Ledeburite

Related terms:

Austenite, Bainite, Eutectics, Ferrite, Martensite, Pearlite, Microstructure, Graphite,

Cast Iron, Cementite

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Solidification of cast irons

Roy Elliott BSc, PhD, in Cast Iron Technology, 1988

White irons
The metastable unalloyed Fe–Fe3C ledeburite eutectic, illustrated in Figure 3.14, is
classified as quasi-regular. Hillert and Subba Rao66 have shown that once Fe3C has
nucleated, edgewise growth of Fe3C plates occurs rapidly. They lead austenite at the
interface and an orientation relationship develops:
Figure 3.14. The solidification of white cast iron. Fe3C is the white phase and
austenite is the black phase(after ref. 66)

Fe3C and austenite also grow in a co-operative manner and form a rod structure
perpendicular to and between Fe3C plates. These two modes of growth form the
quasi-regular structure but the edgewise growth is more rapid than the sidewise
mode and dominates the structure (see Figure 6.1 in Chapter 6). Directional solidi-
fication experiments67 have shown that the operative point on the growth curve for
the quasi-regular structure is close to the extremum point. Powell68 has shown that
the quasi-regular structure can be quench modified, but impurity modification has
not been explored.

The improved toughness of alloyed white irons is associated with the different
eutectic morphology of the Fe–M7C3 eutectic. This is an anomalous structure with
a broken lamellar structure. The structure is a mixture of blades and hollow faceted
rods. The proportion of rods in the structure increases as the cooling rate increases.

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Mechanical properties improvement of

metallic rolls by laser surface alloying
G. Sun, R. Zhou, in Laser Surface Engineering, 2015

3.3.1 Microstructure of the cross section of the laser alloyed

NCIR
The microstructure of the NCIR substrate is shown in Figure 3.1a, which indicated
that the substrate is of hypoeutectic structures, composed of perlite, ledeburite, and
nodular graphite. The laser-alloyed layer was composed of dendrites and interden-
drites, as indicated in Figure 3.1b. One graphite can be detected in the alloyed layer
due to the forces in the molten pool when the powders and substrate are irradiated
by the laser. In the nodular iron, graphite nodules gradually dissolved in the molten
pool and, at the same time, due to hydrodynamic forces and buoyancy forces, they
moved toward the surface. According to the results of Grum et al. [53], detailed
dimensional analysis of the graphite nodules has shown that only larger nodules
reach the surface (they were not completely dissolved) where they may be blown
away at the top surface by the protecting gas or carbon combustion of the laser beam
energy.
Figure 3.1. Microstructure of the cross section of (a) NCIR substrate and (b) alloyed
layer.

The microstructure varies in the cross section of the alloyed layer as shown in Figure
3.2, among which Figure 3.2a-c correspond to the top part, middle part, and lower
part of the alloyed layer, respectively, and Figure 3.2d is from the bonding zone
between the alloyed layer and the substrate. The microstructure in the alloyed layer
is dependent on the cooling rate in the molten pool during heating and cooling.
Figure 3.2a-c shows that the microstructure of the alloyed layer consists of dendrites
and eutectics, especially Figure 3.2b. The microstructure in Figure 3.2a and c is
composed of a majority of dendrites and the eutectics can hardly be detected.
Furthermore, the dendrites size increased from the top to the lower part of the
alloyed layer, as can be seen in Figure 3.2a-c. Chemical composition of the spots
in Figure 3.2b is shown in Table 3.2. The combination of Figure 3.2b and Table 3.2
shows that both the dendrites and eutectics were mainly composed of Fe and C,
while the eutectics had a little higher content of Cr, Mo, and W. The carbon content
in the molten pool was high enough to qualify the hypereutectic reaction due to
the partial dissolution of graphite nodules and the addition of carbides from the
alloying powders. A lot of carbides can be formed in the alloyed layer through the
reaction of carbon and other elements. The bonding area is at the bottom of the
molten pool with a lot of substrate materials melted into it. The solidification and
the subsequent microstructure of this area are different from the top part of the
alloyed layer. There is a coral structure (indicated by the arrow) in addition to the
typical dendrite structure bonded with the substrate.
Figure 3.2. Microstructure of the cross section of the alloyed layer on NCIR, (a) top
part, (b) middle part, (c) lower part, and (d) bonding zone.

