Grain refinement of aluminum alloys: Part I. the nucleant and solute paradigms—a review of the literature

Despite the extensive literature on grain refinement, there is not a consensus on the mechanism of grain refinement in aluminum alloys. Recently, there has been a shift in understanding of the grain-refinement paradigm from purely being concerned with the nucleation event, called here the “nucleant paradigm,” to also being concerned with the effect of solute elements, or, the “solute paradigm,” on the final grain structure. This article is divided into two parts. In Part I, the literature underpinning both paradigms is explained, and the validity of the paradigm shift toward the solute paradigm as a more complete understanding of grain refinement is presented. Part II experimentally confirms the validity of the solute paradigm and details a mechanism which explains the need for both effective nucleants and a solute of a good segregating power in order to obtain grain refinement.     

An analysis of the relationship between grain size,solute content,and the potency and number density of nucleant particles

To be able to determine the grain size obtained from the addition of a grain refining master alloy, the relationship between grain size (d), solute content (defined by the growth restriction factor Q), and the potency and number density of nucleant particles needs to be understood. A study was undertaken on aluminium alloys where additions of TiB₂ and Ti were made to eight wrought aluminum alloys covering a range of alloying elements and compositions. It was found from analysis of the data that . From consideration of the experimental data and from further analysis of previously published data, it is shown that the coefficients a and b relate to characteristics of the nucleant particles added by a grain refiner. The term a is related to the maximum density of active TiB₂ nucleant particles within the melt, while b is related to their potency. By using the analysis methodology presented in this article, the performance characteristics of different master alloys were defined and the effects of Zr and Si on the poisoning of grain refinement were illustrated.     

Study of the mechanism of grain refinement of aluminum after additions of Ti- and B-containing master alloys

A highly sensitive thermal analysis technique has been used to study the mechanisms of grain refinement in high-purity aluminum. Additions of Al-Ti-B master alloys were made both below and above the peritectic concentration in reference to the Al-rich corner of the binary Al-Ti phase diagram (0.15 pct Ti in solution). The experiments were conducted at various times after the addition of grain refiner. From the results, except for formation of TiB₂, no effect of boron on the Al-rich portion of the binary Al-Ti phase diagram can be observed. With hypoperitectic additions of Al-Ti-B master alloys, TiB₂ particles are the most frequent nucleant for aluminum grains. Also, when Al-5Ti-lB additions are made, nucleation frequently occurs above the equilibrium liquidus temperature. From a thermodynamic point of view, this phenomenon can occur only if regions of the melt (which contain bondes and nucleate new grains) have a higher Ti concentration than is present in the bulk of the liquid. A mechanism has been proposed to account for this observation. When hyperperitectic additions of grain refiner were made, a metastable formation of Al solid was often observed to occur at 2 to 5 deg above the equilibrium peritectic temperature. Other researchers have made this observation and proposed that a metastable aluminide phase was formed, even though no X-ray evidence of this phase was found. The experiments reported here show that the metastable nucleation occurs on boride particles when cooling from high temperature, which allow high (metastable) quantities of dissolved Ti to be retained in portions of the melt.     

The role of solute in grain refinement of magnesium

The effect of separate solute additions of Al, Zr, Sr, Si, and Ca on grain size of Mg has been investigated. Increasing the Al content in hypoeutectic Mg-Al alloys resulted in a continuous reduction in grain size up to 5 wt pct Al, reaching a relatively constant grain size for higher Al contents (above 5 wt pct). The effect of Sr additions was investigated in both low- and high-Al content magnesium alloys, and it was found that Sr had a significant grain refining effect in low-Al containing alloys but a negligible effect on grain size in Mg-9Al. Additions of Zr, Si, and Ca to pure magnesium resulted in efficient grain refinement. The grain refinement is mainly caused by their growth restriction effects, i.e., constitutional undercooling, during solidification, but the effect of nucleant particles, either introduced with the alloying additions or as secondary phases formed as a result of these additions, may enhance the grain refinement. A brief review of grain refinement of magnesium alloys is included in this article to provide an update on research in this field.     

