Paper 07-008(05).

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AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

Role of Residual Aluminium in Ductile Iron Solidification

I. Riposan, M. Chisamera, S. Stan
Politehnica University of Bucharest, Bucharest, Romania

D. White
Elkem Metals Inc., Pittsburg, Pennsylvania

Copyright 2007 American Foundry Society

ABSTRACT

The main objective of the present paper was the investigation of the role of a large range of final residual aluminium (0.002-
0.05%) when added through pre-conditioner (FeSi, 5%Al), (0.02-3%Al)-MgFeSi nodularisers and (0.1-5.0%Al) -Ca-FeSi
inoculants. The most important parameters of thermal analysis were beneficially influenced by residual aluminium, and
consequently resulted in higher eutectic temperatures and a lower degree of undercooling, higher temperature at the end of
solidification and a greater negative peak of the depth of the first derivative at this temperature. In lower carbon equivalent
conditions (3.95 4.25%), aluminium appears to have beneficial effects, such as: decreasing free carbides occurrence,
increasing nodule count, and improving castings compactness, without affecting graphite morphology. Adding Al with the
inoculant is by far the best solution to control residual aluminium level. Second best is to include it in the base iron such as
with an Al bearing preconditioner. Including Al in the MgFeSi is the weakest choice. 0.005 0.02wt.% Al residual is
beneficial to improve ductile iron characteristics without the incidence of pinholes.

INTRODUCTION

A large range of residual aluminium content in the iron melt for ductile iron production could be recorded, depending on the
charge materials, such as pig iron, steel scrap, ferrosilicon, aluminium products incidence etc. The nodularisers may also
include a large level of aluminium, from less than 0.1%Al and up to 2-3%Al. Aluminium content in FeSi-based inoculants
covers a larger range, from 0.1%Al up to 4-5%Al. Aluminium is recognized for contributing to pinhole formation in iron
castings: lower contribution in ductile iron than in gray iron castings, especially due to the higher surface tension in Mg-
treated irons. 0.05-0.2%Al appears to be the critical range of residual aluminium in ductile irons, with regard to pinholing.

New knowledge about the fundamental effects of aluminium in the gray iron nucleation process is now available. Complex
(Mn,X)S compounds (where X=Fe, Al, O, Ca, Si, Sr, Ti, Zr etc.) usually less than 5.0 m in size, with an average 0.4-2.0 m
well defined nucleus were found as the major nucleation sites for graphite in both un-inoculated and inoculated gray irons.
Aluminium contributes to the formation of Al2O3-based sites which act as nucleation sites for (Mn,X)S compounds, even at a
very low Al level (<0.003%) in iron melt. Increasing the residual aluminium content in iron melt helps the initiation of
graphite nucleation with lower undercooling. A 0.005-0.01%Al content in melt appears to be beneficial, without the
detrimental effect on pinhole occurrence in gray irons1-4 .

Aluminium appears to play also an important role in nodular graphite nucleation in ductile irons. Generally, aluminium was
found, in specific conditions in nodular graphite, as complex nitride5-7, oxy-nitrides in very low sulfur treated irons6, or as
complex silicates, as result of nodularisation and/or inoculation8,9. A possible difference in micro inclusions system for
induction furnace irons and cupola irons was identified many years ago8.

(Mg,Ca)S inclusions have been established as heterogeneous nuclei for graphite nodules in induction furnace iron. The
inclusions identified in the cupola irons were found to consist of a mixture of sulfides and silicates, which contained Mg, Ca
and Al as primary constituents. The role of Al was also indirectly recognized in the model of graphite nodule formation,
mainly as inoculant contribution9: MgS/CaS/CeS compounds are formed as the primary micro inclusions in the Mg-treated
iron melt; the Mg-treatment process also introduces into the melt complex Mg-silicates, such as estatite (MgO SiO2) and
forsterite (2MgO SiO2). However these phases present a large planer disregistry with graphite and will not act as nucleation
sites. During subsequent inoculation with FeSi containing Al and X (Ca, Ba, Sr) alters many of these inclusions by forming
hexagonal silicate phases of XO-SiO2 or the XO-Al2O3-2SiO2 on the surface of the oxide inclusions. The (001) basal planes
of these compounds can be favorable sites of graphite nucleation forming coherent/semicoherent low energy interfaces
between the nucleant and graphite. The particles which act as nuclei for graphite spheroids in a ductile iron containing small
amount of Mg and traces of Al were also identified as Al-Mg-Si nitrides (Al,Mg2.5Si2.5N), having a trigonal super lattice
crystal structure derived from a hexagonal AlN type fundamental cell5 .
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AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

