NUCLEATION AND MODIFICATION PHENOMENA OF GRAPHITE

IN CAST IRON (GREY AND NODULAR)

TUGAS ESSAY

Disusun oleh :

GALIH SENOPATI
170699376

PROGRAM PASCASARJANA
DEPARTEMEN TEKNIK METALURGI DAN MATERIAL
UNIVERSITAS INDONESIA
DEPOK
2017
Cast iron are alloys containing iron, carbon, and silicon. Cast iron has higher carbon and
silicon content than steel. In the Fe-Fe3C phase diagrams cast iron defined as an iron-carbon
alloy containing more than 2% carbon. Hystorically the classification of cast iron was based
on its fracture. The two types of iron were recognize. They are white cast iron and gray cast
iron. White cast iron exhibits white because fracture along the iron carbide plates. It is the
result of metastable solidification (Fe3C eutectic). Gray cast iron exhibits gray fracture
because fracture occurs along the graphite plate (flakes). It is the result of stable solidification
(Gr eutectic). In gray cast iron usually contain 2.5 to 4 %C, 1 to 3% Si and addition of
Manganese depend on the desired microstructure. Sulfure and phosporus also present in small
amount as residual impurities. Sucessful production of gray iron casting depend on the
fluidity of the molten metal and the cooling rate. The microstructure of gray cast iron usually
is a matrix of pearlite with graphite flakes dispersed throughout. The nucleation and growth
of graphite flakes can be varied to achieve the desired properties. Rapid cooling of cast iron
may produce chilled iron in which the excess carbon is found in the form of massive carbide.
The intermediate cooling may produce mottled iron in which the excess of carbon is found in
cementite and graphite. The slow cooling rate may produce ferrite and pearlite throughout the
matrix together with coarse graphite flakes. Flake graphite is one of seven types of graphite
forms. Flake graphite is subdevided into five type:

Figure 1. Type of graphite flakes in gray cast iron

Ductile cast iron known as nodular iron or spheroidal-graphite (SG) cast irin is cast iron in
which the graphite is present as tiny spheres (nodules) (Fig, 2). In ductile iron, eutectic
graphite separates from the molten iron during solidification in a mannes similiar to that in
which eutectic graphite separates in gray cast iron. However because of additives introduced
in the molten iron before casting, the graphite grows as spheres rather than as flakes of any
forms characteristics of gray cast iron. Ccast iron containing spheroidal graphite is much
stronger and has higher elongation than gray cast iron. It may be considered as a natural
composite in which the spheroidal grpahite imparts unique properties to ductile iron.

Figure 2. Microstructure of as cast ferritic ductile cast iron

Structure of Graphite in Austenite-Graphite Eutectic

The graphite phase is a faceted crystal bounded by low index planes. For graphite
crystallizing from an iron-carbon melt, the normally observed bounding planes are (0001)
and {1010}, as shown in Fig.3. The crystallographic structure of graphite and possible groth
direcctions, A and C. Because unstable growth occurs on {1010} planes the edges of
platelike graphite crystals are not well defined. Graphite growing out of liquid iron-carbon
alloy has a layer-type structure, with string covalent bonds (4,19x105 to 5x105 J/mol) between
atoms in the same layer. There is a trielectronic bond of each atom with its neighnors, while
the fourth electron is common for the layer giving the metallic properties of graphite. Weak
molecular forces exist between layers (4.19 × 103 to 8,38 × 103 J/mol). The prism plane is a high-
energy plane at which impurities absorb preferentially. Strength and hardness are higher in the C
direction of the graphite crystal.

Figure 3. Crystalline structure of graphite

Complete destruction of the graphite structure occurs only at about 4000 °C. This explain the
presence of some graphite aggregares in molten iron even at temperatures considerably
higher tha the liquidus temperature. Depending on the chemical composition and the
temperature greadient/growth rate ratio, G/R, and/or cooling rate, G, R, a variety of graphite
shapes can solidify as part of the austenite-graphite eutectic. Basically they are as follows:
a. Flake (actually plate) graphite FG)
b. Compacted/vermicular graphite (CG)
c. Coral graphite
d. Spheroidal (nodular) graphite (SG)
Schematic of these graphite types showed in Fig. 4.

