Field of the invention
[0001] The invention relates to the use of a binary salt flux comprising NaCl and MgCl
2 for the purification of a metal selected from the group consisting of aluminum alloys,
for the removal of alkali and alkaline-earth metals. The invention also relates to
a method for the purification of said metal with said binary salt flux.
Prior art
[0002] The use of fluxes is well known in the field of metallurgy and these fluxes fulfill
various functions.
[0003] Fluxes can be used to form a protecting layer at the surface of an alloy to prevent
oxidation. When fluxes contain chemical active agents, they can be used to clean furnace
walls by softening accumulated layers of corundum. Some exothermic fluxes are also
used for cleaning dross and removing aluminum trapped in oxide layers.
[0004] Fluxes that are based on alkali chlorides and alkaline-earth chlorides are also used
for the refining of alloys. Those skilled in the art generally define refining as
the removal of alkali and alkaline-earth metals, non metallic inclusions and hydrogen
from the alloys.
[0005] Sodium and calcium are always present as impurities in aluminum obtained from the
Hall-Heroult process. Lithium fluoride is often added to the electrolytic bath to
improve the efficiency of cells. However, a small amount in the metallic state is
found dissolved in the aluminum. These impurities entail quality issues. For example,
in an alloy containing magnesium, the presence of sodium may interfere during the
hot rolling processes. The presence of sodium in aluminum and silicon alloys neutralize
the effect of phosphorus used for the refining of grains. For the above-mentioned
reasons, the use of fluxes containing sodium is not recommended for aluminum and its
alloys, more particularly for aluminum alloys comprising a magnesium content higher
than 3 % by weight or a silicon content higher than 10 % by weight.
[0006] Also, the presence of hydrogen in too high concentration may lead to a too high porosity
of the aluminum during its solidification. During the recycling of aluminum, the presence
of non metallic inclusions is important.
[0007] Reactional kinetics for the withdrawal of calcium and sodium in an aluminum alloy
have been well studied. Naturally, in these alloys, both impurities disappear according
to a kinetic of order 1 for small concentrations and order 0 for high concentrations.
Because of its high vapor tension, sodium oxidizes itself more rapidly than calcium,
that is why calcium is used during cleaning tests. The addition of fluxes involves
an increase of reactional constants and thereby a faster reduction of the content
in impurities. Mixing also has a non negligible effect on the reduction of impurities.
Mixing accelerates the withdrawal of impurities by increasing the contact between
impurities and the salt flux.
[0008] MgCl
2 is one of the chemical active agents used for the withdrawal of impurities in alloys.
Its concentration has a direct effect on the kinetic of withdrawal of calcium and
sodium. Its melting point is 714°C, but in common fluxes, it is mixed with other salts
to obtain a melting point between 400 and 550°C. However, MgCl
2 is hygroscopic and can not be exposed for a long period of time to the surrounding
air. Fluxes obtained by fusion of salts comprising magnesium chloride have hygroscopic
properties. Consequently, the packaging is an important factor in limiting the absorption
of humidity during the manufacturing of such fluxes.
[0009] There are examples of fluxes that are based on magnesium chloride.
US patent no. 1,377,374 relates to the use of a flux having an equimolar composition of sodium chloride and
magnesium chloride for the production of manganese or magnesium alloys.
US patent no. 1,754,788 relates to the use of this same flux in a process for the cleaning of magnesium.
US patent no. 1,519,128 relates to the addition of calcium chloride to this composition and
US patent no. 2,262,105 relates to the addition of potassium chloride and magnesium oxide in addition to
the calcium chloride.
US patent no. 5,405,427 mentions a flux based on sodium chloride, magnesium chloride, potassium chloride
and carbon for the treatment of metal.
[0011] Initially, the refining of aluminum was carried out by bubbling of chlorine and argon
in the liquid metal. However, this created environmental problems due to emissions
of chlorine, chlorhydric acid and particles in suspension. The use of salt fluxes
was later adopted as a more ecologically-friendly solution.
