Professional Documents
Culture Documents
CONTENTS
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1
2. Historical Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2
3. Principles of Milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2
4. Attrition Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4
4.1. SPEX Shaker Mills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4
4.2. Planetary Ball Mills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5
4.3. Attritor Mills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5
4.4. Comparison of Mills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6
5. Milled Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6
5.1. Solid-State Amorphization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7
5.2. Metals, Alloys, and Intermetallics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7
5.3. Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
5.4. Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.5. Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6. Contamination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
7. Characterization of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
8. Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
of strain imparted to particles during the milling pro- Nickel Company (INCO) developed the process around
cess, it is virtually impossible to obtain defect-free crys- 1966. The technique was the result of an intense research
tals via mechanical attrition. As a result, we will adhere effort to produce nickel-based superalloys for gas turbine
to the more general definitions; that is, nanocrystals are applications. Benjamin has summarized the historical ori-
1–10 nm in diameter, and nanoparticles are less than gins of the process and the background work that led to
100 nm in diameter. Thus, it is possible to have both the development of MA [18–20]. To summarize, they pro-
nanocrystalline nanoparticles and coarser particles that duced a nickel-chromium-aluminum-titanium alloy first
contain nanocrystals. Both types of materials produced produced in a small high-speed shaker mill and later in a
by mechanical attrition will be addressed in this chapter. one-gallon stirred ball mill, starting the birth of MA as a
The importance of nanoparticles lies in their inher- method to produce oxide dispersion-strengthened (ODS)
ently large surface-to-volume ratio relative to that of alloys on an industrial scale. The process developed by
larger particles. These high surface areas can potentially Benjamin was initially referred to as “milling/mixing” and
improve catalytic processes and interfacially driven phe- later termed “mechanical alloying” by Ewan C. Mac-
nomena such as wetting and adhesion. Nanoparticles Queen, a patent attorney for INCO. The formation of
have the potential for use in structural and device appli- an amorphous phase by mechanical grinding of a Y-Co
cations in which enhanced mechanical and physical char- intermetallic compound in 1981 [21] and in the Ni-Nb
acteristics are required. As for the internal structure of system by ball milling of blended elemental mixtures
the nanoparticles, it has been found that nanocrystalline in 1983 [22] established MA as a potential nonequilib-
materials have comparative advantages over their micro- rium processing technique. Beginning in the mid-1990s, a
crystalline counterparts in hardness, fracture toughness, number of investigations were carried out to synthesize a
and low temperature ductility [4, 5]. As new methods variety of stable and meta-stable phases, including super-
for surface modification and postattrition processing of saturated solid solutions, crystalline and quasi-crystalline
nanoparticles are developed, the potential applications intermediate phases, and amorphous alloys [23–27]. Since
for them continue to grow. then, mechanical alloying has been applied to virtually all
The early work on the production of nanostructured material classes, including metals, ceramics, and polymers.
materials by mechanical attrition has been reviewed pre-
viously [6–15]. However, significant information contin-
ues to become available in this rapidly evolving field, 3. PRINCIPLES OF MILLING
particularly with regard to the range of material classes The fundamental principle of size reduction in mechan-
to which it is applied. We attempt here to provide an ical attrition devices lies in the energy imparted to
updated review of the subject, as mechanical attrition is the sample during impacts between the milling media.
used to form nanoparticles in new materials such as poly- The impact process is shown in Figure 1. This model
mers [16] and FCC metals [17], and as improvements
in the milling process that optimize the formation of
nanoparticles continue to be made.
2. HISTORICAL PERSPECTIVE
The attrition, or “milling,” of materials has been a major
component of the ceramic processing and powder metal-
lurgy industries for many years. The objectives of milling
include particle size reduction (comminution or grind-
ing); amorphization; particle size growth; shape changing
(flaking); agglomeration; solid-state blending (incomplete
alloying); modifying, changing, or altering properties of
a material (density, flowability, or work hardening); and
mixing or blending of two or more materials or mixed
phases. However, the primary objective of milling is often
purely particle size reduction.
Mechanical attrition began as a way to simultaneously
blend and commute (decrease in size) metal powders in
a process called “mechanical alloying.” Mechanical alloy-
ing (MA) is a powder technique that allows production
Figure 1. Model of impact event at a time of maximum impacting force,
of homogeneous materials from blended elemental pow- showing the formation of a microcompact. Reprinted with permission
der mixtures. John Benjamin and his colleagues at the from [28], E. Kuhn, ASM Handbook, Vol. 7, Materials Park, OH, 1984.
