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Materials Science and Engineering, A 134 ( 1991 ) 1350-1353

Universal high performance ball-milling device and its application for mechanical alloying
A. Calka and A. P. Radlinski
Department of Electronic Materials Engineering, The Australian National University, GPO Box 4, Canberra, A CT 2601 (Australia)

Abstract
We describe the design and modes of operation of a novel ball mill device in which the ball movement pattern is controlled by an external magnetic field. Examples of applications of this ball mill to the synthesis of Ni-Zr alloys, high melting point intermetallics, Mg-Zn alloys and aluminium-based alloys are given. In particular, various modes of operation may result in a different path for the solid state reaction occurring during milling.

1. Introduction The mechanical alloying (MA) process was first developed over 20 years ago for production of composite metallic powders [1]. Over the years it has been successfully used to synthesize a number of commercially important alloys and composites. Renewed interest in mechanical alloying was sparked in the mid-1980s by the discovery that M A may be used for the formation of the amorphous phase [2]. As a result of recent vigorous research, it has been demonstrated that MA may be used for the preparation of numerous equilibrium and non-equilibrium crystalline, quasicrystalline, nanocrystalline and amorphous materials. At this stage, however, the fundamentals of mechanical alloying remain largely unexplored. Three types of milling devices are generally used for mechanical alloying: attritors, vibrating mills and rotating mills. However, none of the commercially available devices was designed with the specific needs of the M A process in mind. This factor became particularly obvious in recent years, when the dependence of final product on the type of milling device and energy regime used have been repeatedly reported. Ni-Zr alloy may be considered a benchmark system in this respect; the kinetics of amorphous phase formation as well as the extent of the glass-forming region were shown to be crucially dependent on the type of milling device, ball movement pattern and the milling energy [3-7].
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In this paper we describe a ball mill in which the pattern of ball movement can be externally controlled. We have previously used this device to produce A1-Pd alloys [8], high melting point Ti-B alloys [9] and to amorphize M g - Z n [10] and Fe-B alloys [11]. In all these cases we employed the ball movement control to induce or enhance the solid state reaction leading to a desired product. Since at the present stage of research very little is known about what milling conditions are to be selected to produce an alloy with an a priori chosen structure, there is a need to develop a simple and versatile device which could be used for studies on mechanical alloying. Ideally, such a mill should offer (1) a wide range of milling conditions (including those encountered in commercial devices) and (2) control of milling parameters. The ball mill described in this paper comes close to those requirements.

2. Description of the ball mill

Figure 1 illustrates the concept of our milling device. This is a planar-type ball mill that consists of a few hardened steel balls confined to a stainless-steel, horizontal type cell. The ball movement during the milling process is confined to the vertical plane by the cell walls and it is controlled by an external magnetic field. The intensity and direction of the field can be externally adjusted. In a simple version of the mill permanent magnets are used. However, to achieve better control of
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Fig. 1. Schematic diagram of the ball-milling device with controlled ball movement. I: rotating cell; 2: balls; 3: magnets. (a) (b) (c) x~

e)

balls both rotate and oscillate around the equilibrium position at the bottom and the powder is worked mostly by shearing. In the third case, illustrated in Fig. 2(e), the ball movement caused by the centrifugal force can be halted in two opposite positions; at the lowest and highest point inside the cell. The ball trapped by the magnetic attraction in the upper position rotates with the frequency ~ob and can be released to fall vertically on top of one of the bottom balls. The two colliding balls rotate in the opposite directions, which results in a combination of shearing and uniaxial pressure at the surface of contact. Two useful variations of mode (a) are shown in Figs. 2(c) and 2(d). By slowing down the cell rotation frequency ~Oc, a situation may be achieved when the ball released from the bottom is not fully pinned to the wall by the centrifugal force and can either hit one of the bottom balls (Fig. 2(c)) or the opposite cell wall (Fig. 2(d)). Milling conditions in situations (a), (d) and (c), (e) are similar, respectively.

Fig. 2. Modes of operation of the ball mill. (a) High energy mode, high rotation frequency; (b) low energy mode, low rotation frequency; (c) high energy mode, two points of equilibrium; (d, e) high energy mode, intermediate rotation frequency; this is a variation of mode (a).

3. Comparison with other milling devices

Mechanical alloying is a complex process of deformation, fragmentation, cold welding and micro-diffusion, occurring within a thin layer of powder trapped between the two colliding surfaces during impact. In commercial ball mills typical impact times are of the order of 10-5 s and the peak stress can reach 50 kbar. Depending on the collision parameters, the orientation of the impact strain may be quite complex and the temperature rise in the collision region may vary from a few degrees to a few hundred degrees [12, 13]. The mechanical energy is utilized most efficiently if the balls collide head-on with maximum possible velocities. Davice et al. [13] reported eight head-on collisions out of the total of 2132 collisions per second in a vibrating mill agitated at 1200 rev. min- ~. There are only one to two collisions per second in our device, but they are strictly head-on because of the guiding of the ball movement by the magnetic field. The free-fall ball velocity during impact is 1.5 m s I (it is increased in the presence of the magnetic field). For comparison, the average relative ball velocity in a vibrating mill varies from 3.9 m s-1 [12] to 6 m s-~ [13];in the planetary ball mill used by Eckert et al. it remains in the range 2.5-4.7 m s J [6], and it is about 0.5 m s 1 in attritors !i12]. Using

the ball movement electromagnets should be employed. By adjusting the spatial and/or temporal profiles of the magnetic field, the ball trajectories, impact energy and the shearing energy can be varied. In Fig. 2 the three general patterns of ball movement that can be achieved using this device are shown. In the case illustrated in Fig. 2(a), the magnetic field holds the balls in the bottom part of the cell rotating with the frequency ~c. Friction causes the balls to rotate in the same direction with the frequency ~Ob=OgcR/r , where R is the radius of the cell and r is the radius of the ball. Periodically, the outer ball on the right-hand side gets released, completes most of the circle being pushed against the cell wall by the centrifugal force, and hits the left-most ball at the bottom. In this mode of operation the powder is worked both by impact and by shearing. The balls may be confined to the bottom part of the cell for all time either by increasing the intensity of the magnetic field or by decreasing the frequency Wo This is illustrated in Fig. 2(b). In this mode, the

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the Hertz theory of collisions as formulated by Maurice and Courtney [12] one can calculate other characteristics of the ball-on-ball collisions in our device: collision time 6.5 10 -5 s, Hertz radius 4.6 10 4 m, and maximum impact stress 37 kbar. All these values are close to the corresponding values quoted for commercial vibrating mills. Thus, the energy released per impact in our mill is not much different from that characteristic of other devices. A feature that is unique to our design, however, is the specific ball movement pattern. In every mode of operation this pattern is well defined and highly reproducible. This contrasts with the chaotic and unpredicted ball movement characteristic of the other ball-milling devices.

(a)

A
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(b)

,;\

10

30

50

70

90

110

Degrees 20

Fig. 3. X-ray patterns taken from mixtures of 62 at.% Ni and 38 at.% Zr after (a) 60 h of milling using mode (c) and (b) 180 h of milling using mode (b) of Fig. 2.

4. Applications
4.1. Results of ball milling of the Ni62Zr38test alloy
The amorphous phase formation in Ni-Zr mixtures by ball milling was studied in detail by other workers [3-7]. It was found that amorphization of these mixtures using various milling equipment occurs via two different paths. The amorphous phase is formed directly when either the vibrating frame [5] or a Fritsch "Pulverisette 5" planetary mill [6] are used, but a crystalline intermetallic phase forms initially when a different type of planetary mill is employed [5]. Furthermore, it has been demonstrated that various milling intensities [6] and different combinations of the planetary mill rotation patterns [7] may influence the outcome of the reaction. We have reproduced both of the amorphization paths for 62 at.% Ni and 38 at.% Zr mixture using two different modes of operation of our device. When the high-energy mode of Fig. 2(c) is used, the amorphous phase is formed directly from the mixture. X-ray diffractometry reveals that upon milling the intensity of diffraction peaks due to elemental zirconium and nickel decreases and simultaneously a washed-out amorphous peak emerges. The diffraction pattern taken after 60 h of milling is shown in Fig. 3(a). In contrast to this, when the low-energy milling mode (b) is used, the intermetallic phases form first and then slowly transform into the amorphous phase. A diffraction pattern taken over 180 h of milling is shown in Fig. 3(b). Even after very long milling (240 h) some traces of the crystalline phase remain visible on top of the amorphous peak.

4.2. High melting point materials

It is well documented that metal-metal type intermetallics can be produced by MA using commercial ball mills. However, very little work has been reported on the synthesis of metal-metalloid systems. It is believed that very high milling energies are necessary to produce these intermetallics. Using our ball mill we have synthesized a large number (more than 50) of metal-metalloid high melting point intermetallics by mechanical alloying. This work is described in detail elsewhere [14]. It is important to note that the high melting point materials produced with our equipment are contaminated with iron (coming from the balls and cell material) at a level generally below 1 at.%. The diffraction peaks due to iron were never identified on the X-ray patterns and other methods (electron microprobe and Rutherford backscattering) were used to detect the iron impurities. Similar to the case of Ni-Zr alloys, the solid state reaction path for the high melting point materials can be dramatically affected by the milling conditions. As an illustration we present in Fig. 4 two X-ray diffractograms obtained from two ball-milled mixtures of the nominal composition 33 at.% Ti and 67 at.% B [9]. The upper trace, obtained from a sample milled for 80 h using the mode (c) of Fig. 2, corresponds to the pure TiB 2 phase. The lower trace was obtained from a sample milled using the same time and rotating speed but without the magnetic field. The

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(a)

TiB 2

II
I

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(b)
.

' "
i TiB 2

.Ti

mode favours the cold welding process and leads to the formation of large lumps of the milled mixtures. The appropriate milling procedure is to use the low energy mode (b) until the mean grain size decreases to about 0.1 /~m and then to switch to the intermediate energy mode (e). Such a procedure enables one to successfully ball-mill the aluminium-based alloys without using surfactants to control the balance between fracturing and cold welding [15]. 5. Summary

: i"

il
I

B(amorphous)

i~ ~i

I!

30

50

70 Degrees 20

g0

110

Fig. 4. X-ray patterns taken from mixtures of 33 at.% Ti and 67 at.% B after (a) 80 h of milling using mode (c) and (b) 80 h of milling using conditions as in (a), but without the magnetic field.

We have described the design and modes of operation of a ball mill with a controlled ball movement pattern. The performance of this device is compared with that of other ball mills and examples of applications to M A of various alloys are discussed. References

latter diffractogram corresponds to a mixture of crystalline titanium and a small amount of TiB 2. Using these conditions we were unable to obtain pure Y i B 2 e v e n after 400 h of milling.
4.3. Low crystallization temperature: M g - Z n amorphous alloys To produce fully amorphous Mgv0Zn30 alloys from the crystalline master alloy a two-step ballmilling procedure has to be used [10]. Initially, the milling is performed using the high-energy mode (d)(Fig. 2), which results in a mixture of the amorphous phase and the metastable crystalline phase Mgs~Zn20. Under the high-energy milling conditions this mixture corresponds to a steadystate dynamical equilibrium between amorphization and crystallization (the crystallization temperature of amorphous Mgv0Zn30 is about 95 C). Full amorphization can be achieved by switching to the low energy mode (b) (Fig. 2). Details of the experimental results are presented in ref. 10. 4.4. Ah~minium-based alloys The high energy milling mode (d) (Fig. 2) is not suitable for MA of AI-V, A1-Ti, and other aluminium-based and magnesium-based alloys. This

1 Y.S. Benjamin, Sci. Am., 234(1976) 40. 2 A. Y. Yermakov, Y. Y. Yurchikov and V. A. Barinov, Phys. Met. Mettaloved., 52 ( 1981 ) (English translation); also C. C. Koch, O. B. Cavin, C. G. McKamey and J. O. Scarborough, Appl. Phys. Lett., 43 (1983) 1017. 3 E. Hellstern and L. Schultz, Appl. Phys. Lett., 48 (19861 124. 4 A.W. Weeber, K. Van der Meer, H. Bakker, F. R. de Boer, B. J. Thitsse and J. F. Jangste, J. Phys. F: Metals" Phys., 16 (1986) 1897. 5 A. W. Weeber, A. J. H. Wester, W. Y. Haag and H. Bakker, Physica, 145B (1987) 349. 6 J. Eckert, L. Schultz and E. Heustern, J. Appl. Phys., 64 (1988) 3224. 7 G. Martin and E. Gaffet, Proc. Conj. on Amorphization by Solid State Reaction, Grenoble, France, Les Editions de Physique, 1990. 8 A. Calka and A. E Radlinski, Scr. Metall., 23 (1989) 1497. 9 A. Calka and A. P. Radlinski, J. Less-Common Metals, 161 (1990)123. 10 A. Calka and A. E Radlinski, Mater. Sci. Eng., A l l 8 (1989) 131. 11 A. Calka and A. P. Radlinski, Submitted to Appl. Phys. Lett. 12 D. R. Maurice and T. H. Courtney, Metall. Trans., 21A (1990) 289. 13 R. M. Davice, B. McDermott and C. C. Koch, Metall. Trans., 19,,4 (1988) 2867. 14 A. P. Radlinski and A. Calka, Mater. Sci. Eng., A134 (1991) 1376. 15 A. P. Radlinski, A. Calka, B. W. Ninham and W. A. Kaczmarek, Mater. Sci. Eng., A 134 ( 1991 ) 1346.