The use of polymeric milling media in the reduction of

contamination during mechanical attrition

Claudio L. De Castro
Department of Chemical Engineering, Tulane University, New Orleans, Louisiana 70118
Brian S. Mitchell
a)
Department of Chemical Engineering, Tulane Institute for Macromolecular Engineering and Science,
Tulane University, New Orleans, Louisiana 70118
(Received 30 August 2002; accepted 16 September 2002)
Aluminum samples were milled in a high-energy ball mill at times ranging from
10 to 500 min in stainless vial/media and nylon vial/media. The crystallite size of
aluminum milled in the stainless steel setup reached a plateau at 25 nm around
100 min, whereas the crystallite size of aluminum milled in the nylon setup reached
the same plateau at 500 min. Contamination studies were conducted using x-ray
fluorescence, hydrogencarbonnitrogen analysis, and thermogravimetric analysis.
Although organic contamination due to the nylon milling media was high at 12 wt%
when milled for 500 min, it is shown that the contaminant could be easily removed
by thermal treatment.
Nanoparticles from the so-called high-energy ball
milling form of mechanical attrition are excellent can-
didates for composite precursors due to their inherently
high surface-to-volume ratio and the relatively broad ap-
plicability of ball milling to a variety of materials classes.
In a recent article,
1
the use of high-energy ball milling in
the formation of metallic, ceramic, and polymeric par-
ticles is described, wherein both nanoparticles (particles
with average diameters less than 100 nm) and nanocrys-
talline microparticles (average crystallite sizes of less
than 10 nm) are discussed. A number of other articles
describe the mechanics behind the process of mechanical
attrition that lead to particle commutation.
2,3
In the sim-
plest case, the energy imparted from the milling media,
which are typically hardened metal or ceramic spheres, to
the powder during spheresphere or spherecontainer
wall impacts causes fracture in the powder. Over time,
often hours or even days, a minimum plateau in particle
size and/or crystallite size is achieved.
Although the basic principles of ball milling are seem-
ingly well-described and the technique is gaining wider
use, few systematic studies have been performed on con-
tamination introduced into the milled powders, herein
referred to generically as nanoparticles. Spheresphere
and spherevial impacts inevitably lead to some commu-
tation of the milling media and vials. In addition, signifi-
cant atomic diffusion can occur in some systems as a
result of the prolonged, intimate contact between the
nanoparticles and milling media, particularly as heat is
generated during milling. Aside from being ill-defined,
the problem of contamination is exacerbated by the dif-
ficulty of postmilling removal from the nanoparticles.
Milling media are often selected on the basis of their high
hardness, e.g., WC or SiC, or their chemical inertness,
e.g., hardened stainless steel. Unfortunately, these two
attributes result in high melting point and/or chemically
stable contaminants that are difficult to remove. De-
scribed here is an attempt to further quantify the con-
tamination effects that result from milling in a common
medium, namely, stainless steel, and a method for reduc-
ing contaminants or at least introducing contaminants
that are more easily removed.
Commercially available aluminum (Fisher Scientific,
Hampton, NH) was milled in a grade 440-C stain-
less steel vial with the same grade of stainless steel mill-
ing media for up to 120 min in a SPEX model 8000D
(Metuchen, NJ) high-energy ball mill. The temper-
ature was maintained at 0 C by placing the unit in a
temperature-controlled laboratory refrigerator. Simi-
larly, the aluminum powder was milled in a nylon vial
with nylon-coated stainless steel spheres for up to
500 min in the same SPEX ball mill. Nylon was selected
due to its availability in large diameter stock sizes for the
machining of vials and the availability of coated milling
a)
Address all correspondence to this author.
J. Mater. Res., Vol. 17, No. 12, Dec 2002 2002 Materials Research Society 2997
media. Other polymeric milling media, such as poly-
urethane, are also available commercially. In all milling
studies, a ball/powder ratio of 10:1 was used, and two
drops of ethanol were employed as a dispersant. The
powders were removed from the milling apparatus,
dried for 30 min at 180 C, and then analyzed for crys-
tallite size and composition using a Scintag XDS2000
(Ecublins, Switzerland) x-ray diffractometer and Siemens
SRS 200 (Munich, Germany) x-ray fluorescence spectrom-
eter, respectively. Particle sizes were estimated using both
BrunauerEmmettTeller analysis (BET) surface area
determinations and transmission electron microscopy
(TEM) observations. Thermogravimetric analysis (TGA)
was performed using ceramic pans in a nitrogen atmosphere
in a TA Instruments 2960 (New Castle, DE) simultaneous
differential scanning calorimeter/thermogravimetric ana-
lyzer. Although heated in flowing nitrogen, traces of
oxygen may still be present in the TGA analysis. A heat-
ing rate of 10 C/min was used. Hydrogencarbon
nitrogen (HCN) analysis was performed on a Fisons
EA1108 (Waltham, MA) elemental analyzer.
