U.S. patent number 3,753,690 [Application Number 05/071,112] was granted by the patent office on 1973-08-21 for treatment of liquid metal.
This patent grant is currently assigned to The British Aluminium Company Limited. Invention is credited to Malcolm Victor Brant, Edward Frederick Emley.
United States Patent |
3,753,690 |
Emley , et al. |
August 21, 1973 |
TREATMENT OF LIQUID METAL
Abstract
A process for removing non-metallic constituents in molten
metal, particularly aluminium and its alloys. In one treatment the
metal is flowed through a multiplicity of flux-lined channels which
are conveniently provided by a bed of flux-coated granules of a
size such that the channels are large enough not to become clogged
during use. In another treatment the metal is degassed by
continuously passing it through a containing vessel while passing a
substantially inert gas such as nitrogen therethrough under a flux
cover; this can be followed by passing the metal through the
flux-lined channels.
Inventors: |
Emley; Edward Frederick
(Chalfont St. Giles, EN), Brant; Malcolm Victor
(Stoke Poges, EN) |
Assignee: |
The British Aluminium Company
Limited (Gerrards Cross, EN)
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Family
ID: |
10436143 |
Appl.
No.: |
05/071,112 |
Filed: |
September 10, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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835872 |
Jun 2, 1969 |
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Foreign Application Priority Data
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Sep 12, 1969 [GB] |
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45,163/69 |
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Current U.S.
Class: |
75/412; 75/680;
266/215; 75/678; 266/220 |
Current CPC
Class: |
C22C
1/02 (20130101); C22B 21/066 (20130101) |
Current International
Class: |
C22B
21/06 (20060101); C22B 21/00 (20060101); C22C
1/02 (20060101); C22b 021/06 (); C22b 009/10 () |
Field of
Search: |
;75/67,68,93,94
;148/23,26 ;210/10,69 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Rosenberg; Peter D.
Parent Case Text
This application is a continuation-in-part of our application Ser.
No. 835,872 filed on 2nd June, 1969, and now abandoned.
Claims
We claim:
1. A process for removing solid, non-metallic constituents from
molten metal which comprises
flowing the molten metal at a temperature up to 800.degree.C.
through a bed of coarse refractory granules substantially of such a
size as to be retained on a 3/8 in. aperture screen, while
maintaining in a molten state on at least some of said granules in
said bed a molten salt flux coating, said bed being submerged
beneath the surface of the molten metal,
maintaining said temperature whereby the salt flux on said granules
is in molten condition, said salt flux being selected from the
group consisting of mixtures, which are molten at said temperature,
of salts selected from the group consisting of chlorides and
fluorides of alkali metals, alkaline earth metals and
magnesium.
2. A process in accordance with claim 1, wherein a layer of said
molten flux is maintained on the surface of said molten metal, and
nitrogen is passed through said molten metal to degas said molten
metal.
3. A process in accordance with claim 1, wherein said coarse
refractory granules are Al.sub.2 O.sub.3 balls of 3/8 in. minimum
size.
4. A process in accordance with claim 1, further comprising flowing
said molten metal through a second bed of substantially uncoated
coarse refractory granules.
5. A process for removing non-metallic constituents including
hydrogen and solid particles from liquid aluminum and its alloys in
a continuous manner which comprises
flowing such liquid metal at a temperature up to 800.degree.C.
through a containing vessel,
maintaining a molten salt flux layer on the surface of metal in the
containing vessel,
simultaneously passing a substantially inert gas into the liquid
metal, and
thereafter flowing the liquid metal through a bed of coarse
refractory granules substantially of a size to be retained on a 3/8
in. aperture screen, said bed being submerged beneath the surface
of the molten metal,
the inert gas being passed into the container and into the liquid
metal in such a manner as to create vigorous turbulence whereby a
coating of said molten salt flux is produced and maintained on at
least some of said granules, said salt flux being selected from
mixtures of salts which are molten at said temperature and which
salts are selected from the group consisting of chlorides and
fluorides of alkali and alkaline earth metals and magnesium.
6. A process in accordance with claim 5, wherein said containing
vessel is divided by a baffle wall to provide a substantially
U-shaped vessel in which the direction of liquid metal flow is down
a first leg of the U and up a second leg of the U, wherein said
process comprises passing said inert gas upwardly through the
liquid metal in said first leg with said molten salt layer being
maintained on the surface of the liquid metal in said first
leg.
7. A process in accordance with claim 5, wherein said substantially
inert gas is nitrogen.
8. A process in accordance with claim 5, wherein said bed of coarse
refractory granules is located in a second vessel downstream from
said containing vessel.
9. A process in accordance with claim 5 for additionally removing
sodium metal from the liquid aluminium, wherein said flux contains
at least 5 percent by weight of MgCl.sub.2 and is substantially
free of the fluoride and complex fluorides of sodium.
10. A process for removing solid non-metallic constituents from
molten aluminum and its alloys in a continuous manner which
comprises
continuously flowing the molten metal at a temperature up to
800.degree.C. through a containing vessel,
maintaining a molten salt flux layer on the surface of molten metal
in the containing vessel,
continuously creating vigorous turbulence in the molten metal in
contact with the molten flux within the containing vessel; and
thereafter continuously flowing the molten metal having some molten
flux entrained therein through a flux trap comprising a bed of
coarse refractory granules substantially of a size to be retained
on a 3/8 in. aperture screen, said bed being submerged beneath the
surface of the molten metal, whereby at least some of said granules
become coated with said molten salt flux,
said salt flux being selected from mixtures of salts which are
molten at said temperature and which salts are selected from the
group consisting of chlorides and fluorides of alkali and alkaline
earth metals and magnesium.
11. A process in accordance with claim 10 for removing hydrogen and
solid particles wherein the residence time of said molten metal in
said containing vessel is at least 11/2 min., said vigorous
turbulence is created by passing a substantially inert gas into
said molten metal at a rate sufficient to provide at least 10 cu.
ft. of inert gas per ton of molten metal.
