Canadian Metallur`ical Quarterly\ Vol[ 26\ No[ 4\ pp[ 232Ð267\ 0887

\ Pergamon
Þ 0887 Canadian Institute of Mining and Metallurgy[ Published by Elsevier Science Ltd
Printed in Great Britain[ All rights reserved
9997Ð3322:87 ,08[99¦9[99

PII ] S997Ð3322"87#99920Ð6

REVIEW
DUCTILE IRON]
FIFTY YEARS OF CONTINUOUS DEVELOPMENT
C[ LABRECQUE and M[ GAGNE
ł
Rio Tinto Iron and Titanium Inc[*Technology\ Tracy\ Quebec\ Canada

"Received 29 April 0887^ in revised form 01 June 0887#

Abstract*The discovery of Ductile Iron in 0837 gave a new lease on life to the cast iron family[ By
combining the castability of gray iron and the toughness of steel\ Ductile Iron compelled a wide recognition
as an economical choice for high performance complex ferrous parts[ Fifty years of research and devel!
opment have led to a material whose properties can be tailored for applications requiring high toughness\
corrosion resistance or high tensile strength[ In this paper\ the state!of!the!art of Ductile Iron technology
is reviewed[ It is shown that\ although considered as a mature technology\ recent process and product
developments open new avenues to this family of materials[ Þ 0887 Canadian Institute of Mining and
Metallurgy[ Published by Elsevier Science Ltd[ All rights reserved[

Resume*La decouverte de la fonte G[S[ en 0837 a assure un second sou/e a la grande famille des fontes[
Combinant la coulabilite de la fonte grise et la resistance de l|acier\ la fonte G[S[ est rapidement devenue
un choix incontournable pour la production de composantes de forme complexe exigeant des proprietes
mecaniques elevees\ et ce a un cou¼t competitif[ Cinquante annees de recherche et de developpement
technologique ont conduit a la creation d|une famille de materiaux pouvant satisfaire des besoins aussi
diversi_es que la resistance a l|impact\ a la corrosion ou a l|usure[ Dans cet article\ la technologie de la
fonte G[S[ est revue et discutee[ Il y est demontre qu|en depit du fait que la fonte G[S[ est souvent consideree
comme un materiau mature\ de recents developpements ouvrent de nouveaux champs d|applications a la
fonte G[S[ Þ 0887 Canadian Institute of Mining and Metallurgy[ Published by Elsevier Science Ltd[ All
rights reserved[

INTRODUCTION
The combination of gray iron castability and steel toughness
was\ in the _rst half of this century\ an engineering objective
which has been partially ful_lled by malleable iron[ This class
of irons is the result of an extended annealing treatment of
white iron during which cementite decomposes to graphite that
precipitates as aggregates in a matrix whose composition "ferrite
or pearlite# depends on the cooling cycle from the annealing
temperature[ However\ the high costs related to the extended
annealing treatment required and the di.culty to cast sound
white iron components have limited its utilization[ The dream
of foundrymen and design engineers become a reality in 0837
when H[ Morrogh of the British Cast Iron Research Association
"BCIRA# announced at the American Foundrymen Society
"AFS# Convention that a small addition of cerium to hyp!
ereutectic gray iron resulted in a casting containing spherical
graphite particles ð0Ł[ In the same year\ International Nickel
Company revealed that a similar cast iron structure could be
obtained by using magnesium as a spheroidizer ð1Ł[ A patent
was issued to Inco in 0838 ð2Ł[ Ductile Iron was born[
Although unpredictable _fty years ago\ Ductile Iron has
undergone a phenomenal development to become\ in 0887\ the
 To whom all correspondence should be addressed[
232
only ferrous casting material with a positive growth rate[ The
objective of this paper is to review the state!of!the!art of the
Ductile Iron technology\ particularly with respect to the manu!
facturing process and the properties of what became\ after a
_fty!year history\ a family of engineering materials[
SOLIDIFICATION OF DUCTILE IRON
Ductile Iron is a ternary Fe!C!Si alloy in which the con!
centrations of carbon and silicon vary typically from 2[4Ð2[8)
and 0[7Ð1[7)\ respectively[ The selection of the composition is
dictated by the casting section size and the targeted mechanical
properties[ Unlike gray iron in which graphite precipitates as
~akes\ it is present as nodules in Ductile Iron[ Although depen!
dent on C and Si contents\ nodule formation is not controlled
by the latter but is rather a consequence of the purity level of
the alloy and of the addition of spheroidizing materials[
However\ the amount of graphite embedded in the metallic
phases is controlled by "i# the Si and C contents and "ii# the
cooling parameters[ Under equilibrium conditions\ the in~u!
ence of C and Si on the DI structure may be deduced from the
Fe!C!Si ternary phase diagram\ although its interpretation is
not obvious[
The well known Fe!C phase diagram "Fig[ 0# and a simpli_ed
view of a cross section through the ternary Fe!C!Si phase diagram
233 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
Fig[ 0[ Schematic Fe!C binary phase diagram[
"Fig[ 1# may be used to illustrate the solidi_cation process of
Ductile Iron[ In Fig[ 0\ the dashed lines delineate the limits of the
stable phases "graphite and ferrite# while the solid lines stand for
the metastable ones "carbide and pearlite#[ Assuming that the
cooling from the liquid state of a well inoculated iron occurs
under equilibrium conditions "cooling rate ½ 9#\ the _rst solid to
crystallize in a hypereutectic iron ")C or CE$  3[4)# at the
liquidus temperature is the graphite phase "Fig[ 1\ Point A#[ These
graphite particles grow by depleting the liquid iron of its carbon
atoms until the temperature reaches the eutectic transformation
range "Fig[ 1 Point B#[ Austenite "g# nucleates in areas depleted of
C^ consequently g shells envelop the graphite nodules "Fig[ 2#[
During this eutectic solidi_cation\ only the austenite is in contact
with the liquid and the controlling mechanism for nodule growth
becomes the di}usion of the carbon atoms through the solid g shells[
In a ternary alloy such as Ductile Iron\ the eutectic sol!
idi_cation occurs over a temperature interval which is deter!
mined by the major alloying elements and the growth kinetics
of the phases "Fig[ 1#[ Because graphite nodules grow via the
transport of carbon atoms through an austenitic shell rather
than by direct contact with liquid iron as for gray iron\ this
temperature interval is much larger in Ductile Iron than in gray
$ C[E[  )C¦0:2")Si¦)P#  carbon equivalent
Fig[ 1[ Schematic diagram showing approximate temperature ranges of
various phase _elds in cast iron[
iron[ After solidi_cation\ the di}usion of C towards preexisting
graphite nodules continues because the C solubility in austenite
decreases with temperature "from 1) at 0043>C to ½ 9[7) at
the eutectoid temperature#[ The eutectoid transformation also
occurs over a range of temperature[ At this stage\ the austenite
transforms to ferrite and more C atoms di}use to the nodules\
the C solubility being lower in ferrite than in austenite
"½ 9[914)#[ The resulting equilibrium microstructure is a fer!
ritic matrix with graphite nodules "Fig[ 3#[
This scenario may occur only if the C atoms have su.cient
time and driving force to escape from austenite and:or ferrite[
If solidi_cation and cooling occur at a rate faster than the C
atoms can di}use\ a totally di}erent structure is formed[ For
instance\ during proeutectic solidi_cation in presence of a high
undercooling\ the metastable phase Fe2C rather than graphite
crystallizes[ In such a case\ the eutectic metastable temperature
is reached before the nucleation of graphite occurs and a car!
bidic eutectic is formed\ followed by the transformation of the
austenite to pearlite[ Such a structure is shown in Fig[ 4[
Although simpli_ed\ the above description illustrates the
basics required to understand a more complex situation[ The
following paragraphs discuss the physical phenomena con!
trolling the nucleation and growth of proeutectic\ eutectic and
eutectoid phases during the solidi_cation and solid state trans!
formation of Ductile Iron[
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
Fig[ 2[ Isothermal growth of a spherulite within a solid halo and growth
of the halo with a smooth interface "a# proeutectic phase solidi_cation ]
growth of the spherulite in contact with the melt\ "b# eutectic sol!
idi_cation ] halo encapsulation\ "c# growth of the spherulite within the
solid halo[
Nucleation
The nucleation of graphite and austenite occurs through a
heterogeneous process and preexisting nuclei compatible with
their crystallographic structure are needed[ In D[I[ the number
of stable centers of eutectic solidi_cation is ½ 199 times higher
than in gray iron at the same undercooling level ð5Ł[ Austenite
preferably nucleates in carbon depleted areas^ elements such as
Ti\ V and Al are e}ective in increasing the number of g dendrites
by forming carbides\ nitrides or carbonitrides which act as
substrates for the crystallization of austenite ð6Ł[ The number
Fig[ 3[ Ferritic ductile iron[
234
Fig[ 4[ Carbidic structure of a hypereutectic iron[
of graphite spherulites formed during solidi_cation "or the num!
ber of nucleation sites# is a function of the chemistry and of the
undercooling "or cooling rate# of the metal[ The inoculation
process\ which is more e}ective in hypoeutectic than in hyp!
ereutectic iron\ changes drastically the nucleation potential for
graphite particles[ Several types of inclusions\ typically the
products of the spheroidization and inoculation treatments\
have been identi_ed at the center of graphite nodules[ A list of
such inclusions is given in Table 0 ð7Ł[ Although the nucleation
of graphite nodules has also been reported in ultra pure iron ð8Ł\
their heterogeneous nucleation has been demonstrated[ Many
theories describing the heterogeneous nucleation of graphite
have been proposed and were reviewed by Skaland et al[ ð7Ł[
Examples are the silicon carbide theory\ the salt!like theory and
the sul_de:oxide theory[ One of the latest developed by the
same authors ð7Ł also explains the fading behavior of inoculants[
In their work\ they analyzed a large number of inclusions
detected in graphite nodules and in the matrix of Ductile Iron
castings[ Two types of nuclei were identi_ed at the center of the
nodules[ The _rst category consisted of a composite nucleus
having a sul_de core "MgS or CaS# covered by an outer layer
of Mg silicate "XMgO[SiO1#[ The second type was a single
Mg silicate phase "MgO[SiO1#[ After inoculation with Ca:Al
containing ferrosilicon\ both types of inclusions serve as nuclei
for the precipitation of a hexagonal silicate phase of the XOSiO1
or XOAl1O2[1SiO1 type "where X denotes Ca\ Sr or Ba#[ The
Table 0[ Summary of element combinations and phases detected in
inclusions serving as nuclei for graphite nodules ð7Ł[
MgS "Mg\Al#2O3
CaS "Mg\Al#SiO2
SrS "Mg\Ca\Al#SiO2
CeS Fe1O2
LaS Fe1SiO3
MgO Mg!Al!Si!Ti!O
SiO1 CeO1
MgO[SiO1 MgSiN1
1MgOSiO1 MgN1
CaO[Al1O21SiO1 CaOSiO1
235 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

