The microstructure and phase relationships in rapidly solidified type 304 stainless steel powders

The microstructure and relative amounts of fcc and bcc phases have been studied for rapidly solidified Type 304 stainless steel powders produced by vacuum gas atomization (VGA) and centrifugal atomization (CA). The VGA powder solidifies with a cellular microstructure while the CA powder has a dendritic microstructure. The volume fraction of fcc phase in the CA powder is found to increase from 40 Pct to 97 Pct with increasing particle size from 30 to 125 μm. In the VGA powder, the volume fraction of fcc phase is found to decrease from about 90 Pct to 77 Pct over the same range of particle sizes. The origins of the fcc and bcc phases in each powder are considered. It is concluded that bcc is present as both a primary crystallization phase in the smaller CA particles (<75 μm) and as compositionally stabilized eutectic ferrite at the cell walls of particles of both CA and VGA powders in which fcc was the primary crystallization phase.     

Nucleation and phase selection in undercooled Fe-Cr-Ni melts: Part II. Containerless solidification experiments

The solidification behavior of undercooled Fe-Cr-Ni melts of different compositions is investigated with respect to the competitive formation of δ-bcc (ferrite) and γ-fcc phase (austenite). Containerless solidification experiments, electromagnetic levitation melting and drop tube experiments of atomized particles, show that δ (bcc) solidification is preferred in the highly undercooled melt even at compositions where δ is metastable. Time-resolved detection of the recalescence events during crystallization at different undercooling levels enable the determination of a critical undercooling for the transition to metastable bcc phase solidifcation in equilibrium fcc-type alloys. Measurements of the growth velocities of stable and metastable phases, as functions of melt undercooling prior to solidification, reveal that phase selection is controlled by nucleation. Phase selection diagrams for solidification processes as functions of alloy composition and melt undercooling are derived from two types of experiments: X-ray phase analysis of quenched samples and in situ observations of the recalescence events of undercooled melts. The experimental results fit well with the theoretical predictions of the metastable phase diagram and the improved nucleation theory presented in an earlier article. In particular, the tendency of metastable δ phase formation in a wide composition range is confirmed.     

Solidification of undercooled Fe-Cr-Ni alloys: Part III. Phase selection in chill casting

In Parts I and II of this series of articles, it was shown that a range of levitation-melted Fe-Cr-Ni alloys, both hypoeutectic and hypereutectic, all solidified with the hypereutectic phase (bcc) as their primary phase, except for the hypoeutectic alloys at low undercoolings. In this article, the effect of heat extraction on phase formation is studied by chill casting the undercooled alloys before nucleation. Two of the previously studied alloys are examined; one hypoeutectic and the other hypereutectic. Chill substrates employed were copper, stainless steel, alumina, zirconia, and a liquid gallium-indium bath. Contrary to the case of levitation melting and solidification, it is found that the dominant primary phase to solidify in both alloys, independent of chill substrate, is the hypoeutectic phase (fcc). It is concluded that chilling the undercooled melt results in nearly concurrent nucleation of bcc and fcc. Two different mechanisms are considered as possible explanations of the subsequent fcc phase selection during growth. These are termed “growth velocity” and “phase stability” mechanisms. Evidence favors a phase stability mechanism, in which the bcc phase massively transforms to fcc early in solidification so that fcc then grows without competition. It is suggested that this mechanism may also explain structures observed in welds and other rapid solidification processes.     

Rapid solidification of martensitic stainless steel atomized droplets

The microstructure of martensitic stainless steel powders produced by inert gas atomization was investigated. Depending upon the powder particle size, the microstructure was found to exhibit a cellular, dendritic, or martensitic morphology. Relationships between the microstructure scale and the particle diameter were identified. It was found that at a critical particle diameter of 25 to 30 μm, the structure changed from cellular/dendritic (96.5 vol pct bcc and 3.5 vol pct fcc) to martensite. The solidification path of the powder particles below and above 25 to 30 μm in size was considered. High-temperature X-ray diffraction (HTXRD) measurements revealed that there is a delay in the appearance of the fcc phase for the small particle size. The delay in the appearance of the fcc phase is a result of different nucleation sites for the fcc phase between the large and the small particle size.     

