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1.1 Grain Refinement
Grain refinement is process to control intentionally columnar grain growth on which
columnar grain growth in ingots and castings is prevented and formation of fine equiaxed grains
all over the material [1]. Columnar grain structure is formed in certain alloys under normal
casting conditions, except if the solidification mode is carefully controlled [2]. The fine equiaxed
grains can be formed upon solidification either by fast cooling which certifies a high degree of
undercooling or by increasing the number of nuclei by heterogeneous nucleation (increment of
nucleation sites) through the use of inoculants and by alloying [2]. The fine equiaxed grains are
desired since the mechanical properties of any metal or alloy such as yield strength, toughness
and extrudeability are raised by fine grain size [2]. Besides, fine grain size improves uniform
distribution of second phase and micro-porosity, resulting in improved machinability, good
surface finish and resistance to hot tearing [2]. Grain refiners (inoculants or hardeners) act as
nucleating agents during solidification and control crystal formation by heterogeneous
nucleation. Nuclei formation by heterogeneous nucleation occurs at preferential sites such as
phase boundaries, surfaces or impurities. The interfacial energies are the controlling factors in
heterogeneous nucleation [3]. The balance between the interfacial energies can be expressed by
Equation (1) and is shown by Figure 2.4 in which






(Nm-2), and



(Nm-2) are

the liquid/nucleant, nucleus/nucleant and liquid/nucleus interfacial energies respectively and θ is
the contact angle (degree) [3].



> σ�S + σ�L cos �

�quation (1)

When nucleation happens. the value of cosθ is very close to unity [3]. it can be concluded that phases with higher melting point will have higher values of σNL and will be nucleants for the lower melting phases. . A Grain Refinement should have the following requirements in order to act as an effective nucleation site [2]: 1. the terms σ Equation (1) and heterogeneous nucleation can be expected if and θ can be neglected in the NS σ NL > σ NS [3] Miedema and Van Den Broeder [4] have shown that interfacial energies are roughly proportional to the melting point. 3. 2. θ is usually very small and does not exceed 20°. As a result. Consequently.IMAM PRABOWO MECHANISM OF GRAIN REFINEMENT IN ALUMUNIUM ALLOY Figure 1. The melting point of the alloy being solidified should be lower than the melting point of the grain refiner.1.Balance of interfacial energies in heterogeneous nucleation [3] Nucleation at low undercooling means there is epitaxy (good crystallographic fit) between the nucleant and nucleus which results to significant reduction of the energy σ �S [3]. It should have the capacity to commenced freezing at very small undercooling. Based on this. Adequate quantities of grain refiners should be equally distributed.

a reaction. in which the optimum contact time is long.7] have shown that the microstructure of a master alloy and in particular its morphology. The most common composition of a master alloy is based on Al-Ti-B with the composition of Al-5%Ti-1%B and the added percentage is usually 1Kg tonne-1.(2)fast acting and early fading. Grain refiners are categorised into 3 types: slow acting. to the melt.(1):slow acting. with time the grain size has increased. The grain refiners should be larger than a critical size. size and size distribution of . Figure 2 :Typical form of grain refiners.(3) fast acting and long lasting [8] At present chemical refinement is widely used due to its simplicity and is sometimes termed grain refinement by inoculation. The literature and the author’s experiences [6. Grain refinement by inoculants is accomplished by the addition of a master alloy in the form of a rod. Figure 2 shows 3 typical grain refiners. As can be seen in the case of number (2).IMAM PRABOWO MECHANISM OF GRAIN REFINEMENT IN ALUMUNIUM ALLOY 4. which depends on the undercooling of the melt. this is termed fading. settling or floating of the grain refiners corresponding to their density difference with respect to the melt [5]. Fading could be due to either the dissolution of the nucleating sites. fast acting if the optimum contact time is short and thirdly the ideal grain refiner which is not only fast acting but also long lasting.

