REVIEW

Interaction of precipitation with recrystallisation and phase transformation in low alloy steels
D. P. Dunne*
The processes of precipitation, restoration and phase transformation can interact in complex ways during thermomechanical processing of microalloyed steels to profoundly alter their structures and properties. Precipitation in austenite during hot deformation can strongly modify the kinetics of recovery and recrystallisation, subsequently affecting the nucleation and growth of ferrite during cooling. For steels containing strong carbide/nitride formers, interphase precipitation (IP) can occur in ferrite at the austenite/ferrite interface, conferring significant coherency strengthening. Much of what is known about this phenomenon is attributable to the impressive research efforts of Robert Honeycombe and his colleagues at Cambridge.
Keywords: Interphase precipitation, Alloy carbonitrides, Microalloyed steels, Hot deformation, Phase transformation

Published by Maney Publishing (c) IOM Communications Ltd

This paper is part of a special issue in memory of Professor Sir Robert Honeycombe

Preamble
Intensive research has been conducted since the 1960s on thermomechanical controlled processing (TMCP) of commercial microalloyed steels. The results of this work have been extensively published in the international literature and have addressed many of the problems in alloy design and process control. Many excellent reviews have been written on the role of alloy carbonitride precipitation on the structure and properties of hot rolled microalloyed steels,14 and although these sources are referred to where relevant, it was not my intention to produce another comprehensive review. Rather, I have attempted to highlight some of the important contributions to the understanding of the science underlying the precipitation process that were made by Honeycombes Alloy Steels Group, as well as referring in some detail to related Australian work based on research projects conducted by the University of Wollongong, in collaboration with BHP Steel at Port Kembla. The outcomes of this Antipodean work are not well known in the international arena because of only limited publication, mostly in Australian journals and national and international conference proceedings. This research effort was concentrated largely on specic commercial microalloyed steels produced by BHP, but it resulted in the discovery and elucidation of some novel, general phenomena. I gratefully acknowledge that the seeds of this work originated in the experience, knowledge and stimulation that I gained during a study leave at Cambridge in 19771778, working with Robert Honeycombe and the Alloy Steels Group. This study
Faculty of Engineering, University of Wollongong, Northfields Road, Wollongong, NSW 2522, Australia *Corresponding author, email druce@uow.edu.au

leave served as an opportunity for me to re-focus my research pursuits on my return to Australia. I was generously supported and encouraged at Cambridge by Robert Honeycombe to conduct research on an aspect of interphase precipitation (IP) in alloy steels. I had the privilege of working in a research group that included David Edmonds, Barry Muddle, Paul Howell and John Bee. Harry Bhadeshia and Peter Southwick were PhD research students at this time, working respectively, and enthusiastically, on bainitic transformations and duplex stainless steels. Lindsay Greer was also a PhD student and I recall that he assisted me in learning to operate a DSC as a tool for another research strand that I pursued with Mike Stobbs on thermoelastic martensitic transformation in FePt alloys. My research activities leading up to my year in Cambridge started with PhD candidature from 1964 to 1968 at the University of New South Wales, supervised by John Bowles who, in collaboration with Jock Mackenzie, developed the phenomenological crystallographic theory of martensite transformation. My PhD research topic was shape strain measurement in (225)F and (3 10 15)F plate martensites in FeC, FeMnC and FeNiC alloys. This research was followed by nearly three years at the University of Illinois, working with Marvin Wayman, on the crystallography of ferrous martensites and thermoelastic martensitic transformation in FePt alloys. My return to Australia to an academic position at the University of Wollongong in 1970 required a period of adjustment to the teaching trade and allowed only limited research on ferrous martensitic transformations and shape memory alloys. For these reasons, the invitation from Robert Honeycombe to conduct research at Cambridge presented an excellent opportunity to take stock and to diversify my research portfolio, by

410

2010 Institute of Materials, Minerals and Mining Published by Maney on behalf of the Institute Received 26 May 2009; accepted 29 August 2009 DOI 10.1179/026708309X12526555493350

Materials Science and Technology

2010

VOL

26

NO

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

Published by Maney Publishing (c) IOM Communications Ltd

1 Linear VLIN and planar VPL anisotropy factors for ferrite grains after a cold rolling and b cold rolling and batch annealing, as a function of percent cold reduction. Following Underwood,6 VPL is dened as the ratio SV(PL)/SV(TOT); VLIN5SV(LIN)/SV(TOT); and VPLLIN5[SV(PL)zSV(LIN))/SV(TOT)], where SV is grain boundary surface area per unit volume and SV(TOT) includes the planar, linear and isometric values, which are determined from grain boundary intercept densities in the rolling direction, the transverse direction and the direction of the rolling plane normal5,6

branching out into research elds that were potentially more funding-friendly than martensite crystallography. A signicant part of the research conducted in the Alloy Steels Group was focused on clarifying fundamental aspects of alloy carbide and nitride precipitation in laboratory prepared ternary alloys, with the ultimate aim of fuller understanding of the inuence of structure on the mechanical properties of commercial microalloyed steels. The project that I proposed to Robert Honeycombe tted with this research emphasis and consisted of an experimental study of the restoration behaviour of cold rolled FeVC alloy that had been heat treated before cold rolling to produce IP of V4C3.