The Interface of TiB<Subscript>2</Subscript> and Al<Subscript>3</Subscript>Ti in Molten Aluminum

In the grain refinement of aluminum, Al₃Ti and TiB₂ particles are introduced to reduce the casting grain size down to 200 micrometer level, which makes cold working possible. The particles are brought in by the addition of Al-Ti-B-type master alloys. It is generally believed that TiB₂ particles are stable and nucleate α-Al grains in solidification in the presence of titanium in solution from the dissolution of Al₃Ti particles in the master alloys. The titanium in solution either forms Al₃Ti layers on the surface of TiB₂ particles to promote the nucleation of α-Al grains or remains as solute to restrict the growth of α-Al grains in solidification. However, a consensus on a grain refinement mechanism is still to be reached due to the lack of direct observation of the three phases in castings. This paper presents finding of the TiB₂/Al₃Ti interfaces in an Al-Ti-B master alloy. It demonstrates a strong epitaxial growth of Al₃Ti on the surface of TiB₂ particles, a sign of the formation of an Al₃Ti layer on the surface of TiB₂ particles in grain refinement practice. The Al₃Ti layer has a crystal coherency with α-Al and hence offers a substrate for heterogeneous nucleation of α-Al grains. However, the layer must be dynamic to avoid the formation of compounded Al₃Ti and TiB₂ particles leading to the loss of efficiency in grain refinement.     

Influence of Solute Content and Solidification Parameters on Grain Refinement of Aluminum Weld Metal

Grain refinement provides an important possibility to enhance the mechanical properties (e.g., strength and ductility) and the weldability (susceptibility to solidification cracking) of aluminum weld metal. In the current study, a filler metal consisting of aluminum base metal and different amounts of commercial grain refiner Al Ti5B1 was produced. The filler metal was then deposited in the base metal and fused in a GTA welding process. Additions of titanium and boron reduced the weld metal mean grain size considerably and resulted in a transition from columnar to equiaxed grain shape (CET). In commercial pure aluminum (Alloy 1050A), the grain-refining efficiency was higher than that in the Al alloys 6082 and 5083. Different welding and solidification parameters influenced the grain size response only slightly. Furthermore, the observed grain-size reduction was analyzed by means of the undercooling parameter P and the growth restriction parameter Q, which revealed the influence of solute elements and nucleant particles on grain size.     

Influence of Mg on Grain Refinement of Near Eutectic Al-Si Alloys

Although the grain-refinement practice is well established for wrought Al alloys, in the case of foundry alloys such as near eutectic Al-Si alloys, the underlying mechanisms and the use of grain refiners need better understanding. Conventional grain refiners such as Al-5Ti-1B are not effective in grain refining the Al-Si alloys due to the poisoning effect of Si. In this work, we report the results of a newly developed grain refiner, which can effectively grain refine as well as modify eutectic and primary Si in near eutectic Al-Si alloys. Among the material choices, the grain refining response with Al-1Ti-3B master alloy is found to be superior compared to the conventional Al-5Ti-1B master alloy. It was also found that magnesium additions of 0.2 wt pct along with the Al-1Ti-3B master alloy further enhance the near eutectic Al-Si alloy’s grain refining efficiency, thus leading to improved bulk mechanical properties. We have found that magnesium essentially scavenges the oxygen present on the surface of nucleant particles, improves wettability, and reduces the agglomeration tendency of boride particles, thereby enhancing grain refining efficiency. It allows the nucleant particles to act as potent and active nucleation sites even at levels as low as 0.2 pct in the Al-1Ti-3B master alloy.     

Influence of rare earth metals on the nucleation and solidification behavior of iron and 1045 steel

Two series of experiments have been conducted to determine the influence of rare earth additions on the nucleation and crystallization behavior of pure iron and 1045 steel. In the first series, additions of rare earth suicide or cerium dioxide powder to two-Kg 1045 steel ingots indicated that rare earth suicide can refine the as-cast structure of such ingots. However, if the holding time after rare earth silicide addition is over two minutes, the grain refinement decreases. With cerium dioxide additions, a relatively large columnar zone was obtained. In the second series, the effects of cerium metal or cerium dioxide powder additions on the degree of undercooling obtainable in pure iron and 1045 steel were examined by the lévitation melting method. Surface tension measurements of the levitated droplets were carried out at the same time to investigate the possible effects of surface tension variations on the nucleation and crystallization behavior of the metals. The experimental data show that rare earth inclusions can greatly reduce the degree of undercooling of iron and steel, and that a small amount of dissolved cerium can further reduce the degree of undercooling of levitated droplets. The structure and reaction products obtained with Fe-Ce levitated droplets were examined with both optical and scanning electron microscopy as well as X-ray diffraction analysis. The experimental results clearly indicated that cerium solute redistribution during solidification is the dominant factor in refining the as-cast structure. A nucleation and solidification model for the Fe-Ce levitated droplets has been developed, which can successfully explain the experimental results. on research leave from Beijing University of Iron and Steel Technology     

