Influence of nitrogen on hot ductility of steels and its relationship to problem of transverse cracking

Abstract

The present review examines the influence of nitrogen on the hot ductility of steels, with particular relevance to the problem of transverse cracking during continuous casting. Nitrogen itself is not detrimental to hot ductility, but when it is present with aluminium or microalloying additions, ductility can be adversely affected through the formation of nitrides or carbonitrides. The addition of aluminium to low nitrogen C–Mn steels (0·005%N)impairs ductility during casting at an acid soluble level as low as 0·02%Al. This arises because segregation of aluminium to the grain boundaries occurs on solidification, and the temperature cycling that takes place when the strand is cooled encourages AlN precipitation. However, for low nitrogen, high strength low alloy (HSLA) steels with carbon levels in the peritectic range 0·08–0·17%C, transverse cracking is not generally encountered until the aluminium level is >0·04%. Higher nitrogen levels are likely to cause problems even at very low aluminium levels, as precipitation of AlN is controlled by the product of the aluminium and nitrogen contents. The microalloying additions vanadium and niobium are detrimental to ductility but, of the two elements, niobium is more damaging, as it gives finer precipitation. Increasing the nitrogen level has a more pronounced influence on ductility in vanadium containing steels, since vanadium forms a nitride while niobium forms Nb (CN), which is mainly carbon based. Nevertheless, the product of vanadium and nitrogen contents has to approach 1·2 × 10^-3, for example 0·1%V and 0·012%N, before ductility deteriorates to that normally given by a niobium containing steel with 0·03%Nb and 0·005%N. When small titanium additions are made to low nitrogen C–Mn–Al steels (0·005%N), the best ductility is likely to be given by a high Ti/N ratio of 4–5 : 1; the excess titanium in solution encourages growth of the TiN particles. For high nitrogen steels (0·01%N), a low titanium level (0·01%)is recommended to limit the volume fraction of TiN particles. A low soluble aluminium level is also needed to prevent the excess nitrogen from combining to form AlN. For C–Mn–Nb–Al steels, similar recommendations can be made with regard to adding titanium. However, the presence of niobium and aluminium appears to have little influence on ductility, since these elements coarsen the titanium containing precipitates.     

Fabrication of in situ TiB2–TiC reinforced steel matrix composites by spark plasma sintering

Abstract

In situ TiB₂ and TiC particulates reinforced steel matrix composites have been fabricated using cheap ferrotitanium and boron carbide powders by spark plasma sintering (SPS) technique. The sintering behaviour and the formation mechanism of the composite were studied. The results show that when the composite was sintered at 1050°C for 5 min, the maximum relative density and hardness of the composite are 99·2% and 83·8 HRA respectively. The phase evolution of the composite during sintering indicates that the TiB₂ and TiC reinforcements were formed in situ as follows: first, the solid/solid interface reaction between Fe₂Ti and B₄C, resulting in the formation of a small amount of TiB₂ and TiC below 950°C; second, the solid–liquid solution precipitation reaction in the Fe–Ti–B–C system, resulting in the formation of the main TiB₂ and TiC reinforcements at ～1000°C.     

Mould heat transfer and continuously cast billet quality with mould flux lubrication Part 1 Mould heat transfer

Abstract

With the drive to cast higher quality, many minimills are adopting mould powder as a lubricant for the continous casting of steel billets. Over the past three decades considerable experience has been accumulated on the relationship between mould behaviour and billet quality for oil lubrication, but comparatively few studies have been conducted for mould powder lubrication. This study, conducted at a Canadian minimill, involved instrumenting four faces of a copper mould with thermocouples and monitoring mould temperatures during casting of 208 × 208 mm billets with mould flux lubrication. Billet samples were also taken to coincide with periods of measurements. Mould temperatures were monitored for two different mould powder compositions, for different mould oscillation frequencies, two mould cooling water velocities, and a range of steel compositions. An inverse heat conduction model was developed to calculate mould heat transfer from the measured temperatures. In this paper, which is the first part of a two part series, details of the inverse heat conduction model and mould heat transfer data are presented. The results obtained for mould flux lubrication have been compared with those for mould heat transfer for oil lubrication. For peritectic steels, with carbon content in the range 0·12–0·14%, it was found that lubricant type has little influence on the measured mould heat flux distribution at the centreline of a face. The peak mould heat flux was found to be approximately 2500 kW m^-2 . In contrast, for medium carbon steels, mould heat transfer with mould powder was significantly lower than when oil was employed as a lubricant. For instance, at the meniscus, the peak heat flux with mould powder was approximately 2500 kW m^-2 , which was half that recorded with oil as a lubricant. The influence of oscillation frequency, mould cooling water velocity, and mould powder type on mould heat flux has also been presented.     