Aluminium was also found in complex nitrides such as (Mg, Si, Al)N or oxy-nitrides (Mg, Si, Al)ON mainly at very low
sulfur level in the base iron (<0.01%S). MgS/MgO compounds appear to be the major nucleation sites fore more than 0.01%S
in treated irons6. A spherical sulfide (Mg, Ca)S of about 1.0 m diameter was found near the center of graphite spheroids and
thought to be a nucleus for graphite. A spherical MgO of about 0.2 m diameter was found in the sulfide and considered to be
nucleus for the sulfide. The main constituent of the core of graphite is (Mg,Ca)S, enveloping MgO inside and accompanying
(Mg,Si,Al)N outside7.

The main objective of the present paper was the investigation of the role of a large range of residual aluminium (0.002-
0.05%) when added through pre-conditioner, nodularisers and inoculants in ductile iron production, at low level of carbon
(3.25-3.40%) and carbon equivalent (3.95-4.25%), respectively. Is there an optimum level of Al? If so, what is the best way
in the ductile iron process to introduce it?

EXPERIMENTAL PROCEDURE

High purity and careful selected charge materials were used for the experimental program, at very low level of aluminium,
sulfur and auxiliary antinodulizing and carbide forming elements (Table 1).

Table 1. Chemical Composition of Charge Materials (wt.%)

Material C Si Mn P S Al
Steel Scrap* 0.12 0.03 0.40 0.018 0.015 0.03
Graphitic Recarburizer 99.1 0.06
FeMn 0.8 1.5 78.8 0.2 0.02
High Purity (HP)-FeSi 75 0.1 0.003 0.011
Foundry Grade (FG)-FeSi 75 0.5 0.04 1.2
*0.035%Cr, <0.0011%Mo, 0.025%Ni, 0.03%Cu, <0.001%Pb, <0.002%Sb, <0.002%Ti

The base primary synthetic iron (1000kg) was prepared in a coreless induction furnace (acid lining, 1000kg, 1000Hz) using
selected steel scrap, high purity recarburizer, low Al-FeSi and FeMn as charge materials. The experimental heats were
obtained by re-melting of the base iron (3.78%C, 1.23%Si, 0.45%Mn, 0.018%P, 0.013%S, 0.004%Al) with 10% premium
quality steel scrap addition, in a smaller induction furnace (acid lining, 100Kg, 2400Hz). Each heat has contained 30 Kg
charge. The iron melt overheated up to 1520 - 1550oC/2768 - 2822oF and maintained 10 minutes at this level. Before tapping
the iron melt was superheated a short time (3 minutes) up to 1570 - 1580oC /2858 - 2876oF and than tapped into the
nodulizing ladle (1560 - 1570oC/2840 - 2858oF).

Three aluminium sources were used for aluminium variation in final ductile iron composition: a) Al-FeSi alloy as pre-
conditioner; b) Mg-FeSi alloys as nodularisers; c) Ca-FeSi alloys as inoculants (Table 2). In the ductile iron production, the
base reference condition and the three variants as aluminium source were considered in the following schedule.

Table 2. Chemical Composition of the Experimental Alloys (wt.%)

Role Material Al Si Ca Mg Fe
Alloy Al Level
Type
Preconditioner Al-FeSi High 5.0 78 0.05 - bal
Nodulariser MgFeSi Low 0.02 46 1.0 5.5 bal
MgFeSi Medium 1.0 46 1.0 6.1 bal
MgFeSi High 2.6 46 1.0 6.5 bal
Inoculant Ca-FeSi Low 0.12 77 0.7 - bal
Ca-FeSi Medium 1.3 76 0.7 - bal
Ca-FeSi High 4.8 76 0.9 - bal

a) Reference/base variant: low Al-base iron was treated with low Al, MgFeSi alloy and inoculated (or not) with low
Al, Ca-FeSi alloy;
b) Preconditioning variant: Al-preconditioning of base iron (0.4% Al-FeSi alloy; in stream addition, before Mg-
treatment), followed by low Al, MgFeSi treatment and (or not) inoculation with low Al, Ca-FeSi alloy;
c) Nodulariser variant: low Al-base iron was treated with medium and high Al, MgFeSi alloys, followed by inoculation
(or not) with low Al, Ca-FeSi alloy;
d) Inoculant variant: low Al-base iron was treated with low Al, MgFeSi alloy and inoculated (or not) with medium and
high Al, Ca-FeSi alloys (Fig. 1).
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AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

