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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

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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: [email protected] 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 159

different variants of graphite morphologies, from a Foundry tests have shown that the depth of the de-
mixture of various graphite shapes (nodular with vari- generated layer affects the fatigue limit for a fatigue
ous degree of compactness, vermicular, lamellar, etc.) stressed crankshaft cast in a shell mold. The cooling
with clear transitions, such as rate, pouring temperature, and residual magnesium are
Lamellar Vermicular Irregular NG other influencing factors[6,7]. Inclusions on the casting
Regular NG (1) surface resulting from metal-mold reactions, such as
where NG refers to nodular graphite. Usually the sur- magnesium oxides/sulphides, also cause fatigue fail-
face-layer structure includes three different strata as ures. Deep rolling and shot peening are usually used to
shown in Fig. 1. impart compressive residual stresses in the fillet area
Outside layer: fine graphite flakes; of crankshafts[8-10]. The formation of a degenerated
Second layer: flakes and/or vermicular particles; graphite surface layer will influence the hardness of as-
Third layer: nodular graphite, close to the normal cast ductile iron castings. Generally, the hardness is
structure. expected to be lower than normal, not only because of
Degenerated graphite forms also accompany dross the presence of fine graphite flakes but also due to the
defects in the surface layer (Fig. 1). predominant ferrite matrix in these areas. Soft spots are
A 0.1 to 3.0 mm thick degenerated graphite layer of- usually found in the metal. In specific cases, the sur-
ten occurs on ductile iron casting depending on the face layer includes flake graphite and pearlite (due to
casting wall thickness and cooling rate. High contami- the influence of nitrogen), so conventional ferritic duc-
nant concentrations and/or low residual magnesium tile iron castings appear to have higher hardness than
produce relatively more graphite flakes. Micro-porosity, normal. Fine graphite flakes in the surface layer also
non-nodular graphite, dross stringers, and other imper- favor oxidation and decarburization sensitivity if the
fections at the surface all reduced the properties, a casting has been heat-treated. The presence of retained
situation observed in all tensile test bars exhibiting surface oxide scale following shot cleaning has an ad-
these defects. Fatigue property effects are significantly verse effect on machinability by increasing tool wear.
affected[5] with flake graphite skins reducing the fa- In the case of ductile irons, the use of very heavy shot
tigue limit by about 15 %, dross stringers reducing the cleaning to remove the retained heat treatment scale
fatigue limit by between 19% and 33% depending on can seriously reduce ductility by distorting the casting
the severity, and pinholes having the greatest effect re- surface, thus reducing the possibility of cracking.
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.

phenolic resin-bonded molding, P-toluol sulphonic

2 Graphite Degeneration at the Sur- acid (PTSA) is usually used as the hardener, but it is
face Layer of Castings also the most important source of sulphur in this sys-
tem, with evident contribution in degenerated graphite
2.1 Sulphur influence
layer formation[6,7,11-13]. Some studies have suggested
Sulphur appears to migrate into the molten metal dur- that the surface graphite degeneration is caused by SO2
ing the casting process which consumes the dissolved from the combustion of PTSA in the resin sand at the
nodulizing elements (Mg, RE) without sufficient time casting temperature. SO2 is absorbed on the metal
for new nodulizing elements to reach the surface by surface where it dissociates into atoms. The sulphur
diffusion from adjoining metal layers. With furan and atoms diffuse into the molten metal and react to form
 160 Tsinghua Science and Technology, April 2008, 13(2): 157-163

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. 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.
Fig. 2 (a) S/Mg ratio[12] and (b) S level[11] in the sur-
Experience has shown that the application of mold
face and center (body) of castings
coating is generally not very effective in eliminating
Other important factors found to influence the thick- sulphur pick-up from the mold, although in some spe-
ness of the abnormal surface structure layer are: cific cases coatings have given good results.
PTSA: higher levels cause greater graphite de- Various coating materials have been tested to deter-
generation[11] (Fig. 3a); mine whether surface deterioration can be prevented
Nodulizer addition: higher amounts reduce the by mold coating including conventional graphite-based
layers thickness but do not eliminate it; coatings, inorganic materials expected to act as desul-
Pouring temperature: higher temperatures in- phurizers (Al2O3, CaCO3, Basic slag, CaF2, Talc), and
crease the layer thickness; sinterable materials expected to act as protective layers.
Casting thickness: heavy castings are more sensi- Surface layer have been significantly reduced by CaO
tive to this defect; coatings, due to its reaction with SO2 and its desul-
Reclaimed sand: higher usage increases the sur- phurization activity. Other experience suggests that the
face layer thickness[11] (Fig. 3b). problem may be minimized through the use of CaO or
The quantity of PTSA must be reduced as low as MgO wash on no-bake molds[12,14]. Dressing with a
possible to improve casting quality, but the accumulat- CaO / MgO / Talc composition is regarded as particu-
ing sulphur in regenerated (reclaimed) circulating sand larly effective[6]. Good results were obtained in a wind
 Iulian Riposan et alSurface Graphite Degeneration in Ductile Iron Castings for 161

