Fig. even at the hyperstoichiometric levels (2. Nb(C.

However. It is well known that the kinetics of AlN precipitation in austenite are generally slow and dependent upon thermal history.06). Boron additions enhance the hardenability of heat-treatable steels and assist in the control of strain ageing in sheet steel for deep drawing (2. however. which are at least as significant as those produced by Nb. However. The precipitation of AlN can. V or Ti additions. Fig. This problem of variability is mostly due to the strong affinity that boron has for oxygen and nitrogen and the very low contents of boron that are desired (~0. AlN nucleates with some difficulty in steel and has a widely different morphology from other nitrides (2. When considering steels containing boron and aluminium the situation is more complicated than for other microalloying elements 2. 2. Al-killed steels have long been known to show improved strain ageing resistance and enhanced deep drawability.001%). such that the true level of active boron has been difficult to control in practice (2. have strong effects on the properties of microalloyed steel. 2.8 Precipitation of BN and AlN in B-bearing Al-killed steels (2.18). The solubility of BN is smaller than that of AlN for temperatures of practical importance so that BN might be expected to precipitate preferentially on thermodynamic grounds. Considerably less investigation has been made into the precipitation of AlN in austenite. 11 2. the total content of aluminium in typical killed steels is at least an order of magnitude greater than the boron additions which are normally used and for this reason AlN often tends to be stabilised.17). Boron has long been known to have a powerful influence when added as a microalloying element to steel but its usage has often been restricted because of variability of its behaviour in practice. Fig.5 The Fe-Al-B-C-N system Aluminium is not usually classified as a microalloying element. .16).18).19). AlN precipitation in ferrite has been extensively studied in connection with the development of favourable crystallographic textures. and for many years the term ”aluminium grain refined” has been synonymous with grain size control (2. Aluminium is normally dissolved in austenite at high temperature prior to rolling but the nitride phase is thermodynamically stable at lower temperatures.8.

2. Ti and Al is shown in Fig. the major part of the precipitate at the highest temperatures is TiN whilst further precipitation at lower temperatures is predominantly Nb(C. The particles are frequently cored. that the uniform composition of second phase particles suggested from the thermodynamic calculations is often not the true situation in practice. Ti and Nb show extensive mutual solubilities which arises from the fact that they have the same cubic crystal structure and have very similar lattice parameters. Thus.Nb)-nitrides. for example forming a NbN-deposit around a core of TiN. Nb and V in M(C. however.6 Chemical composition of precipitated particles in multi-microalloyed steels The carbides and nitrides of V.N). In Fig. This suggests that these primary composite nitrides can act as nucleation centres for subsequently precipitation at relatively low temperatures.N) is also included.9 (a). It is clear from this figure that the volume fraction of microalloy nitrides at high temperatures will be considerably larger in the Ti-Nb-V steel than in the single microalloyed steels. 2. Nb and V in M(C.9 Example showing the precipitation of nitrides and nitrogen-rich carbonitrides in multiple microalloyed steel (a) and the mole fraction of Ti.9(a). where the soluble components are expressed as a function of temperature. the primary precipitates to be formed in austenite are composite (Ti. . Fig. It should be mentioned. Fig. The precipitation of carbo-nitrides in multiple microalloyed steels with V. 2. It may also be seen that AlN (with close packed hexagonal structure) has little or no solubility for other microalloying elements and starts to precipitate above 1200°C in the presence of 0. The Ti and Nb contents of those depend on steel composition and precipitation temperature. These coring effects may be a result of very slow diffusion of Ti in carbo-nitrides or the existence of a miscibility gap as explained further in Chapter 3.V)N particles contain ~20% of Nb and ~5% of V for multiple microalloyed steels. reflecting the high temperature stability of a titanium-rich and nitrogen-rich compound in the interior of the particle with relative enrichment of Nb and V towards the surface of the particle. As expected. primary (Ti. Similar results have been obtained for Nb-V steels where niobium-vanadium nitrides have shown Nb and N enrichment in the precipitates.N) (b). 12 2. in accord with the higher thermodynamic stability of NbN.Nb. 2.035% Al.9 (b) the mole fraction of Ti. Thermodynamic calculations imply that at the high temperature of 1200°C. Nb.

12% V steel.10 (a) Chemical driving force. on the other hand. It can be seen that.V)N particles is not available for subsequent thermo-mechanical treatment. The chemical driving force for nucleation of VN and VC in V-microalloyed steels. (b) Effect of equilibrium and metastable carbon content in ferrite on driving force for precipitation of V(C. ppm Fig.N) 5.5 equilibrum carbon content in ferrite 4 3.5 in ferrite 5 4. ∆Gm/RT. for precipitation of VC and VN in 0. This driving force enters the steady state nucleation rate in a central way and must be known with some accuracy if nucleation rates are to be calculated. 2. 13 Another important aspect of multiple microalloying is that the niobium or vanadium tied up as (Ti.5 0 50 100 150 200 250 300 Nitrogen content in ferrite. 2. a free energy difference between the product and parent phases. that is.9 (b) shows that a significant fraction of added niobium may remain undissolved even at high reheating temperatures and cannot contribute to retardation of recrystallization and/or precipitation strengthening.10. determined from the HSLA database are illustrated in Fig.Nb. Vanadium. Fig. or even estimated.N) at 650°C. as the temperature is decreased the driving force . 2.7 Thermodynamic Driving Force for Precipitation The precipitation process proceeds at a perceptible rate only if there is a driving force. (a) (b) 6 250 ppm carbon DRIVING_FORCE for V(C. 2. exhibits higher solubility and is therefore normally fully available for precipitation strengthening in ferrite.

thereby increasing the strength level of the steel by precipitation hardening. Interactions between alloying elements influence significantly the solubility of V(C. Since the (Ti. This means that there is only one parameter. • Interaction of V with other microalloy element leads to the formation of mixed carbonitrides and decreases the amount of vanadium dissolved in austenite. the most important parameter controlling the nucleation frequency is the chemical driving force for precipitation. • The solubilities of the carbides and nitrides of V differ widely. It should be noted. Fig. 2. especially for the enhancement of the driving force for precipitation. 2. 2. For hard precipitates such as microalloy carbonitrides bypassing of dislocations is expected to occur by bowing between the particles (Orowan-mechanism) under all practical conditions. For example. V-additions increase alloying costs significantly whereas the usage of N at the present levels is free.10(b).N) in austenite and ferrite is much larger than that of other microalloying elements. In precipitation reactions. that the driving force can also be raised by V-addition. but the effect per concentration unit is much less. The smaller is the interparticle spacing the larger is the strengthening effect. expressions describing the chemical potentials of the transition metals and carbon and nitrogen in austenite and ferrite as well as metal carbo-nitride are required as a function of composition and temperature. the stable TiN phase may incorporate a significant amount of V and even AlN has sometimes been detected in complex titanium nitride particles. Since V(C. In turn. is the explanation of the well-known increase in strength by N in V-microalloyed steels (for a full discussion see Chapter 4). however.9 Summary of chapter • The solubility of V(C. A combination of V with other microalloy elements in the same steel can naturally lead to interactions since they compete for the same interstitial elements and may also form mixed compounds with one another. the decisive factor which minimises the interparticle spacing (and maximise the precipitation strengthening) is the rate of nucleation since it determines the particle density.N). Moreover. • To accurately predict the austenite/ferrite carbo-nitride equilibria. 14 increases monotonically and changes slope after the austenite to ferrite transformation. Hence. N) has high solubility in austenite it hardly affects the hot deformation process but rather precipitates during cooling in ferrite.V)N particles are rather coarse such an effect reduces to some extent the contribution which the V can be expected to make towards precipitation strengthening. The dominating effect of N on the driving force is clearly seen in this figure. 2. Fig.10(a).8 Practical consequences of different solubilities of V carbides and nitrides Vanadium is the most soluble of the six elements discussed here and does not readily precipitate in austenite. . which determines the precipitation strengthening namely the interparticle spacing. the strong effect of N in increasing this driving force. This implies that N has a decisive role in V-microalloyed steels. the solubility product of VN is about two orders of magnitude lower than that of VC.

GCT is the experimentally determined grain coarsening temperature of continuously cast 220 mm slabs (2. we can conclude that the temperature for initial precipitation and complete dissolution should be equal for all three steels. V and Nb precipitated as (Ti.1. as the driving force for carbonitride formation increases at lower temperatures in the austenite regime the probability for nucleation of new carbonitride.015%. increases.M)N in a Ti (a). Fig. for Ti are the same for all three steels. are sufficient. The technical background to this is that Ti reacts with the nitrogen in the steel to form a fine dispersion of very stable TiN. MICROALLOYING EFFECTS IN AUSTENITE In commercial V-microalloyed steels small amounts of Ti (~ 0. Of course. rich in V or Nb and eventually pure V. Fig. From this we can see that the precipitation curves.1 Precipitation and dissolution of microalloy-carbonitrides in austenite It is well established that TiN forms as a fine precipitate dispersion early after solidification in Ti-V and Ti-Nb HSLA-steels having less than about 0. Ti-V-.6). 0.1 shows results from calculations for Ti-. At lower temperatures when the solubility of Nb(C. The graphs show the fractions of Ti. may affect the grain coarsening behaviour significantly. Furthermore. the TiN precipitation may by affected by a second microalloy addition. arising in Ti-bearing V-steels.1 Calculated amounts of Ti. and Ti-Nb steels using the thermodynamic database developed for microalloyed steels (3. but especially together with the formation of a second precipitate. such as V.N) has been exceeded many experimental studies have shown that these phases co-precipitate on already existing TiN-particles to a large extent. However. 3. 3. However. are discussed in some detail below. For this to occur in typical HSLA plate and strip steels the normal levels of N in BOF and EAF steel making. as long as all V or Nb on lowering the temperature co- . i. in various ways.or Nb-carbonitrides. V and Nb precipitated as nitrides at equilibrium in the austenite. Ti-V (b) and Ti-Nb (c) steel. as in continuous casting of slabs. Therefore these questions. This alone. 15 3. Hence.01%) are commonly added to prevent excessive grain coarsening at high temperatures.e.004 – 0.N) and V(C.2). to attain the fine TiN size necessary for effective grain growth control fast cooling is needed during the solidification of the steel.02%Ti. 3.3.

This is demonstrated in Fig. A general conclusion is that the stability of TiN itself is not expected to change by additions of other microalloying additions. The rate of particle coarsening during coalescence is given by 3σ V m DγM X γM r 3 − r 3o = (3.and Nb-steels as these elements co-precipitate. as expected the widest spread is observed in the strand-cast condition (220 mm) (3.V) N as particle size decreases (3. Beside the rate of nucleation the density of precipitates is also controlled by coalescence which occurs at a constant volume fraction of particles after the completion of the precipitation reaction. Along the same lines Fig.5). but has sometimes incorrectly been stated as a decline of the stability of TiN.3.6).3 shows how the spread in V and Ti in a (Ti. whereas smaller ones formed at low temperatures are low in Ti and high in V or Nb (3.3). 3. rate equivalent to that of 220 mm concast slab (3.5). In accordance with this reasoning it is generally found experimentally that larger particles that formed at high temperatures are high in Ti and low in V or Nb.3. the separately formed V. V) N-population increases with decreasing reheating temperature. such as V or Nb. This is exactly what has been found experimentally (3. we should expect the density of precipitates also to be the same in the steels. The low N-steel with near stoichiometric Ti/N ratio exhibits a considerably smaller spread due to the fact that nearly all N is consumed to form TiN. However. and the particle size. Fig.2 Relationship between composition of Fig 3.3.V)N-inclusions in a Ti-V-steel with high V particles in two Ti-V-steels with low and and N.4).4).3).V)N- (Ti.3 Spread in composition of (Ti. However. 3. 16 precipitates on pre-existing TiN.and Nb-rich carbonitrides are less stable and dissolve at lower temperatures. at lower temperatures V.1) 4 RT ( X MCN M − X γM ) . 3. The steel was high N in concast condition and for varying made as a laboratory cast but was cooled at a reheating temperatures (3.2 for a Ti-V steel showing a gradual decline of the Ti-content in (Ti. of course the individual particles will grow larger in the V.3. and indeed this is proven experimentally (3.and Nb-carbonitrides are expected to form as new precipitates.

σ is the interphase energy. Changing the Ti and N contents along the stoichiometric lines results in the largest change in solubility. Again we have not found any experimental results opposing this statement. 3. From this we can directly learn that in our case Ti will normally be rate controlling as a result of its much lower solubility compared to V or Nb.3.V)- carbonitrides formed in austenite show furthermore that the compositional gradients of the particles are not always smooth. However.3. At first this may appear natural in view of the sequential precipitation of Ti and V during cooling.3. 3. Electron microscopy and microanalysis of the (Ti. X γM the solubility of M in austenite and X MCN M the concentration of M in the (Ti. Fig.7).6). gives rise to: (i) a higher dissolution temperature of TiN (ii) a smaller fraction of dissolved TiN for a given temperature increase (iii) a reduction of the Ti-content in austenite in equilibrium with TiN.2).5). using over-stoichiometric contents of N. N). Nb) (C.V)- . a prerequisite is then that the interdiffusion of Ti and V in the (Ti. It is only for very high contents of V or Nb in the carbonitrides that these elements become rate controlling.N) precipitation found in austenite of Ti-V steels is that the particles exhibit compositional gradients such that the external parts are richer in V and the interior is richer in Ti (3. The usefulness of over-stoichiometric N-contents in Ti-V-steels for grain size control in the HAZ of welds has been demonstrated (3. An interesting feature of (Ti.2. 17 where r is the mean particle radius at time t. Hence. So again we expect no difference in resistance to coarsening of TiN in Ti-steels and Ti-rich nitrides in V.and Nb- steels.V. as indicated in the graph. ro the initial mean radius. resulting in slower coarsening. DγM the diffusivity of the rate controlling element M. Vm the particle molar volume. showing the solubility curves for TiN in austenite for various temperatures.4.4 Effect of excess nitrogen on dissolved Ti (3. demonstrates that the Ti/N ratio affects the TiN stability in various ways (3. Fig.V)(C.2). The outer V-rich part occurs commonly as dendrites (3.

and above about 1300°C. and consequently leads to the conclusion that there is a miscibility gap in the (Ti.6. particle radius 5 nm and spacing 175 nm. and hence that homogenisation will occur of the (Ti. for instance. even at the highest temperatures. the scatter of reported diffusion coefficients in refractory carbides and nitrides is very large. Hence.5 and 3. The computations have been carried out for different particle dispersions. This. The time for dissolution is about an order of magnitude faster than the time for precipitation. Unfortunately. 3.3. The explanation is the very minute dissolution of TiN as compared to the amount of TiN transferred for complete precipitation. an initial precipitate size of 5.5. 18 carbonitride is substantially lower than in austenite. although this has implied that we have chosen somewhat lower solubilities than the mean of the scatter band.5 we may note that very little dissolution of TiN takes place. The solubility data available in literature exhibit a considerable scatter. as was demonstrated in chapter 2.Nb)C. It should be borne in mind. .Nb)C is only slower by 103 (3. though. in turn. this was exactly the result of a recent thermodynamic analysis of the Ti-V-N system (3. would imply that Ti-rich and V-rich carbonitrides can co- exist in equilibrium. Otherwise there will be ample time for homogenisation of the elements to occur. and for the cases of precipitation and dissolution allowance is made for soft impingement of adjacent solute-enriched zones. Fig.system. The results are displayed in Figs.V)(C. the self diffusion of Ti in TiC is slower by 1010 than Ti in austenite. The computations of coalescence in Fig. In fact. Obviously this effect outweighs the lower Ti-gradient in dissolution as compared to precipitation. these computations show that the grain coarsening temperatures of about 1200°C and even lower that has been observed in thermo-mechanically processed steels and will be discussed below cannot be accounted for TiN-dissolution or TiN-ripening. The rates of coalescence and dissolution depend critically on the solubility of TiN in austenite.5).9).10). From Fig. For instance.3.8. This implies that in the former case any compositional gradient formed during precipitation of (Ti.3. To illustrate the time scale and the temperature dependence of the changes of the precipitation that may occur in the austenite range we have found it instructive to compute • the time for completion (90%) of the TiN precipitation from an initial state of all Ti and N in solution • the time for TiN dissolution (90%) from an initial state of full equilibrium between TiN and austenite at 1000°C • the time for 50% increase of initial precipitate size by coalescence. that only small shifts in the input data for the thermodynamic analysis might cause a change from full inter- solubility to de-mixing. At 1450°C.80 nm.0 nm equilibrated at 1000°C only shrinks to 4.V)N will be frozen whereas in the latter case there will be time for full equilibration in normal processing.V)-particles. whereas the interdiffusion of Nb in (Ti.N). In the selection of data for the present computations our preference has been to use data that produce reasonable agreement with observed ripening of TiN (3.3.6 show furthermore that coalescence does not produce significant particle coarsening for normal heating temperatures and times except for the finest particle dispersion. expressed as interparticle spacings. In view of the fact that it is interdiffusion that is significant in the present situation it seems that we should give more confidence to the reported results on (Ti.

3. However.6 Time for 50% increase of the initial TiN size by coalescence as a function of temperature. and 7000 nm. Labels at data points indicate changes in particle radius. 1750. . Precipitation starts with all Ti and N in solution.2 Grain growth inhibition and grain coarsening It is a common view that abnormal grain growth is invariably associated with ripening and dissolution of the restraining particles. and 7000nm).01%N steel at given particle spacings (175.01%Ti-0. Fig 3. 175. 3. whereas the dissolution starts in a state corresponding to full equilibrium between austenite and TiN at 1000°C.3). 1750.5 Time for 90% completed precipitation and dissolution of TiN as a function of temperature in a 0. this is normally not the case for Ti- microalloyed steels since the TiN-dispersion is virtually unaltered at temperatures below about 1250oC (3. The initial state corresponds to complete precipitation of TiN for 3 given particle spacings. To give a sound understanding of the grain coarsening behaviour of these steels and all the associated important and often intriguing experimental findings it is necessary to go back to the basics of grain growth and its dependence of impeding particles. 19 Fig.

20

The growth rate for an individual grain of diameter D in a distribution of grain sizes with the
mean size D and containing a dispersion of small particles with volume fraction f and mean
radius r is given by (3.11)

dD 1 1 3f
= ασM ( − ± ) (3.2)
dt D D 8r

where α is a constant (~ 1), σ the grain boundary energy, and M the grain boundary mobility.
3f
Thus the impeding effect of particles enters by the term .
8r

From Eq.(3.2) the following conclusions, essential in abnormal grain growth, can be drawn:

(i) Normal grain growth reaches a limiting grain size
8r
Dlimit = (3.3)
9f

(ii) However, if, in an assembly of grains with mean size D limit, there is one grain larger
than 1.5 D limit it can grow and with increasing speeds as it grows. Hence, a few
individual grains can in this fashion cause abnormal grain coarsening.

(iii) The tendency for abnormal grain growth diminishes with increasing D and increasing
3f/8r. In fact, there is a limiting mean grain size beyond which abnormal grain growth is
totally prevented

abnorm 8r
D limit = (3.4)
3f

Thus, a perfectly stable precipitate dispersion causing a total arrest of normal grain growth is
not a guarantee for grain coarsening by abnormal growth. This is the explanation why we see
grain coarsening temperatures in Ti and Ti-V steels of 1200-1250oC, despite the fact that we
do not observe measurable dissolution or ripening of TiN at these temperatures.