Fig. 1. General schedule of experiments and final Al range level

Figure 1. General schedule of experiments and final Al range level

Induction
Furnace

30 kg iron
melt
Uninoculated iron

10
kg
L1
Nodulizing
treatment In-stream
addition
MgFeS Ca-FeSi
xxxxxxx
xxx
10
kg
L2

Fig. 2. Schedule of experimental program

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AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

The nodulizing treatment (2.5% Mg-FeSi alloys) was achieved in 30 Kg Tundish-Cover treatment ladle with a centered
pocket (Fig. 2). Mg-FeSi alloy covered by a resin bonded sand plate. Every time the reaction started after complete filling of
the ladle. After removing of the slag the Mg-treated liquid iron was divided in 10Kg batches, which were or not submitted to
ladle inoculation treatment (0.5% Ca-FeSi alloys).

The inoculated or un-inoculated iron melt were poured by the 10Kg ladle after 15 sec waiting for melt homogenization. The
two 10Kg batches were poured by two workers in the same time (60-70 sec) in furan resin molds (1280 - 1330oC/2336 -
2726oF). The order of pouring different samples was intentionally maintained the same, that is: Cross bar sample (shrinkage
tendency) - Cylindrical samples (structure characteristics) - Quick-cups (thermal analysis) - Coin samples (spectral analysis).
Shake out of the cast samples was performed at room temperature.

RESULTS AND DISCUSSION

FINAL CHEMISTRY OF DUCTILE IRONS

Final chemical composition of Mg-FeSi treated irons, in un-inoculated and inoculated conditions and different sources of
added aluminium is presented in Table 3.

Table 3. Final Chemical Composition of Experimental Ductile Irons

Al MgFeSi Ca-FeSi Sam- Chemical Composition* (wt.%) Equiv.
Source Treatment Inocu- ple Al C Si Mn S P Mg Carbon
(Al level) lation CE,
(Al level) %
Base MgFeSi Un-Inoc 1.01 0.002 3.33 2.57 0.35 0.011 0.019 0.053 4.13
Condit. (Low Al) Ca-FeSi 1.11 0.003 3.31 2.97 0.35 0.012 0.020 0.053 4.23
(No (Low Al) 1.12 0.0023 3.30 2.58 0.38 0.006 0.020 0.054 4.10
precond.) 1.13 0.003 3.32 2.67 0.36 0.0097 0.019 0.049 4.15
Precon- MgFeSi Un-Inoc. 2.01 0.012 3.25 2.39 0.37 0.012 0.019 0.049 3.99
ditioner, (Low Al) 2.02 0.013 3.43 2.58 0.38 0.0096 0.020 0.051 4.23
AlFeSi Ca-FeSi 2.11 0.013 3.28 2.74 0.37 0.012 0.019 0.038 4.13
(Low Al) 2.12 0.013 3.36 2.92 0.37 0.0097 0.020 0.047 4.27
Nodula- MgFeSi Un-Inoc 3.01 0.021 3.26 2.18 0.34 0.008 0.019 0.055 3.94
riser (Med. Al) Ca-FeSi 3.11 0.019 3.28 2.60 0.34 0.010 0.019 0.050 4.09
(No (Low Al)
precond.) MgFeSi Un-Inoc 3.02 0.046 3.27 2.26 0.38 0.009 0.019 0.046 3.97
(High Al) Ca-FeSi 3.21 0.044 3.27 2.60 0.38 0.010 0.019 0.050 4.08
(Low Al)
Inoculant MgFeSi Ca-FeSi 4.11 0.007 3.24 2.61 0.37 0.01 0.019 0.047 4.05
(No (Low Al) (Med.Al) 4.12 0.008 3.29 2.58 0.38 0.006 0.02 0.060 4.09
Precond.) Ca-FeSi 4.21 0.017 3.32 2.58 0.36 0.012 0.019 0.048 4.12
(High Al) 4.22 0.017 3.29 2.66 0.36 0.009 0.019 0.050 4.11
*Residual elements (wt.%): 0.03Cu, 0.01Ni, 0.03Cr, 0.001V, 0.002Ti, 0.002Nb, 0.004Co, 0.01W, 0.003Sn, 0.001Pb,
0.003Sb, 0.01As.