basal planes of these crystals are favorable sites for graphite

nucleation since these facets allow the formation of coher!
ent:semicoherent low!energy interfaces between the nucleus and
graphite[ The fading phenomenon was explained by the coars!
ening of the inclusions with time[ The optimum inclusion diam!
eter falls within the range of 9[3Ð1 mm with a peak of the particle
frequency at 0[0 mm[ Increasing the undercooling during the
eutectic solidi_cation increases the nucleation rate and\ as
expected\ the nodule count[ The temperature range for the
eutectic transformation is also enlarged by an increased cooling
rate ð09Ł[
During the solid state transformation of austenite\ the for!
mation of new nuclei for graphite precipitation is unlikely[
During this reaction\ austenite may either transform to fer!
rite¦graphite or ferrite¦pearlite¦graphite depending on the
temperature and the chemical composition of the metal[ The
decomposition of Fe2C to graphite and ferrite was also observed
ð00Ł[ Under slow cooling conditions\ ferrite usually nucleates at
the austenite!graphite interface due to the occurrence of a car!
bon depleted zone around the graphite particles^ nodules act as
carbon sinks as the solubility of C in the austenite drops with
the decreasing temperature[ At this stage\ the ferrite:austenite
interface becomes the preferred nucleation sites for pearlite Fig[ 5[ Growth rates curves "a# lamellar graphite:austenite eutectic "b#
because of the high carbon content of the austenite[ If pearlite spherulitic graphite growth "c# di}erent graphite growth rates in lamellar
promoting elements decrease the transformation temperature growth ^ R  growth rate "cm:sec#\ DT  undercooling ">C#\
and reduce the rate of ferrite formation\ pearlite may either RG0  growth rate for graphite in ð0909Ł or ððaŁŁ axis\ RG1  growth
rate for graphite in ð9990Ł or ððcŁŁ axis\ Rg  growth rate for austenite ^
nucleate at the g!g grain boundaries or at the graphite!g inter! RG1 is predominant in spherulitic growth and RG0 is predominant in
face[ lamellar "gray iron# growth[

Growth
Under the same undercooling\ the growth rate of graphite zone exists in nodular iron[ The coupled zone de_nes the sol!
and austenite are not equal because of their di}erent growth idi_cation conditions "chemical composition range\ under!
mechanisms[ Austenite being a non!faceted phase\ its growth cooling# under which the growth rate of the eutectic is faster
which has been detailed in many references ð01\ 02Ł is controlled than each of the components separately ð6[ 05Ł[ In gray iron\
by the heat ~ow and the di}usion rate at the liquid!solid inter! this coupled zone exists because the growth axis of the graphite
face[ Figure 5 illustrates the di}erence in growth rate between is ððaŁŁ "or the ð0909Ł direction# for which the growth rate is
austenite\ graphite ~akes and graphite spherulites[ The growth equivalent to that of austenite under speci_c conditions ð05Ł[
rate of graphite particles changes with the crystal growth direc! Beyond a certain undercooling "Fig[ 6#\ the growth rate of
tion and with the impurity level in the melt "{a| or {c| axis\ Fig[ cementite becomes higher than that of graphite and dominates
5#[ Graphite growth is controlled by the rate at which di}erent the proeutectic and:or eutectic formation[ Because the growth
solid!liquid interface structures can be incorporated in the rate of cementite can be equivalent to the one of austenite\ Fe2C
graphite crystal structure on either the basal or prism planes[ and austenite form a normal eutectic and can grow sim!
Basal plane ððcŁŁ is the preferred growth direction because of
its low interfacial energy with the melt[ Growth in this direction
results in spheroidal graphite particles[ However\ if surface
active elements such as oxygen\ sulfur\ lead or tellurium are
present in the melt\ they tend to be adsorbed on the high energy
plane "prism plane ððaŁŁ# whose energy level is then reduced
below that of the ððcŁŁ plane[ Mixed growth conditions give
heterogeneous graphite particle shapes "coral\ compacted\
exploded\ chunky [ [ [ #[ Many models "more than 09# reviewed
by McSwain ð04Ł were developed to explain the graphite growth
mechanisms[ However\ none of them has been fully correlated
with experimental data[ Detailed discussion of the growth the!
ories of the graphite nodules is beyond the scope of this paper[
The reader is referred to specialized literature for more details
ð6\ 01\ 03\ 04Ł[
Assuming that the respective growth rates for graphite
spherulites and austenite dendrites can never be equivalent "see Fig[ 6[ Solid!liquid interface temperature as a function of growth rate
Fig[ 5#\ this leads to a divorced eutectic for which no coupled for growth of cementite eutectic and ~ake graphite eutectic[
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
ultaneously[ In this case the microstructure results from a
coupled eutectic growth[ So\ if too high an undercooling occurs
in hypereutectic iron\ massive carbides precipitate instead of
graphite "solid lines in Fig[ 0# and the eutectic reaction is the
simultaneous growth of g¦Fe2C[
Like the eutectic reaction\ the eutectoid transformation is
also a}ected by the cooling rate[ If the cooling rate is low when
compared to the di}usion rate of carbon\ austenite transforms
to ferrite and graphite^ carbon atoms di}use through the ferritic
shell to the graphite particles[ In ternary Fe!C!Si systems\ ferrite
and graphite grow from the parent phase between 649 and
611>C[ If the eutectoid transformation is not completed when
the metastable eutectoid temperature is reached "½ 611>C#\
pearlite grows competitively with ferrite ð00Ł[ During the pro!
duction of industrial castings\ g transforms to graphite and
pearlite because of the limited cooling time allowed in the mold
prior to shake!out and because of the e}ect of alloying elements[
As for other ferrous alloys\ the interlamellar spacing of pearlite
is a function of cooling rate] the higher the cooling rate\ the
smaller the spacing between lamellae[
CHEMICAL COMPOSITION AND
MICROSTRUCTURE
Elements interactin` with `raphite formation
Carbon\ silicon and phosphorus are graphitizers and their
combined e}ect on graphite formation is estimated via the
Carbon Equivalent "CE# relationship\ CE  )C¦0:2 ")Si¦
)P#\ which is used to determine the nature of the iron\ i[e[
hypoeutectic\ hypereutectic or eutectic[ D[I[ with a CE equal to
3[15 has an eutectic composition[ The e}ects of the graphitizing
elements may be represented using 1D diagrams such as those
shown in Figs 7 and 8[ These graphs were constructed using the
thermal analysis technique which will be described later in this
paper[ As may be seen on these _gures\ Si favors the graphite!
g system via the following phenomena] it decreases carbon
solubility in austenite "Fig[ 7\ Arrow 0#\ increases the stable
eutectic temperature "Fig[ 7\ Arrow 1#\ promotes the pre!
cipitation of graphite "Fig[ 7\ Arrow 2# and increases the interval
between the stable and metastable eutectic temperatures "Fig[ 8\
Fig[ 7[ Stable Fe!graphite eutectic region of the Fe!C!Si solidi_cation
diagram[
236
Fig[ 8[ Metastable region of the Fe!C!Si solidi_cation diagram[
Arrow 3\ and Fig[ 09#[ This last e}ect is of particular importance
because it favors the formation of a graphitic eutectic instead
of a carbidic one[ Si also raises the eutectoid temperature[
However\ Si being present in solid solution in ferrite increases
the hardness\ U[T[S[ and yield strength of the matrix but
reduces its elongation and toughness[ The solubility of Si in
ferrite can reach 3) at room temperature ð07Ł[ When Si is
added as an inoculant "FeSi#\ it raises the number of nucleation
sites and the nodule count[ As a result\ it reduces the carbon
di}usion path during the eutectoid transformation and
increases the amount of ferrite in the structure[
Sulfur plays a major role in the nucleation and growth of the
graphite particles[ It has been shown that S is often found in
the nucleus of the graphite nodules "Table 0#[ However\ S is a
surface active element which may be adsorbed by the graphite
crystal[ It thus a}ects the graphite growth mechanisms and
favors the formation of ~ake graphite particles instead of
nodules[ S content is critical in Ductile Iron] too low a S content
may result in a smaller number of nodules while a too high one
may result in the formation of ~ake graphite[ The recommended
S concentration in D[I[ is within the range of 9[909Ð9[904) wt[
Spheroidizin` elements
The crystallization of carbon as graphite spheroids is the
result of the action of certain elements\ namely magnesium\
calcium\ yttrium or rare earths\ that provide the necessary con!
Fig[ 09[ Di}erence between graphite and carbidic eutectic temperatures
as a function of Si content[
237 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Table 1[ E}ect of RE content on the nodule count of a Mg treated iron also increases the e}ectiveness of the inoculation process by
ð19Ł[ reacting with oxygen to form CaO[ However\ when the amount
Residual Mg ")# Residual RE ")# Nodule count "0:mm1# of added Ca exceeds 9[92)\ the carbide!forming tendency of
Mg appears to be increased ð6Ł[
9[904 9 115
9[904 9[992 231 Rare Earths "Re# ðCe\ La\ Pr\ NdŁ[ The designation {Rare
9[905 9[997 181 Earths| "RE# stands for the elements with atomic numbers 46 to
9[914 9 114 60[ Cerium "Ce#\ lanthanum "La#\ praseodymium "Pr# and neo!
9[916 9[993 164
dymium "Nd# are elements among the RE family used as sphe!
9[914 9[901 149
9[932 9 049Ð064 roidizers ð24Ł[ They may be added in the molten charge as
9[921 9[909 199Ð114 Mischmetal which usually contains ½ 49) Ce\ ½ 14) La and
½ 04) Nd[ If RE is the only spheroidizer used in a low S base
iron\ a fully nodular structure is hardly achieved\ the nodularity
level being usually below 59)[ An optimal combination of RE
ditions for the precipitation of the carbon atoms on the ððcŁŁ
and Mg contents was found to maximize the nodule count
planes of the graphite crystals[ More precisely\ their role is to
as shown in Table 1 ð19Ł[ Moreover\ cerium neutralizes the
neutralize the surface active elements "S\O# which are pref!
deleterious e}ect of elements such as Pb\ Bi\ As\ Sb and Al "as
erentially adsorbed on the ððaŁŁ plane of the graphite crystal[
will be seen in Table 3#] In general\ only 9[991 to 9[994) of Ce
The spheroidizing elements and oxygen and:or sulfur react to
is required to counteract the e}ect of such elements in a Mg!
form compounds that may ~oat to the slag or serve as nucleating
treated melt ð26Ł[ When Ce is present in excessive concentration
sites[ These reactions deoxidize and desulfurize the melt[
" × 9[90)#\ it raises the risk of carbide formation because it
Ma`nesium[ Magnesium is the most commonly used sphe! decreases the nodule count and may a}ect the nodularity in
roidizing element because of its low cost and applicability to heavy section castings[
irons over a wide range of carbon equivalent values and casting Onsoin et al[ ð10Ł compared the e}ect of Ce\ La and Mis!
sections[ Its typical concentration in D[I[ ranges from 9[91 to chmetal additions on the microstructure of Ductile Iron[ Figure
9[97) but its e}ectiveness is related to the S and O contents of 00 summarizes their results[ They showed that Ce is the most
the iron[ An excessive Mg concentration results in a carbidic bene_cial RE element for graphite formation while La strongly
casting[ As previously described\ Mg contributes to the for! promotes carbide crystallization at the expense of graphite[
mation of nuclei for graphite precipitation[ An optimized Mg
content is thus required to obtain a high nodule count and a Alloyin` Elements
good nodularity[ Nevertheless\ magnesium is usually added in Table 2 summarizes the e}ect of the major alloying elements
conjunction with a small amount of rare earths to improve the on the structure and properties of Ductile Iron castings[
reliability of its spheroidizing e}ect ð25Ł[
Copper[ Copper is one of the most common alloying elements
Calcium[ Although this element may be used alone as sphe! used in Ductile Iron[ Cu is a moderate graphitizer and may be
roidizer in D[I[ ð23Ł\ its main role is to reduce the volatility of the used as a partial substitute for Si to minimize chilling tendency
magnesium reaction and to improve the magnesium recovery[ It without promoting free ferrite[ Its graphite!promoting e}ect is

