Grain boundary segregation of phosphorus and molybdenum in 2·25Cr–1Mo steel

Abstract

Segregation of phosphorus and molybdenum to grain boundaries in a commercial grade of 2·25Cr–1Mo steel subjected to different heat treatments has been examined using a field emission gun scanning transmission electron microscope with energy dispersive X-ray microanalysis. The results indicate that P and Mo concentrations at prior austenite grain boundaries increase with aging time. This follows the prediction of McLean's equilibrium segregation model, when modified to take account of the interaction energy between phosphorus and molybdenum.     

Grain boundary segregation in Ni-base (718 plus) superalloy

Abstract

Segregation of phosphorus and molybdenum to grain boundaries in a commercial grade Ni-base (718 plus) superalloy subjected to different heat treatments has been examined using a field emission gun scanning transmission electron microscope with energy dispersive X-ray microanalysis. The results indicate that P and Mo concentrations at grain boundaries increase in linear manner with the square root of aging time.     

Critical time and temper embrittlement isotherms

Abstract

The critical time in a non-equilibrium segregation isotherm will induce a critical time in the relative temper embrittlement isotherm, at which when a steel is held, a maximum extent of embrittlement will occur. This suggestion has been confirmed for the non-equilibrium cosegregation to grain boundaries of Ti, Sb, and Ni in low carbon Ni–Cr steels and for phosphorus non-equilibrium segregation to grain boundaries in some steels.     

Sulphur segregation and precipitation in HAZ of boiler steel thick section welds

Abstract

Stress relief cracking can occur in weld heat affected zones (HAZ) after post-weld heat treatment (PWHT) and periods of service at elevated temperatures. Stress relief cracking is generally believed to occur by sulphur induced decohesion ahead of a growing sharp crack. The impurity segregation behaviour in a microalloyed steel, typical of that used in the construction of a power station boiler where intermittent cracks were observed along the weld fusion boundaries, has been assessed. In particular the type and amount of segregation in the coarse grained HAZ (CGHAZ) before and after PWHT has been determined. It was found that significant sulphur segregation occurred during the CGHAZ thermal cycle resulting in elemental sulphur on the prior austenite grain boundaries. Following PWHT some desegregation of sulphur, coupled with the formation of sulphides and carbides on the prior austenite grain boundaries, was observed; in addition, significant phosphorus segregation to the prior austenite grain boundaries and grain boundary precipitate/matrix interfaces was seen.     

Effect of austenite grain boundary mobility on hardenability of steels containing vanadium

Abstract

A correlation has been established between the rate of grain boundary migration during austenitisation and the hardenability of steels containing 0·2–0·3%C, 1·5–1·7%Mn, up to 0·35% V, and small additions of Al or Ti. Interaction between the austenite grain boundaries and pinning particles was investigated using transmission electron microscopy and segregation to the austenite grain boundaries was examined using Auger electron spectroscopy. It has been concluded that the velocity of grain boundary migration during austenitisation influences the extent of equilibrium segregation to the austenite grain boundaries which, in turn, affects the hardenability. Pinning of the austenite grain boundaries enabled the potential hardenability effect of the alloying elements to be increased. Mechanisms have been discussed for the ways in which segregation, particularly of V, occurs to pinned or immobilised austenite grain boundaries, and the conditions by which most effective grain boundary pinning can be achieved have been considered. Some technological implications have been suggested.

MST/804     

Effects of solution treatment temperature on grain growth and mechanical properties of high strength 18%Ni cobalt free maraging steel

Abstract

The effects of solution treatment (ST) temperature (1073–1473 K) on the prior austenite grain size, microstructure, and mechanical properties of a 2000 MPa grade 18%Ni Co free maraging steel have been investigated. The results show that prior austenite grain size normally increases with increase of ST temperature. Strength and ductility in the solution treated condition are independent of both ST temperature and prior austenite grain size due to constant martensite lath spacing and dislocation tangles. In the solution treated + aged condition, the relationship between yield strength and prior austenite grain size follows the Hall- Petch equation, and ductility improves until the ST temperature used is >1373 K. Accordingly, the fracture mode transforms from intergranular to transgranular at a critical prior austenite grain size of ~ 150 μ m, because of severe segregation of Ni₃(Mo,Ti) and reverted austenite at prior austenite grain boundaries and martensite lath boundaries. The variation of Charpy V notch impact energy with increase of ST temperature in both the solution treated and solution treated + aged conditions is similar to that of the tensile ductility. The fracture toughness K_IC, however, increases with increase of ST temperature. No thermal embrittlement resulted from the Ti(C,N,S) inclusion segregation at prior austenite grain boundaries and martensite lath boundaries in the high temperature solution treatment.     