It is tempting to believe that on heating Ti-microalloyed into the austenite range normal grain
growth occurs and the austenite reaches its limiting grain size set by the TiN-dispersion, Eq.
(3.3). However, there is ample evidence from early investigations by Siwecki, Sandberg and
Roberts (3.4) that the ferrite-austenite transformation produces an austenite grain size well
above D limit. In support for this it has been found that the average grain size at the grain
coarsening temperature is about the same in spite of large differences in amounts of TiN (3.4).
A corollary of this conclusion is that the grain coarsening temperature should be a function of
the heating rate through the ferrite-austenite transition. With decreasing heating rate the grain
size of the transformed austenite increases; hence the driving force for abnormal grain growth
decreases, and as a result the grain coarsening temperature is raised. This explanation is
confirmed by experiments the results of which are summarised in Fig. 3.7. If the grain size
instead was controlled by the TiN dispersion, then the grain coarsening temperature should be
independent of heating rate.

21

Fig. 3.7 Effect of heating rate on the grain Fig. 3.8 The relationship between austenite
coarsening temperature (GCT) for a 0,036V- grain coarsening temperature and N-content
0,013Ti-0,011N steel. Encircled numbers for continuously cast slabs (220 mm) and
refer to the size of small austenite grains at small laboratory ingots of 0,01%Ti HSLA
the GCT (3.4). steels(3.2)

Under the very high heating rates in welding the ferrite-austenite transformation should lead
to particularly fine austenite grains and therefore a strong driving force for abnormal grain
growth. Still we know that Ti-microalloyed steels containing a fine dispersion of TiN exhibit
very good HAZ toughness as a result of fine austenite grain structure. This apparent anomaly
is due to the fact that it takes a considerable time for the few growing grains consuming all the
fine grains and thereby causing an abnormal grain size. The short dwell periods at high
temperatures during welding are not long enough for this to occur. On the other hand the
overwhelming majority of the grains will be totally inhibited from coarsening by normal grain
growth since they, although finer than for slower heating rates, are still likely to be larger
thanDlimit for normal grain growth. Hence, the overall result will be a fine austenite structure.
The theoretical explanations given above are therefore also consistent with the observed
refined austenite in the HAZ of weldments in Ti-micoalloyed steels.

Fig. 3.8 summarises measurements of grain coarsening temperatures for steels with varying
Ti/N ratios and cast at different cooling rates (3.2). The larger cooling rates in laboratory
ingots produce a finer precipitation and a particle density increasing with the N content. The
slower cooling in the continuously cast slab produces coarser TiN, and increasingly so with
increasing N content due to the fact that precipitation commences at higher temperatures. The
increasing precipitate density in the former case progressively prevents abnormal grain
growth, and thus causes a rise in GCT. The decreasing TiN density in the slabs, on the other
hand, gives the opposite behaviour.

Again, assuming that normal grain growth up to the limiting size controlled by the TiN
dispersion would determine the average grain size before abnormal growth sets in, we notice
that this would cause problems in explaining the observations in Fig. 3.8. As a matter of fact,
if 1/ D were to be more decisive than 3f/8r in Eq. (3.2) for controlling abnormal growth, then
we should even expect GCT to be lowered with N content for the laboratory ingots as D limit is
reduced with increasing particle density. In a similar way, this line of reasoning would give
increasing GCT for the slab materials.

22

The GCTs in Fig. 3.8 are assigned to both Ti and Ti-V microalloyed steels (3.5,3.12),
indicating that all observations can be understood in terms of the Ti- and N-contents and the
cooling conditions during casting. So for GCT in as cast material, V additions to a Ti-steel
seem to have no or only marginal effect.

It has long been known that GCT of hot rolled Ti-microalloyed steel is lower than in the cast
condition (3.4). It is also found that as the number of reheatings increases as processing
proceeds the grain coarsening resistance deteriorates. This behaviour can readily be
understood by the refinement of the average grain size engendered by multiple reheating, cf.
Eq. (3.2).

However, Roberts et al (3.4) have convincingly shown that the grain refinement during hot
rolling cannot alone explain the observed reductions in GCT for Ti-V steels in hot rolled
condition as compared to cast. They designed experiments carefully to produce TiN
dispersions and austenite grain sizes with only marginal differences, but widely different V-
carbonitride precipitation by adopting varying cooling through the austenite-ferrite
transformation. Fig 3.9 shows the measured GCT for steels processed in this way, covering
cooling rates from 220 mm concast slab to water quenching of 10 mm plate. Thus the
observed reduction in GCT of about 130oC cannot in this case be accounted for by a reduction
in grain size. Roberts et al propose that the occurrence of bimodal precipitate distributions of
V-carbonitrides and (Ti, V)-nitrides and the rapid dissolution of the former on heating causes
sufficient change in the grain size distribution so as to be conducive to abnormal grain
growth. The results of Fig. 3.9 demonstrate also that GCT is further reduced as the difference
in density of the two precipitate dispersions increases.

Fig. 3.9 The effect of cooling rate during previous processing on the grain coarsening
temperature (GCT) of a 0,036V-0,013Ti-0,011N-steel. Encircled numbers are the average
diameters of the ´matrix´ austenite grains at the GCT (3.4).

23

3.3 Effects on recrystallization
One of the most essential features of microalloying additions is their influence on
recrystallization during controlled rolling, either to prevent recrystallization and thereby
producing ‘pancaked’ austenite grains during hot deformation and conditioning the austenite
to form fine ferrite grains during transformation, or to minimise their effect on
recrystallization thereby allowing repeated recrystallization to occur during multiple
deformation and a gradual refinement of austenite and the subsequent ferrite. The first case is
the controlled rolling route for the Nb-bearing structural steels, and the second is the route,
recrystallization controlled rolling, adopted for the Ti-V structural steels (cf chapter 5). The
effect of the microalloying elements on recrystallization differs widely, especially so for V
and Nb, as demonstrated in the classical graph due to Cuddy (3.13), Fig. 3.10; it shows the
recrystallization stop temperature as a function of the microalloy content (atom %), as
dissolved when the hot deformation starts.

The mechanism by which the microalloying elements act to raise the recrystallization stop
temperature has been the subject of much debate throughout the history of microalloyed steels
and numerous investigations have been performed. Mechanisms based either on solute drag
(3.14,3.15,3.16) or particle pinning have been proposed (3.17,3.18,3.19). The view most
commonly upheld today seems to be that strain-induced microalloy carbonitrides formed
during the hot deformation suppress recrystallization during the interpass time. For Nb-steels
convincing evidence has been presented that the pinning force created by the observed Nb-
carbonitride dispersion at the recrystallization stop temperature exceeds that of the driving
force for recrystallization (3.20,3.21).

Still this leaves us without a full explanation as to why the microalloy elements act so
differently, Fig. 3.10. A partial explanation could be gleaned from solubility diagrams, Fig.
2.4 and 2.7, from which we can see that most Nb can be precipitated in the temperature range
1000-800oC (cf Fig 3.10) for a 0.03%Nb steel whereas only a minor part of V can be
precipitated between 900-800oC (cf Fig. 3.10) for a 0.10%V steel. However, it appears that
this alone cannot account for the large difference between the Nb- and V- curves in Fig. 3.10.

Fig. 3.10 The increase in recrystallization- Fig. 3.11 Dependence of ferrite grain size
stop temperature with increase in the level of on the total area of austenite grain
microalloy solutes in 0,07C-0,25Si-1,40Mn boundary per unit volume. Data points are
steel (3.13). for Ti-V and V microalloyed steels. Curves
refer to Nb-microalloyed steels (3.23,3.24).

.25).7.22). In particular. referring again to the solubility diagrams in Fig. 3.5. are open for Nb-carbonitride precipitation during the full deformation cycle. and the cooling rate. However. on the other hand. produced during the austenite-ferrite transformation (3.3. Traditionally this difference has been accounted for by the additional ferrite nucleation that takes place in the deformation bands of heavily deformed austenite. This leaves us. austenite grain boundary area/unit volume (Sv).4 and 2. 3. 3. Deformed. Interestingly though when the same type of experiments are conducted for V. 2. considering the full temperature range for deformation. 24 A detailed interpretation of the figure is more difficult than one might first think. Fig.3. for the V-steels the ferrite grain size is found to be independent of austenite grain shape and processing method.26). for Nb-microalloyed steels it has been shown that for a given Sv the ferrite grain size is smaller when transformed from unrecrystallized.11. very little strain–induced V-carbonitride precipitation can take place. 3.e. the recrystallization stop temperature has been determined by carrying out a multipass deformation in a temperature range of about 50oC above the recrystallization stop temperature.4 Effects on the austenite-ferrite transformation The primary parameters controlling the ferrite grain size produced in the austenite-ferrite transformation are the effective austenite grain boundary area. a full quantitative explanation of the differences in impact on recrystallization is still lacking. because of the complex experiments behind the results. with a situation where. i. equiaxed grains (3. Thus.12 The effect of N on the refinement Fig. unrecrystallized austenite grains transform to ferrite with virtually the same grain size as that produced from equiaxed. The conclusion of this discussion is that the large differences between the microalloy elements in suppressing recrystallization could possibly be explained by the particle pinning model and the varying precipitation characteristics of the different elements. Fig. deformed and flattened austenite grains than from recrystallized.24).13 The effect of V and high N in of ferrite during the austenite-ferrite refining the polygonal ferrite grain size transformation in Ti-V-(Nb)-N steels (3. The Nb-steels. recrystallized austenite.and Ti-V-microalloyed steels no difference is found (3. However.23.

formed by heavy hot working.5. however. e. It is demonstrated that the TiN-particles are extremely resistant to coarsening due to their high stability and therefore low solubility. Nb.3. about 4 µm.3. involving repeated recrystallization during working. V and Nb co-precipitate on TiN formed at higher temperatures. This does not. reduce the stability of the original TiN dispersion on subsequent reheating.25. provided the effective austenite grain boundary area is large enough. An important and interesting feature of Ti-V and V-steels is that additional N above a level of ~ 0. • It appears that the widely different abilities of V. and Ti to retard recrystallization during hot working is associated with the varying solubilities of the carbonitrides of the elements and the resulting temperature ranges where effective microalloy precipitation can occur to affect recrystallization. • It is shown that in heavily hot worked Ti-microalloyed steels abnormal grain growth of austenite can still take place on prolonged heating at temperatures below 1300°C despite the stability of the TiN-dispersion. and partly as a result of more profuse ferrite nucleation along ‘scalloped’ austenite grain boundaries (3. The driving force for this growth is primarily a fine austenite microstructure. even for the finest dispersions. viz.26). 3. • Experiments have provided conclusive evidence that the Recrystallization-Controlled- Rolling route (RCR). This is attained by small controlled contents of Ti and N resulting in a fine effective dispersion of TiN after casting. Practically no coarsening occurs below 1300°C. Due to the mechanism of abnormal grain growth the short heating periods during welding are not sufficient to produce grain coarsening and under these conditions the TiN-dispersion is capable of effectively preventing excessive grain growth.5.g. can produce ferrite grain sizes in Ti-V-steels with virtually the same size as those produced from heavily deformed. An essential result is that the same degree of ferrite grain refinement can be achieved for the V-steels as for the Nb-steels.13 for normalizing. as shown in Fig.003% further refines the ferrite during the austenite-ferrite transformation (3. • Vanadium especially in combination with N refines the ferrite during the austenite/ferrite transformation.5 Summary of chapter • V-microalloyed steels are frequently co-alloyed with Ti to inhibit excessive austenite grain growth both during hot working and welding.12 for recrystallization controlled processing and in Fig. 3.26). This behaviour has been explained partly as a result of interphase precipitation of V-carbonitrides which slows down the austenite-ferrite transformation and thereby gives more time for ferrite nucleation. 3. thereby ensuring a refined microstructure in the finished product. especially for processes where cooling is fast such as continuous slab casting and thin slab casting. 25 As can be seen from the figure the V-steels occupy an intermediate position between the lines for recrystallized and unrecrystallized Nb-steels. . unrecrystallized Nb-microalloyed austenite.3.

In view of the sparse occurrence of the fibrous mode of V(C. Many investigations have shown that for compositions typical of structural steels the general precipitation takes place at lower temperatures. V-carbonitrides are sometimes observed in a fibrous morphology when cooling is slow or on holding at high temperature in the γ/α range. PRECIPITATION IN FERRITE As regards strengthening. that V(C. Both interphase and general precipitation have been observed. especially if the contents of vanadium and nitrogen are high.N) transformation.1). demonstrated in several electron microscopy studies.N). Precipitation of V-carbonitrides can occur randomly in ferrite in the wake of the migrating austenite-ferrite (γ-α) boundary – general precipitation – or by interphase precipitation characterised by the development of sheets of particles parallel to the γ/α-interface formed repeatedly with regular spacing. It is now a well established fact. as discussed in chapter 3. compared to the other microalloying elements vanadium has a higher solubility and therefore remains in solution to a much larger extent during processing in the austenite range.and γ/α-equilibria and producing the necessary lateral redistribution of V from γ into α+V(C. It places furthermore.N). However. or by the formation of alloyed (Ti.N)-particles are also formed in the pearlitic ferrite (4. At equilibrium the circumstances are such that a certain. Because of the lower transformation temperatures of pearlite this type of precipitation is usually finer. Some solute vanadium can be forfeited during controlled rolling as a result of strain-induced V(C. However. The view of the present authors is that this mode of precipitation is a distorted form of eutectoid γ → α + V(C. The typical feature of this mode of precipitation is that the fibres are perpendicular to the γ/α interface. the kinetics of V(C. it may be shown by analysing isothermal sections of the Fe-V-C system that this kind of eutectoid can only form from certain austenite compositions corresponding to relatively low supersaturation. restrictions on the appearance of the phase diagram. typically below 700oC. 26 4. and the interphase precipitation at higher temperatures. small portion of the vanadium in microalloyed steel should precipitate in austenite. Accordingly.N) precipitation in the steels considered here we will not deal with it further in the present paper.V)N particles during casting and reheating of Ti-V-microalloyed steels. the effective V-carbonitrides are those formed in ferrite during the latest passage through the austenite-ferrite transformation. in steels where especially efficient precipitation strengthening is wanted vanadium is the preferred choice.2). .N) formation in austenite are sluggish and for processing at finishing temperatures higher than 1000oC and for normal steel compositions virtually all vanadium will be available for precipitation in ferrite. Furthermore it occurs sparsely and is never a dominant microstructure. By realising that this type of decomposition is driven by a V-gradient ahead of the α/V(C. In particular the (γ+α)/γ equilibrium surface must slope with increasing V-content to give room for this type of eutectoid transformation (4.N)-precipitation.N) interface and parallel to it given by the γ/V(C.

this situation and the narrow region of the high carbon austenite together with the rapidly moving γ/α-boundary will not make austenite the preferred site of nucleation.13%V steels. However. heterogeneous nucleation at the interface will be the energetically favoured site.3). For this type of steel composition it is normally observed in the temperature range 800-700oC. Already from its appearance one can conclude that such a microstructure is formed in sheets parallel to the γ/α-interface by repeated nucleation of particles as the transformation front moves through the austenite.10%C-0. nature chooses the sites where nucleation is energetically most favoured. under normal circumstances the carbon diffusion driven γ/α-transformation takes place under local equilibrium (with respect both to C and V) in the interface. (a) 0. Instead. the interface.N)-precipitation is the same both in the ferrite and in the austenite close to the interface. Hence. (4. 27 4.1 Electron micrographs illustrating the effect of N in 0. By electron microscopy of steels with high alloy contents that stabilise the austenite to room temperature it has been possible to directly observe V(C. Fig. 0.N) in microalloyed 0.1 shows the typical morphology of interphase precipitation of V(C. Also from a very general viewpoint it is to be expected that. The consequence of this is that the chemical driving force for V (C. 4.4).N)-particles in the γ/α-boundary.0095%N. pseudo-para- equilibrium according to Hillert (4. At lower temperatures where the driving force is large we should expect general nucleation in the ferrite matrix to occur. Sometimes it has been argued that the carbon concentration ahead of the moving interface during γ/α-transformation should favour formation of microalloy-carbides in this location. at high temperatures where the chemical driving force for precipitation is low. viz. ahead of it in the austenite or behind it in the ferrite.0082%N (c) 0.1 Interphase precipitation Figure 4.N) precipitates after isothermal transformation at 750°C for 500 s.0257%N (d) 0. Despite its clear relation to the migrating γ/α-interface there has been discussions in the literature whether the interphase precipitation nucleates in the boundary.1).10C-0. However.13V steels on the spacing of the interphase rows and the density of V(C.0051%N (b) 0. firm experimental evidence now exists showing that it actually nucleates in the interface (4. .04%C.

12V-0.4.10C-0.12V-0. Fig. 4. A characteristic feature of interphase precipitation is that it becomes more refined at lower temperatures.N). for typical compositions of V-microalloyed structural steels the interphase precipitation consists of irregularly spaced.10C-0. 4.2 show that the intersheet spacing is affected considerably by the nitrogen content of the steel.12V-0.2 The effect of transformation temperature (a) and N-content (b) on intersheet spacing of V(C. (001) α // (001)V(C.9).6).10C-0. From about 700oC the interphase precipitation is commonly found to be incomplete.10C-0. B5 0. C9 0.7. The discs are parallel to (110) α. (111)γ// (110) α .10%C-0. ~800oC. which has a f.4. (110) α//(100) V(C.4.N) .8. Figs. With decreasing temperatures the incidence of curved rows of precipitates diminishes and the dominant mode is regularly spaced. A14 0.4.5). forms in ferrite as semi-coherent discs with the orientation relationship. structure. A25 0.1. This crystallographic selection is given two alternative explanations (4.12%V steels in Fig.N) in interphase precipitation exhibits a single variant out of the three possibles in the B-N orientation relationship(4.2. A5 0. as confirmed by many investigations (3. We may also notice that the particle spacing is notably shorter within a sheet than between sheets.4). Fig.10C-0. the variant will be .06V-0.0056N.N)-particles.026N.N) . (4. 28 At high transformation temperatures.c.014N. This is demonstrated for the intersheet spacing in 0. and often curved sheets of V(C.N) interphase precipitation. The interparticle spacing within the sheets of precipitation and the precipitate size decreases also with temperature. 4. In cases where the ferrite and the austenite into which it grows are related by the Kurdjumov-Sachs relationship.026%. B25 0.4).0095N.12V- 0. As is evident it is diminished to almost one third at 750oC on increasing the nitrogen content from 0. and random precipitation from supersaturated ferrite after the γ/α-transformation takes over progressively with decreasing temperature. Many electron microscopy studies have shown that V(C.04C-0.0051N. as expected.2. V(C. first established by Baker and Nutting (4.12V-0.c.025N.1 and 4. planar sheets of particles.005 to 0.