Amorphous Phase Formation Analysis of Rapidly Solidified CoCr Droplets

This paper investigates amorphous phase formation and rapid solidification characteristics of a CoCr alloy. High cooling rate and high undercooling-induced rapid solidification of the alloy was achieved by impulse atomization in helium atmosphere. Two atomization experiments were carried out to generate powders of a wide size range from liquid CoCr at two different temperatures. Amorphous fraction and kinetic crystallization properties of impulse atomized powders were systematically quantified by means of differential scanning calorimetry. In addition, different but complementary characterization tools were used to analyze the powders microstructures. The fraction of amorphous phase within the investigated powders is found to be promoted by high cooling rate or smaller powder size. The critical cooling rate for amorphous phase formation, which is influenced by the oxygen content in the melt, is found to be ~3 × 10⁴ K s^?1 and corresponds to a 160-µm-diameter powder atomized in helium. Hardness of the powders is found to follow a trend that is described by the Hall–Petch relation when a relatively high fraction of crystalline structures is present and decreases with the fraction of amorphous phase.     

Theoretical treatment of the solidification of undercooled Fe-Cr-Ni melts

The solidification behavior of undercooled Fe-Cr-Ni melts is analyzed with respect to the competitive formation of body-centered cubic (bcc) phase (ferrite) and face-centered cubic (fcc) phase (austenite). The activation energies of homogeneous nucleation and growth velocities for both phases as functions of undercooling of the melt are calculated on the basis of current theories of nucleation and dendrite growth using data of thermodynamic properties available in the literature. As model systems for numerical calculations, the alloys Fe-18.5Cr-11Ni forming primary ferrite and Fe-18.5Cr-12.5Ni forming primary austenite under near-equilibrium solid-ification conditions are considered. Nucleation of the bcc phase is always promoted in the under-cooled primary ferrite alloy, whereas the barrier for bcc nucleation falls below that for fcc nucleation for large undercooling in primary austenite alloys. With rising undercooling, tran-sitions of the fastest growth mode were found from bcc to fcc and subsequently from fcc to bcc for the primary ferrite forming alloy and from fcc to bcc for the primary austenite forming alloy. The results of the calculations provide a basis for understanding contradictory experi-mental findings reported in the literature concerning phase selection in rapidly solidified stainless steel melts for different process conditions. Formerly Visiting Scientist at the Institut fur Raumsimulation     

Phase Formation in Isothermally Annealed (Co0.95Fe0.05)89Zr7B4 Nanocrystalline Alloys

This report focuses on the phase relations and transformations in a (Fe_0.05Co_0.95)₈₉Zr₇B₄ melt-spun alloy with an emphasis on crystallization and its effects on thermomagnetic properties. When as-spun ribbons are annealed at relatively low temperatures (near primary crystallization), the nucleation and growth of nonequilibrium body-centered-cubic (bcc) crystallites occurs in a residual amorphous matrix, as determined by transmission electron microscopy (TEM) and X-ray diffraction (XRD). At intermediate temperatures, bcc crystallites continue to grow with the addition of a small volume fraction of the equilibrium face-centered-cubic (fcc) phase. It is expected that after the bcc nuclei are formed, the grains coarsen as bcc phase and do not transform to the more stable fcc phase at intermediate temperatures. At temperatures where the amorphous matrix phase dissociates into Zr intermetallics, the bcc phase is transformed into fcc and the grains coarsen significantly. Thermodynamic modeling has been used to support the nucleation of the nonequilibrium bcc phase during the early stages of crystallization. Thermomagnetic results show little reduction in the saturation magnetization as a function of annealing temperature up to the primary crystallization temperature (~420 °C). This article is based on a presentation made in the symposium “Phase Transformations in Magnetic Materials” which occurred during the TMS Spring meeting, March 12–16, 2006, in San Antonio, TX under the auspices of the Joint TMS-MPMD and ASMI-MSCTS Phase Transformations Committee.

