Progress in Materials Science 49 (2004) 537560

www.elsevier.com/locate/pmatsci

Processing of advanced materials using

high-energy mechanical milling
D.L. Zhang*
Waikato Centre for Advanced Materials, Department of Materials and Process Engineering,
University of Waikato, Private Bag 3105, Hamilton, New Zealand

Abstract
This paper provides an overview of the research on the use of high-energy mechanical mil-
ling in processing advanced materials. The focus is on the major understanding achieved on
each of the major topics in this area. This overview demonstrates that high-energy mechanical
milling can be used to produce several dierent types of materials, including amorphous alloy
powders, nanocrystalline powders, intermetallic powders, composite and nanocomposite
powders, and nanopowders. Good understanding of the mechanisms related to the process for
each of these purposes has been achieved at the phenomenological level. However, accurate
quantication and modelling of high-energy mechanical milling is still not available, even
though several research groups have investigated these topics. The whole area of mathemati-
cally describing and modelling the high energy milling process deserves the close attention of
all materials scientists and engineers working in the area of processing powder materials using
high-energy mechanical milling. Without mastering the art of optimising, controlling and
predicting the process, there is no hope of developing this powerful process into a main-
stream industrial scale materials processing process as has happened for metallurgical pro-
cesses, such as melting, casting, or heat treatment. Issues related to the consolidation of the
mechanically milled powders and future development in this area of high-energy mechanical
milling have also been commented on.
# 2003 Elsevier Ltd. All rights reserved.

* Corresponding author. Tel.: +64-7-838-4783; fax: +64-7-838-4835.

E-mail address: d.zhong@waikato.ac.nz (D.L. Zhang).

0079-6425/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0079-6425(03)00034-3
538 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

Contents

1. Introduction ....................................................................................................................538

2. Outline of the overview ...................................................................................................539

3. Synthesis of amorphous alloy powders ........................................................................... 540

4. Synthesis of alloy powders with other metastable phases ...............................................547

5. Synthesis of intermetallic and other compound powders................................................548

6. Synthesis of nanocrystalline powders .............................................................................. 549

7. Synthesis of metalceramic composites and nanocomposite powders ............................550

8. Synthesis of nanopowders ............................................................................................... 551

9. Quantication and modelling of the high-energy mechanical milling process ................552

10. Consolidation of the powders into bulk materials ..........................................................555

11. The future........................................................................................................................558

12. Summary .........................................................................................................................559

Acknowledgements...............................................................................................................559

References ............................................................................................................................559

1. Introduction

Mechanical milling is a process which is routinely used in powder metallurgy and

mineral processing industries. It is traditionally used for blending powders or
crushing rocks. When mechanical milling is used for these purposes, the powder
particles either remain unchanged or are fractured into smaller particles in the pro-
cess of milling. Excessive plastic deformation of the powder particles and cold
welding between particles are absent in the process. Due to the lack of dramatic and
interesting microstructural changes during milling, the purposes of the process used
to be rather simple. From the early 1970s, Benjamin and co-workers [1,2] found that
by milling a nickel or aluminium alloy powder in an oxidising atmosphere, new
powder with each of the powder particles containing a dispersion of oxide particles
was produced. This means that during milling the oxide layers formed on the surface
of powder particles are fractured and further incorporated into the solid powder
particles through cold welding. The cold welding is so perfect that the interfaces
formed through cold welding become an integral part of the particle. In the mean-
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 539

time, they also found that excessive plastic deformation occurs during milling. Once
excessive plastic deformation and cold welding occur during milling, the nature of
the milling process is revolutionised, since the milling process virtually results in a
new powder material which is totally dierent from the starting powders. When
mechanical milling is used in the traditional sense, the process does not generate a
new material, since the microstructure of the powder does not change. Benjamin
called the milling process mechanical alloying. However, it was not widely
accepted at that time that this milling process was a true alloying process since, other
than the familiar surface oxidation of the particles, no true alloying between
elements occurs during milling.
In early 1980s, Koch et al. [3] published a landmark paper which, for the rst time,
demonstrated that mechanical milling can facilitate true alloying, and the outcome
of the alloying can be a metastable material such as an amorphous alloy. In the
study, they milled a mixture of Ni and Nb powders, and found that over time the
powder became an amorphous NiNb alloy powder. This means that true alloying
does occur during milling. This discovery raised the understanding of mechanical
milling as a materials processing to a new level. Since the publishing of Koch et al.s
work, the term mechanical alloying has been widely accepted and used. Stimu-
lated by this new understanding, many researchers have been attracted into the eld
of mechanical alloying, and an increasingly large number of publications have
appeared in the literature reporting the work undertaken in the area of mechanical
alloying.
In late 1980s, McCormick and Schaer published another important paper [4]. In
this rather short paper, they reported that chemical reactions between Ca and CuO
can be induced by high-energy mechanical milling. This work stimulated a diver-
gence of interest in mechanical milling into another exciting area: mechanochemical
processing, which is a combination of mechanical milling and chemical reactions.
The author of this paper was introduced to this exciting eld by Professor Ted B.
Massalski when the former went to work at Carnegie Mellon University as a young
post-doctoral research fellow in early 1992. Inuenced by Professor Massalski, who
is an internationally well known metal physicist, metallurgist and materials scientist,
the author often thought about how to increase the understanding of this interesting
process. This paper, which provides an overview of the understanding achieved in
the area of high-energy mechanical milling, is dedicated to Professor Massalski to
show the authors appreciation of the enjoyable and life-long benecial experience of
working with Professor Massalski at Carnegie Mellon University and to con-
gratulate Professor Massalski on his many great contributions made to materials
science and engineering in the last 50 years.

