International Journal of Latest Engineering and Management Research (IJLEMR)

ISSN: 2455-4847
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Role of Salt Fluxes in Aluminium Refining: A Review

Saravanakumar P1, Bhoopashram J2, Kavin Prasath M3, Jaycharan M4
1
Assistant Professor, 2, 3, 4 UG Students
1,2,3,4
Department of Mechanical Engineering, Sri Ramakrishna Engineering College, Tamilnadu, India

Abstract: With the consideration of several industries and numerous governments with the increasing energy
efficiency and reducing greenhouse gas emission, the production of aluminium in a sustainable method has
received huge focus recently. Aluminium recycling is crucial as it preserves 95 percentage of energy and the
emissions associated with producing the alloy from the ore. In addition to that, it saves the capital expenditures
and decreases the land space requirements. Recycling of aluminium is an established process and encourages the
recycling of other metals and alloys.Currently, the refining of aluminium is restricted to removal of alkali or
alkali earth metals, non-metallic inclusions and hydrogen. Technologies for removal of these types are
commercially mature and there is a need for focus on the removal of other undesirable or tramp elements such
as copper, silicon, iron, iron or zinc from the aluminium melt and application of chlorine must be discouraged
due to their toxic nature. Considering these problems, a review has been conducted to evaluate the current
industrial practice in the refining of aluminium alloys using solid fluxes. The study has been extended to focus
on the current techniques available for the extraction of aluminium from the drosses generated during
aluminium melting by the application of solid fluxes.
Keywords: Aluminium, degassing, dross, grain refining, recycling, solid flux.

I. Introduction
Aluminium is a silvery white metal that is currently having diverse applications in numerous fields of
science and engineering due to their unique properties. The metal is known for its high strength to weight ratio.
This encourages consumers to apply aluminium in several sectors like medical, aerospace, automobile, and
electrical and electronics are profoundly replacing aluminium over steel. In addition to that, this super metal
encompasses several other immense properties like low density, thermal and electrical conductivity, corrosion
resistance, magnetic neutrality, ductility and malleability. The aluminium family has been classified into Cast
alloys and Wrought alloys. In the first type, the components are manufactured directly through casting the
molten metal by three techniques: Sand casting, Gravity die casting, Pressure die casting. The latter includes
casting into ingots or billets followed by subsequent hot working and cold working operations to produce wires,
plates, rods etc. There are several classes like 2XXX, 3XXX, 5XXX, 6XXX, 7XXX series alloys that includes
heat treatable and non- heat treatable alloys having different alloy compositions based on the requirements of
application[1,2,3].
In order to reduce the wastage and the manufacturing costs the world is moving towards sustainable
method of production. Recycling of aluminium requires only about 3-5 of input energy to produce primary
aluminium. Currently, around 50-60% of aluminium alloys are recycled at the end of its life[4].Aluminium
recycling process is extensively capitalised during the World War II.Brazil recycles about 98%of its can
production every year.Brazil has been ranked among first in the aluminium recycling countries[5].Recycled
aluminium reduces the emission ofgreenhouse gases. For growth in a competitive world,industries have to focus
on recycling to reduce the production cost. There are two types of aluminium scraps available: New scraps and
Old scraps[6].The new scraps comes directly from the manufactures and are therefore easy to recycle and could
be 100% re-melted with minor processing. However, the old scraps require significantprocessing.Newly
improved aluminium recycling process are more efficient and the aluminium scraps are almost recycled to about
higher percentages[7].
Porosity is a major problem during metal casting and that plays a major role in affecting the mechanical
properties,pressure tightness and corrosion resistance of aluminium castings. Porosity mostly occurs when
solidification rate is improper that leads to due to dissolutiongases in the aluminium melt.Hydrogen is the only
gas that wouldbe soluble in aluminiummelt in the liquid state.Therefore, the removal of hydrogen gas from the
molten aluminium is vital for the production of high quality aluminium castings. Therefore, in order to
overcome this issue, several degassing techniques are currently appliedto remove the hydrogen from the molten
metal. Some of the degassing techniques include rotary impeller degassing,spray degassing,vacuum degassing
and ultrasonic degassing,gas degassing[8].
However, these techniques have several parameters to be considered to reduce the porosity in the
aluminium castings.In gas degassing parameters like Rotor speed,Gas pressure and Degassing time must be

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International Journal of Latest Engineering and Management Research (IJLEMR)
ISSN: 2455-4847
www.ijlemr.com || Volume 02 - Issue 09 || September 2017 || PP. 45-51
accounted to reduce the porosity. The castings could be quality checked with several testing techniques like
chemistry, density, hardness, tensile, porosity, inclusion, XRD, PODFA, AlspecQ, K-mould test, SEM, Optical
microscopy etc. This paper presents the current technologies available for the refining of aluminium melt using
solid fluxes as it is economical. A brief review on the extraction of aluminium from drosses has also been
performed.

