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A study of solid-state amorphization in Zr30 at. % Al by mechanical attrition

A. Biswas, G. K. Dey, A. J. Haq, D. K. Bose, and S. Banerjee
Metallurgy Division, Bhabha Atomic Research Centre, Bombay 400085, India (Received 25 January 1995; accepted 6 November 1995)

Elemental powders of zirconium and aluminum in the atomic ratio of 70 : 30 were mechanically alloyed in an attritor under argon atmosphere using zirconia balls as milling media. Samples have been taken out for characterization after different durations of milling. The process of alloying and resultant amorphization had been studied using x-ray diffraction (XRD) and transmission electron microscopy (TEM). Scanning electron microscopy (SEM) was carried out to study the morphological changes occurring during repeated cold welding and breaking of the particles. Samples for TEM study were prepared by dispersing the mechanically attrited particles in the nickel foil by electrochemical codeposition. TEM study of the initial stages of milling revealed that localized structural changes precede the bulk amorphization process during mechanical alloying (MA). The sequence of phase evolution has been identied as (i) the formation of nanocrystalline supersaturated solid solution of aluminum in a -zirconium, (ii) amorphization of localized regions at powder interfaces, (iii) ordering of aluminum-rich regions in the metastable Zr3 Al (DO19 ) phase, and, nally, (iv) bulk amorphization of the powders.


Mechanical alloying (MA) was rst reported in 1966 as a technique for the preparation of the oxide dispersion-strengthened nickel alloys suitable for high temperature applications. Solid-state amorphization by this technique of high energy milling2,3 revived the interest in this topic. Now, MA has become a versatile processing method which is capable of preparing a truly wide range of materials with unique properties, namely intermetallics,4,5 alloys of immiscible metals,6 nanocrystalline phases,7 quasicrystals,8 amorphous,918 and other metastable phases19,20 in bulk quantities. It has been shown that solid-state amorphization can be achieved both from intermetallic powders and mixtures of elemental powders. Usually, the amorphization from intermetallic powders is termed as mechanical milling (MM),21 unlike mechanical alloying. The mechanisms of the solid-state amorphization and associated transformations in different systems are not yet well understood. A number of probable theories have been proposed so far. Yermakov et al.2 explained the process in terms of local melting and subsequent rapid solidication. However, evidence of melting could not be seen in any of the amorphization experiments. Others hypothesized solid-state processes to be instrumental for this transformation. In early papers9,22 it has
J. Mater. Res., Vol. 11, No. 3, Mar 1996

been proposed that negative enthalpy of mixing and widely differing diffusivities are two necessary conditions for amorphization. However, many exceptions have been reported later.23,24 Composition-induced destabilization of the crystal lattice and resultant amorphization has been shown recently25 in the Zr Al binary alloy system, where a supersaturated a Zr solid solution forms up to an aluminum concentration of 15 at. % and amorphization takes place in Zr1002x Alx when 15 , x , 40. At x 50, a metastable nanocrystalline fcc phase (ZrAl) evolves. Ma and Atzmon have studied this system

FIG. 1. Particle size distributions of initial and mechanically attrited powders.

1996 Materials Research Society 599

A. Biswas et al.: Study of solid-state amorphization in Zr 30 at. % Al

TABLE I. Median diameters of initial and mechanically attrited powders. Sample description Initial Al Initial Zr 15 h 30 h 45 h 60 h Median diameter (mm) 27.0 11.8 9.3 5.4 4.7 5.7

found that the intermetallics, namely Zr3 Al, Zr2 Al, and Zr3 Al2 , do not form due to kinetic constraints associated with long-range ordering. In the current investigation, MA of elemental powders of zirconium and aluminum in the atomic ratio of 70 : 30 was taken up for studying the structural evolution, as revealed by TEM which has not been reported earlier. We made an attempt to look into the possibility of the formation of any equilibrium or metastable ordered intermetallic phase in the evolutionary path of mechanical alloying.