2. Outline of the overview

Ever since the publishing of Professor Carl Kock and co-workers work showing
that solid state reactions can be induced during high-energy mechanical milling,
there have been a large number of researchers working in the area of processing
540 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

materials utilising high-energy mechanical milling. An interesting observation made

by the author about 9 years ago was that many published papers were rather repe-
titive in the sense of scientic research. For example, X paper (or papers) showed
that mechanical alloying (MA) can be used to synthesize alloy C from elemental
powders A and B, while Y paper (or papers) showed that MA can be used to pro-
duce alloy G from elemental powders D and E. Because of this repetition, although
a large number of papers have been published (in the order of 10002000 in journals
or conference proceedings in the English language in the last 20 years), the number
of papers which have made major contributions to the development of the eld is
much smaller.
This paper has no intention of providing a comprehensive review of the area, as
several very good review articles and books have already been published [e.g. 511].
This paper touches on important topics and highlights the understanding achieved
on each of the topics. It is hoped that through this overview, this paper will stimu-
late a deeper thinking in this eld. The following topics are covered:

Synthesis of amorphous alloy powders

Synthesis of alloy powders with other metastable phases

Synthesis of intermetallic and other compound powders

Synthesis of nanocrystalline powders

Synthesis of metalceramic composites and nanocomposite powders

Synthesis of nanopowders

Quantication and modelling of the high-energy mechanical milling process

Consolidation of the powders into bulk materials

The future.

3. Synthesis of amorphous alloy powders

Since the early 1960s, it has been established that amorphous alloy powders can be
produced by rapid solidication of alloy liquid and by rapid condensation of alloy
gases. In a way, the discovery of the fact that amorphous alloy powders can be
produced by simply milling a single powder or a mixture of two or more powders
greatly broadens the vision of materials scientists in how metastable materials can be
easily produced. The understanding of the mechanical milling process which results
in the formation of an amorphous phase appears to be rather simple, as shown later.
There are three routes for the production of amorphous alloy powders through
mechanical milling: Route 1, mechanically alloying two or more elemental phases;
Route 2, mechanically alloying one elemental phase and another intermetallic com-
pound, or two or more intermetallic compounds; Route 3, mechanical milling a
single phase elemental or intermetallic compound powder.
When Route 1 is used, a mixture of elemental metallic powders, A and B, are
milled for a period of time, resulting in the formation of an A/B composite powder
with each of the powder particles exhibiting a composite microstructure similar to
that shown in Fig. 1. With further milling, the size of the phase domains and the
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 541

Fig. 1. Microstructure of Al25at%Ni composite powder particles produced by high energy ball milling
for 4 h: the bright phase is Ni and the dark matrix is Al (courtesy of Danyang Ying).

grain size inside the phase domains continue to decrease to nanometer level. At this
point, the mobility of atoms at the interfaces and inside each of the phase domains is
so enhanced by the structural defects that the phases want to react at the ambient
temperature inside the milling chamber and/or at a moderate elevated temperature
achieved during the very short duration (in the order of milliseconds) of collision
between moving objects. Another essential precondition is that there exists a thermo-
dynamic driving force for the reactions between the A and B phases. When the A
and B phases choose to react, the reaction can result in formation of an amorphous
phase, A(B) and B(A) solid solutions, or AxBy intermetallic compounds. If the
kinetic condition is such that the A(B) or B(A) solid solution is unstable, and AxBy
compounds are dicult to nucleate, an amorphous phase often nucleates. With
further milling, the amount of the amorphous phase continues to increase through
growth of the amorphous phase domains and/or through nucleation and growth of
new amorphous phase domains. Based on this understanding, the process of forming
an amorphous phase during milling is very similar to annealing of multiplayer thin
lms consisting of alternating layers of dierent phases.
Attempts have been made to establish the unique feature of the AB systems
which allow amorphous powders to be easily synthesized. Through a large amount
of published research work, it is generally accepted that A and B are most likely to
be transition metals such as Ni and Nb, or Ni and Zr, or Cu and Ti, and AB alloys
are generally easy glass forming systems through rapid solidication, or during solid
542 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