Effects of Cooling Rate and Solute Content on the Grain Refinement of Mg-Gd-Y Alloys by Aluminum

The effect of Al additions on grain refinement of Mg-Gd-Y alloys with different solute contents at different cooling rates has been investigated. For all alloys, significant grain refinement was due to the formation of Al₂(Gd _x Y_1?x ) nucleant particles. The number density and size distribution of Al₂(Gd _x Y_1?x ) were affected by both solute content and the cooling rate. Grain sizes (d _gs) of Mg-Gd-Y base alloys and of Mg-Gd-Y-Al alloys were related to solute content (defined by the growth restriction factor, Q), cooling rate ( \( \dot{T} \) ), and area number density (ρ _ns) and size (d _p) of nucleant particles that can be activated. It is found that grain sizes of Mg-Gd-Y base alloys follow the relationship \( d_{\text{gs}} = a + \frac{b}{{Q\sqrt {\dot{T}} }} \) , while grain sizes of Al-refined samples follow the relationship \( d_{\text{gs}} = \frac{a'}{{\sqrt {\rho {}_{\text{ns}}} }} + \frac{b'}{{\sqrt {\dot{T}} Qd_{\text{p}} }} \) , where a, b, a′, and b′ were constants. In addition, the grain refinement effect of Al additions was more susceptible to solute content and the cooling rate than that of Zr which is regarded as the most efficient grain refiner for Mg alloys.     

The grain refinement of high-purity aluminum by aluminum-transition metal alloys

In view of the continuing interest in the solidification characteristics of dilute Al-Ti alloys,¹ a recent study² of the mechanism(s) of grain refinement induced in high purity aluminum by various additions of master alloys containing Ti, B, Cr, Mo, V and Zr is reported. For alloys containing more than 0.2 wt pct Ti, TiAl₃ was shown to be commonly a nucleant, in both Al-Ti and Al-Ti-B systems. In addition, it was found that the nature of the master alloys is important in determining the degree of grain refinement a given alloying addition will produce. A “saturation” effect is reported for additions of Ti, and ti-B,i.e., further additions of titanium beyond a given level do not provide any further reduction in grain size.     

Influence of rare earth metals on the nucleation and solidification behavior of iron and 1045 steel

Two series of experiments have been conducted to determine the influence of rare earth additions on the nucleation and crystallization behavior of pure iron and 1045 steel. In the first series, additions of rare earth suicide or cerium dioxide powder to two-Kg 1045 steel ingots indicated that rare earth suicide can refine the as-cast structure of such ingots. However, if the holding time after rare earth silicide addition is over two minutes, the grain refinement decreases. With cerium dioxide additions, a relatively large columnar zone was obtained. In the second series, the effects of cerium metal or cerium dioxide powder additions on the degree of undercooling obtainable in pure iron and 1045 steel were examined by the lévitation melting method. Surface tension measurements of the levitated droplets were carried out at the same time to investigate the possible effects of surface tension variations on the nucleation and crystallization behavior of the metals. The experimental data show that rare earth inclusions can greatly reduce the degree of undercooling of iron and steel, and that a small amount of dissolved cerium can further reduce the degree of undercooling of levitated droplets. The structure and reaction products obtained with Fe-Ce levitated droplets were examined with both optical and scanning electron microscopy as well as X-ray diffraction analysis. The experimental results clearly indicated that cerium solute redistribution during solidification is the dominant factor in refining the as-cast structure. A nucleation and solidification model for the Fe-Ce levitated droplets has been developed, which can successfully explain the experimental results. on research leave from Beijing University of Iron and Steel Technology     

Microstructure of Al-Ti-B-Er refiner and its grain refining performance

Al-Ti-B-Er refiner was successfully prepared by CR (contact reaction process), a process based on SHS (self propagating high-temperature synthesis). The microstructure of the alloy was studied by optical microscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with energy-dispersive spectrometry. The results showed that Al-Ti-B-Er alloy was composed of a-Al, block-like TiAl₃ and flocked TiB₂. Compared with Al-Ti-B refiner, formation of TiAlEr compounds, Er modified the morphology of TiAl₃ phase, and dispersed the TiB₂ and TiAl₃. An excellent grain refining performance was obtained when adding 1 wt.% Al-Ti-B-Er in Al-10Zn-1.9Mg-1.6Cu-0.12Zr alloy, the average grain size was about 40 µm. The refinement mechanism of Al-Ti-B-Er was also discussed. Er changed the morphology of TiAl₃, TiB₂ phase, the refiner would be more efficient. The decomposition of TiAlEr compounds which released Er refrained the growth of TiAl₃ and made TiB₂ difficult to aggregate or deposit, therefore resulted in more particles being efficient nucleation substrate.     