Fig[ 00[ Comparison of the e}ect of Ce\ La and Mischmetal on the microstructure of experimental cast irons[
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 238

Table 2[ E}ects of alloying elements

Max[ E}ects on stable E}ects on E}ect on matrix E}ect on E}ect on Segregation

recommended and metastable eutectoid T structure hardenability graphite structure direction
ranges eutectic T

Cu from 9[92) in Increases the Reduces eutectoid Promotes pearlite Raises Promotes First liquid to
ferritic to 0) in di}erence temperature by retarding C hardenability but intercellular freeze negatively
pearlitic between stable "austenite di}usion[ less e}ective than ~ake when in segregating
and metastable stabilizer# Stabilizes pearlite Mo combination element
eutectic with Ti or Pb ð12Ł
temperatures
Ni from 9[0) in Increases the Reduces eutectoid Promotes pearlite Raises Chunky First liquid to
ferritic to di}erence temperature weakly hardenability but graphite\ reduces freeze negatively
9[14) in between stable "austenite less e}ective than the tendency to segregating
pearlitic and metastable stabilizer# Cu chill element
eutectic
temperatures
Mo from 9[91) in Lowers both Increases Promotes pearlite Raises Weak Towards last
ferritic to spec[ in eutectic eutectoid in as!cast\ less hardenability\ the intercellular liquid to freeze
pearlitic temperatures temperature e}ective than Cu more e}ective carbide former
"ferrite stabilizer# and Sn element by  which are
delaying pearlite not broken
formation down by heat
treatment
Mn from 9[04) in Lowers both Reduces eutectoid Promotes pearlite\ Raises Intercellular Towards last
ferritic to 9[24) eutectic temperature _ve times more hardenability\ carbide network liquid to freeze
in pearlitic temperatures "austenite e}ective than Ni delays pearlite if segregation
stabilizer# formation to lower occurs in thick
T sections

Higher contents have been reported to 9[6) ref[ ð6Ł[

Not a general accepted e}ect ð6Ł[

the result of an increase of the interval between stable and the

metastable eutectic temperatures[ Also\ Cu promotes pearlite
formation by retarding C di}usion in austenite[ However\ a
recent publication by Lacaze et al[ ð11Ł suggests that copper has
a pearlite promoting role only in combination with a small
addition of Mn by increasing the temperature gap between the
stable and metastable three!phase eutectoid _elds while Mn
decreases it strongly[ The combined e}ect of both elements
brings the reference temperatures for the stable and metastable
eutectoid reactions close to each other and favors the formation
of a fully pearlitic cast iron[ However\ fully pearlitic castings
containing less then 9[0) Mn were successfully produced with
about 9[5) Cu ð13Ł[ If the Cu concentration exceeds 9[64) wt\
it retards annealing by stabilizing pearlite "Fig[ 01#[ It also
enhances hardenability when combined with Mo and:or Ni[ Cu
is less e}ective than Mo but more than Ni as a hardenability
promoter^ in D[I[ castings\ 0[4) Cu is equivalent to 9[2)
Mo[ The maximum level of Cu in D[I[ varies with the matrix
structure required\ the heat treatment conditions and the pres!
ence of other alloying elements[ For instance\ to achieve a
ferritic casting in the as!cast condition\ Cu content should not Fig[ 01[ The e}ect of copper on the proportion of pearlite formed in
exceed 9[1)[ In normalized pearlitic iron\ quenched and the matrix of nodular iron bars 29 mm diam[ sub!critically annealed
for 29 min to 5 h at 699>C[
tempered\ and austempered irons\ 9[4) to 0[4) Cu may be
used to delay annealing and to raise hardenability[ Because
it promotes pearlite\ copper increases tensile strength\ yield
strength and hardness but decreases ductility\ impact resistance classi_ed as a graphitizer because it reduces the solubility of C
and raises the ductile!to!brittle transition temperature[ The in liquid or solid iron] a 0) increment reduces the solubility of
pearlite promoting potential of Cu is compared to those of Mn carbon in molten iron by 9[94) and raises the graphite!aus!
and Sn in Fig[ 02[ tenite eutectic temperature by 2Ð3>C[ As in other ferrous
materials\ it acts as an austenite stabilizer by lowering the gÐa
Nickel[ Ni is soluble in molten and solid nodular iron[ It is transformation temperature "11>C per 0) Ni addition#[ Ni is
249 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
Fig[ 02[ E}ect of alloying elements on the formation of pearlite[
the most widely used alloying element in the production of irons
to be hardened and tempered or isothermally transformed[ For
example in ADI "Austempered Ductile Iron# production\
increasing the nickel and:or copper contents improves the hard!
enability[ The addition of small quantities of Mo and:or Mn is\
however\ necessary to fully austemper large section castings as
shown in Fig[ 03^ however the concentrations of Mn and:or
Mo should be minimized to limit their segregation to cell bound!
aries[ Ni can also be used as a precipitation hardening element
in ferrite[ Although nickel weakly promotes pearlite formation\
its e}ect is not signi_cant in irons containing less than 9[64)
Ni unless an as!cast fully ferritic matrix structure is required[
An addition of up to 1[4)\ due to its strengthening e}ect in
ferrite and weak pearlite forming tendency\ increases the tensile
strength\ the yield strength and slightly reduces the elongation
in as!cast D[I[ A similar e}ect is seen in annealed ferritic irons[
Even though the ductile!to!brittle transition temperature is
increased by a Ni addition\ the increment is smaller than the
one induced by Cu or Mn for the same percent addition of
alloying element[
Molybdenum[ Two objectives are targeted when alloying Ductile
Iron with molybdenum[ First\ Mo increases the hardenability
of the iron[ Second\ in annealed ferritic grades it raises the high
temperature tensile strength\ the creep strength "½399>C# and
the thermal fatigue resistance[ When Mo is combined with Cu
or Ni\ its hardenability promoting e}ect is even more pro!
nounced ð6Ł[ In austempered irons\ the Mo content should\
however\ not exceed 9[1Ð9[2)^ a strong segregation tendency
to cell boundaries may result in the formation of a martensite
network and in the loss of strength and ductility ð15Ł[ On the
other hand\ Mo delays the aging of ADI and allows the uti!
lization of such castings at temperatures up to 199>C ð69Ł[
Man`anese[ Mn decreases the upper eutectic critical tempera!
ture\ delays the nucleation of ferrite at the graphite:metal inter!
face and lowers the di}usivity of carbon in ferrite[ It is also a
substitute for iron in Fe2C ð16Ł[ Pearlite formation is thus fav!
ored by this element but its e}ect is less pronounced than the
one seen for tin\ copper or arsenic[ As Cu and Ni\ Mn retards
annealing and increases hardenability[ The tensile and yield
strengths are increased and elongation decreased by a Mn
addition due to an increased pearlite fraction in the casting[
However\ to achieve an as!cast fully pearlitic iron a Mn content
exceeding 9[4) is required and often results in a decrease in
the tensile strength due to the embrittling e}ect of Mn!alloyed
intercellular carbides[ In normalized pearlitic iron\ Mn content
may be increased to 0) and in hardened and tempered nodular
iron\ Mn concentration as high as 0[4) is used[ However\ in
both cases\ the elongation decreases with the increased con!
centration of manganese[
Tin[ Instead of being considered as a detrimental trace element\
Sn is sometimes used as an alloying addition because it strongly
promotes pearlite in the as!cast condition[ Sn segregates at the
surface of the graphite nodules and acts as a barrier to the
transfer of carbon atoms to the graphite particles[ This is illus!
trated in Fig[ 02 where 9[0) Sn is as strong as 0) Cu or Mn
for pearlite formation[ To promote pearlite in heavy section
castings or to stabilize it in normalized iron\ Sn is often added
in concentration above about 9[97)[ However\ if as!cast ferritic
castings are targetted the tin level must be kept low "Table
3# This element also delays annealing and is an undesirable
contaminant in irons annealed to obtain a ferritic matrix[
Residual elements
Although promoting graphite formation\ phosphorus is
classi_ed as a deleterious element in Ductile Iron[ Phosphorus
enhances the formation of pearlite and increases the hardness
and tensile strength but reduces the elongation[ Beyond a cer!
tain concentration "solubility of P in iron is 9[0)#\ P reacts
with Fe to form steadite "Fe2P#[ Segregation which occurs in
large section castings exacerbates this phenomenon[ Because
steadite precipitates at cell boundaries as an eutectic "Fe2P¦g#
it embrittles the casting[ In ferritic grades\ under speci_c cooling
conditions\ P has been found responsible for temper embrit!
tlement[ In the range 9[93)Ð9[96)\ a slight reduction of the
impact properties is observed although the occurrence of pre!
cipitates is not detected at cell boundaries[ Beyond this con!
centration "9[97)Ð9[01)#\ an increased P content reduces the
toughness and increases the ductile!to!brittle transition tem!
perature ð08Ł[ Fracture toughness is also reduced by the pre!
cipitation of P at the subgrain boundaries[ The control of this
element is thus critical to achieve high mechanical properties\
especially impact resistance[ The recommended maximum levels
are ½9[92) for as!cast ferritic grades and ½9[94) for pearlitic
grades[
The e}ects of other residuals on D[I[ characteristics are sum!
 Table 3[ E}ects of residual elements and impurities " ³ 9[0)#

Limit ferritic grade Limit pearlitic grade Intercell[~ake Carbide Pearlite

) ) graphite former promoter E}ects Sources

Cr 9[93 9[09 x x Raises nodule count ð6Ł\ pearlite promoter in intercell[ Steel scrap\ pig iron[
9[924 9[94 regions[
Retards anneal[ Reduces range between stable and
metastable eutectic temperatures ð01Ł[
V 9[93 9[94 x Carbides resist to annealing[ Reduces range between stable Steel scrap[
and metastable eutectic temperatures ð01Ł[
Ti 9[91 9[93
9[96 9[96 x x Compacted and vermicular graphite former[ Small quantity Pig irons\ some ferroalloys\
³ 9[990) reduces the susceptibility to spiking "nodule structural steel scrap\ enamels
alignment#[ Reduces range between stable and metastable and paints[
eutectic temperatures ð01Ł[ Promotes hydrogen pinholes
when Al is present[
Sn 9[90 9[92 x Accumulates at surface of spheroids and suppresses the Solder\ steel scrap\ non ferrous
formation of ferrite shells[ alloys[
Retards C di}usion
Al 9[91 9[97 ð6Ł Lowers eutectic temperatures[
9[94 9[94 x Vermicular graphite former\ aggravates hydrogen pinholes\ Ferro!alloys\ steel scrap\
~ake formation can be controlled by Ce addition[ inoculant and treatment alloys[
9[92 9[92
Pb 9[991 9[991 x x Deteriorates graphite "Widmanstatten graphite\ sooty or Painted steel\ soldered auto body\
C[ LABRECQUE\ M[ GAGNE

spiky graphite# when H¦Pb ð01Ł\ e}ect can be controlled steel wheels\ weights[
by Ce addition[
Te 9[91 9[91 x Minimizes pinholes\ reacts with Mg\ white iron former[ Steel scrap\ mold or core wash[
9[991 9[992 Deteriorates graphite shape[
Bi 9[991 9[991 x x Mesh graphite former ð6Ł\ e}ect can be controlled by Ce Bearings\ mould and core coating[
addition[
Zr 9[0 9[0 x Vermicular graphite former[
Cd 9[991 9[991 x Intercellular ~akes former[ Plated bolts and screws[
ł] DUCTILE IRON

Sb 9[992 9[91 x x Accumulates at surface of spheroids[ Reacts with Mg thus Steel and enamelled scrap[
9[990 reduces Mg e.ciency\ e}ect can be controlled by Ce
addition[
Suppresses the formation of ferrite shell[ Controls chunk in
heavy section casting[
As 9[91 9[94 x x Flake formation can be controlled by Ce addition[ Tramp element in steel scrap[
9[90
B 9[991 9[991 x Borocarbides resistant to anneal\ segregates to intercells[
Certain pig iron\ some
ferrosilicon\ enamelled scrap[
V 9[93 9[94 x x Vanadium carbides resist to anneal[ Reduces range between Steel scrap[
9[91 9[93 stable and metastable eutectic temperatures ð01Ł[

In thin sections\ 9[92 in others

240
241 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Fig[ 03[ E}ect of chemical composition on the pearlite fraction in 4[0 cm diameter castings austempered one hour at
259>C "composition ] 2[5) C\ 1[5) Si#[

Table 4[ Segregation of minor elements and impurities ð01Ł[ Table 5[ Typical Mg spheroidizing alloys and treatment methods used
ð24Ł
Segregate toward last liquid to freeze]
Cr\ Cd\ Sb\ Sn\ Pb\ B\ Ti\ V Alloys Technical means

Ni Mg Open Ladle
Cu Mg
Fe Si Mg 2:4) Sandwich\ tundish cover\
marized in Table 3[ The recommended levels in ferritic and Fe Si Mg 4:6) ~otret\ inconod\ inmold
pearlitic grades are also indicated[ Their e}ects may be classi_ed Fe Si Mg 7:09) gazal
into three types] "0# The intercellular ~ake graphite formers Fe Mg pellets 5:09)
"1# The carbide promoters "2# The pearlite promoters[ Some Mg coated wire Plunger\ rotary ladle\
Mag Coke ladle with submerged addition
detrimental elements such as Ti may lead to two types of defects[ Fe Si Mg 29Ð39)
Both defects are then indicated[ Moreover\ the possible sources Pure Mg bar Converter\ pressure ladle
of such elements are enumerated[ Pure Mg powder plunger\ injection
The problems created by trace elements are often emphasized
in heavy section castings because of their segregation to the last
metal to freeze\ reaching high localized concentrations in these
areas[ Table 4 gives a list of the residual elements prone to teristics of the charge materials that should be selected for the
segregate[ production of ferritic D[I[ castings[ He emphasized the need for
high purity steel scrap and for the addition of low Mn\ P\ S
high purity iron units "e[g[ SORELMETAL# to control the
MANUFACTURE OF DUCTILE IRON CASTINGS composition of the castings within the required limits[ As out!
lined by Trudel et al[ ð29Ł\ a large amount of high purity iron is
A schematic ~owsheet of Ductile Iron production is shown required when tight control of the ferritic matrix and avoidance
in Fig[ 04 ð17Ł[ The _rst step of the manufacture of D[I[ castings of intercellular carbides are requested[ Knowing precisely the
is the careful selection of the charge materials[ Steel scrap\ composition of the charge materials applies to other grades as
returns or other materials may contain alloying "e[g[ Mn in well[ For example\ minute variations of copper content would
steel# or residual "e[g[ S in carburizer# elements that may favor a}ect the amount of pearlite formed and increase the variability
metastable eutectic solidi_cation\ prevent the crystallization of of the mechanical properties of the castings ð20Ł[ Kern et al[ ð21Ł
graphite as spheroids or cause the formation of an undesired identi_ed a series of unique characteristics pertaining to D[I[
as!cast structure[ Jenkins ð18Ł discussed in detail the charac! that justify the careful selection of the melting equipment[ These
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 242

added to the melt[ Mg is the most commonly used of these

Fig[ 04[ Schematic ~owsheet of ductile iron production[
are] low S " ³ 9[91)# and Si "0Ð0[4)# contents\ high C con!
centration "2[5Ð3)#\ high tapping temperature "0349Ð0469>C#\
low concentration of residual elements and the consistency of
operation[ The production of high quality D[I[ castings is based
on rigid controls of composition\ tap temperature\ holding
times\ etc[ Cupolas and induction melting furnaces usually meet
the above requirements\ although they do not disqualify other
melting equipment[
The formation of graphite spheroids is obtained through a
special treatment during which spheroidizing elements are
elements and Table 5 lists various Mg alloys used for D[I[
spheroidization treatment and the corresponding addition
method[ Various factors in~uence the magnesium recovery^ for
example] silica linings are reduced by Mg\ high sulfur iron
requires more magnesium[ Although a minimum amount of
sulfur is needed for graphite nucleation ð7Ł\ the excess sulfur
content must react with magnesium to ensure spheroidization[
The choice of a treatment method "which are described in details
elsewhere ð24\ 26Ł# for an individual foundry involves many
factors outlined by Henning ð26Ł and must be based on the
circumstances present in the foundry[
Inoculation\ which may take place at di}erent process steps
in combination or separately "Fig[ 04#\ is a necessary step for
the production of Ductile Iron castings[ As illustrated by
Henderson ð27Ł\ Fig[ 05\ an uninoculated D[I[ will be fully
carbidic while on the other hand\ a properly inoculated iron
may show a deteriorated graphite structure due to the fading
of the inoculating e}ect[ Other bene_ts of inoculants include
a greater structural uniformity and reduction of intercellular
segregation ð24Ł[ As seen in Table 6 ð27Ł\ most inoculants are
Fe!Si alloys containing Al\ Ca\ Ba\ Mn\ Zr[ These elements are
used to increase the solubility and the potency of the alloys[
Graphite is reported to be an e.cient inoculant in gray iron
but not in Ductile Iron ð28Ł^ nevertheless\ when added prior to
or during the magnesium treatment\ an increased nodule count
is reported ð28Ł[ There are three methods to inoculate the metal
which are used individually or in combination ð24Ł] in the ladle
"either during or after the Mg treatment#\ in the stream while
pouring and in the mold[ Because of the fading phenomenon
which causes low nodule count and eutectic carbide formation\
the later the inoculation\ the higher the casting quality[ As
shown in Fig[ 06 ð39Ł inoculating a Mg!treated iron with 9[02)
addition of FeSi64 in the metal stream is more e.cient than a
9[56) addition in the ladle[ Accompanying structures are
shown in Fig[ 07 ð39Ł[ The late in!mold inoculation would be
bene_cial to the casting structure[ However\ the homogeneity
of the casting may be a}ected because undissolved particles
may cause the formation of defects such as chunk graphite ð30Ł[
The selected inoculation process is as critical as the sphe!
roidization step^ strict control of the inoculating parameters\

Table 6[ Compositions of some ferrosilicon!based inoculants for Ductile Iron ð27Ł

Type of Inoculant Si) Al) Ca) Ba) Sr) Zr) Mn) Mg) RE)

64) FeSi\ Ca bearing 64[9 9[5Ð0[14 9[5Ð0[9

FeSi!Ba 59Ð54 0[9 9[7 9[7 5 5
FeSi!Ba 59Ð54 9[4Ð0[6 0[9 8Ð00
FeSi!Ba 59Ð54 0[4 1[9 4Ð5 8Ð09
FeSi!Ba 69Ð64 9[7Ð0[19 9[7Ð0[19 0[64Ð1[14
FeSi!Zr 79 0[4Ð1[4 1[4 0[4
FeSi!Sr 64 ³ 9[4 ³ 9[0 9[7
FeSi!Sr 34Ð49 ³ 9[4 ³ 9[0 9[7
FeSi!Ce 34 9[4 9[4 02 "09) Ce#
FeSi!Ce 34 9[4 9[4 2[4 "2) Ce#
34) FeSi 34Ð49 9[7 9[7
34) FeSi!Mg 34Ð49 9[7 9[7 0[14
FeSi!La 64 0[4 1[9Ð1[4 La
243 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
Fig[ 05[ E}ect of inoculation on ductile iron microstructures "149X#[
i[e[ composition\ amount added\ particle size and temperature\
must be implemented to obtain uniformity and consistency[
The production of high quality D[I[ castings involves many
other steps which need to be carefully controlled[ For example\
holding temperature and time prior to the spheroidizing treat!
ment must be limited to maintain a high nucleation potential
of the melt and retain a high metallurgical quality factor of the
liquid metal ð31Ł[ Pouring temperature must also be optimized
as a function of the casting size to produce shrinkage!free cast!
ings\ Fig[ 08 ð24Ł[ Detailed discussion of such parameters can
be found elsewhere ð6\ 01\ 24Ł[
Thermal Analysis
The use of thermal analysis "i[e[ analysis of cooling curve
"CC# data# at di}erent steps of the manufacturing process of
liquid iron has become widely used in the industry[ It allows an
in!process control of the quality of the metal and\ to a certain
extent\ the identi_cation and prevention of defects in castings
during their manufacture[ The following reviews the bene_ts
and limitations of this technique[
Typical temperatures pertaining to CCs have been described
by several authors ð32\ 34\ 35Ł[ Table 7 summarizes the various
designations given in the literature to the critical temperatures
and their de_nition[ De_nitions for the _rst and second deriva!
tives of CCs are listed in Table 8[ Figure 19 presents a schematic
of the most typical points de_ned in Tables 7 and 8[ Examples
of curves corresponding to three types of iron are presented in
Fig[ 10[ It is seen that the shape of the curves as well as the
temperatures of the typical points are di}erent[
The e}ect of the spheroidization and inoculation treatments
on the CCs is illustrated in Fig[ 11[ The changes in cooling
curves after the di}erent process steps are clearly observable[
For instance\ TEU of the base iron is lower than that of the
iron before Mg treatment[ This phenomenon may result from
the oxidation of the melt between these two measurements^ thus
the nucleation potential of the iron increased[ After the Mg
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 244

Table 7[ CC typical temperature points

Name or acronym Physical signi_cation Reference

Tmax "TPK# Maximum measured temperature[ 33\ 34

TAL Temperature of primary austenite solidi_cation in hypoeutectic and eutectic irons 32\ 33
TGL Temperature of primary graphite solidi_cation in hypereutectic iron 32\ 06
TEN "TES# Temperature of eutectic nucleation "or temperature of eutectic start# 32\ 33\ 34\ 35
TEU Temperature of eutectic undercooling 32\ 33\ 34
TE Eutectic temperature "or mean eutectic temperature# 06\ 37
CET Carbide eutectic temperature measured with Te coated cup 36
TER Maximum temperature of eutectic arrest 32\ 33\ 34
TEE "TES# Temperature of the end of eutectic solidi_cation which corresponds to a minimum of the 33\ 35\ "34#
_rst derivative NPE
TS Solidus temperature 32
TEN!TEU Eutectic undercooling 32
TER!TEU Eutectic recalescence 32

Parentheses denote an alternate terminology[ Not an extensive list[

Fig[ 06[ Nodule count in ferrosilicon!magnesium treated irons inocu!

lated with foundry grade ferrosilicon "64) silicon# added either to the
ladle within one min of casting or to the metal stream[

treatment\ TEU decreases signi_cantly because Mg reacted with

the oxygen and sulfur present in the melt[ Finally\ the increase
in the nucleation potential due to the inoculation step is so
powerful that it masks the e}ect of the other process steps[ It
clearly shows that TEU "and other temperatures# is rep!
resentative of the nucleation potential of the melt and conse!
quently of the capacity of the liquid metal to counteract the
volume contraction of austenite by a graphite expansion during
the eutectic solidi_cation[
After analyzing a large number of CCs\ Chen and Stefanescu
ð33Ł concluded that it is possible to predict the graphite shape
Fig[ 07[ E}ect of ladle and metal stream inoculation upon the structure
of 1 mm "4:53 inch# sections of irons treated with ferrosilicon!mag!
nesium and inoculated with foundry grade ferrosilicon ^ ×499\ 3)
picral etched[
in the castings with this technique[ Moreover\ nodularity can
also be predicted for hypoeutectic and eutectic irons[ However\
they pointed out that a certain margin of error has to be con!
sidered because of the variations in pouring temperature\ nod!
245 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Table 8[ Typical points of the CC _rst and second derivatives

Name or acronym Physical signi_cation Reference

First derivative
AP "MXRRES# Austenite peak ^ area under this peak is representative of the heat generated during 33\ "34#
solidi_cation of austenite
NPAE "NPES# Negative peak between austenite to eutectic solidi_cation\ solidi_cation changes from 33\ "35#
austenite to eutectic
MXCR Maximum rate of recalescence 35
NPE "NPEE# "MXCREE# Negative peak after eutectic[ End of eutectic solidi_cation corresponds to TEE[ 33\ "34\ 35#
Second derivative
MXSDES Maximum second derivative\ corresponds to eutectic nucleation in 5[ 34
MSA Minimum slope of austenite peak 33
MSE Maximum slope of eutectic peak ^ the duration between MSA and MSE represents the 33
rate of eutectic recalescence[
ASEII Average slope of eutectic peak in stage II 33
MXSDEE Maximum of second derivative at the end of eutectic solidi_cation\ related to the accel! 34
eration of the end of solidi_cation
ASE III "MNSDEE# Average slope of eutectic peak in stage III 33\ "34#

Parentheses denotes an alternate terminology[ Not an extensive list[

Fig[ 08[ Recommended pouring temperatures for di}erent section sizes[

ule count and CE in the experimental results[ As shown in
Fig[ 12\ a hypoeutectic D[I[ with an increased nodularity is
accompanied by a reduced maximum rate of recalescence ð49Ł[
In hypereutectic iron\ the relationship between nodularity and
CC parameters was not observed with such precision[
Zhu and Smith ð40Ł have studied CCs obtained for similar
irons "same process and CE# but treated with di}erent sphe!
roidizing alloys[ In their work\ the deterioration of the graphite
particles from nodular to vermicular was not exclusively associ!
ated with an enlarged di}erence between TER and TEU[ This
was not supported by Stefanescu et al[ ð41Ł[ Other parameters
were identi_ed as a}ecting the shape of the CC such as rare
earths in the nodulizer and residual S in the iron[ The chilling
tendency\ which was related to TEU\ varied for each type of
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 246

Fig[ 19[ Typical hypoeutectic ductile iron cooling curve and its derivatives[

Fig[ 10[ CC obtained for three types of iron[

nodulizer^ this a}ected the growth condition of the graphite Inoculation treatment\
particles[ The same authors found that thermal analysis Sulfur level\
measurements were more sensitive to the nodulizer than to the Oxidation state of the melt\
graphite morphology[ They also showed that the degeneration
However\ other parameters\ which are discussed in detail else!
of the graphite particles morphology caused by an excess S in
where ð57Ł\ also a}ect the cooling curves]
Ni!Mg!treated melts was not detected by CC[ It was illustrated
with examples extracted from the literature that the following Temperature of the melt\
variables a}ect the CC characteristics] Sampling method and cup geometry[
Cooling rate of the sample\
Magnesium treatment\
Chemical composition of the iron\ General trends may be drawn for the above variables[ The
247 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
Fig[ 11[ Cooling curves taken from each stage of the melting and treatment processes[
spheroidization treatment reduces the O and S contents of the
melt^ consequently the CC temperatures decrease due to the
reduction of the number of nucleation sites[ The inoculation
treatment has the opposite e}ect by raising the nucleation
potential ð38Ł[ Di}erent chemical compositions of spheroidizing
and inoculating alloys have di}erent e}ects on CC[ The deter!
mination of )C\ )Si\ )P and CE is well documented and
those values can be easily evaluated with CC temperatures
within a narrow margin of error if the sampling method is under
control ð36Ł[ The singular e}ect of other elements on CCs have
not been evaluated in detail and empirical models which include
the e}ect of many elements were described for speci_c appli!
cations ð34Ł[ Being precise when establishing correlations
between process parameters and CC characteristics is not an
easy task because many variables may a}ect CC parameters in
the same direction[
THE DUCTILE IRON FAMILY
Figure 13 presents the worldwide growth curve of Ductile
Iron tonnage since 0849[ In spite of economic recessions and
changes in materials technology\ the Ductile Iron market has
continuously grown to exceed thirteen million tons worldwide
in 0885 ð1\ 42\ 43Ł[ The advantages of Ductile Iron that have
led to its success are numerous\ Fig[ 14[ Although other ferrous
castings may have superior individual properties\ Ductile Iron
o}ers\ at lower cost\ a unique versatility that can be obtained
through microstructure control[ It makes Ductile Iron not a
unique material but a family of alloys o}ering to designers a
wide range of mechanical properties as illustrated in Fig[ 15[
ASTM A!425 Ductile iron `rades
Figure 16 ð1Ł compares the stress!strain behavior of ferritic
and pearlitic Ductile Irons to those of mild steel and gray iron[
In gray iron\ the graphite ~akes act as stress raisers and initiate
microplastic deformation at very low stress[ This plastic defor!
mation causes the slope of the stress!strain curve to decrease
continually and\ as a result\ gray iron does not exhibit a true
elastic behavior[ On the other hand\ mild steel exhibits an elastic
behavior until the yield point at which plastic deformation
occurs suddenly without an increase of the ~ow stress[ Ductile
Iron shows a behavior intermediate to these materials[ As seen
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 248

Fig[ 12[ Correlation between the maximum rate of recalescence and the nodularity for hypoeutectic cast irons with
CE  2[76Ð3[95[

Fig[ 13[ Worldwide growth of Ductile Iron production\ 0849Ð1999[

in Fig[ 16\ Ductile Irons\ either ferritic or pearlitic\ are char!
acterized by an elastic stress!strain relationship similar to that
of steel which is however limited by the gradual onset of plastic
deformation initially concentrated around the graphite nodules
ð44\ 45Ł[ Yield strength of Ductile Iron is determined by the
usual 9[1) o}set method from stress!strain curves as applied
to plain carbon steel[ Designers must however be aware that
this di}erence in behavior should be taken into consideration
when designing components and\ under certain circumstances\
use the proportionality limit for design purposes[
The range of tensile properties achievable with as!cast and
heat!treated Ductile Irons as speci_ed by ASTM A425 ð46Ł is
illustrated in Fig[ 17[ Note that these are minimum properties
which are\ in most cases\ easily exceeded in Ductile Iron cast!
259 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Fig[ 14[ Comparison of the engineering characteristics of Ductile Iron vs competitive ferrous cast materials[

Fig[ 15[ Microstructures and tensile strengths for various types of Ductile Iron[

ings[ Moreover\ the production of as!cast materials meeting the
speci_cations of so!called {annealed| grades is an every day
reality in foundries[ As shown by Trudel et al[ ð29Ł\ the careful
selection of charge materials allows the ful_lment of the
{annealed| material speci_cations in the as!cast condition\ Fig[
18\ and\ as also seen in this _gure\ annealing could then be used
to further enhance the ductility of the material[
Production of as!cast Ductile Iron with consistent mechanical
properties requires careful control of the production steps\ as
outlined in Fig[ 29[ However\ the design engineer must be
assured by the foundrymen that the purchased castings were
produced under continuously controlled conditions[ In 0869\
Siefer and Orths ð47Ł carried out an extensive statistical survey
of the mechanical properties of Ductile Irons and identi_ed the
following relationship]
"Tensile Strength#1×"Elongation#  Q
where Q is a constant later denoted by Crew ð48Ł as Quality
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
Fig[ 16[ Elastic and yielding behavior for steel\ gray iron and ferritic and pearlitic Ductile Irons[
Index\ QI\ for Ductile Iron[ High QI values have been shown
to result from high nodularity\ high nodule count\ absence of
intercellular degenerated graphite\ freedom from carbides\ low
phosphorus content " ³ 9[92)# and freedom from intercellular
porosity[ Figure 20 shows the tensile strength:elongation
relationships for di}erent QI levels of Ductile Irons with the
ASTM A425 speci_cation[ Each curve is an {iso!quality| line
along which strength:elongation values can be displaced by
annealing or normalizing treatments which change the ferrite:
pearlite ratio[ Quench and temper treatments produce similar
curves which are displaced slightly toward higher quality[ For
example\ the properties corresponding to the 54!34!01 grade
de_ne a minimum QI value of 46 to meet the requirements[ As
expected\ the more ductile grade "59!39!07# requires the highest
QI value\ i[e[ 65[
A study similar to that of Siefer and Orths ð48Ł was recently
carried out by Venugopalan and Alagarsamy ð59Ł[ Table 09
250
compares the results obtained[ As might be expected from two
decades of progress in Ductile Iron technology and process
control\ the maximum QI increased by 6[4) but the median
QI increased by 49)\ indicating a signi_cant improvement in
consistency of properties[
In spite of tensile properties that compete successfully with
those of medium carbon steels\ Ductile Iron is often considered
as a low toughness material[ Standard Charpy tests suggest that
Ductile Iron absorbs less impact energy that cast steel having
equivalent strength and tensile elongation[ However short!
comings of the Charpy test that are unfavorable to Ductile Iron
were clearly stated by McKinney et al[ ð50Ł[ They outlined that
the presence of shear lips on the fractured surface of a Charpy
specimen is clear evidence that plane stress conditions were
present over a signi_cant portion of the specimen thickness[ It
is worth noting that Charpy specimens of cast ferritic!pearlitic
steel always exhibit shear lips when tested at temperatures cor!
251 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
Table 09[ Comparison of QI values from two di}erent studies
Siefer and Orths "0886# Venugopalan + Alagarsamy "0889#
Q88[4"metric#  59\999 Qmax"metric#  53\499
Q88[4"Imperial#  019\999 Qmax"Imperial#  018\999
Q49"metric#  29\999 Q49"metric#  34\999
Q49"Imperial#  59\999 Q49"Imperial#  89\999
where ] Tensile strength "metric# is expressed in kg:mm1\
tensile strength "Imperial# is expressed in psi\
Q88[4 and Q49 indicate the quality levels exceeded by 9[4) and 49)
respectively of the samples tested and Qmax is the maximum quality
exhibited by a batch of 23 samples of commercial Ductile Iron[
responding to the upper shelf energy[ In contrast Ductile Iron
specimens do not develop shear lips at any temperature[ There!
fore the comparison of Charpy results for Ductile Iron to those
for cast steel is misleading if both materials are used in
su.ciently thick sections in service to give plane strain
conditions[ In their study\ McKinney et al[ ð50Ł compared the
dynamic fracture toughness behavior "KID# of a ferritic Ductile
Iron "grade 59!39!07 as cast# to that of a cast valve grade WCB
steel "9[14)C#[ Both materials had yield strength of 204Ð219
MPa and elongation of 12Ð17)^ however\ as previously noted
their Charpy impact energy was very di}erent\ i[e[ 9[017 J mm−1
"50 ft!lb# for the steel and 9[916 J mm−1 "02 ft!lb# for the Ductile
Iron[ As seen in Fig[ 21\ the fracture toughness of steel was
superior to that of Ductile Iron at temperatures above 21>C but
this superiority was much less than suggested by the Charpy
test[ Due to a much lower ductile!to!brittle transition tempera!
ture\ Ductile Iron exhibited superior fracture toughness below
21>C[ This _gure also shows that the fracture toughness of good
quality ferritic Ductile Iron is excellent to temperatures as low
as −51>C\ giving a K0D of 30 MPa zm which corresponds to
a ~aw size of 0[14 cm for a design stress equal to the yield stress
under static fracture conditions[ Above −07>C\ the critical ~aw
size is 2[64 cm[ Such ~aw sizes can be prevented "or easily
detected# by Ductile Iron foundries[ Assuming that such ~aws
can be avoided\ Ductile Iron castings can be considered
su.ciently tough to resist unstable crack propagation at tem!
peratures as low as −51>C[
Eighty percent of the service failures occurring in machines
are caused by a fatigue process which usually occurs at stress
amplitude well below the yield strength[ Therefore the design
stresses based on fatigue criteria have to be lower than those
determined using monotonic tensile design values and are
reduced further by stress concentrations caused by material
~aws or component design[ The endurance ratio\ which is the
ratio of fatigue limit to tensile strength\ is often used to charac!
terize the fatigue limit of Ductile Iron[ Typical endurance ratios
for various types of Ductile Iron are presented in Fig[ 22 ð1Ł
as a function of the tensile strength[ As for other properties\
optimum fatigue strength is obtained with optimum micro!
structural characteristics[ For example\ high nodularity has a
direct in~uence on fatigue strength\ Fig[ 23 ð1Ł^ poorly shaped
nodules act as ~aws "or stress raisers# that facilitate crack for!
mation and propagation[ Optimized microstructure\ which is
synonymous with high Quality Index values\ would ensure
maximum fatigue strength[ Major actions as suggested by For!
rest and Mullins ð51Ł to achieve high QI value and fatigue
strength are]
Maximum pearlite and matrix hardness\
High nodularity\ high nodule count and small nodule
size\
Slag:inclusion free castings\
Elimination of shrinkage porosity\
Minimum carbide content\
Freedom from degenerate graphite and dross on cast
surface\
Fatigue strengthening surface treatment[
For the latter\ it is worth noting that Ductile Iron castings when
surface treated may have properties exceeding those of steel\
Table 00 ð1Ł[
In the quest for optimum mechanical characteristics\ one
should prioritize the property that is the most critical for the
selected application[ As shown in Fig[ 24\ small nodules and
high nodule count are favorable to fatigue strength while high
nodule count lowers the upper shelf energy of Charpy curves\
Fig[ 25\ although decreasing the transition temperature[ Simi!
larly\ while increasing matrix hardness favors fatigue strength\
Fig[ 26\ it has the opposite e}ect on impact resistance\ Fig[ 27[
As already seen in Fig[ 14\ conventional Ductile Iron grades
exhibit other engineering properties that are superior or com!
parable to those of steels[ These are discussed in detail elsewhere
ð1\ 24\ 52Ł[
Austempered Ductile Irons
The application of the austempering treatment to alloyed
Ductile Irons has resulted in the development of a new group
of Ductile Iron materials] Austempered Ductile Irons "A[D[I[#[
Alloying with the appropriate Mo\ Ni and:or Cu concentrations
provides the hardenability required to quench the material to
the austempering temperature at which the isothermal trans!
formation of austenite to {ausferrite| "a mixture of ferrite needles
in a stabilized austenite matrix# occurs[ The austempering deter!
mines the re_nement of the ausferrite structure on which the
mechanical properties depend[ Details on the metallurgy of
ADI can be found elsewhere ð17Ł[
The particular microstructure of ADI o}ers a unique com!
bination of tensile and fatigue strengths\ ductility\ toughness\
wear resistance and machinability in conjunction with design
~exibility and low cost ð1Ł[ As shown in Table 01 ð1Ł not only
does ADI signi_cantly outclass the properties of pearlitic D[I[\
it also compares advantageously with forged steels[ Moreover\
the strength!to!weight ratio of the material and its relative cost
per unit of yield strength are among the lowest of all engineering
materials\ including aluminium ð53Ł[ Table 02 lists the _ve ADI
grades standardized by ASTM ð54Ł[ As previously indicated the
strength:ductility combination can be varied by changing the
Table 00[ E}ect of _llet rolling on reversed bending fatigue properties
of a crankshaft
Material processing Endurance limit\ MPa
Ductile Iron\ as cast 196
Ductile Iron\ as cast rolled _llet 558
Ductile Iron\ austempered 303
Ductile Iron\ austempered rolled _llet 875
Steel 0935 Q + T 220
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 252

Fig[ 17[ Tensile and hardness properties of Ductile Iron conforming to di}erent grades of ASTM speci_cation A425[

ausferrite microstructure through careful selection of the heat
treatment parameters[
Its combination of strength and ductility also ensures excel!
lent toughness to ADI[ As seen in Table 03 ð1Ł\ with KIC values
in the range 48Ð75 MPa zm\ ADI has a fracture toughness
which is superior to all other Ductile Iron grades "except Ni!
Resist# and equal to or higher than most of the quenched and
tempered steels[ According to the ratio of KIC to yield strength\
which is a measure of the size of the ~aw that can be tolerated
when materials are stressed to a constant fraction of their yield
strength\ ADI has equal or greater ~aw tolerance than pearlitic
Ductile Iron and quenched and tempered steels[
Properties of ADI for gear applications were evaluated by
the ASME Gear Research Institute ð55Ł[ When properly treated\
ADI has shown properties needed for such applications\ e[g[
bending and contact fatigue characteristics\ Fig[ 28a and b\
which are superior or equivalent to those of through!hardened
and gas!nitrided steels[
A signi_cant advantage of ADI is its outstanding wear resist!
ance due to the strain!induced transformation of the unreacted
253 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Table 01[ Comparison of the mechanical properties of forged steel\ pearlitic Ductile Iron and grade
049:099:6 ADI

Material

Grade
Mechanical property 049:099:6 ADI Pearlitic Ductile Iron Forged steel

Yield strength\ ksi 019 69 64

"MPa# "729# "379# "419#
Tensile strength\ ksi 059 099 004
"MPa# "0099# "589# "689#
Elongation\ ) 09 2 09
Hardness\ BHN 175 151 151
Impact strength\ ft!lb 019 39 029
"joules# "054# "44# "064#

Table 02[ ASTM standard 786M*89 for ADI grades

Tensile Yield Impact Typical

strength strength Elongation energy hardness
Grade ksi MPa ksi MPa ) ft[lb Joules BHN

0 014 749 79 449 09 64 099 158Ð210

1 049 0949 099 699 6 59 79 291Ð252
2 064 0199 014 749 3 34 59 230Ð333
3 199 0399 044 0099 0 14 24 277Ð366
4 129 0599 074 0299 N:A N:A N:A 333Ð444

Minimum values Un!notched charpy bars tested Ý 6126>F "1123>C#

Table 03[ Comparison of properties of ADI\ conventional and austenitic Ductile Irons and Q + T steels

Alloy Heat treatment Yield Strength MPa K0C"MPaZm#

AÐ1 749>C\ 0h^ salt quench

159>C 0194 62[4
329>C 634 63[4
BÐ4 749>C\ 0h^ salt quench\
159>C 0918 64[1
399>C 645 65[9
CÐ0 749>C\ 0 h^ salt quench\
299>C 0040 75[9
CÐ2 749>C\ 0 h^ salt quench\
299>C 0199 67[1
399>C 809 48[3
Ferritic D[I[ 169Ð229 31[7Ð37[2
Pearlitic D[I[ 329Ð374 16[0Ð37[2
Ni!Resist 213 53[0
A0S0 3039 769>C\ 0h\ oil quenched\ 0476 44[9
tempered 179>C
A0S0 3239 769>C\ 0h\ oil quenched\ 0493 55[7
tempered 179>C

high!carbon austenite that occurs when the surface of an ADI a surface strain!hardening e}ect permits the continuous main!
casting is subjected to deformation[ As shown in Fig[ 39 ð1Ł\ tenance of a high surface hardness by the uninterrupted replace!
this transformation results in a signi_cant increase of the surface ment of the abraded layer[ Finally\ in spite of its high strength
hardness with the bulk of the part retaining its ductility[ Such and wear resistance\ A[D[I[ o}ers excellent machinability when
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 254

Fig[ 18[ Tensile properties of annealed and as!cast keel legs[

compared to competitive materials with equivalent properties
ð56Ł[
Alloyed Ductile Irons
Ductile Irons alloyed with 3Ð5) Si\ optionally in com!
bination with up to 1) Mo\ were developed to meet the demand
for high temperature applications[ Because of excellent oxi!
dation resistance\ structural stability\ strength and resistance to
thermal cycling combined with good castability these ferritic
irons are ideal materials for parts such as exhaust manifolds
and turbochargers ð1Ł[
A family of highly alloyed Ductile Irons\ often known as
{Ductile Ni!Resist|\ has been commercialized for a wide range
of applications requiring special chemical\ mechanical\ and
physical properties[ Containing 07Ð27) Ni and up to 5) Cr\
they combine tensile strength of 279Ð449 MPa and elongation
of 3Ð39) with special properties such as corrosion resistance
255 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Fig[ 29[ The important elements of metal production control[

and erosion and wear resistance[ Examples of applications are
listed in Table 04 ð1Ł[ Typical applications for these castings are
parts working in saline environment or at high or cryogenic
temperatures ð1Ł[
CONCLUSIONS
The _fty year history of Ductile Iron has been enlightened
by technical development that makes it\ in 0887\ an engineering
material widely used in automotive\ agricultural\ energy and
other industries[ Considered a mature material by many\ recent
in!roads in the area of high temperature resistant castings\ aus!
tempering and the application of thermomechanical treatment
ð58Ł open new avenues to this material[ Although weight restric!
tions are likely to apply in automotive applications\ a positive
growth index is forecast for Ductile Irons for the next decade
ð43Ł[ Moreover\ supported by the growth of advanced engin!
eering design methods such as^ computer assisted design sof!
twares "CAD# coupled with mold _lling and solidi_cation
modeling computer programs^ improved foundry process con!
trol "automated pouring and inoculation methods\ thermal
analysis#^ reliable non!destructive inspection techniques "Eddy
current\ X!rays\ ultrasonic waves#\ D[I[ advantages can be
applied to more sophisticated and demanding applications such
as thin wall castings[ The unique combination of cost\ safety
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 256

Fig[ 20[ Relationship between Quality Index for Ductile Iron and ASTM speci_cation A425[
257 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Fig[ 21[ Dynamic stress intensity factors K0D for cast steel and ferritic Ductile Iron determined by a modi_ed charpy
test[
 Table 04[ ASTM and ASME speci_cations and typical applications for all types of Ductile Ni!Resist Irons

Chemical analysis and hardness

Min[ Min
Specifying Class or tensile yield ) Heat ) ) ) ) ) )
body Spec[ no[ grade psi psi elongation Treatment T[C[ Si Mn P Ni Cr BHN Typical applications

Min[ 0[49 9[69 07[99 0[64 028 Valve stem bushings\ valve and pump
bodies in petroleum\ salt water and caus!
tic service\ manifolds\ turbocharger
housings\ air compressor parts[
Max[ 2[99 2[99 0[14 9[97 11[99 1[64 191
DÐ1 47\999 29\999 7

C[ LABRECQUE\ M[ GAGNE
DÐ17 47\999 29\999 6 Min[ 0[49 9[69 07[99 1[64 037 Turbocharger housings\ rolls[
Max[ 2[99 2[99 0[14 9[97 11[99 3[99 100
D1ÐC 47\999 17\999 19 Min[ 0[99 0[79 10[99 010 Electrode guide rings\ steam turbine dub!
bing rings[
Max[ 1[89 2[99 1[39 9[97 13[99 9[49 060
DÐ2 44\999 29\999 5 Min[ 0[99 17[99 1[49 028 Turbocharger nozzles and housings\
steam turbine diaphragms\ gas com!
pressor di}users[
Max[ 1[59 1[79 0[99 9[97 21[99 2[49 191
ASTM A328!73 DÐ2A 44\999 29\999 09 Min[ 0[99 17[99 0[99 020 High temperature bearing rings requiring
resistance to galling[

ł] DUCTILE IRON
Max[ 1[59 1[79 0[99 9[97 21[99 0[49 082
DÐ3 59\999 Min[ 4[99 17[99 3[49 191 Diesel engine manifolds\ manifold joints[
Max[ 1[59 5[99 0[99 9[97 21[99 4[49 162
DÐ4 44\999 29\999 19 Min[ 0[99 23[99 020 Guidance system housings\ gas turbine
shroud rings\ glass rolls[
Max[ 1[39 1[79 0[99 9[97 25[99 9[09 074
DÐ47 44\999 29\999 5 Min[ 0[99 23[99 1[99 028 Optical system mirrors and parts for
dimensional stability\ stators for com!
pressors[
Max[ 1[39 1[79 0[99 9[97 25[99 2[99 082
DÐ4S 54\999 29\999 09 Min[ 3[89 23[99 0[64 020 Manifolds\ turbine housings\ turbo!
chargers where high temperatures and
severe thermal cycling occur[
Max[ 1[29 4[49 0[99 9[97 26[99 1[14 082
ASTM A460!60 Min[ 1[19 0[49 2[64 10[99 010 Compressors\ expanders pumps and
other pressure!containing parts requiring
a stable austenitic matrix at minus 312>F
"−123>C#[
ASME "0865# DÐ1M 54\999 29\999 29 Annealed Max[ 1[69 1[49 3[49 9[97 13[99 9[19 060
SA460

258
269 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Fig[ 22[ Relationship between endurance ratio\ tensile strength and matrix microstructure for Ductile Iron[

Fig[ 23[ E}ect of nodularity on fatigue strength reduction factor of pearlitic Ductile Iron[
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 260

Fig[ 24[ E}ect of nodule size and matrix microhardness on the fatigue limit of Ductile Iron[
261 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Fig[ 25[ E}ect of nodule count on the V!notched charpy impact properties of ferritic Ductile Iron[
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 262

Fig[ 26[ E}ect of matrix microhardness and volume fraction of inclusions on fatigue limit of Ductile Iron[
263 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Fig[ 27[ In~uence of silicon content on the V!noted charpy energy of ferritic Ductile Iron[ The higher the silicon
content\ the harder the ferrite[
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 264

Fig[ 28[ Comparisons of ADI gear characteristics with those of conventional Ductile Irons and steels[ "a# bending
fatigue strength "b# contact fatigue strength[
265 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON

Fig[ 28*continued[
 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON 266

Fig[ 39[ Microhardness scan of an abraded ADI sample[

and mechanical properties of the Ductile Iron family makes Conference on Rare Earths Development and Applications\ Beijing\
0245\ 0874[
these materials ready to enter the next century[
10[ Onsoin\ M[ I[\ Grong\ O[\ Skaland\ T[ and Olsen\ S[ O[\ 090st
Casting Congress\ AFS paper è86Ð049\ 0886[
11[ Lacaze\ J[\ Boudot\ A[\ Gerval\ V[\ Oquab\ D[ and Santos\ H[\
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267 C[ LABRECQUE\ M[ GAGNE
ł] DUCTILE IRON
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37[ Monroe\ R[ and Bates\ C[ E[\ AFS Trans\ 0871\ 89\ 296[
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43[ Lapointe\ J[ M[\ Rio Tinto Iron + Titanium\ personal communi!
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0884\ 16[
57[ Labrecque\ C[ and Gagne\ M[\ AFS Castin` Con`ress\ Atlanta\
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