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Nucleation and phase selection in undercooled Fe-Cr-Ni melts: Part I. Theoretical analysis of nucleation behavior

The selection of the primary solidifying phase in undercooled stainless steel melts is theoretically analyzed in terms of nucleation theory. Nucleation phenomena are considered using different models for the solid-liquid interface energy. The classical nucleation theory for sharp interfaces and an improved modification, the diffuse interface theory, are applied. The influence of deviations of the nucleus composition from the overall alloy composition is also revealed. A preferred nucleation of the metastable bcc phase in fcc equilibrium solidification-type alloys is predicted. The critical undercooling of metastable crystallization as a function of alloy composition is calculated for an isoplethal section at 69 at. pct Fe of Fe₆₉Cr_31-x Ni _x alloys. The results are summarized in a phase selection diagram predicting the primary solidification mode as a function of undercooling and melt composition.     

连铸保护渣的熔化温度、凝固温度和结晶温度研究

采用CaO-SiO2-Na2O-CaF2-Al2O3-MgO渣系,通过测定熔渣的熔化温度、凝固温度和结晶温度,研究连铸保护渣的熔化温度凝固温度和结晶温度与化学成分之间的关系。熔化温度高于凝固温度和结晶温度。凝固温度和结晶温度之间的关系与连铸保护的玻璃性能有关。     

Heterogeneous nucleation during rapid solidification by laser surface melting

Crystal nucleation during rapid solidification generally occurs rather slowly except at active heterogeneities or unless very large undercoolings are achieved. Many typical microstructures are then essentially of columnar morphology, for example from the bottom surface of a melt-spun ribbon or from a heterigeneity on the surface of a powder particle. In such cases the microstructure may be considerably refined by the presence of many active nucleants for heterogeneous nucleation distributed throughout the melt. Such microstructural refinement is analysed here during rapid solidification of a laser-melted surface containing fine TiB₂ particles. Simulation of the cooling and solidification conditions confirms these particles to be highly effective nucleating substrates, capable of greatly increasing nucleating rates. As a result it is possible to obtain materials possessing greatly refined grain sizes.     

Effects of Solidification Conditions on Grain Refinement Capacity of TiC in Directionally Solidified Ti6Al4V Alloy

In this study, the effects of solidification conditions on the grain refinement capacity of heterogeneous nuclei TiC in directionally solidified Ti6Al4V alloy were investigated using experimental and numerical approaches. Ti6Al4V powder with and without TiC particles in a Ti6Al4V sheath was melted and directionally solidified at various solidification rates via the floating zone melting method. In addition, by using the phase field method, the microstructural evolution of directionally solidified Ti6Al4V was simulated by varying the temperature gradient G and solidification rate V. As the solidification rate increased, the increment of the prior β grain number by TiC addition also increased. There are two reasons for this: first, the amount of residual potent heterogeneous nuclei TiC is larger. Second, the amount of TiC particles that can nucleate becomes larger. This is because increasing the constitutional undercooling ΔT_c leads to the activation of a smaller radius of heterogeneous nuclei and a higher nucleation probability from each radius. At a cooling rate R higher than that in the floating zone melting experiment (R = 3 to 1000 K/s), the maximum degree of constitutional undercooling ΔT_c,Max has a peak value, which suggests that constitutional undercooling ΔT_c has a smaller contribution at higher cooling rates, such as those that occur during electron beam melting (EBM), including laser powder bed fusion (LPBF).

     

Microstructural transitions during containerless processing of undercooled Fe-Ni alloys

The microstructural development associated with solidification in undercooled Fe-Ni alloys has been reported in different studies to follow various pathways, with apparent dissimilarities existing as a function of sample size and processing conditions. In order to identify the possible hierarchy of microstructural pathways and transitions, a systematic evaluation of the microstructural evolution in undercooled Fe-Ni alloys was performed on uniformly processed samples covering seven orders of magnitude in volume. At appropriate undercooling levels, alternate solidification pathways become thermodynamically possible and metastable product structures can result from the operation of competitive solidification kinetics. For thermal history evaluation, a heat flow analysis was applied and tested with large Fe-Ni alloy particles (1 to 3 mm) to assess undercooling potential. Alloy powders (10 to 150 μm), with large liquid undercoolings, were studied under the same composition and processing conditions to evaluate the solidification kinetics and microstructural evolution, including face-centered cubic (fcc)/body centered cubic (bcc) phase selection and the thermal stability of a retained metastable bcc phase. The identification of microstructural transitions with controlled variations in sample size and composition during containerless solidification processing was used to develop a microstructure map which delineates regimes of structural evolutions and provides a unified analysis of experimental observations in the Fe-Ni system.     

Nucleation of solidification in liquid droplets

Analytical and numerical methods have been developed to analyze the solidification kinetics of a mass of liquid droplets dispersed in a fluid or solid matrix using classical nucleation theory. The resulting analytical expressions and numerical calculations can be compared directly with calorimetric measurements of the droplet solidification exotherms to obtain information about the nucleation mechanism. With increasing contact angle at the solid-liquid-matrix triple point, the solidification onset, peak, and end temperatures and exothermic peak height all decrease sharply and the droplet solidification exotherms become broader. Decreasing either the droplet radius or the number of potential catalytic nucleation sites produces a similar but smaller effect. Distributions in droplet radius, contact angle, and nucleation sites have no effect on the solidification peak temperature, but the droplet solidification exotherms become broader and more symmetric. The solidification onset temperature is independent of cooling rate in the calorimeter, but the solidification peak and end temperatures decrease and the exothermic peak height increases with increasing cooling rate. Predicted droplet solidification exotherms are in excellent agreement with detailed experimental measurements on 10-nm-radius Cd droplets embedded in a solid Al matrix. Analytical predictions give best-fit values of 43 deg and 430 for the contact angle and the number of potential catalytic nucleation sites per droplet, respectively; numerical predictions give best-fit values of 43 deg and 750 for the contact angle and the number of potential catalytic nucleation sites per droplet, respectively.     

3D Quantitative Characterization of Rapidly Solidified Al-36 Wt Pct Ni

The rapid solidification of a peritectic alloy is studied. Various 2D and 3D characterization techniques were effectively utilized to investigate the effect of cooling rate on both the phase fractions and the shrinkage porosity. Particles of Al-36 wt pct Ni were produced using a drop tube impulse system. Neutron diffraction and Rietveld analysis were used to quantify the phases formed during solidification. The microstructure of the produced particles was analyzed using SEM and X-ray microtomography. It was found that increasing cooling rate resulted in decreasing the Al₃Ni₂ to Al₃Ni ratio. Also, quantitative analysis of the microtomography images revealed that the volume percent of porosity increased with increasing particle size. The distribution of porosity was found to be significantly different in small and large particles. It was concluded that the extensive growth of Al₃Ni₂ at lower cooling rates followed by the peritectic reaction made the feeding of the shrinkages more difficult, and as a result, the volume percent of porosity increased. Other findings showed that high cooling rate during solidification would result in the formation of a quasicrystalline phase, known as D-phase, and suppression of the primary Al₃Ni₂. Also, investigation of the 3D structure of the solidified particles revealed that large particles of Al-36 wt pct Ni contain multiple nucleation sites, while smaller particles contain only one single nucleation site.     