II. Degassing the Melt

Fluxing is done to remove alkali metals, alkali earth metals, impurities, non-metallic inclusions,
dissolved, hydrogen and excess magnesium as they affect the final properties of the product. The commonly
used salt fluxes are NaCl-KCl, -KCl with additions of fluorides, chlorides, carbonates [9,10,11,12]. The salt
fluxes must have a low melting point as they fuse with aluminium oxides at lower temperatures and increase the
viscosity of the slags and thereby enabling removal through setting up a chemical reaction or by means of
physical separation[13]. The chemical composition and the amount of salt are crucial factors determining the
metal yield and economics of the process. Pirker et al [10] have demonstrated the effect of KCl in the NaCl-KCl
mixture. KCl is an expensive salt. A limited reduction of KCl in the mixture does not affect the metal loss. Also
reducing the KCl content in the flux reduces emissions. It is also reported that the activity NaCl is greater than
KCl. But the increased reduction in KCl increases the melting point of the slag and thereby affecting metal
recovery. Therefore decreasing the amount of KCl to an optimum level is economically and environmentally
effective. Sometimes, for refining of low-grade scraps, the refiners use liquid flux. The scraps are dipped in the
liquid flux before they are charged into the furnace. However, the composition of the liquid flux must be
carefully monitored. The flux must not thicken up as the impurities are absorbed. Therefore, some quantities of
fluorides are introduced in the flux. In the case of high silicon alloys, sodium salts such as sodium fluorides are
employed. But if iron and manganese content exceed more than 1%, the modification is prevented. In the case of
high magnesium alloys, Magnesium Chloride is used for fluxing. The magnesium chloride on reaction with the
magnesium oxide in the metal forms magnesium oxychloride which is absorbed in the slag. But as Magnesium
Chloride is hygroscopic, it is used along with the salts. This reduces the risk of moisture absorption. It has been
reported that a mixture of one-third of sodium chloride, potassium chloride, and magnesium chloride is most
successful. If the magnesium is present as an impurity in the alloy, they can be removed by degassing
techniques employing chlorine gas, hydrochloric acid gas, silico-fluoride gas, boro-fluoride gas and the
compounds formed are taken into the slag. The temperature required for this process is above 800°C[11,13].
Jun et al [14] investigated the effects on purification, microstructure and properties in A00 melt with
C2Cl6 and several other fluxes. In the melt sheared with C2Cl6 several cracks and porosities existed in the
surface oxide film which led to increased melting loss. In addition to that the slag mainly composed of pure
aluminium and aluminium oxide. The size of the inclusion ranged under 10 µm and the size of the grains ranged
from 100-150 µm extended along the radius. These smaller sized inclusions had no adverse effects on the
strength but on the elongation.
Zhao et al[8] studied the behaviour of gas bubbles in aluminium alloys during the re-melting process
by observation with X-ray micro focus radiography. The experimental observation depicts that the re-melting
has caused a significant effect on degassing. In addition to that it is also benefitted by decreasing the inclusion
percentage in the casting. The fundamental theory behind this experiment is that the surface of the melt remains
calm unlike being agitated in the degassing process. Therefore, the oxides present in the surface could not be
entrained into the melt. However the author failed to address the energy, cost, time and environmental effects
that would be costing during the re-melting process.
Utigard et al[15] projected the role played by solid and gaseous fluxes in the removal of inclusions,
gases and magnesium in the aluminium alloys and in the drosses generated during melting. In addition to that
thermodynamic analysis of aluminium melting was performed. The function of the flux and the temperature to
be applied must be considered before accounting a flux to be incorporated in the aluminium melt. In addit ion to
that, the alloy in which it is added should also be accounted. Sodium or fluoride fluxes must not be incorporated
into aluminium-magnesium alloys. From a thermodynamic view, fluoride salts are stable than chlorides,
sulphide and oxides. Hence, a fluoride salt incorporated to mixture of chlorine and magnesium, it would
stabilise the magnesium present in the salt. Application of C2Cl6 tablets decomposes the melt generating AlCl3
bubbles of gas which collects the hydrogen present in the melt. In addition to the salts also contains salt fluxes
which wets the inclusion of oxidesand thereby enabling the removal of hydrogen entrapped in the inclusions.
For effectiveness, the tablets are plunged inside the melt and stirred and stationed allowing the bubbles to
subside.
Westberg et al[16] studied the environmental effects of application of C2Cl6 in the aluminium melt
refining with particular focus on the emission of Organo chlorine compounds in the atmosphere. Figure 1 shown