Combined quenching and tempering induced phosphorus segregation to grain boundaries in 2·25Cr–1 Mo steel

Abstract

Combined quenching and tempering induced phosphorus segregation to prior austenite grain boundaries in α 0·077 wt-%P doped 2·25Cr–1Mo steel was examined using field emission gun scanning transmission electron microscopy. The results indicate that combined equilibrium and non-equilibrium phosphorus segregation may play an important part in temper embrittlement of the steel caused by direct tempering after quenching. Non-equilibrium segregation requires the formation of sufficient quantities of vacancy–impurity complexes and their migration to grain boundaries is of great importance in the segregation. For this reason, the mechanism for migration of the complexes is discussed in detail.

MST/3419     

Strengths of grain boundaries in pure metals

Abstract

The relative surface energies for brittle fracture along grain boundaries or along crystal planes, at low temperatures, are estimated and used in a criterion for the relative strengths of boundaries and cleavages. It is concluded that the boundary is weaker than the crystal in a wide range of metals; that it becomes weaker as the ratio of shear modulus to bulk modulus increases; and that brittle pure metals, such as iridium and molybdenum, fracture preferentially on grain boundaries. The critical modulus ratio is in all cases lower than that for the ductile–brittle cleavage transition.

MST/1154     

Statistical analysis of phosphorus segregation on intergranular fracture facets in pressure vessel steels

Abstract

A533B and C–Mn steels, widely used as nuclear pressure vessel steels, have been aged at 520°C after tempering at 650°C for various periods of time to produce different levels of embrittlement resulting from the segregation of P to grain boundaries. Metallographic observation and tensile test results showed that the embrittlement heat treatment did not have significant influence on the microstructures or tensile properties of the steels. P segregation at grain boundaries and on intergranular facets was investigated using field emission gun transmission electron microscopy and Auger electron spectroscopy. After such treatment, enhanced segregation was found to be a linear function of the square root of embrittling time. Statistical analysis of the AES measurements indicated that there is a minimum segregation level for intergranular fracture to occur.     

Segregation of reactive elements at oxide grain boundaries in FeCrAlRE alloys

Abstract

Extensive previous research has established that the oxidation of FeCrAl alloys at temperatures ≥1000°C results in the formation of α-Al₂O₃ oxide scales, and that minor alloy constituents (particularly Reactive Elements (RE) such as Y, Hf, Zr, etc.) can change the oxide growth mechanism. A knowledge of the segregation behaviour of these REs is thus central to our understanding of the oxidation behaviour of these, technologically important, range of alloys.

The new SuperSTEM microscope at the Daresbury Laboratory offers considerable potential for a detailed study of the segregation to oxide grain boundaries at the atomic level. The microscope has an aberration corrector fitted to the objective lens, allowing the formation of sub-Angstrom probe for simultaneous ultra-high resolution high angle annular dark field (HAADF) imaging and atomic-column electron energy loss spectroscopy (EELS). This paper reports on an initial study of oxide grain boundary segregation in commercial and model FeCrAlRE alloys containing controlled additions of the reactive elements, yttrium, zirconium and hafnium oxidised at 1250°C, in air, for 50 hours. Both yttrium and hafnium are shown to segregate to the grain boundaries while hafnium rich particules form in the outer region of the scale.     

Non-equilibrium segregation of solute to grain boundary

The behaviour of boron segregation to grain boundaries in Fe-3%Si has been studied by means of particle tracking autoradiography. The results indicate that (i) the binding energy between boron atoms and grain boundaries is 55.7±1.7 kJ mol^–1; (ii) in contrast to the nature of boron segregation in -Fe, no observable non-equilibrium segregation of boron to grain boundaries exists in Fe-3%Si alloy during cooling and isothermal holding.     