state reaction in thin lms. This is understandable, as the ease of formation of

amorphous phases by rapid quenching is a reasonable indicator of the level of di-
culty of nucleating AxBy compounds which compete with the amorphous phase.
When A and B elements naturally have a thermodynamic driving force to be
alloyed into compounds or solid solutions as generally indicated by a negative heat
of mixing, the kinetic condition is the only factor which determines whether an
amorphous phase could form. The kinetic condition is determined by two aspects:
how dicult it is to nucleate the intermetallic compounds; and how restrictive the
environment is. The general observation is that intermetallic compounds with com-
plex or large unit cells are dicult to nucleate, so such systems are often easy glass
forming systems. However, it appears that the metallic electron phases (Hume
Rothery type phases) such as Cu5Cd8, are particularly easy to form during solid
state reactions during milling, even though their unit cells are rather complex and
their energy of formation is not very negative [12]. Once the nucleation of inter-
metallic compounds is suppressed, the range of the composition of the amorphous
phase is determined by the competition between the stability of the solid solutions
and the ease of nucleation of an amorphous phase. It has been recognised that the
dierence in atomic size of A and B elements is an important factor which deter-
mines the composition range in which a solid solution is stable [13,14]. The desta-
bilisation of a solid solution is realised through nucleation of amorphous phases.
The kinetic condition is generally reected by the temperature at which the reaction
can occur.
Although solid state reactions during mechanical milling of powders and during
annealing of multiplayer thin lms are in many ways similar, mechanical milling
adds additional factors to the process. These factors include the structural defects,
such as vacancies, dislocations and grain boundaries, induced by mechanical work-
ing, and the dependence of the structure of reaction couples on the milling process.
The reaction couples in mechanically milled powders are not produced in a con-
trolled manner as are the reaction couples in multiplayer thin lms prepared by
sputtering or vapour deposition. Since the volume fractions and the mechanical
properties of the A and B phases greatly aect the process of forming the A/B
composite by milling, dierent volume fractions of A and B phases can often result
in a completely dierent reaction route. One of the examples showing the dramatic
eect of the volume fractions of the starting powders is the mechanical alloying of
Pd and Si powders. Zhang and Massalski [15] have shown that when a Pd/Si powder
mixture with 19at% Si powder (24.2vol.%Si) was milled by using a high-energy ball
mill under helium, an amorphous PdSi phase formed directly from the solid state
reaction between Pd and Si, as shown by the X-ray diraction (XRD) patterns in
Fig. 2. However, when a Pd/Si powder mixture with 33at% Si (40.1vol.%Si) powder
was milled, a Pd2Si compound formed easily from the solid state reaction between
Pd and Si, and the formation of the amorphous phase was completed avoided, as
shown by the XRD patterns in Fig. 3.
In many binary systems, A and B elements do not have a thermodynamic driving
force to be alloyed, but they can still be mechanically alloyed into amorphous phases.
Here, the kinetic consideration is not paramount, because of a lack of competition
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 543

Fig. 2. XRD patterns of a Pd19at%Si powder as a function of milling time: (a) unmilled; (b) 4 h; (c) 8 h;
(d) 16 h; and (e) 26 h [15].
544 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

from formation of intermetallic compounds. Provision of the required thermo-

dynamic driving force is the most important issue. To satisfy the need for the
thermodynamic driving force, the Gibbs free energy of the starting system has to
be larger than the Gibbs free energy of the amorphous phase formed. This can be
expressed using the following relationship:
xGv A DGd A 1  xGv B DGd B DGi A=B

> Ga DGi a=A DGi a=B 1

where x is the mole fraction of A element in the amorphous phase, Gv(A), Gv(B) and
Ga are the volume free energies of phase A, phase B and the amorphous phase,
Gd(A) and Gd(B) are the free energy increases introduced by the structural
defects in A and B phases respectively, and DGi A=B, DGi a=A and DGi a=B are
the energy increases caused by the A phase/B phase, amorphous phase/A phase, and
amorphous phase/B phase interfaces respectively. Assuming that the amorphous
phase nucleus is a thin layer between A and B phases, and based on Zhang and
Massalskis derivation reported in Ref. [12], Eq. (1) can be rewritten as:
t0
0  1 2 > DGv  DGd 2
Va

Fig. 3. XRD patterns of a Pd33at%Si powder as a function of milling time: (a) 2 h; (b) 4 h; and (c) 16 h
[15].
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 545

where  0,  1 and  2 are the energies of interfaces between the A and B phases,
between the amorphous phase and the A phase and between the amorphous phase
and the B phase respectively, t0 is the thickness of the amorphous phase nucleus, and Va
is the molecular volume of the amorphous phase. Gv=Ga-(x(Gv(A)+(1x)Gv(B))
measures the thermodynamic barrier, while Gd=xGd(A)+(1-x)Gd(B) mea-
sures the free energy increases due to structural defects. If Gv > Gd,  0- ( 1+ 2)
has to be greater than zero for Eq. (2) to be valid. In other words, if the equilibrium
thermodynamic barrier for the amorphisation is greater than what the increase of
the amount of structural defects can compensated for, the amorphisation has to be
driven by the change of interfacial energy caused the nucleation of the amorphous
phase. Due to the balance between the generation of structural defects through
mechanical working and annihilation of the defects through dynamic recovery and
crystallisation, the value of Gd is normally limited to about 5 kJ/mole [1618]. This
means that for any AB system with a thermodynamic barrier much greater than 5
kJ/mole, interfacial energy must play a major role in determining whether amorph-
isation is possible. Several researchers have convincingly demonstrated that Cu and
Ta can be mechanically amorphised in the middle composition range, even though
the Gv of the CuTa system is substantially greater than 5 kJ/mole [1923]. Similar
observations have also been made in other systems with substantial thermodynamic
barriers. This shows that the role of interfacial energies is signicant.
The question is how much the interfacial energy can do to drive the amorphisa-
tion. Va is typically in the order of 10  106 m3/mole, and for a sizeable amorphous
phase nucleus, t0 needs to be around 5 nm. This means that Eq. (2) can be roughly
written as:
0  1 2 > 5  104 DGv  DGd : 3