6).6).2 The mechanism of interphase precipitation The mechanism of interphase precipitation has been the subject of considerable discussions. it is suggested that the variant is chosen that puts the disc plane as close as possible to the γ/α-boundary.N)-particles in the γ/α- interface. Honeycombe and coworkers were among the first to study interphase precipitation more profoundly (4. Among the models based on diffusion control the solute-depletion model due to Roberts (4. as for incoherent interfaces. at a transformation temperature as high as 820°C.4.10. They even found general precipitation. but has been emphasised in particular by Smith and Dunne (4. The ledges move sideways while the remaining part of the released boundary is stationary and enables repeated particle nucleation to occur. as it appears to the present authors. Hence. At a given point of this growth the interplay is analysed between the nucleation of V(C. viz. Local breakaway leads to formation of mobile ledges. 4. in this mechanism the intersheet spacing will be determined by the ledge height. and especially have been able to put it in an analytical form giving it predictive capacity (4. 29 chosen that makes the close packed planes of all three phases parallel. The observed selectivity is not compatible with nucleation in the austenite or the ferrite. The explanation they offered for this apparent anomaly is that the first-formed ferrite may grow too rapidly for interphase precipitation to occur. and steel composition. confirmed by the occurrence of all three Baker-Nutting crystallographic variants of V(C. V and C. An essential characteristic of the V(C. They suggested that interphase particles form heterogeneously on γ/α-boundaries thereby pinning their migration normal to the boundary. and indeed within the same grain. From this follows one of the main drawbacks with the ledge mechanism. to produce a credible explanation of the observed variation of the intersheet spacing with temperature. the accompanying growth of V-depleted zones around the precipitates. The growth rate of a V-depleted zone is infinitely large directly after nucleation but declines gradually with time .13) considers a ferrite grain growing into austenite where the growth is controlled by carbon diffusion in austenite while maintaining local equilibrium at the interface. Two of us have recently developed the model further. This has been observed in many investigations.11). general precipitation occurs both at low and high temperatures and is commonly formed jointly with interphase precipitation in the same grain. It is hard to see how these parameters should generate a corresponding variation of the ledge height. The models that have been proposed to explain the phenomenon fall broadly into two categories: ledge mechanisms and models based on solute diffusion control. thereby again minimising the free energy. forming a new sheet. We will therefore dwell briefly on this and discuss some of its predictions in relation to experimental observations. The quantitative description of the solute-depletion model due to Lagneborg and Zajac (4. and the continued migration of the γ/α-boundary away from the precipitate sheet.12) is the most prominent and promising one. Not only is there a variation of the different modes of interphase precipitation but. In cases without a specific crystallographic γ/α-relationship. From this we realise that the selection of one variant of the B-N orientation relationship is another confirmation of the nucleation of the interphase particles in the γ/α- boundary. as these authors have found.N) precipitation in these types of steels is the considerable variation of the different modes of precipitation within the same sample. especially N.N). leaving the ferrite supersaturated for general precipitation subsequently (4. This choice will minimise the free energy for nucleus formation.13).

N). particle radius ∝ (time)½ .1) K1 where So is the distance grown by the ferrite at the point analysed. Also. (C γc / α _ C γc∞ )2 S2 = Dγc ⋅t (4. However. but its rate can be considered constant for the short distance corresponding to the intersheet spacing relative to the size of the ferrite grain. The boundary has now returned into material with the original V-content. 30 according to a parabolic growth law of type. K2 and K1 are the proportionality factors in the parabolic growth laws for the V-depleted zone around the precipitate. and nucleation of a sheet of particles will repeat itself.4). also quantitatively. CαV∞ the original V-content in α. Fig. Hence. this gives the condition for calculating the intersheet spacing. . The growth of the ferrite obeys a similar parabolic time-law. (4. Cγc / α the C-content of γ at the γ/α-interphase.3) (C γc / α − Cαc )(C γc∞ − Cαc ) where S is the distance from the point of α-nucleation to the location of the γ/α-interphase at time t.2) C VCN V − CαV / VCN where r is the radius of the depleted sphere at a point with 99% of the original V-content ( CαV∞ ). the γ/α- boundary escapes. Dαv the diffusion coefficient of V in α. The computations shown in Fig. This means that profuse nucleation occurs for lower V-concentrations.N) to N-rich will lead to smaller intersheet spacings. The implication of this is that the moving γ/α-interface will after nucleation initially be in a V- depleted zone. and for ferrite. but will eventually catch up the growing depleted zone.2) and ( 4. and Cαc the C-content of α in equilibrium with γ.3 shows the first predictions made with the model.4.4. and CVCN V the V-content of the V(C. this implies that the growth rate of the γ/α-interphase exceeds that of the V-depleted zone. The agreement with observations of temperature dependence of the intersheet spacing is almost perfect. The noticeably smaller spacings observed for the high-N steel as compared to the low-N steel cannot explicitly be accounted for by the expressions above. and thus we should expect that going from C-rich V(C. Carrying out this quantitative analysis gives the following expression for the intersheet spacing l is = 2So . Eqs.3 also predict that the intersheet spacing around 700oC will fall below the approximate size of observed precipitates. C α/VCN the V- content in α at the α/VCN-interface. that the chemical driving force for VN- precipitation is much larger than for VC. respectively. Physically. Hence.N)-precipitation occurs below about 700oC for steel compositions referred to in (4. Cγc∞ the original C-content of γ. K 2 (4. In excellent agreement with experiments it is predicted that general V(C. agreement of the absolute values is very satisfactory.N)-particle. leaving the ferrite in its wake supersaturated with respect to V(C. we do know.3) below C αv ∞ − CVα / VCN r2 = 2 ⋅ 104 ⋅ Dαv ⋅t (4.

13%V steel as a function of the transformation temperature.10%C-0. 31 Fig. As we can see from the electron micrographs in Fig. that the condition of interphase nucleation will be fulfilled.4.14). Again. estimates indicate that particle spacings below about 50nm will permanently pin the boundary (4. no attention seems to have been paid in the literature to this essential feature of interphase precipitation.N)-precipitation becomes increasingly irregular and sparse for compositions typical of V-microalloyed structural steels.4. For the chemical driving force of the γ/α-reaction at 750oC.6). this can be understood from the model. For a final grain size of 10µm this means that the γ/α-transformation has proceeded to 50%.N) directly behind the moving γ/α-interface and hence general precipitation will occur. Under those circumstances it will be very difficult to perceive the observed microstructure as intersheet precipitation. To this should be added that around 850oC the solubility limit of V(C. Above 800oC the (V(C. The general statement often made. that a large variation of precipitation modes are observed. the model predicts that the spacing is directly proportional to the ferrite growth. Beside this. or to the degree of transformation. It predicts an accelerated increase of the intersheet spacing in this temperature range. Any mechanism for interphase precipitation based on nucleation of particles in the interface must be able to account for the release of the boundary from the dense particle population in the intersheet.4. at 850oC the predicted value for the steel examined in Fig. We suggest that this accounts for the observed reduction of the γ/α-transformation rate in V- steels. At any rate this process will temporarily hold the boundary and consequently slow down the average migration rate. they also show that the spacings vary a great deal and that there are gaps allowing the boundary to bulge locally and then sweep out the rest of it from the particle row. 4. 0. Hence.10%C-0.N)-nucleation to take place and it is only later.4. In the first part of the γ/α-transformation the ferrite will therefore be supersaturated with respect to V(C.3 exceeds 500 nm. when the growth rate has declined sufficiently. However.3 are made with the assumption that the ferrite grain has grown to a size of 5µm (So=5µm).N) is approached for the compositions considered. the model predicts that in the early stages of transformation the ferrite growth will be too rapid for V(C.1 the spacings are in that range. is probably largely a reflection of this specific characteristic of the phenomenon. Smith and Dunne (4. At the same time the spacing within the sheet will also increase.4. The computations of Figs. . however.6) made exactly this statement based on their microscopical observations and without the assistance of a model.3 Experimentally measured and computed intersheet spacings in interphase precipitation of a 0. In fact.10%V (4.

it must be interpreted as resulting from the denser particle nucleation in the high-N material.4. thereby producing an earlier soft impingement of V-denuded zones and so slowing down the . 4. 32 4. 4. general precipitation of V(C.3 General precipitation For compositions typical of V-microalloyed steels. Fig. (4. as has been demonstrated both by thermodynamic analysis (4.5 (4. 4.15.005% that the initial V(C.5 supersaturation with respect to V(C.N) starts to increase its C-content. This larger chemical driving force makes N-rich V(C.N). although that is more difficult to measure quantitatively. These effects must be accounted for by an increased nucleation frequency as a result of the larger chemical driving force for precipitation of nitrogen-rich V(C. Fig. both in ferrite and austenite.N) occurs in a temperature range from about 700oC and below.6.15). This is accompanied by a concurrent increase of precipitate density. The thermodynamic background to this is the much larger chemical driving force for formation of VN. Experimentally it is well established that VN has a considerably lower solubility than VC. as is shown in Fig. We have also already seen that general precipitation may also occur locally above that temperature and have discussed how it should be understood. 0. Fig. and (b) as a function of solution during precipitation in ferrite holding time (4.5 Growth of V(C.4. Instead. It is only when the nitrogen content falls below about 0.4).13).N) the preferred precipitation as long as there is sufficient nitrogen in the matrix.10%C-0. For the temperature and holding times in the experiments of Fig.precipitates after of the variation in the composition of transformation at 650°C (a) as a function of the N- VCxNy with content of N remaining in content of the steel.10%V.4. Therefore the observed difference in precipitate growth between high and low-N steels cannot be explained by differences in coalescence. As already discussed in the previous section this transition from interphase to general precipitation can be predicted excellently by the solute-depletion model (4. A technically very important finding is that the precipitate size diminishes considerably with increasing nitrogen content in the steel.4.N).15) and by experiment (4.4.16) in ferrite as well as in austenite.4).4 Thermodynamic calculations Fig.N) still remains.

7. Fig. where no allowance is made for impingement of solute depleted zones. 33 precipitate growth.6 shows clearly that impingement of denuded zones has taken place long before 500 s ageing in the high N-steel. this issue is complex. 4. 4. despite the fact that there is abundant V to combine with the carbon dissolved in ferrite.N) at 650°C.N)-precipitates during isothermal transformation at 650°C for 500s.4.2). the computation can perfectly account for particle growth in the low-N steel with less dense precipitation. Fig. 4.4. In numerous investigations of V-microalloyed steels it has been shown that the observed precipitation strengthening originates seemingly only from N-rich V(C. no allowance is made for impingement between adjacent particles. The size of the depleted zone corresponding to half the original solute content is double the size of a particle growing without impingement. the growth is less than half of this. and recently it has been shown that under certain conditions . Eq. This reasoning is substantiated by the computed curve for precipitate growth inserted in Fig. However.N) is too small for profuse precipitation to occur and hence no added strength is observed.7 this gives a depleted zone with a diameter of 23 nm after an ageing time of 500 s at 650°C. (4. cf. Evidently.N). whereas it has hardly started in the low N steel. According to the calculations in Fig. whereas in the high-N steel where we do expect effects of impingement. The normal explanation of this behaviour has been that when the first formed N-rich precipitates have consumed practically all nitrogen the chemical driving force for formation of C-rich V(C.7 Computation of V-diffusion controlled growth of V(C. Comparing this with the precipitate densities in the micrographs of Fig.6 Electron micrographs illustrating the effect of N on the density of V(C. Comparison with experimental values at two levels of N.

02%Al (4. enhanced cooling through the γ/α-transformation and afterwards augments the particle hardening.4.9. Figs.4.10%V can bring about a strength increase beyond 250 MPa. This question will be treated in the following section. N and C-contents.4 Effects of precipitation on strength Since normal contents of V in structural steels dissolve in austenite at relatively low temperatures. 34 the C-content in the steel can add significantly to precipitation strengthening. Similarly. Base precipitates. and in special cases even up to 300 MPa.4.4. 1.9 Influence of cooling rate on the (laboratory simulation) on the precipitation strength contribution from V(C. A modest addition of 0.4. 4. Fig.2. However.17).4.17).N) strengthening derived from V(C. this is a rather loose statement and is not an entirely correct description of the phenomenon. viz.4.18.20) the strengthening effects of V have been carefully examined in isothermally heat treated steels of varying V. and therefore can contribute fully to precipitation strengthening when the steel is cooled into the α-range. These graphs show another essential feature of V-steels.095%V-0.19.8 Effect of processing method Fig.N)-precipitates the particle strengthening occurs by the Orowan .12%C-0.9. Base composition as for Fig. A physically more correct account would be as follows.35%Si. composition of steel is: 0. unlike the other microalloying elements. in 1980 (4. that nitrogen in small contents adds significantly to precipitation strengthening. possibly due to the larger solubility and lower chemical driving force for VC. and that the remaining V does not combine with C. N and ageing temperature on precipitation strengthening. The technically very important effect of N on the strengthening of V-steels has sometimes been interpreted such that only VN forms as precipitates. In a number of investigations at the Swedish Institute for Metals Research (3.The results of Fig.10 shows the influence of V. 4. V is usually the preferred element when precipitation strengthening is wanted. This was demonstrated in an early work by Roberts et al.8 show also that normalizing at 950oC does not allow all V to go into solution completely and hence produces only modest strengthening.8 (4.35%Mn-0. 4.N). Fig.4.8 and 4. Fig. 4.17). In the present material with hard non-penetrable V(C.4.

20. When nearly all N has been consumed in precipitation of N-rich V(C.2). and for comparison also N- .N).19. V and transformation Fig.N) the process can follow one of the following lines: (i) in the case of continuous cooling.10 (4. but now of C-rich V(C. below) the driving force may be large enough for continued nucleation. the temperature may have dropped sufficiently for V- diffusion to essentially cease. that is determined by the density of the precipitates.4. In turn.4.N). and there we know that it varies relatively strongly with the N-content. This density is controlled by the nucleation frequency and the number of nuclei it creates until the supersaturation has diminished so that nucleation dies. 4.21) have demonstrated very clearly that the precipitation strengthening of V-steels increases significantly with the C-content of the steels. 35 mechanism – bowing of dislocations between particles – and in that case the decisive parameter is the interparticle spacing in the slip plane. Plots of the observed strengthening ∆Rp against the C-content.1%C-V-N steels after with cementite and austenite.N)-precipitation.21). Hence. Obviously it is only case (iii) that will contribute significantly to further precipitation strengthening.19). (ii) the decomposition continues by co-precipitation of C-rich V(C.4. as shown in Fig. Fig.20). of VN than of VC. the larger driving force will cause a denser precipitation in the high-N steels than in the low-N steels. 4.18. (iii) if the carbon content in solution is sufficiently large (cf.4. To put it simply this is a consequence of the larger stability.12 Solvus lines for C in ferrite temperature on the precipitation calculated using Thermocalc for equilibrium strengthening in 0. respectively isothermal ageing at different temperatures (4. as shown in Fig. and therefore continued precipitation stops (in line with the traditional explanation stated above).N) on previously formed N-rich V(C. Recent investigations (4.2.6 (4. The essential parameter governing the variation in nucleation is the chemical driving force for V(C. whereas cases (i) and (ii) will not. or lower free energy. Electron microscopy has clearly confirmed this.10 Effect of N. for 500 s (3.

.4. γ/α or α/cementite. The reason is presumably that there has always been an uncertainty in the procedure of evaluating the precipitation strengthening as to how the contribution of pearlite should be deduced and deducted from the measured yield strength.10. whereas nitrogen raises it by ~ 6 MPa for every 0. which can flow into the ferrite and maintain its high saturation even if precipitation of V(C.21). The essential point here is that the C-content displaces the pearlite formation to longer times.19.13 (4. (ii) The fact that the total C-content affects the kinetics of the transformation of γ to α and eventually to α + cementite. As a matter of fact all the traditional graphs showing precipitation strengthening vs.11 Deduced values of precipitation strengthening for isothermally transformed V-steels (650°C/500s).12.4.The strong effect of the total carbon content. The austenite phase also acts as a reservoir of carbon. The implication of this is that a larger chemical driving force for V(C.01%C in the steel. That carbon dissolved in ferrite should contribute to precipitation strengthening is. no surprise. (a) as a function of N-content (b) as a function of C-content (4.20).8 and 4.N) is occurring.5MPa for every 0. are given in Figs. These results show that carbon raises ∆Rp by ~ 5. 4.4.11(a) and (b) (4. It should also be recognised that the shift to lower C- content in α and therefore lower driving force as a result of the cementite formation occurs very quickly. Fig.4.N)-precipitation will remain longer and hence promote profuse nucleation.20). as the C-content of ferrite is controlled by either of the phase equilibria.18. The key to the understanding of the influence of the total C-content is as follows.001%N. Figs. 36 content. cf. N-content exhibit a considerable residual strength when the curves are extrapolated to a N- content of 0. of course.4. shown in Fig. is at first sight puzzling.4. This important effect of carbon has not previously been noticed. and furthermore nano-hardness measurements were performed in order to unequivocally demonstrate the precipitation hardening in the ferrite (4. however. (i) The considerable difference in solubility of C in ferrite between the γ/α and α/cementite equilibria below A1. because of the fast diffusion of carbon in α. The solubility at 600oC is 5 times larger in γ/α than α/cementite. This procedure was improved in the present case. less than a second for typical microstructures. Fig.21).

22). this chain of interrelations leads with increasing total carbon content to gradually longer dwell times during which nucleation occurs under the high chemical driving force.14a. 4. In view of the observed profuse nucleation in the high-N steels.4.12%V-0.7. i. and k and T have their usual meanings. Fig. Vm the molar volume of V(C.N) surface energy. Fig.2.14 Electron micrographs showing V(C.10C-0.4.4) 3kT∆ G 2m where N& is the rate of nucleation. (b) 0.10% C and (c) 0. 16 σ 3 ⋅ V 2m N ∝ exp (− ) (4. According to classical nucleation theory the decisive factor controlling the nucleation frequency is .013%N steels with different C-contents (4. close to the values suggested values for Nb(C.4. σ the α/V(C.N)-precipitation as the C-content is raised. and therefore we should in this case use the driving force for the low C-content in ferrite according to the α/cementite equilibrium. we do expect denser V(C. and the consequent early completion of precipitation – soft impingement has occurred before 100s at 650oC. b and c (4. cf.22% C.20). before pearlite formation sets in − it seems likely that the particle density in these steels will be controlled by the driving force for high-C-content in ferrite corresponding to γ/α-equilibrium.325J/m2 . ∆Gm the molar free energy for formation of V(C.6. Fig. Consequently. Let us consider the observed precipitation strengthening of the 0.20). (a) 0.N)-α interphase energy of 0. By adopting a value for the V(C. Similarly.10 produced by isothermal ageing at 650°C for 500 s and compare with computed precipitate densities by using the chemical driving forces of Fig.e. 37 Hence.4) will be proportional to the final particle density.N) (4.10.N).4.12V steel in Fig. We will simplify and assume that the initial nucleation rate according to Eq (4.10C-0.N) from α of a given composition. we can compute relative values of the planar interparticle spacing for the two extreme N-contents for the 0.N) precipitation after isothermal transformation at 650°C in 0. the relatively sparse particle density in the low N steels suggests that most nucleation takes place after pearlite has formed.04% C.12V . Integration of this expression over the precipitation period with the variable driving force as the supersaturation declines gives the density of precipitates (numbers of particles per unit volume). This is very clearly demonstrated by the electron micrographs of Figs. As a matter of fact this line of reasoning can be carried steps further and be shown to account for the observed precipitation strengthening in quantitative terms.