Paul D. Merica Research Laboratory of the International © 1984, ASM.
Nanoparticles from Mechanical Attrition 3
Aluminum 10 7
-Iron 30 21
Copper 16 11
Silicon 16 11
Tungsten 59 41
Titanium carbide (TiC) 45 31
Alumina (Al2 O3 ) 58 40
Magnesia 45 31
Hard rubber (ebonite) 06 04
Polystyrene (atactic) 04 03
Polyethylene (branched) 003 002
Figure 9. Average grain size for Fe powders vs. milling time with differ-
ent mills. Reprinted with permission from [32], I. Borner and J. Eckert, Figure 11. Applicability of various classifications of comminution
Mater. Sci. Eng. A 226–228, 541 (1997). © 1997, Elsevier Science. machines to different material types.
Nanoparticles from Mechanical Attrition 7
5.1. Solid-State Amorphization phase had been formed [35]. Lattice measurements sug-
gested that this FCC crystalline phase is due to the
A solid alloy with a noncrystalline atomic arrangement
increased nitrogen contamination of the milled powder,
is called an amorphous (metallic) alloy. The synthesis of
and the crystalline phase has been identified as TiN.
an amorphous phase in the Ni-Nb system by MA starting
from blended elemental powders of Ni and Nb in 1983
[22] has given rise to increased research activity in this 5.2. Metals, Alloys, and Intermetallics
area. Amorphous phases have been synthesized by MA Metals are routinely milled to the nanoparticle size range,
from blended elemental powder mixtures, pre-alloyed with typical crystallite sizes in the 1–10-nm range. The
powders and/or intermetallics, mixtures of intermetallics, average grain size of a NiAl intermetallic compound was
or mixtures of intermetallics and elemental powders. as low as 5 nm after 100 h of milling [36] and as low as
The effect of process variables on amorphization 4.7 nm for Fe-C alloys milled in a horizontal ball milling
behavior has been studied in several alloy systems. The machine [37].
most important variables that have been studied are Kim et al. [30] studied the effect of fixed and cyclic
milling energy and milling temperature. Increased milling operation on the formation of nanocrystalline Fe-Co
energy, which is achieved by higher ball-to-powder weight alloy powders produced by mechanical alloying in a plan-
ratio and increased speed of rotation, is expected to intro- etary ball mill. The first method was conventional milling
duce more strain and increase the defect concentration with fixed velocity (1300 rpm). The second method
in the powder, thereby leading more readily to amor- involved an operation cycle characterized by a time inter-
phization. On the other hand, higher milling energies can val of 4 min at 1300 rpm followed by 1 min of oper-
also produce more heat, resulting in crystallization of the ation at 900 rpm. In both cases, the milling time was
amorphous phase. A balance between these two effects varied from 1 to 100 h. It is generally known that the
will determine the nature of the final product phase. MA process reaches a steady state where the particles
Eckert et al. [33] reported that in Ni-Zr system milled in have homogeneous size and shape. The steady state was
a planetary ball mill at a low intensity did not produce any achieved after 30 h of milling for fixed operation and
amorphous phase, because of the lack of energy. How- 15 h of milling for a cyclic operation. The advantage of
ever, when the intensity was increased, amorphous phase the cyclic operation is due to the fact that the periodical
formation was observed in a wide composition range of changes of the milling velocity in cyclic operation break
30–83% Ni. At even higher intensities, amorphous phase the balance of deformation, fracture, and welding in the
formation was observed between 66 and 75% Ni. These process and maximize the effect of fracture. The steady-
observations suggest that with increasing milling energy, state crystallite grain size obtained was in the range of
the heat generated is also high, which crystallizes the 10–15 nm. Interestingly, during the first hour of milling
amorphous phases. It appears that the maximum amor- the grain size of Fe-Co increased and then decreased to
phization range is observed at intermediate values of the final 10–15 nm after achieving steady state.
