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Abstract
Recycling of aluminum-based scrap (Al alloy scrap and Al alloy matrix SiC composite
scrap) via electrolysis in ionic liquids at low temperatures was investigated. In this
process impure aluminum scrap was electrochemically dissolved at the anode and pure
aluminum was deposited on the cathode. X-ray diffraction, emission spectrometer, and
atomic absorption analyzer were used to characterize both the impure material and the Al
deposit. The electrorefining process yielded current density in the range of 300-600 A/m2
and current efficiency of about 99%. Results indicated that impurities such as Si, Cu, Zn,
Fe, Mg, Cr, Ni, Mn, Pb, and SiC particles were removed as anode residue. Low energy
consumption and no pollutant emissions are the two main advantages of this process
compared to the present industrial process.
Aluminum is the most widely used non-ferrous metal in a variety of fields. The
application of aluminum in automotive and structural components is constantly growing
and increasingly more aluminum is recycled every year. Aluminum products can be
recycled without the loss of the quality of properties. Aluminum recycling requires 5% of
the energy required for its production from bauxite ore [1]. Aluminum and aluminum
alloys are used in wide range of automotive parts because of their lightweight, high
strength and corrosion resistance property. Aluminum metal matrix composites are
extensively applied in defense and aerospace industries, because of their superior
properties to traditional materials
One problem frequently encountered with aluminum scrap is its high impurity content,
which makes economical recycling of aluminum strongly dependent on aluminum
refining technology. Aluminum beverage cans can be recycled after effective
classification, but many other recycled aluminum scraps have to be involved with high
temperature purification processes, which usually result in high-energy consumption and
pollutant emissions. Aluminum recovery from impure and mixed scrap is performed
using furnace for scrap melting, the unmelted metals such as iron can be removed by
raking. The refined aluminum obtained can be used to make aluminum-copper or
aluminum-silicon alloys or used as deoxidant in steel making industries. In this process,
although some high melting impurities can be removed, the refined aluminum has
undesirable components, limiting its applications and value. A process for producing
higher-value wrought products from the secondary or recycled aluminum is in progress
using a thermochemical technique.
The aluminum metal matrix composites with SiC reinforcements are used in aerospace
industry and in commercial applications such as brake rotor disks, bicycle frames,
motorcycle sprockets, seamless automotive driveshaft tubes, chain wheels, golf club
heads, and electrical equipment racks [2]. The cost of metal matrix composites is high
due to complex production procedures, i.e., powder metallurgy technique and in-situ
formation of SiC in Al-Si melts [3]. Recycling of these composites is important for its
commercial application. Most of the commercialized metal matrix composites are
reinforced with short fibers, whiskers, or particulates, and the volume fraction of the
reinforcement is usually less than 30 % [4]. High strength and toughness of the Al-MMC
is attributed to the presence of reinforcement. The SiC reinforced aluminum alloy matrix
composite can not be cut or drilled with regular metal fabrication machine, because the
hard SiC particles in the composites can easily dull the edges of the drill bit or cut saw.
Aluminum electrodeposition using ionic liquids has been reported by a number of authors
[11-15]. Hurley [11] and Wier [12, 13] investigated on aluminum electrodeposition in
ionic liquids. They used aluminum chloride-ethyl pyridinium chloride ionic liquids as the
electrolyte. Welch and Osteryoung [15] studied aluminum electrodeposition in NaCl-
AlCl3 at 175C and in butyl pyridinium chloride-AlCl3 at 30C and measured the system
equilibrium constants. Aluminum electrodeposition in ethyl-methyl-imidazolium chloride
(EMIC) AlCl3 ionic liquid was studied Carlin et al [16]. Good deposition was reported,
but the electrode area was very small (0.25 mm diameter) and the deposition was too
thin, making it difficult to evaluate the feasibility of the application.
In our previous studies aluminum recycling using electrolysis in ionic liquids at near
room temperature has been reported [17, 18]. However, more work is needed to apply the
method to a variety of aluminum scrap materials. In the present study, recycling of Al-
356, Al-360 alloys and Al-MMC via electrolytic process in 1-butyl-3-methyl
imidazolium chloride-AlCl3 ionic liquids at near room temperatures is investigated.
Experimental Procedure
All recycling experiments were performed in 50 ml beaker, fitted with a Teflon cap
having hole for the electrodes. The organic component of the electrolyte 1-butyl-3-methyl
imidazolium chloride (BmimCl) was prepared as described elsewhere [19]. The
electrolyte was prepared by carefully adding the measured quantities of AlCl3 to 1-butyl-
3-methyl imidazolium chloride. The components were mixed in the ratio 1.5: 1.0 of
AlCl3: BmimCl. The mixing reaction is exothermic and the temperature of the mixture
rises above 100C. Hence, care was taken by slowly adding small amounts of AlCl3 to
the mixture preventing the rise in temperature. Initially the organic salt 1-butyl-3-methyl
imidazolium chloride is a white solid and changes to dark colored liquid after adding
anhydrous AlCl3. This entire electrolyte mixing was done in a controlled atmosphere
glove box. The electrolyte was then transferred to the open hood where the electrolysis
experiment was performed. The electrolysis was started when the electrolyte reached the
predetermined temperature. A hot plate was used to maintain the temperature of the
electrolyte. An inert atmosphere, nitrogen or argon was maintained above the electrolyte
at a low flow rate. The electrolyte was constantly stirred with a magnetic stirrer to reduce
the resistance offered by the solution.