a master alloy with lower content B. Al-B and Al-Sr-B for different alloy systems and processing application. Blocky particles with a broader size distribution are fast acting with a long-lasting nature.Ti. Al-Ti-B. Al-5Ti-0. But the ever-increasing requests on the quality of surface critical applications ended in the introduction of Al-3Ti-0. The other member of this family with lower content of Ti like Al-3Ti-1B was developed to meet the requirements to have a potent refiner. when slowly cooled from a low melt temperature block like (Blocky) aluminides are formed. But. The attempts have led to introduction of grain refiners (master alloys) such as Al. [9] have shown that if the melt is cooled rapidly from a high temperature. The results show that Al3Ti particles formed at a higher temperature tend to become acicular (plate-like/flaky) while at low temperatures they become approximately equiaxed [5]. The most applicable family of grain refiners is the one based on the Al-Ti-B system [10]. petallike aluminide crystals are formed. but not to exceed melt Ti contents [10]. which produces shaped castings based on the Al-Si systems.2 Types of Grain Refiners Investigation in order to find effective grain refiners for aluminium alloys backs to the early 1950s [10]. was introduced [10]. The morphology of TiAl3 particles strongly influences the grain refining behaviour of a master alloy.The nominal . 1. Arnberg et al.IMAM PRABOWO MECHANISM OF GRAIN REFINEMENT IN ALUMUNIUM ALLOY TiAl3 particles all have a strong bearing on the grain refining characteristics of a master alloy. while slow cooling from a high temperature would form plate-like crystals. providing benefits over the traditionally grain refiners. However. The plate-like particles are aggregates and form flake-like crystals. they have recently made attempts to make grain refiners especially for this sector.15C [10]. while larger plate-like particles are slow acting and early fading. Al-Ti-C. The foundry sector. In order to reduce or eliminate the number of borides defects in the surface critical products. such as TiBloy. The blocky aluminide particles are more efficient nucleating sites rather than flaky and petal-like crystals and with their (011) surfaces providing suitable substrates on which the (012) planes of aluminium can nucleate easily [6]. The Al-5Ti-1B is the most popular composition due to its high refining effectiveness [10]. traditionally applied the refiners developed in the wrought sector. including improved porosity distribution in wheel castings [10].2B.

Phase diagram/peritectic theory . Carbide/boride theory 2.4 [10]. the alloys cast and the processing conditions applied [12].IMAM PRABOWO MECHANISM OF GRAIN REFINEMENT IN ALUMUNIUM ALLOY chemistry and particle types of the main refiners used in the aluminium industry are summarized in Table 2. By addition of master alloys to the melt an abundance of potent heterogeneous nuclei. depending on the master alloys employed. Studies show that more than one mechanism is responsible for grain refinement of aluminium alloys. Classification of the theories on the mechanisms of grain refinement is as follows [2]. 1. the chemical and physical characteristics of the particles and their subsequent reaction with the melt [1].The nominal chemistry and particle type of the main grain refiners [3] 1. Figure 3. intermetallic particles. But. The terms of disagreement are the types of the particles that released in the melt. are spread in the melt and a plenty of these sites become active during solidification and nucleate the solid [11].3 Mechanisms of Grain Refinement The mechanism of grain refinement is principally quite straight forward [11]. the mechanism of grain refinement in aluminium after addition of Al-Ti-B master alloy is still a matter of debate and the results of work done over the years show that none of the mechanisms of grain refinement can provide a detailed explanation of all the experimental observation [1].

TiB2 and AlB have hexagonal structures and do not have a good match with any of the crystallographic planes of aluminium. Duplex nucleation theory 4. Maxwell and Hellawell [17] and Marcanito and Mondolfo [18] have shown that the nucleation of aluminium requires little or no under-cooling in the presence of Ti3Al as compared to TiC or TiB2. AlB2 and (Al. Cibula [16] suggested that TiB2 particles are dispersed in the molten metal and act as nucleating centres for aluminium. Mohanty and Gruzleski [20] proposed that Al3Ti is formed at 665oC and it would produce a good substrate for Al nucleation due to good wetting and a low contact angle (-Al which is . However. Peritectic hulk theory 1. Ti)B2 which are present in the Al-Ti-B master alloys. Good refinement has been observed at hyperperitectic concentrations and generally Al3Ti appears to be a better nucleant for aluminium than TiB 2 [19] . the grain refining effect of a binary Al-Ti master alloy is due to the presence of TiC or borides such as TiB2. The reactions are as follow: 3TiC+4Al ↔Al4C3+3Ti 9Ti+Al4C3 ↔3Ti3AlC+Al [14] Not only Al4C3 would render the carbide particles unsuitable for the nucleation of aluminium but also. It has been found. According to this theory. Al 4C3 is degraded to Ti3AlC. Much debate is still available as to the stability of TiC.4 Boride/Carbide theory This theory was proposed by Cibula [13] and was supported by Jones and Pearson [8]. that TiC would degrade to Al 4C3 possessing a hexagonal lattice and its lattice disregistry with aluminium is extremely large. Indeed the diresgistry between the AlB 2 and Al is more than that between Al3Ti and aluminium [21] . Also. Davis et al [19] showed the existence of multiple orientation relationships between aluminium and Al 3Ti while no orientation relationship was found between aluminium and TiB2. Concerning borides. Ti3AlC could precipitate which would not aid nucleation [15] . using electron diffraction.IMAM PRABOWO MECHANISM OF GRAIN REFINEMENT IN ALUMUNIUM ALLOY 3. Solute theory 5. Mohanty and Gruzleski [20] have confirmed that borides are pushed to grain boundaries. TiAl3 is known to be a potent nucleating site for aluminium.