[0012] The refining fluxes are usually composed of alkali chlorides or alkaline-earth chlorides,
which are mixed to obtain melting points that are lower than the operating temperature
of alloys -- the melting point of pure compounds being usually quite high.
[0013] Several methods can be used to incorporate salt fluxes in an alloy.
US patent no. 4,099,965 relates to a method where a flux of KCI and MgCl
2 is added in solid form in the bottom of a preheated container before the addition
of aluminum. More currently, fluxes are added by an inert gas in a pipe under the
surface of the metal (lance fluxing). Recently, a method was developed where a hollow
shaft brings the salt flux in the alloy with a gas carrier, and the salt flux is dispersed
by an agitator (rotary flux injection). This method reduces the amount of salt flux
required for carrying out the purification while increasing the dispersion of this
salt flux in the alloy. Following the addition of a salt flux to the metal, impurities
and salts float on the surface of the liquid metal and can be easily removed.
[0014] It is also known from
US5,427,602 a method of treating molten metal containing solid particles suspended therein so as
to reduce the number of said solid particles by passing the molten metal through porous
media so construed and arranged such that the movement of the molten metal therethrough
renders the suspended particles gravity separable, said separation being preceded
by a treatment of said molten metal with a material, said treatment creating liquid
salt particles in said molten metal, said liquid salt particles being suspended in
said molten metal and said material being potentially a material is a chlorinaceous
material such as magnesium chloride, lithium chloride, potassium chloride, sodium
chloride and combinations thereof.
[0016] Advantageously, the use of solid compounds obtained by melting of salts controls
the granulometry. Particles may be used in batch processes or in continuous processes.
[0017] However, costs related to salt fluxes such as binary mixtures of magnesium chloride
and potassium chloride, are high. Furthermore, the use of salt fluxes having a substantial
content in sodium chloride is not recommended by those skilled in the art due to perceived
negative effects of sodium content in the resulting aluminum or aluminum alloys. In
fact, when sodium chloride is present in fluxes for the purification of aluminum or
aluminum alloys, those skilled in the art currently will avoid or limit the use of
sodium chloride. More particularly, in the case of certain kinds of alloys such as,
for example, aluminum alloys having silicon content higher than 10% by weight and
more particularly aluminum alloys having magnesium content higher than 3% by weight,
those skilled in the art currently recommend not using sodium chloride in salt flux.
[0018] During Applicant's search for a more effective solution to the purification problem,
it was surprisingly noted that contrary to current apprehensions and beliefs of those
skilled in the art, it is possible in a salt flux containing MgCl
2, to replace expensive KCI by inexpensive NaCl. Consequently, the present invention
according to the claims offers an economical solution for the treatment of aluminum
alloys with an efficiency of purification that is equivalent to methods presently
used. Indeed, contrary to apprehensions of those skilled in the art, there is no significant
amount of sodium in the resulting aluminum alloys when using the inventive purification
method described herein.
[0019] Embodiments of the present invention show the following advantages:
Summary of the Invention
[0020] The present text describes to the use, which is not encompassed by the wording of
the claims, of a salt flux for the purification of a metal selected from the group
consisting of aluminum alloys, said metal being in liquid phase and said salt flux
being a binary mixture of NaCl and MgCl2.
[0021] This text also describes the use, which is not encompassed by the wording of the
claims, of a salt flux for the purification of a metal selected from the group consisting
of aluminum alloys, said metal being in a liquid phase, wherein the salt flux is in
the form of particles obtained by grinding a fused salt of NaCl and MgCl
2, said binary mixture comprising from 40 to 50 % by weight of NaCl and from 50 to
60 % by weight of MgCl
2.
[0022] The invention relates to a method according to claim 1.