Figure 4. Schematic of graphite typess occuring in the austenite-graphite eutectic. (a) Flake graphite
(b) Compacted/vermicular graphite (c) coral graphite (d) Spheroidal graphite

Nucleation of the Austenite-Flake Graphite Eutectic

Experimental evidence indicates that various type of nuclei become effective at various
temperatures. Indeed, if only one type of nuclei would be active in a cast iron melt, an
undercooling-superheating curve will show a single arrest for the temperature region over
which the nuclei become effective. However, as shown in Fig. 5, a number of steps are
observed in the relation ship, suggesting that various foreign nuclei become effective as
superheating increased. Increasing the superheating apparently destroy the effective nuclei.
Consequently, the number of eutectis grains (eutectic cells) decreases as the superheating
increases, and as a result undercooling increases. However, when undercooling, ∆, is
increased at constant superheat by increasing the cooling rate or the growth rate, R, the
eutectic cell count will increase (Fig. 6).
 Figure 5. Relationship between superheating and maximum undercooling in flake cast iron

Figure 6. Influence of undercooling on eutectic in flake graphite cast iron

Below the equilibrium temperature solid silica is formed by precipitation deoxidation; above
the equilibrium temperature silica is decomposed. Silica serves as nucei for fraphite growth.
The formation of silica particles in turn requires nucleation which can be promoted by
inoculation. Therefores, the inoculation of FG iron can be descraibe as a deoxidation process
whit the following requirements:
a. Enough oxygen must be available in melt
b. The addition of element with high affinity to oxygen, such as calcium, aluminum, and
barium, to form nuclei for silicon dioxide precipitation
c. Inoculation temperature must be a maximum of (50 °C) above the equilibrium
temperature to avoid dissolution of the silicon dioxide particles
d. The cooling rate after inoculation must be low enough to allow sufficient time for
silicon dioxide formation but high enough to prevent coalscence and segregation of
silicon dioxide
Flake Graphite Growth
The austenite-FG eutectic solidifies with the formation of eutectic colonies (cells) that are
more or less spherical in shape. It is generally thought that each eutectic cell is the product of
a nucleation event. The eutectic cel is made of interconected graphite plates surrounded by
austenite. The degree of ramification of graphite within the cell depends on undercooling,
with higher undercooling resulting in more graphite branching Graphite spacing is
determined by the same parameters as for regular eutectics, with branching occuring as a
response to interface instability.

Figure 7. Schematic of solidification of flake graphite (a) typical eutectic colonies (cells). (b)
Growth sequence for a eutectic colony

The variations in graphite structures have been classified, together with the length of the
flakes, by standards that have been utilized for many years. Flake graphite in gray cast iron
can be designated as:
a. Type A, uniform distribution, random orientation
b. Type B, rosette grouping, random orientation
c. Type C, superimposed flake sizes, random orientation
d. Type D, interdendritic segregation random orientation
e. Type E, interdendritic segregation preferred orientation
The formation of the eutectic flake fraphite (Types A, B, C, and D) is greatly influenced by
the amount by which the iron melt cools below the equilibrium temperature for the austenite-
graphite eutectic before appreciable solidification occurs. Gray iron with type A graphite
undergoes only small amounts of undercooling, whereas that with Type D graphite
undercools significantly below this equilibrium temperature. The undercooling that occurs
with Type B graphite is intermediate between the two, producing fine fraphite flakes, like
Type D, in the center of the eutectic cells or rosette and a coarse type like Type AA at the
outer cell boundaries. Type E Graphite occurs in strongly hypoeutectic gray iron with carbon
equivalents well below 4,3%. Figure 8 shows examples of Type A, B, D, and E flake graphite
structures in gray cast iron at various maginfications.

Figure 8 SEM photomicrographs illustrating variety of flake graphite structures present in gray cast
iron Type A structure at (a) 100 and b) 430; Type B structure at (c) 100 and (d) 430x; (e) Type D at
2100x; and (f) Types D (fine) and E (coarse) at 100x.

Spheroidal Graphite Eutectic

Growth of the austenite-SG eutectic is more complicated and less understood than that of the
γ-SG eutectic, although a good number of theories have been proposed. It has been rather
widely accepted that the growth of this eutectic begins with the nucleation and growth of
graphite in the liquid, followed by early encapsulation of these graphite spheroids in the
austenite shells (envelopes). A schematic of the process is shown in Fig 9. Graphite
nucleation and growth deplete the melt of carbon in the vicinity of the graphite; this creates
conditions for austenite nucleation and growth around the graphite spheroid. Once the
austenite shell formed, further of graphite can occur only by solid diffusion of carbon from
the liquid through the austenite.