If, for a binary system, Gv > 10 kJ/mole and Gd  5 kJ/mole, it means that
 0( 1+ 2) must be greater than 2.5 J/m2 to be sucient to drive the formation of
the amorphous layer of 5 nm in thickness.  1 and  2 are in the order of solidliquid
interfacial energy which is normally around 1 J/m2. This shows that  0 has to be
greater than 4.5 J/m2. To have so high an interfacial energy, the interface has to be
far away from equilibrium. Since the A/B interfaces formed by mechanical milling
are the direct result of mechanically forced cold welding, this is possible. However, it
might be very dicult, if not impossible, to achieve amorphisation by mechanical
milling in a system which has a much greater thermodynamic barrier. One example
of this is the CuW system which has a Gv of over 40 kJ/mole at close to equal
atomic composition [24]. If this is to be done, it requires the Cu/W interfacial energy
to be greater than 17.5 J/m2, or t0 to be substantially less than 5 nm. It is doubtful
whether amorphisation in such systems can be achieved. Zhang and Massalski [25]
have made an attempt to amorphise Cu and W, at a Cu40 at.%W composition, by
high-energy ball milling in helium. Fig. 4 shows the XRD patterns of the powders
after two lengthy periods of milling. A broad halo peak appeared in the pattern after
143 h of milling, showing that some kind of amorphous phase formed. However,
when the powder was heated in a dierential thermal analyser to 650  C under
546 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

Fig. 4. XRD patterns of the Cu40at%W powder after milling for 88 h and 143 h respectively [25].

argon, to allow the amorphous phase to partially crystallise, and then quickly cooled
to room temperature, an unknown phase formed in the powder, as shown by the
XRD patterns in Fig. 5. The formation of the unknown phase means that the
amorphisation of Cu and W might be assisted by other elements such as oxygen or
nitrogen. There are other reports [26,27] which claim that amorphisation in systems
with a large positive heat of mixing, such as CuW, CuV, has been achieved
through high-energy mechanical milling on the grounds that broad peaks were
observed in the XRD patterns. These claims are not, as yet, very convincing.
Lee and Koch [28] and Zhang and Massalski [12] have shown that amorphous
powders can be produced by high-energy mechanical milling of a mixture of two
intermetallic compounds or a mixture of elemental powder and intermetallic com-
pound powders. This is Route 2 of the synthesis of amorphous powders using
mechanical milling. In this route, the free energy of the system has to be raised by
introducing structural defects and interfaces to drive the amorphisation in the same
way as that in the AB systems with positive heat of mixing. Interestingly it was
found that when an intermetallic compound such as Cu5Cd8 powder was milled, the
intermetallic compound could not be turned into an amorphous phase, but when it
was milled together with an elemental Cu powder, the compound was completely
destabilised and an amorphous phase formed [12].
It has been shown that mechanical milling of some intermetallic compound pow-
ders can result in the formation of amorphous powders. This is Route 3 of the
synthesis of amorphous powder using mechanical milling. Again, this route requires
storing sucient energy in the intermetallic compounds to overcome the energy
barrier (normally around 5 kJ/mole) for amorphisation. The energy increase of the
intermetallic compound can come from structural defects, such as vacancies, dis-
locations, grain boundaries and anti-phase boundaries and disordering of the crystal
structure. It is believed that the accumulation of vacancies and dislocations can only
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 547

Fig. 5. XRD pattern of the 143 h milled Cu40at%W powder which was heated to 650  C and then
rapidly cooled to room temperature under argon [25].

store a moderate amount of free energy which is not sucient to drive the amor-
phisation. On the other hand, the energy stored through reducing the grain size to a
nanometer level and introducing disordering are the major mechanisms for over-
coming the thermodynamic barrier [29]. The work in this area has been well
reviewed by Bakker et al. [9].

