Environment Friendly Approach to Maximising

Magnesium Recovery and Controlling Slag

within Ladle
CHRIS ECOB
Technical Advisor, Elkem Silicon Products, U.K
SWAPAN KUMAR BISWAS
Metallurgical and Technical Manager,
Elkem Silicon Products, Navi Mumbai
E-mail: chris.ecob@elkem.no

Introduction Accepting that most foundries will be working with either

Since the invention of the current an alloy containing pocket or use a conical design in the
Mg routes for production
ofductile iron in the 1940's, foundries and institutions have bottom of the ladle, the next challenge is to source a clean,
sought methods of most efficiently adding an element with dry and consistent supply of steel coins (or punchings) which
a boiling point of 1190°C into will give a good covering to the alloy and remain within
liquid cast iron at around
1450-1500°C. Using a FeSi carrier giving a MgFeSi with the pocket. These provide a physical barrier to the cast iron
beneficial elements such as rare earth and calcium has coming into immediate contact with the MgFeSi and the
undoubtedly proved the most popular and versatile method delay allows for a small ferrostatic head to build before
Over the years. the Mg reaction starts, thus providing more
Mg vapour/
iron contact than without the coins. However, the coins
This paper will describe developments and products designed
do need to be dry, free from rust and oils, otherwise these
to maximise magnesium recovery. Additionally, elements
will reduce the Mg recovery through preferential reactions.
have been built into the product to change slag constituency
Typically, 1% by weight of cast iron coins are added to the
to give a granular, easily removed slag which will tend
ladle, this causes a 15°C loss of temperature in the iron.
to precipitate in the ladle rather than in subsequent metal
transfers or even in the casting itself. Magnesium recovery and temperature
Other benefits, such as energy saving and ability to move improvements
to lower Mg alloys and demonstrate improvement on The new alloy range, for the purposes of this paper called
in the Conditioner, is a 50% Si bearingFeSi based material
Metallurgical& Mechanical properties are discussed
case study. containing controlled amounts of barium, calcium and
aluminium. Addition of this to the top of the MgFeSi in
Issues with steel punchings the ladle at rates of 0.4-1.0% provides several benefits and
lt is well known in the industry that the efficiency of these will be examinedin more detail throughout this
paper.
magnesium recovery from a MgFeSi alloy is improved
Firstly, the Conditioner provides a significantly superior
unrough ladle design. Figure 1 gives a simple illustration barrier to the onset of the
01 work done in a foundry to step-by-step improve process Mg reaction than steel coins or
other materials. When cast iron is tapped into the
ladle,
efficiency.
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Alloy
Example: 5% MgFeSi-alloy, 0.5 %Ca, 10 -40 mm sizing
adoitlon
(wt%)
Temperature: 1500°C
1.8 Open ladle
S- Level: 0.012%
1.7
Alloy pocket
1.6
Sandwich
1.5
1.4 Tundish
1-20 mm
1.3 sizing
1.6% Caa
1.2
1.1
1.0

Fig 1: Process improvements achieved in a foundry.

it tends to sinter it's way through the Conditioner quite was ladle post-nodularisation slag could
to see whether the

slowly-a 50% Si bearing FeSi has a dissolution

rate up to be transformed into an casily handled form. It is believed
5 times slower than a 75% Si containing alloy - and thus a that adding around 160-180ppm of barium to the treatment

higher ferrostatic head is built, increasing the Mg vapour/ will have a beneficial effect on slag and this proved to be the
iron contact. In tun, this can lead to a higher recovery
case. Figure 2 shows a typical ladle surface comparing when
of Mg, typically 5-15%, although in some cases higher
steel coins were used as the MgFeSi cover and when the
improvements in recovery have been
seen.
Conditioner was used, all other influences being equalised.
The trend in the industry at present is to move to lower Mg
The ladle on the left has a very sticky viscous slag which
as reduced reactivity results in less splash,
fume and
alloys requires the use ofan unexpanded perlite to remove it. Even
slag generation. so, slag will stick to the ladle lining and gives a significant
contribution to savings comes from the volume of material which has to be treated prior to disposal.
A secondary
exothermic properties of the 50% Si portion of the Using unexpanded perlite is a hot, dirty and environmentally
Conditioner. FeSi 50 adds heat to the iron, typically a 1% unfriendly process.

addition of the alloy will add 19°C, compare this to the

the
By contrast, the Conditioner used in the ladle on the right
I5°C lost to steel coins at the same addition. Reducing
has transformed the slag into a dry slag, often said to
fumace temperature to accommodate this can have significant
resemble popcorn. This can easily be skimmed form the
energy savings over the course of a year
as well as having
ladle without the use of silaceous coagulants. Relative to the
benefits on furnace lining wear and ladle life.
first example, the amount of waste material created is low.
Slag considerations It is, however, sometimes noted that the amount of slag in
Elkem examines a lot of customers iron samples in our the treatment ladle is a bit higher with the Conditioner and
laboratories, the most common ductile iron defect seen is this can be true. Slag in the castings is unacceptable and
shrinkage, the second most common is slag inclusions. One last-minute attempts to prevent this, yield reducing sug
of the key drivers in developing the range of conditioners