Table 3.2. Chemical composition of spots in Figure 3.2b (at.%)

Element C Fe Cr Ni Mo W
Spot 1 29.254 68.181 0.277 0.905 0.347 1.036
Spot 2 30.151 65.913 0.622 0.712 0.618 1.984

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Microstructural features of cast irons

Roy Elliott BSc, PhD, in Cast Iron Technology, 1988

Publisher Summary
This chapter presents the microstructural features of different types of cast irons.
White cast iron is of hypoeutectic composition and shows austenite dendrites that
have transformed to pearlite during cooling with interdentritic ledeburite eutectic.
Grey phosphoric cast iron is close to the eutectic composition and shows the
anomalous flake eutectic structure. Type graphite flakes are dispersed in a pearlitic
matrix that has formed from austenite during cooling. The high P content results
in the formation of a pronounced network of phosphide eutectic in the last areas
to solidify that are the eutectic cell boundaries. Grey flake irons show the highly
anisotropic nature of the graphite flakes, which are interconnected and branch
frequently. Abnormal graphite flake forms shows an abnormal flake morphology
known as sooty or spiky graphite. It occurs in irons containing Pb and H; Pb may
be introduced from contaminated scrap. Austenitic irons can dissolve more Pb than
unalloyed irons and display more extensive Widmanstätten graphite patterns.
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SOLIDIFICATION
H. BILONI, W.J. BOETTINGER, in Physical Metallurgy (Fourth Edition), 1996

11.3.2. Cast iron

It is known that cast iron, belonging to the family of high carbon Fe alloys, can
solidify according to either the stable iron-graphite system (grey iron) or to the
metastable Fe–Fe3C system (white iron). As a consequence, the eutectic may be
austenite–graphite or austenite–cementite (ledeburite). Furthermore, the complex
chemical composition of the material has important and powerful effects on the
structure of cast iron. Commercial alloys usually contain Si, minor addition of S,
Mn and P and usually trace elements such as Al, Sn, Sb and Bi as well as the gaseous
elements H, N and O. Both forms of cast irons (white and grey) have technological
importance. Several comprehensive reviews and books have been published in the
last decades both from fundamental and technological points of view (Morrog
[1968a], [1968b]; Minkoff [1983]; Elliot [1988]; Stefanescu [1988]; Craig et al. [1988];
Hughes [1988]; Stefanescu et al. [1988]). Grey iron is the most interesting because
of the different morphologies that the graphite can achieve and the resulting dif-
ferences in mechanical and physical properties. Although semantic problems have
confused scientists and foundrymen in the past, a general understanding of the
mechanisms of nucleation, growth and modification of the graphite phase has
occurred in the last 15 years. In this section, the present status of knowledge in the
area will be discussed briefly.

It is known that the growth of the stable Fe–G eutectic is favoured over the
metastable Fe3C eutectic by slow freezing (See § 8.1.7.) or by addition of elements
such as Si and Al. These elements increase the temperature difference between
the stable Fe–G and metastable Fe–Fe3C eutectic temperatures. In addition a wide
variety of compounds have been claimed to serve as nuclei for graphite, including
oxides, silicates, sulphides, nitrides, carbides and intermetallic compounds. Most of
the nucleation mechanisms are connected with impurities existing in the melt or
with inoculants that promote heterogeneous nucleation of the graphite. Although
other inoculants are used, Fe–Si alloys are the most powerful and popular (Elliot
[1988], Stefanescu [1988]), Skaland et al. [1993]).