Precipitation and recrystallisation

I had previously published a paper on pancake grain formation in batch annealed Al killed deep drawing steels.5 The development of grain shape anisotropy in an annealed steel fascinated me and I set out to map the evolution in ferrite grain shape through the cold rolling and recrystallisation processes used for this type of steel. When nished hot and coiled cold, these steels are supersaturated with AlN, which subsequently precipitates out during batch annealing and interacts with the recrystallisation process. Recrystallisation is severely impeded and is nucleation limited, resulting in large recrystallised grains with a preferred orientation that is favourable for sheet forming by deep drawing. The work that I carried out showed that the description of the recrystallised grain shape as pancaked is incorrect, as some linear anisotropy is retained, effectively mimicking, albeit to a reduced extent, the slab shape present after cold rolling. Figure 1 shows that the recrystallised grains have similar planarlinear anisotropy to that of the cold rolled ferrite grains. Cross-rolling, instead of unidirectional rolling, followed by simulated batch annealing resulted in no linear anisotropy, and the grain shape was truly pancaked. Recrystallised grain shape

anisotropy arises because the AlN precipitates on the boundaries of the subgrains and grains of the unidirectionally cold rolled steel, pinning these boundaries and restricting the nucleation of recrystallised domains by grain boundary bulging or subgrain growth/coalescence. Once nucleated, the growth of recrystallised grains proceeds within a forest of impeding particles distributed in planarlinear layers in the deformed matrix. Therefore, growth is anisotropic. My interest in, and curiosity about, the interaction between precipitates and restoration (and/or polymorphic transformation) led naturally to the project that I undertook at Cambridge: ferrite restoration of cold rolled ferrite in a Fe1?05V0?23C (wt-%) alloy containing networks of ne coherent interphase precipitate particles that were present before cold rolling.7 The heat treatment used to generate the starting structure was annealing under argon at 1160uC for 15 min followed by isothermal transformation in a salt bath for 15 min at 747uC. According to Batte and Honeycombe,8 this treatment results in a volume fraction of 0?0123 of V4C3 precipitates of 35 nm radius. Cold rolling of 7?5 mm strip was used to reduce the thickness by 0?1 mm per pass, and samples were taken after each 10% reduction up to 60%, in order to investigate recrystallisation kinetics at 706uC. Cold rolling resulted in a dense and uniform distribution of dislocations, as well as the development of shear bands for reductions greater than 20%. The shear bands were typically 0?24 mm thick and oriented at an angle of about 30u to the rolling direction. The shear band substructure consisted of elongated subgrains ,0?1 mm thick and provided potent sites for nucleation of recrystallisation. Although recovery and recrystallisation occurred rapidly within the bands on annealing of 60% cold rolled samples at 706uC, restoration of surrounding material was severely retarded, and recrystallisation was incomplete after 1000 h. The rate

Materials Science and Technology

2010

VOL

26

NO

411

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

2 a Optical micrograph of the FeVC alloy, showing partially recrystallised structure after annealing of a 60% cold reduced sample at 706uC for 90?5 h.3 b TEM image showing a boundary between a recrystallised grain and the deformed matrix of a 60% cold rolled sample of the FeVC alloy, annealed at 706uC for 1008 h.7 Note interface bowing around pinning particles

Published by Maney Publishing (c) IOM Communications Ltd

controlling step in migration of recrystallising interfaces was the rate of coarsening of pinning particles. Figures 2a and b shows coarsened V4C3 particles in the wake of the advancing recrystallising interface. Precipitates in the unrecrystallised regions remained coherent longer and coarsened more slowly than those incorporated into the recrystallised grains. Grain shape anisotropy was exhibited by the recrystallised grains because of the distribution of precipitates after cold rolling. However, the grain elongation (average length to average width in a transverse direction section) decreased with grain growth from about 1?5 to 1?2 on annealing for 1000 h at 706uC (Fig. 3). Owing to the extended time required for dissipation of the stored strain energy, the three classical restoration processes (recovery, recrystallisation and grain growth) operated simultaneously and competitively in reducing system energy. This experimental alloy provides a relatively high volume fraction of carbide precipitates, facilitating the study of their morphology and crystallography. In contrast, commercial microalloyed steels have low volume fractions of precipitates and are subject to the complicating, interactive effects of multiple elements, as well as more complex thermomechanical treatment. Nevertheless, commercial alloys are at the production (paydirt!) end of the metallurgical spectrum, and it was

there, post-Cambridge and in collaboration with BHP Steel, that I decided to invest a major research effort.

Precipitation and phase transformation in low alloy steels

The signicant interaction between precipitation and phase transformation is well illustrated by the evolutionary advances, since the 1970s, in procedures for the hot rolling of plate and strip steels.9 These advances have been underpinned by developments in both steel design and TMCP. Microalloyed steels containing small amounts of the strong carbide/nitride formers Nb, Ti and V have allowed the production of strong and tough hot rolled steels with improved weldability due to reduced carbon content.

Fundamental aspects of IP
The carbides and nitrides of the alloying elements used in microalloyed steels have fcc crystal structures with closely similar lattice spacings. Isomorphism is therefore possible, allowing mixing of both the metallic elements and carbon and nitrogen. In general the precipitate species in microalloyed steels is a carbonitride: X(C,N), where X is Ti, Nb or V or combinations of these elements, depending on the steel composition. Honeycombes Alloy Steels Group took up the challenge of advancing fundamental understanding of the physical metallurgy of microalloyed steels by studying more highly alloyed ternary or quaternary laboratory steels that are less complex than commercial steels. In particular, the group claried the nature and mechanism of IP, establishing that various types of IP are possible depending on the temperature of isothermal transformation and/or the nature of the austenite/ferrite interface. The most well characterised form of IP consists of planar layers of particles with a uniform interlayer spacing that form at periodically static semicoherent interfaces before being incorporated into the ferrite by lateral propagation of incoherent steps or ledges [interphase precipitation (planar) IPP].10,11 In addition, curved layers of precipitates have been reported in steels containing Cr12 and V.13 These layers are related to curved incoherent boundaries between the austenite and ferrite and have been described as interphase precipitation (curved) (IPC).12,13 In this case, solute accumulation at a moving a/c interface can arrest its motion long enough for precipitation to occur and

3 Average diameter and elongation ratio of recrystallised grains in transverse direction section as function of annealing time at 706uC (log scale): elongation ratio is average mean intercept length to average mean intercept width of ferrite grains7