12. A process in accordance with claim 11, wherein said molten flux
layer is provided in an amount of at least 1 lb. of flux for each
100 sq. in. of surface area of said molten metal and wherein said
flux is substantially free of oxides, oxysalts, fluorosilicates and
volatile halides.
13. A process in accordance with claim 12, wherein said gas is
nitrogen.
14. A process in accordance with claim 11, wherein said flux trap
further comprises a layer of fluoride.
Description
FIELD OF THE INVENTION
This invention relates to improvements in the treatment of liquid
metal, particularly but not exclusively molten aluminium and
especially molten aluminium intended for the production of ingots
for working.
BACKGROUND OF THE INVENTION
It is well known that liquid aluminium contains varying amounts of
non-metallic constituents, i.e. gas and non-metallic inclusions,
and that their presence may give rise to defects in finished
products. Many procedures have been proposed for the removal of the
gas and inclusions. Thus the gas content may be reduced to an
acceptable level by bubbling chlorine, nitrogen or argon through
the melt or by treatment of the metal with hexachlorethane. The use
of chlorine and hexachlorethane give rise to a fume disposal
problem necessitating expensive equipment, whereas with the
nitrogen treatment as heretofore proposed, the metal becomes
contaminated through formation of non-metallic inclusions.
For removal of inclusions various filtration procedures have been
suggested, for example, those of British Patent Specifications Nos.
701,273 and 831,637 in which the metal is caused to flow from one
chamber to another through a bed of refractory granules, the two
chambers being separated by a baffle. The preferred filter material
of British Patent Specification No. 831,637 is a tabular alumina of
3-14 A.S.T.M. mesh size (0.056-0.250 ins. aperture) supported on a
bed of coarse granules 1/4 in. - 3/4 in. size. In U.S. Pat. No.
3,039,864 it is proposed to pass the metal down through a filter
bed and at the same time to pass an inert gas, e.g. argon, through
the bed in an upward direction, thereby effecting a degree of
degassing at the same time as the filtration. It is, however, usual
to carry out a degassing operation, e.g. with chlorine, in a
holding furnace prior to passage of the metal through the filter
unit. U.S. Pat. No. 3,039,864 states that nitrogen can be used in
place of argon if the formation of nitrides can be tolerated, but
that chlorine is undesirable since it gives rise to chlorides which
cause rapid blocking of the filter. Examination of the filter bed
of such a filter after use shows that oxide and other non-metallic
inclusions are trapped in the metal in the interstices between
flakes of tabular alumina, but that the metal does not wet the
flakes. In consequence, the filtered impurities are loosely
contained in the filter bed and are readily released if the filter
is accidentally jolted or is prodded in order to promote a faster
metal flow. The action of the filter bed is not one of filtration
but of settlement of impurities from the liquid during quiescent
flow through the many channels between the flakes. Special
procedures are needed at the outset to persuade the liquid metal to
pass through this type of filter bed, the minimum thickness of
which is 6 in., and partial blockage of flow may occur during use
so that a considerable hydrostatic head is needed to maintain the
desired rate of flow which, for multi-strand casting of large
blocks, may exceed 600 lb/min.
SUMMARY OF THE INVENTION
We have discovered that non-metallic inclusions can be removed from
molten aluminium by causing the aluminium to flow through a
cleaning device comprising a bed providing a multiplicity of
flux-lined tortuous channels, e.g. very coarse granules the surface
of which have been coated with a thin layer of liquid flux. Alumina
balls of 3/4 in. diameter are suitable. With such a cleaning device
removal of inclusions is at least as effective as with the flake
filter of U.S. Pat. No. 3,039,864 but the present invention
presents additional advantages. Because of the flux layer on the
alumina balls, they are wetted by the metal and inclusions therein
coming in contact with the flux film readily adhere thereto. In
consequence, the inclusions are retained in the bed and are not
readily released on jolting the bed. Furthermore, because of the
coarse nature of the granular bed which can be used, no special
steps are needed to start the metal flow, there is no fear of
blockage of the system, and metal flows through the bed without the
need for a hydrostatic head of metal.
According to one aspect of the present invention there is provided
a process for removing non-metallic constituents in motlen metal
especially aluminium which comprises flowing the metal through a
multiplicity of flux-lined channels.
The channels are desirably provided by a bed or layer of coarse
refractory granules coated with a flux.
The coarse refractory granules are preferably of alumina and may be
in the form of alumina balls of approximately 3/4 in. diameter and
preferably not less than 3/8 in. diameter. Suitable flux
compositions are given in Table I below.
Although tests have shown little tendency for the flux coating to
be removed from the coated alumina balls by passage of the metal
over them, the treated metal can, if desired, be stripped of any
entrained chloride by passing it through a bed of uncoated
granules, for example, alumina balls, which are readily wetted by
chloride-base fluxes.
Whilst the cleaning step of the present invention is very effective
in removing non-metallic constitutents, it is less so in removing
clusters of intermetallic particles, e.g. titanium-rich particles,
which may be suspended in the liquid metal. To remove these, the
metal may be flowed through a second bed composed of uncoated
refractory granules, whereby the intermetallic particles settle out
in the interstices of the second bed.
Advantageously, the metal is flowed upwardly through the second
bed.
The dirtying effect of nitrogen in the degassing of aluminium is
well known, and because of this effect nitrogen has found little
practical favour as a degassing agent for aluminium. The inclusions
produced on nitrogen treatment give rise to bubbling when a sample
of the liquid is solidified under low pressure, as in the
Straube-Pfeiffer test, even when the hydrogen content of the metal
is very low. In consequence, the progress of gas removal by
nitrogen cannot readily be assessed by using this test. Instead use
has been made of more expensive degassing agents such as chlorine
and hexachlorethane which do not give rise to inclusions and in
fact exert a cleaning effect by virtue of their fluxing action.