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Fig 2: Left: Liquid slag coagulated with unexpanded perlite before removal.
Right: Conditioner used as the MgFeSi cover gives a "popcorn" like Environmentally unfriendly, labour intensive and dificult operation.
slag which can easily be skimmed without the need for coagulants.
traps and expensive filters, are often used. The
comparison Silicon balance
is that these are the asprin to cure the
headache,
but do not
Silicon balance is the lynchpin of most
address the cause of the headache. In this case,
slag. casting charge
calculations and the key factor in this is the silicon content
So, precipitating the slag early in the
process is clearly a of foundry returns, the
big benefit and can be achieved by using the conditioner. objective being to use all of these
whenever possible and prevent
stockpiling. By the time
Figure 3 shows normal precipitation of the main 5 slag silicon from other metallic sources, the
MgFeSi and
types in an unheated pouring box. inoculants have been factored, sometimes there is little
flexibility for other silicon additions. For this reason, several

PrLRESSEANASVA
RREaSRH RIARKLESAKiV2A8HLHa Magnesium contalring slags
Caldum contalning slags
suphide slag
Iron containing slags
Aluminiumphases

Slag precipitation without and with Topseed

Barium containing slag8

Note that slag has to precpitate somewhere. When tsall preclpitated in the
ladle, t can gve the ülusion of more
slag belng
deposited. It Is
slag In the ladle where it s more easily remaved In a dry form. far better to have

Fig 3: Precipitatio
Ilation of slag phases in an unheated pouring
box with and without the conditioner

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Consistency
Whilst not a major claim for the
Typical additlons Conditioner, it has been noted
Topseed2005Conditioner
0,3-0,4% Conditloner (5%Ba) Good
that the recovery of
magnesium
ladles/pockets or/and Low Mg containing
9 , 7 4 1 %

MgFeSi is very stable, allowing for

even

0,7-1,0% ditioner with 2%Ba "Poor" other influencing factors in the

ladles/pockets or/and High Mg containing
Topseed5005Conditioner
MgFeSi
foundry. One foundry reported
0,340,49% Replacing all types of coverlng materlal such
the Mg recovery graph shown
asFeSiBa9%, Fesi, steel punching/colns, as Fig 5.
machining chips, etc.

Nucleation effect
Poor Good
Shape Shape
Quality of Treatment Ladle and Its Alloys Pocket In general terms, the addition of
magnesium to liquid cast iron
Fig 4: Typical addition rate ranges for the conditioner at high and low Ba levels creates a reaction of suchviolence
that considerable nucleation is
Stability of Iron destroyed. This is the main reason
100
0,06 why ductile irons require higher
95
addition rates of inoculant than,
90 0,055
for example, grey iron.
0,05
80

75
www.i 0,045
It is also well known
that
70 0,04
barium/calcium/aluminium
65
type inoculants provide a
0,035
60 reasonable base nucleation (or
0,03 first stage
inoculation) in ductile
irons. Figure 6 shows two
Fig 5: Stability of Mg recovery over a 2 shift
production run
N

photomicrographs of ductile iron,

versions of the Conditioner have been uninoculated otherwise, taken
barium. For example, a high barium version developed containing different amounts of with and without the
added at 0.4% will Conditioner
contribute
silicon to the iron.
Examples of chemistries and addition rates are shown only 0.2% as a cover for
the MgFeSi.
in Fig 4.
This shows an
example in application of two Conditioner Before moving to some case
5% Ba, the other 2% Ba.
In each case, around
chemistries, one containing
180ppm of barium is being added to studies which will demonstrate the
the iron to
give the desired slag conditioning effect, however use of the
the conditioner, it would be
with the 5% barium the silicon wouldbe
alloy are lower at 0.15-0.2% additions
5% Ba alloy. compared to 0.35-0.5% with the useful .useful to recap the main benefits
of this
Increasingly, higher silicon content materials are interesting material.
notably SiMo irons and SSF irons, in being manufactured these days, Proper
of silicon. which cases the Conditioner is a addition of the conditioner
good source to cover
MgFeSi in the dutile
iron treatment ladle will:
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The benefits of these
relatively
demonstrated
new alloys are

by two case studies taken from

foundries in India.
Case Study of Foundry A
This foundry was regularly using
MgFeSi at an addition of 1.2.
plus a 0.6% FeSi cover with steel
punchings as a treatmentpackage.
This was followed by a stream
Fig 6: Microstructures (al00) of ductile iron. uninoculated. without (left) and with (right) use of the inoculation with 0. 15% inoculant.
conditioner
The problem in the foundry
DConvert the slag into a dry and easily removable form was variation in mechanical

Less disposal costs. environmentally friendly properties. Some results shown

below highlight the problems with
Precipitate slag early to help prevent build up in treatment vessels or within the
theprevioustreatment package.
casting
The microstructure is taken from
Increased stopper rod life. lower reject castings an area specified by the end-user
Delay the onset ofthe Mg reaction and provide a higher Mg recovery and shows a low nodule number

Allows lower MgFeSi addition rates or use of lower Mg alloy and poor nodularity.

