INCLUSIONS AND PINHOLE FORMATION

IN DUCTILE IRON CASTING

 Gas defects can be caused by:
1. Rejection of gas during solidifications due to a decreased solubility of the gas in
the solid
2. Forcing of gas into the metal from high pressure areas of mold or core
3. Reactions in the metal
 Gas in hole can be described by the equation:

2
P( gas bubble)  P( metal head ) 
Where
r

P(gas bubble) is the pressure of the gas in the hole

P(metal head) is the pressure of the metal head

 Is the surface tension of liquid metal

r is the bubble radius of the gas
 Fracture Containing
Pinholes

Occurrence of Small
Spherical Holes Adjacent to
Core, Often Revealed
Immediately after Knockout

Close Up of Fracture
Showing Shiny Lining of the
Pinhole
Effect of Alloying Elements on the Solubility of Nitrogen in a Pure Iron
Solubility of Nitrogen at One Under a Nitrogen Partial Pressure of
Atmosphere Pressure in Liquid One Atmosphere
Binary Iron Alloys at 1600C
Fissure Defects Caused by Nitrogen Pinholes Caused by High-
High Nitrogen Content nitrogen Resin-bonded Cores. The Defects
Occur Where the Core Forming the Hub of
the Casting Meets the Greensand Mould
 PINHOLING IN CLAY-BONDED SANDS

 Location of pinhole defects suggests that the primary mechanism is related to mold-metal
interactions.

 Gases form as a result of direct chemical reaction between the metal and mold
constituents rather than from simple dissociation of water vapor.

 The most likely reactions are:

C + H2O  CO + 2 H
FeO + C  Fe + CO

 The FeO is present because of the reactions,

Fe + H2O  FeO + 2 H, and to a limited extent

Fe + ½ O2  FeO

 The presence of strong deoxidizer in the melt can increase the available hydrogen further
by such reactions as:

2 Al + 3 H2O  Al2O3 + 6 H
and
Mg + H2O  MgO + 2 H
Pinholes

may be categorized as:

evolution

reaction

aspiration

entrapped

Reaction Pinholes

 are either isolated or few in number

 slag or dross is always nearby

 are frequently located at a distance from ingates, but slag is still there

 the number greatly increases if much slag enters in the mold

Blowhole in nodular iron casting

Schematic of typical blowholes

Effect of Sulfur and Manganese Section Showing Manganese Section Showing Complex
Content on Occurrence of Sulfide Segregation and Slag Contained in Gas
Subsurface Gas Holes in Gray Slag Contained in Gas Holes. Mag. 100X, Unetched
Iron Castings Holes. Mag. 100X, Unetched
 REACTIVE SLAG FORMATION
 Reactive slag is a reoxidation product that form
when molten cast iron is cooled from melting
process temperature.

 Main constituents are:

SiO2, MnO and FeO

Gray iron low in Mg and Al

 Typical slag formation temperature on cooling

is 1400C (depending on Si-contents).

 Temperatures in the figure refer to the

beginning of selective Si oxidation on cooling
which initiates siliceous slag formation.

 Above this temperature, C is preferentially

oxidized rather than Si.

 The oxidation of Si to a slag particle is Equilibrium Temperature of Silica Reduction

or Silicon Reoxidation as Related to %C and
associated with entry into the SiO 2-FeO %Si. Reoxidation of Silicon and Initial
system, in which FeO becomes a dominant Silicate Slag Formation can Begin on
part of the slag composition as temperature Cooling Below the Indicated Temperature
decreases. When Oxygen is Present

 Fayalite, Fe2SiO4 is an increasing portion of the

siliceous slag as FeO increases in cast iron.
 REACTIVE SLAG FORMATION (Cont’d.)

 If reoxidation continues on a falling temperature, the FeO-content of slag could reach 60-90%.

 Because iron is over 95% of the cast iron composition, Fe oxidizes more readily as temperature
decreases, there is a continuing increase in % FeO in the slag during the temperature regime from
pouring to solidification.

 The FeO in the slag provides the pinhole reaction:

FeO + C  Fe + CO (g)
 SLAG ANALYSIS

 The range of oxide percentages in slag can be expected over the

range of temperature from initial film formation downward (from
1470C to below 1280C).

 Over this range, MgO, Al2O3, SiO2, MnO and FeO would be the order
of reoxidation during cooling, based on thermodynamic considerations
alone.

 The formation of FeO would increase throughout the decreasing

temperature range because Fe is the principal element present, is
oxidizable throughout the temperature range, and more reactive as
temperature decreases.

 The highest FeO slag, ~90% FeO, appears in the slag stringers.
 MECHANISM OF SLAG BLOWHOLE FORMATION

 The entrapment of slag in the molten iron during pouring is a key factor in the formation of
blowholes in ductile iron castings.

 The reactions that are operative in the generation of blowhole porosity:

SiO2 + 2 C Si + 2 CO

MnO + C Mn + CO

FeO + C Fe + CO

 Kinetics of the reaction appear to be controlled by the physical nature of the slag

 Both temperature and composition are important in achieving a fluid slag, which can wet
the graphite that forms on solidification.

 Slag fluidity increases with the increase of MnS in its composition:

FeS + Mn MnS + Fe
Lower Temp.
 FORMATION OF PINHOLES

 The gas producing reactions, forming pinholes is:

FeO + C  Fe + CO(g) + Fe

FeO will also reaction with Si at any temperature, leading to an FeO-rich siliceous slag,
according to the reactions:

FeO + Si  SiO2(s) + Fe

and FeO + SiO2  Fe2SiO4 (Fayalite)

 The proportions of FeO and SiO2 and SiO2 can vary considerably, depending on oxidizing
potential during the cooling period and time spent in the temperature regime.

 The temperature regime covered during pouring and solidification permits all the
reoxidizing reactions to occur. They are all more spontaneous as temperature falls, but
still dependent on the concentration of elements and oxidizing agents present.

 Since Fe is the principal element present, FeO forms most readily through mass action
effects. On a gross scale, this same slag may produce blowholes in ductile iron castings.
 SLAG DEFECTS IN DUCTILE IRON

 Magnesium and other deoxidizers can alter the course of slag

formation.

 With Mg in ductile iron, the slag initiation temperature may be raised.

 The principle effect of Mg is to raise the temperature at which

reoxidation begins the slag formation process on melt surface.

 Slag composition moves in the same direction as on gray irons, as the

Mg is gradually oxidized from the melt.

 Formation of this slag in furnace and ladles, in gating systems and

mold cavities leads to its appearance on casting surfaces.

 Reaction pinholes accompany this process and casting dross defects

become evident.
 EFFECT OF Al-CONTENT

 Presence of Al in the range of 0.015-0.20% promotes hydrogen pinholing in gray

iron due to increased probability of reactions producing nascent hydrogen for
dissolution in the iron.

 In ductile iron, significant amounts of Al are often present due to additions of

spheroidizers and inoculants. Nevertheless, the presence of Al does not always
produce pinholing.

 The effect of similar amounts of Al on pinhole formation in gray and ductile irons
is significantly different

 may be associated with the presence of Mg

 both Al and Mg are strong oxide formers

- combine with dissolved oxygen or reduce less stable oxides

- formation of significant amounts of CO is unlikely and gas bubble

nucleation becomes less probable
 EFFECT OF Al-CONTENT (Cont’d.)

 Al has a significant value in elimination of nitrogen-type pinholing by forming

stable nitrides and effectively lowering the amount of atomic nitrogen in liquid
metal:

Al + N  Al N

 Late Al additions are preferable as early additions may lead to:

 Oxidation of Al

 Al2O3 may even promote pinholing by furnishing substrate particles for

nucleation of bubbles
 EFFECT OF Al-CONTENT (Cont’d.)

 Effectiveness of large amounts of

Al in limiting pinholing is explained
as a diffusion-barrier phenomenon
at the mold-metal interface:

• Limits hydrogen pickup

• Formation of Al2O3 with

dissolved oxygen

 Dependence of pinhole formation

on Al-content in both gray- and
ductile irons has been explained
in the light of the influence of Al-
content on the surface tension of
molten iron.

 The relative change in ductile iron

is less because the influence that
Al exerts on surface tension
containing Mg is lower-Mg already
both O2 and S and the increase in
surface tension from higher Al-
content is less.
 EFFECT OF Mg-TREATMENT ON PINHOLING

 Much contradiction is noticed in the

literature – may be due to:

 Mg-additions up to 0.1%
increase the amount of
hydrogen pickup from green
sand, but in the same time:

 Mg increases the surface

tension of molten iron which
would decrease the probability
of pinholing.

 Reduction of pinholing at high

Mg levels has been explained
by the formation of a diffusion
barrier of MgO

 Mg-vapor in the form of

bubbles may exert a flushing
action on both N- and H-
contents in the molten iron.
 EFFECT OF Mg-TREATMENT ON PINHOLING (Cont’d.)

 The relative effect of surface tension

on the threshold value for pinholes
to form in ductile, gray and white
irons may also affect the formation
of pinholes:

 For ductile iron, the increase

hydrogen pickup and/or more
favorable nucleating conditions may
enhance pinholing even at higher
surface tension values.

 In white iron, the lower threshold

value of surface tension at which
pinhole occur indicatives:

 Lower hydrogen pickup and/or

 Less favorable nucleating

conditions due to more rapid
solidification rate
Flowchart of Sources and
Compositions of Dross
Produced in Nodular Iron
 Schematic of the Classification of Ladle Dross
(Oxygen in these reactions should also be in the gaseous form, reaction 4 is highly
importable)
REACTIONS TREATED EXPERIMENTALLY:

Sequential Reactions which may be Take Place in the Mg-Si-O System

 ROLE OF MAGNESIUM AND POURING TEMPERATURE

 High magnesium content with

low pouring temperature
drastically increase the
pinholes.

 It is best to keep pouring

temperatures high and Mg-
levels low to minimize the
reactive pinhole type.
 OTHER PROCESS VARIABLES

Base Si-content

 Increasing the base Si-content to over 1.5% reduces the magnitude and
frequency of the high percent defect periods.

 Low % Si greatly increases reoxidation to FeO in the metal handing system

and, thus, produces more of the fluid reactive slag and subsequent
pinholes defects.

Carbon Equivalent

 At flotation carbon equivalent CE, the iron precipitates its excess of oxides
along with C, slag initiation, dross formation and reoxidation occur as a
result.

 The dross or slag material was found to contain significant amounts of

forsterite, enstatite the dross of the bulk slag and fayalite (the pinhole
reactive slag).
Superheating and Pouring Temperature

 Both low and high pouring temperatures have been reported as increasing
pinholing.

 Increasing superheating temperature over about 1480C is usually

accompanied by more extended reoxidation temperatures and time during
pouring and the associated reoxidation slags.

Casting Configuration and Gating

 Mold cavity geometry can provide locations where slag in the iron can
accumulate.

 Horizontal sections that fill slowly are particularly subject to reactive slag
pooling and pinhole or gas hole formation.

 Turbulent gating systems, which aspirate air and mold moisture add to
these reoxidation slag accumulations.
Mold Filling Simulation Showing Considerable Turbulence at Locations Identical with the
Pinhole Formations
Effect of Pouring Temperature

 It is difficult to state that an increase or decrease in pouring

temperature will promote pinholing. The effect will vary
depending on the section size and resultant solidification rate.

 Proper combined conditions of gas pickup and solidification

rate must be present for pinholes to form.

 Higher pouring temperature: favors gas pickup in green sand,

but also promote slow solidification rates that permit the gases
to escape more readily.

 Lower pouring temperature: result in less gas pickup and less

evolved gas, but more rapid solidification rates can trap more
gas near the surface before diffusion towards the casting
interior or escape from the mold.
Corrective Action

 Prevent slag from entering the mold cavity

 Constantly monitor the critical areas for slag formation

 Proper gating and runner design can be extremely effective

 Avoid pouring cold metal

 Monitor Mn and S-contents in iron

 PROCESS PRECAUSTIONS

 Metallurgical processing to produce optimum quality iron must occur within

the limits of the chemical principles described in the preceding
discussions. To minimize adverse effects of oxidation, important practices
can be observed:

 Charge Materials: Quality charge materials produce the best results,

but may be more costly. Minimum surface rust and dirt is preferred,
especially on thin scrap materials. Oxidized iron is a term long used
by foundrymen to describe iron that causes unexpected casting
results, such as excessive chill, carbides, gas holes, pinholes, metal
penetration, unusual shrinkage, slag defects and others. Research
attempts to relate these problems to iron oxygen contents are still
going on.

 Temperature-time Cycle of Processing: Temperatures in excess of

1500C extended melting, holding and pouring times promote more
dissolved oxygen, total oxygen, and oxidation and reoxidation slags.
Molding iron below 1400C on a falling temperature should be better
avoided.
 PROCESS PRECAUSTIONS
(Cont’d.)

 Casting Geometry and Gating: Mold cavity geometry has been shown
to provide considerable turbulence inside the mold at locations almost
identical with the formation of the detected dross inclusions and the
resulted pinholing defects. As it seems that there is little to do with the
gating system and casting geometry, the use of ceramic filters may be
considered. Use of filters will not only help in retaining any dross
formations coming with the poured molten metal, but also will
decrease any turbulence dictated by the casting configuration and/or
gating system. Filters usually promote laminar flow. The type,
porosity, dimensions of the filter as well as its location inside the
gating system should be discussed in close collaboration with the
filter supplier.