USOO7988763B2

(12) United States Patent (10) Patent No.: US 7.988,763 B2

Tremblay et al. (45) Date of Patent: Aug. 2, 2011
(54) USE OF A BINARY SALT FLUX OF NACL 2,073,018 A * 3/1937 Lepp ............................... T5/604
AND MGCL, FOR THE PURIFICATION OF 2,262,105 A ly 1941 Ryland et al.
ALUMINIUM OR ALUMINIUMALLOYS, AND 33.78 A .333 Ea
METHOD THEREOF 3,189,491. A 6/1965 Robbins
3,650,730 A 3, 1972 Derham et al.
(75) Inventors: Sylvain Tremblay, Chicoutimi (CA); 4,053,304 A 10, 1977 Tsuda
Luc Desrosiers. Sherbrooke (CA); is:
k- w
A ck 3. aly guin. . .et. . . .al.. . . . . . . . . . . . . . . . . . . . . . . . T5,681
Daniel Levesque, Sherbrooke (CA) 4.261,746 A 4, 1981 Langston et al.
4,295,884 A 10, 1981 Hicter et al.
(73) Assignee: Pyrotek Inc., Spokane Valley, WA (US) 4.451,287 A 5/1984 El
4,501,614 A 2f1985 Bauer et al.
(*) Notice: Subject to any disclaimer, the term of this 4,695,320 A 9, 1987 Christini et al.
patent is extended or adjusted under 35 4,790,873 A * 12/1988 Gesing et al. ................... 75/4O7
U.S.C. 154(b) by 0 days. (Continued)
(21) Appl. No.: 12/480,010 FOREIGN PATENT DOCUMENTS
(22) Filed
1C 8, 2009 JP 57051230 A * 3, 1982
9 OTHER PUBLICATIONS
(65) Prior Publication Data
Derwent Acc-No. 1982-36138E for JP 57051230 A published Mar.
US 2010/0307293 A1 Dec. 9, 2010 26, 1982.*
(51) Int. Cl. (Continued)
C22B 2/06 (2006.01)
(52) U.S. Cl. ............................................ 75,682, 75/685 Primary Examiner — George WySZomierski
(58) Field of Classification Search .................... 7s.68s. Assistant Examiner - Tima M McGuthry-Banks
75/682, 308, 329 (74) Attorney, Agent, or Firm — Choate, Hall & Stewart
See application file for complete search history. LLP; Charles E. Lyon; Kristen C. Buteau
(56) References Cited (57) ABSTRACT
U.S. PATENT DOCUMENTS
A method for the purification of a metal selected from the
group consisting of aluminum and aluminum alloys, wherein
1,377,374. A 5/1921 Veazey the metal is in a liquid phase and is contacted with a salt flux
S; A
- K-1
3. E. alyal
consisting of a binary mixture of NaCl and MgCl2. Prefer
O
1,534,105 A 4, 1925 Gann ably, more than 22% by weight of the binary mixture consists
1,754,788 A 4, 1930 Gann of NaCl.
1975,084 A * 10/1934 Davies ............................ 75/307
1989,456 A 1/1935 Luschenowsky 34 Claims, 4 Drawing Sheets

Efficiency of the withdrawal of calcium in a 2 kg 1100 aluminum alloy at 700°C

140

120
d

10

80 8NaCl-MgCl2 (45-55) Fused

NaCl-KC-MgCl2 (20-20-60) Fused
9. XNaCl-MgCl2 (45-55) mix
Reference (no flux)
SO Promag SI