[0023] The invention pertains to a method as defined hereinabove, wherein the salt flux:
consists of particles resulting from the grinding of a fused salt of NaCl and MgCl
2 in solid state.
[0024] The invention relates to a method as defined in any one of the above-mentioned embodiments,
wherein the binary mixture comprises: a) from 40 to 50% by weight of NaCl; and b)
from 50 to 60% by weight of MgCl
2. More particularly, this binary mixture comprises 45% by weight of NaCl and 55% by
weight of MgCl
2 to form an eutectic mixture having a melting point of about 439°C.
[0025] The binary mixture may comprise:
- a) 45 % by weight of NaCl; and
- b) 55 % by weight of MgCl2;
to form an eutectic binary mixture having a melting point of 439°C.
[0026] Another embodiment of the invention relates to a method as defined in any one of
the above-mentioned embodiments, wherein when the salt flux is in the form of particles,
those particles have an average particle size between 100 µm and 3.35 mm. Preferably,
said particles may have a particle size between 0.85 mm and 3.15 mm or between 100
µm and 1 mm. The present text describes such a use.
[0027] Another embodiment of the invention relates to a method as defined in any one of
the above-mentioned embodiments, wherein the particles are contacted with the liquid
metal by injection with a gas injection equipment. A non limiting example of a gas
injection equipment may consist of a rotary injector known under the tradename SNIF
PHD-50 commercialized by the Applicant. The present text discloses such a use.
[0028] Another embodiment of the invention relates to a method as defined in any one of
the above-mentioned embodiments, wherein the metal is an aluminum alloy having a magnesium
content higher than 3% by weight. The present text describes such a use.
[0029] Another embodiment of the invention relates to a method as defined in any one of
the above-mentioned embodiments, wherein the metal is an aluminum alloy having a silicon
content higher than 10% by weight. The present text discloses such a use.
[0030] The present invention will be better understood with reference to the following drawings:
Figure 1: a phase diagram of a fused salt KCl/NaCl/MgCl2;
Figure 2: a phase diagram of a fused salt KCl/MgCl2;
Figure 3: a phase diagram of a fused salt NaCl/MgCl2; and
Figure 4: a comparative graphic concerning examples 5 to 8.
Phase diagrams of Figures 1 to 3 were extracted from factsage web site (http://factsage.com).
DESCRIPTION OF EMBODIMENTS OF THE INVENTION
[0031] In the following examples, the Applicant has noted, contrary to apprehensions of
those skilled in the art, that formulations of salt fluxes comprising a binary mixture
of NaCl and MgCl
2 do not involve an increase of the concentration of metallic sodium in an aluminum
alloy having magnesium content. A non limiting example of such an aluminum alloy may
consist of an aluminum alloy having a magnesium content of 5 % by weight. Consequently,
it appears that there is no counter-indication of using a binary salt flux comprising
NaCl and MgCl
2 for cleaning aluminum, especially in the case of an aluminum alloy with high magnesium
content.
[0032] Formulations based on NaCl and MgCl
2 proposed according to the present invention, show melting points that are lower than
those of salt flux compositions sold by the Applicant under the trademark Promag (40
wt % KCI, 60 wt % MgCl
2), for equivalent amounts of MgCl
2 which is the chemically active agent for the withdrawal of impurities. The lowering
of melting points represents a lowering of energy costs when melting the solid salt
flux.
[0033] Two fused salts have been evaluated in examples hereinafter, that is (on a weight
basis) the following binary system salt flux and ternary system salt flux (prior art):
- 45 % NaCl and 55 % MgCl2 with a melting point of 439°C; and
- 20 % NaCl, 20 % KCI and 60% MgCl2 with a melting point of 396°C.
[0034] Also, example 1 illustrates an unexpected effect with regard to the sodium concentration
in an aluminum alloy when NaCl is added in a liquid aluminum alloy, that is, no increase
of the sodium content in the alloy obtained.