New treatment package:

Improve consistency
To overcome the inconsistencies
Better machining and process stability
that the foundry was trying
DIncreases nucleation to overcome, a new treatment

Reduced inoculant additions package was used.

The MgFeSi addition rate was kept

Table-1: Mechanical properties, previous practise at 1.2%, whilst a 0,46%addition
Mechanical properties with previous treatment package of the Conditioner replaced the
Surface Remark previous FeSi and steel punchings
Tensile Yield Elongation
hardness of as cover for the FeSiMg. Final
strength strength % (12%
cut sample metal stream inoculation was
(Spec- (Spec- min)
448 Mpa | 310 Mpa (Spec 156- @0.15% as before.

Min) Min) 217HB) The improvements in mechanical

167HBW % Elongationlowerthanspec properties and microstructure, the
S35 Mpa 310 Mpa 10%
153 HBWHardness, Yield strength| foundry has also reported
305 Mpa 12%
525Mpa lower than spec i) Tapping temperature has been
12.5% 147 HBW Hardness, Yield strength reduced by 15°C
500 Mpa 295 Mpa
lower than Spec ii) Reaction less violence with
486 Mpa 285 Mpa 11% 147 HBWHardness, Yield strength &%| a consequence of less metal
Elongation lower than
spillage and safer working
295 Mpa 12.5% 158 HBWYieldstrength lowerthan spec| conditions
496 Mpa
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1) MIcrostructure results of cut sample-1

100 100 ageon

Soroatrucaure -odulr7s% (Unetchad condiion) Microstructue-r 50-55 % krie appa. 45%

Fig 7: Microstructure showing poor nodularity

Table-2: Mechanical properties after changing to new process

Mechanical properties after changing to the Conditioner
Properties Top half ofthe Bottom half Top half of Bottom half ofRemarks
casting ofthe casting the casting thecasting
Tensile strength (Spec-448 605.7 613.6 613.8 614.7 All are
| Mpa Min) above limit
Yield strength (Spec-310 Mpa 395.9 396.5 396.2 399.4 All are
Min) above limit
Elongation % 10.45 11.98 12.2 12.1 3 results
(12% min) acceptable
Surface hardness of cut sample 184 178 194 200 All are
(Spec156-217 HB) within limit

Nodularity 85 to 90%
Nodule Count 80 to 100 per
square mm

Fig 8: Microstructures after changing to the new practice

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Fig 9: Microstructures of casting

Fig10: Photomicrographs of the final structures

1i) Magnesium recovery improved by 10-12% metallurgical and mechanical properties this grade is
typically very challenging because ahigh tensile strength
Case Study of Foundry B
along with a high elongation is difficult to achieve.
This foundry was trying to develop a new casting in a 600/10
PTrevious best treatment
pearlitic grade. As this will be used in the wind energy sector,
FeSiMg(Mg6.5%) at addition rate ofl.2%t steel punchings,
casting integrity was of paramount importance.
The main challenges were to achieve mechanical properties.2aby weight in the treatment ladle and a two stage

inoculation, 0.45% ofa Ca/Ba inoculant in the ladle followed

and consistence microstructure without any chunky graphite.
by 0.05% of a Ce based inoculant in-stream.
package to achieve
The foundry tried several different
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The OEM had specitied locations on the casting for Mechanical properties are checked
on the separate test bar
metallographic examinations as shown in Fig 9. Their and casting body. Results achieved were Tensile 640 & 666

requirement was a carbide and chunky graphite free matrix 10.36%, all exceeding to
Mpa respectively and elongation
with 70-85% pearlite. the customer requirement.
The Elkem solution The customer has also been able to achieve the following:
15-20°C
The alloys proposed were completely different to what the Tapping temperature reduce by
foundry had been used to. 0.6% addition of the Conditioner Reaction less violence consequence less metal spillage
replaced the 1.2% steel punchings and the first stage
8-10%
inoculant, leaving only the in-stream inoculant at 0.07%. Mg recovery improve by
The MgFeSi was unchanged for this project. DEliminate inconsistence quality about steel punching

Final result: Microstructure at 3 diferent locations as before. DEliminate primary inoculation

All 3 locations are chunky free and nodularity/nodule count More stable metallurgical & mechanical properties.
is very good and an improvement on the previous alternative

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