40

2 Y
After
addition of
: 2g of salt
|s H --
O 20 40 SO 80 100 120 140
Time (min)
 US 7,988.763 B2
Page 2

U.S. PATENT DOCUMENTS Roy et al., “The role of Salt Flux in Recycling of Aluminum.” Light
4,808.222 A 2f1989 Reeve-Parker Metals pp. 1237-1243 (1998).
5,405,427 A 4, 1995 Eckert Roy et al., “Inclusion Removal during Chlorine Fluxing of Alumi
6,053,959 A 4/2000 Ireland num Alloys.” Light Metals, pp. 871-875 (1998).
6,171,362 B1 1/2001 Osumi et al. Utigard et al., “The properties and Uses of Fluxes in Molten Alumi
6,206,950 B1 3, 2001 Ireland num Processing.” JOM, 50:38-43 Nov. 1998.
6,379,418 B2 4/2002 Ireland Crepeau, "Molten Aluminum Contamination, Gas, Inclusions and
6,936,089 B2 8/2005 Fujimoto et al. Dross.” Modern Casting, pp.39-41 Jul. 1997.
7,537,639 B2* 5/2009 DeVries et al. ................ 75,588 Tenorio et al., “Optimization of Salt Composition in the Recycling of
OTHER PUBLICATIONS Aluminum Cans.” Light Metals, pp. 1105-1108 (1997).
DeYoung, David H. "Salt Fluxes for Alkali and Alkaline Earth Ele Friesen et al., “Coalescence Behaviour of Aluminum Droplets Under
a Molten Salt Flux Cover.” Light Metals, pp. 857-864 (1997).
ment Removal from Molten Aluminum.” 7' Australian Asian Pacific Samuel et al., “Fluxing of a 359/SiC/10p composite with alkali chlo
Conference, Alulminum Cast House Technology, pp. 99-113, 2001.* rides: effect of inclusions,” Journal of Materials Science 31:43-48
International Search Report and Written Opinion for PCT/CA2010/ (1996).
000866, mailed Sep. 24, 2010. Beland et al., “Improving Fluxing of Aluminum Alloys.” Light Met
Courtenay et al., “A new Insight into the Melting Behaviour and als, pp. 1189-1195 (1995).
Performance of Fused MgCl/KCl refining fluxes.” Aluminium Inter Crepeau et al., “Solid Fluxing Practices for Aluminum Melting.”
national Today 20, No. 2:24-26 (2008). Modern Casting, pp. 28-30 Jul. 1992.
Chesonis et al., “Chloride Salt Injection to Replace Chlorine in the Stevens, et al., “Mechanisms of Sodium, Calcium and Hydrogen
Alcoa A622 Degassing Process.” Light Metals pp. 569-574 (2008). Removal from an Aluminum Melt in a Stirred Tank Reactor The
Majidi et al., “Study of fluxing temperature in molten aluminum Alcoa 622 Process.” Light Metals pp. 437-443 (1988).
refining process,” Journal of Materials Processing Technology Robelin et al., “Thermodynamic evaluation and optimization of the
182:450-455 (2007). (NaCl-KCl+MgCl-CaCl-MnCl+FeCl+CoCl-NiCl) system.”
Ahmed et al., “Elimination of Chlorine at the Aluminium Bahrain Journal of Chemical Thermodynamics 36:809-828 (2004).
Casthouses.” Aluminium Cast House Technology, pp. 25-30 (2007). Chartrand et al., “Thermodynamic Evaluation and Optimization of
Ohm et al., “Process Improvement by application of Innovative the LiCl-NaCl-KCl-RbCl-CsCl-MgCl-CaCl System Using the
Fused Fluxes.” Aluminum Cast House Technology, pp. 199-208 Modified Quasi-chemical Model.” Metallurgical and Materials
(2007). Transactions 32A:1361-1383 Jun. 2001.
Deyoung et al., “Air Emissions from Rotary Gas and Rotary Salt Perry et al., “The Magnesium Chloride-Potassium Chloride Phase