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Laser surface modification of steel and
cast iron for corrosion resistance
R. Vilar, in Laser Surface Modification of Alloys for Corrosion and Erosion Resis-
tance, 2012

1.5.1 Laser surface treatment of cast irons

Cast irons are relatively inexpensive and widely available materials, which can easily
be formed into complex shapes by casting, a near-net shape process that allows
the manufacture of large series of relatively low cost parts used in many industrial
sectors, such as the automotive industry, pipe and tube fittings, machinery, etc. The
low added-value of many cast iron parts could discourage the application of laser
surface treatment to these materials, but its application may be justified in special
situations, for example in the localised treatment of expensive large cast iron parts
for the chemical or energy-production industries and in the refurbishment of used
components. Solidification of laser-melted grey [106] and nodular [107] hypoeutectic
cast irons is characterised by a shift from the Fe C equilibrium phase diagram
to the metastable Fe − Fe3C phase diagram, leading to microstructures formed
of proeutectic austenite dendrites and interdendritic austenite cementite eutectic
(usually called ledeburite). If the processing parameters are properly selected, the
graphite existing in the material prior to the laser treatment dissolves completely in
the melt, an essential requirement to minimise cracking and surface defects caused
by the combustion of graphite. In unalloyed cast irons austenite transforms, at least
partially, into martensite during cooling to room temperature, but in alloyed cast
irons large proportions of austenite may persist. Retained austenite may have a
beneficial effect on the mechanical properties of the surface layer because, due to
the brittleness of cementite and the large residual stresses that develop during the
laser treatment, cracks often form in the laser-treated layer and retained austenite
may reduce the propensity to cracking, due to its ductility.

One of the first studies on the corrosion resistance of laser-treated grey cast iron
was by Damborenea et al. [108]. The corrosion resistance was evaluated by electro-
chemical methods using concentrated sulphuric acid, 3 and 10% NaCl, and 10%
NaOH aqueous solutions as electrolytes. The authors observed a shift of the open
circuit potential towards more positive values, indicating an improvement of the
corrosion resistance, which was explained by the refinement and homogenisation of
the microstructure. However, the results achieved depended on the surface finish,
much better corrosion resistance being achieved when the surface defects resulting
from the laser treatment (pores, oxide particles, etc.) were eliminated by polishing.
The importance of the surface finish was confirmed by later work [109]. Gadag et al.
[110] also observed a marked improvement of the corrosion resistance of a pearlitic
ductile cast iron in diluted sulphuric acid by laser surface melting, provided that the
surface layer was crack-free and structurally homogeneous. Laser surface melting
reduced the corrosion rate in acid solutions by nearly 40%, but the improvement in
synthetic seawater was less noticeable. Laser surface alloying with copper was also
tested as a potential method to improve the corrosion resistance of Ni-alloyed cast
irons, with positive results [111].

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The camshaft
Hiroshi Yamagata, in The Science and Technology of Materials in Automotive En-
gines, 2005

5.3.1 Chilled cast iron

The camshaft should combine a strong shaft with hard cam lobes. Table 5.2 lists five
types of camshaft.4Table 5.3 lists the chemical compositions of the various materials
used. The most widely used material for camshafts at present is chilled cast iron ((1)
in Table 5.2), using a high-Cr cast iron. This type of camshaft is shown in Fig. 5.4,
and has hard cam lobes with a strong but soft shaft.

Table 5.2. Various camshafts. The counterpart of the camshaft uses a forged steel
plated by hard chromium, a sintered metal chip dispersing carbide or a nitrided
JIS-SKD 11 plate. The dispersed carbide in the chilled cam lobe gives excellent wear
resistance