This is evident from Fig.4.that the reduction of effective N and V due to formation of (Ti. 0. corresponding to temperatures between A3 and A1 and slow cooling.4. 4. But clearly in qualitative terms. This computed value is virtually a perfect match with the observed strengthening of 71% (Fig. Fig.22C-0. • At low supersaturations for V-carbonitride precipitation. It is known that the precipitation strengthening of Ti-V steels is notably smaller than for V- steels with the same V-content. It is possible that the remaining part can be explained by the faster γ/α-transformation and hence earlier pearlite formation in the Ti-V steel as compared to the V steel (4.10 transformed at 650°C (4.V)N in the austenite cannot alone account for the substantial difference in strengthening between the 0. ageing at 650°C). 4.21).12V-Ti and 0. 38 steel and from that a strength increase of 70%.19). Fig. A quantitative comparison between the precipitation strengthening of 0.12V.12V steels in Fig.22%C steels in Fig.19).10%C and 0. nature takes advantage of easier nucleation in . the longer time for profuse nucleation in the 0.15 Deduced values of precipitation isothermal transformation at 650°C for V-N strengthening in steels isothermally steels with C-contents varying between 0.22% (4.5 Summary of chapter • Precipitation strengthening in microalloyed steels benefits from the γ/α-transformation because the chemical driving force for precipitation of microalloy carbonitrides increases suddenly and strongly as γ is transformed to α .15.4. and 0.13 Pearlite start time during Fig.10C-0. V-microalloyed steels are particularly suited for generating large precipitation strengthening because of their ability to dissolve large quantities of V-carbonitrides at relatively modest temperatures in the γ-range due to the larger solubility as compared to other microalloy carbonitrides. This again creates conditions for a high driving force and therefore dense precipitation.4.13.4.22%C steel will give rise to a much larger strengthening.22C-0. 4.10.19).15 (4. It is readily shown - along the same lines as above . cf.11 is considerably more complicated since the large difference in duration of high C-content in ferrite before pearlite formation must then be accounted for.also reflected in the widely different solubilities in the two phases – and thereby gives rise to profuse precipitation in the ferrite.

010%N typical of EAF steels precipitation strengthening up to 250MPa. It is only until almost all N has been consumed that the C-content of the carbonitride rises. so called interphase precipitation. • A model for interphase precipitation with predictive capacity is presented. should be maximised. The growth rate of the depleted zone is initially high but declines. in the former case the ferrite C-content is 5 times larger than in the latter at 600°C.N). • In steels with hard and for dislocations non-penetrable particles such as V(C. • V(C. the γ/α-interface catches up and enters material with the original V-content. 39 interfaces and carbonitrides are formed repeatedly in the moving γ/α-boundary .N)-nucleation. It considers the growth of the V-depleted zone around a V(C.particle and the simultaneous motion of the γ/α-boundary in which it was nucleated.N) the one microstructural parameter determining the precipitation strengthening is the interparticle spacing. It is unambiguously shown that the lower growth rate of V(C.01% C as compared to ~6MPa per 0. so is general precipitation commonly also found at high temperatures jointly with interphase precipitation.N)-nucleation to occur. Enhanced cooling through the γ/α-transformation and in the ferrite range causes significant further increases in strength. which determines the density of the precipitate population.10% engenders in steels with 0. For compositions typical of microalloyed structural steels general precipitation takes place below about 700°C and interphase precipitation at higher temperatures. On lowering the temperature the interface will gain speed relative to the rate of precipitation. cf. • Recent studies have demonstrated that the precipitation strengthening in V-microalloyed steels increases significantly with the total C-content of the steel. and nucleation of V(C.rather than the α/cementite-equilibrium. The model exhibits excellent agreement with observed values of intersheet spacing. .001% N.N) in high N-steels. This originates from the fact that the chemical driving force for this reaction increases as more N is dissolved in ferrite and therefore increases the nucleation rate. resulting in a smaller particle size. • It has been shown that the first V(C. particularly at high N- contents. Therefore to obtain the largest possible strengthening the nucleation rate of V(C. its temperature dependence and the transition from interphase to general precipitation. ∆Rp ~5. The strong effect of N in precipitation strengthening of V-microalloyed steels is due to its ability to enhance V(C. this implies that there must be sufficient C in solution and chemical driving force for fresh V(C.N). a V-content of 0.5MPa per 0. • Experiments show clearly that the V(C. previous paragraph. However.N) beyond this point. there is a considerable variation of the different modes of precipitation. To benefit from continued precipitation strengthening of C-rich V(C.N)-precipitation becomes denser and the particles finer with increasing N-content.N) to be formed is N-rich. It is demonstrated that such a situation is at hand when the ferrite C-content is controlled by the γ/α.N)-precipitation generates considerable strengthening at moderate additions of V. implying that the boundary escapes the precipitates leaving supersaturated ferrite in its wake for subsequent general precipitation to occur behind the migrating γ/α-boundary.N) will repeat itself. an effect previously not recognised. This is explained by the fact that the C-content of the steel delays the pearlite formation and thereby maintains the higher content of C dissolved in ferrite corresponding to the γ/α- equilibrium for a longer time. is caused by an earlier depletion of V in the surrounding ferrite due to the larger density of precipitates.

40 5. In order to obtain optimum ferrite refinement. controlled rolling and accelerated cooling and 3) recrystallization controlled rolling or controlled rolling with air-cooling.13). TMCP 5. PRINCIPLES AND PRACTICE OF THERMO-MECHANICAL CONTROLLED PROCESSING. 5.1 General principles of recrystallization-controlled rolling. when the finish rolling temperature is relatively high (see Fig. This procedure is intrinsically more economical than controlled rolling at low finish rolling temperatures (lower than the recrystallization stop temperature. Fig. The improvement in properties of plates.1-5.1 Thermo-Mechanical Controlled Processes.9). processing Good combination of strength.1). 1) Recrystallization controlled rolling and accelerated cooling 2). RST) and also lends itself well for use in mills which are not sufficiently strong for low temperature controlled rolling practice and for rolling of long products with high inherent finishing temperature. . it is necessary to maximise the area of austenite grain boundary per unit volume at the on-set of phase transformation (5. 5. This may be achieved either by low temperature controlled rolling (CR) or by recrystallization controlled rolling (RCR). and controlled rolling. The aim of recrystallization controlled rolling (RCR) is to make use of grain refinement by repeated recrystallization of austenite. The fine austenite structure is retained during inter-pass delays and during cooling down to Ar3 by a suitable dispersion of second phase particles that together with accelerated cooling (ACC) lead subsequently to a minimisation of the ferrite grain size after transformation. CR. fracture toughness and weldability of V-microalloyed HSLA steels in the as hot rolled condition can be obtained by careful choice of thermo-mechanical controlled processes (TMCP) (5. 5. The concept of RCR is attractive in that it is a relatively uncomplicated and high productivity process and can be applied on conventional mills. strips and forgings is associated with different strengthening mechanisms of which the most important is grain refinement whereby both strength and toughness are improved at the same time. long products. RCR.8.

While precipitation strengthening of Nb(C. .N) precipitation in austenite is usually rather slow unless the finish rolling temperature is below 850oC (controlled rolling). Steel chemistry.N) or V(C. the yield stress and tensile strength decrease because lower reheating temperature reduces the amount of dissolved vanadium (or niobium) in the austenite and accordingly the potential for precipitation hardening after cooling. 41 In very many commercial HSLA steels processing is controlled in such a way as to ensure that precipitation occurs during or after thermo-mechanical treatment. Proper processing of microalloyed HSLA steel should aim to combine the maximum grain refinement with an effective utilisation of the strengthening potential of the microadditions. . The key to success with TMCP-processing is to define rolling schedules combining a maximum degree of microstructural refinement with acceptably low rolling loads. Reheating temperature (Treh). Thus. V. both for enhancing strength through precipitation hardening and for providing stable particles to inhibit grain growth in austenite.2 Mechanical properties and microstructure of TMCP material The mechanical properties and the final microstructure of V-(Ti-Nb)-microalloyed steels are dependent on the following process parameters: . computer models for calculation of microstructure development and precipitate evolution during hot rolling (5. The precipitated particles play an important role in control of structure and final properties of microalloyed steels. This is mainly attributed to the more profuse fine precipitation remaining after low temperature reheating which more effectively resists grain growth of austenite. A low slab reheating temperature gives finer austenite grains. The slab reheating temperature has a strong influence on the strength.14-5. Ti and/or Nb are essential for successful TMCP processing. 5. . and thereby the potential hardening contribution is considerable. the amount of vanadium available for precipitation in ferrite. on transformation from hot worked austenite.17) are invaluable for design of rolling schedules. Accelerated controlled cooling after hot rolling alters the microstructure of plate from ferrite- pearlite to fine-grained ferrite-bainite and consequently increases the strength without a loss in low temperature toughness. toughness and microstructure of microalloyed steel in the as thermo-mechanical controlled processed condition. V(C.N) is also enhanced by accelerated cooling. Cooling parameters: accelerated cooling rate (ACC) and finish accelerated cooling temperature (FACT).5). However. . good shape control and high productivity. Rolling schedules: reduction (Red) and finish rolling temperature (FRT). For Ti-V-N microalloyed steels it was found that a reduction in reheating temperature from 1250o to 1100oC reduced the yield stress by about 40MPa while at the same time decreasing the ductile-brittle transition temperature by about 15oC (5. refines the final microstructure of the materials and as a consequence improves the low temperature toughness for steels processed in a similar manner. the deleterious effect of this on impact toughness is counteracted by improved grain refinement. In this context.

steels changes the dependence of yield strength on FACT.4. Effects of the finish rolling temperature on the microstructure and mechanical properties for various microalloyed steels are summarised in Fig. It is apparent from the figure that the final microstructure and mechanical properties are greatly influenced by cooling rate. yield strength and toughness of Ti-V-(Nb)-N-steels after RCR are illustrated in Fig. 5.3. conventional CR practice).09V microalloyed steel.1. The effect of cooling rate and finish cooling temperature on the final microstructure.e.8.2 shows that the very best combinations of low temperature toughness and tensile strength are obtained in Ti-V-(Nb)-N steels for finish rolling temperatures close to Ar3 (i.2 using data from various sources (5. The appearance of bainite in the structure of Ti-V-N and Ti-V-Nb. On-line accelerated cooling (ACC) processes after hot rolling. Yield strength. The highest yield stress was observed in the 0. 5. 5.18) for V. However. 5. 5. At very high cooling rates (15oC/s) the austenite transforms to a ferrite / bainite microstructure. impact toughness and ferrite grain size of Ti-V-(Nb)-N steel (5. RCR processed followed by ACC to room temperature as shown in Fig. from recrystallized or non- recrystallized austenite are very important because the ACC rate and the finish ACC temperature have a strong influence on the final microstructure and mechanical properties. although the variation of strength with cooling rate is smaller at higher rates than lower (<7oC/s). affecting strength and toughness.2 Effect of finish rolling temperature (FRT) on the strength. . Rolling schedules. The final ferrite grain size depends only weakly on the finish accelerated cooling temperature (FACT) in the range of 400-600oC although the second phase consists of bainite when FACT is below 500oC.9).3. These observations are in good agreement with the results reported by Chilton and Roberts (5. depends on the finish accelerated cooling temperature and increases with decreasing FACT down to 500oC or even lower. (without Ti). an almost equally good combination of strength and toughness is obtained for a FRT of 950oC by recrystallization controlled rolling. The yield stress of Ti-V-(Nb)-N-steels rises as the cooling rate increases. Fig. 42 Fig.9). on the other hand. the finish-rolling temperature and deformation in the final pass are important TMCP-parameters. 5. 5. 5.N steels that FRT has little marked effect on the mechanical properties.

N) and at low FACTs the increasing volume fraction of bainite in the microstructure.5).Nb) (C. Cooling rate is a principal factor influencing the size distribution of precipitates. 5. 43 Fig. Final reduction was 25%. Impact transition temperatures of RCR+ACC material increase. restricted to a maximum 10-12oC/s and the finish accelerated cooling temperature should not be lower than 500oC if the formation of martensite or bainite is to be avoided.3 Effect of cooling rate from finish-rolling temperature of 1030oC to finish-cooling temperature (FCT) on the ferrite grain size. This is a result of the precipitation strengthening of V(C. direct quenching (DQ) and tempering (T) processes can also be utilised in the production of heavy plates of high strength steels. yield stress and toughness of Ti-V-(Nb)-N steels. as the cooling rate becomes higher despite the fact that the ferrite grain size decreases. A greater proportion of smaller particles and reduced particle spacing have been observed when the cooling rate was increased (5. The cooling rate subsequent to RCR (during γàα transformation) should be. However. so producing more efficient precipitation strengthening.N) or (V. . in principle.

Moreover.5. Siwecki et al. Finish rolling temperature and cooling start temperature or delay time prior to quenching may be quite important parameters with respect to control of the final austenite grain size and toughness. Heavy plate (40mm thick). The reason for this. 5. 5.12). the process conditions of final rolling temperature do not strongly affect the yield stress. notch toughness and weldability was reported during the 1960s by Melloy (5.4 Effect of cooling rate from FRT or reheating temperature (920°C) to RT as well as tempering at 680°C on the yield strength of V-Mo-B steel (FRT=920°C and 970°C. The optimum combination of strength and toughness properties of steels microalloyed with V-Mo-B are obtained for the direct quench and tempering process with a finish rolling temperature (FRT) at about the recrystallization stop temperature (~940oC) followed by quenching with the highest practical rate (~30oC/s) and then tempering at 680oC.5(b).4). As shown in this figure. the influence of these parameters on yield stress and hardness is weaker than that of cooling rate (see Fig. RQ denotes off-line quenching. thin plate (10mm) or 10mm bar of V-steel can be processed by controlled rolling or RCR with attractive strength properties only weakly dependent on FRT.19). which controls the transformation during quenching (5.12). the direct quench and tempered steel has almost equally good mechanical properties (strength and toughness) as those achievable by conventional off-line quenching and tempering (RQ+T). However. as can be deduced from Fig.3 Effect of nitrogen content The positive effect of higher nitrogen content in V-microalloyed steel on the yield strength. respectively) with total reduction ~50% (5. However.5). 44 It has been shown that a sufficiently high cooling rate is the most important factor of the DQ process. Fig. the cooling rate is an important parameter affecting yield stress and microstructure.1) have also shown that nitrogen in V-microalloyed steel is conducive to improved grain refinement and raised yield stress (see Fig. 5. (5. 5. is that higher temperature RCR rolling provides a .

For one thing. 5.24oC/s). Material with higher N content is significantly stronger than that with low N processed in the same manner. 4. 15 mm plate (0.09V steel with 0. but that low temperature CR processing gives a finer grained structure although with less precipitation strengthening and these two effects almost cancel one another.6.01Ti-0. However. . Fig.003N) the yield stress after low temperature CR was found to be almost identical with that following RCR+ACC processing since almost no precipitation of VN in austenite could take place.88oC/s) or 10 mm bar (5oC/s)) Nitrogen's effect in connection with recrystallization controlled rolling and accelerated cooling is demonstrated in Fig. in particular for slow cooling rates. 5. for V-N steels are presented in Fig.9oC/s) on the precipitation strengthening contribution to yield strength. for higher N steel (0.1). with Ti-microalloyed steels the effectiveness of nitrogen in the low temperature controlled rolled condition is much smaller than in the RCR and ACC condition. (Cooling rates during simulations correspond to natural air cooling of 40mm thick plate (0.5 Dependence of yield stress (a) and precipitation strengthening (b) on nitrogen level in 0.12C and 1.08V-0. ferrite grain sizes of low nitrogen steel are significantly larger than those of the higher N steel.5. although with some sacrifice of toughness.1). (5.013%N) the yield stress was ~50MPa less after the CR treatment.35Mn content for the various processing methods and cooling rate (5. 45 higher precipitation strengthening effect. For low N steel (0. It may be seen that the strengthening potential of vanadium can be utilised effectively only at higher levels of nitrogen and that increased cooling rate has a profound effect especially at these higher levels. Some results illustrating the effect of processing method by recrystallization hot rolling. ∆Rp.8). controlled rolling and normalising (the processes were followed by air cooling at 0.8 (5. 5. In particular. which is attributed to the loss of precipitation hardening effect due to premature formation of coarse VN particles in austenite.

01Ti-0.5 - .4 - RCR+ACC 1250 1050 10 3 min. toughness and ferrite grain size for various microalloyed steels are shown in Fig. This difference in ∆Rp can be reconciled with the loss of precipitation hardening potential when deformation-induced precipitation of V(C. The 0. long product and strip processing using TMCP practices obtained at high (RCR) and low (CR) finish rolling temperature practice with and without application of accelerated cooling are discussed below. Table 1. 5.8).4 Application of TMCP practice Results of full scale industrial plate. Fig.8. These were also CR processed with a low finish rolling temperature (800oC) such that the austenite was in a substantially deformed condition prior to transformation.6. For normalised material.5 also demonstrates that ∆Rp is lower after processing by CR with FRT=800oC than after RCR with FRT=950oC. the precipitation hardening contribution to yield stress saturates at high nitrogen levels because of the increasing amount of V(C. 5. Treh FRT No of Time Thickness Cooling rate FCT Process o ( C) (oC) passes (min) (mm) (oC/s) (oC) RCR 1250 1050 10 3 min. Table 1 summarises the important parameters relevant to their processing. and Ti-V-Nb- microalloyed steels were studied as a function of the finish rolling temperature.08V steels described in the previous section have also been rolled to 15-25 mm plates on a commercial mill at SSAB Oxelösund. plate thickness and cooling parameters.Process parameters for full-scale production.4. N) accompanies rolling at low finishing temperatures. The influence of these parameters on the yield strength. The effect of nitrogen. N) remaining undissolved at the normalising temperature. 5. vanadium (niobium) and cooling rate on the yield stress and impact toughness of Ti-V-(Nb)-N-steels after recrystallization controlled rolling (5. 46 660 LOWER YIELD STRENGTH (N/mm2) Reheated to 1200°C 640 V–Nb–N V–Nb–Ti 620 V–Nb V–N V–N–Nb–Ti 600 580 560 540 520 500 20 30 40 50 60 70 80 90 SLAB THICKNESS (mm) Fig.1 Heavy plate rolling Changes in the mechanical properties and the microstructure of Ti-V. 5. The steels were rolled using RCR practice with and without application of ACC. 20 0.7 and 5. 25 7 600 CR 1250 800 13 8 min. 5. 25 0. ∆Rp increases linearly with nitrogen content. however. For RCR steels.

015Ti-0.7. FRT=950°C.0.10) reported that good mechanical properties of Ti microalloyed steels were obtained.08V-steel are summarised in Fig. As shown in Fig. .3Si . The mechanical properties of 12 mm thick plate (manufactured at POHANG (5. processed by RCR followed by ACC with the following parameters: Treh=1250°C. Fig. Bodnar et al (5.8. Strength and toughness depend not only on FRT but also on the plate thickness and cooling rate. ACC=5°/s and FACT=550°C. 5. The best toughness was obtained for 30mm thick beam. Tamminen (5.20) have also reported an increase of strength with decreasing thickness of RCR rolled beams (44 mm -> 15 mm) of V-steel.013N steel plates produced by different full scale processing routes (5.5Mn . despite the finer grain size of the CR plates these have slightly lower strength than the RCR+ACC ones as a result of premature precipitation of VN in austenite during the final low temperature CR-rolling passes.7) on a 0.8 demonstrate that the yield strength of CR-processed steels increases with decreasing the FRT from 840oC to ~730oC.08V-steel with a base composition: 0. 5. (5.5) have been obtained by Lee et al. Very similar results to these reported by Zajac et al (5.01Ti-0. Changes in the mechanical properties of heavy plates of Ti-V and Ti-V-Nb steels processed by low temperature controlled rolling have also been studied. whereas the toughness decreases at the same time. the strength increases with decreasing plate thickness. 5. Rm=490 MPa and E-40°C=300 J.08V-0. The results in Fig.01Ti-0. were Re=~360 MPa.1.7)). 47 Mechanical properties of the as hot rolled plates of 0. flatness as well as residual stress levels of these plates was better than those produced by CR practice.7 The mechanical properties of the commercially processed 0. Moreover.005N.0.5). 5. Toughness is in all cases excellent (ITT40J <-80oC) but best for the CR treatment because of the very fine ferrite grain size and smaller precipitation hardening contribution. RCR + ACC was applied by Rautaruukki Oy for heavy plate production. The finest grain structure is obtained from the CR route and this should be capable of some further refinement with application of accelerated cooling. whereas for both lower and higher beam thicknesses deterioration in toughness were observed. However.09C .

