Accepted Manuscript

Synthesis of onion-like carbon-reinforced AlCuFe quasicrystals by high-energy ball

milling
C. Patio-Carachure, J.E. Flores-Chan, A. Flores Gil, G. Rosas
PII:

S0925-8388(16)33024-9

DOI:

10.1016/j.jallcom.2016.09.261

Reference:

JALCOM 39095

To appear in:

Journal of Alloys and Compounds

Received Date: 11 August 2016

Revised Date:

22 September 2016

Accepted Date: 23 September 2016

Please cite this article as: C. Patio-Carachure, J.E. Flores-Chan, A. Flores Gil, G. Rosas, Synthesis
of onion-like carbon-reinforced AlCuFe quasicrystals by high-energy ball milling, Journal of Alloys and
Compounds (2016), doi: 10.1016/j.jallcom.2016.09.261.
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ACCEPTED MANUSCRIPT

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Synthesis of onion-like carbon-reinforced AlCuFe quasicrystals by high-energy ball milling

C. Patio-Carachure1, J. E. Flores-Chan1, A. Flores Gil1, G. Rosas2
Facultad de Ingeniera, Universidad Autnoma del Carmen, Campus III, Av. Central S/N,

C.P. 24115 MSNH, Ciudad del Carmen, Campeche, Mxico.

2

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Instituto de Investigacin en Metalurgia y Materiales, UMSNH, C.P. 58000, Morelia,

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Mich. Mxico

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Abstract

High-energy ball milling of a hexagonal carbon and AlCuFe pure quasicrystal (QC) powder
mixture was performed to prepare a nanocomposite material. The structure and morphology
of as-milled powders were investigated using X-ray diffraction (XRD), Raman
spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy

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(TEM). XRD results revealed that, with increasing milling time, the peaks of the
quasicrystalline phase become broader, whereas the peaks of the hexagonal carbon phase
gradually disappeared, indicating the nanostructured nature of the sample. The Raman

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spectra observations revealed the presence of nanocrystalline carbon particles used as

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reinforcements in the composite. TEM results confirm that the high-energy ball milling
method led to the formation of a nano-quasicrystalline material with highly deformed
onion-like carbon (OLC) particles in a relatively short period of milling time. In the SEM
analysis, it was found that the powder particles are refined during the milling process.
However, it was observed by TEM that the particle size of the QC is clearly larger than the
OLC particles, indicating the ability to obtain good dispersion and homogeneity of the
reinforcement. The OLC particles have diameters ranging from 4 to 12 nm, and the number

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of graphite layers varies from 8 to 22. High-resolution TEM images show that the asprepared OLC shows an intershell spacing around 0.33 nm, which corresponds to the (002)
crystallographic planes of hexagonal graphite. The obtained OLC can be used as

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reinforcement in the QC matrix to get a product with high hardness and wear resistance.

Keywords: Quasicrystals; Composite materials; Mechanical alloying; Microstructure;

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Trasmission electron microscopy

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1. Introduction

In the last decades, onion-like carbon (OLC) has attracted the considerable attention of
many researchers due to their unique chemical and physical properties. They are described

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as quasi-spherical, multiple-concentric graphitic shells consisting of fullerene-like carbon

layers [1]. The OLC is another important nanostructure of the allotropic carbon formed
with sp2 hybridization [2]. This nanostructure has some interesting potential applications in

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areas such as lubrication, biomedicine, catalysis, electrochemical energy storage, water

treatment, and others [3-9]. Different physical and chemical methods and combinations of

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these have been employed successfully for the preparation of OLC and include electronbeam irradiation, chemical vapor deposition, arc discharge, and thermal annealing of
nanodiamond [1, 9-16]. Most of these methods are complex and produce small quantities of
OLC. The process of mechanical milling has also been employed to generate curved
graphene sheets and spherical nanoparticles with a small inner space [17-19]. Due to its low
cost and simplicity, high-energy ball milling is a good alternative for producing
nanocrystals and nanocomposites materials. On the other hand, quasicrystals (QCs) with a

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novel atomic ordered structure are composed of transition metals such as the Al-Cu-Fe
system. Furthermore, the crystals are quasiperiodic and have forbidden rotational symmetry
according to the conventional crystallography [20]. QCs are brittle materials with structural

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similarities of the intermetallic compounds. One of the forbidden rotational symmetries that
they pose is a five-fold axis, similar to the icosahedra. Establishing the quasiperiodic

atomic structure is a complex task. However, a step forward in this fascinating field was to

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consider QCs as atomic clusters [21-22]. Therefore, each cluster has its atomic structural
arrangement. Some clusters may have a similar atomic structure according to the elements'

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participation and the binding energy. The structure of the OLC formed by fullerenes with a
five-fold symmetry (icosahedral) has, in some way, likened to the quasicrystalline materials
[23]. Carbon onions have unusual physical properties that could be acting as reinforcing
material to improve a quasicrystalline matrix. OLC dispersed in QCs' phase (hard) combine

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the abrasive nature of both materials, Herein, we report a high-energy ball milling method
for the synthesis of onion-like carbon/AlCuFe quasicrystalline nanocomposite. The novel
process involves the mechanical milling of carbon with the Al-Cu-Fe icosahedral pure

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phase.