Figure 9. Iisothermal growth of a graphite spheroid within an austenite shell and growth of the shell
with a smooth interface. (a) Growth of spheroidal graphite in contact with melt. (b) Envelopment by
austenite, (c) Growth of spheroidal graphite within the austenite shell

K. Theuwissen et al. study the phenomena of precipitation of graphite in cast iron using transmission
electron microscope. He was found that inner structure of graphite precipitates consist of groth blocks
stacked upon each other, for all investigated morphologies. This suggests that graphite crystals
develop mainly by a 2D nucleation and growth mechanism, and that the final shape of the precipitates
is associated to the occurence of crystallographic defects in the graphite lattice (such as twins,
misorientations and rotations)) during growth.
Figure 10. (a) optical micrograph of spheroidal graphite cast iron section and (b) SEM image of
extracted spheroids.

Figure 10(a) showed metallograpgic structure of spheroidal graphite cast iron with good nodularity.
An average diameter of 19μm and a density of 400 mm-2 were determined by image analysis of 4
fields of viwe of about 0,8 mm2 on the base material. These precipitates have an irregular outer
surfaces as shown in the micrograph (Fig 10(b)) obtained after deep etching of the samples. Such a
feature has been described as cabbage leaf-like and relates to lateral extension of the outermost
graphite layers along the surface of the spheroids, presumbably during solid-state cooling of the
materials.
The bright field image (Fig.11) of one part of a spheroidal graphite precipitates shows an
inner structure composed of sectors and a thin outer layer with a less defined structure. Graphite at the
periphery of such spheroids appeared to be much less orginized than in the bulk sectors as shown by
spotty rings in the diffraction pattern of Fig 2(a). For comparison, a selected area diffraction pattern
was taken in the bulk of a sector with the same aperture size showing one clear orientation (Fig
11(b)). It can be conluded from these result that, at periphery of the sphereoids, domains of similiar
orientation have a smaller size than in the bulk of sector. Growth blocks are thus smaller in these
locations and or present higher relative misorientation between each other.

Figure 10. Bright field TEM image of a sector in a graphite spheroid combined with SAED pattern (a)
at the periphery and (b) in the bulk of the sector the selected area used to perform diffraction are
schematized by the two black circle in the bright field image
The inner structure of such spheroidal graphite precipitates was investigated in a previous
study by means of Automated Crystal Orientation Mapping in a TEM (Fig 12) clearly show
boundaries between neighbouring sectors as well as misorientations within them. Most of the
misorientation angles were observed to have valued of 10-15°, 20-22°, and 27-30° which
correspond to known twin angles, though some other valued could also be measured. Sharp
colours changes within sectors such as the blue green alternating in the lower right part of Fig
3 represent rotations of 27° of the c axis of graphite. This value correspond to a low energy
stacking fault in the graphite lattice predicted by the coincidence site lattice theory.

Figure 12. Photomontage of TEM image of a diametrical section of graphite spheroid cmbined with
the crystal orientation map of graphite obtained by ACOM; aparent boundaries between sectors are
highlighted by white dotted lined (dark areas at the periphery of nodule are iron-rich particles that
were not indexed)

The obeservation can be summerized as follows: graphite growth blocks nucleate and grow
during solidification of cast iron and are stacked to form conical sectors or fan-like areas.
Defects in the graphite structure (misorientations and rotations) are found at the interface
between neighbouring sectors creating apparent grain boundaries and alos within conical
sectors. The spheroidal precipitates formed by multiple sectors can be surrounded by areas
presenting small-sized orientation domains which are presumably formed in the solid-state,
after solodification.
References
ASM Handbook , ASM Internasional., Vol. 1, pp. 34-100 , 2005.
ASM Handbook , ASM Internasional., Vol. 15, pp. 372-402 , 1998.
K. Theuwisse, J. Lacaze, L. Laffont, “Structure of graphite precipitates in cast iron,” Carbon.,
Vol. 96, pp. 1120-1128, 2016.