Injection Furnace Fluxing Processes.” Aluminum Cast House Tech Diagram.” Journal of Phase Equilibria 14, No. 2, pp. 172-178
nology, pp. 7-16 (2005). (1993).
Zhou et al., “Performance improvement of industrial pure aluminum Linet al., “Computation of Ternary Salt Phase Diagrams,” Journal of
treated by stirring molten fluxes.” Materials Science and Engineering the American Ceramic Society 62, Nos. 7-8, pp. 414-422 (1979).
A347:280-290 (2003). Gibbons et al., “Crystal Structures of K-MgCl4 and CSMgCl,”
Bridiet al., “Improvement in Casthouse Processing Using In-Furnace Canadian Journal of Chemistry 53:114-118 (1975).
Refining Systems.” 8' Aluminum Cast House Technology Confer R. Bridi, Substitution of Chlorine as a Furnace Addition in Aluminum
ence, pp. 1-15 (2003). Industry Cast Houses by Fused Refining Agents, Proceedings of the
Tenorio et al., “Effect of salt oxide interaction on the process of 6' Australian Asian Pacific Conference on Aluminum Cast House
aluminum recycling.” Journal of Light Metals 2:89-93 (2002). Technology held Jul. 26-29, 1999, Novotel Brighton Beach, Sidney,
Gallo et al., “Development, Evaluation and Application of Solid Australia, 9 pages.
Fluxes.” Modern Casting, pp. 30-33 (2002). FoSeco Brochure, Development, Evaluation and Application of
Deyoung, "Salt Fluxes for Alkali and Alkaline Earth Element Granular and Powder Fluxes in Transfer Ladles, Crucible and Rever
Removal from Molten aluminum.” 7 Australian Asian Pacific Con beratory Furnaces, Proceedings of the 6' International Conference
ference Aluminum Cast House Technology, pp. 99-113 (2001). on Molten Aluminum Processing held Nov. 11-13, 2001, Orlando,
Williams, “Alkali Removal and Reduced Chlorine use during Fur FL, pp. 8-16.
nace Fluxing.” Light Metals pp. 1053-1059 (2001). Foseco Brochure, Granular Fluxes for Aluminum Alloys, Environ
Utigard et al., “Properties of Fluxes used in Molten Aluminum Pro mental and technological Advances, Proceedings of the 4' Interna
cessing.” High Temperature Materials and Processes 20 Nos. 3-4, pp. tional Conference on Molten Aluminum Processing held Nov. 12-14.
303-307 (2001). 1995, Orlando, FL, pp. 16-20.
Ohno, “The Latest Molten Metal Refining Processes in Cast Shop.” Quackenbush et al., Testing and Alternative Method for Treating
Journal of Japan Institute of Light Metals 51:134-137 (2001). Molten Aluminum at Florida Extruders, Presented at a Pyrotek Sales
Utigard et al., “The Roles of Molten Salts in the Treatment of Alu Conference, Jun. 2002, 9 pages.
minum.” Canadian Metallurgical Quaterly 40 No. 3, pp. 327-334 Gruzleski et al., “The Treatment of Liquid Aluminum-Silicon
(2001). Alloys.” American Foundrymen's Society, Inc. pp. 204-205 (1990).
Williams et al., Removal of Alkali Metals from Aluminum, Light Office Action mailed from CIPO on Jan. 6, 2011 in Canadian Appli
Metals pp. 785-793 (2000). cation No. 2,668.473.
Beland et al., “Rotary Flux Injection: Chlorine-Free Technique for
Furnace Preparation.” Light Metals pp. 843-847 (1998). * cited by examiner
U.S. Patent Aug. 2, 2011 Sheet 1 of 4 US 7.988,763 B2