[0035] Preparation of each salt flux was made by mixing the salts in an anhydrous solid
phase in an appropriate oven. Then, by increasing the temperature of the oven, a fused
compound in liquid form was obtained. The liquid was then cooled down quickly, grinded
and sifted to obtain a granulometry that was appropriate for the selected method.
In example 7 hereinafter, the salt flux was made only by mixing the salts in an anhydrous
solid phase.
[0036] Salt fluxes have shown an optimal efficiency for the withdrawal of Ca, Na and Li
when used with a rotary injector such as a SNIF PHD-50 (tradename) commercialized
by the Applicant (Pyrotek). Of course, other methods of addition well known to those
skilled in the art and already mentioned for use in connection with prior art purification
methods can be used to carry out the purification. The concentrations of salt fluxes
required to carry out the purification may vary depending on the selected method.
Example 1 (out of the invention)
[0037] In a crucible made of graphite, one hundred grams (100 g) of NaCl in powder form
and sold under the trademark SIFTO INDUSTRIAL, were agitated in 1.5 kg of a liquid
AA110 aluminum (sold under the trademark Alcan) in which 5 wt % of solid magnesium
were added. The crucible was maintained at 850°C during the whole test. Samples were
taken every day during 7 days. According to these daily analyses, the sodium content
of the resulting aluminum alloy was at a minimal level of 2 ppm during the whole test,
showing that, contrary to apprehensions of those skilled in the art, an addition of
NaCl does not involve an absorption of sodium in an aluminum alloy with high magnesium
content.
Example 2
[0038] In a graphite crucible, fifteen grams (15 g) of a salt flux consisting of a binary
mixture of 45 wt % NaCl and 55 wt % MgCl
2 were agitated in 1.5 kg of a liquid AA1100 aluminum alloy (sold under the trademark
Alcan) in which 5 wt % of magnesium were added. The crucible was maintained at 720°C
during 90 minutes and samples were taken every 30 minutes. The sodium level in the
crucible was maintained at a minimal level of 3 ppm during the whole experiment, showing
that an addition of a flux comprising NaCl does not involve an absorption of sodium
in an aluminum alloy with high magnesium content. The salt flux was prepared from
NaCl in powder form and sold under the trademark SIFTO INDUSTRIAL and MgCl
2 in flake form and sold under the trademark SKYLINE.
Example 3 (prior art)
[0039] In a graphite crucible, fifteen grams (15 g) of a salt flux consisting of a ternary
mixture of 20 wt % NaCl, 20 wt % KCI and 60 wt % MgCl
2 were agitated and added in 1.5 kg of a liquid AA1100 aluminum alloy (sold under the
trademark Alcan) in which 5 wt % of magnesium were added. The crucible was maintained
at 720°C during 90 minutes and samples were taken every 30 minutes. The sodium level
in the crucible was maintained at a minimal level of 3 ppm during the whole experiment,
showing that an addition of a ternary flux comprising a small amount of NaCl does
not involve an absorption of sodium in an aluminum alloy with high magnesium content.
The salt flux was prepared from NaCl in powder form and sold under the trademark SIFTO
INDUSTRIAL, KCI in powder form and sold under the trademark IMC KALIUM and MgCl
2 in flake form and sold under the trademark SKYLINE.
Example 4:
[0040] About seventy-five kilos (75kg) of A356 alloy were melted and maintained in a liquid
state at 700°C in a crucible made of silicon carbide. Then, 535g of an aluminum alloy
containing 10 % by weight of calcium were added to the liquid A356 alloy while mixing
it with an agitator having straight blades. Then the resulting aluminum alloy contained
in the crucible was left without agitation for 5 hours. During this time, the calcium
content of the resulting aluminum alloy was reduced from 350 ppm to 150 ppm. Then,
three hundred and sixty grams (360g) of a salt flux made of 45 wt % NaCl and 55 wt
% MgCl
2 were added to the resulting alloy while agitating it in order to further purify it.