turbine casting foundry using two mold coatings, CaO/ These two steps in the metal-mold reaction should be
MgO to protect from the sulphur and Zr-oxide for the considered to explain the high S/Mg ratios and sulphur
refractory. Thus, mold coatings based on the genera- accumulation in the surface layer of the casting:
tion of desulphurization agents (such as CaO or MgO) Mg + S = MgS, MgS + O = MgO + S (2)
are more effective than protective coatings where the Water bearing no-bake binder systems, such as ester-
density is a problem. cured phenolic (1.5% resin / 25% catalyst), furan no-
Phosphoric acid has also been considered as an al- bake (1.25% resin / 35% catalyst), and an inorganic
ternative resin mold hardener for blending with or even no-bake binder (3.5% liquid / 1.5% hardener) exhibited
replacing PTSA to reduce sulphur presence in the sys- more prominent flake or vermicular graphitic struc-
tem. But the replacement of sulphonic acid by phos- tures at the mold/metal interface compared with non
phoric acid may lead to phosphorus pick-up and segre- water binder systems, such as phenolic urethane no-
gation on the surface of the ductile iron castings. bake (1.0% resin / 4% catalyst based on Part I) and al-
Lower compactness of the nodular graphite is also kyd oil (1.25% resin / 20% catalyst) systems[15].
typical which results in a slight reduction of 3%-5% in Tests have also shown that the atmosphere inside the
the mechanical properties of the ductile irons. Far more mold after assembly is likely to be saturated with mois-
significant effects have been observed in castings pro- ture and perhaps gases from the alcohol based coating.
duced in reclaimed sand molds catalyzed with phos- Flushing of the mold with fresh air before pouring re-
phoric acid, depending on the phosphate (PO4) content duced the risk of casting defects in wind turbine cast-
of the sand and the section thickness being poured. For ings. The surface degeneration should also be greatly
heavy sections, the PO4 level must be limited to about reduced by using low pouring temperatures (less than
1360). Tests on automotive castings show that the
0.75%. Pitting defects are usually present when the
degenerated zone on the surface of a crankshaft (shell
phosphate level in the sand is above 1.0%. A typical
mold) could arise not only through oxidizing gases but
60% reclaimed sand/40% new sand ratio is recom-
also through the reduction of silica sand in accordance
mended, with mold coating based on magnesite having
with the reaction[6,15]:
been shown to minimize the problem (except in re-
SiO2 + 2Mg = Si + 2MgO (3)
entrant sections, which act as hot spots)[5]. Research in
a heavy castings foundry making wind turbine parts 2.3 Nitrogen influence
successfully tested an alternative 3-compound acid mix
with equal parts of PTSA, phosphoric acid, and lactic Nitrogen may also promote flake graphite. This possi-
acid. The combination gives a low enough sulphur ble mechanism is important since nitrogen is usually
content to reduce the sulphur pick-up in the iron and present at different levels in furan resins. Generally, in
the SO2 in the environment. The phosphorus contribu- treated ductile iron, the effect of nitrogen is much less
pronounced because it is purged from the system by
tion should also be low. In these castings the furan ad-
Mg treatment. Prior to nodularization, the nitrogen
dition was also reduced from 1.2% down to 0.9%.
level of a base ductile iron can be expected to be 50 to
2.2 Oxygen influence 160 ppm (higher for cupola melting), but this content
will decrease by up to 50-90 ppm after nodulariza-
Existing or generated oxidizing gases in the mold cav- tion[16,17]. The use of high nitrogen binders in cores and
ity may be another important factor causing graphite molds is a major source of nitrogen, which has a pro-
degeneration in the surface layer of ductile iron cast- found effect on the frequency and severity of pinholes.
ings. Dissolved oxygen will react with Mg or MgS to Organic resins decompose below the liquid iron tem-
form MgO. The data in Fig. 2 shows that when the sul- perature to generate ammonia (NH3), an important
phur content is increased, the magnesium content is source of both N2 and H2. The absorption of these
drastically decreased due to the sulphur emerging from gases into the liquid metal provides the dissolved gases
the mold combining with Mg to form MgS, with the responsible for pinhole formation. Resins with more
MgS created at the mold-metal surface reacting with than 3% nitrogen usually give significant pinhole prob-
oxygen to release the sulphur and retain MgO[12]. lems[16,18]. The influence of nitrogen on the matrix is
 162 Tsinghua Science and Technology, April 2008, 13(2): 157-163

visible with more pearlite and/or carbide formed, but Use maintained and calibrated mixers;
its influence on the graphite morphology is disputed. Reduce reclaimed sand usage, usually less than
Nascent nitrogen, produced in metal/mold reactions, 70%;
can dissolve in liquid iron, with levels in excess of 60 Use effective size classification in reclaimed
ppm suspected to cause flake graphite and pearlitic sand systems;
matrix[11]. The first iron entering the mold is in direct Use CaO/MgO/Talc composition mold coatings,
contact with the N-rich mold, evolving nascent (solu- which contribute to desulphurization;
ble) gas. Use high density protective mold coatings, but
In one test, a part of a casting obtained in under- they have limited effects;
treated conditions to produce more vermicular graphite, Blend phosphoric acid with the PTSA, but this
was cast in a no-bake sand core set with a high N- may lead to P pick-up.
containing binder. All the surfaces cast against this (3) Oxygen influence must be also considered in
core contained flake graphite to a depth of about 0.13 resin mold technologies, especially for containing sul-
mm, while surfaces cast against green sand were free phur systems, with turbulent flow, water bearing no-
of flake graphite. Both oxidation and sulphur pick-up bake binders, Mg-silica reactions, or dross formation.
can be ruled out as causes because the defect disap- The MgS-O reaction is possible with the resulting sul-
pears after changing to a low N-containing binder. phur regeneration increasing the Mg loss.
However, the formed pearlitic layer, which is associ- (4) Nitrogen bearing resins have a profound effect
ated with this flake graphite is known to be promoted on the frequency and severity of surface pinholes, but
by nitrogen[2]. In an other foundry test, one side of the limited influence on surface graphite degeneration.
test mold was washed with a N-free binder, while the More than 60 ppm N is suspected to cause flake graph-
other side was washed with a binder containing 3.0% ite and pearlitic matrix, but its negative influence can
N. A degenerated graphite layer was found only on the be limited by Ti, RE, or Zr addition.
surfaces exposed to the nitrogen containing binder[11]. (5) The surface degenerated graphite layer has the
The conversion of soluble nitrogen to an insoluble effect of a notch in the casting, so all the properties are
form by adding Ti and Ce (RE) proved to be effective reduced, especially the fatigue limit and impact resis-
in minimizing the flake graphite formation. Therefore, tance. Fine flake graphite usually accompanied by
0.02%-0.04% titanium may be desirable in ductile ferrite (S and O contribution) reduces the hardness in
irons[2]. pearlitic iron castings, with pearlite caused by nitrogen
creating an abnormally high hardness in ferritic irons.
3 Conclusions Oxidation/decarburization sensitivity during heat
treatment can also cause other negative effects.
(1) Surface degenerated graphite layers (up to 3.0 mm
thick) include a mixture of various graphite morpholo- References
gies with transitions from fine lamellar through ver-
micular to nodular graphite morphologies. [1] Ductile Iron TechniquesSuggestions for Ductile Iron
Production. Montreal, Canada: R.T.I.T Inc., 1971.
(2) Sulphur from the PTSA has been identified as one
[2] Karsay S I. Ductile Iron Production (I)The State of the
factor causing graphite degeneration at the metal-mold in-
Art. Revised in part by QIT Technical Staff, QIT, Montreal,
terface. Thus, the sulphur content should be less than
Canada, 1992: 51.
0.15% S in the mold (or even less than 0.07% S) to re-
[3] Elkem. Common metallurgical defects in ductile iron chart.
duce the surface layer depth. The following policies are
ELKEM Foundry Products Division. Oslo, Norway, 2004.
recommended:
Reduce the PTSA, ideally to less than 50% of the http://www.foundry.elkem.no.

resin; [4] Goodrich G M. Cast iron microstructure anomalies and

Increase the nodulizer addition, but this usually their causes. AFS Trans., 1997, 105: 669-683.

will not eliminate the defects; [5] Fallon M J. Experiences in the manufacture of ductile

Reduce the pouring temperatures, usually less irons. The Foundrymen, 1995, 88(9): 308-318.
than 1360; [6] Baier J, Koppen M. Manual of Casting Defects. Incidence
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and Avoidance of Defects Attributable to Molding Sands. [13] Bauer W. Research on the surface graphite degeneration in
Marl, Germany: IKO-Erbsloh, 1994: 32-35. the ductile iron casting in PTSA-furan resin molds.
[7] Golovan N A, Dudni K J A, Dubrov V V. Formation of Giesserei-Praxis, 1982, (11): 175-183.
flake graphite near the surface of nodular cast iron casting. [14] Morita S, Inoyama N. Behavior of nitrogen in cast iron.
Russian Casting Production Journal, 1977, (7): 35-36. AFS Cast Metals Res. Journal, 1969, 5(3): 109.
[8] Watmough T, Malatesta M J. Strengthening of ductile iron [15] Tinebra J P, Wilson S J. No-bake chemical binder systems:
for crankshaft applications. AFS Trans., 1984, 92: 83-99. Their effect on microstructural and physical properties of
[9] Yamamura H, Sekiguchi M, Inoue K. Influence of defects ductile iron. AFS Trans., 1993, 101: 169-174.
on the fatigue life of ductile cast iron with As-cast surfaces. [16] Farquhar J D. Nitrogen in ductile ironA literature review,
In: Proc. of 1998 K. Millis World Symposium on Ductile AFS Trans., 1979, 87: 433-438.
Iron, DIS. South Carolina, USA, 1998: 433-453. [17] Robinson M. Nitrogen levels in ductile iron: AFS commit-
[10] Lawerenz M. Shot peening of ductile iron. Modern Cast- tee 12-H report. AFS Trans., 1979, 87: 503-508.
ing, 1990, (2): 51-53. [18] Strong G R. A literature survey on nitrogen on malleable
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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.

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