Fig. N-steel (5.9.8). 48 Fig.11). 5.01Ti-0.9 Comparison of observed rolling Fig. and V microalloyed steels on the strength vs.01Ti-0.04V (HS-350) and 0. . toughness of specimens processed in a similar manner (5. 5. The longer time necessary for CR is mainly due to the delay for cooling from 1100°C to 920°C at the 40mm gauge but partly also due to the greater number of finishing passes.10 Effect of carbon content in the Ti-V loads during RCR and CR rolling of Ti-V. 5. 5.085V-0. For these reasons. RCR processing offers intrinsically higher productivity than does CR for a given plate product while at the same time making more efficient use of the microalloying additions for precipitation strengthening.04Nb (W-500) steels as a function of: (a)- FRT and (b)-plate thickness (5. The measured rolling loads for the two types of processing when rolling identical plates are compared in Fig.8 Mechanical properties and ferrite grain size of the commercially CR-processed 0.9). It is evident that the maximum loads are ~ 25% higher for the CR process due to the lower temperatures and the accumulated deformation below the recrystallization stop temperature. Important advantages of the RCR process are its high productivity and lower mill loading as compared to CR.

of the former steels.4.9.10 shows a plot of impact transition temperature against yield strength for the long product steels and comparably treated plate steels (FRT=1000-1050oC. The difference between chemistry of the steels which are intended for long products and plate steels lies in the higher carbon contents.5 – 6. ~>0.4. ACC=8oC/s and FCT=500-550oC). (5.21) claimed to have achieved RCR conditions in hot rolled strip of Ti-V microalloyed steel using with FRT of 930oC followed by laminar cooling. the RCR processing route together with appropriate micro- alloying should lend itself well for obtaining improved mechanical properties (5. whereas nitrogen content shows a very strong effect on yield stress due to precipitation strengthening (see Fig. 5. This suppression of the γ → α transformation temperature leads to a refinement of the final structure by decreasing the growth rate of the ferrite grains.2% C. Water cooling for obtaining high strength steel following hot rolling was first introduced on strip mills about 35 years ago. for 8-10mm thick strips.22). 49 5. .2 Long products Carbon content and alloying elements such as Mn and Ni stabilise the austenite and lower the Ar3-temperature.3.0 mm strips with hot rolling finishing at 900oC and coiling at a temperature of ~600oC (5.11) and some further ferrite grain refinement (Fig. Since the processing of strip necessitates relatively low finishing temperatures (usually ≤900oC). A yield strength of 550 MPa was achieved. along with a 35J transition temperature at –40oC . A maximum refinement of ferrite microstructure was achieved by increase of cooling rate after hot rolling.13). 5.08%C) of the former steels. 5. High cooling rate suppresses the γ→α transformation start temperature and increases the rate of ferrite nucleation. Kovac et al.3 Strip rolling The principal difference between the steels which are intended for strip and plate steels lies in the usually lower carbon contents (≤0.12). The results of microstructure and strength properties of V-Nb-N strip steels processed via direct charging of thin slab (50mm) showed that a yield strength of ~600MPa and elongation of 24% were obtained for 3. the CR processing route together with appropriate microalloying should lend itself well for obtaining improved mechanical properties. Improvement in toughness of long products while maintaining or enhancing the strength level remains an important area for further research and development. The rolling parameters and the thickness of strips are important for refinement of austenite contributing to ferrite grain size strengthening. The impact transition temperature is seen to be strongly dependent on the carbon content of the steel. The amount of pearlite is greater and they show a stronger tendency to develop bainitic or other acicular microstructures. Figure 5. Since processing of sections and other long products necessitates relatively high finishing temperatures.

This can be explained in the following way. 5. and as a result reduces the potential for V(C. The reduced strength in Ti containing steels is similarly in part due to the . N addition to a V-Nb steel has little influence on the precipitation strengthening. N) precipitation strengthening in ferrite. In nitrogen-alloyed steel. The effect of slab thickness on the mechanical properties of strips has also been studied. 660 LOWER YIELD STRENGTH (N/mm2) Reheated to 1200°C 640 V–Nb–N V–Nb–Ti 620 V–Nb V–N V–N–Nb–Ti 600 580 560 540 520 500 20 30 40 50 60 70 80 90 SLAB THICKNESS (mm) Fig. It was found that a higher reheating temperature of 1200oC produced the highest strengths with FRT ~850oC followed by cooling at ~18oC/s and coiling at ~600oC. Crowther (5.23). slab thickness for a number of microalloyed steel combinations (Ti-V-Nb-N) are shown in Fig.s.11 Strengthening effect of (a) ferrite grain size and (b) nitrogen content to the yield stress of the commercially processed HSLA strip steels microalloyed with V and Nb. The results also show that Nb addition to a V-N steel and similarly.12 Effect of steel chemistry and slab thickness on lower yield strength (5. This not only removes nitrogen but also tends to co-precipitate some of the V present. the Ti-free steels exceed comfortably a yield strength of 550MPa for the studied slab thickness although the Ti containing steels failed to meet this strength level in some cases. Little additional effect of Nb on strength is therefore seen. Results of the yield strength v. N) formation during rolling in the lower austenite temperature range. Nb will tend to remove N by Nb(C.12. With increasing slab thickness some reductions in grain size and precipitation strengthening were observed which tended to decrease the yield stress but contributed to improved Charpy toughness. As can be seen.23) has reported the results of a study on high strength V-microalloyed strip steels produced by thin slab casting. 5. 50 Fig. 5.

fp=0.50% C) ferrite-pearlite steels (5. N) which also reduce the potential for precipitation strengthening in ferrite.2Mn-0.24-5.26). the steel chemistry and the cooling following forging are the only parameters available in practice.and N-additions for precipitation strengthening of these steels is clearly demonstrated in Fig. All data have been normalized to 0.4 Forging In forging the reheating temperature.40-0. The effect of V. According to these results 5 parts per weight of N are equivalent to one part of V. V)(C. 5. The temperature dependence of the solubility of V-carbonitrides makes dissolution possible at convenient temperatures and thereby gives potential for a considerable precipitation strengthening.3Si. High strength ferrite-pearlite V-microalloyed steels have aroused considerable interest over the last decades. N) or (Ti. hence completely escaping the elaborate heat treatments of Q-T steels. such as (Ti.10V steel by 120 MPa (5. 5. . range of forging temperature. often with complex geometries. Fig. when attempting to attain adequate mechanical properties of the component directly after forging we are restricted to much fewer processing variables as compared to rolling.26).13 (5. In fact.25). All steels contain 0. Consequently.13 Effect of precipitation strengthening by V and N on Rm. 51 presence of the large Ti-rich particles. Nb)(C. Microalloying with V is an efficient method of strengthening medium-carbon (0. From electron microscopy it has long been known that this occurs by fine N-rich V-carbonitrides in the polygonal ferrite as well as in the ferrite-lamellae of pearlite. Strength properties equivalent to those of quenched and tempered (Q-T) steels can be reached by adopting controlled air or forced air cooling.24. 5.4. raising the cooling rate from 1°C/s to 4° C/s increases the tensile strength of a 0.7%Mn and were austenized at 1200-1250°C (5. and reductions are largely governed by the material flow necessary to reach the final shape of components.26).8 and a section size of 20mm Φ. V-microalloying is therefore commonly preferred to other microalloying additions in these types of steels.4C-1. 5. Enhanced cooling is an efficient method to increase precipitation strengthening.

which have been processed by recrystallization controlled rolling in one of the mini-mills of NUCOR Steel. to expand the use of these steels improvement of their toughness is vital.01Ti-V-Nb steels having different levels of vanadium. as long as the rolling schedule involves more than 3 . 5. are influenced strongly by: strain. As evident from Fig.5 Microstructure development during TMCP rolling Knowledge of the microstructure development in association with hot rolling is very important for optimising rolling schedules with the aim of improving properties of TMCP steels. where the normal growth rate of spherical` grains with radius R is dependent on average grain size. it has been possible to double the Charpy impact toughness of the standard V-microalloyed steel while maintaining the level of strength (5. 5. 0.08V-0. The static recrystallization kinetics.15). Hence. For the lower alloyed steel. Fig. temperature and pre-existing grain size as well as steel chemistry. The model is based on the concept that the resulting structure is dependent on the static recrystallization.01Ti-V-N steels and 55µm for the Ti-V-Nb steel. starting from 1100°C.04V-0. 52 Although other properties are equivalent to those of Q-T steels the toughness of the microalloyed ferrite-pearlite steels is clearly not. 5.16). .01Ti. The data refer to rolling of 25 mm plate in 11 passes. This refines the final ferrite-pearlite microstructure and thereby increases toughness. By combining this method with a reduction of the C-content and an increase of the Mn-content to dilute the pearlite with respect to cementite.01Ti-V-N and 0. the inhibition caused by second phase particles (Zener parameter).14-5. A general observation is that the grain size existing after thin slab casting or slab reheating has almost no effect on the final austenite grain size resulting from recrystallization rolling.14 the steel with high vanadium and nitrogen is characterised by the most effective microstructural refinement. niobium and nitrogen.25.018N or similar HSLA steels (5.4 passes. The optimisation of rolling schedules for TMCP-processing by recrystallization hot rolling requires detailed knowledge pertaining to the coupling between rolling schedules (reduction. The initial grain sizes after reheating were taken to be 20 µm for both 0. After large reductions.17). the effect of abnormal grain coarsening is demonstrated by using an initial grain size of 500 µm.01N-0. when subjected to the same rolling schedule (5. Grain growth of austenite following static recrystallization is described in accordance with Hillert´s theory. 5. and recrystallized austenite grain size. The microstructure evolution routine has also been used to compute austenite microstructure development during strip rolling of 0. With intelligent design of the rolling schedules it is possible to obtain a very fine and uniform austenite microstructure. strain rate. The computer model MICDEL developed at the Swedish Institute for Metals Research has been extended to many different steel compositions and permits comparison to be made of the effect of various material parameters (5. temperature and pause time) and development of microstructure.14 shows examples of predicted microstructure evolution during realistic full scale hot rolling of 0. By microalloying with Ti or alternatively raising the Al-content somewhat above normal levels and with close control of N it is possible to reduce the austenite grain size to below 50 µm. recrystallization takes place via copious nucleation of new grains and refinement of the structure can be achieved. static recovery and grain growth of austenite. the specific grain boundary energy and mobility of the grain boundary. A computer model for calculation of microstructure evolution during hot rolling is therefore extremely useful for optimising rolling schedules.26).

53 The nucleation of recrystallization decreases strongly as the level of strain is reduced.27). The surface in rolling of plates (5. 5.14 Development of austenite Fig.27) shows that undesirable coarse grain structures can be expected (Fig. Fig.15 demonstrates the result in ε-T-t space where a surface is defined which separates the safe working region for the final processing from that region where undesirable coarse grain structures can be expected (arbitrarily defined at an austenite grain size of 30 µm). ε-T-t space separates the original fine structure from coarse-grained regions created by recrystallisation or grain growth (5.15). No grain coarsening was observed following a strain of 3% for any of the combinations of holding time and temperature. Holding time at temperature is also important for microstructure coarsening and a practical conclusion is that accelerated cooling applied rapidly after the final pass can be of great benefit in reducing the danger of structure coarsening.15 Processing window for avoiding microstructure for Ti-V-(Nb)-N-steels coarse grained austenite structures in Ti-V-N during simulation of industrial hot steel after the final sizing pass. . from the ‘critical strain anneal’ phenomenon. 5. this process leads to a mixture of recovered pre-existing grains of approximately 10 µm diameter together with some very much coarser grains. A study of sizing passes on the final microstructure of Ti-V-N- steel (5. nucleation of new grains takes place only infrequently at a few favoured sites followed by extensive growth.15). at lower temperatures. Instead of refinement. and hence small rolling reductions at high temperatures can cause abnormally large recrystallized grains. With small reductions in final sizing passes. Figure 5. 5. This is most serious at the end of the hot rolling sequence when a small `sizing` pass applied for control of thickness or shape may destroy the fine-grained austenite structure created by RCR processing. Coarsening of the austenite can occur as a result of grain growth at high temperatures or.

• RCR+ACC is a superior alternative to CR as a TMCP-process for manufacturing V- microalloying steel plate and long product with high strength and toughness. long products as well as strip production of V-(Nb)-Ti microalloyed steels. Advantages of the RCR process are its high productivity and lower mill loading as compared to CR. . as well as more efficient utilisation of V in precipitate strengthening. 54 5. • Accelerated cooling increases the strength of the V-microalloyed HSLA steel product both by refinement of microstructure (ferrite.6 Summary of chapter • Recrystallization controlled rolling (RCR) or low temperature controlled rolling (CR) followed by accelerated cooling (ACC) lend themselves well to plate. • In order to prevent the occurrence of grain coarsening following the final "sizing pass" in the Ti-V-microalloyed steel it is recommended that the finishing temperature should be low and that reductions smaller than 10% should be avoided in this pass. preferably followed by accelerated cooling. bainite) and by generating smaller and denser microalloy precipitates • A computer routine for prediction of microstructure evolution during TMCP processing is available and good agreement between calculated and observed final microstructure of Ti- V-(Nb)-N microalloyed HSLA steel plate has been obtained.

Similarly. those which are persistent and may directly affect the final properties and others which are modified beyond recognition during subsequent stages of the manufacturing process.1 Optical micrographs of as-cast HSLA steel slab. CAST STRUCTURES 6. and (c) dendritic structure of the original δ-ferrite. 200x 25x 25x Fig.13%C. However. 6.1 is taken from the work of Bruce (6. when comparing conventional slab casting and reheating prior to rolling with thin slab casting and direct hot rolling it is advisable to consider more carefully the influence of as-cast structures. 55 6. Broadly. On the one hand.1. (a) grain structure. Among the persistent features can be listed inclusion morphology.0. Transient microstructures include grain structures and microalloy precipitates in the form of eutectics or other coarse carbonitrides. this is often not apparent in the final ferrite+pearlite or bainite microstructure due to the sequence of transformations δ−γ−α on cooling. In fact.01%Ti). the as-cast structures contain two types of features.1) on 220mm thick cast slabs of a V-Ti-microalloyed steel (0. . the distinction between such persistent and transient features is not always clear cut. Nevertheless.1 Microstructural features Much less attention has been devoted to the microstructures of as-cast slabs than those of rolled products for obvious reasons. For example. Figure 6. which may be refined by recrystallization or dissolved by diffusional processes. Few systematic studies on thin slab structures have so far been reported so it is not possible to draw clear conclusions but it is probably wise to assume at least some differences from the behaviour in traditional processing. (b) prior austenite grain boundaries. some knowledge of these structures is necessary. especially in connection with down-stream processing such as hot rolling.042%V.0. with implications for precipitation strengthening in the final product. sampling of these thick gauges (typically 220mm) is troublesome and on the other hand their influence on final properties is often only indirect. The absence of the γ−α−γ phase transformation prior to rolling and the smaller total reduction may mean that the initial grain structure still has some influence on the final grain size. the lower temperature and shorter holding time before rolling may not be sufficient to dissolve eutectic alloy carbides. TiN dispersion and segregations which can lead to banded structures and inhomogeneous dispersions of microalloy carbonitrides. Continuously cast slabs of structural steels usually show evidence of columnar solidification near to the surfaces with equi-axed structure towards the centre.46%Mn.

The austenite grains tended to be columnar except close to the surface and were smaller by a factor of about two than those in the CC slab described by Bruce (6. 6. In this sub-surface region the austenite grains are seen to be columnar with a thickness of about 1mm and are several millimetres in length.6. After etching in nital the dendrites appear as light coloured ferrite in a background of darker tempered martensite (Fig 6.3(b)).1.2(a)). and (b) prior austenite grains.1).1). especially near to corners. Fine scale precipitates around 100nm in diameter are thought to arise during cooling through the low temperature austenite range (Fig. The as-cast structures of thin (50mm) slabs of V-Nb microalloyed steel (0.1(b)) reveals the prior austenite grain boundaries decorated by continuous networks of ferrite. At the centres of these crosses can be .3(a)). thermal effects or.3)) contain large ‘dendritic’ particles with arms extending in three mutually perpendicular directions (Fig.06%C.11%V.1(a)) but low magnification (Fig.6. On the other hand. The columnar as-cast structure was almost continuous except for a layer of finer equi-axed grains at the surface (Fig. 6.49%Mn.N) phases.0.6.1(c)).2 Optical micrographs of as-cast thin (50mm) slab showing (a) original dendrite structure. possibly from strains caused by the peritectic reaction.6.Nb)(C. The original dendritic structure of this steel was revealed by a heat treatment involving austenitizing at 950oC followed be slow cooling to 770oC. (6. 25x 25x Fig. There are indications that titanium additions can assist this austenite refinement or alternatively hinder grain growth in the newly transformed austenite (6.2). In steels containing also Nb these may occur as mixed (V. the austenite grain boundaries were visible at low magnification decorated by ferrite films (Fig. 56 At higher magnification the microstructure is a relatively uniform mixture of ferrite and pearlite (Fig. Steels alloyed with both V and Ti (Zajac et al. It is apparent here that the as-cast δ-ferrite grains were considerably larger than the subsequent austenite in this case.2(b)). giant austenite grains centimetres in diameter may also occur in such microallyed steel. water quenching and tempering at 400oC. Vanadium in cast slabs of microalloyed steel is found in carbo-nitride particles that may adopt at least three types of morphology. Also here.0. These give the appearance of secondary recrystallization or of a critical strain recrystallization phenomenon arising from bending.017%Nb) have been examined by Siwecki (6. 6.

must be complete before any part of it (face. 6. 1. It can be supposed that the microalloy addition is therefore made available for precipitation strengthening as intended.4.3(c) from unpublished work at SIMR.6. both the holding time and temperature prior to hot rolling are less and it is possible that some of the coarse particles remain with detriment to the final properties. It is well known that a trough in ductility exists over a certain range of temperature where surface cracking of the strand is likely to occur and that the problem is exacerbated in microalloyed as compared to plain C-Mn steels.g. the situation with regard to V-steels has not been clarified to our knowledge. nucleating on the pre-existing TiN precipitates. 57 found cuboidal TiN particles on to which the arms of almost pure VN have grown. This seems to be the case for some Nb-microalloyed steels (6.N) phase which has been found in cast slabs is much coarser still and appears to be a eutectic product similar to the NbC eutectic phases that have been reported by Priestner and coworkers (e.5) in solidified niobium microalloyed steels. 6. For direct rolling of thin slabs.3 V(C.09%C. edge or corner) falls below this temperature. and (c) optical micrograph. .2 Ductility during casting Probably the most important practical consequence of the structure and chemistry in as-cast steels is how these affect ductility of the slabs when the strand is bent and unbent at high temperature in the production process. (a) (b) (c) Fig. The low ductility region usually lies in the range 700oC – 1000oC but the most critical factor is the upper temperature at which ductility deteriorates since bending of the slab. which is cooling continuously. The third type of V(C.6. 0.5). 0. when the solubility limit was exceeded during slab cooling. as yet.41%Mn.01%Ti) is shown in Fig. The vanadium-rich carbonitride phases normally dissolve during the prolonged high temperature reheating of slabs before hot rolling in conventional processing. 0. Even the coarse eutectic phases are seldom apparent in final rolled products. Occurrence of such products in these steels is attributed to microsegregation which leads to enrichment of the alloy elements within the liquid phase so that solidification terminates with a eutectic reaction in inter-dendritic regions An example of such a phase in a cast slab structure (0. 6.N) phases precipitated in as-cast HSLA steel slab.013%N.08%V. Their size indicates that diffusion must have occurred over relatively long distances and accordingly that these structures formed at higher temperatures in the austenitic range. (a) and (b) replicas in TEM.