412

Materials Science and Technology

2010

VOL

26

NO

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

4 a Schematic diagram illustrating how IPR can arise by uncoordinated precipitation of alloy carbide/nitride particles at advancing incoherent a/c interface; and b diagram showing how coordinated precipitation can result in curved layers of particles in ferrite (IPC)18

induce more effective interfacial pinning. Eventual unpinning allows further advancement of the interface before the process repeats itself, and the ferrite grain is decorated with curved, parallel layers of ne precipitates. Ricks et al.1214 proposed an additional subdivision of regular (Reg.) and irregular (Irreg.) layer spacings. It was hypothesised that regular spacing can arise from the formation of quasi-ledges due to localised but restricted break-out of the interface that is followed by lateral propagation of the ledges to incorporate another layer of particles into the ferrite. This mechanism is similar to that occurring at a semicoherent interface to give rise to IPP. In the irregular case, the interfacial pinning process occurs more erratically, leading to layers of variable spacing. In all of these cases, surprisingly, the plate shaped fcc carbide precipitates are characterised by a single variant of the BakerNutting orientation relationship15 with the bcc ferrite: {100}fcc||{100}bcc and n011mfcc||n001mbcc. It was concluded by Honeycombe11,16 that, of the three possible variants, the one selected makes the smallest angle with the interface in order to maximise growth kinetics by interfacial diffusion and to reduce interfacial energy. There are two other types of IP that have been identied by Honeycombe and his research colleagues.2,13 One is a brous form (IPF) observed typically in higher carbon, higher alloy steels. Fibrous carbide precipitation has been reported in Mo17 and V8 steels under conditions favouring slow coupled growth at an incoherent interface. Interphase precipitation (brous form) is essentially a eutectoid type transformation product similar to lamellar pearlite, but with ner carbide particles and a smaller volume fraction of carbide. The second type is referred to as interphase precipitation (random) (IPR) because the single variant particles are randomly dispersed rather than distributed in layers. If a migrating, incoherent a/c interface is undulating due to transient pinning by precipitates, IPR could arise. Unlike a planar or smoothly curved interface, precipitation at such a boundary occurs in an uncoordinated way (Fig. 4a). However, it should be noted that an apparently random distribution of particles may occur for planar precipitate arrays because of the orientation of the foil surface plane relative to the layer plane. The Honeycombe group reported layers with spacings typically between 5 and 30 nm for the more concentrated alloys that they investigated, whereas

Published by Maney Publishing (c) IOM Communications Ltd

Smith et al.1822 found that layer spacings were between 15 and 150 nm for the more dilute commercial steels that they studied. For an untilted, 200 nm thick TEM foil, IPP with layer spacings of 20 and 75 nm will only appear to be in the form of distinct layers in the image if the layers are respectively aligned closer than 6 and 22u to the foil normal.18,19 For small spacings, therefore, particles in layers can be easily construed as randomly dispersed particles. The layer morphology may also be indistinct because the precipitates have formed with a coarse and irregular spacing by the IPC (Irreg.) mode. The type of IP is temperature dependent because the nature of the transforming a/c interface is temperature sensitive. Incoherent boundaries are favoured by high transformation temperatures, and semicoherent boundaries provide the most energetically frugal and kinetically preferred boundaries at lower temperatures. Therefore, the dominant form of the precipitate layers would be expected to shift from IPC (Irreg.) to IPC (Reg.) to IPP with decreasing temperature. However, the variable nature of the transforming interface at a given temperature will ensure that there is considerable overlap of precipitate types. Furthermore, it has been established that different types of IP can occur within the same ferrite grain, associated with a change in the nature of the interface or interfacial boundary segments of different character.2,8,19 It should be noted that there is a nite temperature window over which IP can occur, even if carbonitride precipitation is thermodynamically possible over a wider temperature range. Precipitation can be suppressed on transformation of austenite both at high and low temperatures. The resulting supersaturated ferrite is amenable to subsequent precipitation of carbonitride during continuous cooling, isothermal holding or subsequent aging. In such cases, all three variants of the BN relationship are equally feasible, leading to multivariant precipitation, typically nucleating at dislocation sites.

Interphase precipitation in commercial steels

Investigations of structureproperty relationships in microalloyed steels accelerated sharply in the 1960s, not only in universities such as Shefeld, where Honeycombe and his colleagues were active, but also within research laboratories of major steel producers and materials resource industries, e.g. British Steel, United States Steel, Great Lakes Steel Corp. and Union Carbide. This decade was an especially fruitful one, in which the rst electron micrographs of row precipitation of NbC were reported, initially by Morrison in the UK25 and then by Gray and Yeo26 in the USA. The observation of these precipitates conrmed the inference drawn in earlier reports2730 that precipitation in ferrite resulting from the addition of small concentrations of Nb, V or Ti could produce signicant strengthening of low carbon steels. Initial problems with toughness were overcome by the development of controlled rolling to rene the prior austenite grain size and effect transformation to ne grained ferrite.31,32 Curiosity about the mechanism of precipitation and how it can be optimised to improve strength and toughness of low carbon structural steels drove much of Honeycombes research, initially at Shefeld and then at Cambridge, following his appointment as Goldsmith Professor of Metallurgy in 1966.

Materials Science and Technology

2010

VOL

26

NO

413

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

5 Dark eld electron micrograph using {002}VC electron diffraction spot for V steel isothermally transformed for 180 min at 810uC:18 irregularly spaced, curved layers of V(C,N) are present, i.e. IPC (Irreg.); bar represents 1 mm

The modes of IP identied and characterised by Honeycombes group using laboratory ternary alloys have largely been conrmed in more dilute multicomponent microalloyed steels in the isothermally transformed and hot rolled conditions. For example, research at the University of Wollongong1822 on commercial low carbon V, Nb and Ti microalloyed steels has demonstrated that, apart from IPF, isothermal transformation of these steels resulted in the same types of IP of alloy carbonitride particles that were documented by Honeycombes group for higher alloy, experimental steels. Moreover, continuously cooled hot rolled strip samples showed the same types of IP as for isothermally transformed samples. Early work was concentrated on a commercially hot rolled 0?07%C, 0?14%V alloy.1820 This alloy has about one-third of the C and one-seventh of the V for the ternary alloy studied at Cambridge. Nevertheless, reaustenitising at 1200uC followed by isothermal transformation in molten salt at selected temperatures in the range 820650uC showed that IPC (Irreg.) was dominant for temperatures .810uC (Fig. 5), with IPC (Reg.) and IPP being prominent for temperatures ,810uC (Fig. 6). Interphase precipitation (planar) increased in frequency with decreasing temperature. Hot deformation by up to 50% by rolling in the temperature 920800uC resulted in profound renement of the precipitate size and spacing on subsequent isothermal transformation at a lower temperature. Figure 7 shows IPP in a sample of the V steel, which had been