We have now discovered that the dirtying effect produced by
nitrogen treatment of the molten metal can be materially reduced,
if not entirely obviated, by introducing the nitrogen into the
molten metal whilst maintaining a continuous liquid flux cover over
the molten metal. This treatment is not limited to the use of
nitrogen as other gases inert to the molten metal being treated,
such as argon, carbon monoxide and carbon dioxide may be used at
least with some alloys.
Thus, in another aspect the invention provides a process for
removing non-metallic constituents from molten metal, especially
aluminium, by passing a substantially inert gas therethrough whilst
maintaining a liquid flux cover over the molten metal and
subsequently flowing the metal through a device comprising a
plurality of flux-lined channels.
It is preferred to introduce the gas, e.g. nitrogen, into the
molten metal through a tube or brick of porous non-carbonaceous
refractory material.
The worst conditions for dirtying the metal are provided by
introducing the gas through porous graphite or carbon tubes in the
absence of a flux cover. However, such carbonaceous tubes can be
employed if the liquid flux cover is maintained over the molten
metal and especially where the latter is subsequently flowed
through a bed or layer of coarse refractory granules coated with
flux. Even a perforated iron tube can be used, but this is not
preferred since, even though the metal does not become dirtied, any
protective dressing applied to the tube is liable to become wetted
by the flux cover with consequent attack of the tube by the motlen
aluminium. The iron tube may be coated with a vitreous enamel to
reduce attack by molten aluminium.
If a porous non-carbonaceous refractory tube or brick is used for
introducing the nitrogen and a liguid flux cover is applied to the
metal surface, then dirtying of the metal does not occur. In fact,
metal which has been made dirty for experimental purposes, e.g. by
addition of a porportion of oily swarf and/or by nitrogen treatment
through a graphite tube in the absence of a flux cover, can
actually be cleaned by providing a liquid flux cover and gassing
the metal with nitrogen. The more rapid the stream of nitrogen the
greater the cleaning action because of the increased contact
between metal and flux cover. By contrast, in the conventional
treatment of aluminium through carbonaceous tubes in the absence of
a continuous liquid flux cover, the more rapid the nitrogen flow
the dirtier the metal becomes. When nitrogen degassing is carried
out with porous refractory tubes, no difficulty is encountered in
applying the Straube-Pfeiffer test to assess the progress of gas
removal.
If the turbulence produced in the liquid aluminium which gives rise
to intimate contact between metal and flux is sufficiently
prolonged, it is possible not only to remove oxide and other
non-metallic inclusions originally present in the metal to be
treated but also to wet and absorb inclusions arising from the
introduction of nitrogen through carbonaceous refractories as
rapidly as these inclusions can form. Under such circumstances it
is not essential to flow the degassed metal through a bed of
flux-coated coarse refractory granules in order to produce clean
degassed metal, and we have found that when dirty gassy metal is
degassed with nitrogen under a flux layer metal of very low gas
content is readily obtained in a high state of cleanliness and
showing complete freedom from bubbles when subjected to the
Straube-Pfeiffer vacuum solidification test, even though the
nitrogen is introduced through porous carbonaceous
refractories.
Such a process of degassing under a liquid flux is not readily
applicable to the treatment of metal in a holding furnace such as
the large reverberatory furnaces used in conventional practice,
because of the quantity of flux required to maintain a liquid flux
film over such a large area; it may however be carried out in a
forewell to, or alcove, or cubicle within, such a reverberatory
furnace or in a vessel of small cross-sectional area placed between
the holding furnace and the casting machine and through which the
metal is caused to flow.
The achieve best results it is necessary to provide a minimum
quantity of nitrogen in relation to the quantity of metal to be
treated, a sufficiently long time of contact between the metal and
flux, a minimum quantity of flux per unit area of metal surface,
and adequate turbulence.
According to a further aspect of the present invention liquid
aluminium is cleaned and degassed in continuous manner by causing a
stream of liquid metal to flow through a containing vessel of such
capacity in relation to the metal flow that the residence time of
the metal in the containing vessel is at least 11/2 min., passing a
substantially inert gas into the metal in the containing vessel at
a rate sufficient to provide at least 10 cu.ft. per ton of liquid
metal, and maintaining a cover of liquid flux upon the surface of
the metal in the containing vessel.
Preferably the residence time of the metal in the degassing chamber
is at least 3 min.
The inert gas is preferably nitrogen.
The nitrogen flow rate may conveniently be such as to provide 30
cu.ft. per ton liquid metal in order to give a wide margin of
safety, but good results have been obtained with flow rates as low
as 10 cu.ft. per ton.
The minimum quantity of flux required is 1 lb for each 100 sq.in.
of surface area of liquid metal in the degassing chamber and 2-3 lb
per 100 sq.in. is preferred.
The degree of turbulence required is vigorous but should not be so
great as to give rise to splashing of metal from the containing
vessel. Introduction of the required flow rate of gas into a
chamber of the required size will normally result in an adequate
degree of turbulence when the gas is diffused in through porous
refractory bricks, tubes or diffuser plates. If a greater degree of
turbulence is needed it is possible to introduce a proportion of
the nitrogen into the degassing chamber through one or more narrow
tubes whereby the jets of gas so produced give rise to a tumbling
action of the metal which enhances the cleaning and degassing
effect. It is possible in this way to reduce the total flow rate of
gas required. Satisfactory results have also been obtained where
the whole of the nitrogen is introduced via jets.
The temperature of the molten aluminium during treatment should
normally be in the range of 675.degree.-800.degree. C.
700.degree.-750.degree. C being preferred.
We have now applied our discoveries of the cleaning effect of
coarse flux-coated refractory granules and of how to degas
aluminium with nitrogen under non-fouling conditions to the
problems of devising a single metal treatment unit capable of
receiving on the ingoing side, liquid metal which has been given no
degassing or settling treatment whatever, and delivering, on the
outgoing side, cleaned, degassed metal suitable for immediate
casting into billet or rolling block intended for the most exacting
applications. We have shown that such a result can be achieved by
combination of the following features:
1. The metal enters the first chamber of the unit by falling
through a liquid flux cover on the metal in the chamber, or is
introduced into the first chamber under a flux cover, e.g. by the
use of a baffle.