A number of investigations have been reported comparing the high temperature ductility behaviour of different types of steels. At a given temperature the strength of ferrite is only about 60% that of austenite so the tendency for deformation to concentrate to the boundary regions becomes magnified with rapid localised rupture as a consequence.8). deformation and sliding concentrate at these. As the grain boundaries act as softer material than the grain interiors.1). .6) to become more serious at large grain sizes as in the case of these cast products.6. viz: • Void initiation at coarse carbonitride particles located on austenite grain boundaries • Hardening of the grain interiors by fine scale carbonitride precipitation • Inhibition of dynamic recrystallization by precipitation on deformation substructures thus preventing relaxation of stresses built up at grain boundaries.4 Example of cracking along an austenite grain boundary in a cast slab of Ti-V-microalloyed steel. all using different ranges of steel chemistry. In this case the ferrite films delineating the original austenite grain boundary have formed after the cracking took place.6. These have mostly made use of tensile testing or in some cases bending to simulate more closely the steelworks situation.6.7. An additional effect in steels comes into play when the temperature falls below Ar3 and ferrite starts to form. Results of four sets of hot tensile tests are compared in Fig. Reduction in cross-sectional area at failure was the measure of ductility.5. Microalloyed steels have been postulated to be sensitive to such cracking for several reasons (6. Only when the structure becomes mainly ferritic at lower temperatures can the deformation become more uniformly spread and ductility be restored. leading to void initiation at triple junctions or second phase particles lying in the boundaries. 200x Fig. 58 Magn. The most reliable data come from tests where the steel is melted and solidified and then cooled directly to the testing temperature but in some cases a very high prior austenitization temperature was used to achieve coarse grain structures having the microalloying elements in solid solution. The normal appearance of these cracks is that they follow austenite grain boundaries as shown by the example of a corner crack in a slab of Ti-V-microalloyed steel in Fig.4 from Bruce (6. commencing along the austenite grain boundaries. The cracking along austenite grain boundaries at high temperature and rather low rates of deformation is an example of typical creep rupture behaviour which is known (6. 6.

2x10-3.12. This seems reasonable in view of the temperatures that were all below 900oC. 6.9 (b) 6. Plain C-Mn steels show the least sensitivity to cracking. These various results are not easy to compare in absolute terms of deformation or temperature that can have been affected by the particular conditions of cooling or strain rates that were applied.10 (c) 6. 6. this is the most relevant parameter for steelworks practice.5 Comparative hot ductility data for steels from various literature sources. However. Interpretation of the ductility trough results in Fig. Vanadium microalloyed steels show an intermediate behaviour between the plain and the Nb steels. from Crowther et al.10) as does Fig. both in terms of the depth of the ductility trough and the range of temperature over which it exists. (6.12) were considered to be partly a result of ferrite formation along austenite grain boundaries.(6.5(c) from the work of Karjalainen et al.5(a) is from Mintz and Abushosha (6. The cracking data of Crowther et al.6.(6.9) for samples pre-heated at 1330oC while Fig. All the tensile tests show that loss of ductility commences at much .(a) 6. An alternative measure of hot ductility in Fig.11). especially towards the higher temperatures. Fig.6. As mentioned above.5(b) refers to solidified samples (6. It is seen that higher nitrogen contents in the V-steels extend the low ductility trough. According to Mintz and Abushosha the hot ductility of V- steels are superior to Nb-microalloyed ones provided that the V and N levels in the steel expressed in weight % are such that [V][N]<1. they show a fairly consistent trend when different steel compositions are compared in each case.5(d) is the length of the largest crack found in 50mm thick slabs bent at various temperatures after casting.11 and (d) 6. A curious feature in some of these reports is that the presence of V in Nb-microalloyed steels seems actually to improve the resistance to hot cracking even though the level of Nb remained the same. The most susceptible steels are those microalloyed with Nb and this appears to be particularly true when the upper temperature of the embrittlement range is considered. 6. 59 Figure 6.12).5 is not entirely straightforward.

This is fully compatible with the lower solubility of Nb than V in austenite such that precipitation of NbC occurs at higher temperatures.17%. Addition of V to Nb- steel appears to have a beneficial effect associated with coarsening of the (Nb. V-microalloying even when combined with an enhanced N-content is capable of remedying these problems. full agreement concerning the mechanism of ductility loss still seems to be lacking.N) takes place. Furthermore. are avoided.07 – 0.3 Summary of chapter • Grain structures in as-cast steels are not strongly dependent on the presence of V as a microalloying element. Furthermore the hot cracking during casting in Nb-steels leading to impaired surfaces can be avoided in V-steels. First the loss in strength by reducing the C-content below 0.07% can be satisfactory compensated by proper V/N microalloying. of course. • The reheating treatment of slabs prior to conventional hot rolling is normally adequate to ensure that V is re-dissolved and is available to provide precipitation strengthening in the final rolled products. Dynamic recrystallization would not normally be expected for the strains of less than 1% which occur in practice. Fine precipitates are expected to have a greater strengthening effect than coarse ones so would be more deleterious. • The tendency for hot cracking of cast slabs is more severe in Nb-microalloy steels than in V-steels. carbon contents in the peritectic range. however. It can also be reconciled with the effect of nitrogen on the driving force for VN as discussed in chapter 2. High N-levels increase the susceptibility for hot cracking. 6. it has been demonstrated that Nb- microalloying deteriorates the surface quality of hot rolled strips because of surface microcracking during thin slab casting (6.12).N) particles in the cast material. not due to a change in the Ar3 temperature but must be associated with precipitation of carbonitride particles. the beneficial effect of V- additions to the hot ductility of Nb-microalloyed steels was seen to be associated with an increase in size of the precipitated particles. The higher casting speeds in thin slab casting appear to make further demands upon the hot ductility of microalloyed steels. 60 higher temperatures. Vanadium exists in carbonitride particles having a wide range of sizes as a result of precipitation in different temperature ranges during solidification. the strains involved in these tests are much larger than those in the real steelworks situation. . The effect of the microalloying elements is. In one study at least (6.V)(C. However. In the case of direct hot rolled thin slabs there remains some uncertainty as to whether complete dissolution of V(C. Strengthening of the austenite grain interiors by precipitated particles which in turn raises loading on the grain boundaries is suggested by some test results and the same effect may possibly become magnified when softer grain boundary ferrite develops.13). The idea that dynamic recrystallization is inhibited by Nb is in qualitative agreement with many observations on hot working and could indeed be true for the hot tensile test conditions. However. ~0. As a consequence of this.

heating rate for various HSLA-steels subjected to weld simulation (7.N) and VN which engender the greatest precipitation hardening. High nitrogen (wt%N>0.2). Austenite grain coarsening during welding which depends critically on the heat input and steel chemistry has a significant effect on the toughness of steel by controlling the ductile to brittle fracture transition temperature. The affinity of microalloying elements to nitrogen decreases in the order Ti.5). 7. such low nitrogen content is very costly and also troublesome to achieve in practice. It is shown there that the average austenite grain size of the Ti-bearing steels is ~6-15 times smaller than that of C-Mn steel after 30 min. However. but it is Nb(C. Fig. 7. Nb as well as N in the HSLA steels and their effects on properties of weldments (7. . these steels are still better than the C-Mn steel.009) in HSLA steel containing V has sometimes been considered as having an unsatisfactory weldability due to "free" nitrogen which has been claimed to impair toughness in the HAZ. 7.1 as the average austenite grain size after welding simulation at varying heating rates. sulphur and nitrogen content (below 40 ppm N) and microadditions of Ti and/or Ca. However.1). It can also be seen that the Ti-microalloyed steel has excellent resistance to grain growth for temperatures up to 1300°C.2) for various microalloyed steels are shown in Fig. Nb and V. 61 7. some of the results obtained lately show that the V steel with high nitrogen can have a good HAZ strength and toughness by careful selection of microadditions and the welding parameters. Al.1 Austenite grain size vs.1. However. The presence of V and/or Nb in Ti-steel deteriorates grain coarsening resistance. Ti. 7.1-7. WELDABILITY 7. The results of grain coarsening studies (7.2 (7.1 Structure and properties of coarse grained HAZ In recent years the need for structural steels having satisfactory low-temperature heat affected zone (HAZ) toughness has resulted in a general reduction in the carbon. holding at 1350°C. The tendency for austenite grain growth at different temperatures demonstrating the effect of different microalloying elements is shown in Fig. Many features of various microalloyed steels have been studied at the Swedish Institute for Metals Research and particular attention has been paid to the important role of the microalloying elements V.

3). as shown in Fig.1 % V steels (7. re-precipitates in the subsequent passes and these particles inhibit grain coarsening and allow transformation to fine grained ferrite which results in high toughness. Effect of N on toughness of heat affected zone of welded 0.3.3). . 7. During multi-run welding the VN. but rather constant ITT values for low and medium heat input using multi-run welding. Fig.4. 7. 7.003 % N) and high (0.08V plates with low (0. 7.5) for commercial 0.013 % N) nitrogen contents show that extensive grain growth occurs just above 1250°C in low N steel whereas the high nitrogen steel preserves small grains up to 1350°C. The results of grain coarsening studies (7.01Ti-0.3 (7.2 Effect of nitrogen and welding parameters on HAZ toughness of V-steels Several investigations showed that V-microalloyed steels gave increased impact transition temperature (ITT) with increasing nitrogen content for high heat input. 7.2 Effect of peak temperature and steel chemistry on the austenite grain size (7. single pass welds. 62 Fig. which is dissolved in the earlier passes.2).

7.01Ti steel was reported by Mitchell (7. as shown in Fig. titanium additions to a weldable steel can be a useful instrument to restrict grain growth (see Fig. This low toughness (40J at –5oC) is most likely not due to free nitrogen because the nitrogen level had almost the stoichiometric ratio to Ti. and should therefore all have been combined as TiN.5. some improvement in HAZ toughness (40J at -25oC .4b for comparison.4 Impact transition temperature at 40J of: (a) simulated HAZ and (b) HAZ after full scale welding of low (0.08V-N steel plates with high (0. RCR+ACC and CR routes have been subjected to temperature cycles simulating the heat affected-zone of 25 mm plates during high. However. a) b) Fig.5). For this reason.05Nb-0. TiN is stable up to very high temperatures. medium and low heat-input welding in order to investigate the influence of plate production processing route.013N) nitrogen plates with different heat input (7.003N) and high (0.013 %N) exhibits the highest HAZ-toughness for the cooling time of 10s (low heat input). For this heat input (cooling condition ∆t8/5≤30s) one does not expect precipitation of VN in austenite during cooling to the transformation temperature and the amount of "free" nitrogen in ferrite should be higher than in the slower cooled specimens.4(a). there is virtually no effect of the previous TMCP parameters on the toughness of the coarse grained HAZ after welding. However.4. where niobium. 7. Commercial 0.08V-0. Combined effect of heat input and N-content for V-Ti-N steels is shown in Fig. On the contrary. Quite low impact toughness in the HAZ of 0. vanadium and/or aluminium nitrides are dissolved. nitrogen content and heat input on HAZ toughness and microstructure (7.013 % N) and low (0. With increasing cooling time precipitation of V(C.003 % N) nitrogen contents and produced by RCR. higher N steel (0. 7.01Ti-0. Changes in the impact toughness of the HAZ of 0.N) should be more abundant reducing the amount of nitrogen in solid solution.4.01Ti-0.4.6). 7. As seen here.08V-N steels obtained from thermal simulation of HAZ are shown in Fig. 7. 63 Another method of mitigating the effect of nitrogen in HSLA steel is by microaddition of titanium.1) and thereby increase the toughness in the HAZ adjacent to the fusion line. it was these specimens which exhibited low toughness. 7. These results do not allow us to directly associate the low toughness after high energy welding with "free" nitrogen.5). 7. 7. whereas the results of full scale welding trials are shown in Fig.

0. The ITT40J of 0.9) reported on improvement in the HAZ impact toughness in multipass welds with increasing V level up to 0. Note also that hot rolling conditions do not affect HAZ structures in these steels to any significant extent. 7. The poorer toughness of the high heat input HAZ in high N steel is considered to be caused by the presence of a significant volume fraction of coarse grain boundary ferrite in association with V(C.8. It was suggested that the improvement in as welded toughness is connected with the formation of a favourable microstructure. Mitchell et al. whereas some reduction of toughness was observed with higher V level.4) of multi-pass welding of 0. This is in general agreement with our own observation.003N steel plate reached -60°C.6). grain boundary (PF(G)) and intragranular ferrite (PF(I)) (see Fig.25%Mo to the V-Nb-Ti steel. No significant effect of vanadium up to 0. The investigation (7.4). 7.08V-N steels shows a positive effect of the second pass.6-7. intragranular ferrite.08 V plates. It was also reported that higher heat input (>2kJ/mm) had a positive effect on the CTOD toughness and a slight negative effect on 40J ITT. (7. A marked improvement in HAZ toughness after the second pass was observed as compared to the single pass welding with high heat input.0. that the HAZ microstructure at high heat input is usually a mixed structure of fine ferrite with second phases (FS).7) for cooling times ∆t8/5< 100secs. N) (7. . Fig. According to Swedish standard welding practice 25mm plates are normally welded in two or more passes.01Ti-0.16%. although the CTOD transition temperature increased slightly at the same time.8). (7.01 Ti . 64 for synthetic HAZ at ∆t 8/5=50secs) was obtained by addition of 0.1% on the HAZ toughness of synthetic/thermally simulated welds was reported by Hannerz et al.5 Effect of heat input and nitrogen content on the HAZ impact transition temperature of RCR + ACC. which allows good toughness even at high heat input. 7. The effect of vanadium content on the HAZ toughness of welds has been reported in a number of investigations (7. cooling time ∆t8/5 = 100s.013N steel plate decreased by 50 degree to -48°C and for 0.

8) and this seems to be independent of nitrogen.7). 7. it can be concluded that the notch toughness properties of coarse grained HAZ of the 0. The excellent notch toughness properties of the HAZ of high nitrogen plates subjected to thermal simulations of heat input with ∆t8/5<40s and particularly at ∆t8/5=10s can be attributed to the characteristics of the fine ferrite with second phase (FS) (see Fig. the drastic changes in 40J ITT with varying of heat input / cooling time.6.08V-N steels can be explained on of the basis of their microstructures.01Ti-0. 7. 7.4) . Relation between volume fraction of microstructure constituents and the heat input (cooling time ∆t8/5 from 1350°C) for Ti-V steel with low and high nitrogen content processed by RCR+ACC and by normal rolling (NR) (7.4 and 7.5.6 and 7. 7.3 Toughness-Microstructure Relationships Concerning the results in Figs. 7. 65 Fig. For high nitrogen steel the results show that the presence of coarse grain boundary ferrite in the HAZ makes the most significant contribution to the overall low notch toughness properties rather than "free nitrogen". Thus the cooling time which gives 50% of fine FS-phase is sufficient to confer good impact notch toughness (see Fig. .

4). a number of very small particles. Although the reason for this is not entirely clear. The transformation temperature of plates of 0. if the specimen was cooled slowly down to 800°C and then quenched. Some effort has been expended to study the particle size distribution and its chemistry in the HAZ of HSLA steels (7.4). However.08V-steel plate had an average size of ~24 nm at a top temperature 1350°C. it provides an explanation for the occurrence of the networks of coarse ferrite grains seen in the high N steel. In a specimen of high N steel cooled slowly (∆t8/5=100s) to room temperature. 7.7 Microstructure of HAZ of the Ti-V-N steels with low – 0.003% and high – 0. This suggests that these small TiN particles re-precipitate during the cooling stage of the thermal cycle. 66 Fig. medium and high heat input was studied by Zajac et al (7. less than 5 nm in diameter were observed. the detrimental effect of high heat input is caused by coarse grained microstructure with assistance of precipitates.013%N after heating to 1350°C and cooling down with the rate equivalent to welding with low.013% nitrogen content after thermal simulation at 1350°C and cooling down with ∆t8/5=10s (a). 40s (b) and 100s (c) (7. The coarse. These results have shown that the TiN particles in the HAZ of high N 0. the impact toughness values found can mainly be understood by considering the general microstructure. additional round particles of V(C. Altogether.4).3. whereas in the low nitrogen steel plate only a few large cuboids.N) were observed.003%N and 0. The results showed that the transformation start temperature of the high N steel is more than 75°C higher than that of low N steel for low heat input and 45°C higher for high heat input welding conditions. . intergranular ferrite structure developed in the coarse grained HAZ of plate subjected to the simulation with ∆t8/5>40s was responsible for the poor low temperature notch toughness properties. 7. ~100nm. were observed.

toughness becomes sometimes critical at the coarse grained HAZ due to formation of the upper bainite and associated martensite-austenite islands.3-7. An increase in nitrogen content in Ti-V-N plates. Steels modified by these microadditions show satisfactory HAZ toughness at -20oC for the high input of 15 kJ/mm. and therefore good toughness. fine particles of TiN or other compounds restrict the austenite grain coarsening and act as nucleation sites of ferrite. This effect is very small in the low nitrogen steels that showed only a slight deterioration in toughness. REM and Ca. B. As discussed previously. 67 Fig. • The austenite in the HAZ of V. (7. 7. above the stoichiometric level for TiN suppresses grain coarsening of the HAZ. could be obtained for high nitrogen steel by balancing heat input to provide a fine transformation product. The problem can be solved by deliberate addition of Ti (ca 0.013 % N) rises drastically for cooling times above 30-40s.9). 7. The transition temperature of the high nitrogen steels (0.4 Summary of chapter • High nitrogen in V microalloyed steel can be compatible with good weldability. In high heat input welding exceeding 10 kJ/mm. The results presented above show that proper microstructure. By Ti-microadditions to V. which results in a decreased fraction of upper bainite.FS. • Plate production processing route seems to have insignificant effect on HAZ toughness.8 Relationship between ITT40J of HAZ and volume fraction of ferrite with second phase . • There is a general trend of decreasing HAZ toughness with increasing heat input (cooling time).and Nb-steels this coarsening can be minimised. by careful selection of microadditions and welding parameters. as regards HAZ hardness and toughness. .and Nb-steels coarsens significantly during welding.015%) or various combinations of Ti.