7 Bright eld electron micrograph of V steel, deformed 50% at 800uC, then isothermally transformed at 800uC for 2 min before quenching:18 bar represents 0?5 mm

6 Bright eld electron micrograph of V steel, isothermally transformed at 750uC for 15 min:18,19 precipitate layers are typical of IPP; bar represents 0?5 mm

reduced 50% by rolling at 800uC and quenched after a 2 min hold. The precipitate layers are typical of IPP, and the layer spacing (y80 nm) is close to that shown in Fig. 6 for the transformation from undeformed austenite at a temperature 50uC lower.22 Progressive transformation to ferrite on holding at 800uC resulted in ferrite grain renement well in excess of that expected from the increase in austenite grain surface area/unit volume SV by deformation.22 For >50% reduction of austenite with a coarse starting grain size (150 mm), the transformation product consisted of a series of layers of ne ferrite grains,22 produced by a process termed cascade nucleation.23 This behaviour is different to that typically found for Nb steels in which continued ferrite formation tends to proceed by selective growth of preferred grains.24 It was inferred that, as a result of higher solubility of V(C,N) in austenite, solute drag and copious IP during transformation limit boundary mobility, allowing nucleation of new grains in successive layers ahead of the advancing transformation front. Another important conclusion of this work was that transformation to ferrite from deformed austenite is, in effect, a surrogate recrystallisation process driven by both stored strain energy and chemical free energy. As a result of continuous cooling during transformation of either recrystallised or deformed austenite in commercial processing, the nature of the a/c interface is likely to be highly variable. Therefore, IP is not expected to be as extensive nor as well developed or readily observable as in isothermally transformed samples. Nevertheless, both IPP and IPC have been observed in commercially hot rolled steels. Figure 8 shows IPP in the commercially rolled V steel. In addition, carbonitride precipitation has been found on sub-boundaries of the deformed austenite. These particles do not exhibit the BN orientation relationship and have clearly formed in deformed austenite during nish rolling before being incorporated into the ferrite formed during continuous cooling. The important role of carbonitride precipitation in austenite in controlled, non-recrystallisation, hot rolling is discussed further in the section on Precipitation and retardation of austenite recrystallisation. It is apparent that carbonitride that is preprecipitated in austenite is lost to precipitation in, and strengthening of,

Published by Maney Publishing (c) IOM Communications Ltd

414

Materials Science and Technology

2010

VOL

26

NO

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

8 Bright eld electron micrograph of V steel in as hot rolled condition: IPP of V(C,N) is evident;18,19 layer spacing is ,15 nm, and bar represents 0?2 mm

Published by Maney Publishing (c) IOM Communications Ltd

ferrite that forms on cooling. Nevertheless, the full potential for precipitation of the remaining carbonitride in solution in ferrite is unlikely to be realised during commercial TMCP of strip steels.

Effect of precipitation on ferrite strength and toughness

The effect of isothermal holding time on the hardness of ferrite produced in the temperature range 600750uC for a commercial NbzV microalloyed steel is shown in Fig. 9a. In general, the hardness of the rst formed ferrite grains increased with decreasing temperature in the range 750650uC. Interphase precipitation is a major microstructural contributor to the hardness (strength), and its effect intensies with decreasing temperature of formation because of decreasing particle size and layer spacing.9,33 Holding at the isothermal transformation temperature resulted in a decrease in hardness, mainly due to particle coarsening. Another, more minor, softening factor is the recovery of the dislocation substructure resulting from the polymorphic transformation. An exceptional result occurred for 600uC. The initial hardness was relatively low because the ferrite formed without IP. However, isothermal holding resulted in a hardness peak due to multivariant precipitation of VC

from the supersaturated ferrite. These hardness changes mirror trends in yield strength which indicate that precipitation hardening can increase the yield stress of Nb microalloyed steels by up to ,200 MPa, depending on the particle size and volume fraction.33 Experiments on aging of commercially hot rolled V, Nb and VNb strip steels demonstrated that they had additional precipitation hardening capacity because the ferritic transformation product formed on continuous cooling remained supersaturated with alloy carbonitride (Fig. 9b). This additional precipitation is clearly distinguishable from IP through its multivariant nature.20,21 Ferrite grain renement is a strong toughness enhancing factor for structural steels, and carbonitride precipitation in both austenite and ferrite can affect the as rolled ferrite grain size. The solubilities of Ti, Nb and V carbonitrides in austenite have been thoroughly examined,2 and it has been concluded that Ti carbonitrides are least soluble and V carbonitrides have the highest solubility. Furthermore, the nitrides are more stable than carbides and coarsen more slowly on isothermal holding in the austenitic state.2 Undissolved carbonitrides can limit austenite grain size during reheating for hot rolling and thereby enhance renement through recrystallisation during successive hot rolling passes. Precipitation of ne carbonitrides during the nish rolling stage can strongly inhibit recrystallisation and ensure that stored strain energy catalyses ferrite nucleation during cooling below the Ar3 temperature as well as reducing growth rate by IP. The net result is a ne grained ferrite structure with impact transition temperatures as low as 250uC, combined with yield strengths above 400 MPa.33

Interphase precipitation in Cu bearing steels

Ricks et al.14 established that the IP mode in steels is not unique to carbonitrides by demonstrating the presence of IP in FeCuNi alloys. Interphase precipitation (planar) of e-Cu was obtained by isothermal transformation of Fe2Cu2Ni alloy at 720uC. This form of precipitation has also been reported for a commercial ASTM A710 type steel produced by BHP Steel, with the composition of 0?055C1?40Mn0?25Si0?85Ni1?10Cu 0?02Nb0?013Ti0?012P0?003S0?0075N.3437 This type of steel is being increasingly used as a more weldable