Homogeneity and Equiaxed Grain Structure of Billets

The homogeneity of as‐cast structures is essential to the application of advanced steel materials. The relationship between as‐cast equiaxed grain structure and homogeneity was examined by means of OPA (Original Position Analysis) technology. The results indicate that macrosegregation of the solute elements was obviously suppressed in silicon steel billets with equiaxed grain structure. Furthermore, two methods to achieve an equiaxed grain structure were described. One is to use titanium‐based inoculation technology. TiN particles and TiN/ Ti₂O₃ complex particles can precipitate at the early stage of solidification and then play an important role of heterogeneous nucleation when the solidification condition is carefully controlled. The other method is to maintain a small temperature gradient in the mould to enhance the constitutional undercooling As a result, the as‐cast equiaxed grain structure was well developed in the experimental billets.     

Nucleation of Fe-intermetallic phases in the Al-Si-Fe alloys

Nucleation of Fe-intermetallic phases (i.e. binary Al-Fe, α-AlFeSi, β-AlFeSi, δ-AlFeSi, and q₁-AlFeSi phases) on the surface of different inclusions in six experimental Al-Si-Fe alloys was studied through a quantitative evaluation of the number of inclusion particles that have a direct physical contact with the nucleated phase as seen through the optical microscope. It was found that nucleation of each of the Fe-intermetallic phases was promoted on the surface of several inclusions under the same conditions of alloy composition and cooling rates. Some inclusions exhibited high potency for the nucleation of particular Fe-intermetallic phases under certain conditions and poor potency under other conditions. The potent nucleants for the primary α-Al phase such as γ-Al₂O₃ exhibited poor potency for the nucleation of the Fe-intermetallic particles that lie within the primary phase (intragranular particles). Reactive inclusions such as CaO and SiC are very potent nucleants for the intragranular Fe-intermetallic phase particles. The nucleation of the Fe-intermetallic phases in Al-Si-Fe alloys obeys the general features of nucleation, in particular, the effect of cooling rate and solute concentration on the potency of the nucleant particles: (1) it was observed that increasing the cooling rate enhances the heterogeneous nucleation of the Fe-intermetallic phases on the surface of different inclusions, and (2) the nucleation potency of inclusion particles in both α-Al and interdendritic regions improves with increasing solute concentration up to a certain level. Above this level, the solute concentration poisons the nucleation sites. Nucleation of the Fe-intermetallics in the alloys studied does not seem to be largely affected by the type of the nucleating surface.     

Grain refinement of magnesium alloys

The literature on grain refinement of magnesium alloys is reviewed with regard to two broad groups of alloys: alloys that contain aluminum and alloys that do not contain aluminum. The alloys that are free of aluminum are generally very well refined by Zr master alloys. On the other hand, the understanding of grain refinement in aluminum bearing alloys is poor and in many cases confusing probably due to the interaction between impurity elements and aluminum in affecting the potency of nucleant particles. A grain refinement model that was developed for aluminum alloys is presented, which takes into account both alloy chemistry and nucleant particle potency. This model is applied to experimental data for a range of magnesium alloys. It is shown that by using this analytical approach, new information on the refinement of magnesium alloys is obtained as well as providing a method of characterizing the effectiveness of new refiners. The new information revealed by the model has identified new directions for further research. Future research needs to focus on gaining a better understanding of the detailed mechanisms by which refinement occurs and gathering data to improve our ability to predict grain refinement for particular combinations of alloy and impurity chemistry and nucleant particles. This article is based on a presentation made in the symposium entitled “Phase Transformations and Deformation in Magnesium Alloys,” which occurred during the Spring TMS meeting, March 14–17, 2004, in Charlotte, NC, under the auspices of ASM-MSCTS Phase Transformations Committee.     