NaCl-KCl - MgCl,
Calculated liquidus projection
MgCl,
(714)

(771) Mol. 96 (801)

FIGURE 1
(PRIOR ART)
U.S. Patent US 7.988,763 B2

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 US 7,988,763 B2
1. 2
USE OF A BINARY SALT FLUX OF NACL Fluxes obtained by fusion of salts comprising magnesium
AND MGCL, FOR THE PURIFICATION OF chloride have hygroscopic properties. Consequently, the
ALUMINIUM OR ALUMINIUMALLOYS, AND packaging is an important factor in limiting the absorption of
METHOD THEREOF humidity during the manufacturing of Such fluxes.
There are examples of fluxes that are based on magnesium
FIELD OF THE INVENTION chloride. U.S. Pat. No. 1,377,374 relates to the use of a flux
having an equimolar composition of Sodium chloride and
The invention relates to the use of a binary salt flux com magnesium chloride for the production of manganese or mag
prising NaCl and MgCl, for the purification of a metal nesium alloys. U.S. Pat. No. 1,754,788 relates to the use of
selected from the group consisting of aluminum and alumi 10 this same flux in a process for the cleaning of magnesium.
num alloys, more particularly for the removal of alkali and U.S. Pat. No. 1,519,128 relates to the addition of calcium
alkaline-earth metals. The invention also relates to a method chloride to this composition and U.S. Pat. No. 2.262,105
for the purification of said metal with said binary salt flux. relates to the addition of potassium chloride and magnesium
oxide in addition to the calcium chloride. U.S. Pat. No. 5,405,
BACKGROUND OF THE INVENTION
15 427 mentions a flux based on Sodium chloride, magnesium
chloride, potassium chloride and carbon for the treatment of
metal.
The use of fluxes is well known in the field of metallurgy The article entitled “Salt Fluxes for Alkali and Alkali and
and these fluxes fulfill various functions. Alkaline Earth Element Removal from Molten Aluminum
Fluxes can be used to form a protecting layer at the Surface by David H. DeYoung shows the use of a ternary salt based on
of an alloy to prevent oxidation. When fluxes contain chemi magnesium chloride, Sodium chloride and potassium chlo
cal active agents, they can be used to clean furnace walls by ride for the removal of sodium, calcium and lithium from
softening accumulated layers of corundum. Some exothermic aluminum alloys. However, the article entitled “The Treat
fluxes are also used for cleaning dross and removing alumi ment of Liquid Aluminum-Silicon Alloys' by Gruzleski et
num trapped in oxide layers. 25 al., pp. 204-205 indicates that it is important to those skilled
Fluxes that are based on alkali chlorides and alkaline-earth in the art, not to use fluxes containing sodium salts. Therefore,
chlorides are also used for the refining of alloys. Those skilled even if a ternary flux salts having low content in Sodium salts
in the art generally define refining as the removal of alkali and may be tolerated, those skilled in the art are expressly invited
alkaline-earth metals, non metallic inclusions and hydrogen to avoid using Sodium salts.
from the alloys. 30 Initially, the refining of aluminum was carried out by bub
Sodium and calcium are always present as impurities in bling of chlorine and argon in the liquid metal. However, this
aluminum obtained from the Hall-Héroult process. Lithium created environmental problems due to emissions of chlorine,
fluoride is often added to the electrolytic bath to improve the chlorhydric acid and particles in Suspension. The use of salt
efficiency of cells. However, a small amount in the metallic fluxes was later adopted as a more ecologically-friendly solu
state is found dissolved in the aluminum. These impurities 35 tion.
entail quality issues. For example, in an alloy containing The refining fluxes are usually composed of alkali chlo
magnesium, the presence of sodium may interfere during the rides or alkaline-earth chlorides, which are mixed to obtain
hot rolling processes. The presence of sodium in aluminum melting points that are lower than the operating temperature
and silicon alloys neutralize the effect of phosphorus used for of alloys—the melting point of pure compounds being usu
the refining of grains. For the above-mentioned reasons, the 40 ally quite high.
use of fluxes containing Sodium is not recommended for Several methods can be used to incorporate salt fluxes in an
aluminum and its alloys, more particularly for aluminum alloy. U.S. Pat. No. 4,099,965 relates to a method where a flux
alloys comprising a magnesium content higher than 3% by of KCl and MgCl, is added in solid form in the bottom of a
weight or a silicon content higher than 10% by weight. preheated container before the addition of aluminum. More
Also, the presence of hydrogen in too high concentration 45 currently, fluxes are added by an inert gas in a pipe under the
may lead to a too high porosity of the aluminum during its Surface of the metal (lance fluxing). Recently, a method was
Solidification. During the recycling of aluminum, the pres developed where a hollow shaft brings the salt flux in the alloy
ence of non metallic inclusions is important. with a gas carrier, and the salt flux is dispersed by an agitator