further and given calorimetric evidence for chemically induced polymorphic transformation by determination of enthalpies of both the supersaturated solid solutions and the amorphous alloys of varying aluminum concentrations. They have shown that the critical concentration of aluminum required for amorphization is 17.5 at. %. However, in both of these investigations it has been

Elemental powders of zirconium and aluminum of the purity of 99.5% were alloyed in an attritor under argon atmosphere. Five mm diameter zirconia balls were used as milling media, and the ball-to-powder weight ratio was kept at 10 : 1. The milling had been done in

FIG. 2. Change in particle morphology during milling. (a) Initial Zr, (b) initial Al, (c) 10 h milled powder, and (d ) 15 h milled powder.
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A. Biswas et al.: Study of solid-state amorphization in Zr 30 at. % Al

a water-cooled vessel to keep the milling environment close to the ambient temperature. Milling was carried out for up to 60 h at a constant milling speed of 550 rpm. Samples were taken out of the milling vessel for characterization after different degrees of milling. Particle size distributions and corresponding median particle sizes of the samples after different durations of milling were determined in a Sedigraph. Changes in the morphology of the attrited powders were studied by SEM. Phases forming during alloying were characterized by XRD analysis using Cu Ka radiation. TEM investigations of selected samples were performed. Samples for TEM were prepared by dispersing mechanically alloyed particles in a nickel foil by electrochemical codeposition from a nickel solution containing the attrited particles in suspension.27 Subsequently, samples were thinned initially by ion milling followed by electropolishing using either the jet or the window technique. This technique ensured the absence of an ion-damaged area in the electron transparent region.

In the course of milling, the particles rst became shiny and nally lost their luster and ended up as dark ne powders with no visible heterogeneity. During this process, the zirconia balls became coated, as was evident from visual examination. Particle size distributions of the initial unmixed powders and that of the powders attrited for different durations are given in Fig. 1. Median particle sizes of the starting powders of zirconium and aluminum were found to be 11.8 mm and 27 mm, respectively. The median size of the mixed powder decreased to 9.3 mm after 15 h milling and to 4.7 mm after 45 h (Table I). Still further milling did not cause any rening; instead, a coarsening effect was observed. Figures 2(a) and 2(b) show the initial morphologies of aluminum and zirconium powders, while Fig. 2(c) depicts the cold-worked morphology after sufcient time of milling, which is a typical feature of this process. Figure 2(d ) clearly shows the broken pieces of mechanically attrited powder particles. X-ray diffraction of samples taken from different stages of milling provides information of the changes that took place during the milling process. The (111) and (200) peaks of fcc aluminum gradually diminished and hcp a -zirconium peaks broadened and shifted toward high-angle values, as shown in Figs. 3(a) and 3(b). These are in agreement with observations made earlier.25,26,28 After 15 h of milling, XRD results showed the presence of a solid solution of aluminum in a -zirconium. Powders obtained after the 20 h milling sample did not exhibit any sharp Bragg peak, except one broad peak corresponding closely to (1010) of a -zirconium. Powders milled

FIG. 3. XRD patterns after different periods of milling. (a) Formation of solid solution. ( b) Ordering and bulk amorphization.

for 25 h sample showed some extra reections that disappeared during further milling. These were found to

J. Mater. Res., Vol. 11, No. 3, Mar 1996

A. Biswas et al.: Study of solid-state amorphization in Zr 30 at. % Al

FIG. 4. TEM of 3 h milled sample. (a) Microstructure of powders embedded in nickel matrix ( b) SAD pattern of Zr Al solid solution, (c) unalloyed Al, and (d ) microdiffraction from local amorphous region.

correspond to a lattice spacing of 5.4 nm, which matches closely to the superlattice reections of the metastable DO19 (Zr3 Al) structure. On further milling, the powders transformed into amorphous phase. This bulk amorphous phase remained unchanged up to 60 h of milling. The width of the broad peak corresponding to the rst nearneighbor distance in the amorphous phase gradually increased. Another interesting observation was that after 10 h of milling the (1010) peak of a -zirconium became the most intense, and remained so up to the time of bulk amorphization.