Metal Matrix Composites Produced by Spray Codeposition

Abstract

A new technique for producing metal matrix particulate composites, consisting of the spray deposition of the metal matrix and the particles, is described. The deposit is removed from the substrate and hot rolled to produce composite strip for examination and testing. It is shown that up to 36 vol.-% of SiC, Al₂0₃, chilled iron, graphite, and sand particles, and mixtures of these, 75–120 μm in size, can successfully be incorporated in aluminium and Al–5Si alloy matrixes. The friction properties of some of the composites were shown to be particularly promising. High coefficients of friction of ～0·6 were obtainable under dry contact conditions, and these were remarkably constant with time. The friction properties compared very favourably with conventional asbestos based and sintered friction materials which showed lower coefficients of friction that increased with time. PM/0310     

Characteristics of AA6061/BN composite fabricated by pressureless infiltration technique

Spontaneous infiltration and strengthening behaviors were analyzed in terms of microstructures and tensile properties of AA6061/BN composite fabricated by pressureless infiltration technique in the presence of both Mg and nitrogen. The microstructure and properties were compared with control AA6061 without BN fabricated by the same method. The Mg₃N₂ formed by the reaction of Mg vapor and nitrogen gas, which coated the particles in the powder bed, is believed to induce spontaneous infiltration through greatly enhancing wetting by means of the reaction Mg₃N₂ + 2Al → 2AlN + 3Mg. This was identified by the finding of AlN particle layers on the surfaces of prior Al particles in the powder bed, which made contact with the infiltrating melt. In addition, unreacted Mg₃N₂ was observed outside the composite, where the Al melt did not come into direct contact. Fine AlN particles formed in situ resulted in significant strengthening, even in the control alloys with no addition of BN. In the composite reinforced with BN, additional AlN was formed by the interfacial reaction of the BN and Al melt as well as by the in situ reaction. Consequently, both the BN particles and the additional AlN particles formed by the interfacial reaction led to a further strengthening in the composite, as compared to the control alloy, which was strengthened only by the AlN particles formed in situ. In addition, the flake shape of BN may have lent considerable strength, due to the high aspect ratio it demonstrates, as compared with that of a spherically shaped particle.     

Synthesis of Al-AlN metal matrix composites by nitrogenation

Metal matrix composites containing AlN in aluminium matrices is synthesized using NH₄Cl and NH₄Cl+CaO powders as sources of nitrogen in molten aluminium in the temperature range of 700 1000°C. Active nitrogen dissociated from ammonia at high temperature is used to form AlN. The addition of CaO to NH₄Cl is found to have a more pronounced effect as a nitrogenation agent in comparison with NH₄Cl. MMCs synthesized at 700°C and 900°C using NH₄Cl+CaO showed the highest hardness of 83 Hv₁₀₀ (814 MPa). The clustering of AlN nanoparticles at few locations indicate insufficient turbulence of the melt during the chemical reactions of powder with aluminium-melt.     

Grain structure development and eutectic solidification of discontinuous magnesium borate whisker reinforced AA2024 matrix composite

Abstract

In the present research, the solidification behaviour of MBO whisker reinforced 2024 aluminium alloy matrix composite (MBO/AA2024) was studied by employing computer based thermal analysis, scanning electron microscopy and differential scanning calorimetry. The results show that the addition of MBO whiskers refines the grain structure in the matrix of the MBO/AA2024 composite. The nucleation of primary α-Al phase took place away from the whisker surfaces and started within the interstice of whiskers. The whiskers had almost no significant influence on the refinement of the eutectic phases.