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Emission, pg/g HCE

International Journal of Latest Engineering and Management Research (IJLEMR)
ISSN: 2455-4847
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below depicts the emissions of octachlorosty- rene (OCS), hexachloroethane (HCE), hexachlorobenzene (HCB),
carbon monoxide (CO), total hydrocarbons (THC) and hydrogen chloride (HCl).
Emission, pg/g HCE

Figure 1: a) Emissions of octachlorosty- rene (OCS), hexachloroethane (HCE) and hexachlorobenzene (HCB);
b) Emissions ofcarbon monoxide (CO),total hydrocarbons (THC) and hydrogen chloride (HCl)

III. Grain Refining

Metals solidify with a coarse columnar grain structure under natural conditions. Coarse grains affect
the property of the castings. Coarsening phenomenon can be inhibited by carefully controlling solidification by
restricting the columnar growth of the grains[17]. Several grain refining experiments were attempted in the past
using Zr, Nb, W, V, B, Cr and Ta. Murty et al has stated that by increasing the number of nucleation sites,
grain size can be reduced and also by increasing the undercooling temperature.The grain size is inversely
proportional to the degree of undercooling. There are also other methods of grain refinement like melt agitation
and vibration[18].Grain refinement is an important function in the aluminium melts processing. The increasing
interest in grain refinement arises from the fact that finer grains provide better properties to the castings.
Addition of grain refining elements results in the achievement of fine equiaxed grain structure that enhances the
yield strength, plastic strength, formability, ductility and toughness[19,20]. The most common practice used is
the application of the grain refiner Al-5Ti-1B master alloy to the aluminium melt to attain the fine grain
structure. It is produced by inoculation of halide salts such as K2TiF6 and KBF4in the aluminium melt. Several
parameters like Ti/B ratio, reaction time, temperature, frequency of salt additions, stirring conditions contribute
to the grain refining efficiency[18,17].
Han et al[20] discussed high-intensity ultrasound effect in the production and melting of Al–5Ti–1B
master alloy on its grain refinement microstructure. The ultrasound enhances the distribution of Ti and the TiB 2
particles in the melt, makes the TiAl3 phases more uniform, and changes the morphology of agglomerated TiB 2
into loose corals. The ultrasound makes the bulky TiAl3 phase distribute evenly. In addition to that, the
agglomerated TiB2 disintegrates like loose spawn. The grain refining efficiency increases with the ultrasound.
Majidi et al[21] studied the effect of fluxing temperature in aluminium refining process. Increased
temperature caused a loss of energy and produced fumes and gases. In addition to that it causes skimming and
fluxing difficult and also it decreases the accuracy and refining efficiency. Majidi et al discovered the optimum
temperature for fluxing as 740°C as it does not pose any problems.
Murty et al[22] reported the influence of Si, Zr and Cr on the efficiency of grain refining by Al-5Ti-1B
master alloy. It was determined that the poisoning effect ascends in the order of Si, Zr and Cr. It is due to the
formation of borides, silicides, aluminiudes upon interaction of grain refining constituents’ 5/1TiBAl with
alloying elements. This problem could be recuperated by increasing the proportion of grain refiner or by adding
Mg in the case of Aluminium- Silicon alloy.
Birol et al[19] studied the efficiency of grain refining with the stirring conditions. The stirring action
had detrimental effect on grain refining of Al-Ti-B master alloy. However, the effect was not as it was observed
in stirring while holding. However, the possible mixing of potassium aluminium fluoride with aluminium melt
is responsible for the loss of efficiency of grain refining. The boride particles are wetted by the salts present in
the molten alloy which acts as the nucleation sites and assists in the agglomeration
Kumar et al[17] investigated the grain refining efficiency of Al-Ti-C master alloy. Grain refinement
could not be attained at increased addition of Al-Ti-C master alloys as TiC particles get agglomerated. In
addition to that increased holding times causes fading of the grain size. However higher magnesium and finer
TiC particle is required for better wetting behaviour of the master alloys and thereby reducing the
agglomeration. Figure 1 shown below depicts the comparative grain size analysis of LM25 alloy a) grain refined
using Al–5Ti–0.8C master alloy; b) Grain refined using different grain refiners at different Ti or B addition; c)
Grain refining efficiency of Al-5Ti-1B at different holding times; d) Grain refining efficiency of Al-3B at
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different holding times; e) Grain refining efficiency of Al-5Ti-1B at different holding times; f) Grain refined
using Al–5Ti–1.2C master alloy.