The salt flux was prepared from NaCl in powder form and sold under the trademark SIFTO
INDUSTRIAL and MgCl
2 in flake form and sold under the trademark SKYLINE.
[0041] Analyses made on the purified aluminum alloy have shown a reduction of the Ca content
from 150 ppm to 70 ppm, that is a reduction of 53 %, immediately after the addition
of the salt flux, and this Ca content drops to 25 ppm 3 hours after the addition.
Also, analyses have shown that the sodium content was in the order of 2 ppm.
Example 5
[0042] Fifty grams of a flux were prepared in a small alumina crucible by mixing 22.5 grams
of NaCl in powder form and sold under the trademark SIFTO INDUSTRIAL, and 27.5 grams
of MgCl
2 in flake form and sold under the trademark SKYLINE. The mixture was subjected to
a temperature of 550°C during 45 minutes. The liquid mixture obtained was then poured
into an enamelled-coated bowl for quick solidification. The salt flux obtained was
then grinded with in a mortar and sifted. The fraction having a particle size lower
than 3150 microns and higher than 105 microns was recovered.
[0043] Two kg of AA1100 aluminum alloy (sold under the trademark Alcan) were melted and
kept in liquid state at 700°C in a graphite crucible. To this alloy, 2 grams of an
aluminum alloy consisting of 90 wt % of aluminum and 10 wt % of calcium (sold under
the trademark KB Alloys) were added in a vortex formed with an agitator in the liquid
metal, said agitator having straight blades. The agitation was maintained during 2
minutes. A sample of the metal was taken for analysis. Two grams of the flux formed
hereinabove were added to the liquid aluminum alloy doped with calcium while agitating
for 2 minutes. Samples were taken immediately after the end of the agitation as well
as 30, 60 and 90 minutes later.
[0044] Analyses of samples have shown a reduction of the Ca level from 115 ppm to 3 ppm
after the addition of the salt flux. Thirty minutes later, the calcium level was under
2 ppm. No increase in the sodium content was noted during the test. The level of sodium
in the alloy was in the order of 2 ppm.
Example 6 (prior art)
[0045] Fifty grams of a salt flux were prepared in a small alumina crucible by mixing 10
grams of NaCl in powder form and sold under the trademark SIFTO INDUSTRIAL, 10 grams
of KCI in powder form and sold under the trademark IMC KALIUM, and 30 grams of MgCl
2 in flake form and sold under the trademark SKYLINE. The mixture was subjected to
a temperature of 550°C during 45 minutes. The liquid mixture obtained was then poured
into an enamelled-coated bowl for quick solidification. The salt flux obtained was
then grinded in a mortar and sifted. The fraction having a particle size lower than
3150 microns and higher than 105 microns was recovered.
[0046] Two kg of AA1100 aluminum alloy (sold under the trademark Alcan) were melted and
kept in liquid state at 700°C in a graphite crucible. To this alloy, 2 grams of an
aluminum alloy consisting of 90 wt % of aluminum and 10 wt % of calcium (sold under
the trademark KB Alloys) were added in a vortex formed with an agitator in the liquid
metal, said agitator having straight blades. The agitation was maintained during 2
minutes. A sample of the metal was taken for analysis. Two grams of the salt flux
formed hereinabove were added to the liquid aluminum alloy doped with calcium while
agitating for 2 minutes. The agitation was stopped and samples were taken immediately
after the end of the agitation as well as 30, 60 and 90 minutes later.
[0047] The analysis of samples shows a reduction of the Ca level from 108 ppm to 7 ppm after
the addition of the salt flux. Thirty minutes later, the calcium level was at 2 ppm
and after 60 minutes the calcium level was under 1 ppm. No increase in sodium content
was noted during the test. The sodium level was in the order of 2 ppm. This example
shows that a ternary flux having a low content in NaCl does not increase the level
of sodium in the alloy.
