Ceramics Intern&ml 23 (I 997) 39-44

(‘ 1996 Elsevier Science Limited and Techna S.r.1.

Printed in Great Britain. All rights reserved
0272-8842(95)00138-7 0272.8842197 $17.00+ .OO

Synthesis of Nanostructured Materials

by Mechanical Alloying
Paolo MatteazzLa Gerard Le Ca6rb & Alain Mocellit@

“Dipartimento di Scienze e Tecnologie Chimiche, Universita di Udine, Via Cotonificio 108, L-33100, Udine, Italy
‘Laboratoire de Science et Genie des Materiaux Metalliques associe au CNRS U.R.A. 159, Ecole des Mines, F-54042, Nancy
Cedex, France

(Received 3 August 1995; accepted 28 September 1995)

Abstract: Materials can be processed by grinding not only for comminution, but
also to obtain a variety of structures (amorphous, nanophased), fine mixing
of phases, alloys and to directly synthesize compounds such as carbides.
Nanocomposites can also be synthesized by reduction, exchange and mixing
reactions driven by grinding, as well as by combining the above processes. Large
scale economical production of such materials is feasible by grinding in mills
designed for that purpose. The mechanical properties of materials are enhanced
by the nanophase structure. i‘ 1996 Elsevier Science Limited and Techna S.r.1.

1 INTRODUCTION growth and without porosity, giving rise to

materials with improved mechanical properties.
Grinding is no longer used for the sole purpose of For instance, superplasticity is expected to be
reducing the sizes of particles of all kinds of mate- significantly enhanced in large, fully dense nano-
rials. Grinding is also a method of synthesis of crystalline ceramic compacts.5 More generally, all
advanced materials, called mechanical alloying,’ kinds of oxide or non-oxide ceramic materials,
which has received considerable attention in recent alloys strengthened by a dispersion of refractory
years.2 Mechanical alloying (MA) is basically a oxide particles, and ceramic-metal composites,
dry, high-energy milling process, which was origin- may be synthesized by MA of powder mixtures or by
ally developed as a means to manufacture oxide reactive milling. 6,7The use of grinding for inducing
dispersion-strengthened superalloys for jet engine phase transformations and even amorphization has
parts. The feasibility of synthesis of a large variety been/is being thoroughly investigated, in particular
of materials, from metallic to ionic (alloys, com- in oxides.8$9 The present paper describes the
pounds, composites) with a diversity of structures considerable potential of MA for synthesizing
(quasi-crystalline, crystalline, amorphous) by mil- ceramic and ceramic-metal composite powders
ling of elemental mixtures in a ball mill is now well with nanometre-sized grains and some properties
established (mechanosynthesis). of materials consolidated from such powders.
Moreover, grinding is a way of disordering solids
and of inducing or activating phase transformations
or chemical reactions (mechanochemistry).‘.” MA 2 SYNTHESIZED MATERIALS
also appears to be an attractive method of synthesis
(mechanosynthesis) in view of its potential for large 2. I Experimental conditions
scale production. The synthesized materials, often
with non-equilibrium structures, include among Reaction milling experiments were mainly per-
others, crystalline materials with nanometre-sized formed in high energy mills at laboratory scale,
grains. such as in the vibratory ball mill Spex:Q 8000
MA will be of great interest if the synthesized mixer/mill and in the planetary ball mill Fritsch”
powders can be consolidated with a limited grain Pulverisette. Experiments reported in this paper

39
40 P. Matteazzi et al.

were all performed in dry conditions, using grind- obtained in this way include aluminides (Fe3A1,
ing means and vial constituted of WC or steel. The TiA13, TaAls, NiAl), stannides (FeSnz, FeSn), and
ball to powder weight ratio (BPR) is varied in the germanides (FeGe, FesGe).
range 5:140:1. The initial powder mixture (either Exchange and mixing reactions driven in a
elements and/or compounds) is introduced in the high energy mill can give rise to the formation of
vial, usually under controlled atmosphere, and nanocomposites.‘* Iron-containing compounds
milled either using continuous milling or adopting (nitride, cementite) were used in the following
rest periods to allow cooling of the vial. The tem- generic reaction schemes:
perature raise of the vial does not usually exceed Fe2.5N + Al + AlN + 2.5Fe (1)
100 “C, and processing is assumed to be essentially 4Fe2.5N + 3Si + SijN4 + 1OFe (2)
at room temperature. In general, milling times
required to complete the syntheses do not exceed Fe& + Cr + (Fe, Cr),-orhidP (3)
l&15 h. The powders were characterized by 57Fe In the cases of reactions (1) and (2), the formation
Mijssbauer spectroscopy (isomer shifts are referred of Al and Si nitrides (crystallite sizes of 8 and 22
to a-Fe) and X-ray diffraction (XRD) using CoKcl nm, respectively), together with iron aluminides or
(h = 0.1789 nm) radiation. The mean crystallite size silicides, and iron alloys were obtained. Milling of
was calculated from the broadening of the X-ray FesC with Cr [reaction (3)] led to a complete
peaks corrected for instrumental broadening. transformation of cementite to an amorphous
(Fe-Cr,i,h)C ph ase and a mixed (Fe,Cr)C carbide.
2.2 Synthesis of compounds from elemental
powders: carbides and intermetallics 2.3 Synthesis of metal1 oxide nanocomposites

The direct synthesis of carbides was obtained by Chemical reactions may be influenced by exter-
grinding a powder (or chips, or even pieces of some nal mechanical actions. 3,‘5 A mechanical action
mm in size) mixture of a metal and graphite.‘O,” may..” ( 1) involve a chemical reaction which serves
The formation of stable, metastable, mixed and as one channel for the dissipation of mechanical
new carbides having crystal sizes in the range energy which is provided to the ground powders,
10-20 nm was observed (some of the syntheses or (2) lead to non-equilibrium states with enhanced
were also performed in air), such as for Sic, TIC, reactivity which may be retained over a long period
WC, ZrC, VC, MoC, ReC, HfC, (x<O.82), VC, after removal of the action. Both ways may be used
(x < 0*5), NbC0.75, NbC, (x < 0.5), MoC, (x < 0.5), to synthesize materials in one-step or in multi-step
Cr3C2, Mn$, Fe& Fe&s, Fe-C alloy (marten- processes. Metal-oxide composites are in general
site-like), CosC, Ni$, Al&, mixed-(TiAlV)C, prepared either by direct grinding of mixtures of
(TaRe)C,, (Few)&. Mixed carbides were formed metallic and oxide powders, or by reactive milling
either by milling an alloy with graphite or a involving redox reactions. The former composites
powder mixture of metals and graphite, or from a mainly belong to the family of oxide-dispersion
carbide and a metal.10~‘2 Metalcarbon alloys can strengthened (ODS) alloys, while the latter mainly
also be synthesized as shown in Refs 10 and 13 in belong to the cermet family with a large oxide
the Fe, -,C, system (x < 0.15) in which an Fe-C volume fraction. We will successively describe
alloy, martensite-like, was obtained. some general characteristics of ODS alloys and of
The direct, room temperature synthesis of cermets synthesized by mechanical alloying.
nanophased (crystal size in the range 9-15 nm)
silicides,1’,‘4 mainly with composition MS& 2.3.1 ODS alloys
(M= Fe, Co, Ni, Cr, Mn, MO, Re, Hf, Ta, V, Zr, MA has been extensively used for producing Fe-,
Nb, Ti, W), was similarly obtained by grinding Ni- and Al-based ODS alloys.‘,16 In general they
“M”’ metals with Si. Single phases according to the contain a volume fraction of oxide particles of
respective phase diagrams are often obtained, but about l-2 ~01%. The ODS alloys have already
in some cases polyphased products were observed, found applications in various areas due to a unique
such as in the FeSil and MoSi2 systems, where both combination of high temperature strength and
low (B-FeSi2, a-MoSi2) and high (a-FeSi2, P-MoSi2) environmental resistance.16 Yttria is the most
temperature phases were observed.14 The following widely used oxide, but alumina or rare-earth oxides
silicides have been obtained by mechanosyn- have also been recently dispersed in intermetallic
thesis: FeSi, (~1,P)-FeSi2, HfSi2, ReSiz, Re$i3, (a, compounds. I6 For instance, a fine and homo-
j3)-MoSi2, ZrSi2, TaSi2, TasSi3, VSi2, Ni$i, NisSi2, geneous dispersion of alumina (1 wt%) formed
MnSi, Mn& TiSi2, CoSi, CoSi2, NbSi2, WSi2, p- during attrition of a B2 FeAl aluminide improves the
W5Si3 and y-CrSi2. Other intermetallic compounds creep resistance at high temperature (z 700 C).17
Synthesis of nanostructured materials 41

