See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/222298364

Surface Graphite Degeneration in Ductile Iron

Castings for Resin Molds

Article in Tsinghua Science & Technology April 2008

DOI: 10.1016/S1007-0214(08)70028-2

CITATIONS READS

22 190

4 authors, including:

Mihai Chisamera Stelian Stan

University of Bucharest Polytechnic University of Bucharest
65 PUBLICATIONS 287 CITATIONS 48 PUBLICATIONS 265 CITATIONS

SEE PROFILE SEE PROFILE

All in-text references underlined in blue are linked to publications on ResearchGate, Available from: Stelian Stan
letting you access and read them immediately. Retrieved on: 18 August 2016
TSINGHUA SCIENCE AND TECHNOLOGY
ISSN 1007-0214 08/20 pp157-163
Volume 13, Number 2, April 2008

Surface Graphite Degeneration in Ductile

Iron Castings for Resin Molds

Iulian Riposan**, Mihai Chisamera, Stelian Stan, Torbjorn Skaland

Department of Materials Science and Engineering, Politehnica University,

Bucharest 060042, Romania;
Windcast Group, Kristiansand 4673, Norway

Abstract: The objective of this paper is to review the factors influencing the formation of degenerated graph-
ite layers on the surfaces of ductile iron castings for chemical resins-acid molding and core-making systems
and how to reduce this defect. In the resin mold technique the sulphur in the P-toluol sulphonic acid (PTSA),
usually used as the hardener, has been identified as one factor causing graphite degeneration at the metal-
mold interface. Less than 0.15% S in the mold (or even less than 0.07% S) can reduce the surface layer
depth. Oxygen may also have an effect, especially for sulphur containing systems with turbulent flows in the
mold, water-bearing no-bake binder systems, Mg-Silica reactions, or dross formation conditions. Despite the
lower level of nitrogen in the iron melt after magnesium treatment (less than 90 ppm), nitrogen bearing res-
ins have a profound effect on the frequency and severity of surface pinholes, but a limited influence on sur-
face graphite degeneration.

Key words: ductile iron castings; surface graphite degeneration; resin mold; sulphur; oxygen; nitrogen

cast iron, forming a flake (lamellar) graphite seam.

Introduction This defect can occur with any molding technique, but
has peculiar characteristics for each one and is affected
Chemically bonded sand molds (self-set, no-bake, cold
by various factors.
box) are commonly used to produce ductile iron cast-
The objective of this paper is to evaluate the occur-
ings, especially with large cooling moduli. High, me-
rence of degenerated graphite layers on the surface of
dium, or low nitrogen furan acid and phenolic acid no-
ductile iron castings in foundry chemical resins-acid
bake systems are very attractive in ductile iron foun-
molding and core-making systems and the factors
dries due to strong mold occurrence and the use of di-
which influence this defect to more effectively use this
rectly applied risers. In this case only the contraction
foundry technology, especially for heavy castings, such
of the cooling liquid needs to be compensated for;
as for wind turbines.
hence, fewer and smaller risers will suffice, or even
riserless designs can be considered (>2.0 cm cooling 1 Graphite Anomalies in Ductile Iron
modulus)[1]. While favorable for ductile iron casting,
resin mold technology also contributes to graphite de- The structure of ductile iron castings usually includes
generation on the surface of the spheroidal graphite not only spheroidal graphite particles, but also other
objectionable deviations from the highest compactness
Received: 2007-10-07; revised: 2007-11-05
(Table 1), resulting from many different causes[2-4].
To whom correspondence should be addressed.
E-mail: riposan@foundry.pub.ro Superficial layers on ductile iron castings can include
158 Tsinghua Science and Technology, April 2008, 13(2): 157-163

Table 1 Objectionable deviations from spheroidal graphite shapes

No. Graphite Potential causes Typical shape
High holding temperature/time
Poor inoculation
1 Irregular
Excessive fading
Antinodulizing elements

