Arch. Metall. Mater.

63 (2018), 2, 601-607

DOI: 10.24425/122383

J. ROUČKA*#, E. ABRAMOVÁ*, V. KAŇA*

PROPERTIES OF TYPE SiMo DUCTILE IRONS AT HIGH TEMPERATURES

Ductile irons of the type of Si-Mo are characterized by increased resistance to long-term influence of high temperatures and
cyclic temperature changes. They are mainly used in castings of combustion engine exhaust piping and other castings utilized at
temperatures of up to 850°C. The aim of the study is to verify the mechanical properties of non-alloyed cast iron EN CSN GJS
450, SiMo4-0.5 and SiMo5-1 ductile irons at temperatures of 700 to 800°C, and the extent of their superficial oxidation after long-
term annealing at a temperature of 900°C. Via chemical microanalysis the composition of oxidation products in the surface layer
was evaluated.
Keywords: Si-Mo cast irons, mechanical properties at high temperatures, thermal stability of structure, oxidation resistance

1. Introduction For the highest operating temperatures at which iron cast-

ings are no longer functional, economically and technologically
At operating temperatures of iron castings exceeding ca more demanding ferritic or austenitic steels are used.
650°C for prolonged periods there appears in-depth oxidation of A typical example of castings in which cyclic thermal stress
the structure along graphite shapes and the metastable structure appears at high temperatures can be seen in the combustion en-
components are decomposed into stable ones. With a cyclically gine exhaust piping. Operating temperatures of exhaust manifold
repeated transition of the cast iron across eutectoid temperatures castings of serially produced automobiles are, according to the
A1 there occurs a transformation of ferrite into austenite and manufacturers [2], as high as 800°C by exhaust gas temperature
back, accompanied by repetitional volume changeovers. The up to 850°C. High-temperature corrosion of exhaust parts take
transformation changes coupled with heat stress due to thermal place under intensive chemical action of the exhaust gases.
expansion and chemical effects result in a degradation of the Exhaust gases mainly contain nitrogen, water vapour,
initial structure and a gradual appearance of thermal fatigue in oxygen, carbon oxides and lower amounts of SOx, NOx and
the metal. The in-depth oxidation proceeds mainly along graphite compounds of HC. At low temperatures, water vapour in which
shapes. Therefore the oxidation rate in ductile irons and also exhaust gas components get dissolved in the exhaust piping
irons with vermicular graphite is lower than in the cast iron with condensate, with H2SO4 and HNO3 being formed [3]. These
lamellar graphite. products are on the one hand responsible for the direct oxidation
Preventing cyclic structural changes is based on thermal of some elements in the cast iron, on the other hand chemically
stabilization of ferrite up to actual operating temperatures of aggressive condensates of the type of nitric or sulphuric acid
castings or, vice versa, on austenite stabilization over the whole support intensive in-depth corrosion.
temperature range so that there is no structural transformation at The reaction of the exhaust gases or the condensate with
all. Ferrite stabilization in cast irons can be obtained in particular the exhaust piping material yields, according to the equation
by increasing the silicon content to 4-6% Si while austenite can x . M + y . O = MxOy products of oxidation reaction, which form
be stabilized by high nickel content [1]. Limiting the growth rate a transition layer on the surface of the piping. The intensity of
of the oxidic layer in the mostly ferritic cast irons is enhanced by oxygen penetration into the wall depth depends on the diffusion
the formation of compact oxides of some further elements with of oxygen into the metal and, vice versa, on the diffusion of
high affinity to oxygen, in particular chromium and aluminium, reaction products towards the surface, and also on the oxidation
in addition to silicon. Based on cast irons alloyed in the above potential of the elements in the cast iron and on the compactness
way, cast irons referred to as SiMo ductile irons have been devel- of the oxidic layer. For a given alloy and oxidation conditions, the
oped, which have proved reliable with operating temperatures of dependence of the oxidic layer thickness on time has a roughly
up to ca 850°C particularly in many mass-produced automobiles. parabolic course.