For the future, MA may be used to synthesize aluminium as in the latter materials. It would be
advanced alloys for aero-engines including inter- interesting to compare the properties of the cermets
metallic compounds and composites based on Ni, consolidated from those two types of powders.
Ti. Al and Nb.i6 Composites of alumina with an alloy, for instance
a-Alz03-(Fe, _,,_YNi,XCr,,),are obtained by grinding
2.3.2 Cermets a mixture of aluminium and iron, nickel and chro-
Much attention has been devoted to the aim of mium oxide powders in the required proportions.
combining metals and ceramics in order to gen- In many cases, a self-sustaining (combustion)
erate materials with improved properties. More reaction takes place during MA owing to a high
recently, processes based on mechano-chemical negative enthalpy. 6 MA significantly increases
reactions have been investigated3-7~15*‘8-23 and kinetics in such displacement reactions by the
attention has been paid to the understanding of the dynamic maintenance of high reaction volumes
mechanisms and principles which govern such and rapid diffusion rates related to short diffusion
reaction syntheses. The synthesis of alumina-based paths, enhanced defect density and high reaction
cermet powders involves displacement reactions interface areas6 In highly exothermic redox
between aluminium and either one or a mixture reactions, a mechanically induced combustion
of metal oxides. Such oxido-reactions induced by propagates through the unreacted powders after an
the grinding process can be schematically written incubation period, which is the time required for
as (3/y)M,O,. + 2Al + A1203 + (3x/y)M when they the process to reduce the critical ignition temp-
are performed in stoichiometric proportions. The erature to less than the local temperature reached
latter reactions yield, in general, composites mainly by particles during a collision event.6
made of r-A1203 and M with nanometre-sized Exchange reactions of the type‘above (MO + R -+
grains. The calculated volumetric fraction of A4 + RO) have been used to produce a variety of
alumina ranges between 48 and 72% according to metal-oxide nanocomposites by MA, such as for
the metal oxide.’ Systems of particular interest are M= (Fe, V, Cr, Mn, Co, Ni, Cu, Zn, Nb, MO, W,
cx-A1203-Fe,Cr,Ni. Alumina-iron composites have Si) and R= (Al, C, Ti, B, Cr, Si).7.24 Some of the
been prepared by the reduction of hematite7$20P25 nanocermets obtained are listed below: OI-A1203-
or of magnetite by aluminium.‘5 In both cases, the (M listed above or alloys such as Fe,Ni,Cr);
composite synthesis takes place in three stages:25 m-A1203-Ti; cx-A1203-Sn; B203-FeeFe2B; Cr@-
(i) incubation period; (ii) high temperature com- FeCr,ii,,; SiOz-Fe; TiO,-W; SiO?-Nb.
bustion during which a non-uniform mixture of
final and intermediate phases, like hercynite
FeA1204, forms;7.‘0 23.15 and (iii) gradual dis- 3 EVALUATION OF PRODUCTION
appearance of transient phases7*“0~23~25 and particle ASPECTS
refinement of the reaction products by grinding.
57Fe Mossbauer spectra clearly reveal that a-Fe The production of nanophase materials in large
dissolves some at% of A1.7,‘oP23They also show quantities and at low costs requires a mill having:
low intensity central components observed after Fe (a) high impact velocities of the grinding balls; (b)
implantation in alumina.26 They are associated high impact frequency for each ball; and (c) easy
partly with Fe’+ in hercynite type environments scale-up of the mill capacity. At least one of
and partly with either Fe3’ , Fe4+ or, more likely, the above criteria is not satisfied in currently,
with iron clusters in CX-A~~O+*~ The experimental commercially available mills. A high-capacity high-
results reported for the mechano-chemical reduc- energy mill (HCM) was therefore developed,27 and
tion of hematite by aluminium in stoichiometric is shown in Figs 1 and 2: it basically consists of a
proportions are consistent with a model involving vial, a system to compensate the inertial forces and
three separate reaction steps.*’ If the redox reaction a driving mechanism.
of magnetite is performed with varying proportions The vial oscillates along the vertical axis through
of aluminium,‘5 transition alumina y-Alz03 is the vials, with frequency in the range 13-20 Hz and
observed to occur. Such transition aluminas are, amplitude of 30 mm. Impact speeds of the balls at
however, transformed into et-Al203 by prolonged 17 Hz frequency are 2.6-3.8 m/s (criterion “a”)
grinding. Alumina-iron nanocomposites may as well and the impact frequency of each ball is close to
be prepared by direct grinding of a mixture of A1203 the movement frequency (criterion “b”).28 A
and of Fe powders. 22 Their Miissbauer spectra also dynamic compensation of inertial forces (becoming
show a central component, as for those composites particularly critical for scaling-up the mill capacity)
synthesized by reactive milling, but with a slightly is provided by 4 +4, counter-acting, pre-loaded
lower intensity. Moreover, iron does not dissolve springs, to fulfill the requirement of criterion “I?.
42 P. Matteazzi et al.

Fig. 2. Steel vial and balls being prepared for milling in the
HCM.

I I

Fig. 1. Section view of the high-energy high-capacity mill

(HCM).

The compensation of inertial forces allows an easy

scale-up of the mill capacity (actually 1 kg of
powders to be processed), by providing: (1) an
increase in the size of the vial; and (2) design of the 20 40 60 60 100 120
2 teta (deg)
spring system to withstand the increased loads.
Experiments were performed to assess the ability Fig. 3. XRD patterns for milled (in the HCM): (a) W and C for
of HCM to perform the synthesis of materials 19 h [WC (Cl); W& (0)]; (b) MO and Si (1:2 atomic) for I8 h
[P-MoS& (0); cr-MoS& (m)]; (c) Si and C for 8.5 h [Sic (A)].
described in Section 2, such as silicon carbide,
tungsten carbide and molybdenum disilicide.
Elemental powder (+ 99%, 3&60 urn, Si in
pieces of some cm) mixtures of Si or MO or W and and E,=N 1/2mbv2 is the kinetic energy (of N
graphite (stoichiometric proportions) were milled balls, travelling with speed v and each having mass
at room temperature in the HCM, using BPR mb>.
20: l-15: 1, 0 25.4 mm carbon steel bails and a In common working conditions (f’= 17 Hz,
charge weight 100-130 g. Powders were introduced BPR = 10-20, t = 10 h and v = 2.6-3.8 m/s, such as
in the vial and sealed under Ar. Silicon carbide (Sic, shown above for the mechanosynthesis of nano-
rhombohedral, JCPDS 22- 1316) and molybdenum phase carbides and silicides), Etot can be evaluated
disilicide (MoSi2, mostly hexagonal B-MoSi2 with a within 20 and 50 kWh/kg. The effective energy
small amount of tetragonal a-MoSi$ are both required (E,-eq), taking into account a restitution
obtained by grinding for less than 10 h and 20 h, coefficient of the impact and the effective impact
respectively. Complete tranformation (Fig. 3) of W frequency and velocity for each ball (lower than f
and C to hexagonal WC (JCPDS 25-1047) was and v), would be about 0.2-0.3 x Etot. Considering,
obtained (with a weak amount of WlC) after 19 h for example, the synthesis of nanophase carbides
milling. After sintering, the presence of WzC was and silicides reported above (requiring BPR = 20,
no longer detected. ball weight =2 kg and R = 25.4 mm, t = 10 h,
To perform an estimation of the processing charge weight 100 g), Eres is less than 5 kWh/kg
costs, it is first necessary to estimate the energy (also in agreement with experimental data on the
required. The maximum specific (per unit weight of electric power absorption of the mill).
powder produced) energy available in the HCM Such an evaluation of energy requirements,
would be given by: E,, = EC2 ft/m = l/2 v22 ft BPR, allows to estimate the transformation cost (energy
where m is the powder mass, f the mill frequency, plus maintenance and consumables of the mill) to
t is the milling time required to complete the produce nanophase materials to be below about
synthesis, BPR is the ball to powder weight ratio, $1 (US) per kg.
Synthesis of nanostructured muterials 43

Table 1. Results obtained in the consolidated (HIP) Fe/Fe& (85 ~01%) and Fe/A1203 (75 ~01%) composites
obtained bv mechanosynthesis
-___
Relative Indentation
HIP cycle density Microhardness Hardness toughness (Kc)
Sample (“C/MPa) (%) (HVo5) (HRA) (MPa fi)
__
Fe/A1203 75 ~01% 1000/200 100 1492 89 6.7
1150/200 100 848 83 No cracks
Fe/Fe& 85 ~01% 950/100 100 950 84.5 6.4
600/150 98 1050 87 4.6

4 PROPERTIES OF CONSOLIDATED cold isostatic pressing (CIP) at 300 MPa of

NANOCERMETS powders) which were encapsulated in low carbon
steel cans.
The properties of fully dense solids were inv- The reaction was almost completed after 2 h
estigated for mechanosynthesized Fe/Al203 and milling, but it was prolonged to 8 h to also com-
Fe/Fe& nanocomposites. Alumina-based cermets plete crystal size refinement. The XRD patterns
have been extensively studied since the 1950~.~~ clearly showed the main phases present to be
The combination of metal and ceramic toughens a-Al203 and iron with crystal sizes of 12 and
the brittle phase (ceramic) by using a ductile phase 15 nm, respectively. Consolidation by UP/HIP
(metal) and should improve the brittleness and (HIP cycles in Table 1, performed by heating and
reliability of ceramics. cooling from temperature in 30 min, and holding
The Fe/Al203 (75 ~01%) nanocomposites were at temperature/pressure for 60 min) gave materials
obtained in the HCM (Section 2.4) using a mixture with slightly increased crystal sizes (below 40 nm
of starting powders (hematite, aluminium and for both the phases, for the HIP cycle at lOOO’C>,
alumina) of 50 g, which were introduced in the vial which, however, remained in the nanoscale range.
together with the grinding balls (2 kg, giving a ball The microstructures obtained in the consolidated
to powder ratio of 40:1), the vial was then sealed, material reveal a high level of intermixing of the
evacuated and filled with Ar.21 The powders were ceramic (alumina, dark zones in Fig. 4) and metal
mixed in stoichiometric proportions (an excess of (white zones in Fig. 4) phases. Table 1 shows that
alumina was used to reach 75 ~01%) according to full densities were obtained even at 1000°C with
the reaction: an interesting combination of hardness and tough-
ness. Such properties can even be compared to, and
Fe203 + 2Al+ O.66AlzO3--$ 1.66AlzO3 + 2Fe (4) are not far from, the more sophisticated Sialon
ceramics3” used as cutting tool materials.
Hot isostatic pressing (HIP) was performed The synthesis of Fe/Fe3C (85 vol%, correspond-
by forming green cylinders (@ 5 x 20 mm, by ing to 5.7 wt% C) composites was performed in the

Fig. 4. SEM image of Fe/A1203 (75 ~01%) nanocermet Fig. 5. SEM image of Fe/Fe3C (85 ~01%) nanocermet HIPed
HIPed at 1050 “C/200 MPa. at 950 “C/100 MPa.
44 P. Matteazzi et al.

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