Type Cam lobe portion Shaft portion Processing Characteristics

(1) Chilled cam Chill Flaky or Sand cast- Most general.
spherical ing combined Hardness con-
graphite cast with a chiller trol is difficult
iron
(2) Remelted cam Chill Flaky or Remelting the Increasing the
spherical cam lobe sur- hardness of the
graphite cast face of the cam edge por-
iron shaped mate- tion is dif-
rial of gray ficult
cast iron
(3) Quench-tem- Martensite Quench-tem- Quench-hard- Applicable to
pered cam pering or ening the cam forged carbon
normalizing lobe by steel, nodu-
induction or lar cast iron
flame heating or hardenable
cast iron
(4) Carburized- Martensite Sorbite Carburizing Strong shaft
cam the forged portion using a
part (SCM thin wall tube
420)
(5) Bonded cam Steel tube
 Wear-resis- Brazing, dif- Flexible choice
tant sintered fusion bond- and combina-
material ing or me- tion of various
Martensite chanical join- materials
ing of the cam
lobe with the
shaft

Table 5.3. Compositions of camshaft matrials (%). The high-Cr cast iron is used
for chilled camshafts. The chromium concentration is slightly raised to obtain hard
chill. The hardenable cast iron generates a martensitic microstructure through
quench-tempering. The Cr-Mo steel SCM 420 is forged and carburized. The sintered
metal has a martensitic microstructure dispersing Cr and Fe complex carbide

Material C Si Mn Cr Mo Cu V W Fe
High-Cr 3.2 2.0 0.8 0.8 0.2 – – – Balance
cast iron
Harden- 3.2 2.0 0.8 1.2 0.6 – – – Balance
able cast
iron
Cr-Mo 0.2 0.3 0.8 1.0 0.2 – – – Balance
steel
JIS-SCM420
Sintered 0.9 0.2 0.4 4.5 5.0 3.0 2.0 6.0 Balance
metal
for cam
lobe

The chilled camshaft utilizes the unique solidification characteristics of cast iron.
Figure 5.10 illustrates the production process. Let us consider a gradual increase in
carbon concentration towards 4.3% in the iron-carbon phase diagram. (Please refer
to Appendices C and D for more detail on the phase diagram of the iron-carbon
system.) Pure iron solidifies at 1,536 °C. The solidification temperature decreases
with increasing carbon concentration to give a minimum value of 1154 °C at a carbon
concentration of 4.3%, the eutectic point, (see Fig. C.1).
5.10. Casting process. First, the electric furnace melts steel scraps, carbon content
raiser (carbon powder) and ferro-alloys (Fe-Si, Fe-Cr alloys, etc.). Then the melt taken
in the ladle is poured into the mold. The mold is a sand mold. A chiller is inserted
in advance at the cam lobe position where chilled microstructure is required. After
solidification, the sand mold is broken and the camshaft is taken out. The sand
mold contains a binder and appropriate water content. It should be breakable after
solidification without break during pouring. The sand is reused. The iron shots blast
the shaped material to remove the sand. The unnecessary gate, sprue and runner are
cut. The remnants are remelted and reused. Grinding deburrs the shaped material.
Then it is directed to the final machining. Casting is an extremely rational production
process.

Molten iron is transferred from furnace to molds using a ladle covered with a
heat-insulating lining. In manual pouring, one ladle of molten iron can be poured
into several molds one after another, which takes around five minutes. If the solidif-
ication temperature of the metal is high, then the pouring must be finished within a
very short period of time otherwise the molten iron will solidify in the ladle. Hence,
with a lower solidification temperature there is more time for pouring.

Sand molds produce a slow solidification rate because the insulating effect of the
sand slows cooling. Under these conditions, the carbon in the cast iron crystallizes as
flaky graphite (Fig. 5.11(a)) and the casting expands. This expansion ensures that the
casting fits the mold shape very well. The resultant microstructure of the iron matrix
becomes pearlite. The microstructure of flaky graphite cast iron has sufficient
strength for the shaft portion.
5.11. (a) Flaky graphite of a shaft portion and (b) the chilled microstructure of a
cam lobe. Chill has a mixed microstructure of cementite (white portion in (b)) and
pearlite (gray portion). The hardness is around 50 HRC. Austenite and cementite
appear simultaneously by eutectic solidification. The austenite portion transforms
to pearlite during cooling. The eutectic solidification is called Ledeburite eutectic
reaction. The additional quench-tempering changes pearlite to martensite. This heat
treatment raises the hardness to 63 HRC.