2. Nitrogen is passed through the liquid metal in the first chamber
under the flux cover, preferably using non-carbonaceous porous
refractory tubes or bricks to introduce the gas.
3. The metal is passed through the bed or column of flux-coated
coarse refractory granules into a second chamber.
4. The metal is passed through a layer or column of uncoated coarse
refractory granules in the second chamber and is then ready to be
cast.
BRIEF DESCRIPTION OF THE DRAWING
Some embodiments of the invention will now be described by way of
example, reference being made to the accompanying drawings in
which:
FIG. 1 is a somewhat schematic sectional view of an apparatus for
degassing and cleaning molten aluminium in accordance with the
invention;
FIG. 2 is a view similar to FIG. 1 illustrating a modification;
FIGS. 3, 4 and 5 illustrate modifications of a part of the
apparatus shown in FIG. 1;
FIG. 6 is a view similar to FIG. 1 but illustrating a further
modification;
FIGS. 7 and 8 illustrate still further modifications;
FIG. 9 is a sectional view of an apparatus suitable for cleaning
and degassing molten metal;
FIG. 10 is a fragmentary view illustrating a modification of the
apparatus of FIG. 9;
FIG. 11 is a sectional view of another cleaning and degassing
apparatus;
FIG. 12 is a sectional view of a further cleaning and degassing
apparatus;
FIG. 13 is a sectional view of another cleaning and degassing
apparatus;
FIGS. 14A and 14B are plan and sectional views respectively, of
part of a reverberatory furnace modified for use in the method
according to the invention; and
FIGS. 15A and 15B are plan and sectional views respectively, of
part of a reverberatory furnace modified in an alternative manner
for use in the method according to the invention.
DETAILED DESCRIPTION OF EMBODIMENTS
In the arrangement shown in FIG. 1, a crucible 1 having a long
pouring lip 1a is fitted with a baffle 2 which extends into the
crucible and effectively divides it into two chambers A and B which
are in communication by way of a space left below the baffle 2. A
tube 3 extends into the chamber A towards the floor thereof and
terminates in a porous plug 3a of non-carbonaceous refractory
material. A gas jet 4 is provided externally of the crucible 1 to
heat the contents thereof. A bed of flux-coated alumina balls 5 of
about 3/4 in. diameter is provided in the chamber A and a bed of
uncoated alumina balls of about 3/4 in. diameter is provided in the
chamber B. The bed of uncoated balls 6 can extend below the baffle
2 and below the bed 5. A launder 7 is provided to flow molten
aluminium from a holding furnace (not shown) to the chamber A. The
pouring lip 1a extends from the chamber B to a casting launder
8.
In the operation of the apparatus described, a body of molten
aluminium is maintained in the chamber A and a flux cover 9 is
maintained thereover. Molten aluminium enters the chamber A from
the launder 7 by falling through the flux cover 9. The metal is
degassed by a gas such as nitrogen which is supplied through the
tube 3 and escapes from the plug 3a to bubble up through the molten
aluminium in chamber A. As the pouring lip 1a is below the level at
which molten aluminium is maintained in the chamber A, there is a
continuous flow of molten aluminium from chamber A to chamber B and
out over the pouring lip 1a to the casting launder 8. The molten
aluminium therefore leaves the launder 7, falls through the flux
cover 9 into chamber A where it is degassed by the nitrogen, flows
downwards through the bed of flux-coated balls 5 in which
non-metallic inclusions are removed, passes under the baffle 2 and
upwards through the bed of uncoated balls 6 in which intermetallic
particles and residual flux are removed and then flows out over the
pouring lip 1a to the casing launder 8 in a condition ready for
casting.
The arrangement shown in FIG. 2 is similar in many respects to that
described with reference to FIG. 1 and like references are used to
denote like parts. In this case, the crucible 1 of the previous
example is replaced by a box 1b lined with refractory brick and the
plug 3a is replaced by a porous refractory tube 3b of
non-carbonaceous material. In this case, the launder 7 opens to the
chamber A below the level of the flux cover 9 which is confined
between the baffle 2 and a further baffle 2a and the walls of the
box 1b. The baffle 2a also serves to skim the molten aluminium
flowing to the chamber A from the furnace tap hole which is shown
at 10.
As the gas jet 4 of the previous example is not essential, it is
omitted from FIG. 2. In this case, the box 1b would be pre-heated
with a gas flame before being charged with molten aluminium and the
balls 5 and 6. Also, immersion heaters may be placed in the chamber
A to provide a greater control over the metal temperature.
FIGS. 3, 4 and 5 illustrate alternative ways in which the molten
aluminium can be introduced into the chamber A from the launder 7.
In FIG. 3, the launder 7 terminates in a spout 7a which extends
through the flux cover 9. In FIGS. 4 and 5 the launder 7 terminates
in a slight bowl the floor of which is in the form of a perforated
refractory screen 7b which breaks up the molten metal as it enters
the chamber A. In the embodiment shown in FIG. 4, the porous screen
7b is disposed within the flux cover 9 and in the embodiment shown
in FIG. 5 it is disposed above the flux cover 9. In addition to use
of a perforated refractory screen 7b or as an alternative thereto,
a splash plate (not shown) immersed in the flux cover 9 may be used
in order to break up the molten aluminium as it enters the chamber
A and so assist in the cleaning and degassing of the molten
metal.