Inhibition of scale growth on 20Cr–25Ni–Nb stabilized stainless steel by yttrium ion implantation revealed by analytical electron microscopy

Abstract

Yttrium ion implantation significantly improves the oxidation behaviour of the 20Cr–25Ni–Nb stabilised stainless steel in carbon dioxide at 750–900°C by the incorporation of this reactive element within the scale. The exact location and chemical state of the yttrium ion were established by transmission and scanning transmission electron microscopy. The implanted yttrium atoms are incorporated as Y₂O₃ grains and as ionic segregants along the oxide grain boundaries within the outer spinel layer. of the scale next to the inner Cr₂O₃ layer. As a consequence of the yttrium segregation, the cation diffusion along the oxide grain boundaries, which is responsible for continuing scale growth, becomes energetically less favourable. Scale growth is inhibited to an extent according to the proportion of grain boundaries so affected. The improved spallation resistance could derive from the yttria grains and yttrium segregants inhibiting scale failure, the prelude to decohesion, by increasing the energy for through scale crack initiation and propagation.

MST/932     

Impurity and vacancy segregation at symmetric tilt grain boundaries in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped ZrO<Subscript>2</Subscript>

Segregation energies of impurity ions and oxygen vacancies at grain boundaries in Y₂O₃-doped ZrO₂ as calculated from atomistic simulations using energy minimization and Monte Carlo methods are reported. Based on these energies, local defect equilibrium concentrations have been estimated. It is found that it is more energetically favorable for an yttrium ion to be accompanied by an oxygen vacancy at grain boundaries, although decrease in energy when associated with an oxygen vacancy differs from boundary to boundary. The segregation energy for a neutral defect complex consisting of a two yttrium ions and an oxygen vacancy at infinitely dilute concentration is highly correlated with the coordination environment of each site in the vicinity of the grain boundary (GB), and, in turn, GB energy. Although the estimated local equilibrium concentrations of these defects are similar, detailed analysis of the atomic coordination and defect distributions in the vicinity of a GB reveal that defect distributions, especially of oxygen vacancies, are dependent on the characteristics of the particular GB and that segregation in effect reduces lattice strains at the GB. Equilibrium concentration distributions of yttrium at grain boundaries are also given as a function of spatial resolution, and are useful for interpretation of experimental results.     

Non-equilibrium intergranular segregation in ultra low carbon steel

Abstract

Impurity segregation to grain boundaries in ultra low carbon steel was investigated by Auger electron spectroscopy and SEM during isothermal annealing at 900°C and continuous cooling. The results of isothermal annealing at 900°C show that a concentration peak appears at different times for phosphorus, sulphur, and boron, which is contrary to the equilibrium segregation theory of McLean. The phenomena could be satisfactorily explained by the non-equilibrium segregation theory based on the impurity–vacancy complex mechanism. Under continuous cooling, the segregation concentration at the grain boundary largely depends on the cooling rate. At a low cooling rate the concentration of phosphorus and boron at the grain boundary is higher than that of sulphur, while at the higher cooling rate the concentration of sulphur is higher.     

Deformation and fracture in Al–Li-base alloys

Abstract

Aluminium–lithium-base alloys are of considerable interest because of their low density and high modulus. However, they have been shown to have low ductility and poor fracture toughness. This has been attributed to a variety of factors, including intense shear band formation, segregation to grain boundaries, and weakened grain boundaries due to precipitation and precipitate-free zones. The authors have investigated the deformation structures observed in binary and more complex commercial alloys. As would be expected, considering the microstructure of the alloys, extensive strain localization and shear band formation occurs in these alloys. However, it is shown that the commercial alloys are less sensitive to strain localization than the model binary alloy systems investigated. The stresss–train behaviour has been investigated. The alloys exhibit jerky flow, which is indicative of negative strain rate sensitivity, and strain rate change tests showed this to be the case. This is consistent with the deformation structures observed. The effect of weakened grain boundaries due to precipitation and precipitate-free zones has been studied by comparing the fracture characteristics of aged and unaged material. It is shown that the mode of failure is identical under appropriate conditions. It is concluded that segregation to grain boundaries is the major cause of the lower ductility and toughness of Al–Li alloys. This possibility has been investigated using in situ fracture surface analysis techniques. Results are presented on grain boundary segregation, and methods of reducing its influence on fracture behaviour are indicated.