TEM studies were carried out with powder particles embedded in a nickel matrix. The sequence of the gradual transformation, as observed through XRD analysis, was investigated by TEM. Additional local features could be observed that XRD was unable to reveal. The micrograph and corresponding electron diffraction patterns shown in Fig. 4 are for a sample milled for 3 h. They show the presence of unalloyed aluminum, partially alloyed a -zirconium conforming to XRD results, and, interestingly, some local amorphous regions that were not observed in the XRD pattern. Figure 5

J. Mater. Res., Vol. 11, No. 3, Mar 1996

A. Biswas et al.: Study of solid-state amorphization in Zr 30 at. % Al

FIG. 5. TEM of 15 h milled sample. (a) Nanocrystalline structure containing both ( b) Zr Al solid solution and (c) amorphous phase.

shows the nanocrystalline structure of the 15 h milled sample whose corresponding electron diffraction showed the presence of both the amorphous phase and the solid solution of aluminum in a -zirconium. The 20 h milled sample showed a still ner structure of predominantly a -zirconium-aluminum solid solution, as shown in Fig. 6. Ordering was noticed in the 25 h milled sample by the appearance of the weak innermost ring (superlattice reection-1010) of the diffraction pattern, as

shown in Fig. 7. This sample was found to be composed of three phases, namely, DO19 (Zr3 Al), a ZrAl solid solution, and amorphous. The micrograph and diffraction pattern in Fig. 8 corresponds to the 60 h milled sample, demonstrating the presence of the bulk amorphous phase.

The new ndings of the present study are (i) local amorphization at the interface of the particle in the early

J. Mater. Res., Vol. 11, No. 3, Mar 1996

A. Biswas et al.: Study of solid-state amorphization in Zr 30 at. % Al

FIG. 6. Microstructure of 20 h milled sample. (a) Bright eld. ( b) Dark eld.

stage of milling, and (ii) formation of the metastable DO19 structures. Local amorphization results due to the compositional heterogeneity at the interface, which is quite likely at the initial stages of milling when a sharp composition gradient is present from the core to the periphery of each powder particle. Similar compositional gradients at the particle interface have also been reported earlier for the Ni Zr system, where the concentration depth prole was measured by Auger Electron Spectroscopy.29 The appearance of the DO19 ordered phase was observed after 25 h of milling. This was detected in the selected area diffraction pattern (Fig. 7), where the weak innermost diffraction ring corresponds to the 1010 d-spacing of the metastable Zr3 Al phase of the DO19 structure. The sequence of structural evolution can be described in the following scheme: a Zr 1 Al ! a Zr Al solid solution 1 Al ! nanocrystalline