High equivalent carbon (CE)

Excessive pouring temperature
2 Flotation
Slow cooling rate
Insufficient inoculation

Excessive rare earth (RE)

Particularly high purity charge
3 Exploded
Normally in thick castings
Usually for high CE

Usually at the center of castings

Excessive RE, high purity charge
4 Chunky
High Si, CE, Ni, Ca
Within eutectic cells

Antinodulizing elements
5 Spiky
Typically: Pb, Bi, Ti, Sb

Strong intercellular segregation

6 Intercellular flake Bi, Pb, Sb, As, Cd, Al, Sn, Cu
Commonly in heavy castings

Low residual Mg/RE

Excessive S/O
7 Vermicular
High temperature/ long holding time
Antinodulizing elements

Excessive S build-up
Excessive Mg/RE oxidation
8 Flake/Surface structure
Sand mold conditioners
High pouring temperature

Inadequate slag control

Excessive slag forming materials
9 Dross association
Turbulent mold filling
Metal-mold reaction
 Iulian Riposan et alSurface Graphite Degeneration in Ductile Iron Castings for
different variants of graphite morphologies, from a
mixture of various graphite shapes (nodular with vari-
ous degree of compactness, vermicular, lamellar, etc.)
with clear transitions, such as
Lamellar Vermicular Irregular NG
Regular NG (1)
where NG refers to nodular graphite. Usually the sur-
face-layer structure includes three different strata as
shown in Fig. 1.
Outside layer: fine graphite flakes;
Second layer: flakes and/or vermicular particles;
Third layer: nodular graphite, close to the normal
structure.
Degenerated graphite forms also accompany dross
defects in the surface layer (Fig. 1).
A 0.1 to 3.0 mm thick degenerated graphite layer of-
ten occurs on ductile iron casting depending on the
casting wall thickness and cooling rate. High contami-
nant concentrations and/or low residual magnesium
produce relatively more graphite flakes. Micro-porosity,
non-nodular graphite, dross stringers, and other imper-
fections at the surface all reduced the properties, a
situation observed in all tensile test bars exhibiting
these defects. Fatigue property effects are significantly
affected[5] with flake graphite skins reducing the fa-
tigue limit by about 15 %, dross stringers reducing the
fatigue limit by between 19% and 33% depending on
the severity, and pinholes having the greatest effect re-
ducing the fatigue limit by about 40%.
Fig. 1 Typical structures of superficial layer of ductile iron castings. Matal-mold (a, b) and dross (c) reaction effects.
2 Graphite Degeneration at the Sur-
face Layer of Castings
2.1 Sulphur influence
Sulphur appears to migrate into the molten metal dur-
ing the casting process which consumes the dissolved
nodulizing elements (Mg, RE) without sufficient time
for new nodulizing elements to reach the surface by
diffusion from adjoining metal layers. With furan and
159
Foundry tests have shown that the depth of the de-
generated layer affects the fatigue limit for a fatigue
stressed crankshaft cast in a shell mold. The cooling
rate, pouring temperature, and residual magnesium are
other influencing factors[6,7]. Inclusions on the casting
surface resulting from metal-mold reactions, such as
magnesium oxides/sulphides, also cause fatigue fail-
ures. Deep rolling and shot peening are usually used to
impart compressive residual stresses in the fillet area
of crankshafts[8-10]. The formation of a degenerated
graphite surface layer will influence the hardness of as-
cast ductile iron castings. Generally, the hardness is
expected to be lower than normal, not only because of
the presence of fine graphite flakes but also due to the
predominant ferrite matrix in these areas. Soft spots are
usually found in the metal. In specific cases, the sur-
face layer includes flake graphite and pearlite (due to
the influence of nitrogen), so conventional ferritic duc-
tile iron castings appear to have higher hardness than
normal. Fine graphite flakes in the surface layer also
favor oxidation and decarburization sensitivity if the
casting has been heat-treated. The presence of retained
surface oxide scale following shot cleaning has an ad-
verse effect on machinability by increasing tool wear.
In the case of ductile irons, the use of very heavy shot
cleaning to remove the retained heat treatment scale
can seriously reduce ductility by distorting the casting