By contrast, the cam lobe needs high hardness to provide good wear resistance. If
the rate of solidification of cast iron is fast, the included carbon forms into hard
cementite (Fe3 C). Iron combines with carbon to form cementite because graphite
is difficult to nucleate at high solidification rates. Detailed explanations are
given in Appendix C. Figure 5.11(b) shows the microstructure associated with rapid
solidification. This microstructure is referred to as Ledeburite or chill, it is very hard
and is highly suitable for the hardness requirements of cam lobes.

The cam lobe portion should be cooled rapidly in order to generate hard chill. An
iron lump called a chiller is used for this purpose. The chiller is positioned at the
cam lobe and takes heat away from the casting, giving a rapid solidification rate. The
chiller is normally made of cast iron. Figure 5.10 illustrates the relative positioning
of the chiller and cam. The chiller has a cam lobe-shaped cavity and is inserted into
the sand mold prior to casting. Except for the chiller, the master mold consists of
compacted sand. The shape and volume of the chiller determine how effective it is
at absorbing heat, and it must be designed carefully to give the optimum cooling
rate.

Figure 5.12 shows a section of a cam lobe, produced by etching the polished surface
with dilute nitric acid. The pillar-like crystals, known as a columnar structure, align
radially at the periphery, whilst they are not seen at the center. In Fig. 5.11(b), the
columnar structure is aligned vertically, indicating that solidification advanced along
the direction of heat flow. The crystal formation process during solidification was
discussed more fully in Chapter 2.

5.12. Macrostructure of a cam lobe. The hardness measurement has indented small
dents.

Figure 5.13 shows the distribution of hardness at a cam lobe section, measured in

three directions from the center to the periphery. The convex portion of the cam
lobe shows a hardness of around 45 HRC, which is sufficient for this application,
whilst the central portion is softer at 25 HRC. These microstructures correspond to
the chill of Fig. 5.11(b) and the flaky graphite of Fig. 5.11(a), respectively. Generally,
solidification starts from the surface, where the cooling speed is faster. Solidification
in the central portion is slow due to the slow heat discharge rate, as confirmed by
the hardness distribution.
5.13. Hardness distribution of the cam lobe section. The surface shows a high
hardness around 50 HRC because of rapid quenching by the chiller. The chiller has
contacted the molten cast iron only at the gray part in the illustration.

It is not easy to produce hard chill without any graphite in mass production. A chill
micro structure including graphite is soft and defective. The manufacturing process
must control the chill hardness of the cam lobe to achieve the required value (45
HRC), while avoiding hard chill in the shaft portion. Hard chill in the shaft portion
can break an expensive gun drill in subsequent machining operations, as described
below. Generally, insufficient concentrations of C and Si are likely to cause chill
even at slow solidification rates.

Inoculation5 is a procedure aimed at solving the paradox that the hard chill and soft
but strong shaft go together. As shown in Fig. 5.10, the inoculant is placed in the
ladle before pouring. The inoculant adjusts the graphite shape (see Appendix D),
preventing chill where it is not required. The inoculant is an alloy powder, such as
Fe-Si, Ca-Si, or an alloy containing rare earth metals. The inoculation effect lasts for
a limited period of time and gradually disappears after the inoculation (known as
fading), thus it is important to time the inoculation accurately. The effect is similar
to that of a nodularizer, as discussed in Chapter 2.

An alternative process to ensure hard chill at the cam lobes is remelting (see (2),
Table 5.2). This process controls casting and chilling separately. The material is first
cast to produce the flaky graphite microstructure. Then the surface of the cam lobe
is partially remelted and then solidified rapidly to generate chill. Although it requires
an additional process, this method provides better control of the hardness. However,
if remelting is too slow, it can cause the shaft section to melt, so a high-energy heat
source, such as a tungsten inert gas (TIG) torch, is used. The concentrated heat melts
the surface of the cam lobe instantaneously.

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