The cathode material on which the deposition was performed is a copper plate (90% Cu)
was obtained from Alfa Aesar. Anode material consisted of different alloys of aluminum
Alloys Al-356 and Al-360 have application in automotive part like engine heads, covers,
levers, and break cylinders etc [20]. These alloys exhibit high tensile strength and elastic
modulus. The recycling of these alloys was performed using the electrorefining process
in ionic liquids. The two reactions taking place in the electrolytic process are the anodic
reaction Eq. (1) and cathodic reaction Eq. (2). In the anodic reaction the impure anode i.e.
aluminum alloy is being dissolved. The dissolved aluminum from the anode is transferred
to the cathode where it is deposited onto the cathode. These two reactions occur due to
the application of electrochemical potential between the two electrodes, anode and
cathode.
The effect of voltage on the electrolytic process was studied by varying the applied cell
voltage from 1.3-1.8 volts, shown in Fig. 1. On increasing the voltage an increase in the
average current density was observed for both the alloys. The current efficiency
decreased slightly on increasing the voltage for the Al-356 alloy, but an increase was
observed in case of Al-360 alloy. For both the alloys current efficiencies higher than 95
% were obtained. High current efficiency indicates that there are no side reactions taking
place in the electrolytic process. The electrolytic process was stabilized after an initial
transient period, which lasts for about 10 minutes. Thereafter the current density
remained constant throughout the experiment and the electrolysis experiments were
conducted for 10 hrs.
250 150 0
1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
Voltage, V Voltage, V
(a) (b)
Figure 1. The variation of average current density and cathode current efficiency with
the applied cell voltage (a) 356 Al alloy and (b) 360 Al alloy.
Micrographs of the typical Al-356 and Al-360 alloy microstructure are shown in Fig. 2.
The light colored portion is aluminum and the dark colored portion represents the
impurity content of the alloy. The chemistry of these alloys is shown in Table. 1. In the
electrolytic process, the dissolving or oxidation of different elements at the anode is
dependent on the electrode potentials. Because of the higher oxidation potential than Si,
Cu, Zn, and Fe, aluminum dissolves before these impurities. The impurities either remain
on the anode as residue or precipitate to the cell bottom. The removal of these impurities
from the final product is very high and the product obtained is about 99%-wt Al. These
impurities precipitated into the electrolyte do not contaminate the electrolyte and the
electrolyte is chemically stable. Aluminum was deposited at the cathode and no other
active impurities are deposited due to their low concentrations.
(a) (b)
Figure 2. Optical micrographs of the alloys (a) Al-356 and (b) Al-360 alloy.
The common method of recycling the ceramic particulate reinforced MMC metals is by
salt fluxing technique [21]. This process is based on the principle of effective dewetting
of the ceramic particles from the aluminum matrix. The molten salts are
thermodynamically stable in the presence of liquid aluminum and can be effective in
removing nonmetallic inclusions or ceramic particles. This takes place when the salt
phase wets the ceramic particles, but is not wet itself by the liquid aluminum. The
ceramic particle that come in contact with the salt/metal interface can be absorbed at the
interface or directly into the salt phase, resulting in their removal from the molten salt.
where Al3C4 is formed at the interface of SiC particulate and Al alloy, as SiC crystal is
dissolved in molten Al solution. The formation of Al3C4 seriously degrades the molten
MMCs fluidity, its resistance to corrosion, and ultimately the mechanical properties of
the MMC casting.
In the present process the formation of Al3C4 is completely eliminated, as the operating
temperature is well below the temperature of liquid aluminum used in the above process.
The electrolytic process does not influence the reinforcement SiC, as the anodic reaction
Eq. (1) dissolves the aluminum matrix only. And the dissolved aluminum by the anodic
reaction is deposited on the copper cathode by the cathodic reaction Eq. (2). The cell
voltage controls the rate of the reaction, and this rate is measured by the current density
of the cathodic reaction. The current density increases with the increase in cell voltage as
340 100
280 60
260
240 40
220
20
200
180 0
1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
Cell voltage ,V
Figure 3. The variation of average current density and cathodic current efficiency with
cell voltage for Al-MMC.
3500
+ + Al
3000 Si
* SiC Al
2500
Intensity, cps
2000
Figure 4. X-ray diffraction pattern and photomicrograph of the high silicon (9 wt. % Si)
MMC alloy containing 20 vol. % SiC particles.
2500
Al
2000
Intensity, cps
1500
Al
1000
Al Al
500
Al
0
20 40 60 80
2
Ionic Liquids
Ionic liquids are salts that are liquids over a wide range of temperatures, including room
temperature. They are comprised entirely of ions as the name suggests. The properties of
the ionic liquids depend on their structure. Ionic liquids have good electrochemical
properties i.e., high conductivity and a wide electrochemical window (the range between
the anodic and the cathodic decomposition potential limits of the solvent). In particular,
this wide electrochemical window promises the potential use of these ionic liquids as
solvents for electrochemical investigations. Negligible vapor pressure, low viscosity,
Conclusions
Aluminum alloy scrap and aluminum matrix SiC composite scrap can be recycled using
electrolysis in ionic liquids at near ambient temperatures. High purity aluminum product
of wrought Al-grade applicable for most of the wrought aluminum applications is
obtained. Operating at low temperatures and low voltage resulted in low energy
consumption. Low energy consumption, low temperatures and no pollutant emissions are
the advantages of the present process over the current industrial processes.
Acknowledgements
The authors are pleased to acknowledge the financial support for this research by
National Science Foundation (NSF), Center for Green Manufacturing (CGM) and The
University of Alabama, Tuscaloosa (UA).
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