4. Synthesis of alloy powders with other metastable phases

For some systems, such as AlMg, or under some milling conditions such as at
elevated temperatures, an amorphous phase does not form, but other metastable
phases may form. There are a few examples of this. Zhang et al. [30] found that an
Al23at%Mg supersaturated solid solution formed after milling a mixture of Al and
Mg powders with 40at%Mg, but when a Al/Mg powder mixture with 60at%Mg was
milled, the equilibrium (Al12Mg17) phase formed directly during milling. Another
example is mechanical alloying of Al and Ti. It was found that, during mechanical
alloying, a supersaturated Al(Ti) solid solution, or an Al3Ti compound with a cubic
L12 crystal structure rather than a Al3Ti compound with a tetragonal DO22 crystal
structure formed [31,32]. In the same way as the formation of amorphous phases
during milling, formation of the metastable phases is due to the kinetic conditions
which prevent the formation of the equilibrium phase, but allow the formation of
metastable crystalline phases. For the formation of supersaturated solid solutions,
nucleation is not required, while for the formation of other metastable phases,
nucleation is required. Often the metastable phases have a more simple crystal
structure which makes their nucleation easier than the equilibrium phases.
548 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

Zhang and Ying [33,34] have demonstrated that unlike the amorphous phase and
supersaturated solid solutions, metastable intermediate phases can be formed by
heating mechanically milled powders. The precondition is that the composite
microstructure of the powder particles are suciently rened to lower the reaction
temperaturethe temperature regime which make the nucleation of metastable
phases rather than the equilibrium phase more favourable.

5. Synthesis of intermetallic and other compound powders

There have been numerous reports showing that an intermetallic compound, or

silicide or carbide powder, can be produced by high-energy mechanical milling of a
mixture of elemental powders. The process is simple to understand. In the same way
as the formation of amorphous phases which occurs during mechanical milling,
formation of the compound is due to an enhanced diusivity of the elements in the
composite powder formed during milling. With the enhanced diusivity, the compound
can nucleate and grow at the low temperatures experienced by the powder. The
enhanced diusivity is believed to be due to the introduction of structural defects
such as grain boundaries and interfaces. Whether the mechanical stress plays any
major role in enhancing the diusivity is not clear. The correlation between the
enhanced diusivity and the composite microstructure is often reected by the
decrease of reaction temperature with renement of the composite microstructure
[35,36]. It appears that the interface plays a major role in reducing the reaction
temperature. With the reduction of layer thickness and the increase of interface area,
the reaction becomes easier. When the reaction becomes easy enough, it can occur
during milling, leading to mechanical alloying.
The general observation is that complete conversion of a powder mixture into a
compound powder often requires a lengthy milling. This is costly and impractical.
To avoid this, one should think about combining the milling and thermal treatment
process in synthesizing the compound powder. In some cases, this combination has
to be used as milling alone does not result in the formation of the compound pow-
der. In other cases, combining the two processes will greatly shorten the required
milling process. In synthesizing compound powders, one should realise that the
merit of mechanical milling is to enable formation of the composite powder parti-
cles, comprising A and B phases, which can be viewed as a collection of numerous
reaction couples. The reaction couples are the essential precursors for producing the
compound powder. Once the reaction couples are established, the value of further
milling lies in the need for rening the reaction couples into nanometer sizes. In
some cases, such as when nanocrystalline compounds are to be produced, this is
necessary. In other cases, this is not essential. There are also exceptions to this
generalisation. In the unpublished work by Richmond and Zhang [37], it was found
that the SiC phase can be formed by mechanical alloying of Si and C powders, but it
was very dicult to form the SiC phase by heating the Si/C composite powders to a
high temperature ( > 1000  C). This shows that, due to the low bulk diusivity of
silicon and carbon, the reaction between Si and C is limited to the Si/C interface.
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 549

Mechanical alloying keeps producing fresh Si/C interfaces, allowing the accumula-
tion of a sizeable amount of SiC, while heating the composite powder only allows a
limited amount of SiC to be produced, and the amount of interface does not change
during heating.

6. Synthesis of nanocrystalline powders

It has been well established that high-energy mechanical milling is one of the
major techniques for producing powders with nanocrystalline structures [29]. When
a single phase elemental powder or intermetallic compound powder is milled, the
grain size of the powder particles continues to decrease until it reaches a minimum
levelin the range of 325 nm. For some intermetallic compounds, the powder
becomes amorphous beyond this point. For intrinsic brittle powders, such as silicon
powder or ionic compound (e.g. carbide and oxide) powders, the reduction of the
grain size is a natural outcome of the transgranular fracturing and cold welding, and
the minimum grain size is determined by the minimum grain size which does not
allow nucleation and propagation of cracks within grains. No study has been seen
which attempts to theoretically determine this minimum grain size. For metallic and
intermetallic powders, it is believed that fracturing and cold welding are not the
major mechanism for the reduction of the grain size. Instead, the reduction of the
grain size is due to localisation of plastic deformation in the form of shear bands
containing a high density of dislocations, formation of subgrains or cells by annihi-
lation of dislocations and the conversion of subgrains/cells into grains through
mechanically driven grain rotation and subgrain boundary sliding. In other words,
the mechanism of forming nanometer sized grains during high-energy mechanical
milling is very similar to the dynamic recrystallisation which occurs during hot
forming of metals and alloys, except the mechanical working temperature in milling
is very low and limits the opportunities for the new grains to grow. The low tem-
perature is essential in keeping the nanograins. The minimum grain size is deter-
mined by the balance between dislocation accumulation, and dynamic recovery
through formation of subgrain boundary and new grains. It appears that for FCC
crystals with moderate to low melting points (< 1800 K), the minimum grain size
inversely scales with the melting point of the metal [17,29]. This correlation suggests
that the deformation theory of grain size reduction is valid. For metals with melting
points higher than 1800 K, there is no such correlation between the minimum grain
size and melting point, but their minimum grain size stays at a low level.
Nanocrystalline intermetallic compound powders can be produced by mechanical
alloying elemental powders. In this case, the nanograins are not a direct result of
plastic deformation or fracturing and cold welding. Instead, they are a result of
numerous nucleation events followed by limited growth of the new phase. The
advantage of the mechanical milling process is that the processing temperature is
low, so the newly formed grains grow very slowly, and the complete conversion of
the powder has to rely on the accumulation of numerous nucleation events during
milling. As discussed in previous sections, nanocrystalline intermetallic powders may
550 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