Exemple 7 (out of the invention)
[0048] Fifty grams of a salt flux were prepared only by mixing 22.5 grams of NaCl in powder
form and sold under the trademark SIFTO INDUSTRIAL with a granulometry 95% lower than
840 microns and 95 % higher than 300 microns, and 27.5 grams of MgCl
2 in flake form and sold under the trademark SKYLINE with a granulometry 90 % lower
than 4.7 mm and 85 % higher to 1 mm.
[0049] Two kg of AA1100 aluminum alloy (sold under the trademark Alcan) were melted and
kept in liquid phase at 700°C in a graphite crucible. To this alloy, 2 grams of an
aluminum alloy consisting of 90 wt % of aluminum and 10 wt % of calcium (sold under
the trademark KB Alloys) were added in a vortex formed with an agitator in the liquid
metal, said agitator having straight blades. The agitation was maintained during 2
minutes. A sample of the metal was taken for analysis. Two grams of the salt flux
formed hereinabove were added to the liquid aluminum alloy doped with calcium while
agitating for 2 minutes. Agitation was stopped and samples were taken immediately
after the end of the agitation as well as 30, 60 and 90 minutes later.
[0050] Analyses of samples have shown a reduction of the Ca level from 77 ppm to 2 ppm after
the addition of the salt flux. Thirty minutes later, the calcium level was under 1
ppm. No increase in the sodium content was noted during the test. The sodium level
was in the order of 2 ppm.
Example 8
[0051] Two kg of AA1100 aluminum alloy (sold under the trademark Alcan) were melted and
kept in liquid state at 700°C in a graphite crucible. To this alloy, 2 grams of an
aluminum alloy consisting of 90 wt % of aluminum and 10 wt % of calcium (sold under
the trademark KB Alloys) were added in a vortex formed with an agitator in the liquid
metal, said agitator having straight blades. Stirring was maintained during 2 minutes.
A sample of the metal was taken for analysis. Two grams of the PROMAG SI (trademark)
formed of 40 wt % KCl and 60 wt % MgCl
2, with a granulometry 99% lower than 3150 microns and 95 % higher than 850 microns,
were added to the alloy doped with calcium while agitating for 2 minutes. The agitation
was stopped and samples were later taken immediately after the end of the agitation
as well as 30, 60 and 90 minutes later.
[0052] Analyses of samples have shown a reduction of the Ca level from 75 ppm to 7 ppm after
the addition of the salt flux. Thirty minutes later the calcium level was under 5
ppm (see Figure 4). These analyses show that binary fluxes of NaCl and MgCl
2 are more efficient than a ternary flux of NaCl, KCl and MgCl
2 or binary flux, KCl and MgCl
2.
| |
Ex. 5 NaCl-MgCl2 (45-55) Fused |
Ex. 6 NaCl-KCl-MgCl2 (20-20-60) Fused |
Ex. 7 NaCl-MgCl2 (45-55) Mix |
Ex. 8 Promag SI* (KCl - MgCl2) (40-60) |
Reference (no flux) |
| Time |
|
|
|
|
|
| After Ca |
115 |
108 |
77 |
75 |
77 |
| After salt |
3 |
7 |
2 |
7 |
- |
| 30 min |
<1 |
2 |
<1 |
<5 |
58 |
| 60 min |
<1 |
<1 |
<1 |
<5 |
- |
| 90 min |
<1 |
<1 |
<1 |
<5 |
- |
| 120min |
- |
- |
- |
- |
39 |
| * trademark |
[0053] The present invention has been described with respect to its preferred embodiments.
The description and the drawings are only intended to aid to the understanding of
the invention and are not intended to limit its scope. It will be clear to those skilled
in the art that numerous variations and modifications can be made to the implementation
of the invention without being outside the scope of the invention. Such variations
and modifications are covered by the present invention. The invention will be now
described in the following claims: