THE GRAPHITISATION

PROCESS IN MEDIUMCARBON STEEL

David V Edmonds and Kejian He
Institute for Materials Research,
University of Leeds, Leeds, UK

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Research Programme Objectives

To study graphitisation in steels, with the

overall aim of identifying a new route to the
development of a plain carbon cold-forging
steel with good machinability.

To accelerate the kinetics of graphitisation.

To examine the mechanism of graphite

formation in steels by high-resolution
microanalytical electron microscopy.
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Outline of Presentation

Background to overall research programme

objectives.

Choice of steel alloying - thermodynamic

modelling.

Examination of graphite nodule formation

using transmission electron microscopy
(TEM), electron energy loss spectroscopy
(EELS) and energy-filtered transmission
electron microscopy (EFTEM).
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Machining Operation
(after Metal Cutting, EM Trent, Butterworths, 1977)

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Traditional Free-Machining
(Free-Cutting) Steels

The world market is very large from threaded

screws and bolts to accurately machined
components e.g. in the automotive industry.

Plain carbon steels are alloyed with elements such

as Pb, S, Te, Bi and P to act as a lubricant at the
tool/workpiece interface, and additionally, to assist
with chip break-up.

Disadvantages can be toxicity, impairment of cold

forgeability, and, at least for Te and Bi, steel that is
more expensive and difficult to recycle.
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Free-Machining Plain Carbon Steels

An Alternative

Why not anneal plain carbon steels to exchange cementite for

graphite?
The presence of graphite (rather than cementite) in the
microstructure of a plain carbon cold-forging steel would act as
an internal lubricant during machining, and also assist chip
break-up, as in the case of grey cast irons which have
customarily exhibited excellent machinability. Forgeability
should also be improved.
However, the annealing time required to convert cementite to
graphite in steels has traditionally been too long (of the order of
100+ hours) to integrate successfully into a production heat
treatment schedule.
Thus, consider whether graphitisation can be influenced by
alloying, to reduce these heat treatment times.

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Thermodynamic Assessment of Alloying

The effect of various alloying elements on graphitisation were
evaluated in terms of the driving force for the precipitation of
graphite in an Fe-0.54wt%C system at 680C using Thermo-Calc.

Si and Al have
equivalent effects.

strong

and

roughly

Ni and Co are similar but less strong.

Cu has a positive effect but is much weaker.
Mo is mildly suppressive, Mn more so.
Cr is strongly suppressive.

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Experimental Steels
Alloying Philosophy
Increase Si and Al alloying
Minimise Mn alloying
(Avoid alloying with Cr)
C

Si

Steel 1 0.47 0.19

Al

Mn

Ni

0.32 1.5

Time for
graphite to
appear in
microstructu
re at 680C
(hours)

Approx.
time for
completion
of
graphitisati
on at 680C
(hours)

18

115

Note faster graphitisation

in0.5
Si-Al steel.
-

Steel 2 0.38 1.82 1.44 0.07

3.5

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Light Microscopy
Steel 2 : Si-Al steel

Steel 1

Annealed 115 hours

Annealed 3.5 hours

Light micrographs of steels 1 & 2, austenitised at 1150oC,

quenched to martensite, and annealed at 680oC.

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Experimental further examination of

graphitising Si-Al steel (Steel 2)
As-quenched (martensite)

Quenched and annealed 0.5 hours

50 m

50 m

Graphitisation has started

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Si-Al steel (Steel 2)

0.5 hours

3.5 hours

50 m

50 m

55 hours

Progress of
graphitisation at
680C.
50 m

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Transmission Electron Microscopy

0.5m
0.5m

5 m

Bright field TEM image

showing coarsened cementite
particles located mainly at the
interfaces of ferrite laths after
0.5 hours at 680.

Bright field TEM image showing

only graphite nodules present in
a more equiaxed ferrite structure
after 1.5 hours at 680.

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Further Electron Microscopy

Observations Particle Nucleation
G

Nucleation of graphite (G)

on an aluminium oxide
inclusion (O) after 0.5
hours. Note also the
carbide particle dispersion
and remnants of the
martensite structure.

Nucleation on an AlN particle. Note the

irregular
graphite
morphology
and
structure.
The inner ring of the diffraction pattern is
(002) graphite, and the single crystal
reflections are from the [111] zone of AlN.

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Graphite Nodule Morphology

5 m

Small, ~4m diameter, regular

spheroidal graphite nodules,
apparently without a coring
oxide or nitride particle, after 1.5
hours at 680C.

____
0.5m

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Graphite (002) Lattice Fringes Within

Conical Segments

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Structure of Spheroidal Nodules

BF image

DF image: non-diametric
section

DF image: diametric section

Schematic diagram
illustrating cone-helix
growth model for
graphite nodules in
cast irons [after DD
Double and A
Hellawell, Acta
Metall., 22(1974)481].

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(002) Lattice Fringes in a Spheroidal

Graphite Nodule
Central region of nodule (BF image)

Away from centre

Near centre

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High-Resolution Images - Pitch

Graphitization Series
200oC

All images
show (002)
fringes.

600oC

2730oC

1200oC

2000oC

Howard
Daniels,
IMR,
Leeds
University

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EELS- Shifting of the + Plasmon as a

Function of Graphitisation
lowloss2

Plasmon Position / HTT

70

26.5
26
25.5
25
24.5
24
23.5
23

60
50

Plasmon
Energy (eV)

40

30

1000

2000

3000

HTT (oC)

20
10
0

-0

10

20
30
Energy Loss (eV)

40

50

Plasmon peak energy closely

follows the change in density.
Not a perfect match due to the
effect of crystallite size.

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EFTEM Plasmon Mapping

By taking the ratio of the intensities in the windows shown for a
large number of different plasmon positions, it is possible to
calibrate the intensity in the image.

27/22ev using 3ev windows

lowloss2
70

60

1.5

50
40

30

0.5

20

0
Ratio
27/22ev

10
0

-0

10

20
30
Energy Loss (eV)

40

50

21

23

25

27

Plasmon energy (eV)

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29

EFTEM Plasmon Imaging of a Graphite

Nodule
23 eV

24 eV

25 eV

26 eV

0.5m
27 eV

Bright Field ( montage of 25 images)

Plasmon (27eV/22eV) Ratio Map

(montage of 25 images)

Plasmon ratio map suggests a more amorphous core.

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Coarsened Carbide Particles

0.5m

100nm

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BF TEM Images of Surviving Carbides

100nm

Annealed 50 min.

Annealed 58 min.

Annealed 58 min.

Are these carbide particles?

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Carbon K-edge ELNES Pitch

Graphitization Series
As order within the carbon
increases, the electronic structure
follows suit, resulting in higher
definition of the unoccupied states.
750oC

1500oC

Howard Daniels,
IMR, Leeds University

2730oC

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Carbon K edge EELS Spectra

Fe3C

1.7

centre
1.2

centre1
Counts
0.7

edge 1
edge

0.2

680 graphite
-0.3
280

285

290

295

300

305

310

315

320

325

330

Energy Loss (eV)

EELS spectra collected from coarse particles, and cementite and

graphite for comparison.
Carbon content - 30 atom% in crystalline cementite part, 70 atom%
in amorphous part.

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EFTEM Jump Ratio Images of a Particle

C

Fe

Mn

The particle is not simple

cementite it consists of
crystalline cementite and a
more amorphous part.
Remaining cementite

TEM BF image; C K- jump ratio image; O K- jump ratio image;

Fe L2,3- jump ratio image and Mn L2,3 - jump ratio image.

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Jominy Bar Analysis after Annealing for

6 hours at 680C
600
550
500
450
400
350
300
250
Hardness
(HV30)
200
150
100
0
5

Martensite
Martensite

Lower bainite
Lower

bainite

Upper bainite / acicular ferrite

Upper

bainite

Si-Al

/ acicular ferrite

Si-Al-B

Ferrite + pearlite /
Widmanstatten ferrite
Ferrite +

pearlite

Widmanstatten

10

15

Si-Al 6hr

ferrite

20

25

30

Distance from quenched end (mm)

Different graphite nucleation kinetics

and
microstructural
dispersions
result
from
different
starting
microstructures, possibly related to
the different routes for carbide
formation
between
martensite,
bainite and pearlite in the Si-Al
experimental steels.
160

1200

140

1000

120

800
Si-Al

600

Si-Al-B

400

100

Si-Al

80

Si-Al-B

60
40

200

20
0

0
0

10

15

20

10

15

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20

Conclusions

Graphitisation of carbon steels in the tempered martensitic condition can

be achieved after short annealing times (2-3 hours) by alloying.
Regular spheroidal nodules appear to consist of cone-shaped segments
radiating from a central core.
Within the cones the circumferential stacking of the graphite layers during
growth is very regular, equivalent to that which can be achieved in the
graphitisation of carbonaceous materials only at temperatures around two
thousand degrees higher.
Microanalysis by high-resolution TEM suggests that, in the experimental
steels, either cementite dissolution is accompanied by loss of crystallinity
and the formation of amorphous regions, or these regions form on the
decomposing cementite.
Observations of a more amorphous centre to the small spheroidal
nodules (lacking an obvious nucleating particle), suggests that the
amorphous carbon regions associated with the decomposing cementite
may be the nuclei for these graphite nodules an intermediate stage in
graphite nodule formation.

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