Dendritic solidification in binary alloys

Alloys generally solidify dendritically, and associated with that is the microsegregation of impurities. Pure metals also solidify in dendritic form as “thermal” dendrites, which actually segregate the system’s enthalpy. In this investigation, small additions of solute to succinonitrile have been studied and dendritic growth observed in a supercooled melt. This free dendritic growth-mode is similar to that experienced by equiaxed dendrites found in alloy castings. Observations of these free dendrites include measurement of velocity and tip radius of the dendrites at different supercoolings and solute concentrations.     

Decomposition and dissolution kinetics ofδ′ precipitation in Al-Li binary alloys

Aside from its technological importance, the Al-Li alloy system also exhibits interesting phase transformations involving both equilibrium and metastable states. Recent theoretical studies have shown that a supersaturated solid solution could take different transformation paths when it is quenched into theα +γ′ field. Suggestions were made that a rapidly quenched solution phase should first undergo a congruent ordering transformation before it decomposes into a two-phase mixture by either a secondary spinodal decomposition or the classical nucleation and growth process. Moreover, a metastable miscibility gap was predicted at lower temperatures. The objective of this research is to study the transformation paths and dynamics in Al-Li binary alloys of three compositions (5.2, 7.0, and 12.0 at. pct Li). This investigation emphasizes thein situ small-angle X-ray scattering (SAXS) observations on specimens subjected to various aging conditions. Special attention is paid to the early stages of the transformation in an attempt to characterize the various possible modes of phase separation on one hand and to study the dynamics of the precipitation process on the other. The following results are obtained: the congruent ordering precedes decomposition at low temperatures; the metastableγ′ solvus curve is reconfirmed; but the predicted metastable miscibility gap is not found. Guinier radii measurements of the particles showed Ostwald ripening is quickly reached upon heating to the aging temperatures. Slowing down behavior is seen at aging temperatures close to the solvus boundary. Activation energies for Li diffusion were obtained using the modified Lifshitz, Slyozov, and Wagner (MLSW) model. A test of dynamical scaling behavior is carried out for the Al-12.0 at. pct Li alloy. Formerly Visiting Scientists at the University of Illinois     

Decomposition and dissolution kinetics ofδ′ precipitation in Al-Li binary alloys

Aside from its technological importance, the Al-Li alloy system also exhibits interesting phase transformations involving both equilibrium and metastable states. Recent theoretical studies have shown that a supersaturated solid solution could take different transformation paths when it is quenched into theα +γ′ field. Suggestions were made that a rapidly quenched solution phase should first undergo a congruent ordering transformation before it decomposes into a two-phase mixture by either a secondary spinodal decomposition or the classical nucleation and growth process. Moreover, a metastable miscibility gap was predicted at lower temperatures. The objective of this research is to study the transformation paths and dynamics in Al-Li binary alloys of three compositions (5.2, 7.0, and 12.0 at. pct Li). This investigation emphasizes thein situ small-angle X-ray scattering (SAXS) observations on specimens subjected to various aging conditions. Special attention is paid to the early stages of the transformation in an attempt to characterize the various possible modes of phase separation on one hand and to study the dynamics of the precipitation process on the other. The following results are obtained: the congruent ordering precedes decomposition at low temperatures; the metastableγ′ solvus curve is reconfirmed; but the predicted metastable miscibility gap is not found. Guinier radii measurements of the particles showed Ostwald ripening is quickly reached upon heating to the aging temperatures. Slowing down behavior is seen at aging temperatures close to the solvus boundary. Activation energies for Li diffusion were obtained using the modified Lifshitz, Slyozov, and Wagner (MLSW) model. A test of dynamical scaling behavior is carried out for the Al-12.0 at. pct Li alloy. Formerly Visiting Scientists at the University of Illinois     

Natural convective effects in directional dendritic solidification of binary metallic alloys: Dendritic array primary spacing

This paper is concerned with the effect of natural convective patterns evidenced in a previous paper [Acta metall.37, 1143 (1989)], on the dendritic primary spacings. Primary spacings in normal gravity environment have been found to be much smaller than those measured in a microgravity environment, the latter being in good agreement with the diffusion controlled theoretical predictions. The scaling analysis of convective effects developed in the first paper allows us to propose a relationship, which gives the primary spacing as a function of the experimental parameters, in convective transport conditions of the solute in the liquid. This correlation is in good agreement with our experimental results, and those of the literature.     