milling intensity; too low an intensity does not provide Raghu et al. [38] studied the differences between
enough energy to amorphize, while at very high intensi- nanocrystalline copper-tungsten alloys milled in argon
ties, the amorphous phase formed would crystallize. and air. They determined that the particle size initially
There have been conflicting results on the effect of decreases and then increases in powders milled in air
milling temperature on the nature of the phase formed. (Fig. 12). The crystallite sizes of copper and tungsten
Koch et al. [34] summarized the results of varying the decrease continuously with milling time in all milling
temperature of the mill on the kinetics of amorphization atmospheres (Fig. 13). Crystallite size levels off at a value
in intermetallics. They concluded that generally a lower of 10 nm for copper and 15 nm for tungsten after 8 h of
milling temperature accelerated the amorphization pro- milling. It was concluded that whereas fracture is dom-
cess. Since a nanostructured material can easily be pro- inant in milling in argon, adequate welding for the MA
duced at lower milling temperatures, the increased grain process appears to be available during milling in air.
boundary area drives the crystal-to-amorphous transfor- Eckert and Borner [36] studied nanostructure forma-
mation. For example, the time required for amorphiza- tion of ball-milled NiAl intermetallic compounds in a
tion in NiTi was 2 h at −190 C, 13 h at 60 C, and 18 h planetary ball mill with hardened steel balls and vial at a
at 220 C [34]. rotation speed of 180 rpm. Figure 14 illustrates that the
Mechanical alloying introduces contamination into the average grain size and the rms strain scale with composi-
milled powder and thus alters the constitution and stabil- tion of the material. Whereas the grain size is reduced to
ity of powder products. Generally, the presence of addi- only 12 nm for Ni46 Al54 , it decreased to about 5 nm for
tional elements favors amorphization. Contamination has Ni-rich compounds. Blending Ni46 Al54 with elemental Ni
also been found to affect the stability of the amorphous to give an overall composition of Ni50 Al50 and subsequent
phases formed. Formation of a crystalline phase has been mechanical alloying reduced the grain size from 12 nm
reported on milling of Ti-Al powders after an amorphous after 100 h to about 9 nm after 300 h of total milling time
8 De Castro and Mitchell
Figure 14. Average grain size (filled symbols) and atomic-level strain
Figure 12. Particle size of Cu-5vol%W powders milled in different (open symbols) for Nix Al100−x powders after 100 h of milling as a func-
atmospheres. Reprinted with permission from [38], T. Raghu et al., tion of composition. Reprinted with permission from [36], J. Eckert and
Mater. Sci. Eng. A 304–306, 438 (2001). © 2001, Elsevier Science. I. Borner, Mater. Sci. Eng. A 239–240, 619 (1997). © 1997, Elsevier
Science.
(Fig. 15). On the other hand, the grain size of 100-h ball-
milled Ni60 Al40 increased upon blending with elemental
Al and further mechanical alloying. This demonstrates
that the ultimate grain size is coupled with the com-
position of the material. Table 3 summarizes grain size
results obtained by milling different metals, alloys, and
intermetallics.
Figure 15. Average grain size obtained for Ni56 Al54 and Ni60 Al40 pow-
ders after 100 h of ball milling and after addition of elemental Ni or
Al and subsequent mechanical alloying as a function of total milling
time. For comparison the average grain size for Ni50 Al50 obtained after
100 h of continuous ball milling is also shown. Reprinted with permis-
sion from [36], J. Eckert and I. Borner, Mater. Sci. Eng. A 239–240, 619
(1997). © 1997, Elsevier Science.
Table 3. Typical grain sizes for metals, alloys, and intermetallics for
MA.
Milling Milling
Composition technique Grain size (nm) time (h) Reference
5.3. Ceramics
Recent studies show that highly exothermic reactions, for
example, the formation of TiC [39], can be initiated by
high-energy ball milling. This process is referred to as
a mechanically induced self-propagating reaction (MSR).
In the studies of Xinkun et al. [39], raw powders of Ti
and C were mixed in a mole ratio of 1:1 and milled.