In the arrangement shown in FIG. 6, the chambers A and B of the
previous examples are followed by further chambers C and D defined
by additional baffles 2b and 2c, the baffle 2b extending upwardly
from the floor of the crucible 1 or box 1a (as the case may be) to
below the level of the molten aluminium and the baffle 2c extending
downwardly into the molten aluminium and into a further bed of
uncoated coarse refractory balls 6a, e.g. of alumina, of about 3/4
in. diameter. Thus, the molten aluminium leaving the chamber B
flows over the baffle 2b into the chamber C, downwardly through the
bed of uncoated balls 6a, under the baffle 2c, upwardly through the
bed of uncoated balls 6a and out over the casting launder 8. This
passage of the metal through the bed of balls 6a renders the
treatment more effective particularly in respect of stripping the
metal of any residual flux entrained therein due to the downward
flow of the metal through the uncoated balls 6a in the chamber C.
The flux, being lighter than the molten aluminium tends to rise in
the chamber.
It will be appreciated that the two stages of the process described
above, namely, the first stage of degassing the molten aluminium
and flowing it through the bed of flux-coated balls 5 and the
second stage of flowing it through a bed of uncoated balls 6, can
be carried out in separate vessels. In such event, the chamber B
could be omitted and replaced by chambers C and D, also where space
between the holding furnace is not sufficient to accommodate
apparatus such as shown in FIG. 2, at least one of the beds of
balls 5 and 6 could be disposed along the casting launder 8 and
retained by suitable baffles. The degassing step could be carried
out under a flux cover in the holding furnace, for example, in an
alcove or forewell thereof.
Another way of separating the process into two convenient stages is
shown in FIG. 7. This is very similar to that shown in FIG. 6
except in this case the chambers A and B are contained in one
crucible 1 and the chambers C and D are contained in a separate
crucible 11, the two crucibles communicating by way of a launder
12. Also, in this example, the molten metal is introduced into the
chamber A below the flux layer 9 by way of baffle 2a as in the
example illustrated in FIG. 2 and the nitrogen is introduced
through a side wall to escape from the porous refractory tube
3b.
In the arrangement illustrated in FIG. 8, the degassing under the
flux is carried out in a separate first vessel 13 which may be a
brick-lined box, the metal being introduced below the flux-layer 9
by means of baffle 2a and flowing under baffle 2 upwards to spill
over into the launder 12 from which it pours into the baffled
crucible 14 containing a bed of alumina balls of which at least the
upper layers are flux-coated balls 5 followed on the other side of
the baffle 2 by a bed of uncoated balls 6. As mentioned previously,
for practical purposes, the bed of balls 5 need not initially be
coated with flux as it takes but a few minutes of operation of the
process for at least enough of them to become sufficiently coated
with flux for the process to operate efficiently. As can be seen
from FIG. 8, the nitrogen is supplied to the molten metal under the
flux cover 9 through two porous refractory tubes 3b.
The porous refractory non-carbonaceous material used to introduce
the gas, e.g. nitrogen, into the molten aluminium may be of any
suitable known type. Examples are refractories with a high alumina
content, silicon carbide, silicon carbide bonded with silicon
nitride and zircon. These are generally satisfactory if of
sufficient porosity, but a high silica content should be avoided.
Lumps of the refractory material may be shaped into plugs or bricks
and drilled to receive a refractory tube through which the gas is
fed to the plug, or the refractories may be in tube form. The
porous plugs or tubes may be cemented into the walls of the vessel
or may even form part of the floor.
The coarse refractory granules used in the beds 5, 6 and 6a may be
of chromite, corundum, forsterite, magnesia spinell, magnesium
fluoride, periclase, tyanite, silicon carbide or zircon, all of
which may be regarded as chemically inert to molten aluminium. They
may be, in the case of beds 6 an 6a of porous or non-porous
graphite, but balls of tubular alumina are, in general preferred to
provide the loose packing and freedom from blockage which is
desirable and which the concept of a bed of flux-coated coarse
balls 5 makes possible.
The granules should be of such a size as to be retained by a 1/2
in. screen and 3/4 in. diameter balls are preferred.
The temperature of the molten aluminium during treatment should be
in the range of 675.degree.-800.degree. C, 700.degree.-750.degree.C
being preferred.
Suitable compositions for the flux cover 9 and the flux coating of
the bed of balls 5 are given in Table 1. The flux should be
substantially free from oxides, oxysalts and fluosilicates and from
volatile halides. It should consist essentially of the chlorides
and fluorides of the alkali and alkaline earth metals including
magnesium and should be thinly fluid at the melting point of the
metal; when melted it should have a lower density than liquid
aluminium. ##SPC1##
As a flux for coating the balls and for providing a liquid flux
cover on the top of the metal in the degassing chamber, mixtures of
KC1 and NaCl with small additions of CaF.sub.2 are normally
preferred (Flux A). Additions of NaF or cryolite may be included to
reduce the melting point (Flux B), but a small amount of sodium
will then be introduced into the metal and this may be detrimental
to aluminium-magnesium alloys, e.g. of the A A 5356 type. For such
alloys it is preferable to use a flux which, far from introducing
sodium into the alloy, will reduce the very small content initially
present as an impurity in primary metal. Suitable fluxes contain
MgCl.sub.2 (Fluxes C, F.G.H.).
Thus by using a suitable flux cover such as one of Fluxes C.F.G. or
H the method of the present invention may be applied to the
continuous removal of sodium from liquid metal without the
generation of objectionable fumes such as occur when liquid
aluminium is treated with chlorine or hexachorethane.
If desired a heavy fluid flux may be used to coat the alumina balls
and thereby obviate the risk of flux being washed off the balls by
the flow of aluminium (Fluxes D and E). Such fluxes contain
BaCl.sub.2 and are in consequence more expensive. There is some
advantage in using a flux of type A in that as the cleaning process
proceeds any flux which becomes entrained in the metal is absorbed
on the uncoated balls which thereby become flux coated and so
extend the available area to which inclusions can adhere. Once the
chloride layer on the balls has become completely coated with
non-metallic inclusions this does not exhaust the useful life of
the filter, since more inclusions (e.g. oxide particles and films)
can adhere to those already adhering to the flux layer.