be produced by heating nanostructured A/B composite powders, produced by

mechanical milling, to a temperature which allows nucleation of the intermetallic
phase at the interfaces and growth to a limited extent.

7. Synthesis of metalceramic composites and nanocomposite powders

High-energy mechanical milling is a very eective process for synthesizing metal

ceramic composite powders as it allows incorporation of the metal and the ceramic
phases into each powder particle, as shown schematically in Fig. 6. In the initial stage,
the microstructure of the composite powder particles is at the micrometer level.
With further milling, the metal phase is deformed and fractured, while the ceramic
phase is mainly fractured. If it is a metal matrix composite, the ceramic particles are
continually fractured into smaller particles, so the ceramic particle size will keep
decreasing until such a point that the fracture strength of the small particles will be
equal to or greater than the stress caused by the collision. Often this balance point
corresponds to a ceramic particle size in the range of a few nanometers to 100 nm.
As an example, Fig. 7 shows the development of the powder particle micro-
structure of a Cu20wt%W soft metalhard metal composite [37]. In the initial stage
of milling, only a few W particles are incorporated into each of the Cu particles.
Then with further milling, which causes working hardening of the Cu and W phases,
most of the W particles are deformed, fractured and incorporated into the Cu
matrix, forming Cu/W composite powder particles as shown in Fig. 7. With con-
tinued milling, the size of the W particles is reduced to a nanometer size level
through continued fracturing. It is envisaged that when the W particles become too
small, further fracturing would become impossible during milling. At this point, the
composite microstructure will cease to change. It is not yet clear how large the W
particles should be at this critical point.
In a similar way, metalceramic nanocomposites with nanometer sized ceramic
particulate reinforcement or ceramicmetal nanocomposites with a nanometer sized
metallic phase can be produced, as shown in Fig. 8 [38]. Since the nanostructure of
each powder particle evolves through numerous deformations, fracturing and cold

Fig. 6. Schematic diagram showing the formation of composite powder after high-energy mechanical
milling.
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 551

welding events, after a certain period of milling, powder microstructure homo-

geneity can be achieved at the same time as the nanostructure. Sometimes the
as-milled nanocomposite powder is not a stable system, and it is converted into a
dierent metalceramic nanocomposite during heat treatment or sintering. One
example of this case is the production of CuAl2O3 nanocomposite powder by con-
verting Cu(Al)CuO nanocomposite powder produced by high-energy mechanical
milling of a Cu(Al)CuO powder mixture (Fig. 9) [39]. This technique has also been
used to produce Al(Cu)Al2O3 nanocomposites and other MAl2O3 nanocomposites,
where M represents the metal (or a metalaluminium solid solution) produced by
reducing a metal oxide by Al [40,41].

8. Synthesis of nanopowders

Powders with particle sizes in the range of a few naometers to 100 nm are called
nanopowders. Nanopowders have many practical applications. High-energy
mechanical milling can be used to produce nanopowders. There are two routes for
producing nanopowders using mechanical milling: (a) milling a single phase powder

Fig. 7. The microstructural evolution of the powder particles during high-energy mechanical milling of
Cu20wt%W powder. The dark phase is Cu and the bright phase is W (courtesy of Jennie Richmond).
552 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

and controlling the balance point between fracturing and cold welding, so that par-
ticles larger than 100 nm will not be excessively cold welded; and (b) producing
nanopowders using mechanochemical processes. Professor Paul McCormicks group
in the Western Australia University have been very successful in using this process
to produce metallic and ceramic nanopowders. The principle behind this process is
quite simple. This principle can be easily explained by using an example of produ-
cing a Fe nanopowder [42]. The process starts by high-energy milling a mixture of
FeCl3 powder and Na pieces. The milling induces a reaction between FeCl3 and Na,
forming Fe nanoparticles mixed with NaCl. The NaCl can be easily leached out
from the powder by using water, and Fe nanopowder is produced.