TiC particles with 20-nm crystallites were fabricated just
after reaction at 120 min. It took 10 to 20 h for the Ti
and C powders to react completely. The reaction of Ti
and C powders was investigated by measuring the tem-
perature of the vial outer wall. Figure 16 shows the rela-
tion between the temperature of the outer wall and the
milling time and indicates that the temperature of the vial
increased slowly as the milling time was extended. When
Figure 17. Lattice parameter as a function of MA time for 70wt%
the milling time reached 115 min, the temperature of the TiC + 30wt% TiN as determined from XRD patterns. Reprinted with
vial increased abruptly and reached its maximum (from permission from [41], S. Zhang and S. C. Tam, J. Mater. Processing 67,
319 to 332 K). The temperature peak was associated with 12, (1997). © 1997, Elsevier Science.
the exothermic reaction of Ti and C. After the peak, the
vial temperature decreased gradually during subsequent lattice parameter with MA time is almost the same for
milling. the two compositions; this shows that in MA, the reac-
Traditionally, the raw materials used in mechanical tion rate is independent of the “concentration” of the
alloying include at least one ductile material used as a “reactant” as long as the latter is not depleted, which
host or binder for the other ingredients. However, Davis is different from a chemical reaction, where the reac-
and Koch [40] mechanically alloyed a brittle Si-Ge sys- tion rate is proportional to the concentration of reac-
tem to obtain a solid solution Si(Ge) and observed a lat- tants. The reduction of crystallite size was very rapid in
tice change with the increased duration of MA. Recently, the beginning, and after 40 h it was in the range of 20–
Zhang and Tam [41] studied the mechanical alloying of 30 nm (Fig. 18). In the studies of Indris et al. [42], the
an all-ceramic-phase component, TiC + TiN. Two com- system 1 − x
Li2 O:xB2 O3 reacts either at high temper-
positions were explored, 70% TiC + 30% TiN and 50% atures or because of mechanochemical treatment. Indris
TiC + 50% TiN (by weight). MA was conducted for up determined that the reaction product is not determined
to 80 h in a Fritsch planetary ball mill at a ball-to-powder by the overall composition of the mixture, but by the con-
ratio of 20:1. Figure 17 shows a plot of the lattice param- ditions at the particle interfaces.
eter as a function of milling time for 70% TiC + 30% Indris et al. [42] also studied the oxide ceramics Li2 O,
TiN milled with steel balls. A similar plot was obtained LiNbO3 , LiBO2 , B2 O3 , and TiO3 as monophase materi-
for 50% TiC + 50% TiN milled with WC balls. The two als. Nanostructures of these oxides were prepared in a
compositions show a similar trend in lattice parameter
change, irrespective of milling media, and therefore it is
indicated that solid solutions occur during the MA pro-
cess. It was also determined that the rate of change of the
5.4. Composites
Mechanical alloying (MA) has been successfully used to
synthesize a number of commercially important alloys
and composites [46–51]. The mechanically alloyed pow-
ders have attributes such as fine powder size and flexi-
bility of alloying choices. In particular, MA has unique
advantages in producing metal matrix composite pow-
ders. The low-temperature solid-state process eliminates
reactions between the reinforcement particles and the
matrix. It is commonly known that for particulate rein-
forcement of metal matrix composites, the mechanical
Figure 20. Evolution of Mg-Ti-C nanocomposite during milling and
properties are influenced significantly by the quantity and after heat treatment. Reprinted with permission from [54], S. Hwang
the distribution mode of the reinforcements and by the and C. Nishimura, Scripta Mater. 44, 2457 (2001). © 2001 Elsevier
nature of the interfaces between the reinforcements and Science.
Nanoparticles from Mechanical Attrition 11
Figure 21. Average grain size of MmM5 phase in MmM5 -Mg composite
prepared by 20 h of milling as a function of Mg content. Reprinted
with permission from [58], M. Zhu et al., Mater. Sci. Eng. A 286, 130
(2000). © 2000, Elsevier Science.
6. CONTAMINATION
A major concern in the processing of nanoparticles by
MA is the nature and amount of impurities that contam-
inate the milled powder. Contamination can arise from
several sources, including
• impurities in starting powders, Figure 25. Contamination of aluminum powders milled in stainless
• vials and grinding media, steel vials.