surface, thus reducing the possibility of cracking.
phenolic resin-bonded molding, P-toluol sulphonic
acid (PTSA) is usually used as the hardener, but it is
also the most important source of sulphur in this sys-
tem, with evident contribution in degenerated graphite
layer formation[6,7,11-13]. Some studies have suggested
that the surface graphite degeneration is caused by SO2
from the combustion of PTSA in the resin sand at the
casting temperature. SO2 is absorbed on the metal
surface where it dissociates into atoms. The sulphur
atoms diffuse into the molten metal and react to form
 160
sulphides of Mg, RE, Mn[11]. Usually, a sulphur rich
layer develops in ductile iron castings in furan resin
sand molds catalyzed by PTSA, as shown in Fig.
2[11,12]. Sulphur level drastically decreases more than
1.0 mm from the casting surface, to the normal content
in the ductile iron. The five-fold increase of the S/Mg
ratio, from 0.5 (center/body of the casting) up to more
than 2.5 at the casting surface is either fully or partially
responsible for the defects. Generally, sulphur is con-
sidered to be the major contributor to the problem, but
in many cases sulphur is not the only element in the
mold causing flake graphite.
Fig. 2 (a) S/Mg ratio[12] and (b) S level[11] in the sur-
face and center (body) of castings
Other important factors found to influence the thick-
ness of the abnormal surface structure layer are:
PTSA: higher levels cause greater graphite de-
generation[11] (Fig. 3a);
Nodulizer addition: higher amounts reduce the
layers thickness but do not eliminate it;
Pouring temperature: higher temperatures in-
crease the layer thickness;
Casting thickness: heavy castings are more sensi-
tive to this defect;
Reclaimed sand: higher usage increases the sur-
face layer thickness[11] (Fig. 3b).
The quantity of PTSA must be reduced as low as
possible to improve casting quality, but the accumulat-
ing sulphur in regenerated (reclaimed) circulating sand
Tsinghua Science and Technology, April 2008, 13(2): 157-163
Fig. 3 Influence of (a) PTSA and (b) reclaimed sand
rate on the abnormal surface layer thickness[11]
is also a very important factor causing graphite degen-
eration on the surfaces of castings. Generally, for cold-
setting resins using regenerated sand, the sulphur con-
tent should not exceed 0.15%[6,7]. Similarly, the
amount of sulphur in the lustrous carbon producer in
clay sand molding material should be limited to 1.0%
with a maximum of 0.1% S in the sand mold[6]. In
highly susceptible areas, such as the metal surrounding
a thin cod of sand, the limiting sulphur content may be
lower, less than 0.07% S.
Experience has shown that the application of mold
coating is generally not very effective in eliminating
sulphur pick-up from the mold, although in some spe-
cific cases coatings have given good results.
Various coating materials have been tested to deter-
mine whether surface deterioration can be prevented
by mold coating including conventional graphite-based
coatings, inorganic materials expected to act as desul-
phurizers (Al2O3, CaCO3, Basic slag, CaF2, Talc), and
sinterable materials expected to act as protective layers.
Surface layer have been significantly reduced by CaO
coatings, due to its reaction with SO2 and its desul-
phurization activity. Other experience suggests that the
problem may be minimized through the use of CaO or
MgO wash on no-bake molds[12,14]. Dressing with a
CaO / MgO / Talc composition is regarded as particu-
larly effective[6]. Good results were obtained in a wind
 Iulian Riposan et alSurface Graphite Degeneration in Ductile Iron Castings for
turbine casting foundry using two mold coatings, CaO/
MgO to protect from the sulphur and Zr-oxide for the
refractory. Thus, mold coatings based on the genera-
tion of desulphurization agents (such as CaO or MgO)
are more effective than protective coatings where the
density is a problem.
Phosphoric acid has also been considered as an al-
ternative resin mold hardener for blending with or even
replacing PTSA to reduce sulphur presence in the sys-
tem. But the replacement of sulphonic acid by phos-
phoric acid may lead to phosphorus pick-up and segre-
gation on the surface of the ductile iron castings.
Lower compactness of the nodular graphite is also
typical which results in a slight reduction of 3%-5% in
the mechanical properties of the ductile irons. Far more
significant effects have been observed in castings pro-
duced in reclaimed sand molds catalyzed with phos-
phoric acid, depending on the phosphate (PO4) content
of the sand and the section thickness being poured. For
heavy sections, the PO4 level must be limited to about
0.75%. Pitting defects are usually present when the
phosphate level in the sand is above 1.0%. A typical
60% reclaimed sand/40% new sand ratio is recom-
mended, with mold coating based on magnesite having
been shown to minimize the problem (except in re-
entrant sections, which act as hot spots)[5]. Research in
a heavy castings foundry making wind turbine parts
successfully tested an alternative 3-compound acid mix
with equal parts of PTSA, phosphoric acid, and lactic
acid. The combination gives a low enough sulphur
content to reduce the sulphur pick-up in the iron and
the SO2 in the environment. The phosphorus contribu-
tion should also be low. In these castings the furan ad-
dition was also reduced from 1.2% down to 0.9%.
2.2 Oxygen influence
Existing or generated oxidizing gases in the mold cav-
ity may be another important factor causing graphite
degeneration in the surface layer of ductile iron cast-
ings. Dissolved oxygen will react with Mg or MgS to
form MgO. The data in Fig. 2 shows that when the sul-
phur content is increased, the magnesium content is
drastically decreased due to the sulphur emerging from
the mold combining with Mg to form MgS, with the
MgS created at the mold-metal surface reacting with
oxygen to release the sulphur and retain MgO[12].
161
These two steps in the metal-mold reaction should be
considered to explain the high S/Mg ratios and sulphur
accumulation in the surface layer of the casting:
Mg + S = MgS, MgS + O = MgO + S (2)
Water bearing no-bake binder systems, such as ester-
cured phenolic (1.5% resin / 25% catalyst), furan no-
bake (1.25% resin / 35% catalyst), and an inorganic
no-bake binder (3.5% liquid / 1.5% hardener) exhibited
more prominent flake or vermicular graphitic struc-
tures at the mold/metal interface compared with non
water binder systems, such as phenolic urethane no-
bake (1.0% resin / 4% catalyst based on Part I) and al-
kyd oil (1.25% resin / 20% catalyst) systems[15].
Tests have also shown that the atmosphere inside the
mold after assembly is likely to be saturated with mois-
ture and perhaps gases from the alcohol based coating.
Flushing of the mold with fresh air before pouring re-
duced the risk of casting defects in wind turbine cast-
ings. The surface degeneration should also be greatly
reduced by using low pouring temperatures (less than
1360). Tests on automotive castings show that the
degenerated zone on the surface of a crankshaft (shell
mold) could arise not only through oxidizing gases but
also through the reduction of silica sand in accordance
with the reaction[6,15]:
SiO2 + 2Mg = Si + 2MgO (3)
2.3 Nitrogen influence
Nitrogen may also promote flake graphite. This possi-
ble mechanism is important since nitrogen is usually
present at different levels in furan resins. Generally, in
treated ductile iron, the effect of nitrogen is much less
pronounced because it is purged from the system by
Mg treatment. Prior to nodularization, the nitrogen
level of a base ductile iron can be expected to be 50 to
160 ppm (higher for cupola melting), but this content
will decrease by up to 50-90 ppm after nodulariza-
tion[16,17]. The use of high nitrogen binders in cores and
molds is a major source of nitrogen, which has a pro-
found effect on the frequency and severity of pinholes.
Organic resins decompose below the liquid iron tem-
perature to generate ammonia (NH3), an important
source of both N2 and H2. The absorption of these
gases into the liquid metal provides the dissolved gases
responsible for pinhole formation. Resins with more
than 3% nitrogen usually give significant pinhole prob-
lems[16,18]. The influence of nitrogen on the matrix is
 162
visible with more pearlite and/or carbide formed, but
its influence on the graphite morphology is disputed.
Nascent nitrogen, produced in metal/mold reactions,
can dissolve in liquid iron, with levels in excess of 60
ppm suspected to cause flake graphite and pearlitic
matrix[11]. The first iron entering the mold is in direct
contact with the N-rich mold, evolving nascent (solu-
ble) gas.
In one test, a part of a casting obtained in under-
treated conditions to produce more vermicular graphite,
was cast in a no-bake sand core set with a high N-
containing binder. All the surfaces cast against this
core contained flake graphite to a depth of about 0.13
mm, while surfaces cast against green sand were free
of flake graphite. Both oxidation and sulphur pick-up
can be ruled out as causes because the defect disap-
pears after changing to a low N-containing binder.
However, the formed pearlitic layer, which is associ-
ated with this flake graphite is known to be promoted
by nitrogen[2]. In an other foundry test, one side of the
test mold was washed with a N-free binder, while the
other side was washed with a binder containing 3.0%
N. A degenerated graphite layer was found only on the
surfaces exposed to the nitrogen containing binder[11].
The conversion of soluble nitrogen to an insoluble
form by adding Ti and Ce (RE) proved to be effective
in minimizing the flake graphite formation. Therefore,
0.02%-0.04% titanium may be desirable in ductile
irons[2].
3 Conclusions
(1) Surface degenerated graphite layers (up to 3.0 mm
thick) include a mixture of various graphite morpholo-
gies with transitions from fine lamellar through ver-
micular to nodular graphite morphologies.
(2) Sulphur from the PTSA has been identified as one
factor causing graphite degeneration at the metal-mold in-
terface. Thus, the sulphur content should be less than
0.15% S in the mold (or even less than 0.07% S) to re-
duce the surface layer depth. The following policies are
recommended:
Reduce the PTSA, ideally to less than 50% of the
resin;
Increase the nodulizer addition, but this usually
will not eliminate the defects;
Reduce the pouring temperatures, usually less
than 1360;
Tsinghua Science and Technology, April 2008, 13(2): 157-163
Use maintained and calibrated mixers;
Reduce reclaimed sand usage, usually less than
70%;
Use effective size classification in reclaimed
sand systems;
Use CaO/MgO/Talc composition mold coatings,
which contribute to desulphurization;
Use high density protective mold coatings, but
they have limited effects;
Blend phosphoric acid with the PTSA, but this
may lead to P pick-up.
(3) Oxygen influence must be also considered in
resin mold technologies, especially for containing sul-
phur systems, with turbulent flow, water bearing no-
bake binders, Mg-silica reactions, or dross formation.
The MgS-O reaction is possible with the resulting sul-
phur regeneration increasing the Mg loss.
(4) Nitrogen bearing resins have a profound effect
on the frequency and severity of surface pinholes, but
limited influence on surface graphite degeneration.
More than 60 ppm N is suspected to cause flake graph-
ite and pearlitic matrix, but its negative influence can
be limited by Ti, RE, or Zr addition.
(5) The surface degenerated graphite layer has the
effect of a notch in the casting, so all the properties are
reduced, especially the fatigue limit and impact resis-
tance. Fine flake graphite usually accompanied by
ferrite (S and O contribution) reduces the hardness in
pearlitic iron castings, with pearlite caused by nitrogen
creating an abnormally high hardness in ferritic irons.
Oxidation/decarburization sensitivity during heat
treatment can also cause other negative effects.
References
[1] Ductile Iron TechniquesSuggestions for Ductile Iron
Production. Montreal, Canada: R.T.I.T Inc., 1971.
[2] Karsay S I. Ductile Iron Production (I)The State of the
Art. Revised in part by QIT Technical Staff, QIT, Montreal,
Canada, 1992: 51.
[3] Elkem. Common metallurgical defects in ductile iron chart.
ELKEM Foundry Products Division. Oslo, Norway, 2004.
http://www.foundry.elkem.no.
[4] Goodrich G M. Cast iron microstructure anomalies and
their causes. AFS Trans., 1997, 105: 669-683.
[5] Fallon M J. Experiences in the manufacture of ductile
irons. The Foundrymen, 1995, 88(9): 308-318.
[6] Baier J, Koppen M. Manual of Casting Defects. Incidence
 Iulian Riposan et alSurface Graphite Degeneration in Ductile Iron Castings for 163