Reactional kinetics for the withdrawal of calcium and (rotary flux injection). This method reduces the amount of salt
sodium in an aluminum alloy have been well studied. Natu 50 flux required for carrying out the purification while increas
rally, in these alloys, both impurities disappear according to a ing the dispersion of this salt flux in the alloy. Following the
kinetic of order 1 for small concentrations and order 0 for high addition of a salt flux to the metal, impurities and salts float on
concentrations. Because of its high vapor tension, sodium the surface of the liquid metal and can be easily removed.
oxidizes itself more rapidly than calcium, that is why calcium Advantageously, the use of Solid compounds obtained by
is used during cleaning tests. The addition of fluxes involves 55 melting of salts controls the granulometry. Particles may be
an increase of reactional constants and thereby a faster reduc used in batch processes or in continuous processes.
tion of the content in impurities. Mixing also has a non neg However, costs related to salt fluxes such as binary mix
ligible effect on the reduction of impurities. Mixing acceler tures of magnesium chloride and potassium chloride, are
ates the withdrawal of impurities by increasing the contact high. Furthermore, the use of salt fluxes having a substantial
between impurities and the salt flux. 60 content in Sodium chloride is not recommended by those
MgCl2 is one of the chemical active agents used for the skilled in the art due to perceived negative effects of sodium
withdrawal of impurities in alloys. Its concentration has a content in the resulting aluminum or aluminum alloys. In fact,
direct effect on the kinetic of withdrawal of calcium and when sodium chloride is present influxes for the purification
Sodium. Its melting point is 714°C., but in common fluxes, it of aluminum or aluminum alloys, those skilled in the art
is mixed with other salts to obtain a melting point between 65 currently will avoid or limit the use of sodium chloride. More
400 and 550° C. However, MgCl2 is hygroscopic and can not particularly, in the case of certain kinds of alloys Such as, for
be exposed for a long period of time to the Surrounding air. example, aluminum alloys having silicon content higher than
 US 7,988,763 B2
3 4
10% by weight and more particularly aluminum alloys having between 100 um and 3.35 mm. Preferably, said particles may
magnesium content higher than 3% by weight, those skilled have a particle size between 0.85 mm and 3.15 mm or
in the art currently recommend not using sodium chloride in between 100 um and 1 mm.
salt flux. Another embodiment of the invention relates to a use or a
During Applicant’s search for a more effective solution to method as defined in any one of the above-mentioned
the purification problem, it was Surprisingly noted that con embodiments, wherein the particles are contacted with the
trary to current apprehensions and beliefs of those skilled in liquid metal by injection with a gas injection equipment. A
the art, it is possible in a salt flux containing MgCl, to replace non limiting example of a gas injection equipment may con
expensive KCl by inexpensive NaCl. Consequently, the sist of a rotary injector known under the trade name SNIF
present invention offers an economical solution for the treat
10 PHD-50 commercialized by the Applicant.
ment of aluminum or aluminum alloys with an efficiency of Another embodiment of the invention relates to a use or a
purification that is equivalent to methods presently used. method as defined in any one of the above-mentioned
Indeed, contrary to apprehensions of those skilled in the art, embodiments, wherein the metal is an aluminum alloy having
there is no significant amount of Sodium in the resulting a magnesium content higher than 3% by weight.
15 Another embodiment of the invention relates to a use or a
aluminum or aluminum alloys when using the inventive puri method as defined in any one of the above-mentioned
fication method described herein.
Embodiments of the present invention show the following embodiments, wherein the metal is an aluminum alloy having
advantages: a silicon content higher than 10% by weight.
Economical advantages BRIEF DESCRIPTION OF THE DRAWINGS
Lower production costs because the melting point of the
flux is lower. The present invention will be better understood with refer
Lower costs of raw material. ence to the following drawings:
Efficiency equivalent to the purification methods using an FIG. 1: a phase diagram of a fused salt KC1/NaCl/MgCl;
existing well known salt flux sold under the trademark 25 FIG. 2: a phase diagram of a fused salt KCl/MgCl2:
Promag (40 wt % KC1-60 wt % MgCl). FIG. 3: a phase diagram of a fused salt NaCl/MgCl; and
Economical alternative to existing product sold under the FIG. 4: a comparative graphic concerning examples 5 to 8.
trademark Promag without creating any significant Phase diagrams of FIGS. 1 to 3 were extracted from factsage
accumulation of sodium within aluminum or aluminum web site (http://factsage.com).
alloys. 30
DESCRIPTION OF EMBODIMENTS OF THE
SUMMARY OF THE INVENTION INVENTION