N) and V(C. the solubility product of VN is about two orders of magnitude lower than that of VC. In retrospect one can say that the basic idea behind this development was. This implies that N as a microalloying element has a decisive role in V- microalloyed steels. (ii) As opposed to Nb but similar to Ti. a ferrite grain size of ~4µm. Nb(C. . The most significant properties of V as compared to Nb and Ti are: (i) The solubility of V(C. the processing routes to achieve this are totally different because of the widely different solubilities of Nb(C. Eventually recrystallization stops and on continued rolling the unrecrystallized austenite grains are gradually more flattened. Today it is a well documented fact that one can reach the same level of grain refinement in V-steels as in Nb-steels. alloyed with Nb. Weldabilty is normally maintained in both cases but. and in fact still is. when grain refinement can be retained during welding. implying that the solution temperature is lower or alternatively that larger amounts of V can be dissolved at a given temperature. especially for the enhancement of their precipitation strengthening. Mainly because of the increasing austenite grain boundary area this produces after transformation a much refined ferrite microstructure.N) is much larger. HOW IS V BEST USED IN MICROALLOYED STEELS . the solubilities of the carbides and nitrides of V differ widely. this is particularly evident at higher temperatures. V or Ti or combinations of them. However.1 Austenite conditioning by thermomechanical processing The primary objective of thermomechanical processing of microalloyed steels is to condition the austenite to produce as refined ferrite as possible. to capitalise on the effects of (i) grain refinement and (ii) microalloy precipitation Grain refinement is unique in that it adds both strength and toughness to the steel whereas microalloy precipitation increases strength at the expense of some loss in toughness.N) precipitates already in austenite during hot rolling and thereby retards recrystalliza- tion effectively. 8.EXECUTIVE SUMMARY The rapid development and use of welded structures after World War II soon made it clear that strengthening of structural steels by increased C was unacceptable because of low tough- ness and poor weldability. 68 8. toughness and weldability over the last 40 years resulting from the development of microalloyed steels and routes for thermomechanical processing of these. In such a general description of the development one can see a common ground for all the microalloyed steels. it is substantially improved. In short this is the background to the arrival of new structural steels with steadily improved strength.N) at the temperatures for hot rolling. when it comes to the real development of steels with optimised composition and processing route proper account must be taken to the differences between the various elements. However. In this technical environment the development of microalloyed steels and the thermomechanical processing of such steels took off with a great thrust.

11. (iv) The repeated recrystallization in RCR breaks down prior austenite microstructure efficiently. During continued rolling such grains will gradually be flattened but could still produce a local. after a sufficient number of passes. (iii) V is retained in solution before the austenite/ferrite transformation due to its larger solubility and the higher finishing temperature in RCR. ~ 4µm.01%Ti and ~ 0. this creates a dispersion of fine. ~ 0. such as in HAZ of welds. Beside the fact that it was first on stage its primary advantage appears to be . a very efficient austenite grain refinement which after transformation can produce a ferrite grain size equally fine as with the former method. prevents coarsening of the bulk of the austenite micro- structure well above that temperature. this is a matter of a few . it is also an efficient means of ensuring the finest possible grain size during RCR processing since it prevents austenite grain growth between the rolling passes and after finishing. Controlled rolling (CR) of Nb-steels by extending to low temperatures in the range of non- recrystallization was already developed and applied in the mid 60’s. 69 V offers no effective resistance for austenite recrystallization during hot rolling since its larger solubility engenders no impeding precipitates. But it is important to recognise that during prolonged heating. this gives a secure control of the grain growth inhibition. During short heating periods. there is risk for initiation of abnormal grain growth despite the stability of the TiN dispersion. 3. which is the name given to the latter process. V-microalloyed plate steels are commonly co-alloyed with Ti.01%N offer very competitive combinations of strength. (ii) ferrite microstructure can be further refined by forced cooling and by somewhat enhanced N-content (typical of EAF steel making). Ti-V-N. The very stable TiN dispersion of the Ti-microalloyed steels. Precipitation strengthening of 250-300MPa may be reached in V-N-microalloyed steels. Although traditional CR of Nb-steels is probably dominant RCR of V-microalloyed steels offers important advantages which probably are still not fully utilised: (i) economical hot rolling practice (high productivity) by low reheating and high finishing temperatures. such as during reheating. and therefore generates a con- siderable precipitation strengthening in the austenite/ferrite and ferrite ranges. very stable TiN-particles that effectively prevents austenite grain coarsening at high temperatures. Forced cooling and enhanced N-content add significantly to the strengthening. was developed later and was first practised ~ 1980. Traditional CR characterised by a high recrystallization stop temperature may retain large austenite grains. Provided cooling during casting is sufficiently fast. Recrystallization-Controlled-Rolling (RCR). toughness and weldability.01%. cf. The absence of hindering particles offers on the other hand a new opportunity for grain refinement: Repeated austenite recrystallization after each rolling reduction generates. as in concast slabs. showing no measurable coarsening below about 1300oC. chapter 5.given the provision that the mill is strong enough for the large rolling forces at low temperatures – that it is relatively easy to control. deviating microstructure causing detrimental properties.plate steels with ~ 0. However. see Fig. Ti-addition is therefore often a preferred choice in V-microalloyed plate steels. Although this effect is primarily used to improve the HAZ weldability of the steel. typical of the beginning of abnormal grain growth during reheating.

As an example the present results.2 Precipitation strengthening Of the different microalloying elements used. will be dissolved in ferrite over a wide temperature range. in the former case the C-content is 5 times larger than in the latter at 600oC.01% C.11(b). V is clearly the one best suited for strong and reliable precipitation strengthening. The strengthening by enhanced N is quite considerable. ~ 5. indicate that by adding N from a level of 0.001%N and is rather independent of the C-content of the steel. should be maximised.12% to 0.06%. The present results show clearly essential differences between N and C when it comes to the practical use of them for V(C. cf. For hard particles such as microalloy carbonitrides the sole parameter determining pre- cipitation strengthening is the particle spacing. Fundamentally this is due to an increasing chemical driving force for this reaction and this causes in turn a larger nuclea- tion rate. 8. However. of say 0. this implies that a very large N-content for a steel. The solubility of N at the eutectoid temperature is about 0. a very important advantage with N is that the content of N dissolved in ferrite at the onset of precipitation equals. ~ 800-350oC. Experimentally it is well proven that the V(C. influence on the precipitation strengthening by microalloy carbonitrides in view of fact that the content of dis- solved C in ferrite is normally controlled by the austenite/ferrite or the ferrite/cementite equilibria. that will slowly con- sume the fine grained microstructure. and it is only when almost all N has been consumed that the C-content of the carbonitride starts to increase. unless reheating is not excessively long. especially in their precipitation strengthening. As a result of the lower solubility of VN than of VC the first formed V(C.005% to 0. The reason for this is that pure ferrite dissolves much larger contents of N than C. Differently expressed. or very closely so.015% makes it possible to reduce V from 0. Therefore. large enough to grow through the TiN-dispersion.12%V-steel it is typically 6 MPa/0. Instead of adding strength this effect can be used to save alloying costs.N) is N-rich for all normal N-contents. This circumstance together with the much lower . 4.N) density and thereby the size of precipitation strengthening. in a 0.N)-nucleation to occur.N)-pre- cipitation becomes denser and finer with increasing N-content.02%.5 MPa/0. this phenomenon creates only streaks of coarse microstructure.N) precipitation strengthening. which determines the density of the precipitate dispersion. the principal reason being the larger solubility product of its carbonitrides resulting in a lower solution temperature and a larger capacity to dissolve them at elevated temperatures. It has been shown that such a situation exists when the ferrite C- content is controlled by the austenite/ferrite rather than the ferrite/cementite equilibrium. A long upheld view is that the total C-content of the steel has little. Therefore to obtain the largest possible strengthening the nucleation rate of V(C.10.02% for C. if any. Fig. the total N-content of the steel.10% whereas it is 0. To benefit from continued precipitation strengthening beyond this point there must be sufficient C in solution and chemical driving force for fresh V(C. 4. A special feature of V as compared to Nb is that its nitride is much less soluble than its carbide and this gives N a very important role in V-steels. Beside the fact that the N-con- tent largely determines the V(C. 70 exceptional grains. recent studies have shown that the precipitation strengthening of V- microalloyed steels increases significantly with the total C-content.N). The explanation is that the C-content of the steel delays the pearlite (ferrite+cementite) formation and thereby maintains the higher C-content in ferrite given by the austenite/ferrite equilibrium for a longer time. Fig.

The higher solubility of V as compared to Nb in austenite implies that the temperature range where precipitation can occur is removed to lower temperatures.013N steel up to heat inputs of 4kJ/mm. microstructure and ITT of HAZ has clearly shown that the observed increase of ITT at high heat inputs in high N-steels cannot be explained by solute N. 8. however. A method to further enhance the grain coarsening resistance in these steels is to increase N above the stoichiometric level of TiN. Hence. The C-content on the other hand is difficult to use and control for the continued precipitation of C-rich V(C. in V-microalloyed steels are often considered to cause unsatisfactory HAZ-weldability due to solute nitrogen which has been claimed to impair toughness. V is still less harmful than Nb in the respect and it has furthermore been found that additions of V to Nb- microalloyed steels can actually reduce the tendency for hot cracking in these. 71 solubility of VN as compared to VC makes the combination of V and N especially advantageous in precipitation strengthening. Accordingly. the explanation lies in variations of microstructure. can be obtained in plate welds of a 0. This view is supported by several investigations where solidified samples of steels were bent or tensile tested at elevated temperature. Recent investigations show. provide an efficient means of suppressing grain coarsening in the HAZ. ~ -70oC. a technology applied in the Ti-V-N plate steels.4 HAZ weldability High N-contents. This is apparently due to a change in morphology of the (Nb.3 Cast structures A practical problem with processing of microalloyed steels is their greater susceptibility for cracking as the continuously cast slabs are bent and unbent in the hot as-cast condition. On the other hand it has been shown that quite adequate ITT.V)(C. multipass welding of V-N steels produces very low ITT. which is the relevant parameter for the precipitation. Figs. This is due to the fact that the solute content of C in ferrite.01%. Although the mechanism causing this loss of ductility is not fully clarified. it is certainly exacerbated by precipitation of microalloy carbonitrides in some form. Moreover. not only does N add significant precipitation strengthening to the steel but it also facilitates the control of the strengthening. Nevertheless. independent of the N-content up to 0. Higher N contents in V-steels increase the susceptibility for hot cracking to occur since the temperature range over which precipitation of VN occurs is extended to higher temperatures. and in particular the presence of coarse grain boundary ferrite makes the most significant contribution to the lower toughness at high N levels and high heat inputs. Instead. that such generalising statements are incorrect and that satisfactory welding results can be achieved also at high N-contents by selective choice of welding parameters.010%. pearlite and eventually to cementite.N) after the consumption of most N. It is true that the HAZ impact transition temperature (ITT) increases with increasing N con- tent in high heat input single pass welds (8kJ/mm). ~ 0.4.7. Microadditions of Ti. . depends in a complex manner on the transformations of austenite to ferrite.N) precipitation. -45oC. Detailed analysis of results on the relationship between welding parameters.01Ti-0. the hot cracking problem is less severe with V-steel.08V- 0. 8.3 and 7. >0.016%.

011%. 72 8. 0. The following general trends in steel technology we find especially worthy of mentioning in this context: • growth of EAF steelmaking. in strip and plate steels processed by thin slab casting V is often the preferred microalloying because of the greater demand of resistance to hot cracking in this process.007-0. • limitations of traditional controlled rolling into the non-recrystallization region • cost advantages of recrystallization-controlled-rolling in a high temperature regime • recrystallization-controlled-rolling of long products where a high finishing is an inevitable consequence of the process • application of the TiN technology for controlling austenite grain coarsening • growth of thin slab casting. .5 Interplay between general trends in steel technology and the technology of V- microalloyed steels As a final remark we think that it is worth noting that the technology of V-microalloyed as described above is in good accord with many of the prevalent trends in steel technology. typified by high N-content.

S. 73 ACKNOWLEDGEMENTS This review rests primarily on research carried out during the last 25 years at the Swedish Institute for Metals Research (SIMR) with economical support by the U. We would also like to acknowledge the financing of some of the underlying work by the General Research Programme of SIMR and by SSAB. In this context the outstanding work of William Roberts should be given special recognition. The authors are indebted to him for countless technical discussions over the years. Vanadium Corporation/ Stratcor (and its predecessor Union Carbide) and technical cooperation with Michael Korchynsky of that organisation. beside the present authors. . so rewarding and indeed essential for the outcome of the work. The personal interest and engagement of Michael Korchynsky through all these years have been a prerequisite for the fulfilment of this work. and his research increased our understanding of the behaviour of these steels significantly and made improved alloy design and processing possible. Finally it should be noted that many researchers at SIMR. He laid the foundation for the research on microalloyed steels and hot working at SIMR. have contributed to this review as investigators and authors of individual projects and papers.

33 (1988) pp. Wilson and T. The influence of vanadium on the activity of carbon in the Fe-C-V system at 1000°C. PA (1981) pp. (1967) pp. 224 (1962) pp.. 2. Gladman.. and B. Parthé. 29B. Trans.Ta) and rare earth elements in steel.A. K. S. 34 (1994) pp.5 M. Report IM-3566.13 S. 205. Swedish Institute for Metals Research. 2. Jansson.3 K.7 B. Ishii and K. ISIJ. 2. 2. 74 REFERENCES Chapter 2 2. CALPHAD. (1998). 2. A thermodynamic assessment of the Fe-N-V System. CALPHAD.. Zajac. Thermocalc databank system. Hillert. Fountain and J. Materials Rev. Grain-refined C-Mn steels. Wagner.14 N.. 236 (1966) pp. correlation of the influence of substitutional solutes on the activity coefficient of carbon in iron-base system.8 K. Chicago. Int. Akisue. 2. 15 (1975). AIME. Wriedt and H. 37 (1973) pp. Gladman. Precipitation Behaviour of Sulfides in Ti-added Ultra Low-carbon Steels in Austenite. 24- 32. Irvine. (1970) pp. 25-39. 24... 1998. Va (V.J. Physical chemistry.6 S. 221-287. 2. The physical metallurgy of microalloyed steels. AIME. Yvon and E. Hu. 599-606.O. Crystal chemistry of the close-packed transition-metal carbides. pp. 153-159. Gladman.Zr). 2.A. Zupp and D. (1981) TSM-AIME.W. Chipman. Stevennon. Addison-Wesley Co. 149-153. Acta Chemica Sc. Mass. F. Thermodynamics of the Fe-Nb-C-N System and the Solubility of Niobium Carbonitrides in Austenite.B.10 H. Trans.16 F. 3618-3626.15 S. 171-194. 2. Sundman. 2. 163-176 2. 26 (1970) pp.9 R. Thermodynamics of alloys. Japan Inst.G.4 C.11 H. Pickering and T. .1 T. 9 (1985) pp. pp. pp. Physical chemistry of the group IVa (Ti. 191-195. Metall. Staffanson.R. T. Metals. Ohtani and M. Andersson. Trans.2 K. The Institute of Metals. Thermodynamic model for the precipitation of carbonitrides in microalloyed steels. Koyama. 2. (1952). Zajac. B.. Warrendale.Nb. Aluminium nitride in steel. J. Symp.12 R. Trans. Feb. Crystal structure of the zeta-vanadium niobium and tatanium carbides. 1316-1323. Chemical Metallurgy. Proc. Wagner. Narita. Pt1. Acta Cryst. 2. 145-152. 161-182. The regular solution model for stoichiometric phases and ionic melts. Reading. Solubility and precipitation of boron intride in iron- boron alloy. Vol. (1997). Narita. 2. Hillert and J. JISI. Ushioda. B. 2. A Tribute to C.. ISIJ Int. Akamatsu and O. 15 (1991). Yoshinaga. Jansson and J.

Processing characteristics and properties of Ti- V-N steels. Mat. Sandberg. pp. 3. C. and I. Characterisation of microalloy precipitates in HSLA steels subjected to different weld thermal cycles. 1998.. Jan. Hayakawa. 3. 3-6. Aluminium nitride precipitation in C-Mn-Si and microalloyed steels. PA.Microalloyed Steel. Siwecki. 211-219. A. Conf. Svensson. Swedish Institute for Metals Research. Zajac. Takahashi. Metall. Lehtinen. The influence of processing route and nitrogen content on microstructure development and precipitation hardening in vanadium- .6 B. (1982) pp. in Proc. 4 (1975) pp. Yamamoto. PA. pp. 3. Roberts. 3. Ti-V-N. Philadelphia. 75 2. Conf.9 M. Shubata. Proc. 1991. G. Trans. ed.4 T. AIME. W. Chapter 3 3. Kroupa. Microstructure and Properties of Microalloyed and Other Modern Low Alloy Steels. B. 619- 634. 2. Recent innovations in alloy design and processing of microalloyed steels. P. On the Effect of Second-Phase Particles on Grain Growth. Internal Report IM-2532. N. Tretyakoo. and Tech. 3. Conf. Precipitation Behaviour in a Medium Carbon.11 P.19 H-R.V. Contribution to the 1983 Int. W. Contribution to the 1983 Int. Kakuta and K. L. Metallurgy. Zajac. Lagneborg. Physics of Metals and Metallography 14 (1962) pp.17 E. AIME. Weatherly. PA.J. 1995. 1983. Roberts. R. 2. K. T.8 S. Ed. Sandberg. Thermomechanical Processing of Microalloyed Austenite. Sci.3 W. 86-90. Oct. Oct. Siwecki and L.L.-E. Met. Zajac.511-523. Heat Input and Nitrogen on the HAZ Toughness in Ti-V Microalloyed Steel. Siwecki. W diffusion in monocarbides of W. Conf. A. DeArdo. Eds. Siwecki. A. pp. Lin and G-H. Hutchinson. Baskin. H. June 1989. G.10 M. Recrystallization controlled rolling and accelerated cooling for high strength and toughness in V-Ti-N steels. J. Prikryl. 2681-2694. Appl. (1982) pp. Trans. M.2 S. 27A (1996) pp. PA. 6 (1990) pp. Y. Internal Report IM-3566. 3515-3520.5 S. T.1149-1165.12 T. T. 3-6.J. 321-340. Chaporova. Diffusion of Ti in TiC. 3. 1983.1 S. Physics 40 (1969) pp. on Technology and Applications of High Strength Low Alloy (HSLA) Steels. The Influence of Plate Production Processing Route. A. Bramfitt and Mangono. J. pp. Microalloying “95”. Warrendale.7 S. on Processing. The role of nitrogen in microalloyed steels. Ratz and P. J. and S. 3. Attlegård. Furuno. Contribution to the Int. Ta and Ti in the solid solution TiC WC and TiC WCTaC. 3. Siwecki. Boron-bearing steels for continuous annealing to produce deep drawing and high strength steel sheets. A. Subramanian. Zajac. W. DeArdo. June 11-14. A 22A (1991) pp. M. 3. Cheng. June 1995. Analysis of hardenability effect of boron. on Technology and Applications of High Strength Low Alloy (HSLA) Steels.A. I.J. 319-341. 133-153. 3. Hillert. Ardo. Brown and A. Roberts. Iron and Steel Society Inc. Philadelphia. Sarian. V. 3.18 N. TMS. 67-84. Hansson. Hellman and M. Wray. Conf. Mat.. Scand. 724-729. Pittsburgh. Thermodynamic model for the precipitation of carbonitrides in microalloyed steels. Swedish Institute for Metals Research.