and Avoidance of Defects Attributable to Molding Sands.
Marl, Germany: IKO-Erbsloh, 1994: 32-35.
[7] Golovan N A, Dudni K J A, Dubrov V V. Formation of
flake graphite near the surface of nodular cast iron casting.
Russian Casting Production Journal, 1977, (7): 35-36.
[8] Watmough T, Malatesta M J. Strengthening of ductile iron
for crankshaft applications. AFS Trans., 1984, 92: 83-99.
[9] Yamamura H, Sekiguchi M, Inoue K. Influence of defects
on the fatigue life of ductile cast iron with As-cast surfaces.
In: Proc. of 1998 K. Millis World Symposium on Ductile
Iron, DIS. South Carolina, USA, 1998: 433-453.
[10] Lawerenz M. Shot peening of ductile iron. Modern Cast-
ing, 1990, (2): 51-53.
[11] Xiaogan H. Nodular iron surface deterioration due to
PTSA in resin. AFS Trans., 1992, 100: 9-15.
[12] Marti F, Karsay S I. Localized flake graphite structure as a
result of a reaction between molten ductile iron and some
components of the mold. AFS Trans., 1979, 87: 221-226.
[13] Bauer W. Research on the surface graphite degeneration in
the ductile iron casting in PTSA-furan resin molds.
Giesserei-Praxis, 1982, (11): 175-183.
[14] Morita S, Inoyama N. Behavior of nitrogen in cast iron.
AFS Cast Metals Res. Journal, 1969, 5(3): 109.
[15] Tinebra J P, Wilson S J. No-bake chemical binder systems:
Their effect on microstructural and physical properties of
ductile iron. AFS Trans., 1993, 101: 169-174.
[16] Farquhar J D. Nitrogen in ductile ironA literature review,
AFS Trans., 1979, 87: 433-438.
[17] Robinson M. Nitrogen levels in ductile iron: AFS commit-
tee 12-H report. AFS Trans., 1979, 87: 503-508.
[18] Strong G R. A literature survey on nitrogen on malleable
iron. AFS Trans., 1977, 85: 29-36.

Tsinghua Research Achievements Win 2007 State Science

and Technology Awards

Seventeen Tsinghua research achievements recently won 2007 State Science and Technology Awards. Tsinghua
professors accepted the awards on January 8, 2008, in Beijing at the annual National Science-Technology Award
Ceremony in the Great Hall of the People.
Tsinghuas research achievements ranked first among Chinese universities. Of Tsinghuas seventeen awards, one
was a State Natural Science Award second prize; eight were State Technological Invention Award second prizes;
and eight were State Scientific and Technological Progress Award second prizes. Altogether nine research achieve-
ments were completed by Tsinghua as the lead research institution in collaboration with others.
By the end of 2007, Tsinghua had won a total of 353 State Science and Technology Awards, including 36 State
Natural Science Awards, 104 State Technological Invention Awards, and 213 State Scientific and Technological
Progress Awards.

From http://news.tsinghua.edu.cn, 2008-01-11