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2. Experimental

Graphite powders with 99.9% purity were used as starting materials for the carbon onions
preparation. An AlCuFe quasicrystalline (QC) alloy ingot was prepared using a method
described previously [24]. The alloy was prepared in the air with a nominal composition of
Al64Cu24Fe12 at % and then solidified at room temperature. Subsequently, the as-cast ingot
was annealed at 700 C for 96 hours under an argon atmosphere to obtain pure i-phase. The

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icosahedral QC phase is a brittle material and tends to fracture during the milling process.
Furthermore, the AlCuFe quasicrystalline alloys, like other materials of an intermetallic
character, suffer environmental hydrogen embrittlement, as reported in the past [25]. In this

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process, water in the air reacts with the aluminum in the alloy to form an Al2O3 layer. At
the same time, monoatomic hydrogen releases provoke cleavage fracture of the material; in
some cases, the entire alloy ingot transforms into a fine powder in a few days. We worked

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precisely on these finer quasicrystalline QC particles of the Al-Cu-Fe. Both the QC pure

phase and graphite material were blended in a weight ratio of 1:1 and then subjected to the

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high-energy ball milling without atmosphere control. The process was performed in a
SPEX 8000 mixer mill for 1.5h, 3h, 6h, and 10h periods of time. Hard steel vials and balls
were used as milling media, with a ball-to-powder weight ratio equal to 7:1. The size of the
grinding medium was 12.7 mm in diameter. The structure of the ball-milled powders was

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examined by X-ray diffraction (XRD) on a Bruker D8 Advanced (DAVINCI design)

diffractometer using CuK radiation. Raman spectra were obtained with an Ocean Optics
Raman spectroscopy (Model- QE65000), with a 785nm laser and spectral resolution of 1.52

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cm-1, covering the spectral range of 02100cm1. Transmission electron microscopy was

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performed in a Phillips Tecnai F20 microscope operated at 200KeV.

3. Results and Discussion

Fig. 1a shows the XRD pattern of the starting as-cast QC alloy after their heat treatment at
700 C, indicating a pure quasicrystalline phase as starting material. Figure 1b shows the
powder mixture before bal-milling corresponding to the pure QC and the commercial
carbon. The high-intensity diffraction peak at 2 = 26.1 can be assigned to the (002)

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crystallographic planes of the hexagonal graphite. All the other diffraction peaks with low
intensities can be listed as diffraction peaks of the AlCuFe icosahedral phase. Fig. 1b-f
shows the XRD patterns of the two components, milled at different times from 1.5-10 h.

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With increased milling time, the XRD peaks of the cubic and QC phases become broader,
and the peak intensities decrease, indicating small crystallite sizes and an increase in

Figure 1

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internal strain.

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For 10h milling, it is observed that the peaks related to carbon material disappear,

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suggesting their tendency toward amorphization, whereas the XRD peaks of the QC phase
tend to transform into the crystalline -Al(Cu, Fe) cubic phase [24]. The XRD results
indicate the mechanical mixing between the primary constituents, as well as the
nanostructured nature of the composite. The G-peak (graphite) comes from the stretching
vibration of sp2 bonded carbon atoms in the basal plane of hexagonal graphite. The D-peak
(disordered) is related to the dangling bonds for the in-plane terminations of disordered
graphite [26]. The broadening of the D-peak suggested the presence of low-crystalline

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carbon from defects generated by mechanical attrition, causing disordered carbon layers.
Also, there are significant variations in the relative intensities of the D and G peaks with

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particles used as reinforcement in the composite.

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milling time. Thus, the Raman spectra also revealed the presence of nanocrystalline carbon

Figure 2

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Fig. 3a shows the scanning electron microscopy (SEM) image of unmilled powders
illustrating carbon particles irregular in shape in comparison to the alloyed powders. Figure
3b-c shows the corresponding EDS mapping images from C-signal monitoring as a

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function of milling time. The gradual reduction of the particle size and the homogeneous

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distribution of the elements are observed as a function of milling time.

Figure 3

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To complement the structural characterization of the as-milled material, a TEM analysis of

the powders was performed. Fig. 4a shows a bright-field TEM micrograph of the
quasicrystalline (QC) alloy, as well as carbon particles prepared after 10 hours of high-

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energy ball milling. The microstructure obtained through the milled powders reveals larger
QC particles (< 400 nm), irregular in shape, in contact with well-distributed small OLC
particles (~10 nm). The TEM pictures give an idea of the amount of carbon particles

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obtained after a relatively short milling time. The marked differences in the particle size of
both types of phases ensure the ability to get good dispersion and homogeneity in the

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reinforcement material.

Fig. 4b shows an HRTEM image, and its corresponding FFT pattern, of the large particles
(QC), which is illustrated in Fig. 4a. One can recognize the five-fold zone axis of the
typical quasiperiodic lattice, showing the icosahedral quasicrystalline nature of the

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powders. By the other side, Figure 4c shows high-magnification TEM images of the
smaller carbon particles that indicate the presence of onion-like carbon (OLC) particles.
From the HRTEM images shown in Figure 4d, concentric graphite layers typical in OLC

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nanomaterials, are observed. It is found that the lattice planes, with an interlayer spacing of
around 0.33 nm, coincide with the lattice spacing of (002) crystallographic planes of

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hexagonal graphite. The OLC particles exhibit a highly deformed structure embedded in
amorphous carbon material residue. It is important to point out that for samples milled for
shorter times (< 10h), onion-like particles, with greater particle size and not a close-packed
structure, were observed by TEM.

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Figure 4

Figure 5a-d shows respectively a series of HRTEM images that reveal, precisely, a very

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highly deformed structure of OLC particles. It can clearly be seen that the diameter of the
OLC particles varies in size from 4 nm to 8 nm. Relatively small particles are formed by
about eight concentric shells while the larger particles are composed of 22 concentric

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shells. It is well-known that the mechanical milling process can induce high plastic

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deformation in the powder particles, which indicates that there exist a significant number of
crystalline defects. Thus, it is not a surprise that the materials obtained here have high
crystallographic plane deformation. Past investigations have synthesized deformed OLC,
which contains various planar defects [27-28]. Also, annealing treatments have commonly
been employed to improve the crystalline nature of the carbon onions. The particle size
refinement and the formation of the OLC could also be affected by the mechanical milling
process conducted without atmosphere control (in the air atmosphere).

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Figure 5

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It is well-known that carbon reacts with oxygen very spontaneously at relatively low

temperatures. However, in the case of nanomaterials, carbon is chemically active enough to

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be slightly reactive in the air at room temperature. Hence, more carbon vacancies could be
produced that enhance the curved structure nature of nano-carbon and provoke a greater
crystal size reduction. On the other hand, past investigations [17-19] performed using the
ball milling technique of pure carbon have not determined carbon onions' closed packed

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shapes. In the present work, it is clearly noted that the QC phase presence in the highenergy ball milling of pure carbon influenced the formation of carbon onions after
relatively short milling times (10h). Thus, the procedure to obtain carbon onions in here

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seems to be technically facile and low-cost to produce larger amounts of these

nanostructures after a simple sedimentation method. We also think that one of the following

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aspects was able to control the formation of the onion phase. First, the QC nanostructure
symmetry assisting the carbon nanostructures formation may be acting as the atomic model.
Second, the transition metal clusters applied as a metal catalyst supporting the onion
structure.

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4. Conclusions

In this paper, we have successfully synthesized onion-like carbon-AlCuFe quasicrystal

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nanocomposite by a high-energy ball milling of carbon and pure icosahedral QC. XRD and
TEM analysis shows the coexistence of OLC QCs individual phases with an entirely
different size dimensions. HRTEM observations show carbon onions with diameters

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ranging from 4 to 12 nm, and the number of graphite layers varied in 8 of 22. This method
produces highly deformed carbon nanoparticles with many planar defects observed by

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TEM. We attribute the rapid formation of carbon onions to the presence of the QC phase,
which is, in some way, structurally similar to the fullerenes. Also, the milling process
conducted without atmosphere control influenced the carbon nanoparticles' formation.

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Figure Captions

Figure 1 XRD patterns of the powders after high-energy ball milling for different times.

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Figure 2 Raman spectra of OLC after high-energy ball milling for various times.

Figure 3 (a) SEM image of the starting materials. (b)-(d) Their corresponding EDS carbon
maps for 0h, 6h, and 10h of milling time, respectively.

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Figure 4 (a) TEM image of the OLC-AlCuFe quasicrystal nanocomposite after 10h highenergy ball milling. (b) HRTEM image of the quasicrystalline phase. (c-d) HRTEM images

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of the OLC particles at different magnifications.

Figure 5 HRTEM images of highly deformed carbon nano-onions with several planar

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defects. The TEM images illustrate that the OLC particle size varies from 4 to 12nm.

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Highlights

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AlCuFe quasicrystalline and graphite carbon are processed by high-energy ball

milling
This method produces an OLC/AlCuFe quasicrystalline nanocomposite
The nanocomposite is obtained after a relatively short milling time (10 h)
Carbon nanostructures have diameters ranging from 4 to 12 nm
Highly deformed OLC closed-packed particles are obtained

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