18 A. Precipitation in Microalloyed High- Strength Low-Alloy Steels. De Ardo. 3. Iron and Steel Society Inc.24 R. Pittsburgh June 1995.17 J. Conf. Conf. Contribution to the Int. Gong. Onchi. T. Interaction Between Deformation. T. Controlled Rolling of Low-Carbon Niobium-Treated Mild Steels.22 I.E. Proc. 3. AIME. Hot Deformation of Austenite. Jonas. Recrystallization Controlled Rolling and Accelerated Cooling of Ti-V-(Nb)-N Microalloyed Steels. Korchynsky.120 –135. pp. TMS-AIME 1977. pp 307 – 820. The Effect of Microalloy Concentration on the Recrystallization of Austenite during Hot Deformation.129-140. T. Ed.. Cuddy. 411-420. Metals 27 (1975) pp. Pittsburgh. 100-102. Metals Sci. Proc. pp. Hot Rolling as a High-Temperature Thermo-Mechanical Process. Conf.C. Effect of precipitation on recrystallization in microalloyed steels. “MICROALLOYING ‘95”. 1981. pp.197-212. B. pp. 1981 Met. 3. Influence of processing route and nitrogen content on microstructure development and precipitation hardening in V- microalloyed HSLA-steels. B. Swedish Institute for Metals Research.15 – 33. Roberts. Luton. pp. Palmiere.Miner. Dynamic precipitation and solute hardening in a V microalloyed steel and two Nb steels containing high levels of Mn. Pittsburgh. PA. Internal Report IM-1488 Oct. Proc. 1995. Siwecki.25 T. ISI Publication 108. Brossard and R. 3. Swedish Institute for Metals Research. 3. Conf. Trans. W.1981. Cincinnati.111. Internal Report IM-1582. 1980. J.441– 451. Jones and A.19 A. pp. Okita. 1981. 21 –27. 3. Modern Thermomechanical Processing of Microalloyed Steel: A Physical Metallurgy Perspective. USA 1990. Proc. . 238 – 245. Zajac. Davenport. 3. pp. Siwecki and S.15 M. T. 13 (1979) pp. Aug. 3. J. New York.14 J.23 T. J. Zajac. Microalloying ’75. Plassiard and J. 3. Thermomechanical Processing of Microalloyed Austenite.13 L.20 A. Precipitation Phenomena in Microalloyed Steels. Conf. J. 11A (1980) pp. 76 microalloyed HSLA steels. 177. Pittsburgh June 1995.163 – 194.517-536. Weiss. TMS-AIME. S. Pittsburgh PA. Kozasu. Soc. J Jonas and I. Aug. Microalloying ’95.16 M. USA. The 32nd Mechanical Working and Steel Processing Conf. G. 3. Sampei and T. Proc. Proc.26 S. 3. Iron & Steel Soc. Siwecki. A. Hutchinson.78-82. pp. L. Thermomechanical Processing of Microalloyed Austenite.. Sandberg and T.121. 3. 29 (1981) pp. C. 3. Cincinnati. Proc. London 1968. Conf. D. Recrystallization and Precipitation in Niobium Steels. Recrystallisation controlled rolling of HSLA steels. Metal. Acta Met. Iron & Steel Soc. Microalloying ’95. 3. Rothwell. Chandra. Conf. P. Akben.J. Lagneborg. Deformation under Hot Working Conditions. J. Aug. June 11-14. The influence of vanadium on the austenite–ferrite transformation in microalloyed steels.21 E. Davenport. Warrendale.

4. A Todd. Influence of faceting upon the equilibrium shape of nuclei at grain boundaries. K. Techn. The composition of V(C. London 322 (1971) pp.18 S. 7A (1976) pp. 1978. Russell. M.A.15 W. Phase Equilibria Phase Diagrams and Phase Transformations. Fundamental Aspects of Precipitation in Microalloyed Steels. H. 799 . Siwecki. pp. Research Report to Vanitec from Massachusetts Institute of Technology. A. Zajac. P. Precipitation of carbides at austenite/ferrite boundaries in alloy steels.5 R. G. Zajac. N) as precipitated in HSLA steels microalloyed with vanadium.11 R. 4. Sandberg. C. Vanadium Steels. USA. Precipitation Processes in Steels.A. 1980. 6A (1975).22%C structural steels. Conf. 4. 9 (1993) pp. pp. pp. Davenport and R. Honeycombe.16 M. 19A (1988) pp. 2139-2151. Nutting. Honeycombe. Schmutz. Metall. Conf. Oct. Precipitation phenomena in V- microalloyed 0. 191-205. Korchynsky. Roy. Importance of nitrogen for precipitation phenomena in V-microalloyed steels. Wade. K. 4. D. Krakow.D1-D12. Marth. V. 4. Transformation from austenite in alloy steels. Lagneborg and S. Oct 1983. Proc. 1993. to be published. 1998. P. Mat. 384-396. R. pp. 4. Sci. I Aaronson. 77 Chapter 4 4. P.N) in HSLA steels microalloyed with V. B. 4. Baker and J.1 F. Private Communication. Sandberg.4. K. Edmonds. K. London 1969. 4. 4. S. Acta Met.6 R. Lagneborg. Swedish Institute for Metals Research. 1981. W. Soc. Smith and D. 1996. Oct.7 R. Siwecki. T. L. on Low Carbon Steels for the 90’s 1993 ASM/TSM Materials Week. Influence of crystallography on aspects of solid-solid nucleation theory.Trans.15-0. Hillert. White. 4. T. 139-150. M.9 J. I Aaronson. Hot deformation studies on a V-microalloyed steel. 4. S. Int. Siwecki and W. Pittsburgh. K. 4. 4. Swedish Institute for Metals Research. ASM. 23 (1975) pp. Press. 1980. A. Roberts. Khalid and D. Structural Aspects of Alloy Carbonitride Precipitation in Microalloyed Steels. 915-936. Zajac.2 R. Vanitec. Cambridge Univ. The Tempering of a Cr-Mo-V-W and a Mo-V Steel. Tuominen.3 M.A. Interphase Precipitation in Microalloyed Engineering Steels and Model Alloy. 4.166-181. Application of a new model to the interphase precipitation reaction in V Steels. E.12 W.14 P. Proc. pp.243-250. 4. Honeycombe. M.17 W. 911-919. Roberts. Philadelphia PA. Materials Forum 11 (1988) pp. 4. Internal Report IM-3453 Dec. Internal Report IM-1333. T. and T. W. Johnson. C. 4. Li and J. on Technology and Applications of HSLA Steels.Trans. ISI Report No 64. Proc.808. Int. 17-21. L. Symp. Ruf.10 A. Internal Report IM-1489 Oct. Lee and H. Dunne.13 R. W. Metall. Swedish Institute for Metals Research. . Roberts.8 W. 1-22. J. C. Metal Trans. Precipitation of V(C. Hutchinson.

Zajac. 5. Int.163-192.Attlegård. 22A (1991) pp. Spain. B. Zajac. M. ISIJ Int. Cincinnati. pp. M&M Soc. Jan. Lagneborg. T. (1995).9. 295-302. (1997). Beijing. Conf. by A. pp.20 S. W.619-634. R. 1995. Siwecki and G. by J. Metals Park. PA. TMS- AIME. T. PA. Strengthening mechanisms in vanadium microalloyed steels intended for long products. 441-451. pp. Siwecki and S. by J. T.W. Engberg. pp. Conf. Lagneborg. ASM. B. R.19 S. R. A. Asfahani et al.Hutchinson and M. Internal Report IM-3568.Z. Korchynsky). 38 (1998) pp. and R. “Microalloying in Steels: New Trends for the 21st Century. 1985. Siwecki.121-144. B. ISS-AIME. and M.Siwecki. OH. 1990. W. ASM. Modelling & Practice. Warrendale.3. Met.251-257. 4. and P. (1991). DeArdo And Y. ISS- AIME. Int. 1982. Ratz. Zajac. Hutchinson.Y Choo and C. The role of nitrogen and carbon in precipitation strengthening of V- microalloyed steels. T.2. Recrystallization Controlled Rolling of HSLA Steels. 1985.197-211. ASM Intern. Wray). Gray. Stockholm. Conf.21 S. pp.M. 1984. T. on HSLA steels -85. Lee. 4. T.J.2681-2694.1130-1139. and W. M. 7-9. Sandberg. USA. 4. The influence of Processing Route and Nitrogen Content on Microstructure Development and Precipitation Hardening in V-microalloyed HSLA Steels. A.S. Recrystallization Controlled Rolling and Accelerated Cooling as the Optimum Processing Route for High Strength and Toughness in V-Ti-N Steels. PA. Internal Report 1997. Ohio. G. Effects of Recrystallization Controlled Rolling on the Properties of TMCP Steel for Ship Building application. OH.8. S. Symp.219-227.4. 5. Korchynsky. on HSLA Steels – Technology and Application (Ed. (1986).J. by R. Roberts. 1998. pp. 5. Gray. Chapter 5 5. Mechanical Properties of V-Ti Microalloyed Steels Subject to Plate Rolling Simulations Utilizing Recrystallization Controlled Rolling. Zajac.22 S. 1996. (Ed. 78 4. Swedish Institute for Metals Research. San Sebastian. Recrystallization Controlled Rolling of Steels. Zajac. Siwecki. W. pp. Sandberg.. Pittsburgh (1993). ASM.. Int. Warrendale.A.6. Siwecki.7. 1998. on HSLA steels -85. Recrystallization Controlled Rolling and Accelerated Cooling of Ti-V-(Nb)-N microalloyed steels. W. Ed.1. ASM Intern. Siwecki.227-234. M. Processing Characteristics and Properties of Ti-V-N Steels.Siwecki. Metals Park. Beijing. 5. Warrendale. Trans. New trends in Science and Technology of Microalloyed Steels. A. 32nd Mechanical Working and Steel Processing Conference. USA. pp. DeArdo. Lee. The role of carbon in enhancing precipitation strengthening of V-microalloyed steels. Kinetics of precipitation during hot rolling and cooling in microalloyed steels. B. Zheng.5. Thermo- Mechanical Processing in Theory. Zajac. Hutchinson. Fix. M. Symp. on Low- Carbon Steels for 90`s. Sept. Thermomechanical Processing of Microalloyed Austenite. . Pittsburgh. OH. T. MICROALLOYING-95. Int. (1986).. 5. Roberts. Swedish Institute for Metals Research. S. Zajac. ed. 5. Lagneborg. 5. 5. pp. T. Hutchinson and S. Contribution to the Int. . Ed.J.

1983. 5. Roberts. Swedish Institute for Metals Research. 225-233. How changes in composition and processing affect HSLA steels. Chilton and M. 1991. 5. G.17. Technol. Engberg and A. 1996. Trans. pp. by M Korchynsky. pp.67-84. TMS. 5. Crowther. Pittsburgh. Warrendale. Roberts. Contract Report No 39. pp.R.M. ASM/TMS Materials Week 92 Conference. M. pp. PA. Siwecki and T.213-230. Watkins.11.129-133. Lagneborg. Internal Report IM-3101.J.863-873. Minerals. UEM SAV Kosice. Congress and Expo. Thermo-Mechanical Processing in Theory. Development of Recrystallization Controlled Rolling and Accelerated Cooled Structural Steels. PA. ISS-AIME. Modelling of Microstructure Evolution during Recrystallization Controlled Rolling.23. High Strength Steel Processing via Direct Charging using Thin Slab Technology. 79 5. pp. 5. Stockholm. Prediction of Microstructure Development during Recrystallization Hot Rolling of Ti-V-Steels. ed. S. R.N. Metals.Paules. MICRPOALLOYING 95.1-11. Beijing. ASM Internat. Thermomechanical Controlled Processes for High Strength and Toughness in Heavy Plates and Strips of HSLA Steels.21. Jurko and B. PA. British Steel Report (1996). Optimization of Hot Rolling and Cooling Parameters for Long Products. A. 5. 5. P.F. Proc. Materials.. (1997). pp.18. (ASM. (1989). Bodnar and E. 1990. 5. Blomqvist and T. Swedish Institute for Metals Research. Metals Park. Philadelphia.L. J. 89 (1966) pp. 5. pp.16.14. Werlefors. Siwecki. G.J. 279-290. Cuibe. 1984). The Influence of Thermo-Mechanical Process Parameters on the Strength and Toughness in Direct Quenched and Tempered Boron- Steels (Re>700Mpa). T. Siwecki and B.24. Detroit. 5. Tamminen. PA. T.19. S.20. 5. Sandberg. USA. Metall. Siwecki. D. November (1992). Wollongong. ISIJ International. 1994. Report. Intern. Johnson. . Stefan. Warrendale. HSLA steels. SAE_Paper 890801. Pettersson and T. T. Roberts. Louis. (1992).757- 763.397-406. Lubensky. Hutchinson. Siwecki. O. Kovac.25. Melloy.15. THERMEC 97. Siwecki. Microstructure Evolution during Recrystallization Controlled Rolling of V-Microalloyed Steels.13. 32 (1992) pp. 5. MO. Australia. S. Microalloyed Ferrite-Pearlite Forging Steels with Improved Toughness. 5. OH. Microalloyed Forging Steels-State of the Art Review.357-368. 11A (1980) p. St. Metal Progr. L.190 (1998). W.10. Wigman and D. F. Modelling & Practice. V. J. A. Ahlblom. 1995. Sandberg and W. (1995). 33rd Mechanical Working and Steel Processing Conference. pp. T.J.368-376.Korchynsky and J. 1997. HSLA Steels` 85. 34th MWSP Conference. A.1711-1721. ISS-AIME (1992) pp.12. Modelling of Microstructure Evolution during Recrystallization Controlled Rolling of HSLA Steels. 5. T. 5. Recent developments in V-steel structural shapes. Microalloying effects in hot rolled low-carbon steels finished at high temperatures. and Application. Siwecki.22. Zajac and B. Physical Metallurgy of Direct Quenched Steels. (1985). 5. Chicago. V containing High Strength Strip using Thin Slab Casting. R. (1997). ISS-AIME.

Abushosha. Porter. 6. 6. (1979) pp. Trans. Recrystallised controlled rolling and accelerated cooling for high strength and toughness in V-Ti-N-steels.5 C. The influence of composition on the hot cracking susceptability during casting of microalloyed steels processed to simulate thin slab casting conditions. (1990) (In Swedish). Johnson. (1995).J. Chapter 6 6.. 373-375. Suzuki. .N. S.Mitchell.4 R. Surface and structure of thin slab and precipitates in hot strip rolled steel microalloyed with V and Nb. pp. Zhou and R. 6.39-54. Zajac. Internal Report IM-2568.2 T.10 B. Technol. Trans. B. Kinnunen and D. F. Transverse corner cracks in continuously cast microalled steels. Zajac.S. Abushosha. Pittsburgh (1995) pp. O. A. Crowther. (1982) pp. The hot ductility of V. H. Hutchinson and S. Nb/V and Nb containing steels. ISIJ International. T. 22. (1986). Bruce. R. 2284-286. Ironmaking and Steelmaking. 6. 1503- 1506.27. 207. 5. Priestner and C. 22. 6.. 461-468. Ironmaking and Steelmaking. 6. S. High strength steel processing via direct charging using thin slab technology. ISIJ. 2284-286. The evolution of precipitates in Nb-Ti microalloyed steels during solidification and post solidification cooling. Hot ductility behaviour of C-Mn-Nb-Al steels and its relationship to crack propagation during the straightening of continuously cast strand. Zhou.8 B. (1969) pp.P. Lagneborg. Characteristics of hot ductility in steels subjected to melting and solidification. Mintz and R. Finishing Conditions Appropriate for Recrystallization Controlled Rolling of Ti-V-N-Steel. Swedish Institute for Metals Research Confidential Report (1996). in conference proceeding – Fundamentals of Microalloying Forging Steels. Sandberg and W. 477-484. Iron and Steel Inst. 2681-2694.48-56. Arrowsmith. 6. Nishimura and S.. 20. Roberts. T. (1998) pp. 6.9 B. The effect of grain size and precipitation of carbides on the creep properties of Fe-20%Cr-35%Ni alloys. 6.L. Simulation of microstructural evolution in Nb-Ti microalloyed steel during direct hot rolling. Attlegård. Iron and Steel Society Inc. Proc.1 H. pp.7 H. Metall. (1998) pp. 326-332. M.. Trans. (1991) pp. 23A (1992) pp. 6. 24-32. Materials Science Forum. Priestner. Swedish Institute for Metals Research. (1993) pp. Lagneborg. Golden. Mintz and R. Green and P.. Lubensky. Materials Science Forum.W. 469- 476. 326-332.6 R. Materials Science Forum. 2284-286. W.J.26.225-233. Siwecki. Wigman and D. 6.G. Mintz and J. Optimisation of Microalloyed Ferrite - Pearlite Forging Steels. Metall. . Met.13 P. Hutchinson and M. Microalloying ’95. (1998) pp. . 6. 36.L.11 L. Hot ductility of certain microalloyed steels under simulated continuous casting conditions. Siwecki.B. Colorado. Karjalainen. Kovac. 22A.12 D.3 S. (1996) pp. 80 5. Yamaguchi.445-452. J. 6. Siwecki. Influence of vanadium on hot ductility of steel.M. May.

(1995). Symp. 7. pp. I&SS. J.S.Attlegård. S. G. B. The Effect of Vanadium on the Parent Plate and Weldment Properties of Accelerated Cooled API 5LX100 Steels. and W. Pittsburgh. Internal Report IM-2300 (1988). Pittsburgh.337-334. Hart.Orr.T. Heat Input and Nitrogen on the Toughness in Ti-V Microalloyed Steel. The Effect of Vanadium on the Mechanical Properties and Weldability of High Strength Structural Steels. 7. 7. Hannerz. Swedish Institute for Metals Research. Korchynsky et. USA..6. TSM.B. (1993). Welding of HSLA (Microalloyed) Structural Steels.Bowker. ASM/TSM. Ze. T. pp. Zajac. and L-E. Unpublished work . Siwecki. Internal Report IM-2205 (1987). S. Swedish Institute for Metals Research. Mitchell.Ruddle and P. The influence of Steel Chemistry and Weld Heat Input on the Mechanical Properties in Ti-Microalloyed Steels. from Conf. USA. Svensson.E. R.Crowther.(1993)pp. 7. Al. (1986). Rome (1976).. T. The influence Plate Production Processing Route. P.3. 7. Low Carbon Steels for the 90`s.H.1. Mitchell.S. P. Hutchinson. T.511-523.Working and Steel Processing Conf. pp.B. Eds. 81 Chapter 7 7. J. (1990). on Low Carbon Steel at Material Week 93.149-162. 7.Mech.8.Swedish Institute for Metals Research. Siwecki.Ti and N. pp. P. . Ed. Morrison. Hansson. al. 7.F.M.Pittsburgh. Z. The Effect of Microalloying on HAZ Toughness.V. Mitchell. L-E. Weldability of high nitrogen Ti-V microalloyed steel plates processed via thermomechanical controlled rolling. Pittsburgh. P. 7. M. Svensson. Zajac. P. Internal Report IM-2764 (1991).2.4. by A. Intern. Swedish Institute for Metals Research. N.S. DeArdo.5. Siwecki.9.N.403-412.E. 35th. Morrison and D. Influence of nitrogen content and weld heat input on Charpy and COD toughness of the grain coarsened HAZ in vanadium microalloyed steels. Proc. Weld metal and HAZ toughness and hydrogen cracking susceptibility of HSLA steels influenced by Nb. W. and M.365-385. MICROALLOING 95. Hansson and X.7. USA.