Low ranges of carbon content (3.25 - 3.4%C) and carbon equivalent level (3.95 - 4.25%CE) were selected, to increase the
sensitivity of experimental ductile irons to chill and shrinkage formation. The other representative elements in the base
chemical composition are included in the normal range of ductile irons: 0.34 - 0.38%Mn, 0.006 - 0.012%S, 0.019-0.020%P
and 0.04 - 0.06%Mgres.

Residual elements (excepting Al) were achieved at low level. Final residual aluminium content in the un-inoculated and
inoculated ductile irons was obtained in a large range, depending on the source variant (Tables 3, 4 and Fig. 3).

Very low final aluminium content (<0.005%Al) is typically for high purity base iron, subjected to treatment with low Al,
MgFeSi and inoculated (or not) with low Al, Ca-FeSi alloy. Medium (usual) Al, Ca-FeSi inoculant increased Al-content up to
0.01%Al. The general 0.01-0.02%Al range was obtained in different conditions: Al-FeSi preconditioning, medium Al,
MgFeSi treatment or high Al, Ca-FeSi inoculation. The highest aluminium level, i.e. more than 0.04%Al in the final iron is
typically for high Al, MgFeSi treatment.
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AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

[Al], %
0.06
I - Al - PRECONDITIONING II - Al - NODULARISER III - Al - INOCULANT
0.055
No Precond. Al-FeSi Low Al-MgFeSi Med. Al-MgFeSi High Al-MgFeSi
0.05
No Al - Preconditioning
0.045 Low Al - MgFeSi No Al - Preconditioning
Low Al - MgFeSi
Low Al - CaFeSi Low Al - CaFeSi
0.04
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
I c. I c. I c. I . I c. I w d. l .
U o U o U o U oc U o U
Lo Me gh
A
In In In In In i
H
Al - CaFeSi

Fig. 3. Final Al content in MgFeSi-treated, un-inoculated (UI) and

Ca-FeSi inoculated irons (Inoc.)

Table 4. Al Level in Final Ductile Irons, Depending on Al Source

Al Level Al-FeSi MgFeSi Treatment Ca-FeSi Inoculation Un-
In Final Precondi- Low Al Med. Al High Al Low Al Med. Al High Al Inoc.
Irons (%) tioning (<0.1%) (0.8- (2-3%) (<0.1%) (1.0-1.5%) (4-5%)
1.2%)
max.0.002 x x
0.002-0.003 x x
0.007-0.008 x x
0.012-0.013 x x x
x x
0.017-0.021 x x
x x
x x
0.04-0.05 x x
x x

SOLIDIFICATION PATTERN
The experimental hypo-eutectic (3.95-4.25% carbon equivalent) ductile iron heats were subjected to thermal analysis, so
cooling curves and their first derivatives were recorded (Fig. 4). Standard Quick-cups were used, with a cooling modulus of
0.75 cm, equal to a test bar 30 mm in diameter.

The basic cooling curve gives some important information about the solidification (Fig. 4a): the lowest (TEU) and the highest
(TER) eutectic temperatures, eutectic undercooling degree ( Tm = Tst - TEU) comparing to equilibrium stable eutectic
temperature (Tst), eutectic recalescence degree ( Tr = TER - TEU) or the temperature at the end of solidification (TES).
Additional information can be obtained from the first derivative of the cooling curve, which shows the cooling rate and its
direction (dT/d , fig.4a): the maximum rate during recalescence (TEM) and the minimum value of the first derivative at the
end of solidification (FDES). A low value for FDES is favorable, as is correlated to high amount of eutectic graphite at the
end of solidification. Usually it is associated with a high nodule count and a low tendency for micro-shrinkage, especially if
FDES < -3.0oC/s10 .

In the present experiments, the theoretical temperatures in the stable system (Tst) and metastable conditions (Tmst) were
calculated, depending on the final silicon content (Tst = 1153 + 6.7%Si and Tmst = 1147 12%Si).

The Ts = Tst - Tmst difference was obtained in the 48 - 62oC range (48 - 55oC for un-inoculated irons and 55 - 62oC for
inoculated irons, respectively). According to low carbon equivalent, a higher level of eutectic undercooling degree ( Tm
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AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

given Tst) was obtained: 51 - 76oC for un-inoculated irons and 23 - 35oC for inoculated irons. More accurate information
could be obtained if Tmst is considered as reference for solidification pattern of cast irons (Fig. 5).

seconds

seconds
Fig. 4. Cooling curve and first derivative parameters (a) and influence of Al-Ca-FeSi inoculant (b)
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AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

T1 = TEU Tmst, oC T2 = TER Tmst, oC

40 40
a) b)
30 30 Inoculated Irons
Inoculated Irons
20 20

10 10
Al, % Un-inoculated Irons
0 0 Al, %
0 0.01 0.02 0.03 0.04 0.05 0.06 0 0.01 0.02 0.03 0.04 0.05 0.06
-10 -10

-20 Un-inoculated Irons -20

-30 -30

T1 / Ts T2 / Ts
0.8 0.8
c) d)
0.6 0.6
Inoculated Irons
Inoculated Irons
0.4 0.4

0.2 0.2

Al, % Al, %
0 0
0 0.01 0.02 0.03 0.04 0.05 0.06 0 0.01 0.02 0.03 0.04 0.05 0.06

Fig. 5. Influence of residual Al on the undercooling parameters of un-inoculated (UI) and inoculated ductile irons
(Inoc.)

T1 = TEU - Tmst parameter illustrates the position of irons at the start of eutectic reaction, while T2 = TER -Tmst at the
end of this stage. In the experimental conditions, un-inoculated irons mainly present a white iron solidification pattern
( T1 < 0, T2 < 0), while inoculation moved the ductile irons to the positive value range of these parameters, in all of cases.
But, also inoculated irons remain in a visible undercooling stage as T1/ Ts ratio is mainly less than 0.6 level, while T2/ Ts
ratio is prevalent less than 0.7 reference.

Cooling curves and their first derivatives show a visible difference at low and high residual aluminium level, such as Fig. 4b
illustrates. 5.0%Al-bearing Ca-FeSi alloy inoculation led to upper position of the cooling curve (higher TEU, TER) and the
lower position of the depth of the first derivative at the end of solidification (lower FDES), as compared to max. 0.1%Al
bearing Ca-FeSi alloy use. Fig. 5 shows that the increasing of residual aluminium levels resulted in a positive trend of the
representative parameters, higher level of T1 and T2, in both un-inoculated and inoculated irons and T1/ Ts and T2/ Ts
ratios in inoculated irons, respectively. In inoculated ductile irons, 0.01-0.02 wt.% Al appears to be an efficient range, while
the Al-addition via inoculation is more efficient than Al-preconditioning or Al-bearing MgFeSi alloys.

CARBIDES FORMATION SENSITIVITY

For a first evaluation the A-wedge Test (W3 and W31/2 samples), ASTM A 367-94, was used. Two methods to evaluate chill
sensitivity were applied. These were macrostructure (fracture) analysis and microscopic (metallographic) analysis (2% Nital
etching) to differentiate clear and total chill areas. Metallographic analysis of chill test samples is a more realistic method to
evaluate the chill sensitivity of ductile irons, due to difficulty to separate the white, mottled and free carbide areas in these
irons by the visual difference in color technique. This is because the white color of carbides is very close to the silver color of
the carbide free fracture, so it is difficult to identify very exactly the chilled area by visual rating.

Iron melt condition, as un-inoculated and inoculated irons and cooling rate, as size of wedge test samples, was found as the
most important clear influencing factors on the chill tendency. Lower carbon equivalent level led to a higher chill tendency of
all of Mg-FeSi treated irons for both cooling rates (W3 and W31/2 samples), in un-inoculated state. Ca-FeSi inoculated irons
are visibly less sensitive to chill formation, for both clear and total chill parameters and for both cooling rate conditions.
Aluminium residual in the final iron melt does not appear to influence chill tendency in the experimental conditions, as chill
test evaluation. The round bar samples (25mm diameter, 100 mm length, 0.59 cm cooling modulus) were also used for
microstructure analysis, as free carbides, metal matrix and graphite characteristics (Table 5, Fig.6).
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AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

Table 5. Structure Characteristics

Al MgFeSi Ca-FeSi Sam- Al, Graphite Graphite Ferrite/ Free

Source Treatment Inoculation ple (%) Nodularity, Nodule Pearlite Carbides
(Al level) (Al level) (%) Count Amount, Amount,
(1/mm2) (%) (%)
Base MgFeSi Un-Inoc 1.01 0.002 35
Condition (Low Al) Ca-FeSi 1.11 0.003 85 106 40/60 25
(No (Low Al) 1.12 0.0023 90 124 40/60 0
precond.) 1.13 0.003 90 104 30/70 20
Precon- MgFeSi Un-Inoc. 2.01 0.012 40
ditioner, (Low Al) 2.02 0.013 40
AlFeSi Ca-FeSi 2.11 0.013 70 100 40/60 3
(Low Al) 2.12 0.013 85 119 40/60 20
Nodula- MgFeSi Un-Inoc 3.01 0.021 40
riser (Med. Al) Ca-FeSi 3.11 0.019 90 105 30/70 20
(No (Low Al)
precond.) MgFeSi Un-Inoc 3.02 0.046 40
(High Al) Ca-FeSi 3.21 0.044 80 102 30/80 25
(Low Al)
Inoculant MgFeSi Ca-FeSi 4.11 0.007 80 90 30/70 5
(No (Low Al) (Med.Al) 4.12 0.008 90 127 30/70 5
precond.) Ca-FeSi 4.21 0.017 80 107 40/60 3
(High Al)
Obs. Un-inoculated irons: White/Mottled Structure

50 100
45
Graphite Nodularity, %

40 Un-inoculated irons 90
35 Inoculated irons
Carbides, %

30 80
25
20 Al-MgFeSi 70
15
10 Al-Ca-FeSi Inoculated irons 60
5
a) b)
0 50
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05 0 0.01 0.02 0.03 0.04 0.05

Aluminium in final iron, % Aluminium in final iron, %

160
2

140
Nodule Count, Nod./mm

120
Inoculated irons
100

80

60

40

20
c)
0
0 0.01 0.02 0.03 0.04 0.05

Aluminium in final iron, %

Fig. 6. Influence of residual aluminium on the free carbides amount (a), the graphite nodularity (b)
and nodule count (c)
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Free carbides are normally present in un-inoculated irons, when white iron was primarily obtained (35-40% carbides),
without residual aluminium visible influence. Less than 25% free carbides amount is typically for inoculated irons, with two
representative ranges (Fig. 6a):
20 25% free carbides, for MgFeSi as Al-source;
less than 5% free carbides for Al-bearing Ca-FeSi inoculant addition.

The both positions were obtained also for Al-FeSi preconditioning of the base iron melt. As the base metal matrix, it was
considered that Ferrite (F) + Pearlite (P) = 100%.

GRAPHITE CHARACTERISTICS
More than 80% nodularity was generally obtained, typically for commercial ductile irons, at a medium level of nodules
compactness, specific for synthetic base iron. As experimental procedure pointed out, selected steel scrap was used as
metallic charge, to obtain a strong controlled base iron melt in foundry conditions charge. No detrimental influence of
residual aluminium on the graphite nodularity was identified in these experiments (Fig. 6b). Nodule count appears to be
beneficially influenced by the residual aluminium level in inoculated irons. The upper level of this parameter (more than 100
N/mm2) is typically for Al-bearing Ca-FeSi inoculation. The intermediary position was found for Al-FeSi preconditioning,
while the lowest nodule count is typically for MgFeSi as Al source (Fig. 6c).

SHRINKAGE TENDENCY
Ductile iron shrinkage tendency was evaluated by shrinkage cross bar sample (110x80x40mm, 0.86cm cooling modulus),
which was cast in horizontal position, without risers. In this case, the main objective has focused on the obtaining of
shrinkage with as much as possible concentration to a more precise evaluation. Numerical simulation of sample solidification
was applied in order to establish the optimum radius between the cross arms. By this way, it was established that 12 mm
radius between the cross arms ensures a controlled solidification (moving the shrinkage towards to the center of the cross
bar). Encouraging of the directional solidification of the sample, which ensures the shrinkage concentration in the upper side
of the cross section center and forestalls the chaotic spreading of the shrinkage was also considered. In this reason, 20x3 mm
thermal insulation disc was inserted in the mold on the upper side of the cross section favoring the late solidification of the
skin in this region. By this way, a very concentrated macro-shrinkage was obtained for each sample that has permitted high
accuracy of its measurement.

The shrinkage tendency has been evaluated by the following parameters:

Vcsh -open concentrated shrinkage volume, cm3 or %;
d1 -the relative density of the sample (shrinkage porosity is included), g/cm3;
d2 -the apparent density of the sample (the total shrinkage is included):
d2 = Sample mass/Sample apparent volume, g/cm3;
ds -the relative density of the sound piece (it can also include micro-porosity):
ds = mass of the sound piece/volume of the sound piece, g/cm3.
Ks=ds/d2 -the rating of the sample soundness (it shows the deviation of the sample containing defects density from
the density of the sound piece). The optimum value is Ks=1 for a complete sound sample.

The sample volumes were measured based on the Archimedes principle weighing the samples, both in air and water with a
precision on 0.01g. In the calculation, water density was considered unity ( W =1 g/cm3). Table 6 and Figure 7 illustrate the
sensitiveness of cast irons to contraction defects formation. Open concentrated shrinkage volume (Vcsh), the apparent density
of samples, which include shrinkage (d2) and the Ks factor were found the most representative parameters.

At lower carbon content (3.25 - 3.4%C) and lower equivalent carbon level (3.95 - 4.25%CE), Mg-treated irons are
characterized by higher shrinkage level after inoculation compared to un-inoculated irons in all of cases (Fig. 7a). Higher
residual aluminium content, lower shrinkage amount, for both un-inoculated and inoculated irons, but without a visible
influence of the Al-source.

The specific density of the cross samples, which included concentrated shrinkage (d2), is accorded to found shrinkage level:
higher d2 values in un-inoculated irons (Fig. 7b). No visible influence of the residual aluminium content was found in
inoculated irons, but with beneficial effect in un-inoculated irons. The ds/d2 specific ratio could be also an important
parameter, to illustrate the incidence of the contraction defects in ductile cast irons (Fig. 7c): lower level in un-inoculated
irons according to lower shrinkage level. The increasing of residual aluminium content appears to have a positive influence
on this parameter, but without visible influence of the Al-source:
-the more narrow range in inoculated irons;
-the decreasing level in un-inoculated irons.
 Paper 07-008(05).pdf, Page 10 of 11
AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

5 7.2

Un-inoculated irons
SHRINKAGE, Vcsh, %

7
4

6.8 Inoculated irons

3
Inoculated irons

d2, g/cm
3
6.6

2 Un-inoculated irons 6.4

1 6.2
a) b)
0 6
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05

Aluminium in final iron, % Aluminium in final iron, %

1.05

1.04

Inoculated irons
Ks = ds / d2

1.03
Un-inoculated irons
1.02

1.01

c)
1
0 0.01 0.02 0.03 0.04 0.05

Aluminium in final iron, %

Fig. 7 Influence of the Al level in iron melt on the concentrated shrinkage (a), samples density in the shrinkage area
(b) and the densities ratio (c) (ds-density of samples, without contraction defects)

