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Efek Fe Dalam Al-Si-1
Efek Fe Dalam Al-Si-1
John A. Taylor
Cooperative Research Centre for Cast Metals Manufacturing (CAST)
The University of Queensland
Brisbane, Australia
Abstract
Iron is a common impurity in aluminium and its alloys that is not readily removed and which can
cause adverse effects to ductility and castability, particularly in Al-Si based casting alloys. The choice
of whether to use primary aluminium or secondary aluminium alloys for a cast product, with their low
and moderate/high iron levels respectively, is a commercial decision that must be made. The decision
often means a compromise between the need to reduce metal cost and the need to maximise casting
productivity via reduced defect formation and/or to minimise the deleterious effect of iron on the
mechanical properties of the final casting. This paper discusses the various sources of iron and how it
enters aluminium alloys, the way that iron leads to the formation of complex intermetallic phases
during solidification, and how these phases can adversely affect mechanical properties, especially
ductility, and also lead to the formation of excessive shrinkage porosity defects in castings. The paper
offers guidelines to the levels of iron that can be tolerated, how to maintain these levels and how to
minimise the negative effects of iron.
Introduction
Iron is a common impurity in aluminium alloys that arises from a number of possible sources and
which, at least for Al-Si based casting alloys, is usually considered detrimental in one or more ways.
These will be discussed later in this paper. It should be noted that iron does not always exert a negative
influence; in certain wrought aluminium alloys (that is, alloys used in forged, extruded or rolled
forms), iron can be a deliberate alloying addition that is made to improve the processing capabilities of
the alloy and/or the strength of the final wrought product. However, these wrought alloys are not of
normal interest to the foundry industry, who instead work with the casting/foundry alloys, particularly
those based on the Al-Si family.
Iron is a natural impurity that arises during the manufacture of primary aluminium via the Bayer
Process that converts bauxite (the ore) into alumina (the feedstock) and the Hall-Hroult electrolytic
reduction process that converts alumina into molten aluminium (>900C) with the consumption of
both electricity and carbon. Depending on the quality of the incoming ore and the control of the
various processing parameters and other raw materials, molten primary aluminium typically contains
between 0.03 0.15 wt.% iron, with ~ 0.07 0.10 % being average.
There is no known way to economically remove iron from aluminium so these primary values are the
typical baseline and all further melt activities only serve to potentially increase the iron level. Iron can
enter the melt during further downstream melt activity through two basic mechanisms:
1. Liquid aluminium is capable of dissolving iron from unprotected steel tools and furnace
equipment, and with long exposure times, Fe levels can reach 2 wt% at normal melt
temperatures of ~700C (an Al-Fe eutectic exists at 1.7 wt.% Fe, 655C see Figure 1). For a
melt held at 800C, the Fe level can reach up to 5%;
2. Iron can also enter an aluminium melt via the addition of low-purity alloying materials, e.g.
Si, or via the addition of scrap that contains higher background iron than the primary metal.
Figure 1
These are the reasons that iron levels in aluminium alloys continue to increase with each remelt cycle,
and why secondary alloys, particularly those Al-Si alloys destined for high pressure die casting
(HPDC) operations, can end up containing iron levels of up to 1.5%. In the case of HPDC, this is not
always a bad thing as high iron levels assist in minimising the costly problem of die soldering.
However, typical secondary Al-Si alloys for non-HPDC operations usually contain much lower Fe
levels ranging from ~ 0.25 to 0.8 wt%, with values around 0.4-0.7 being most common. The reason
these moderate iron level alloys find such wide use arises from the necessary commercial balance
between the benefits of a reduced metal cost and the acceptable loss of some processing capability
and/or final mechanical properties. These detrimental effects of iron are considered in later sections,
after first considering what happens to the iron impurity during solidification of Al-Si alloys.
appear to be needles. The differing shapes of these iron intermetallics are in part responsible for the
impact of iron on castability and mechanical properties.
50 m
50 m
(a)
(b)
20 m
(c)
Figure 2
40 m
(d)
Another critical issue for iron intermetallics and their effects is the timing at which the different phases
form during solidification, and this is influenced by both the concentrations of the elements involved
and cooling rates. Figure 3 shows a typical cooling curve of an Al-Si-Cu-Mg-Fe alloy with the
location(s) of intermetallic phase formation indicated. Intermetallic particles that form prior to the
solidification of the aluminium dendritic grain network (i.e. that grow freely within the liquid) or that
form at the same time as the dendritic network (but within the remaining liquid) tend to grow much
larger than those that form much later, during or after the period of Al-Si eutectic solidification,
because there is less liquid space available for growth to occur during these later stages. Generally
speaking, the larger the particle, the more detrimental it is likely to be. Increasing the concentration of
Fe (and also Mn) tends to result in earlier formation of intermetallic phase particles and hence more
unconstrained growth is able to occur. A slower cooling rate also increases the risk of forming large
particles because the time available for growth is increased. Iron-bearing intermetallics (especially Al5FeSi platelets and -Al15(Fe, Mn)3Si2 script) can grow up to two or more millimetres in slowlycooled Al-Si alloy castings with high Fe and/or Mn levels. However, under normal casting conditions
and moderate Fe levels, these intermetallics grow more typically in the size range of 50 500 m. In
castings with very high cooling rates (e.g. HPDC) and/or when using low Fe levels (e.g. primary alloy
ingot), the intermetallic particles are typically of the order of 10 - 50 m. The effects of Fe level and
cooling rate (as indicated by SDAS) can be seen in Figure 4.
Temp ( C)
600
0.5
dT/dt ( C/s)
650
550
-0.5
500
-1
-1.5
450
0
100
200
300
400
Time (s)
Figure 3
Cooling curve and rate of cooling curve for an Al-9Si-3Cu-0.5Mg-1.0Fe alloy. The
labelled peaks represent the following reactions; (1) primary Al dendrites, (2) -Al5FeSi,
(3) Al-Si eutectic, (4) complex Mg2Si eutectic, (5) complex Al2Cu eutectic [2].
Figure 4
Graph showing the maximum observed length of phase platelets versus secondary
dendrite arm spacing for an AlSi7Mg0.3 alloy containing various amounts of iron [3].
The critical iron level is directly related to the silicon concentration of the alloy. Figure 5 shows a
section of the Al-Si-Fe ternary phase diagram that highlights the reason for the existence of a critical
iron content. As the silicon content of the alloy increases, the amount of iron that can be tolerated
before the -phase starts to form prior to the Al-Si eutectic increases. At 5% silicon, the critical iron
content is ~0.35%, at 7%Si it rises to ~0.5, at 9% it is ~0.6 and by 11% it reaches ~0.75%. Also for a
given Fe content, the temperature (and therefore time) at which can form prior to Al-Si eutectic
decreases with increasing Si content. The line AB between the -phase field and the Al phase field is
the period during which the larger and more detrimental intermetallic particles form.
wt% Fe
2.0
Al8Fe 2Si
Aluminium
615 C
- Al5FeSi
x
y
1.0
x
Si
Fe crit
577 C
0.0
4
Figure 5
575 C
10
11
12
wt% Si
Ternary Al-Si-Fe phase diagram showing primary Al solidification paths for all alloys
with Fecrit iron levels, and for 5%Si (x-x), 7%Si (y-y)and 9%Si (z-z) alloys with 0.8%Fe.
The points of intersection with line AB is where the formation of large phase platelets
can start to occur before formation of eutectic at B.
When a given cast aluminium alloy (at a given heat treatment, if any) is subjected to tensile testing and
elongated to the point of failure, and the fracture points of each test are plotted, they are seen to fall
along a line of the form shown in Figure 6. These various points of fracture occur because of the
combined effects of several variables such as casting defects (e.g. oxides and porosity), cooling rate
(secondary dendrite arm spacing, SDAS) and Fe content. As an alloy contains fewer defects, has
higher cooling rate (reduced SDAS) and lower Fe content, the fracture points of the tensile specimens
move to higher levels of both ductility and tensile strength. If we take only the best fracture points of
samples with the same SDAS and Fe content (thus effectively eliminating the role of defects) and plot
them against elongation to fracture, as in Figure 7, we can see the effect of Fe content in controlling
ductility. In the example shown in Figures 6 and 7, an Al-7%Si-0.4%Mg alloy made from low iron
primary aluminium given a particular under-aged T6 treatment demonstrates a very strong influence of
even small amounts of iron, even when cooling rates are high (i.e. low SDAS). Unfortunately, iron
intermetallics are not substantially altered during heat treatment.
In many instances however, the effect of iron on an alloys ductility is not so clearly demarcated
because as the Fe level increases above Fecrit, the cooling becomes slower and/or there are lots of
casting defects present, the ductility tends to drop to extremely low levels, < 1%, and sometimes
tensile specimens even break before yielding (i.e., < 0.2%).
The reason that Fe-containing intermetallic particles are detrimental to an alloys mechanical
properties is that they are much more easily fractured under tensile load than the aluminium matrix or
the small silicon particles (if modified). Micro-cracks tend to initiate at these particles and they
provide easy pathways for macro-cracks to propagate through. Figure 8 shows samples of both Al5FeSi platelets and -Al15(Fe, Mn)3Si2 script particles that have fractured under tensile loading. It
should be noted that the -platelets tend to be much more prone to fracture and crack linkage than the
-script particles.
340
320
Stress (MPa)
300
280
y = 225.39x 0 .102 6
R2 = 0.9839
260
240
y = 2.470 9x + 259.31
R2 = 0.8004
220
200
180
160
0
10
12
14
16
18
20
22
24
Strain (%)
Figure 6
Graph showing the best average fracture points for under-aged Al-7%Si-0.4% Mg alloy
(with varying Fe levels and SDAS values) and the possible lines of best fit [7].
24
22
20
18
16
14
12
No Fe
10
0.05% Fe
0.12% Fe
0.20% Fe
4
2
0
0
Figure 7
20
30
40
SDAS (m)
50
60
70
Graph showing maximum ductility (i.e. best elongation to fracture) as a function of SDAS
for various Fe contents (including hypothetical zero iron) for tensile specimens of underaged Al-7%Si-0.4% Mg alloy [7].
(a)
Figure 8
10
(b)
Micrographs of fractured (a) -Al5FeSi platelets, and (b) -Al15(Fe, Mn)3Si2 script
particles in tested tensile bars of Al-5%Si-1%Cu based alloys (courtesy C. Cceres).
This observation has led to the commonly accepted practice of adding Mn to the moderate to high Fe
aluminium-silicon alloys to promote the formation of the -phase instead of the more detrimental phase. This process is called iron neutralisation, or iron correction. The Mn is often added at a Mn:Fe
ratio of at least 0.5, however detailed microstructural observations of a range of Al-Si-Cu-Mg alloys
has shown that even when Mn is added to these levels it is not always possible to completely eliminate
the platelets. Furthermore, the addition of Mn actually results in a higher volume fraction of iron
intermetallic particles that can counter some of the ductility gains to be made. This can also lead to
machining difficulties, especially when the hard phase forms in very large, colonies within the alloy.
Other iron neutralising/correcting elements have been identified and proposed, such as Co, Mo, Cr, Ni
and Be, all of which change the iron intermetallic phase that forms, but none of these find any
widespread use, partly because of cost and also because of health and safety issues. Beryllium,
unfortunately a toxic substance, has been claimed to be particularly effective and has been shown to
result in dramatic improvements to ductility even at addition levels of ~ 0.2%. It is not entirely clear
how beryllium improves ductility. It may in part be due to improved melt oxidation resistance thus
reducing oxide defects, or else the formation of smaller intermetallic particles that form at the centre
of aluminium grains rather than at the more sensitive interdendritic or grain boundary regions.
0.1
0.4
0.7
1.0
1 mm
Figure 9
0.24
2.00
0.22
1.80
0.20
1.60
1.40
0.16
Porosity (%)
Extended-Defect Size
0.18
0.14
0.12
0.10
0.08
1.20
1.00
0.80
0.60
0.06
0.40
0.04
0.20
0.02
0.00
0.00
0.20
0.40
0.60
0.80
1.00
0.00
0.00
0.10
0.20
0.30
0.40
0.60
0.70
0.80
0.90
1.00
(b)
(a)
Figure 10
0.50
Porosity (%)
1.5
1.0
0.5
0.0
0.1Fe
Figure 11
0.6Fe
1Fe
1Fe + 0.5Mn
Graph showing the continual increase in total casting porosity with increasing Fe content
in both copper-free and copper-containing Al-9%Si alloy plate castings. The addition of
Mn, an iron-correcting element reduces porosity in the copper-free alloy, but not in
the Cu-containing alloy [2].
The use of iron correcting elements, particularly Mn and Be, for reducing casting porosity in Al-Si
alloys with high Fe levels has been reported [12]. Addition of Mn to achieve specific Mn:Fe ratios is a
widespread practice in Al-Si based casting alloys to obtain improved mechanical properties (see
earlier section), however it has also been observed to be beneficial in reducing porosity, but the means
by which this occurs and under what circumstances has been unclear. It has been proposed that the phase does not restrict feeding like the -platelets do, or that the feeding temperature range is extended
with manganese, but neither has been clearly shown. The work of Dinnis et al [2] has more recently
shown that the presence of Mn in an alloy does not ensure improved porosity. Manganese alone in the
absence of iron does not appear to do anything beneficial, even although the -phase is dominant.
Additionally, manganese appears to provide greater reductions in iron-related porosity in the absence
of Cu (Figure 11). It appears that the benefits provided by Mn additions relate to a reduction in the
poisoning of Al-Si eutectic nucleation sites by Fe (Figure 12). This results in the formation of a greater
number of smaller Al-Si grains during solidification and this in turn results in improved permeability
and feeding, and hence a reduction in porosity. It can also be seen in Figure 12, that the addition of
0.5%Mn to a 1%Fe-containing Al-9%Si alloy is sufficient to reduce porosity levels to those obtained
in the same alloy with 0.6%Fe (i.e. the critical iron content for that composition).
18
16
12
1.0Fe
1.0Fe-0.5Mn
0.1Fe
0.1Fe
1.0Fe
1.0Fe
0.6Fe
1.0Fe-0.5Mn
10
0.0Fe
14
0
Al-9Si
Figure 12
Al-9Si-0.5Mg
Nominal Composition
Al-9Si-0.5Mg-3Cu
The effect of iron and manganese additions on the Al-Si eutectic grain nucleation density
for three Al-9%Si alloys. Increasing iron levels reduce nucleation density, while Mn
alleviates the poisoning effect of iron to some extent [2].
Wherever possible, iron levels in Al-Si alloys should be kept as low as practical in order to avoid
the detrimental effects on mechanical properties, particularly ductility and fracture toughness. This
means minimising iron contamination through careful selection of raw materials (i.e. ingots,
silicon, etc.) and the maintenance of good refractory coatings on all steel tools used to prepare and
handle melts.
Iron levels above the critical level for the silicon content of the alloy should be avoided as these
can cause serious loss of ductility in the final cast product and decreased casting productivity
through increased rejects due to shrinkage porosity, and particularly leakers.
The critical iron content (in wt%) for an alloy can be calculated using Fecrit 0.075 x [%Si] 0.05.
If solidification/cooling rates are very high (e.g. high pressure die casting), super critical iron
contents may not be detrimental, but as the cooling rate decreases (gravity die casting sand
casting, etc.) the probability of super critical iron levels causing problems dramatically increases.
Traditional heat treatment regimes for Al-Si alloys, e.g. T6, do not alter the nature of the offending
Fe-containing phases. As-cast intermetallics are retained and although the overall performance of
an alloy may be improved by heat treatment, it would be better still with low iron levels initially.
Additions of Mn to neutralise the effects of iron are common, at Mn:Fe ratios of ~ 0.5, however,
the benefits of this treatment are not always apparent. Excess Mn may reduce -phase and promote
-phase formation, and this may improve ductility but it can lead to hard spots and difficulties in
machining. Mn additions do not always improve castability and reduce porosity in high Fe alloys.
Its affect is sensitive to alloy composition.
The addition of Mn to melts with high iron levels can also promote the formation of sludge, if the
sludge factor (derived by [%Fe] + 2[%Mn] + 3[%Cr]) exceeds a particular value for a given alloy
and melt holding temperature. This is a serious problem for die-casters who use low melt
temperatures and high impurity secondary alloys.
Acknowledgements
The CRC for Cast Metals Manufacturing (CAST) was established under and is supported in part by
the Federal Governments Cooperative Research Centres Scheme. The author gratefully acknowledges
the research efforts of three postgraduate students over the past few years: Matthew Otte, Stuart
McDonald and, more recently Cameron Dinnis.
References
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