It is also possible to incorporate KF or potassium cryolite into
the flux in place of NaF or cryolite. When MgCl.sub.2 is also
present, the KF will be converted to KC1 however, and the
MgCl.sub.2 to MgF.sub.2.
By way of example the following experiment is cited. An apparatus
essentially as shown in FIG. 2 was constructed preheated by
removable gas jets, and a 6 in. deep layer of preheated 3/4 in.
diameter alumina balls added to each chamber. Metal was run into
the equipment until the chambers were approximately half full.
Preheated 3/4 in. diameter alumina balls were then dipped in a bath
of liquid flux and removed by means of a preheated hand ladle for
transfer to the ingoing side (Chamber A) of the baffle 2. A 4 in.
layer of flux-coated balls 5 was built up in this way in Chamber A.
A 6 in. layer of preheated 3/4 in. diameter alumina balls was then
built up in chamber B. When this was complete, approximately 20 lb.
of flux was placed on the metal in chamber A, and as soon as this
had melted the nitrogen supply was turned on and a flow rate of 2
cu.ft/min established. 5 tons of liquid A A 6063 type alloy which
had been subjected to neither a degassing nor a settling treatment
was passed through the equipment at a temperature of approximately
725.degree.C and a flow rate of 150 lb/min and cast by the
semi-continuous direct chill process into two rolling blocks of
sections 30 in .times. 10 in. Samples were taken from the metal
entering and leaving the equipment to determine gas and inclusion
content. The results obtained are shown in Table II. ##SPC2##
The metal charge used consisted entirely of scrap metal and
included approximately 1 ton of scalpings. In this particular
experiment the porous refractory tube shown in FIG. 2 was replaced
by porous carbon, so that the experiment represented a severe test
of the efficiency of the equipment in removing inclusions as well
as gas. We have carried out comparative experiments with the
process described by U.S. Patent No. 3,039,864 on the same scale as
the experiment described and subjecting the metal to a prior
chlorine degassing treatment, but even so the hydrogen contents
which result have been in the range 0.12-0.17 cm.sup.3 /100g which,
though very satisfactory for normal purposes, is not as low as the
figures obtained with the process of the present invention
(0.04-0.12 cm.sup.3 /100g). In considering why the latter process
should be the more effective, even though starting from completely
undegassed metal, it is probably significant that a solid froth of
chilled metal and argon, together with oxide formed from
adventitious air, tends to accumulate on the surface of the metal
in the degassing chamber during operation of the process of U.S.
Patent No. 3,039,864, whereas in the process of the present
invention the metal surface is maintained free from oxide. It is
well established that oxide scum on liquid aluminium hinders both
pick-up by and escape of gas from the metal, whereas a very thin
fluid flux layer on the metal surface allows gas to pass in or out
readily. The fluid flux layer used in the present invention
prevents all dross formation, despite the turbulence, and a clean
metal surface through which gas can readily escape is continually
maintained. Maintenance of a continuous layer of liquid flux is
unnecessary so long as the metal surface remains well fluxed.
If desired, argon may be used in place of nitrogen but there is no
obvious technical advantage in doing so, since metal of high
cleanliness and low gas content can be prepared with the cheaper
gas nitrogen. For best results the "white spot" grade of nitrogen
may be used but the ordinary commercial grade is nevertheless
satisfactory.
It is to be appreciated that although the bed of flux-coated
alumina balls 5, is the preferred way of obtaining the flux-lined
channels through which the molten metal is flowed, such channels
can be obtained in other ways. Thus, for example, the metal could
be flowed between overlapping spaced flux-lined baffles which
together form a tortuous path for the metal and provide the same or
similar effect as the flux-coated balls, or flowed through one or
more pads of coarse steel wool or turnings which have been first
dipped in liquid flux and then placed in a trough launder or
crucible, the pads being kept in position by means of suitably
placed baffles.
Whilst however the step of flowing the degassed molten metal
through the bed or column of flux-coated granules followed by the
bed or column of uncoated granules will ensure a high degree of
freedom from oxide inclusions etc., it is possible by controlling
the conditions, as already indicated, to remove non-metallic
inclusions so effectively at the prior stage of nitrogen treatment
under a liquid flux cover that subsequent passage through one or
more columns of granules may not be required even for critical
applications, provided some alternative means is available for
stripping from the outflowing metal any entrained flux which may be
present. In operating the present invention in the absence of a
column of granules we find that some liquid flux passes into the
exit chamber and coats the walls with a thin layer any excess of
which is displaced upwards to the metal surface. By placing one or
more baffles in the exit launder from the degassing chamber it is
possible to prevent seepage of liquid flux into the casting, but
this can be more effectively ensured by applying to the metal
surface on the inflowing side of an exit launder baffle a thin
layer of powdered CaF.sub.2 or MgF.sub.2. This layer may be
confined by two baffles to a short length of the launder, e.g. 6-9
in. The CaF.sub.2 may if desired, be applied also to the surface of
the metal in the exit chamber. Alternatively, CaF.sub.2 may be
replaced by an inspissated flux of the kind well known in the
magnesium industry so as to form a pasty viscous flux cover with a
high absorptive power for fluid fluxes of the type shown in Table
1.
The operation of the present invention whereby the columns of balls
is reduced in depth or eliminated is further illustrated by the
examples of FIGS. 9-15.
In the arrangement illustrated in FIG. 9 there is provided a
crucible 101 provided with a baffle wall 102 extending towards the
floor of the crucible to form the chambers A and B. A launder 103
supplies molten metal to the chamber A allowing it to pass through
a flux cover 104 floating on the metal in the chamber A. As will be
appreciated, the launder 103 can be disposed to admit molten metal
to the chamber A under the flux cover 104 or into the flux cover
104. Within the chamber A is disposed a porous plug 105 for
admitting the inert gas, which is preferably nitrogen, into the
molten metal. Molten metal flows through the chamber A under the
baffle 102 to the chamber B and overflows along an exit or casting
launder 106.