9. Quantication and modelling of the high-energy mechanical milling process

As a materials processing process, high-energy mechanical milling must be quani-

tiable and controllable in the same way as any traditional metallurgical or chemical

Fig. 8. Microstructure of powder particles in the Ti3Al/10vol%SiC powder at dierent stages of milling:
(a) milling for 2 h; (b) milling for 8 h; (c) milling for 16 h. The dark particles are SiC. The starting materials
were Ti, Al and SiC powders (courtesy of Jing Liang).
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 553

Fig. 9. The microstructure of a Cu20vol%Al2O3 nanocomposite produced by mechanical milling and

sintering (courtesy of Danyang Ying).

processing process before it can be used as a main-stream materials processing pro-

cess in industry. At this stage, researchers in the area of high-energy mechanical
milling have a very good understanding at the phenomonlogical level. That is, high-
energy milling is a process in which moving objects collide, trap and forge a mini-
powder compact. When the stress induced by the high-speed forging impact is high
enough, the powder particles are plastic deformed, fractured and cold welded. Since
the forging process involves a powder compact, rather than a single powder particle
as shown in Fig. 10, the densication process of the powder compact is also very
important. Various attempts have been made to quantify and simulate the high-
energy mechanical milling process by several research groups, including the authors
own group [4356]. However, these attempts are still limited to a semi-quantitative
level, and only cover a limited number of aspects of the process. Unlike typical
metallurgical processes such as melting, casting, and solid state heat treatment, high-
energy mechanical milling is a dynamic process, so it is a great challenge to establish
mathematical models which accurately describe the various mechanisms involved in
the process. Nevertheless, the contributions made by the initial modelling work
should not be underestimated. Without these initial attempts, a more in-depth
understanding cannot be achieved. Based on previous work and the common
understanding of mechanical working, it is not dicult to foresee that the following
aspects of the milling process must be described mathematically to establish a com-
prehensive set of models for a high energy milling process:

The dynamics of moving objects in the milling chamber: how does the milling
machine work? How fast are the moving objects when they collide? At what
angle do they collide? Is there any sliding? Fig. 11 shows three examples of the
preceived manners in which ying balls could collide.

The amount of powder which is trapped in each collision.
554 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

The densication process of the powder compact: how does the powder densify
under the high speed impact?

The elastic and plastic deformation process of the powder particles: how large
are the elastic/plastic strain and strain rate? How much are the powder par-
ticles work hardened? How is the shape of the powder particles changed?

The cold welding process of the powder particles: what is the criterion for the
two contacting solid particles to be cold welded?

The fracturing process of the powder compact: does the fracture occur along
inter-particle interfaces or through particles? How many new particles are
produced after each impact?

The temperature change during collision: what is the maximum temperature;
how does the temperature change during impact?

Fig. 10. Schematic diagram showing the impact process of balls on a mini powder compact trapped
between two balls [56].

Fig. 11. Schematic diagram showing the dierent forms of impact which might occur during high-energy
ball milling [56].
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 555

The change of mechanical properties of the powder particles as they change

their microstructure: how do the mechanical properties change while forming
composites, forming solid solutions, or forming new phases?

The energy balance of the mill: how much energy is consumed to achieve a
particular particle microstructure? Where does the energy go?

Coupling of the global milling dynamics and the individual powder compact
deformation process.

The ultimate aims of the quantiaction and modelling of the high-energy milling
process are: (a) to predict how long it takes and how much energy is to be consumed
to achieve a particular powder particle microstructure; and (b) to optimise the mil-
ling machine design and milling parameters, such as ball number, size, ball:powder
weight ratio, and milling chamber shape and size. At this stage, researchers still
mainly rely on their own or others experience in deciding which milling machine
and what milling parameters are to be used for high-energy mechanical milling.
Recently Dr Wei Wang studied several aspects of a high-energy ball milling pro-
cess using the popular SPEX viboratory mill [56]. He developed a visco/plastic
model for describing the deformation process of the powder compact, utilised clas-
sical dynamics models to describe the motion and rotation of balls, and then cou-
pled the two processes together. By employing a limited number of balls, he used a
computer simulation to follow the movement of each ball in the milling chamber
and monitored and simulated each single collision event. The results are very infor-
mative. Fig. 12 shows the collision frequency as a function of number of balls for
dierent sizes of balls. In the gure, ball weight rather than ball diameter is quoted
for convenience. It shows that with a small number of balls, the frequency increases
parabolically with ball number, but when the ball number is sucently high, the
impact frequency increases very rapidly, showing that the number of balls is too
large for the ball size and the chamber size. Fig. 13 shows the impact velocity (rela-
tive velocity between two colliding balls just before they collide) distribution. It
clearly shows that with a large number of balls, or bigger balls (meaning a higher
colliding frequency) the fraction of impacts with high-impact velocity is actually
lowered. By examining these results, the trade o between impact frequency and
impact eciency can be determined. For the purpose of high-energy mechanical
milling, impact eciency is an important consideration, as only those impacts which
cause plastic deformation, fracturing and cold welding, matter in the process.