A first preferred aspect of the invention relates to the use of In the following examples, the Applicant has noted, con
a salt flux for the purification of a metal selected from the 35 trary to apprehensions of those skilled in the art, that formu
group consisting of aluminum and aluminum alloys, said lations of salt fluxes comprising a binary mixture of NaCl and
metal being in liquid phase and said salt flux being a binary MgCl2 do not involve an increase of the concentration of
mixture of NaCl and MgCl2. metallic sodium in an aluminum alloy having magnesium
A second preferred aspect of the invention relates to a content. A non limiting example of Such an aluminum alloy
method for the purification of a metal selected from the group 40 may consist of an aluminum alloy having a magnesium con
consisting of aluminum and aluminum alloys, wherein said tent of 5% by weight. Consequently, it appears that there is no
method comprises: counter-indication of using a binary salt flux comprising
heating the metal to a liquid phase; and NaCl and MgCl2 for cleaning aluminum, especially in the
contacting the liquid metal with a salt flux consisting of a case of an aluminum alloy with high magnesium content.
binary mixture of NaCl and MgCl. 45 Formulations based on NaCl and MgCl, proposed accord
Another embodiment of the invention relates to a use or a ing to the present invention, show melting points that are
method as defined hereinabove, wherein more than 22% by lower than those of salt flux compositions sold by the Appli
weight of said binary mixture consists of NaCl. cant under the trademark Promag (40 wt % KC1, 60 wt %
Another embodiment of the invention relates to a use or a MgCl), for equivalent amounts of MgCl, which is the chemi
method as defined hereinabove, wherein the salt flux: 50 cally active agent for the withdrawal of impurities. The low
is a binary mixture of particles of NaCl and particles of ering of melting points represents a lowering of energy costs
MgCl2, or when melting the solid salt flux.
consists of particles resulting from the grinding of a fused Two fused salts have been evaluated in examples hereinaf
salt of NaCl and MgCl, in solid state; or ter, that is (on a weight basis) the following binary system salt
is a liquid mixture of NaCl and MgCl2. 55 flux and ternary system salt flux (prior art):
Another embodiment of the invention relates to a use or a 45% NaCl and 55% MgCl, with a melting point of 439° C.:
method as defined in any one of the above-mentioned and
embodiments, wherein the binary mixture comprises: a) from 20% NaCl, 20% KCl and 60% MgCl, with a melting point
40 to 50% by weight of NaCl; and b) from 50 to 60% by Of 396° C.
weight of MgCl2. More particularly, this binary mixture com 60 Also, example 1 illustrates an unexpected effect with
prises 45% by weight of NaCl and 55% by weight of MgCl, regard to the sodium concentration in an aluminum alloy
to form an eutectic mixture having a melting point of about when NaCl is added in a liquid aluminum alloy, that is, no
439 C. increase of the Sodium content in the alloy obtained.
Another embodiment of the invention relates to a use or a Preparation of each salt flux was made by mixing the salts
method as defined in any one of the above-mentioned 65 in an anhydrous solid phase in an appropriate oven. Then, by
embodiments, wherein when the salt flux is in the form of increasing the temperature of the oven, a fused compound in
particles, those particles have an average particle size liquid form was obtained. The liquid was then cooled down
 US 7,988,763 B2
5 6
quickly, grinded and sifted to obtain a granulometry that was EXAMPLE 4
appropriate for the selected method. In example 7 hereinafter,
the salt flux was made only by mixing the salts in an anhy About seventy-five kilos (75 kg) of A356 alloy were melted
drous Solid phase. and maintained in a liquid state at 700° C. in a crucible made
Salt fluxes have shown an optimal efficiency for the with of silicon carbide. Then, 53.5g of an aluminum alloy contain
drawal of Ca, Na and Li when used with a rotary injector such ing 10% by weight of calcium were added to the liquid A356
as a SNIF PHD-50 (tradename) commercialized by the Appli alloy while mixing it with an agitator having straight blades.
cant (Pyrotek). Of course, other methods of addition well Then the resulting aluminum alloy contained in the crucible
known to those skilled in the art and already mentioned for was left without agitation for 5 hours. During this time, the
10 calcium content of the resulting aluminum alloy was reduced
use in connection with prior art purification methods can be
used to carry out the purification. The concentrations of salt from 350 ppm to 150 ppm. Then, three hundred and sixty
fluxes required to carry out the purification may vary depend grams (360 g) of a salt flux made of 45 wt % NaCl and 55
ing on the selected method. wt % MgCl, were added to the resulting alloy while agitating
it in order to further purify it. The salt flux was prepared from
15 NaCl in powder form and sold under the trademark SIFTO
EXAMPLE1
INDUSTRIAL and MgCl, in flake form and sold under the
trademark SKYLINE.
In a crucible made of graphite, one hundred grams (100 g) Analyses made on the purified aluminum alloy have shown
of NaCl in powder form and sold under the trademark SIFTO a reduction of the Ca content from 150 ppm to 70 ppm, that is
INDUSTRIAL were agitated in 1.5 kg of a liquid AA110 a reduction of 53%, immediately after the addition of the salt
aluminum (sold under the trademark Alcan) in which 5 wt % flux, and this Ca content drops to 25 ppm 3 hours after the
of solid magnesium were added. The crucible was maintained addition. Also, analyses have shown that the Sodium content
at 850° C. during the whole test. Samples were taken every was in the order of 2 ppm.
day during 7 days. According to these daily analyses, the
Sodium content of the resulting aluminum alloy was at a 25 EXAMPLE 5
minimal level of 2 ppm during the whole test, showing that,
contrary to apprehensions of those skilled in the art, an addi Fifty grams of a flux were prepared in a small alumina
tion of NaCl does not involve an absorption of sodium in an crucible by mixing 22.5 grams of NaCl in powder form and