Figure 2: Comparative grain size analysis of LM25 alloy a) grain refined using Al–5Ti–0.8C
master alloy; b) Grain refined using different grain refiners at different Ti or B addition; c) Grain refining
efficiency of Al-5Ti-1B at different holding times; d) Grain refining efficiency of Al-3B at different holding
times; e) Grain refining efficiency of Al-5Ti-1B at different holding times; f) Grain refined using Al–5Ti–
1.2C master alloy[17]
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IV. Dross Processing
Aluminium salt slag is produced during the melting of scraps in secondary aluminium production.
These slags are heterogeneous by mass. It consists of metallic aluminium, aluminium oxides, salts such as NaCl,
KCl, nitrides, phosphides, sulphides etc. depending upon the nature of the scrap and the type of salt used. There
are two types of dross, Black dross and white dross. White drosses contain 20-45% of metallic aluminium and
black drosses contain 10-20% of metallic aluminium. These slags are toxic and hazardous in nature which will
lead to explosions, odorous gases, such as NH3, CH4, and H2S etc. that pollutes the groundwater. Therefore,
environmental regulations have been passed on the disposing of the drosses in specialized land filling sites.
However, it increases the disposal cost and also aluminium and the salts within the slag have to be
recovered[23]. Recycling of aluminium dross is an eco- friendly and economical process of waste
utilization[24].
The most commonly used method is the B.U.S process. It consists of five steps:
• Manual hand separation, Eddy current separation[25]and Electrostatic separation[26]
• Leaching
• Solid-liquid separation
• Gas treatment
• Evaporation and Crystallization[27].

Alternative processes have also been proposed for black dross treatment: 1) Hydrometallurgical and 2)
Pyrometallurgical processes[28]The usual approach is pulverizing the dross powder and screening them and the
undersized drosses are landfilled. This method reduces the amount of dross, energy and salt cake generated at
the end of the process[25]. The aluminium recovery from the dross by salt additions was studied by Tenorio et
al[29]. Tenorio’s initial analysis stated that the compositions of the drosses are mostly oxides and metallic
aluminium. The initial washing with water dissolves sodium or potassium salts present in the dross[30]. The
drosses were then treated with NaCl-KCl equimolar mix. The chloride due to their corrosive nature breaks down
the oxide layer into fragments. The incorporation of fluorine salts such NaF, CaF enhances the fragmentation
process. The segregated aluminium droplets then collage and sinks back into the bath. As we are aware that the
drosses consist of other reactive metals and inclusions entrapped, the complex reactions that occur due to the
salt additions were not considered by the author. Also, the viscosity of the slag was not considered which is a
major factor for reaction kinetics[31].

V. Future Aspects
Although recycling of aluminium has been followed since its commercial production, the sector still
demands growing concern of focus and research in many areas.
 Implementation of chlorine-free aluminium melt treatment
 Reduction of harmful impurities in the solid waste
 Reduction energy consumption
 Implementation of filtration techniques that focuses on the removal of large harmful particles
 Improved testing techniques for measuring entrapped oxides inclusions.
 On-line monitoring of melt quality which is still in the research stage must be commercialised.
 Lack of methods to remove undesirable or tramp elements: Zn, Cu, and Fe that are picked up
in the supply chain.

VI. Conclusion
There is a growing consumption of recycled aluminium in the market. Recycling will certainly benefit
the current situation of growing demand for aluminium products. The various techniques for refining of
aluminium melt using solid fluxes that are currently available at the industrial scale and the lab scale have been
discussed in this paper focusing on the technical, economic and environmental aspects. However, drastic
improvements are still profoundly required in the areas of inclusion removal, studying the effects of trace
elements in the castings, reduction of environmental damage, reduction of energy and cost. The future
researches that appear in this field must be a life cycle analysis rather than a single stage development so that
not only the useful resources can be recovered but also other materials harmful to the environment can be
disposed of appropriately.

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