Interstitial precipitation in Fe-Cr-Al alloys

Two separate stages of precipitation have been identified during the aging of ternary Fel8Cr3Al and Fel8Cr5Al alloys at temperatures in the vicinity of 475 °C. The first stage involves the formation of interstitial precipitates resulting from C and N impurities; the second and slower stage is the formation of the Cr-rich α′ phase. Transmission electron microscopy (TEM) results show that carbonitride precipitation occurs preferentially at dislocations, stacking faults, and grain boundaries, and also uniformly through the matrix. Aging for times in excess of 400 hours at 475 °C promotes coarsening of the heterogeneous precipitates and dissolution of the uniformly distributed matrix particles. A resistometric analysis shows that the kinetics of the initial stages of precipitation can be described by a (time)^2/3 relation. This kinetic behavior is explained in terms of stress-assisted diffusion in the highly stressed matrix resulting from coherency strains accompanying carbonitride precipitation. Experimental values of the activation energy for the first stage reaction correlate closely with those reported for the interstitial diffusion of C and N in alpha iron.     

Dendritic solidification of alloys in low gravity

Gravity-driven convective flow influences dendrite morphology, interdendritic fluid flow, dendrite interface morphology, casting macrosegregation, formation of channel type casting defects, and casting grain structure. Dendritic solidification experiments during multiple parabolic aircraft maneuvers for iron-carbon type alloys and superalloys show increased dendritic spacing in low-gravity periods. Larger dendrite spacings for low-gravity solidification have also been reported for sounding rocket and space laboratory experiments for metal-model and binary alloys. Convection decreases local solidification time and increases the rate of interdendritic solute removal. The elimination of convection in low gravity is thus expected to increase dendritic spacing. Convection's effect on dendritic arm coarsening is expected to be dependent on the coarsening mechanism. Decreased coarsening in low gravity found for Al-Cu is indicative of coarsening predominately by arm coalescence. This paper is based on a presentation made in the symposium “Experimental Methods for Microgravity Materials Science Research” presented at the 1988 TMS-AIME Annual Meeting in Phoenix, Arizona, January 25–29, 1988, under the auspices of the ASM/MSD Thermodynamic Data Committee and the Material Processing Committee.     

Discontinuous precipitation in aluminum-base zinc alloys

The kinetics of discontinuous precipitation in Al-21.6 at. pct. Zn and Al-22 at. pct. Zn-0.01 at. pct Sn alloys was determined by quantitative metallographic measurements on solution-treated and aged specimens. The growth rate of the discontinuous precipitate appears to be controlled by interfacial diffusion. It was found that the addition of a small amount of tin reduced the overall reaction rate. Nucleation of the discontinuous precipitate was confined to grain edges or boundaries, filling the available sites (site saturation) at a very early stage in the reaction. It was observed that a variation in quench rate markedly affected the growth rate of the precipitate and the site-saturating-dimensionality during a room-temperature aging treatment.     

Laves phase precipitation in Fe-Ta alloys

Development of an iron-base alloy hardened by particles of an intermetallic compound rather than a carbide is a desirable goal because of the greater thermal stability of such a dispersion. As a first step in the development of iron-base alloys hardened with the Laves phase, structural studies of binary Fe-Ta alloys have been undertaken. The structures of two phase Fe-Ta alloys have been studied by means of optical and transmission electron microscopy, X-ray diffraction, electron beam microprobe analysis, and scanning electron microscopy. The hardness change as a function of time at 600°, 700°, and 800°C has been determined for binary alloys with 1 at. pct Ta and 2 at. pct Ta in iron. Also, the uniaxial tensile strengths of solution treated, quenched, and aged samples have been determined. These studies suggest that the compound, Fe₂Ta, is isomorphous with the structure type, MgZn₂, (C14) and has a range of compositional homogeneity. The latter results correspond with the predictions of the Engel-Brewer correlation. Also, it has been found that precipitation occurs at grain boundaries, dislocations, and randomly throughout the matrix. Particles which form at dislocations have a (100)α habit plane; whereas a (110)α habit plane has been reported by others^1,3 for the hexagonal Laves phase in α iron. Hypereutectoid composition alloys quenched from the ö phase field have a completely retained § structure. Isothermal decomposition at 600°, 700°, and 800°C of alloys with the retained § structure results in a sizable hardness increase in 2 at. pct Ta alloys but only a modest increase in 1 at. pct Ta alloys. Brittle fracture of aged tensile specimens tested at room temperature reveals that the ductile-brittle transition temperature in tension is above room temperature.     