Dans cette recherche, on a étudié le comportement de solidification du composite (MBO/AA2024) à matrice d’alliage d’aluminium 2024 renforcée par des barbes de MBO, au moyen de l’analyse thermique automatisée, de la microscopie électronique à balayage et de l’analyse calorimétrique à compensation de puissance. Les résultats montrent que l’addition de barbes de MBO affine la structure de grain dans la matrice du composite MBO/AA2024. La nucléation de la phase primaire α-A1 prenait place à l’écart des surfaces de la barbe et commençait à l’intérieur de l’interstice des barbes. Les barbes n’avaient presque pas d’influence sur l’affinement des phases de l’eutectique.     

Coating microstructure development during Zinquench galvanising of sheet steel

Abstract

The influence of an elevated strip entry temperature on the kinetics of the galvanising reaction has been investigated for a titanium stabilised, interstitial free steel. Elevated strip entry temperatures (>550°C) have been shown to accelerate greatly alloying between the substrate and the molten zinc, increasing the growth rate of the δ phase from 1 to ～7 μm s^-1 and preventing the formation of the ζ phase. The substantial Fe–Zn phase layer seen at the coating/substrate interface at high strip entry temperatures (>550°C) is attributed to the dissolution of iron from the substrate into the molten zinc in the first second of immersion, and the limited inhibition provided by the bath aluminium content (<0·15 wt-%effective).     

On hot deformation of aluminium–silicon powder metallurgy alloys

Abstract

The growing field of aluminium powder metallurgy (PM) brings promise to an economical and environmental demand for the production of high strength, light weight aluminium engine components. In an effort to further enhance the mechanical properties of these alloys, the effects of hot upset forging sintered compacts were studied. This article details findings on the hot compression response of these alloys, modelling of this flow behaviour, and its effects on final density and microstructure. Two aluminium–silicon based PM alloys were used for comparison. One alloy was a hypereutectic blend known as Alumix-231 (Al–15Si–2·5Cu–0·5Mg) and the second was an experimental hypoeutectic system (Al–6Si–4·5Cu–0·5Mg). Using a Gleeble 1500D thermomechanical simulator, sintered cylinders of the alloys were upset forged at various temperatures and strain rates, and the resulting stress–strain trends were studied. The constitutive equations of hot deformation were used to model peak flow stresses for each alloy when forged between 360 and 480°C, using strain rates of 0·005–5·0 s^?1. Both alloys benefited from hot deformation within the ranges studied. The experimental alloy achieved an average density of 99·6% (±0·2%) while the commercial alloy achieved 98·3% (±0·6%) of its theoretical density. It was found that the experimentally obtained peak flow stresses for each material studied could be very closely approximated using the semi-empirical Zener–Hollomon models.     

Contributors

Abstract

The chemistry of a high performance cast superalloy, ZhS6–K (Ni–10Cr–5Co–5W–5Al–3·5Mo–3Ti–0·2C–0·02B), was modified by slight reductions in carbon, titanium, and aluminium content and minor additions of niobium and hafnium. Two variants of the modified alloy chemistry with different boron contents (0·02 and 0·08 wt–%) were prepared by vacuum induction melting, argon atomization, and consolidation by hot isostatic pressing at three temperatures. It was observed that, unlike carbon, an increase in boron content did not promote the formation of continuous precipitates at the prior powder particle boundaries. Increased boron content narrowed down the consolidation temperature range and changed the morphology of γ′ particles from cuboidal to dendritic. Precipitation of an eutectic γ + γ′ structure and formation of continuous boride films at the grain boundaries severely degraded the mechanical properties of the high boron PM superalloy that was consolidated at a temperature marginally above the γ′ solvus. An optimum consolidation schedule was determined for the high boron alloy, which after a suitable heat treatment produced significant property improvement in stress rupture and tensile properties. PM/0416     

Microstructural modelling of electrical conductivity and mechanical properties of sintered ferrous materials

Abstract

The role of microstructure on mechanical properties of sintered ferrous materials was studied using a method based on electrical conductivity measurement. The method was accompanied by quantitative fractography to evaluate the dewaxing and sintering process in iron compacts. The effects of manufacturing parameters, such as compacting pressure in the range of 150–800 MPa, sintering temperature from 400 to 1300°C, sintering time up to 8 h, and lubrication mode were investigated. Several mathematical models were checked to obtain the best one for prediction of electrical conductivity changes as a function of manufacturing parameters. The mechanical properties of the sintered compacts were also evaluated to establish a relationship between conductivity, total porosity, pore morphology, and mechanical behaviour. The results show that the electrical conductivity/resistivity of sintered materials is closely related to its microstructure, so that measuring these properties can replace destructive test methods for prediction of mechanical strength of sintered materials with homogeneous matrix microstructure. The application of the method is shown for sintered Fe, Fe–0·8%C, and Fe–1·5%Mo–0·7%C compacts.     