14. 1996. 1999. Murty. J. [3] L. [6] B. . 5. Vol. lattice disregistry between borides and aluminium is large and borides could not be good nucleants [22]. .g.A. [5] B. J. Bhat and M. . 34(5). PP. Vol.2002. Kori.1979. 47(1). In general. 247-260 [2] B. Mater. Mater Metal Trans B. The phase diagram theory was developed to explain how Al 3Ti could be the active nucleant in a hypoperitectic composition.February 1989.223-234. Pearson. References [1] D. S. 3-29. S. B. .S. 47. . Chakraborty Grain Refinement of Aluminuim and its Alloys by Heterogeneous Nucleation and Alloying [Journal] // International Materials Reviews. Int. 1976. 3-29. Venkateshwralu. TiAl3 is not stable and TiB2 particles have been observed by secondary electron images and X-rays to be at the centre of grains [22]. Chakraborty.pp. 70. K. PP.1989. Metallkd. .Vol. For the hypoperitectic. S.IMAM PRABOWO MECHANISM OF GRAIN REFINEMENT IN ALUMUNIUM ALLOY formed at 660oC) for the process of nucleating Al on TiAl 3.7B. McCartney Grain Refining of Aluminuim and its Alloys Using Inoculants [Journal] // International Materials Review .Vol. Kori and M. Mater Process Technol. R. In fact.791-800 [8] G. PP.A. Also. this theory suggests Ti is a powerful segregant and restricts growth of grains allowing therefore further nucleation events. borides are known to need some undercooling in order to nucleate aluminium [17] while aluminides need negligible undercooling. Murty.pp. .152-158 [7] A.R.Vol.P. F. Van Den Broeder On the Interfacial Energy in Solid-Solid and Solid-Liquid Metal Compositions [Journal] // International Journal of Materials Research (Z. A.S. Arjuna. . Kori.). Vol. .2002. Rev.refining behaviour of aluminium” Metal Mater Trans A. S.. G.89-90. . F. Jones and J.p. R. Chakraborty. Murthy and M. Also the stability of carbides (e. Miedema. Murty. Mondolfo Effect of Interfacial Energies on Heterogeneous Nucleation [Journal] // Materials Science and Technology. M. 118-122. A.S. TiC) is a matter of debate as discussed above. . “Influence of chromium and impurities on the grain. Chakraborty.27A. .Vol. .pp. [4] A.

Johnsson.and B-Contaning Master Alloys [Journal] // Metallurgical Transactions A. TMS.43.IMAM PRABOWO MECHANISM OF GRAIN REFINEMENT IN ALUMUNIUM ALLOY [9].F. 1972.29.S. Mohanty J. 1970.1995. Hellawell. PP. 1995.3. Cibula. 1970. E. PP. L. L. PP. PP. G. Cibula.23-27 [19] I.1.98. Warrendale.751-753 [17] I. 1994.3. Gruzleski Mechanism of Grain Refinement in Aluminuim [Journal] // Acta metall. 1951-1952. J. Mater Sci Technol. . PA. 1983.). . Metall Trans. S.Inst Metal. Vol.M. Backerud and H. . Flower and D. Vol. Vol. . W. Easton and D. Riaz. 2000. PP. Inst Metals.February 1993. Backerud. PP. mater. 1972. PP. 1487-1493 [18] J.1613-1622 [23] .984-992 [16] A. Mondolfo. Hellawell. Vol. [11].3-50 [22] M. Reif. Banerji. J.pp. . J Mater Sci.275-280 [20] P. [13]. L. Vol. 1983. Vol. [12] M. 1-16 [14] A. Metall Trans. Gruzleski. West. [10] Dr Paul Cooper Allan Barber Review of the Latest Development and Best Use of Grain Refiners [Article]. H. Proceedings of grain refinement in castings and welds. Feng. Q.2003. PP. Vol. A. Maxwell and A.G. PP. Metall Trans. 24A. 2001-2012. Mohanty and J.2001-2012 [21] L. Arnberg.80. Conference on Solidification Technology in Foundary and Casthouse. StJohn.30A. London. PP.1958-1965 [15] S. Vol.16. J.pp. Metall Mater Trans A. The Metal Society. .Vol. . Davis. PP. Dennis and A.Vol. In Proc. Vol. G. Acta Metall.M. Sigworth Study of the Mechanism of Grain Refinement of Aluminuim after Addition of Ti. P. K.74-78.A. Abbaschian (Ed. 1999. 481-491.R.F. Klang. Marcantino and L.F. Mondolfo.E. 43(5).J.