solid solution 1 amorphous ! Zr3 AlDO19 1 solid solution 1 amorphous ! bulk amorphization. Free energy-composition (G-X) plots have been used earlier by previous workers25,26,28 for explaining the transformation that occurred during mechanical alloying in the ZrAl system. In these investigations the free energy values were either theoretically calculated or the measured enthalpy values of the samples (having different aluminum concentrations) were used as an approximation of the free energy. Prior to enthalpy measurements in the aforementioned studies, samples at different mixture compositions were milled for sufciently long times until they attained the steady state. The observed amorphization was explained in terms of a concentration invariant polymorphic process (depicted in G-X plot as vertical lines). Aluminum enrichment of a ZrAl solid solution to a level of approximately 15 at. % Al made the polymorphic amorphization thermodynamically possible. It was envisaged25 that in the rst phase of milling, the aluminum concentration continues to build up in the a -zirconium lattice to a level of 15 at. % when the a -lattice becomes unstable with respect to the polymorphic amorphization process. This conclusion was reached as there was no evidence of a two-phase structure (a ZrAl solid solution and amorphous) in XRD results. The present work demonstrates that even after 3 h milling amorphization can take place locally at the particle interface and metastable ordering takes place intermediately before bulk amorphization. Similar intermediate ordering was also reported in the Ti Al30 system. Although the solute concentration progressively changes during the course of milling, as alloying is a gradual process, the G-X plot does not reect the transformations that occurred during the milling. Moreover, as pointed out by Yavari et al.,31 it does not differentiate between the amorphization from pure components and that from any intermediate intermetallic products. In order to explain the observed course of transformation and phase evolution, we have considered partitioning of solute element between the competing phases. A schematic G-X plot shown in Fig. 9 was used, and the possibility of establishing local chemical equilibrium was considered. With an increasing degree of aluminum enrichment, the free energy at the interface region gradually moves along the path 12. Once the composition crosses point 2, it becomes thermodynamically possible to nucleate the Zr3 Al phase. Though the equilibrium structure of Zr3 Al is L12 , there exists a competing metastable DO19 structure, the latter being a superlattice of the hcp a phase. As reported earlier,32 DO19 nucleation is kinetically favored when precipitation occurs from the supersaturated a phase, presumably because of a one-to-one lattice correspondence with a Zr and nearly equal spacings in the corresponding di-

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A. Biswas et al.: Study of solid-state amorphization in Zr 30 at. % Al

FIG. 7. TEM of 25 h milled sample. (a) Fine microstructure, ( b) SAD pattern showing DO19 ordering, (c) SAD pattern of solid solution, and (d ) microdiffraction from amorphous phase.

rections that ensures very good registry between the two phases. With further aluminum enrichment, the composition crosses point 3 when nucleation of the amorphous phase becomes possible. It is to be emphasized that the compositional change occurs gradually from the interface and, therefore, the core of a particle remains crystalline even when the amorphous phase starts appearing at the interface. The present work points out that nucleation of the DO19 phase and of the amorphous phase occurs through alloy partitioning. As the composition of powder particles crosses point 4, each particle as a whole can transform into an amorphous phase by a polymorphic process.

The competition between the disordering process by mechanical alloying and the reordering process due to the thermodynamic tendency for the formation of the more stable structure determines the steadystate structure in a given system. The evolution of the steady-state structure in a driven system has been studied theoretically by Haider et al.33 Experimental observations reported here clearly point out that the crystalline order is not sustainable in Zr30 at. % Al alloy in steady state under the milling condition employed. It is also possible that the DO19 phase formed locally had also undergone amorphization due to the damage introduced by mechanical working.

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A. Biswas et al.: Study of solid-state amorphization in Zr 30 at. % Al

FIG. 9. Schematic free energy versus composition diagram of Zr Al alloy system.

Compositional inhomogeneity resulting from concentration gradients present at the initial stages of milling is responsible for the formation of localized amorphous regions.

The authors wish to thank Mr. A. R. Biswas, Dr. D. D. Upadhaya, Dr. N. C. Soni, and Mr. S. N. Athavale for their useful services. We gratefully acknowledge the valuable suggestions of Dr. S. K. Roy and Dr. P. Mukhopadyay. The authors are indebted to Dr. C. K. Gupta, Director, Materials Group, B.A.R.C. for his support and encouragement during the course of this work.
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FIG. 8. TEM of 60 h milled sample. (a) Microstructure of amorphous phase (dark region) in nickel matrix and ( b) SAD pattern showing bulk amorphization.


The sequence of phase evolution in mechanical alloying of the ZrAl binary system is (i) the formation of hcp zirconium-aluminum solid solution, (ii) intermediate formation of metastable intermetallic Zr3 Al and an amorphous phase in localized regions at the interfaces of the particles, and (iii) bulk amorphization. This has been rationalized by a schematic free energy-composition plot.

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