钢中第二相诱导铜元素析出的晶体学分析

对钢液凝固温度下钛的化合物、Al2O3、MnS等基底与形核相铜元素的二维点阵错配度进行了计算,并对其成为铜元素非均质形核核心的有效性进行了分析.结果表明:基底与形核相的错配度δ越小,越有利于非均质形核.Ti2O3、MnS和Al2O3与铜元素的错配度较小,具有良好的匹配关系,可以作为铜元素形核的质点并促进其异质形核.Ti2O3和MnS是钢中残余铜元素非均质形核的最有效核心;Al2O3为中等有效核心;TiC、TiN为无效核心.     

An investigation of the effects caused by electromagnetic vibrations in a hypereutectic Al-Si alloy melt

In order to investigate the mechanism by which electromagnetic vibrations affect the solidification structure of metallic alloys, an experimental apparatus which enables the simultaneous application of electric and magnetic fields under different cooling conditions (ranging from rapid to furnace cooling) is developed. The objective is followed by inducing vibrations in a hypereutectic Al-Si alloy melt containing suspended silicon particles and interrupting the process at different temperatures before and after the start of solidification by water quenching. Interrupting the process at temperatures higher than the liquidus has revealed the effects of vibrations independent of the influences of the nucleation and growth phenomena. Establishing the conditions for obtaining identical cooling rates in experiments with different experimental conditions has lead to the exclusion of effects resulting from the differences in cooling rates and recognition of the effects caused only by electromagnetic vibrations. It is found that the application of either of the two fields alone has no significant effect on the solidified structure, while profound effects are observed when the two fields are applied simultaneously. An increase in the number of suspended silicon particles and a reduction in their average size are the effects noticed before the start of solidification. In this research, it has for the first time been clearly verified, through microscopic observation of the quenched samples, that these effects are brought about by the cavitation phenomenon. After the start of solidification, particles are locally agglomerated and expelled toward the surrounding walls under a combined influence of electromagnetic vibrations and pinch force squeezing the liquid. The final structure obtained is composed of an almost completely eutectic matrix surrounded by agglomerates of silicon particles along the outer surface.     

Ordering–separation phase transitions in a Co<Subscript>3</Subscript>V alloy

The microstructure of the Co₃V alloy formed by heat treatment at various temperatures is studied by transmission electron microscopy. Two ordering–separation phase transitions are revealed at temperatures of 400–450 and 800°C. At the high-temperature phase separation, the microstructure consists of bcc vanadium particles and an fcc solid solution; at the low-temperature phase separation, the microstructure is cellular. In the ordering range, the microstructure consists of chemical compound Co₃V particles chaotically arranged in the solid solution. The structure of the Co₃V alloy is shown not to correspond to the structures indicated in the Co–V phase diagram at any temperatures.     

The undercooling of aluminum

An important parameter affecting microstructure development during solidification is the amount of undercooling prior to nucleation. The undercooling potential of aluminum has been assessed by thermal analysis measurements on powder dispersions of the liquid metal. A number of variables have been identified which influence the undercooling of powder Al samples including powder coating, powder size, melt cooling rate, and melt superheat. Surface analysis by Auger electron spectroscopy indicates that changing the medium in which the powders are produced is an effective method of altering the coating chemistry. Factorial design analysis has been employed to quantify the potential of processing variables to increase the undercooling level obtainable in aluminum. The factorial analysis indicates that control of the powder coating through changing the medium in which the powders are produced is most effective in decreasing the nucleation temperature. Additionally, the finest powders produced in the medium which induces the least catalytic coating, when cooled at high rates,T = 500 °C/s, from low superheats,T _s = 710 °C, are found to achieve the deepest undercooling, ΔT = 175 °C. These studies provide the basis for further increases in undercooling and for future investigations into the solidification reactions which produce both stable and metastable structures in aluminum alloys. Formerly Research Assistant in the Department of Metallurgical and Mineral Engineering, University of Wisconsin-Madison