9 a Effect of isothermal holding temperature and time on hardness of rst formed ferrite in commercial NbzV steel, reaustenitised at 1200uC for 15 min, then quenched into molten salt at each of the indicated temperatures21 (steel composition: 0?09C1?00Mn0?051Nb0?057V0?05Al0?012N) and b aging responses at 500uC of three commercial, TMCP strip steels containing ,0?08%C and 0?14%V, 0?057%Vz0?051%Nb and 0?049%Nb (Ref. 21)

Materials Science and Technology

2010

VOL

26

NO

415

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

10 Bright eld electron micrograph of Cu steel, isothermally transformed at 600uC for 160 min: particles are predominantly single variant, and layer morphology is consistent with IP;34,35 bar represents 0?5 mm

11 Aging response curves of Cu steel samples at 500uC, in ferritic, bainitic and martensitic conditions36

substitute for HY80 as structural plate for naval and offshore structural applications. Although normally used in the quenched and tempered condition (ASTM A710, grade A, class 3), BHP Steel developed the above, more alloy lean steel for production by a TMCP route. The processing schedule involved recrystallisation rolling to produce ne recrystallised austenite, nonrecrystallisation nish rolling to ensure that ferrite transformation occurred from deformed austenite, controlled cooling to 500550uC to minimise e-Cu precipitation and, nally, aging at 550uC for 30 min to induce e-Cu precipitation.37 The specied minimum yield stress of this steel, designated CR HSLA 80, is 550 MPa. The e-Cu precipitates that were observed in hot rolled and aged steel were often in arrays of a single variant. The orientation relationship between the fcc e-Cu and bcc a-ferrite is KurdjumovSachs: {111}e||{110}a and 0me||n1 12ma. Although there are 24 possible variants, n11 single variant planar arrays were observed both in isothermally transformed samples (see Fig. 10) and also in rolled and aged material. In many cases, the precipitates of e-Cu were apparently in a random distribution but with a single orientation variant. These observations suggest that the precipitate arrays form in an uncoordinated way during cooling, in association with the motion of an incoherent interface (see Fig. 4a). Subsequent aging may have served to coarsen the particles without substantial new multivariant precipitation. The apparently random distribution of particles may arise from a layered distribution that is not obvious because of the foil section relative to the layers, as mentioned previously, or because they have formed by the IPC (Irreg.) mode. After solution treatment and cooling slowly enough to generate a ferrite plus pearlite structure, samples were aged at 500uC. The hardness increased above that of the unaged condition (185 HV) due to precipitation hardening, before falling due to particle coarsening and overaging (Fig. 11). Alternative heat treatments were carried out that involved re-austenitising at 1200uC for 15 min, followed by quenching to ambient to form martensite and isothermal transformation to bainite at 440uC for 5 min. The bainitic and martensitic samples were also aged at 500uC, resulting in signicant

secondary hardening because of multivariant precipitation e-Cu.36 The peak hardnesses shown in Fig. 11 are 225 HV (ferrite), 245 HV (bainite) and 292 HV (martensite), but the hardness increment relative to the base hardness is similar in each case (in the range 2540 HV points). These results and those shown in Fig. 9 indicate that alternative processing routes to conventional TMCP can produce signicantly higher strength levels by taking full advantage of the precipitation hardening potential of the microalloyed steel as well as the form of the matrix phase. Despite the typically adverse effect of precipitation hardening on impact toughness,33 this low carbon, copper bearing steel exhibited Charpy V notch (CVN) values in the TMCP and aged condition that exceeded the minimum specied for ASTM A710-84 (27 J at 245uC) as well as for HY80 (MIL-S, US military specication: 47 J at 251uC). The minimum CVN values were also found to be surpassed for simulated heat affected zone (HAZ) microstructures, equivalent to welding of 20 mm plate without preheat, at a heat input of 2?9 kJ mm21.38 However, after post-weld heat treatment at 550uC for 1 h, the average CVN for the simulated grain coarsened HAZ was 18 J lower than the MIL-S specied minimum of 47 J at 251uC. In contrast, post-weld heat treatment at 450 or 650uC for 1 h gave CVN values .120 J, and so it was concluded that signicant rehardening by precipitation of e-Cu at 550uC compromised the impact toughness.38 The low impact toughness is associated with maximum precipitation strengthening by ne precipitate particles or zones (,5 nm in diameter). However, for the solution treated and the overaged conditions, exceptional toughness is exhibited. In the latter case, it is likely that the coarsened e-Cu particles deform plastically, absorbing impact energy, rather than cracking or decohering from the matrix in the stress concentration zone ahead of a sharp crack. Tomita et al.39 proposed a similar interpretation for the unexpectedly high toughness of high strength Cu bearing steels. They examined a range of low carbon, Cu bearing steels designed for a 590 MPa minimum yield stress and suitable for medium to high heat input welding of 2580 mm plate. The steels developed showed excellent Charpy impact energies (260uC) and fracture toughness for the grain coarsened HAZ at medium (5 kJ mm21) heat input, as well as

Published by Maney Publishing (c) IOM Communications Ltd

416

Materials Science and Technology

2010

VOL

26

NO

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

acceptable results for a high heat input (10 kJ mm21). They concluded that the weld thermal cycle dissolved the Cu, and it was not reprecipitated for weld cooling rates that exceeded 5uC min21 [0?08uC s21 or a cooling time between 800 and 500uC (Dt825) of y1 h].