* BRNO UNIVERSITY OF TECHNOLOGY, INSTITUT OF MECHANICAL TECHNOLOGY, FACULTY OF MECHANICAL ENGINEERING, TECHNICKÁ 2, CZ-616 69 BRNO, CZECH REPUBLIC
# Corresponding author: [email protected]
602
The presence of the sulphur oxides SO2 or SO3 increases 2.1. Recommended composition and structure
the intensity of oxidation. The condensate formed in particular of basic types of SiMo ductile irons
after a cold start penetrates via potential cracks in the oxidic layer
into the material depth and increases the corrosion intensity. In Type SiMo ductile irons are defined in the EN CSN 16124
the case of complex SiMo alloy castings there is also oxidation Standard [9]. This directive specifies the range of Si and Mo con-
of other elements with high affinity to oxygen, Cr or Al in par- tents, requirements for the structure, and the standard deviations
ticular. From the viewpoint of protective effect it is important of mechanical properties at ambient temperature. Informative
for the oxidic layer no to contain pores and not to peel off the appendices of this standard give tentatively the values of some
base metal. mechanical and physical properties under increased tempera-
In addition to oxygen, nitrogen can also penetrate into tures. Regarded as the basic alloys of this type are the ductile
the metal and form the Si3N4 or MgSiN2 phases. The nitrides, irons EN-GJS-SiMo40-6 and EN-GJS-SiMo50-10 with content
however, do not form a continuous layer. of silicon and molybdenium:

EN-GJS-SiMo40-6: 3.8-4.2% Si, 0.5-0.7% Mo

2. SiMo ductile irons
EN-GJS-SiMo50-10: 4.8-5.2% Si, 0.8-1.1% Mo

Materials denoted as SiMo are irons with increased content – The carbon content should be chosen with a view to the
of silicon and molybdenum. They can have graphite of arbitrary silicon content such that the iron has the carbon equivalent
shape but from the viewpoint of obtaining high mechanical CE in the interval from 4.6 to 4.8 (CE = C + 1/3 Si) [2],
properties and corrosion resistance, ductile irons, exceptionally – Mn content not prescribed, usually <0.3% Mn,
also irons with vermicular graphite, are used almost exclusively. – The content of the other elements is the manufacturer’s
The content of silicon is usually increased to 4-5.5% Si, the choice,
molybdenum content is 0.5-1.5% Mo. – Structure: a minimum of 85% of ferrite, a maximum of 5%
The high silicon content increases the temperature of eu- of carbides of the type of Fe2MoC or Fe2MoC/M6C, and
tectoid transformation A1 to values of ca 900°C or even higher the rest is pearlite [2,4],
[4]. Molybdenum partially segregates during solidification and – Graphite – recommended dispersity: a minimum of 100
forms a carbidic phase on grain boundaries. This carbidic net- nodules/mm2 [2].
work improves dimensional stability, increases tensile strength The tendencies in the effect of silicon and molybdenum
and creep resistance [5,6]. At the same time, however, it reduces on structure and properties given in [6,7] are also confirmed by
plastic properties. Both Si and Mo increase the resistance to Ekström [10].
scale formation and thermal fatigue. The properties can be
further improved via complex alloying with other elements
(Ni, Cr, Al, V, and Ti), which improve the resistance to scale 2.2. Corrosion resistance of SiMo ductile irons
formation and crack formation [4]. For example, ductile iron
denoted SiMo1000 [7] for use at temperatures of ca 900°C is Using the Thermo-Calc program, the composition and
such a complex alloyed material. phase proportion in the transition layer in SiMo ductile irons
The maximum operating temperatures of exhaust manifold were established. It was found that in the direction from the
and the maximum temperature of exhaust gases for individual surface into the manifold wall the transition layer was succes-
types of cast irons are approximately as given in Table 1 [3,8]. sively formed by the Fe2O3 phase, deeper in the wall by Fe3O4,
(The difference between the maximum temperatures of exhaust then by FeO+Fe2SiO4 and a thin layer of β-SiO2 separating the
gases and the temperatures of exhaust manifold depends on the band of oxides from the base metal – Fig. 1. The SiO2 layer was
engine design.) more compact than the ferrous oxides and represented the most
significant barrier to oxygen diffusion [10]. If the alloy contains
TABLE 1 chromium, the layer of Cr2O3 oxides formed in the region of SiO2
Maximum operating temperatures of exhaust manifold castings of layer reduces the speed of oxidation very significantly.
various kinds of cast iron

Exhaust manifold Maximum temperature [°C]

3. Experimental verification of the effect of silicon
alloys Exhaust manifold Exhaust gases
and molybdenum alloying on the structure
EN-GJS 400-15 700 770
and mechanical properties
EN-GJS Si4Mo0,5 750 820
EN-GJS Si5Mo1 780 820, (870) [2]
Since the strength of cast irons under temperatures corre-
EN-GJS SiMoNi 795 835
sponding to actual temperatures in exhaust manifold decreases
Niresist D-5S 870 950
dramatically in comparison with the strengths under normal
temperatures, experimental testing of mechanical properties was
 603
the Alphaset method. The plate edges were cut off as shown in
Fig. 2. The centre part of the plate was used to make mechanical
test specimens and specimens for structure analysis.

Fig. 1. Composition of oxidic phases in the surface layer as calculated

Fig. 2. Test-plate casting
by Thermo-Calc [10]

performed for two alloys of the SiMo type corresponding to the 3.2. Mechanical properties testing
SiMo4-0.5 and SiMo5-1 specifications, and for the basic non-
alloyed ductile cast iron corresponding to the material according In tensile tests, cylindrical test specimens with threaded
to EN-CSN GJS 450 by ambient temperature and temperatures heads according to the standards CSN ISO 6892-1 and 2 were
of 700 and 800°C. used, diameter do = 5.5 mm, measured length 40 mm. The tests
Resistance to oxidation was tested on specimens prepared were performed using the methodology given in these standards.
from these cast irons, under long-term annealing at a temperature Hardness was measured on the heads of tensile test specimens.
of 900°C. The following properties were tested:
– tensile strength at normal temperature and at temperatures
of 700 and 800°C, yield point, elongation and contraction
3.1. Alloys under examination and specimen casting values,
– HB hardness at normal temperature.
Melting was performed in the BUT foundry in an induction The values of mechanical properties given in Table 3 are
furnace with 80 kg crucible capacity. The base alloy charge was an average of 4 measurements, the hardness values an average
made up of 45% of raw iron, 20% of steel, 35% of GJS scrap, of 3 measurements.
FeSi70 and FeMo65.
Modification – 0.8% Elmag 5800, inoculation with 0.5% TABLE 3
FeSi70, using the tundish ladle. Mechanical properties of cast irons
Modification temperature – 1530°C.
Tempe-
The resultant chemical composition of the tested cast irons rature Alloy
Rm
s
Rp0,2
s
A5
s HB
[MPa] [MPa] [%]
is given in Table 2 [oC]
GJS 450 497 4.3 354 6.7 14.2 0.7 161
TABLE 2 20 SiMo 4-0,5 582 6.5 483 7.9 8.3 2.9
SiMo 5-1 610 17.3 595 6.0 0.7 0.3
Chemical composition of the tested cast irons
GJS 450 91.4 3.1 34.5 8.2 239
Cast iron C Si Mn Mo Cr S P 700 SiMo 4-0,5 107.7 2.2 41.2 7.8
GJS 450 3.35 2.52 0.22 0 0.075 0.021 0.049 SiMo 5-1 118.7 3.7 22.7 4.6
SiMo 4-0.5 3.25 3.50 0.26 0.54 0.039 0.021 0.039 GJS 450 46.2 2.5 44.6 8.9 236
800 SiMo 4-0,5 49.8 3.0 48.8 7.8
SiMo 5-1 3.2 5.24 0.25 1.02 0.062 0.024 0.050
SiMo 5-1 53.4 1.9 33.9 4.6
Note: The tensile curves for elevated temperatures have a course from
Test specimens of the above alloys were cast in the shape of which the device software does not evaluate the value Rp0,2 – Fig. 3. The
plates 20 mm thick, with thickened lateral edges for the purpose tensile curves for the temperatures 700 and 800°C have a similar course.
of metal feeding during solidification and thermal homogeniza-
tion of the plates during solidification used by Ekström [10]. The values of strength Rm and elongation A are given in
The moulds were made of a self-setting moulding mixture using Figs 4 and 5. (The connecting line of the curves between the
604

Fig. 5. Effect of temperature on elongation

3.3. Structure analysis

3.3.1. Structure analysis of irons as cast

Metallographic optical analysis was performed on speci-

mens of cast irons as cast, Fig. 6. The subject of evaluation was
the graphite size and the pearlite content in the structure. Graphite
in all the cast irons was spheroidal and its share was >95%.
The structure of the base metal in the as-cast state was
ferritic-pearlitic in the basic non-alloyed cast iron while in the
SiMo ductile irons it was ferritic with pearlite and carbide content
of up to 10-15%.

Fig. 3. Tensile strength diagrams for the temperatures 20°C and 700
(800)°C
3.3.2. Effect of annealing on the formation
of surface oxidic layer
temperatures 20 and 700°C is not real, it is only given for the
sake of clarity.) It is obvious that in static tests the cast iron The effect of long-term action of high temperatures on the
strengths in the range of operating temperatures are markedly cast irons under examination was simulated via annealing the
lower than at the normal temperature. At elevated temperatures specimens in an electric resistance furnace at a temperature of
the elongation increases significantly. 900°C for a period of 72 hours in calm-air environment. After
annealing, the specimens were cut transversely. The structure
of the surface oxidic layer was evaluated on a Philips XL 30
electron microscope, and selected points on the cross-section
of layers were chemical microanalysis performed.
Fig. 7 shows the oxidized layer on the basic cast iron, with
the analysed points marked 4 and 5, and with the area of thin
contact layer between the oxidic layer and the base metal – see
the detail A, points 1-3. It is obvious from the chemical analysis
given in Table 4 that the highest oxygen and silicon content in
this zone was analysed which indicates the formation of a bar-
rier of SiO2.
In the two SiMo ductile irons the Si content near the speci-
men surface, point 3 is very low or even zero, in the central part
it is somewhat higher than indicated by the average chemical
composition – see Fig. 8, point 2. The Si content on the contact
between oxides and the base metal is substantially increased
Fig. 4. Effect of temperature on tensile strength and high content of chromium and manganese were analysed
 605
TABLE 4
Chemical composition and thickness of oxidic layer after
annealing 900°C-72 h

Layer
Spot Fe O Si Cr Mn thickness
[mm]
EN GJS 450
1 metal 92.0 5.3 2.4 — —
2 metal-oxid 56.8 34.9 8.3 — —
3 oxid 66.0 30.1 3.9 — — 0.4-0.6
4 oxid 68.1 28.3 3.6 — —
5 oxid-gas 70.8 28.9 0.8 — —
SiMo 4-0.5
1 metal-oxid 36.8 36.3 16.0 3.95 6.95
2 oxid 63.5 31.3 5.3 — — 0.2-0.3
3 oxid-gas 68.8 31.2 0 — —
SiMo 5-1
1 metal-oxid 31.3 39.1 19.8 6.41 3.48
2 oxid 59.3 37.7 6.9 — 1.08 0.1-0.2
3 oxid-gas 69.1 31.0 — — —