Influence of cooling rate and composition on formation of intermetallic phases in solidifying Al–Fe–Si melts

Abstract

Aluminium alloys containing 0·3%Fe and 0·05%Si, 0·3%Fe and 0·15%Si, 0·3%Fe and 0·45%Si, and 0·5%Fe and 0·2%Si were solidified with different cooling rates. Shapes of intermetallic particles and their spatial distribution in the alloys were characterised by optical and scanning electron microscopy. X-ray diffraction analysis was used to establish the types of intermetallic phases extracted from the alloys by dissolving the FCC matrix in boiling phenol. The influence of melt superheating on the microstructure was analysed by comparing phase portraits of alloys solidified from melts whose temperatures before casting were 100 and 350°C above the liquidus.

On a solidifié des alliages d’aluminium contenant 0·3%Fe et 0·05%Si, 0·3%Fe et 0·15%Si, 0·3%Fe et 0·45%Si et 0·5%Fe et 0·2%Si, à différentes vitesses de refroidissement. On a caractérisé la forme des particules intermétalliques et leur distribution spatiale dans les alliages, au moyen de la microscopie optique et de la microscopie électronique à balayage. On a utilisé l’analyse de la diffraction des rayons X pour établir les types de phases intermétalliques extraites des alliages par dissolution de la matrice FCC dans du phénol en ébullition. On a analysé l’influence de la surchauffe du bain sur la microstructure en comparant les images de phase des alliages solidifiés à partir des bains dont les températures avant le moulage étaient de 100 et de 350°C au-dessus du liquidus.     

Influence of cryogenic temperature on magnetic properties of soft magnetic composites

Abstract

Magnetic properties of Fe based composite materials with different particle sizes under a cryogenic condition have been investigated. Realisation of this venture has been carried out at the liquid nitrogen temperature. Results of energy loss density were obtained from measurements of the static (dc) hysteresis cycles ranging from 0·1 to 1·0 T. In turn, results of power loss density were obtained from measurements of the dynamic (ac) hysteresis cycles ranging from 50 to 1000 Hz and at the maximum flux density of 0·5, 0·8 and 1·0 T. The study confirmed the influence of temperature on magnetic parameters. It has been shown that total power loss density has increased with decreasing temperature. We report changes in a nature of energy loss after immersing specimens made of soft magnetic composites in liquid nitrogen. Measurements of the maximum relative permeability were also conducted.     

Strain hardening characteristics of deep drawing quality steels with geometric constraints

Abstract

Strain hardening characteristics of two rolled deep drawing quality (DDQ) steels, namely, interstitial free (IF) and aluminium killed (AK), have been studied with and without the presence of geometric constraints at room temperature. Strain hardening exponent and rate are investigated for plain, centre holed and double notched sheet specimens for both longitudinal and transversal orientations. Four empirical relations based on total and incremental stress and strain components are considered to get a deeper insight into the deformation and workhardening behaviour of annealed sheets. Strain hardening exponents and yield strengths for steel with ultralow carbon contents (IF) are found in the range of 0·22–0·30 and 145–170 MPa respectively. The steel grade (AK) with higher carbon content (0·028%) and yield strength (174–197 MPa) exhibits strain hardening exponent around 0·18–0·27. Single and two-stage workhardening is observed for the IF and AK grades. Workhardening as a function of plastic strain follows the power law relation of the form workhardening rate (WHR)?=?α(?_T)^β . A transition from high to low hardening rate tends to occur for strains ranging from 0·05 to 0·10. An analytical model is formulated for theoretical estimation of strain hardening exponent from true strain data. The experimentally determined and the theoretically computed strain hardening exponent data match fairly well.

On a étudié les caractéristiques d’écrouissage de deux aciers laminés de qualité emboutissage (DDQ), nommément sans interstitiel (IF) et calmé à l’aluminium (AK), avec et sans la présence de contraintes géométriques, à la température de la pièce. On examine l’exposant et la vitesse d’écrouissage pour des échantillons de tôle lisse, à trou central et avec entaille double, tant dans l’orientation longitudinale que transverse. On considère quatre relations empiriques basées sur les composantes de contrainte et de déformation, totales et incrémentales, afin d’obtenir une compréhension plus profonde du comportement de déformation et de durcissement des tôles recuites. La valeur des exposants d’écrouissage et les limites d’élasticité pour l’acier à teneur extrêmement basse en carbone (IF) se trouvent dans la gamme de 0·22–0·30 et 145–170 MPa, respectivement. La nuance d’acier (AK) avec une teneur plus élevée en carbone (0·028%) et une limite d’élasticité plus élevée (174–197 MPa) exhibe un exposant d’écrouissage autour de 0·18–0·27. On observe le durcissement simple ou en deux étapes pour les nuances sans interstitiel ou calmé à l’aluminium. Le durcissement en fonction de la déformation plastique suit une relation de loi de puissance de la forme WHR?=?α(?_T)^β. Une transition d’une vitesse élevée à basse du durcissement tend à se produire pour les déformations allant de 0·05–0·10. On formule un modèle analytique pour l’estimation théorique de l’exposant d’écrouissage à partir de véritables données de déformation. Les données d’exposant d’écrouissage déterminées expérimentalement et calculées théoriquement se rapprochent relativement bien.     

Effects of AlN Nanoparticles on the Microstructure,Solderability, and Mechanical Properties of Sn-Ag-Cu Solder

The addition of nanosized AlN particles to Sn-3.0 wt pctAg-0.5 wt pctCu (SAC305) lead-free solder alloy has been investigated. The various weight fractions of AlN (0, 0.03, 0.12, 0.21, 0.60 wt pct) have been dispersed in SAC305 solder matrix by a mechanical mixing and melting route. The influences of AlN nanosized particles on the microstructure, mechanical properties, and solderability (e.g., spreadability and wettability) have been carried out. The structural and morphological features of the nanocomposite solder were characterized by scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), and transmission electron microscope (TEM). The experimental results show that the best combination of solderability and mechanical properties is obtained at 0.21 wt pct AlN in the solder matrix. The reinforced composite solder with 0.21 wt pct AlN nanoparticles shows ≈25 pct improvement in ultimate tensile strength (UTS), and ≈4 pct increase in the spreadability. In addition, the results of microstructural analyses of composite solders indicate that the nanocomposite solder, especially reinforced with 0.21 wt pct of AlN nanoparticles, exhibits better microstructure and improved elongation percentage, compared with the monolithic SAC305 solder.

     

Study on Quantification of Oxide Phases in Ex-situ AlN/Al Metal Matrix Nanocomposites

Al based metal matrix nanocomposite (MMNC) is synthesized by dispersing nanocrystalline aluminium nitride (AlN) particles in Aluminum matrix using ex-situ melt metallurgy method. The entrapment of atmospheric oxygen along with ex-situ particulate has been a long standing issue during fabrication of metal matrix composites. In the present investigation, presence of oxygen has been quantified in synthesized Al-AlN MMNCs with varying AlN content. The high resolution scanning electron microscopy is used to study morphology and distribution of AlN in Al matrix. Energy dispersive spectroscopy analysis is used to quantify in situ oxide phases along with AlN particles in the synthesized MMNCs using thermodynamic mass balance calculations. Present study also attempts to understand the role of in-situ oxide phases on the mechanical properties of MMNCs using microindentation hardness and nanoindentation test.     