The apparatus, so far described, is broadly sufficient for the
purpose of the present invention. However, various modifications
may optionally be made to improve it. Thus a shallow bed 7 of 3/4
in. diameter alumina balls may be disposed in the chamber A to
provide a layer a few balls thick over the porous plug 105 to
reduce buoyancy effects and to assist in absorbing inclusions.
Furthermore, as shown, the bed 107 of balls may extend to a point
above the level of the base of the baffle 102 to reduce possible
channelling effects of the molten metal in its flow from chamber A
to chamber B. Additionally, also as shown, the bed 107 of balls may
extend into the chamber B.
The bed 107 of balls tend to remove any flux entrained in the metal
passing therethrough. Instead of the bed 107 of balls, or in
addition thereto, a launder baffle 108 may be disposed in the exit
or casting launder 106 to prevent seepage of liquid flux to the
casting location. This can even more effectively be prevented by
applying to the metal surface on the inflowing side of the exit
launder baffle 108 a thin layer 109 of powdered CaF.sub.2 or
MgF.sub.2. This can extend over the surface of the metal in the
chamber or can be confined between two baffles 108a and 108b in the
exit or casting launder a shown in FIG. 10.
The apparatus of FIG.11 is generally similar to that of FIG.9 and
comprises a crucible 101 divided by a baffle 102 into chambers A
and B. Chamber A is supplied with molten metal through a launder
103, the molten metal passing under a flux cover 104 being
prevented from running back along the launder by a baffle 110. An
open ended graphite tube 111 extends into the chamber A for
admitting nitrogen into the molten metal. The molten metal flows
through the chamber A under the baffle 102 to the chamber B and
overflows into an exit launder 112. The launder 112 may lead direct
to a casting launder (not shown) or to an intermediate baffled
crucible (not shown) filled with coarse alumina balls or other
coarse refractory granules.
The apparatus of FIG. 12 comprises a box 120 of refractory brick
divided by a baffle 102 into two chambers A and B. Immersion
heaters each consisting of a refractory sheath 121 of silicon
carbide or nitride containing a gas burner 122 extend into the
chamber A. Molten metal enters the chamber A from a launder 103 and
falls in a short unsupported stream 123 through a flux cover 104.
Rows of porous brick 124 communicate with steel tube inserts 125
through which nitrogen is directed into the chamber A. As in the
previously described apparatus, the molten metal flows through the
chamber A, under the baffle 102 to the chamber B and overflows into
an exit launder 126 where entrapped salts are removed by means of a
baffle 127 and a layer 128 of fluospar.
In the apparatus of FIG. 13 a refractory brick box 120 is divided
into three chambers A, B and C by baffles 102 and 132. A low
deflecting wall 133 extends upwardly from the base of the box 101
between the baffles 102 and 132. Molten metal enters the chamber A
from a launder 103 and falls in a stream 123 through a flux cover
104 as described with reference to FIG. 12. Nitrogen is introduced
into the chamber A through a graphite tube 111 as described with
reference to FIG. 3. The molten metal flows through the chamber A
under the baffle 102 and is deflected upwardly into chamber C by
the wall 133. The metal flows from the chamber C under the baffle
132 into the chamber B and overflows into an exit launder 134. As
the metal flows from chamber C to chamber B entrained flux is
deposited on the surface 135 of the baffle 132 leaving little, if
any, to be removed in the exit launder 134.
Example 1
dirty, undegassed Al-2.sup.1 /2%Mg alloy at 710.degree.C was flowed
at a speed of 600 lb per min into a brick box divided by a baffle
wall to form two chambers, the ingoing chamber having a capacity of
2,400 lb of metal corresponding to a residence time of the metal in
this chamber of 4 min. Commercial purity nitrogen was introduced
via porous graphite diffuser tubes into the ingoing chamber at a
flow rate of 400 cu.ft/hr corresponding to approximately 27 cu.ft.
nitrogen per ton of metal. Flux (c) was applied to the metal
surface in the ingoing chamber in amount corresponding to 3 lb per
100 sq.in. of surface area. Coarse alumina balls (3/4 in. diameter)
were used to cover the diffuser tubes to a depth of two balls in
the degassing chamber and to a few inches above the base of the
baffle in the exit chamber. Frequent Straube-Pfeiffer test samples
were taken from the exit launder during the progress of the cast
and the metal (12 ton) found to be of excellent quality, all the
test samples being bubble-free on solidification at a pressure of
approx. 2 Torr.
Example ii
dirty, undegassed primary metal at 730.degree.C was flowed at a
speed of 250 lb per min into a brick box divided by a baffle wall
to form two chambers, the ingoing chamber having a capacity of
1,000 lb of metal corresponding to a residence time of 4 min. White
spot nitrogen was introduced via porous graphite diffuser tubes
into the ingoing chamber at a flow rate of 150. cu.ft/hr
corresponding to approx. 20 cu.ft/ton. Coarse alumina balls (3/4
in. dia) were placed in the bottom of the brick box to a depth
sufficient to cover the bottom of the baffle. Flux F was applied in
amount corresponding to approx. 3 lb per 100 sq. in. of surface
area. Straube-Pfeiffer test samples were taken from the exit
launder at frequent intervals during the course of the cast (12
tons) and no bubble was developed in any of the tests during
solidification at a pressure of 2 Torr. The sodium content of the
ingoing metal was 0.0020-0.0025 percent and all outgoing samples
analysed less than 0.0005 percent. Two refractory baffles were
placed in the outgoing launder approximately 8 in. apart and
between them a layer of CaF.sub.2 approximately one-eighth in. deep
was sprinkled on the metal surface. Chloride tests carried out on
skimmings taken from the metal surface in the launder at a position
6 inches beyond the surface baffle gave negative results.
Example iii
in a test similar to that of Example II, dirty undegassed alloy of
the A A 6063 type flowing at a rate of 200 lb/min, was successfully
cleaned and degassed to show nil bubbles in the Straube-Pfeiffer
test using a nitrogen flow rate corresponding approximately to 30
cu.ft. per ton of metal introduced via porous graphite diffusers.
During the course of the cast two 1/4in. steel tubes were inserted
into the degassed chamber and nitrogen passed through at a flow
rate corresponding approximately to 5 cu.ft. per ton. The nitrogen
passing through the diffusers was then reduced to approximately 15
cu.ft/ton making a total consumption of 20 cu.ft/ton of nitrogen.
Straube-Pfeiffer samples were again bubble-free. Under the original
conditions of operation i.e. with all the nitrogen entering via the
diffuser tubes it was not possible to obtain nil bubbles
consistently in the Straube-Pfeiffer test with only 20 cu.ft/ton of
nitrogen passing, although the degassing achieved was
satisfactory.
Actual hydrogen analyses on samples of metal degassed and cleaned
in accordance with the present invention have shown the gas
contents achieved to be extremely low, i.e. 0.04-0.15 cc/100 g in
comparison with 0.15-0.20 cc/100g for conventional furnace
degassing with chlorine.
Metal processed by the present invention has been shown to be
suitable for production of high quality semi-fabricated products
for critical applications. In particular the incidence of blister
defects in soft annealed sheet for deep drawing purposes is
extremely low and frequently nil. The corrosion resistance of the
metal is somewhat better than that of conventionally furnace
degassed metal, as judged by the Cass test.
Operation of the process of the present invention brings with it a
number of important practical advantages. Its use eliminates the
capital and operating costs of fume treatment equipment.
Substitution of nitrogen and flux for chlorine brings savings in
degassing costs. The time of treatment of metal with chlorine or
hexachlorethane in a holding furnace is saved so that the output
can be increased. Most valuable of all economically, metal losses
are greatly reduced since dross formation in the holding furnace is
far less than with conventional furnace degassing where chlorine or
a chorine-nitrogen mixture is being passed into a reverberatory
furnace for periods up to 60 min.
In addition to carrying out the process of the present invention in
a containing vessel such as a brick box or crucible placed between
holding furnace and casting point, it is also practicable to use as
a containing vessel a forewell to, or an alcove within, the holding
furnace itself, particularly where this is of a reverberatory type.
Best results will then be obtained if the metal in the forewell or
alcove is protected from direct contact with the products of
combustion of the furnace. In the case of the alcove or cubicle
within the furnace, brick walls may be built inwards from the wall
of the furnace which includes the tapping hole, or from this wall
and an adjacent wall, so as to partition off a cubicle of suitable
size from the main part of the furnace, metal entering the cubicle
by a passage underneath the partitioning walls or through holes
left therein for the purpose. A drossing door is needed through
which to apply flux to the metal within the cubical walls. Nitrogen
or other inert gas may be introduced via porous bricks built into
the floor of the cubicle or more conveniently by porous or
non-porous graphite tubes, or steel or cast iron tubes protected by
vitreaous enamelling. These tubes may be introduced through the
furnace walls into the cubicle. Operation of the process in a
forewell or a cubicle within a reverberatory furnace has advantages
under some conditions and particularly where it is desired to make
frequent alloy changes or to operate the process
intermittently.
When operating with a forewell it is convenient to divide the
forewell by means of a baffle into two chambers so that molten
metal enters one chamber, flows underneath the baffle or through
one or more holes therein to the other chamber, and then through a
tap hole into a casting launder.
The molten metal in the forewell being in direct communication with
that in the main body of the reverberatory furnace will be
maintained hot thereby, but if desired additional heating may be
provided.
FIGS. 14a and 14b show a reverberatory furnace R with a cubicle C
defined by walls 140 of refractory brick extending inwardly from
walls 141 of the furnace R. The walls 140 may, if desired, extend
up to the ceiling (not shown) of the furnace. A tapping hole 142
and a door 143 for dross removal are provided in respective walls
141 of the furnace to communicate with the cubicle C. A drain hole
144 may also be provided in one of the walls 141 at a location
outside the cubicle C, the floor 145 of the cubicle preferably
sloping downward towards the drain hole 144. Apertures 146 are
provided at or near the bases of the walls 140 so that the cubicle
C is in communication with the furnace R. A flux cover 147 extends
over the surface of the molten metal in the cubicle C and a
graphite tube 148 extends into the cubicle for admitting an inert
gas into the molten metal.
FIGS. 15a and 15b show a reverberatory furnace R with a forewell F.
Walls 150 extend outwardly from a wall 151 of the reverberatory
furnace R to define the forewell F which is divided by a baffle 152
into two chambers F.sub.1 and F.sub.2. Openings 153 at or near the
base of the wall 151 permit the flow of molten metal to the chamber
F.sub.1 into which nitrogen is introduced through graphite or
enamelled steel tubes 154. A flux cover 155 is maintained over the
liquid metal in the chamber F.sub.1. The molten metal flows under
the baffle 152 into the chamber F.sub.2 from which it flows to a
casting launder (not shown) through a tapping hole 156. Heat is
conserved in the molten metal by use of refractory lined lids 157.
Additional heating is provided, where required, by means of gas
burners 158.
It will be seen that the present invention provides a process for
cleaning and degassing molten aluminium in a continuous manner
which comprises flowing molten aluminium through a chamber in which
a substantially inert gas such as, for example, nitrogen is passed
into the metal whilst a liquid flux layer is maintained on the
aluminium in the chamber, followed, if desired, by flowing the
molten aluminium through a bed or column of coarse refractory
flux-coated granules and then flowing the molten aluminium through
a bed or column of uncoated coarse refractory granules. Metal
treated by this process has given excellent results when used for
the production of bright anodised and other critical products.
The invention has application to the treatment of molten metals
other than aluminium.
* * * * *