aluminum alloy with high magnesium content. sold under the trademark SIFTO INDUSTRIAL, and 27.5
30 grams of MgCl, in flake form and sold under the trademark
EXAMPLE 2 SKYLINE. The mixture was subjected to a temperature of
550° C. during 45 minutes. The liquid mixture obtained was
In a graphite crucible, fifteen grams (15 g) of a salt flux then poured into an enameled-coated bowl for quick solidifi
consisting of a binary mixture of 45 wt % NaCl and 55 wt % cation. The salt flux obtained was then grinded with in a
MgCl, were agitated in 1.5 kg of a liquid AA1100 aluminum 35 mortar and sifted. The fraction having a particle size lower
alloy (sold under the trademark Alcan) in which 5 wt % of than 3150 microns and higher than 105 microns was recov
magnesium were added. The crucible was maintained at 720° ered.
C. during 90 minutes and samples were taken every 30 min Two kg of AA1100 aluminum alloy (sold under the trade
utes. The sodium level in the crucible was maintained at a mark Alcan) were melted and kept in liquid state at 700° C. in
minimal level of 3 ppm during the whole experiment, show 40 a graphite crucible. To this alloy, 2 grams of an aluminum
ing that an addition of a flux comprising NaCl does not alloy consisting of 90 wt % of aluminum and 10 wt % of
involve an absorption of sodium in an aluminum alloy with calcium (sold under the trademark KB Alloys) were added in
high magnesium content. The salt flux was prepared from a Vortex formed with an agitator in the liquid metal, said
NaCl in powder form and sold under the trademark SIFTO agitator having straight blades. The agitation was maintained
INDUSTRIAL and MgCl, in flake form and sold under the 45 during 2 minutes. A sample of the metal was taken for analy
trademark SKYLINE. sis. Two grams of the flux formed hereinabove were added to
the liquid aluminum alloy doped with calcium while agitating
EXAMPLE 3 for 2 minutes. Samples were taken immediately after the end
of the agitation as well as 30, 60 and 90 minutes later.
Prior Art 50 Analyses of samples have shown a reduction of the Calevel
from 115 ppm to 3 ppm after the addition of the salt flux.
In a graphite crucible, fifteen grams (15 g) of a salt flux Thirty minutes later, the calcium level was under 2 ppm. No
consisting of a ternary mixture of 20 wt % NaCl, 20 wt % KCl increase in the Sodium content was noted during the test. The
and 60 wt % MgCl, were agitated and added in 1.5 kg of a level of sodium in the alloy was in the order of 2 ppm.
liquid AA1100 aluminum alloy (sold under the trademark 55
Alcan) in which 5 wt % of magnesium were added. The EXAMPLE 6
crucible was maintained at 720° C. during 90 minutes and
samples were taken every 30 minutes. The sodium level in the Prior Art
crucible was maintained at a minimal level of 3 ppm during
the whole experiment, showing that an addition of a ternary 60 Fifty grams of a salt flux were prepared in a small alumina
flux comprising a small amount of NaCl does not involve an crucible by mixing 10 grams of NaCl in powderform and sold
absorption of sodium in an aluminum alloy with high mag under the trademark SIFTO INDUSTRIAL, 10 grams of KCl
nesium content. The salt flux was prepared from NaCl in in powderform and sold under the trademark IMC KALIUM,
powder form and sold under the trademark SIFTO INDUS and 30 grams of MgCl2 in flake form and sold under the
TRIAL, KCl in powder form and sold under the trademark 65 trademark SKYLINE. The mixture was subjected to a tem
IMC KALIUM and MgCl2 in flake form and sold under the perature of 550° C. during 45 minutes. The liquid mixture
trademark SKYLINE. obtained was then poured into an enameled-coated bowl for
 US 7,988,763 B2
7 8
quick solidification. The salt flux obtained was then grinded in the Sodium content was noted during the test. The Sodium
in a mortar and sifted. The fraction having a particle size level was in the order of 2 ppm.
lower than 3150 microns and higher than 105 microns was EXAMPLE 8
recovered.
Two kg of AA1100 aluminum alloy (sold under the trade Two kg of AA1100 aluminum alloy (sold under the trade
mark Alcan) were melted and kept in liquid state at 700° C. in mark Alcan) were melted and kept in liquid state at 700° C. in
a graphite crucible. To this alloy, 2 grams of an aluminum a graphite crucible. To this alloy, 2 grams of an aluminum
alloy consisting of 90 wt % of aluminum and 10 wt % of alloy consisting of 90 wt % of aluminum and 10 wt % of
calcium (sold under the trademark KB Alloys) were added in 10 calcium (sold under the trademark KB Alloys) were added in
a Vortex formed with an agitator in the liquid metal, said
a Vortex formed with an agitator in the liquid metal, said agitator having straight blades. Stirring was maintained dur
agitator having straight blades. The agitation was maintained ing 2 minutes. A sample of the metal was taken for analysis.
during 2 minutes. A sample of the metal was taken for analy Two grams of the PROMAG SI (trademark) formed of 40
sis. Two grams of the salt flux formed hereinabove were wt % KCl and 60 wt % MgCl, with a granulometry 99%
15
added to the liquid aluminum alloy doped with calcium while lower than 3150 microns and 95% higher than 850 microns,
were added to the alloy doped with calcium while agitating
agitating for 2 minutes. The agitation was stopped and for 2 minutes. The agitation was stopped and samples were
samples were taken immediately after the end of the agitation later taken immediately after the end of the agitation as well
as well as 30, 60 and 90 minutes later. as 30, 60 and 90 minutes later.
Analyses of samples have shown a reduction of the Calevel
The analysis of samples shows a reduction of the Ca level from 75 ppm to 7ppm after the addition of the salt flux. Thirty
from 108 ppm to 7 ppm after the addition of the salt flux. minutes later the calcium level was under 5 ppm (see FIG. 4).
Thirty minutes later, the calcium level was at 2 ppm and after These analyses show that binary fluxes of NaCl and MgCl,
60 minutes the calcium level was under 1 ppm. No increase in are more efficient than a ternary flux of NaCl, KCl and MgCl,
Sodium content was noted during the test. The Sodium level or a binary flux of KCl and MgCl2.

Ex. S Ex. 6 Ex. 7 Ex. 8

NaCl-MgCl, NaCl-KCl–MgCl, NaCl-MgCl2 Promag SI*
(45-55) (20-20-60) (45-55) (KCl–MgCl2) Reference
Time Fused Fused Mix (40-60) (no flux)
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
120 min 39

trademark

was in the order of 2 ppm. This example shows that a ternary 40 The present invention has been described with respect to its
flux having a low content in NaCl does not increase the level preferred embodiments. The description and the drawings are
of sodium in the alloy. only intended to aid to the understanding of the invention and
EXAMPLE 7
are not intended to limit its scope. It will be clear to those
skilled in the art that numerous variations and modifications
Fifty grams of a salt flux were prepared only by mixing
45 can be made to the implementation of the invention without
22.5 grams of NaCl in powder form and sold under the trade being outside the scope of the invention. Such variations and
mark SIFTO INDUSTRIAL with a granulometry 95% lower modifications are covered by the present invention. The
than 840 microns and 95% higher than 300 microns, and 27.5 invention will be now described in the following claims:
grams of MgCl, in flake form and sold under the trademark 50 What is claimed is:
SKYLINE with a granulometry 90% lower than 4.7 mm and 1. A method for the purification of a metal selected from the
85% higher to 1 mm.
Two kg of AA1100 aluminum alloy (sold under the trade group consisting of aluminum and aluminum alloys, wherein
mark Alcan) were melted and kept in liquid phase at 700° C. said method comprises:
in a graphite crucible. To this alloy, 2 grams of an aluminum heating the metal to a liquid phase; and
alloy consisting of 90 wt % of aluminum and 10 wt % of 55 contacting the liquid metal with a salt flux consisting of a
calcium (sold under the trademark KB Alloys) were added in binary mixture of NaCl and MgCl, wherein said salt
a Vortex formed with an agitator in the liquid metal, said flux is in the form of particles obtained by grinding a
agitator having straight blades. The agitation was maintained fused salt of NaCl and MgCl2.
during 2 minutes. A sample of the metal was taken for analy 2. The method according to claim 1, wherein said particles
sis. Two grams of the salt flux formed hereinabove were 60 have an average particle size between 100 um and 3.35 mm.
added to the liquid aluminum alloy doped with calcium while 3. The method according to claim 1, wherein said particles
agitating for 2 minutes. Agitation was stopped and samples have an average particle size between 0.85 mm and 3.15 mm.
were taken immediately after the end of the agitation as well 4. The method according to claim 1, wherein said particles
as 30, 60 and 90 minutes later. have an average particle size between 100 um and 1 mm.
Analyses of samples have shown a reduction of the Calevel 65 5. The method according to claim 1, wherein said particles
from 77 ppm to 2 ppm after the addition of the salt flux. Thirty are contacted with the liquid metal by injection with gas
minutes later, the calcium level was under 1 ppm. No increase injection equipment.
 US 7,988,763 B2
10
6. The method according to claim 1, wherein the metal is an 20. The method according to claim 19, wherein said binary
aluminum alloy having a magnesium content higher than 3% mixture comprises:
by weight. a) from 40 to 50% by weight of NaCl; and
7. The method according to claim 1, wherein the metal is an b) from 50 to 60% by weight of MgCl.
aluminum alloy having a silicon content higher than 10% by 21. The method according to claim 20, wherein said binary
weight. mixture comprises:
8. A method for the purification of a metal selected from the a) 45% by weight of NaCl; and
group consisting of aluminum and aluminum alloys, wherein b) 55% by weight of MgCl2:
said method comprises: to form an eutectic binary mixture having a melting point
10 of about 439° C.
heating the metal to a liquid phase; and 22. The method according to claim 19, wherein said par
contacting the liquid metal with a salt flux consisting of a ticles have an average particle size between 100 um and 3.35
binary mixture of particles comprising: .
a) from 22% to 50% by weight of NaCl; and 23. The method according to claim 19, wherein said par
b) from 50% to 78% by weight of MgCl2. 15 ticles have an average particle size between 0.85 mm and 3.15
9. The method according to claim8, wherein the metal is an .
aluminum alloy having a magnesium content higher than 3% 24. The method according to claim 19, wherein said par
by weight.
10. The method according to claim 8, wherein the metal is ticles have an average particle size between 100 um and 1
.
an aluminum alloy having a silicon content higher than 10% 25. The method according to claim 19, wherein said par
by weight. ticles are contacted with the liquid metal by injection with gas
11. A method for the purification of a metal selected from injection equipment.
the group consisting of aluminum and aluminum alloys, 26. The method according to claim 19, wherein the metal is
wherein said method comprises: an aluminum alloy having a magnesium content higher than
heating the metal to a liquid phase; and 25 3% by weight.
contacting the liquid metal with a salt flux consisting of a 27. The method according to claim 19, wherein the metal is
binary mixture of particles comprising: an aluminum alloy having a silicon content higher than 10%
a) from 40 to 50% by weight of NaCl; and by weight.
b) from 50 to 60% by weight of MgCl. 28. A method for the purification of a metal selected from
12. The method according to claim 11, wherein said binary 30 the group consisting of aluminum and aluminum alloys,
mixture comprises: wherein said method comprises:
a) 45% by weight of NaCl; and heating the metal to a liquid phase; and
b) 55% by weight of MgCl; contacting the liquid metal with a salt flux consisting of a
to form an eutectic binary mixture having a melting point liquid binary mixture of NaCl and MgCl2, wherein more
of about 439° C.
13. The method according to claim 11, wherein said par
35 than 22% by weight of said binary mixture consists of
NaCl.
ticles have an average particle size between 100 um and 3.35 29. The method according to claim 28, wherein the metal is
.
14. The method according to claim 11, wherein said par an aluminum alloy having a magnesium content higher than
ticles have an average particle size between 0.85 mm and 3.15 3% by weight.
.
40 30. The method according to claim 28, wherein the metal is
15. The method according to claim 11, wherein said par an aluminum alloy having a silicon content higher than 10%
by weight.
ticles have an average particle size between 100 um and 1 31. A method for the purification of a metal selected from
.
16. The method according to claim 11, wherein said par the group consisting of aluminum and aluminum alloys,
ticles are contacted with the liquid metal by injection with gas
45 wherein said method comprises:
injection equipment. heating the metal to a liquid phase; and
17. The method according to claim 11, wherein the metal is contacting the liquid metal with a salt flux consisting of a
an aluminum alloy having a magnesium content higher than liquid binary mixture of NaCl and MgCl2 comprising:
3% by weight. a) from 40 to 50% by weight of NaCl; and
18. The method according to claim 11, wherein the metal is
50 b) from 50 to 60% by weight of MgCl.
an aluminum alloy having a silicon content higher than 10% 32. The method according to claim 31, wherein the liquid
by weight. binary mixture comprises:
19. A method for the purification of a metal selected from a) 45% by weight of NaCl; and
the group consisting of aluminum and aluminum alloys, b) 55% by weight of MgCl,
wherein said method comprises:
55 33. The method according to claim 31, wherein the metal is
heating the metal to a liquid phase; and an aluminum alloy having a magnesium content higher than
contacting the liquid metal with a salt flux consisting of a 3% by weight.
binary mixture wherein more than 22% by weight of 34. The method according to claim 31, wherein the metal is
said binary mixture consists of NaCl, and wherein said an aluminum alloy having a silicon content higher than 10%
60 by weight.
salt flux is in the form of particles obtained by grinding
a fused salt of NaCl and MgCl2.