Production of NiAl–matrix composites by reactive sintering

Abstract

This work was devoted to the development of NiAl–matrix composite and its production by reactive sintering powder metallurgy. Various types of reinforcement (aluminium oxide, silicon and tungsten carbides, titanium silicide) were tested. The best chemical compatibility and the highest hardness and wear resistance were achieved by Al₂O₃ fibres. Electroless nickel plating pretreatment of Al₂O₃ fibres improves both distribution of fibres and hardness of the composite. However, it strongly reduces the wear resistance, probably due to phosphorus content in the nickel coating. In situ formation of NiAl–Al₂O₃ composites by reactive sintering of a pressed powder mixture of Ni, Al and NiO was unsuccessful. Only a small amount of cubic γ-Al₂O₃ was detected after reactive sintering and hence no significant hardness increase was observed.     

Mould heat transfer and continuously cast billet quality with mould flux lubrication Part 2 Quality issues

Abstract

With many billet producers adopting mould powder lubrication, there is a need to clarify the gains in quality that can be achieved with this practice. Over the past three decades considerable research has been conducted to establish the relationship between mould behaviour and defect formation for billets continuously cast with oil lubrication, but little has been done to compare oil cast billets with powder cast billets. In this study, conducted at a Canadian minimill, four faces of a copper mould were instrumented with thermocouples and mould temperatures and billet quality were monitored with mould powder lubrication during casting of 208 × 208 mm billets. In the first part of this two part series (in Ironmaking & Steelmaking No. 1 2000), the results of the mould heat transfer analysis and the influence of variables were presented, together with a comparison between oil and powder lubrication. In the present paper, Part 2, billet quality is examined in detail. The difference in turbulence at the meniscus between oil and powder lubrication is established, and the need to tune mould level sensors when switching to mould powders is demonstrated. Previous work has shown that mould level fluctuations have a strong influence on defects such as offsquareness and transverse depressions, both of which are markedly reduced when casting with mould powders. The inherent stability of the meniscus is improved when employing mould powder lubrication and a submerged entry nozzle. Furthermore, the significant reduction in mould heat transfer at the meniscus, when mould powders are employed, particularly for medium carbon steels has been shown to correlate well with the observed reduction in offsquareness. The paper also elucidates the reasons for the reduction, and in most cases, elimination of transverse depressions in B–Ti grades when casting with mould powders. The mechanism of longitudinal depression formation and subsurface cracking observed in many of the powder cast, medium carbon billets has also been established.     

Fabrication and characteristics of AA6061/Si3N4p composite by the pressureless infiltration technique

The tensile properties and microstructures of AA6061/Si₃N₄ particle composites fabricated by pressureless infiltration under a nitrogen atmosphere were analyzed. In addition, the control AA6061 without Si₃N₄ particles fabricated by the same method was investigated to separate the effect of Si₃N₄ particle addition. It was found that AlN particle layers formed on the surface of Al particles in the powder bed, which replaced the Mg₃N₂ coated layers through the following reaction: Mg₃N₂ + 2Al → 2AlN + 3Mg. Thus, the spontaneous infiltration results from a great enhancement of wetting via the formation of Mg₃N₂ by the reaction of Mg vapor and nitrogen gas. The increased tensile strength and 0.2 pct offset yield strength in the control AA6061 were largely due to fine AlN particles formed by the aforementioned in situ reactions, as compared to commercial AA6061. In the composite reinforced with Si₃N₄ particles, of course, the AlN was also formed through the following additional reaction at the Si₃N₄ particle/Al melt interfaces: Si₃N₄ + 4Al → 4AlN + 3Si. However, this AlN may not contribute to the increase in strength because its formation is compensated by the consumption of Si₃N₄ particles. Consequently, the strength increase of the composite fabricated by the present method is attributed to the fine AlN particles formed in situ, as well as the fine reinforcing Si₃N₄ particles, as compared to commercial AA6061.     

DETERMINATION OF HOOP STRESSES INDUCED IN A CYLINDRICAL STEEL DIE BY COMPACTING METAL POWDERS

Abstract

Because of the lack of stress data, steel dies for compacting metal powders were designed in the past on the assumption of hydraulic pressure transmission by powders.

True die stresses existing in a hardened steel die during the compacting of various lubricated and non-lubricated powders have been measured by mounting strain-gauges on the periphery of the die at numerous points along its length.

Values of the hoop stress varied from approximately 0·05 to 0·40 of the calculated and measured hydraulic fluid stress. For a particular metal powder, the stress was a function of the average particle size, the powder height, and the amount of lubrication.