Figure 1 shows the relationship between crystallite
size and milling time for the milled aluminum. In both
cases (milling in nylon and stainless steel), the limiting
crystallite size of 25 nm that is common to this material
is achieved.
4
However, the crystallite size of the samples
milled with the nylon setup reach this plateau around
500 min, which is longer than the roughly 100 min the
stainless steel setup requires. In both instances, a mean
particle size of approximately 300 nm was obtained at
the longest milling times, as determined from BET and
TEM analysis, although the particles were distinctly non-
spherical as observed by TEM.
Figure 2 shows metal contamination introduced due to
milling with stainless steel and nylon. It is evident that by
milling with a nylon vial and media no metal is intro-
duced into the samples. The trace metal contamination
weight percent remains the same for the nylon setup
whereas it increases dramatically for the stainless steel
setup. However, organic contamination is observed when
nylon is used as a vial/milling media as shown in Fig. 3.
Here, the analyses of the milled powder using TGA
(% weight loss) and HCN analysis provide essentially the
same information (HCN provides consistently lower con-
tamination amounts due to its limitation to only three
elements) regarding the level of contamination via an
organic species, which is presumed to be nylon from the
milling media.
Despite a higher level of contamination (in terms of
weight %) due to the introduction of nylon in the milled
samples relative to the introduction of metal contami-
nants in the stainless-steel-milled samples, we note that
the polymeric contaminant can be easily removed by heat
treating the sample to a temperature below the melting
point of aluminum. Figure 4 shows that nylon and mois-
ture can be removed from the sample by heating it to
about 440 C. The weight loss indicated in Fig. 4 and
those reported in Fig. 3 from TGA analysis are deter-
mined after accounting for the initial weight loss due to
moisture. It should be noted that the weight gain after
removal of the organic constituents above 500 C is at-
tributable to oxidation due to trace quantities of oxygen
in the flowing nitrogen stream. In addition to removal by
thermal, oxidative means, nylon, and other polymeric
contaminants, can in principle be removed by use of an
FIG. 1. Crystallite size of milled aluminum.
FIG. 2. Metal contamination in milled aluminum samples.
FIG. 3. Contamination in aluminum milled in nylon vial and media.
Rapid Communications
J. Mater. Res., Vol. 17, No. 12, Dec 2002 2998
appropriate solvent. These methods of contaminant re-
moval represent a tremendous advantage over other mill-
ing media such as stainless steel, which is difficult to
remove from as-milled powders.
In summary, polymeric media can be used in mechani-
cal milling to produce nanocrystalline structures. The
mechanism by which seemingly soft materials like ny-
lon can lead to particle size commutation in harder ma-
terials such as aluminum is currently under investigation.
Despite the fact that it adds considerably higher contami-
nation to the milled powders than traditional metal or
ceramic media do, nylon can be easily removed by ther-
mal treatment, therefore producing a powder free of mill-
ing media contaminants.
REFERENCES
1. C.L. De Castro and B.S. Mitchell, in Synthesis, Functionalization
and Surface Treatment of Nanoparticles, edited by M.I. Baraton
(American Scientific Publishers, Los Angeles, CA, 2002), p. 1.
2. C.C. Koch, Nanostruct. Mater. 2, 109129 (1993).
3. E. Kuhn, in Powder Metallurgy (ASM, Materials Park, OH, 1984),
p. 5670.
4. Y.D. Kim, J.Y. Chung, J. Kim, and H. Jeon, Mater. Sci. Eng. A
291, 17 (2002).
FIG. 4. Nylon weight percent loss versus temperature for sample
milled for 500 min in nylon.
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J. Mater. Res., Vol. 17, No. 12, Dec 2002 2999