Precipitation and retardation of austenite recrystallisation

It is well known that nish rolling of Nb steels at relatively low temperatures signicantly increases the rolling load. This increase in load is widely considered to be due to NbC precipitation in austenite, which effectively prevents austenite softening by recrystallisation.33,40,41 Research on hot deformation of austenite in V and Ti bearing steels has also demonstrated that static recrystallisation is profoundly retarded by deformation below a specic temperature in the approximate range 1000850uC, which, for the purpose of industrial hot rolling, is called the non-recrystallisation temperature, since nishing below it ensures that ferrite forms from deformed austenite. Strain in the austenite catalyses precipitation and the precipitates then stabilise the deformed austenite against restoration by recovery and recrystallisation. Subsequent cooling produces phase transformation in a heterogeneous environment with a high density of potential nucleating sites. Substantial ferrite grain renement occurs, provided that nucleation, rather than grain growth, dominates in driving transformation. The resulting ne grained, hot rolled steel typically exhibits a yield stress well in excess of 350 MPa, a minimum often used to dene a low carbon structural steel as a high strength low alloy steel. The toughness is simultaneously increased because of grain renement. Despite the inference drawn from hot mechanical testing that alloy carbonitride precipitation in deformed austenite is responsible for retarded recrystallisation, direct evidence remained sparse for many years because the polymorphic transformation of austenite to ferrite destroys the nexus between the precipitates and the deformed austenite. This uncertainty generated some controversy about whether it was Nb in solution or NbC precipitation that was responsible for the retarded restoration of deformed austenite in Nb microalloyed steels. This difference evaporated over time with the realisation that the issue was not either/or and that both Nb in solution and NbC precipitation exert retarding effects on recovery and recrystallisation. Retardation of austenite restoration through the presence of Nb, Ti or V in solution in steels with very low interstitial contents (0?002C0?002N, wt-%) has been demonstrated by Yamamoto et al.42 The effectiveness of retardation decreases in the order listed and is consistent with decreasing atomic distortion by the solute atom.2 Precipitation of ne alloy carbide in deformed austenite is, however, much more effective than the solid solution of the carbide forming element in retarding recovery and recrystallisation of deformed austenite.40,41 However, the polymorphic transformation makes it difcult to distinguish ne particles that formed in austenite and those that formed in ferrite. Indirect evidence of precipitation in deformed austenite has been obtained using TEM replicas of samples of Nb microalloyed steels quenched after austenite

12 Dark eld electron micrograph, using {002}VC, for V steel deformed 50% at 840uC and held for 20 min at 840uC before quenching: precipitates have formed on deformation substructure of austenite;18 bar represents 0?5 mm

Published by Maney Publishing (c) IOM Communications Ltd

deformation (see, for example, Ref. 42). Similar observations18 for thin foil samples of V microalloyed steel showed that V4C3 particles were distributed along grain and subgrain boundaries of austenite deformed during the nishing rolling pass (Fig. 12). The sites and morphologies of the precipitates and their orientation relationships with the matrix can be used to infer particle formation in austenite, as shown for the subgrain network distribution of V4C3 particles in Fig. 12. However, quenching was used in this case to try to preserve vestiges of the grain and subgrain structure of the deformed austenite, and it would obviously be preferable to retain the as deformed austenite at room temperature. This concept was pursued by Abdollazadeh et al.,43,44 who designed an austenitic alloy (Fe0?15C30?7Ni0?02Nb) as an analogue of a low carbon Nb microalloyed steel to allow direct observation at room temperature of NbC precipitates in the retained, hot deformed austenite. Uniaxial compression was used for hot deformation. This work conrmed that both recovery and recrystallisation in the Nb steel were retarded relative to a Nb free reference steel with similar contents of the other elements. Retardation of both recovery and recrystallisation was even stronger following strain stimulated precipitation of NbC on grain boundaries and the subgrain network of the deformed austenite. The research established that carbide precipitation not only served to maintain the work hardened condition of the austenite, but it also conferred a transient precipitation hardening effect (Fig. 13). The orientation relationship between austenite and the cubic carbides, nitrides and carbonitrides of Nb, V and Ti is cubecube.11 Since the lattice parameter of NbC is close to 0?44 nm and that of austenite in an Fe30Ni alloy is about 0?360?37 nm (ignoring effects of thermal expansion), there is a relatively large atomic mismatch of about 20% along directions in the {100} planes. Nevertheless, age hardening does occur as demonstrated by the peak recorded for the analogue steel. The carbideaustenite interface in these cases is likely to be semicoherent, producing a strain eld that inhibits dislocation motion. However, overaging occurred

Materials Science and Technology

2010

VOL

26

NO

417

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

14 Time to 50% recrystallisation as function of deformation temperature at strain levels of 0?25 and 0?5 for Nb containing and Nb free austenitic steels43 13 Hardness of austenite in Nb containing and Nb free Fe30?5Ni0?15C alloys as function of isothermal holding time at 850uC, after hot compression to strain of 0?25 (Ref. 44)

rapidly at the relatively high aging temperature used to generate the data in Fig. 13. The precipitation of NbC inferred from the aging peak in Fig. 13 is consistent with the substantial delay, evident in Fig. 14, in the progress of static recrystallisation at 850uC. Figure 14 compares the times to 50% recrystallisation in the Nb and Nb free steels for two strain levels 0?25 and 0?50. The delay in recrystallisation below 900uC for the Nb steel reects the stabilising effect of NbC precipitation on the deformed austenite structure. At higher temperatures, recrystallisation is still retarded in the Nb steel compared with the Nb free steel because of the effect of solute Nb. Figures 13 and 14 are consistent with hot working results reported for many investigations of austenite deformation and restoration in microalloyed steels by laboratory hot rolling, torsion and uniaxial and plane strain compression. The interaction of precipitation, recrystallisation and phase transformation during the nishing stages of hot deformation can be rationalised by considering the processes that are possible over different temperature regimes. At higher temperatures, precipitation does not exert any effect on recrystallisation if it occurs after recrystallisation is complete. However, when precipitation occurs on the deformation substructure, it can severely retard the progress of recrystallisation, as shown in Fig. 14. A hot rolling investigation of a 0?076% Ti microalloyed steel45 also showed that recrystallisation was strongly retarded on rolling below 1030uC. Moreover, a CMn reference alloy also showed retarded recrystallisation on rolling below 950uC, and it was suggested that AlN precipitation on the substructure of the deformed austenite can, over an appropriate temperature range, exert a similar effect to alloy carbonitride precipitation, especially if the starting austenite grain size is large and solute drag contributes to a delay in recrystallisation until precipitation commences. These observations return the discussion full circle to the starting analysis of the effect of AlN precipitation in deformed ferrite on recrystallisation during batch annealing. The general principle