• milling atmosphere, and
• control agents added to the powders. contamination is reported as the sum of the atomic per-
centages of Fe, V, and Cr, as determined from X-ray flu-
During MA the powder particles become trapped
orescence (XRF). Vanadium and chromium are common
between the grinding medium and undergo severe plastic
alloying elements in stainless steel. For milling in WC,
deformation; fresh surfaces are created because of the
contamination is reported as percentage WC as deter-
fracture of the powder particles. Collisions occur between
mined by XRF. As can be seen, contamination increases
the grinding medium and the vial and among the grinding
dramatically with milling time, especially in the WC vial.
balls. All of these effects can cause deterioration of the
The objective of current studies is to reduce the contam-
grinding medium and vial, resulting in the incorporation
ination caused by the milling media/vials and at the same
of these impurities into the powder. The extent of con-
time retain, or further reduce in size, the desired nanos-
tamination increases with increasing milling energy and tructure of the powders.
milling time.
Various attempts have been made to minimize powder
contamination during MA. One way of minimizing the 7. CHARACTERIZATION OF NANOPARTICLES
contamination from the grinding medium and the con- The powders obtained after MA must be characterized
tainer is to use a material for the container and grinding for their size, shape, surface area, phase constitution,
medium that is the same as the powder being milled. and microstructural features. Additionally, one could also
For example, one could use copper milling balls and a characterize the transformation behavior of the mechan-
copper vial for milling copper and copper alloy powders. ically alloyed powders in annealing and other treatments.
However, milling effectiveness may be limited in such The measurement of crystallite size and lattice strain in
cases. In general, to minimize contamination from the mechanically alloyed powders is very important, since the
container and grinding medium, the container and grind- phase constitution and transformation appear to be crit-
ing medium should be harder/stronger than the powder ically dependent upon them. We attempt here to give a
being milled. Nonetheless, contamination is difficult to very brief overview of the common techniques used to
completely avoid in MA. determine both particle and crystallite size, in an attempt
The problem of milling atmosphere is serious and has to help differentiate between nanocrystals and nanopar-
been found to be a major cause of contamination. It has ticles, both of which can result from mechanical attrition.
been observed that if the container is not properly sealed,
the atmosphere surrounding the container, usually air,
leaks into the container and contaminates the powder.
This is particularly problematic for oxidation-sensitive
materials, such as pure metals. De Castro and Mitchell
studied contamination caused by high-energy milling with
a SPEX 8000 mixer/mill [73]. Aluminum with a purity of
99.9% or better and an initial particle size in the range
of 50–100 m was milled in stainless steel and tungsten
carbide vials with milling media of the same composition
as the vial. A ball-to-powder ratio of 10:1 was used in all
cases. Ethanol was added as surfactant during milling and
subsequently removed. Figures 25 and 26 show contami-
nation as a function of milling time in stainless steel and Figure 26. Contamination of aluminum powders milled in tungsten car-
tungsten carbide, respectively. For the stainless steel vials, bide vials.
14 De Castro and Mitchell
Those wishing to obtain more detailed information on which reach minimum values at extended milling times.
these well-established analytical techniques are directed The distinction between nanoparticles and nanocrystals
to their respective literature sources. in the current MA literature is not clear. Grain sizes, as
The crystalline size or grain size in nanoparticles can determined with standard X-ray diffraction techniques,
be determined with several techniques that rely upon the are typically reported as a function of milling time; how-
peak width in X-ray diffraction patterns. In the Hall– ever, the actual particle sizes that result from milling,
Williamson method [74, 75], crystalline size, D, is given while assumed to be larger than the reported grain sizes
by for polycrystalline materials, often go unreported. More-
over, what are often reported as nanocrystals may not be
094 such in the technical definition of the term (<10-nm grain
cos = 2 sin + (3)
D size), especially for polymeric materials, where grain
where
is the peak full width at half-maximum sizes in excess of 100 nm are still being obtained. Par-
(FWHM), is the diffraction angle, is the wavelength ticle agglomeration, where nanoparticles stick together
of the X-ray, and is the effective strain associated with because of attractive forces, is also a serious issue at long
mechanical alloying and ultrafine grain size. The crys- milling times. Finally, contamination from milling media
talline size D can be obtained by extrapolating sin to (e.g., stainless steel vials and balls) is a serious problem
zero to eliminate the strain term. that has not yet been thoroughly investigated. Despite
The most widely used equation to determine grain size these difficulties, MA is more widely used than ever and
from XRD data is the Scherrer equation, continues to be applied to the formation of nanoparti-
cles and nanocrystalline structures in an ever-increasing
K variety of metals, ceramics, and polymers.
Lo = (4)
cos
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