S dhan Vol. 28, Parts 3 & 4, June/August 2003, pp. 731737.

Printed in India a a

Future developments and applications of nitrogen-bearing steels and stainless steels

J FOCT
Laboratoire de Metalturgie Physique et Genie des Matetiaux-UMR CNRS 8517, Universite de Lille 1, Bdt, C6-2ene Etage, 59655 Villeneuve dascq Cedex, France e-mail: jacques.foct@univ lille1.fr Abstract. After considerations related with the global frame of the demand of society in the eld of materials and some recalling of basic properties and principles of nitrogen alloying, possible future developments are listed and discussed. Keywords. N2 -bearing steels; stainless steels, nitrogen alloying.

1. Introduction Verba volant, scripta manent, so thought the Romans for whom the fate of speech was to y away and to disappear in the general noise, in contrast to that of writing that was likely to stay. Because this Latin sentence was written much before Gutenberg and the Internet, the erosion of scripta was not so well-established, although even now some people believe that what is simply written is in fact engraved in unperishable marble. Doubts about this eternity can be expressed and therefore it is worth taking the risk to document the future of high-nitrogen steels (HNS). This exercise demands at the same time several contradictory qualities: prudence and imprudence, modesty and pride. This precautionary paragraph offers the right if not the duty to abandon a cautious attitude in order to explore still undiscovered elds. A strict, rigorous and scientic process is to be replaced by a soft philosophical and imaginative approach. Meanwhile, this approach needs to be supported by more arguments and observations the basic principles of physical metallurgy and materials sciences some of the results and interpretations have already been published119 . Trends in steel making and technology as well as the attitude of the global society are to some extent more risky to decipher and base predictions on. After a reasonable attempt to deduce generic trends, some special domains where nitrogen alloying could be promising are listed and commented upon in this paper. 2. Deciphering of global trends likely to inuence future developments of HNS Sociological, political, economical studies brought out many aspects about the present evolution of society: globalisation, efciency, exibility . . . and contradiction. A rather important
References

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ignorance about these domains has to be admitted by the author, who proposes a caricatural resume of the attitude of society in many parts of the world, as depicted by a cartoon which shows a top tribune triumphalanty announcing Now you got everything, and to whom the crowd answers, We demand everything else. This anecdote is rather consistent with the very common feeling according to which society simultaneously desires one thing and its converse: risk and security, quality and cheapness, equality and privilege. Despite the difculty in evaluating the impact of these human factors on the future of HNS many demands of society may inuence positively the development of HNS. Safety in the eld of transportation (cables for telphers, blades of reactors, landing parts of aircraft, wheels for trains, bodies for cars, double shells for fuel tankers . . . ). Environment-friendly technologies (safety in oil pipelines, oil exploration . . . ). Safety and reliability of industrial plants and equipment (mechanical industry, car industry, nuclear reactors, control devices, cutting machine, paper industry . . . ). Reliability and new possibilities in civil engineering and structures. Leisure and sport industry (high demand for extreme mechanical resistance and lightness). Defence and space industry. All the possible niches afforded to HNS by above domains correspond to high mechanical resistance (yield stress, ultimate tensile stress, ductilebrittle temperature transition, fatigue life, critical stress intensity factor, ductility . . . ) and increased corrosion resistance (pitting corrosion, crevice corrosion, stress corrosion, corrosion fatigue . . . ), i.e. all properties for which the addition of nitrogen is found to be benecial. The industrial society also imposes some constraints to the development of HNS and even poses some obstacles. Constraints are related to price, availability of materials (need for different suppliers), well-established qualication and norms, data bank of properties. These constraints suggest that there exists some sort of threshold that has to be overcome for spreading the applications of HNS over a wider range. Time scales of economics and research do not always coincide. Time scale in industrial management results from the actualisation of assets, expenses and revenue. Since the required time to nalise new HNS grades, protocol of use and implementation is decreasing with new techniques of modelling and simulation, and because some clear and appreciable advantages from the usage of HNS are established, matching the two a priori different time constraints is far from being insurmountable. Obstacles are also related to inertia and intellectual laziness which have some consequences on education and research. The probable and implicit reasoning which leads to this attitude is based on a biased interpretation of the kinetics of evolution of any domain according to which an S-shaped curve would be followed (see gure 1). If axes are considered in arbitrary units, any domain is equivalent to the other. If in contrast with this view relevant units such as gross global product (P ) vs/time (t) is considered, domains for which the derivative dP /dt decreases may be much more promising than other domains with larger derivatives (see gure 1), and this because the residual potential of growth of a domain such as steel considered classical, may still be large. What is observed in economics is also shown by research, it would appear more fruitful to explore a new promising domain rather than a more classical one and this because the return (publication, advertisement . . . ) is fast. Meanwhile other very specic demands for already existing grades of HNS or new grades likely to be developed in the future also exist in the following disciplines. Biomaterials necessary for new prostheses (articial heart, articial joints and bones . . . ).

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1 Figure 1. Curve 1: Kinetics of evolution of a traditional industrial activity PR residual product from year 2001 till the asymptote; curve 2: same curve (2) obeying the same master curve of a new eld, fascinating the new economy in 2001 dP2 /dt dP1 /dt but residual return could be disappointing: w 1 PR PR .

Complex devices such as activators for which a functional property (magnetic, shape memory effect, chemical property, electrical property . . .) is coupled with the mechanical and corrosion resistance of a nitrogen-containing alloy (HNA). Nanotechnology development also needs new high performance materials such as nanostructured HNS and nitrocermet (nitride ceramicmetal composite). 3. Scientic foundations of HNS In contrast with most other alloying elements which under normal conditions are in solid or liquid state, nitrogen is gaseous. This results from the stability of the N2 molecule which is also consistent with the fact that no natural nitride appears to exist. In order to achieve nitrogen alloying it is therefore necessary to utilise a nitrogen source in which the chemical potential of alloy nitrogen source is higher than that of the alloy N . Because the gas phase is nearly always N gas present in an elaboration process, N has to be at least equal to that of the source2021 , G S A , N N N G = gas, S = source, A = alloy.

Means to control G , S and A are: pressure of gas phase, temperature, decomposition of N N N nitrogen-containing molecule (NH3 , . . .) plasma, composition of the slag . . . composition of the base metal . . . (see gure 2). It has been shown120 that low nitrogen solubility in liquid steel led to a special steelmaking process: high pressure electro slag remelting (PESR) which is a rather expensive and high tech area to produce steels with very high nitrogen contents. The nitrogen content corresponding to about 1% mass roughly requires 5 interstitial atoms for 100 metal atoms. In case of a repulsive NN interaction22 about 30% of metal atoms can have one N nearest neighbour. Because the NM and N-defect interactions are very important it is easy to understand why nitrogen alloying dramatically affects all properties of the metallic matrix. The cost of the PESR process stimulated a more classic and cheaper steel-making process in which the solubility of N is increased by addition of alloying elements such as Cr, Mn,

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Figure 2. Principles of HNS and HNA syntheses, schematized by the variation of the chemical potential of N in different phases present during elaboration.

Mo, . . . these elements decrease the chemical potential of N. This process which does not need a high pressure of the gas phase is suitable for producing steel with nitrogen content less than 04%. The utilization of austenitic and duplex ferriticaustenitic HNS grades in Austria, France, Germany, India, Japan, Scandinavia, should permit exceeding the threshold under which potential users are subject to some inhibition regarding HNS suppliers. It should also be noticed that in case of very specic applications of HNS a solid state production of alloys is possible by adaptation of HIP (high-temperature isostatic pressuresintering) and CIP (cold-temperature isostatic pressure-sintering). Mixtures of 316 steel powder with (CrN or FeN, MnN) nitrides is likely to provide a very elegant and efcient means to obtain near net-shape parts of hard HNS. Another method which can still be considered to be reliable is mechanical alloying which has been proven to be efcient in the preparation of different grades of HNS. Mechanical alloying can also be used very effectively in the preparation of nitrides with high melting temperatures23 . Initially nitrogen was used only as an alloying element and as a substitute for nickel in steels. The synthesis of a special category of steels with high nitrogen content has been carried out to meet specic properties. In transition metal alloys, N as well as C occupy interstitial positions therefore electronic structures are strongly modied and NM interactions are important. The elastic interaction between N interstitials, possible clusters, precipitates, ordered domains and dislocations is large, therefore the effect on mechanical properties is also important. Since the electronic structure of metal atoms is changed, the core structure of dislocations is likely to be strongly affected and therefore the decomposition of a perfect dislocation into partial ones occurs. The larger the stability of nitrides of the transition metals, the smaller is the d electron density: example Ti, V, Cr, Zr, Nb, Mo nitrides are much more stable than Mn, Fe nitrides and Ni, Cu nitrides are actually unstable. In contrast, with carbides there is often a structural compatibility between the crystallographic lattices of solid solutions and nitrides which often are Haggs compounds. One may therefore expect that nitrides should be more coherent with the matrix than carbides and that the interfacial energies should therefore obey this inequality, { carbide/matrix > nitride/matrix }. Hence, the driving force for growth of nitrides is comparatively less than that of carbides.

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Since the nitrogen-enriched solid solution was supersaturated at high temperature TH , under high pressure (PH G), the chemical driving force for atomic redistribution in the matrix in the solid steel under low pressure PL and at low temperature TL simultaneously results from T = TH TL and P = PH PL . One can expect that in comparison with similar C alloyed grade, HNS would present a higher | G| and therefore the nucleation of precipitates is likely to be easier when C is replaced by N. The reduction of critical radius for nucleation rc = 2 /| G| has two origins: reduction of and increase of the driving force | G| . The efcient strengthening in HNS is derived from the ne size, the uniform distribution and the coherence of nitrides with the matrix. In this interplay of micromechanisms it is observed that the 01% N composition range which is considered to be relevant for steel making, a considerable number of different steel grades with very different properties are worth thinking about. It was shown24 , for example, that it is possible to promote cleavage of austenite in a duplex steel by an excessive nitrogen concentration (> 1%) and a coarse solidication microstructure. An intermediate nitrogen content (035%) of the austenite improves the stress-corrosion cracking resistance in both austenitic and duplex steels and this because plastic deformation of the gamma phase is reduced and therefore corrosion at the unpassivated slip lines is less25 . Another benecial effect of nitrogen in steel has been observed in the eld of hydrogen-induced embrittlement for which it has been shown that HNS presents a higher resistance than similar unnitrided steel26 . The rate of improvement or deterioration of various mechanical properties depends upon the nitrogen content, microstructure, method of processing etc. However it is not possible to achieve simultaneous improvement in strength and toughness by adding nitrogen. However, some mapping of different mechanical properties could be made which delineate that clear improvement in a given property (yield stress or ultimate tensile stress) is not counterbalanced by as negative an effect as could be expected for other properties (ductility, toughness, . . . ). The probable reason for this benecial inuence of nitrogen is related on the one hand to its interstitial behaviour and on the other hand to the change in the electronic structure. Nitrogen offers an extremely wide range of possibilities for improving the mechanical properties by modifying the basic processes involved in plastic deformation: solid solution hardening, ordering, large variety of precipitates, localisationdelocalisation of deformation, stacking fault energy, grain boundary segregation, grain size renement, recovery, recrystallisation, . . . dislocation core structure etc. It is well-known that a key parameter controlling mechanical properties is microstructure (morphology, texture, grain shape, grain size, grain orientation, . . . ). Nitrogen alloying has proven that efcient27 interaction between segregated metal atoms at grain boundaries with nitrogen impedes grain growth and phase growth2829 . In addition a modication of the recovery process specially in ferrite is likely to change grain nucleation30 . In conclusion it can be said that the effect of nitrogen on basic mechanisms involved in the alteration of mechanical and corrosion properties is considerable and varying. Therefore a wide range of compositions and microstructures of HNS would be necessary to characterize the properties. For effective utilization of HNS grades, a databank concerning thermal and thermomechanical treatments, microstructures, properties are necessary. Simulation and automatisation of experiments dramatically reduce the time necessary to achieve a programme of certication. Numerical simulation performed for different time scales and length scales [it means at the atomic scale (ab-initio, molecular dynamics, Monte Carlo), the mesoscopic scale (phase eld, Monte Carlo, . . . ), macroscopic scale (nite elements, thermodynamics codes, . . . )] and the coupling of these codes now allows us to achieve virtual experiments

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which replace real ones completely. Therefore the required time which separates the idea from the marketing of the new steel, as well as other new materials is vanishing dramatically.

4. Actual, future and possible applications Industrial applications of existing austenitic, martensitic and duplex HNS have been described by Speidel in his book. HNS nd applications in chemical industry, transportation, ship yard biomaterials, sporting equipment, environment-friendly technology. Hard and wearresistant HNS are likely to be used for cutting tools or for erosion-wear resistant parts. Many applications for HNS are likely to emerge such as, high temperature-resistant alloys (in case the Ti Zr, V, Nb, Cr, Mo content is high), nanostructured HNS, composite nitricermet, parts of actuators, some shape-memory alloys, nitrides with very high saturation magnetisation (Fe16 N2 ), gradient materials based on the diffusion of N2 under chemical gradient or stable stress eld, wear resistant coating, thermal barrier coatings, creep resistant NDS (nitride dispersion steel) and NDA (nitride dispersion alloy) based on similar principle to ODS (oxide dispersion steel) and superplastic HNS and nitrogen-enriched alloys for which the grain size has to be kept at a nanometric size. When nitrogen alloying does not lead to a clear improvement or to cost reduction as compared to well-known classical steel grades, the motivation for developing new grades should be limited. It is reasonable to foresee applications of HNS and HNA (high nitrogen alloys) to take advantage of a specic property improvement resulting from nitrogen addition.

5. Conclusion Although ceramics and metallic materials are different, similar breakthroughs resulted from nitrogen alloying: in the rst case hybridation of oxides Al2 O3 , SiO2 with nitrides AlN, Si3 N4 led to the discovery of SiAlON, in the second case analogies and differences between C and N resulted in new HNS and HNA. As the properties of nitrogen alloy are to a large extent unexplored, this offers a wide eld of innovations and promising solutions. The two alloying elements for development of HNS and HNA are in fact nitrogen and . . . imagination. Since one has to have condent in the remarkable abilities of researchers, engineers and users, it can be concluded that the future of HNS and HNA is bright. References*
1. 2. 3. 4. 5. 6. High nitrogen steels 1988 HNS88 Proc. Int. Conf. (eds) J Foct, A Hendry (The Institute of Metals) High nitrogen steels 1990 HNS90 Preprints 2nd Int. Conf. (eds) G Stein, H Witulski High nitrogen steels 1993 Proc. 3rd Int. Conf. (eds) V G Gavrilijuk, V M Nadutov Special issue on high nitrogen steels 1996 ISIJ Int. 36 (7): High nitrogen steels 1998 Proc. 5th Int. Conf. on High Nitrogen Steels (eds) H H nninen, a S Hertzman, J Romu Speidel M O, Uggowitzer P J 1991 Ergebnisse der werkstoff - Forschung, vol. 4, Verlag der Schweizerischen Akademie der Werkstoffwissenschaften