emerges that precipitation of ne particles in a hot or cold deformed, ferritic or austenitic structure can be expected to signicantly retard subsequent static recrystallisation. The age hardening effect shown in Fig. 13 is consistent with many reports on hot mechanical testing of austenite in Nb microalloyed steels, which show substantial increases in ow stress with decreasing test temperature (e.g. Ref. 40). This austenite strengthening is generally assumed to arise from NbC precipitation that prevents static recrystallisation. In the analogue alloy case, the hardening of the austenite on isothermal holding was followed by direct structural analysis using TEM.43 Hardening started on holding at 850uC for .12 s. For shorter times, the austenite in the Nb steel showed a higher dislocation density and ner cells with more tangled dislocation cell walls compared with the Nb free steel at the same strain. The higher hardness of the austenite in the Nb steel for times up to y10 s (Fig. 13) is a result of the difference in dislocation substructure arising from the presence and absence of Nb in solution. No precipitation of NbC was detected until holding time exceeded about 20 s, but once precipitation occurred, the dislocation substructure was strongly stabilised, as illustrated by the comparative TEM images shown in Fig. 15 for a 40 s holding time. The time to 5% static recrystallisation at 850uC after 0?25 strain was found to be ,10 s for the Nb free steel and ,100 s for the Nb steel.43 A TEM image of a sample of the partially recrystallised Nb steel (450 s at 850uC, 0?25 strain) is given in Fig. 16 and shows a grain boundary separating a recrystallised grain from the deformed austenite structure. As for recrystallisation of ferrite in the FeVC alloy (see Fig. 2b), the precipitates of NbC were signicantly coarser after passage of the recrystallising interface as a result of transient pinning of the interface and coarsening by grain boundary diffusion. In both cases, ne carbides were present before, and exerted a retarding effect on, recrystallisation of the deformed matrix. Similar recrystallised grain structures evolved in the two cases, with a common feature of dispersed, coarsened carbide particles within the matrix of the recrystallised grains.

Published by Maney Publishing (c) IOM Communications Ltd

418

Materials Science and Technology

2010

VOL

26

NO

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

a Nb free steel; b Nb containing steel 15 Images (TEM) showing deformation substructures in austenite after holding for 40 s at 850uC, following 0?25 strain in uniaxial compression at same temperature:43,44 bar represents 2 mm for both images

Conclusions
Precipitation during nish rolling of microalloyed steels stabilises the deformed austenite structure, increasing the rolling load and ensuring that substantial strain is retained to augment the driving force for subsequent polymorphic transformation to ferrite. A high density of potential nucleating sites for ferrite is generated by the increase in SV by deformation and the structural heterogeneities associated with the excess dislocations. The result is transformation to ferrite with a small average grain size. Despite pre-precipitation of alloy carbonitride in austenite, its lower solubility in ferrite generally ensures that precipitation also occurs in ferrite, producing a strength increment by precipitation hardening. The alloy composition and the TMCP route are typically designed to balance the extents of precipitation in austenite and ferrite to optimise the contributions of grain renement and precipitation strengthening to the mechanical properties of the ferrites. Nevertheless, the research conducted at the University of Wollongong has established that the relatively fast cooling rates associated with strip rolling normally ensure that the ferrite remains supersaturated with alloy carbonitride because of incomplete precipitation in ferrite during continuous cooling. Subsequent aging treatment has been shown to enable enhanced precipitation strengthening. A similar

Published by Maney Publishing (c) IOM Communications Ltd

conclusion applies to the type of Cu bearing precipitation hardening microalloyed steel considered in this paper. Heat treatment to produce a martensitic or bainitic structure, followed by a suitable aging treatment, can result in signicantly higher strength levels than those achieved by the TMCP and aging route. For both alloy carbonitride and e-Cu precipitation in ferrite, relatively small volume fractions of precipitate particles can exert an unexpectedly profound effect on mechanical properties. My intention in writing this contribution was to show how effectively the science underpinning the development of microalloyed steels was elucidated by Honeycombe and his research colleagues at Cambridge and how profoundly it inuenced international research in this area. This component of Robert Honeycombes research output stands both as a legacy to metallurgical science and engineering and a tribute to his outstanding abilities as a researcher and research leader.

Acknowledgements
I have already expressed my gratitude for the contribution of Robert Honeycombe and I would also like to acknowledge Ross Smith, Amir Abdollah-Zadeh and Ghasemi Banadkouki who, as PhD students under my supervision, generated many of the results referred to in this review of work undertaken at the University of Wollongong. In addition, I would like to record my appreciation for the enthusiastic co-operation and support of colleagues at BHP Steel (now BlueScope Steel) over many years. In particular, I would like to thank Jim Williams, Chris Killmore and Frank Barbaro.

References
1. J. H. Woodhead and S. R. Keown: A history of microalloyed steels, in HSLA steels metallurgy and applications, Proc. Int. Conf. HSLA steels 85, (ed. J. M. Gray et al.), 15; 1986, Beijing, ASM International. 2. R. W. K. Honeycombe: Fundamental aspects of precipitation in microalloyed steels, in HSLA Steels metallurgy and applications, Proc. Int. Conf. HSLA steels 85, (ed. J. M. Gray et al.), 243; 1986, Beijing, ASM International. 3. A. J. DeArdo: New concepts in the design and processing of high performance steels, in Proc. HSLA steels 95, (ed. G. Liu et al.), 99112; 1995, Beijing, China Science and Technology Press. 4. T. N. Baker: Microalloyed steels an invited review, in Developments in metals and ceramics, Proc. Conf. on 70th birthday meeting of Sir Robert Honeycombe, (ed. J. A. Charles ET AL.), 76119; 1992, London, Institute of Materials. 5. D. P. Dunne and R. L. Dunlea: Metall. Forum, 1978, 12, 156164.