Table 6. The Density and Shrinkage Characteristics

Al MgFeSi Ca-FeSi Sample Al Gsa Densities, g/cm3 Ks= Vcsh
source Treatment Inoculation (%) (g) d1 d2 ds ds/d2 cm3 %
(Al level) (Al level)
Base MgFeSi Un-Inoc. 1.01 0.002 1047.4 7.14 6.94 7.15 1.030 4.14 2.74
Conditions (Low Al) 1039.4 7.06 6.95 7.12 1.024 2.29 1.53
(No precond.) Ca-FeSi 1.11 0.003 1043.0 6.92 6.72 6.90 1.027 4.46 2.87
(Low Al) 1031.1 6.95 6.69 6.91 1.033 5.95 3.86
1.13 0.003 1043.1 6.95 6.75 7.01 1.039 4.55 2.94
1049.3 6.97 6.75 7.01 1.039 4.92 3.17
Preconditioner, MgFeSi Un-Inoc. 2.01 0.012 1046.2 7.16 7.02 7.20 1.026 2.96 2.00
AlFeSi (Low Al) 1060.5 7.16 6.95 7.20 1.036 4.47 2.93
2.02 0.013 1049.7 7.02 6.91 7.10 1.027 2.41 1.59
1048.9 6.96 6.83 7.06 1.034 2.88 1.88
Ca-FeSi 2.11 0.013 1038.0 6.97 6.72 6.98 1.039 5.47 3.54
(Low Al) 1041.3 6.97 6.70 6.99 1.043 5.99 3.85
2.12 0.013 1054.5 6.93 6.69 6.92 1.034 5.51 3.49
1040.2 6.92 6.72 6.93 1.031 4.57 2.95
Nodulariser MgFeSi Un-Inoc. 3.01 0.021 1052.3 7.14 7.04 7.17 1.018 2.19 1.45
(No precond.) (Med.Al) 1058.1 7.15 6.99 7.15 1.023 3.40 2.24
Ca-FeSi 3.11 0.019 1035.6 6.97 6.74 6.95 1.031 5.24 3.41
(Low Al) 1065.3 7.00 6.76 6.98 1.033 5.41 3.43
MgFeSi Un-Inoc. 3.02 0.046 1057.7 7.20 7.06 7.22 1.023 2.94 1.96
(High Al) 1049.7 7.19 7.06 7.18 1.017 2.75 1.85
Ca-FeSi 3.21 0.044 1045.2 7.01 6.77 6.97 1.030 5.32 3.44
(Low Al) 1016.6 6.95 6.78 7.02 1.035 3.65 2.43
Inoculant MgFeSi Ca-FeSi 4.11 0.007 1044.4 6.98 6.73 7.03 1.045 5.58 3.60
(No precond.) (Low Al) (Med.Al) 1044.6 6.97 6.75 6.99 1.036 4.77 3.08
4.12 0.008 1059.4 7.00 6.80 6.99 1.028 4.39 2.82
1045.4 6.98 6.80 6.96 1.024 4.08 2.65
Ca-FeSi 4.21 0.017 1052.0 6.96 6.79 7.00 1.031 3.76 2.43
(High Al) 4.22 0.017 1050.6 6.98 6.75 6.95 1.030 5.26 3.38
1037.6 6.98 6.73 6.96 1.034 5.63 3.65
 Paper 07-008(05).pdf, Page 11 of 11
AFS Transactions 2007 © American Foundry Society, Schaumburg, IL USA

CONCLUSIONS

The presumptive role of residual aluminium proceeded from different sources, in low carbon equivalent level (3.95 - 4.25%)
ductile iron, melted in acid lined induction furnace, was investigated. The conclusions drawn in the present paper based
mainly on the thermal analysis, carbides sensitivity, graphite characteristics and shrinkage tendency.
In the conditions of high purity charge materials and synthetic base iron, a large range of final residual aluminium was
obtained (0.002 - 0.05%Al), depending on the Al-source: less than 0.005%Al without aluminium addition, 0.012 -
0.013%Al as preconditioning addition, 0.007 - 0.017%Al by inoculation contribution and 0.019 - 0.046%Al by Mg-FeSi
treatment source.
Generally, Al-residual was found as an important, medium potency graphitizing influencing factor, in both un-inoculated
and inoculated ductile irons.
As for solidification pattern, the most representative parameters of thermal analysis were improved by residual
aluminium, such as higher eutectic temperatures and lower undercooling degree, higher temperature at the end of
solidification and greater peak of the first derivative at this temperature etc.
In lower carbon equivalent conditions, Al had not capacity to influence chill tendency as wedge chill test samples
evaluation, but it may be efficient to control free carbides amount in conventional castings, especially by inoculation
addition.
There was a visible beneficial effect of Al-content on increasing the nodule count; and the most effective means was to
add Al within the inoculant.
Inoculated irons shown higher shrinkage occurrence and lower correspondent density, as compared to un-inoculated
irons. Al-content appears to have a beneficial influence, as casting compactness increased.
Recommendations to ductile iron production practice:
- 0.005 - 0.02wt.%Al residual is beneficial to improve ductile iron characteristics without the incidence of
pinholes
- The greatest benefits were achieved when Al was introduced into the iron via the inoculant.
- The next best was to have Al present in the base iron, added as an Al bearing preconditioner.
- Al added via the MgFeSi provided the minimum benefit.

ACKNOWLEDGMENTS

This research was conducted with the funds provided by the Elkem s Foundry Products Division, Norway. In addition
Torbjorn Skaland and Svein Olsen are to be thanked for their contribution to the work.

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