Nucleation of solid aluminum on inclusion particles injected into Al-Si-Fe alloys

Systematic inoculation experiments were carried out to study the influence of various inclusions on the nucleation of the α-Al phase in Al-Si-Fe alloys at different cooling rates. The results showed that in dilute alloys, containing less than 1.5 pct Si+Fe, almost all the inclusion types have high percentages of occurrence within the α-Al phase, indicating that nucleation can be promoted on the surface of such inclusions. In a hypoeutectic Al-Si alloy containing 6.3 pct Si, the inclusion particles of MgO, TiB₂, TiC, α-Al₂O₃, and SiC become mostly inactive nucleants and are pushed to the interdendritic regions because of the dominating poisoning effect of Si. The current results were used successfully to explain the efficiency differences between the commercial grain refiners in the hypoeutectic Al-Si alloys. Silicon is observed to preferentially segregate to the liquid-Al/inclusion interfaces so as to lower the free energy of such interfaces. A theoretical analysis of the poisoning effect of Si showed that Si segregation to the liquid/nucleant interface alters the interfacial energy balance so that the catalytic efficiency of the nucleant particles is dramatically reduced. Careful analysis showed that the poisoning effect of Si in the hypoeutectic alloy is overcome when the nucleant particles have active surface characteristics, as represented by the high catalytic potencies of γ-Al₂O₃, CaO, and Al₄C₃ particles in nucleating the α-Al phase of the hypoeutectic Al-Si alloy. Although some inclusions have comparable or higher occurrence levels than TiB₂ in the α-Al phase, they cannot be used as efficient nucleants because of either their poor wettability with liquid aluminum or their chemical reactivity, which can change the alloy chemistry.     

Behavior of Boron in Molten Aluminum and its Grain Refinement Mechanism

The mechanism of heterogeneous grain refining of aluminum by ultrafine elemental boron particles was investigated. In order to facilitate the observation of the boron-aluminum interface, a boron filament was introduced in a melt at 1013 K (740 °C) containing different levels of Ti. The Al/B interface was studied using transmission electron microscopy and different phases were identified using the electron diffraction method. The experimental results showed that boron is dissolved in pure aluminum while its dissolution is inhibited in presence of titanium solute. A thin layer of TiB₂ formed at the surface of boron thickens with residence time in the melt. The mechanisms by which aluminum is crystallized on boron are discussed.     

Denucleation

Ultrarapid cooling may result in material with extremely fine grain size and interdendritic spacing, or containing supersaturated solutions or nonequilibrium phases. Unfortunately, ultrarapid cooling cannot be obtained in large masses of metal; thus the interesting properties cannot be exploited commercially. The same structures can be obtained by denucleation, that is removal or neutralization of the nucleants that act at low undercooling. A denucleated melt, regardless of its size, can be undercooled to a temperature well below its freezing point, where it can be made to freeze rapidly on a chosen nucleant. Electro-lytically refined aluminum crystallizes normally with a fairly coarse grain at 1 to 2°C undercooling. By removing all nucleants with less than 5°C undercooling a grain size of less than 1 mm diam was achieved in a furnace cooled sample. In aluminum-manganese alloys, denucleation produces refinement of the grain structure in continuously cast billets and retention in solution of a higher percentage of manganese, in pure aluminum columnar grain and crystallization twins are found in plaster molds. By denucleation of aluminum-iron alloys, the FeAl₆ phase can be made to appear in samples cooled at commercial rates of a few °C/sec and eutectic structures can be obtained in alloys with 4 pct Fe. In cast iron removal of nucleants with low undercooling shifts the crystallization from primary graphite to primary austenite. Formerly Metallurgist, Revere Copper and Brass Incorporated     

Nucleation Catalysis in Aluminum Alloy A356 Using Nanoscale Inoculants

Different types of nanoparticles in aluminum (Al) alloy A356 nanocomposites were shown to catalyze nucleation of the primary Al phase. Nanoparticles of SiC β, TiC, Al₂O₃ α, and Al₂O₃ γ were added to and dispersed in the A356 matrix as nucleation catalysts using an ultrasonic mixing technique. Using the droplet emulsion technique (DET), undercoolings in the nanocomposites were shown to be significantly reduced compared to the reference A356. None of the nanocomposites had a population of highly undercooled droplets that were observed in the reference samples. Also, with the exception of the A356/Al₂O₃ α nanocomposite, all nanocomposites showed a reduction in undercooling necessary for the onset of primary Al nucleation. The observed nanocomposite undercoolings generally agreed with the undercooling necessary for free growth. The atomic structure of the particles showed an influence on nucleation potency as A356/Al₂O₃ γ nanocomposites had smaller undercoolings than A356/Al₂O₃ α nanocomposites. The nucleation catalysis illustrates the feasibility of, and basis for, grain refinement in metal matrix nanocomposites (MMNCs).