16 Image (TEM) showing grain boundary separating recrystallised grain from deformed austenite structure in FeNiNbC alloy: sample uniaxially compressed to 0?5 strain at 850uC and held for 450 s at 850uC;43 bar represents 0?5 mm

Materials Science and Technology

2010

VOL

26

NO

419

Dunne

Precipitation, recrystallisation and phase transformation in low alloy steels

Published by Maney Publishing (c) IOM Communications Ltd

6. E. E. Underwood: Quantitative Stereology; 1970, Reading, MA, Addison Wesley. 7. D. Dunne: Met. Sci., 1982, 16, 259267. 8. A. D. Batte and R. W. K. Honeycombe: J. Iron Steel Inst., 1973, 211, 284. 9. R. W. K. Honeycombe and H. K. D. H. Bhadeshia: Steels microstructure and properties, 2nd edn; Chap. 10, 1995, London, Metallurgy and Materials Science. 10. A. T. Davenport, F. G. Berry and R. W. K. Honeycombe: Met. Sci. J., 1968, 2, 104. 11. R. W. K. Honeycombe: Metall. Trans. A, 1976, 7A, 915. 12. R. A. Ricks and P. R. Howell: Met. Sci., 1982, 16, 317. 13. R. A. Ricks and P. R. Howell: Acta Met., 1983, 31, 853. 14. R. A. Ricks, P. A. Howell and R. W. K. Honeycombe: Metall. Trans. A, 1979, 10A, 1049. 15. R. G. Baker and J. Nutting: ISI special report no. 64, 1959, 1. 16. R. W. K. Honeycombe: Ferrite, Hatfield Memorial Lecture, 1979, Met. Sci., 1980, 14, 201214. 17. F. G. Berry, A. T. Davenport and R. W. K. Honeycombe: in The mechanism of phase transformation in crystalline solids, Institute of Metals Monograph no. 33, 328, 1969. 18. R. M. Smith: Structural aspects of the hot working of vanadium and niobium high strength low alloy steels, PhD thesis, University of Wollongong, Wollongong, NSW, Australia, 1987. 19. R. M. Smith and D. P. Dunne: Mater. Forum, 1988, 11,166181. 20. R. M. Smith, D. P. Dunne and J. G. Williams: Met. Forum, 1982, 5, (2), 109. 21. D. P. Dunne, R. M. Smith and T. Chandra: Proc. Thermec 88, Tokyo, Japan, June 1988, Iron Steel Institute, 275. 22. R. M. Smith, D. P. Dunne and T. Chandra: in High strength low alloy steels, (ed. D. P. Dunne and T. Chandra), 188; 1984, Port Kembla, NSW, South Coast Printers. 23. R. K. Amin and F. B. Pickering: in Thermomechanical processing of microalloyed austenite, (ed. A. J. de Ardo et al.), 377; 1982, Pittsburgh, PA, AIME. 24. W. Roberts: Scand. J. Metall., 1980, 9, 13. 25. W. B. Morrison: J. Iron Steel Inst., 1963, 201, 317. 26. J. M. Gray and R. B. G. Yeo: Trans. ASM, 1968, 61, 225. 27. Great Lakes Steel Corp.: Mech. Eng., 1959, 81, 53. 28. C. A. Beiser: ASM preprint no. 138, 1959. 29. W. C. Leslie: NPL Conf. Proc., 334; 1963, London, HMSO. 30. W. B. Morrison and J. H. Woodhead: J. Iron Steel Inst., 1963, 201, 43.

31. E. R. Morgan, T. E. Dancy and M. Korchynsky: J. Met., 1965, 829. 32. R. Phillips and J. A. Chapman: J. Iron Steel Inst., 1966, 204, 615. 33. F. B. Pickering: Physical metallurgy and the design of steels; 1978, Essex, Applied Science Publishers Ltd. 34. S. S. Ghasemi Banadkouki: Transformation characteristics and structure-property relationships for a copper-bearing HSLA steel, PhD thesis, University of Wollongong, Wollongong, NSW, Australia, 1996. 35. D. P. Dunne, S. S. Ghasemi Banadkouki and D. Yu: ISIJ Int., 1996, 36, 324. 36. S. S. Ghasemi Banadkouki, D. Yu and D. P. Dunne: ISIJ Int., 1996, 36, 61. 37. C. R. Killmore, J. F. Barrett, A. Cabello, I. F. Squires and J. G. Williams: Proc. Conf. on Offshore mechanics and arctic engineering, The Hague, The Netherlands, March 1989, ASME. 38. D.P. Dunne: Weldable copper strengthened low carbon steels, Proc. HSLA steels 95, (ed. G. Liu, H. Stuart et al.), 99112; 1995, Beijing, China Science and Technology Press. 39. Y. Tomita, T. Haze, N. Saito, T. Tsuzuki, Y. Tokunaga and K. Okamoto: ISIJ Int., 1994, 34, 836. 40. C. M. Sellars: The influence of particles on recrystallisation during thermomechanical processing, Proc. 1st RISO Conference on Metallurgy and Materials Science: Recrystall 1 section and Grain Growth in Multiphase and Particle Containg Materials, (ed. by N. Hansen, A. R. Jones and T. Leffars), Raskilde, Denmark, 1980, 291. 41. I. Weiss and J. J. Jonas: Metall. Trans. A, 1979, 10A, 831. 42. S. Yamamoto, C. Ouchi and T. Otsuka: in Thermomechanical processing of microalloyed austenite, (ed. A. J. de Ardo et al.), 613; 1982; Pittsburgh, AIME. 43. A. Abdollah-Zadeh: Investigation of deformation, recrystallisation and precipitation in austenitic HSLA steel analogue alloys, PhD thesis, University of Wollongong, Wollongong, NSW, Australia, 1996. 44. A. Abdollah-Zadeh and D. P. Dunne: Recovery and recrystallisation in steel, Proc. 37th MWSP Conf., Hamilton, Ont., Canada, 1996, ISS-AIME, 74. 45. D. P. Dunne, T. Chandra and S. Misra: HSLA steels metallurgy and applications, in Proc. Conf. Microalloying 85, (ed. J. M. Gray et al.), 207; 1985, Beijing, ASM.

420

Materials Science and Technology

2010

VOL

26

NO