MST/570     

Influence of phosphorus on the hot ductility of 2.25Cr1Mo steel

Abstract

The effect of phosphorus at two levels (0.01 and 0.06 wt-%) on the hot ductility of 2.25Cr1Mo steel has been investigated over the temperature range 700-1200 °C using a Gleeble machine. Auger electron spectroscopy indicated that phosphorus segregation to austenite grain boundaries had occurred in the higher phosphorus steel. A trough in the ductility - temperature curve was observed for both steels with the minimum ductility occurring at about 750 °C. The higher P containing steel gave the worst ductility throughout the temperature range examined. The ductility trough was caused by the formation of a thin pro-eutectoid ferrite layer along austenite grain boundaries, and this trough was accentuated by the presence of phosphorus at the austenite grain boundaries.     

Grain boundary complexion and transparent polycrystalline alumina from an atomistic simulation perspective

Transparent alumina is often processed with sintering additives such as, Y, La, and Mg, in order to limit its grain growth at high sintering temperatures. Usually, these additives segregate to the grain boundaries due to their larger cationic size than Al and low solubility in bulk α-alumina. The grain boundary excess of these additives plays a key role in determining stable grain boundary complexions and thereby, the grain growth characteristics of the polycrystalline alumina. In the current work, the grain boundary segregation of trivalent (Y, La) as well as bivalent (Mg) dopants on several alumina grain boundaries was simulated using the force field based energy minimization method. Calculated segregation energy plots and atomistic structure analysis, for the case of trivalent dopants, suggest that there is a critical concentration (3–4 atoms/nm²) for achieving the lowest mobility monolayer grain boundary complexion. The bivalent dopant Mg plays a role in grain boundary complexion through creating ordered arrays of oxygen vacancies at the grain boundary and helps create the space for the easier occupation of the grain boundary cationic sites by the trivalent dopants in case of codoping. It was also observed that the twin grain boundaries are more preferable in comparison to general high angle grain boundaries to obtain monolayer complexions, which are necessary for limiting grain growth. The use of atomistic simulations can thus guide the experimentalist towards optimum dopant concentrations to better control ceramic microstructures. In a more general sense the possibility of second phase formation or an incipient second phase for high grain boundary concentrations >8 cations/nm² is briefly discussed.     

Some effects of heat treatment on grain boundary chemistry and precipitation in type 316 steel

Abstract

The effects of solution treatment temperature and cooling rate, carbon content, and aging at 600°C on the precipitation and grain boundary composition of AISI type 316 stainless steel were investigated. No matrix precipitation was observed even in a high carbon cast aged for 1000 h. Carbides of M₂₃C₆ type were the only precipitates observed and these formed on grain boundaries. Nucleation of a second phase in these solution treated specimens was difficult, despite the carbon supersaturation. The grain boundary regions were investigated using high spatial resolution X-ray analysis to show that chromium depleted and nickel enriched zones formed when grain boundary carbides occurred. The behaviour of molybdenum was more complex; it segregated strongly to grain boundaries either during a slow cool from the solution treatment temperature or during aging, but was also incorporated into any carbides that formed.

MST/890     

Method for determining the elastic modulus at grain boundaries for polycrystalline materials

Abstract

On the basis of the model of non-equilibrium grain boundary segregation induced by tensile stress, a set of kinetic equations is derived to formulate this process. These kinetic equations allow excellent simulation of the grain boundary segregation of phosphorus and sulphur observed in steels subjected to low tensile stresses. In the present paper, based on such a widely approved model, a new approach is proposed to quantify the elastic modulus at grain boundaries for polycrystalline materials. Using the observation of Misra, the grain boundary elastic modulus E _gb = 2.03 × 10⁹ Pa at 883 K for Cr-Mo-V-2.6Ni steel is obtained for the first time. This result shows excellent agreement with the local elastic constants simulated theoretically by Kluge et al., and indicates that the grain boundary elastic modulus for a polycrystalline material is much lower than the commonly assumed value.     

Calculation for grain growth rate of carbon steels by solute drag model considering segregation effect of each substitutional element

Abstract

Based on the solute drag model, a practical model incorporating the segregation effect is proposed to calculate grain growth rates in carbon steels. The segregation effect is modelled using two factors: the difference in atomic diameter between a solvent and a substitutional element, and the solubility of a substitutional element. By including the segregation energy, the proposed model enables the simulated retardation of grain growth by the addition of microalloying elements. The calculated grain growth rate by the proposed model shows reasonable correspondence between grain growth rates for experimental and calculated results. The temperature dependence of the grain growth rate is also well simulated.