4. Results and discussion

The mechanical properties tests performed have confirmed

that the tensile strength values at temperatures that actually cor-
respond to the operating temperatures of exhaust piping are in
all the cast irons evaluated markedly lower than at the normal
temperature. At a temperature of 700°C they attain approxi-
mately 20% of the strength value for the ambient temperature,
at 800°C only 10% of the strength at ambient temperature.
Under the high temperatures given above, all the cast irons
exhibit plastic behaviour, with the elongation values increasing
considerably. In all the test modes the SiMo5-1 ductile irons
display the highest tensile strength and the lowest elongation.
It is obvious from these results that for a proper dimensioning
of castings working under such high temperatures it is neces-
sary to respect the mechanical properties that actually hold for
a given operating mode.
The evaluation of the oxidic layer after annealing to 900°C
has confirmed a pronounced protective effect of the alloying
elements silicon and molybdenum on the oxidation extent. The
SiMo5-1 ductile iron is substantially more resistant to oxidation
than the SiMo4-0.5 ductile iron. The oxidic layer thickness in
the SiMo4-0.5 ductile iron is roughly half this thickness in non-
Fig. 6. Structures of as-cast irons alloyed cast iron GJS 450 while in the SiMo5-1 ductile iron it
is approximately one quarter. The chemical microanalysis has
there, which participates on creating the protective barrier. This shown that the barrier to the oxidation advance into the metal
elements were in outward oxide layer not detected. With the depth consists in a thin layer of silicon oxide (probably β-SiO2),
SiMo5-1 ductile iron the situation is similar, Fig. 9. which is formed at the oxidic layer/base metal interface. This
In the SiMo ductile irons the average oxidic layer thickness layer also contains a considerable amount of chromium, which
decreases significantly in comparison with non-alloyed GJS was contained in the basic cast iron in only trace amounts. The
while in the higher-alloyed SiMo5-1 ductile iron the thickness chromium oxides obviously participate in the barrier effect of
of oxidic layer is again considerably lower than in the SiMo4- the silicon oxide. The outer parts of the oxidic layer are mostly
0.5, see Table 4. formed by ferrous oxides. The results obtained are in good
606

Fig. 7. Structure of oxidic layer on GJS-450 iron

agreement with the computation results from the Thermocalc Acknowledgement

program (without influence of Cr content).
The test conditions do not reflect the actual situation during This investigation was realised under support of the project of BUT-FME
the cyclic thermal stress of exhaust piping, the adhesion of oxidic CZ-Brno, Nr. FSI-S-16-3686
layer to the base metal or the chemical effect in corrosion caused
by actual exhaust gases. These effects can only be established
when testing under operating conditions.
 607

Fig. 8. Structure of oxidic layer on SiMo4-0.5 iron Fig. 9. Structure of oxidic layer on SiMo5-1 iron

REFERENCES [6] P. Matteis, G. Scavino, A. Castello, D. Firrao, Procedia Materials

Science 3, 2154-2159 (2014).
[1] W. Fairhurst, K. Röhrig, Foundry Trade Journal 152, 62-64 (1979). [7] European patent EP 1 386 976, 2003.
[2] D.J. Wirth, Modern Casting 88, 12-18 (1998). [8] http://www.wmlee.co.uk/manufacturing/material/SiMo.
[3] F. Tholence, M. Novell, Oxid. Met. 69, 13-36 (2008). [9] ČSN EN 16124, Slévárenství – Nízkolegovaná feritická litina
[4] K.J. Papis, S. Tunzini, W. Menk, G. Fischer, Livarski Vestnik 62, s kuličkovým grafitem pro použití za zvýšených teplot, 2012.
2-16 (2015). [10] M. Ekström, Development of a Feritic Ductile Cast Iron for
[5] L.M. Aberg, C. Hartung, Trans. Indian Inst. Met. 65, 633-636 Increased Life in Exhaust Applications, PhD thesis, KTH Royal
(2012). Institute of Technology, Stockholm, 2013.