10. Consolidation of the powders into bulk materials

In many cases, the powders produced by using high-energy mechanical milling are
used directly in powder form. One such example is metal nanopowders which exhibit
unique chemical and physical properties and are used in powder form for achieving
desirable functions. In most cases, the purpose of high-energy mechanical milling is
to produce bulk materials or components with desirable mechanical, physical and
chemical properties. In these cases, consolidation of high-energy mechanically milled
556 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

powder is an essential process for achieving the nal objectives. In a general sense,
the mechanically milled powders can be sintered in the same way as powders pro-
duced by other means, such as atomisation and chemical vapour condensation. The
particle shapes in the mechanically milled powders are rather irregular, and often the
as-milled powder particles are heavily work hardened. These features might aect
the sintering behaviour of the powders, but to date, no study has been carried out to
compare the sintering behaviour of high-energy mechanically milled powders with
that of the powders produced using other methods.
Since, high-energy mechanical milling is often used to produce powder particles
with a nanostructure (nanograins and/or nanocomposites) and often it is essential to

Fig. 12. Frequency of ball to ball impacts, as a function of the number of balls, for dierent ball sizes
during milling in the SPEX-8000 Mixer/Mill, determined by computer simulation. The ball material is 304
stainless steel [56].
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 557

Fig. 13. Velocity distribution of the ball to ball impacts for dierent ball numbers and sizes during milling
in the SPEX-8000 Mixer/Mill, determined by computer simulation. The ball material is 304 stainless steel
[56].
558 D.L. Zhang / Progress in Materials Science 49 (2004) 537560

maintain the nanostructure in the nal bulk material, dening the right conditions
for consolidation of the mechanically milled powder can be very challenging. The
dilemma one has to deal with in consolidating nanostructured materials is that you
need diusion to achieve atomic level bonding between particles, but in the mean-
time, diusion also causes coarsening of grains and interfacial reactions. It is not
easy to dene a condition window (the range of temperature and pressure) in which
the positive eect of the diusion is attained, without having the side eects. It is
worthwhile to note that simply achieving full density by hot pressing the powder
compact does not mean that a full scale sintering is achieved. Very often, when a
fully dense nanostructured material produced by hot pressing a nanostructured
powder is tested by tensile testing, it was found that the fracture occurred along the
original inter-particle boundaries. This is a typical sign showing that the material is
not fully solid, as the particles are not completely bonded together at atomic level.
With fully sintered materials, we should only see grain boundaries, interfaces, pores,
and dierent phases. Much more research is needed in developing the art of sinter-
ing nanostructured powders.

11. The future

The research on high-energy mechanical milling is not a matter of scientic curi-

osity any more. It has become a major potential process for processing advanced
materials which awaits to be used in industry. Whether the research in the area of
mechanical milling will further develop or shrink will very much depend on whether
the process will be used in producing advanced materials at an industrial scale.
At the moment, the future looks very challenging. To scale up the process, the
required milling time to achieve the desired powder microstructure must be shor-
tened to a few hours or less. This will require a lot of work in optimising the design
of the mills and modelling of the milling process. Hopefully, modern computer
technology will make this goal achievable in the not too distant future. The problem
with contamination from materials from the milling media and process control
agents must be minimised to a level accepted by industry. Normally this level should
be less than 1at%. Although many fantastic things about high energy mechanical
milling have been reported, there has not been much eort on investigating how
the process can be scaled up to producing materials at a few tons per batch level or to
make the process continuous. Again process modelling is essential for the scaling
up.
In a way, it is now time for materials scientists and engineers, who are interested in
developing high-energy mechanical milling into an industrial process, to learn from
scientists and engineers who have mastered the art of low-energy mechanical milling
for the purpose of mineral processing and powder consolidation. This could be very
benecial. In the last 2 years, the authors research group has learnt from colleagues
in industry how to utilise a discus mill to perform mechanical alloying at a scale of
half a kilogram per batch. Discus mills have typically been used for crushing rocks
in mineral processing industry.
 D.L. Zhang / Progress in Materials Science 49 (2004) 537560 559

12. Summary

The understanding reached on each of the major topics related to the use of high-
energy mechanical milling in processing advanced materials has been overviewed
and commented on. This overview demonstrates that high-energy mechanical mil-
ling can be used to produce many dierent types of materials, including amorphous
alloy powders, nanocrystalline powders, intermetallic powders, composite and
nanocomposite powders, and nanopowders. Good understanding of the mechan-
isms related to the process for each of these purposes has been achieved at a phe-
nomenological level. However, accurate quantication and modelling of high-energy
mechanical milling are still lacking, even though several research groups have made
serious attempts on quantication and modelling of the process. The whole area of
mathematically describing and modelling the high-energy milling process deserves
the close attention of all materials scientists and engineers working in this area.
Without mastering the art of optimising, controlling and predicting the process,
there is no hope of developing this powerful process into a main-stream industrial
scale materials processing process in the same way as melting, casting, or heat
treatment. There are also some important issues related to consolidation of the milled
powders. One of the issues is dening the process condition window which allows
fully solid nanostructured materials to be made from a nanostructured powder.

Acknowledgements

The author would like to thank his past and present postgraduate students and
other colleagues who have contributed to the research on processing advanced
materials using high-energy mechanical milling at Waikato University. They
include: Dr Wei Wang, Dr Danyang Ying, Jennie Richmond, Geogees Adam, Egan
Bowden, Zhihong Cai and Jing Liang. The work of the authors research group in
the area of processing advanced materials using high-energy mechanical milling has
been nancially supported by The Foundation for Research, Science and Technol-
ogy, New Zealand and Titanox Development Ltd through major research grants,
which are gratefully appreciated. The author would also like to thank Martyn
Newby for many stimulating discussions.

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