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Duplex stainless steels 1991 Les Editions de Physique (eds) J Charles, S Bernhardsson, Beaune, Bourgogne, France, vols. 1 & 2 Stainless steels 1991 Int. Conf. on Stainless Steels (Chiba, Japan: ISIJ) vols. 1 & 2 Stainless steel 1993 Process & materials; Innovation stainless steel (Florence: Associazione Italiana di Metallurgia) vols. 13 Stainless steel 1994 4th Int. Conf. DUPLEX 94 Duplex stainless steels 1997 5th World Conf. book 1 and 2 (Maastricht: KCI Publishing BV) Enter the Structure of Stainless Steel 1997 The First Stainless Steel Congress in Thailand 2000 6th World Duplex (Venezia: Associazione Italiana di Metallurgia) Kunze J 1990 Nitrogen and carbon in iron and steel thermodynamics (Berlin: Phys. Res. Akad. - Verlag) Grigorova N 1995 Carbonitrides in nitrogen die and high speed steels Chemical phase analysis (Soa: Intelsoft) Rashev T 1995 High nitrogen steels; Metallurgy under pressure (trans. & ed.) S Semerdijiev (Soa: Bulgarian Acad. Sci.) Murata T, Sakamoto M 1997 Nitrogen-alloyed steels Fundamentals and applications (ed.) Y Imay (Tokyo: Agne Publishing) Gavrilijuk V G, Berns H 1999 High nitrogen steels: structure, properties, manufacture, application (Berlin, Heidelberg: Springer-Verlag) Vogt J-B, Ait Saadi B, Foct J 1999 Analysis of the fatigue structures in a duplex stainless steel alloyed with nitrogen. Z. Metallkd. 90: 323328 Foct J 1990 High nitrogen steels: From science to technology. High nitrogen steels, Proc. HNS 90 (eds) G Stein, J Witulski (D sseldorf: Stahl und Eisen) u Foct J 1993 High nitrogen steels: Principles and properties. Innovation stainless steel, Process and materials (Associazione Italina di Metallurgica) Vol. 2, pp. 2.3912.396 Foct J 1973 Conditions impos es aux congurations dinterstitiels dans laust nite ferazote e e par les r sultats de spectrom trie M ssbauer. C. R. Acad. Sci. Paris 276: 11591163 e e o Foct J, Mostorakis A 1992 High nitrogen steels and nitrides obtained by mechanical alloying. Solid state phenomena (eds) (ACD Chaklader, J. A. Lund (Trans. Tech. Pub.) vol. 2526, pp 581588 Foct J, Akdut N 1993 Cleavage-like fracture of austenite in duplex stainless steel. Scr. Metall. Mater. 29: 153158 Foct J, Magnin Th, Perrot P, Vogt J-B 1991 Nitrogen alloying of duplex stainless steels. Duplex Stainless Steels (eds) J Charles, S Bernardson (Les Editions de Physique) vol. 1, pp. 4965 Shivanyuk, Foct J, Gavriliuk V G 2001 Hydrogen-enhanced microplasticity of austenitic steels studied by means of internal friction. Mater. Sci. Eng. A300: 284290 Akdut J, Foct J 1997 The inuence of nitrogen and orientation on the rolling deformation mechanisms of austenitic single crystals. Steel Res. 68: 495500 Keichel J, Crumbach M, Schraven P, Gottstein G, Foct J 1999 Recrystallisation texture development in cold rolled super duplex stainless steel. Proc. Twelfth Int. Conf. Textures of Materials, ICOTOM-12 (eds) J A Szpunar (NRC Research Press) vols. 1 & 2 pp 817823 Keichel J, Gottstein G, Foct J 1999 Recrystallisation in high nitrogen alloyed super duplex stainless steels. (eds) H H nninen, S Hertzman, J Romu, Materials Science Forum, (Trans. a Tech. Publ.) vol. 318320, pp 785792 Keichel J 2001 Untersuchung zur Verformung und Entfestigung in Stickstogglegierten ferritisch-austenitischen Duplexstahlen. Doktor Arbeit, RWTH, Aachen, Germany