Radiation-induced solute segregation and precipitation in alloys

Solute segregation and precipitation in dilute alloys during irradiation have been studied by means of the Johnson-Lam kinetic model. The model is based on a combination of chemical reaction rates and diffusion equations for free defects, solutes, and bound defect-solute complexes. The enrichment of solute at sink surfaces and solute depletion in the matrix have been calculated as functions of temperature, damage rate, defect-solute bind-ing energy, and initial solute concentration. Using parameters appropriate for Be in Ni, significant solute segregation is found in the temperature range from 0.2 to 0.7 Υ_m. The temperature for maximum segregation is higher for the high displacement rates typically used in charged-particle bombardment experiments than for the low displacement rates used in fast-reactor irradiations. The solute concentration at the sink surface builds up at high temperatures, without surpassing the solubility limit, until a steady state is at-tained. However, at lower temperatures solute enrichment at sinks becomes larger and the solubility, in general, becomes lower. Precipitation will occur when the local solute concentration reaches that of the phase boundary. The solute concentration at the precipi-tate-matrix interface is determined by the solubility limit, and precipitation continues until the matrix is sufficiently solute-depleted to achieve a steep concentration gradient that will balance the defect-induced solute flow by back-diffusion. Hence, the steady-state matrix composition is determined by radiation conditions and is independent of the initial alloy composition when precipitation occurs. The solute depletion at steady state is more severe at low displacement rates than at high rates. The calculations are quali-tatively compared with recent experimental observations of the temperature and com-positional dependence of solute precipitation in the Ni-Be system. This paper is based on a presentation made at a symposium on “Radiation In-duced Atomic Rearrangements in Ordering and Clustering Alloys” held at the annual meeting of the AIME, Atlanta, Georgia, March 7 to 8, 1977, under the sponsorship of the Physical Metallurgy and Nuclear Metallurgy Committees of The Metallurgical Society of AIME.     

Discontinuous precipitation and coarsening in Al-Zn alloys

The morphology and kinetics of discontinuous precipitation (DP) and discontinuous coarsening (DC) in solution treated and isothermally aged Al-Zn alloys containing 39.3 and 59.3 at.% Zn have been investigated at temperatures ranging from 323 to 523 K by light microscopy, electron microscopy and X-ray diffraction. At all aging temperatures the supersaturated α solid solution was observed to decompose rapidly by DP into a lamellar mixture of solute depleted α phase and β phase precipitate. DP occurred so rapidly in the 59.5 at.% Zn alloy that the heat of transformation raised the temperature of the alloy significantly. With further aging a slower DC reaction transformed the lamellar DP into a coarser lamellar structure of the same two phases; however, the composition of the α phase of the DC was closer to the equilibrium solvus composition than that of the DP. With still further aging a second, much slower DC reaction was observed to decompose the lamellar product of the first DC reaction in the 59.5 at.% Zn alloy into a still coarser lamellar structure. Analysis of the kinetics of both the DP and DC reactions showed them to be controlled by boundary diffusion in the advancing reaction interface. Reaction front migration rates for both DP and DC increased markedly with increasing Zn content. This increase seems to be associated partially with an increase in boundary diffusivity with increasing Zn content.     

Correlation between solid-state transformations and solidification in Ni-Mn-Ga alloys

The influence of solidification morphologies, planar and cellular, on the solid-state transformations, martensitic and premartensitic transformations, was studied, respectively, for Ni-Mn-Ga martensitic materials. The martensitic transformation was observed in both planar and cellular morphologies, but the premartensitic transformation was suppressed in the cellular morphology. Moreover, after homogenization, the premartensitic transformation was monitored again. The correlation between the solidification and the solid-state transformation is revealed. The chemical disorder during solidification is considered to understand this correlation.