Pin holes

Bubbles or cavities predominantly occurring at the outside of the casting or just below the
surface of flake, nodular or vermicular graphite cast iron, malleable cast iron, and cast steel
castings.

Pin holes occur individually and over a large area and can affect all casting sections. In many
cases they are not visible until after machining, but always with the naked eye.

The appearance of pin holes ranges from nodular bare metal bubbles or bubbles covered with
graphite skins to larger cavities of irregular shape accompanied by slags or oxidation
(Figures 1 to 6).

They are referred to as hydrogen pin holes and hydrogen-nitrogen pin holes, which cannot be
distinguished from each other, and as CO-slag pin holes. Specific properties of the iron, on
the one hand, and specific properties of the mold material system, on the other handare
known to be possible root causes of these defects. In practice, the formation of pin holes is
often not caused by an individual factor, but by the cumulative effect of several overlapping
factors. Pin holes can lead to Impairments in coatings such as enameling hot-dip galvanizing,
powder coatings etc. With respect to the structural load-bearing capacity, this defect has
hardly any influence, particularly in case of ductile cast iron types and low stress levels. With
machined functional surfaces which also have to be impervious, this defect leads to rejection.
Moreover, if the defect occurs in an unfavorable location, this will impair the fatigue
strength, and consequently pin holes cannot be tolerated in safety components subject to
fatigue loading.

The formation of hydrogen and hydrogen-nitrogen pin holes is a process in three stages:

1. Reaction of the water vapor with other elements in the iron. This leads to the formation of
metallic oxides and atomic hydrogen which diffuses into the liquid metal. Nitrogen-

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 hydrogen compounds are broken down in similar ways and can also diffuse into the liquid
metal.
2. Formation of micro gas bubbles due to reaction of the metallic oxides with the carbon of
the melt.
3. Diffusion of hydrogen and potentially nitrogen into the micro gas bubbles and size
increase of the bubbles.

These are the causes of pin hole formation from a metallurgic point of view:

Excessive hydrogen content in the melt which may be caused by hydrogen carriers such
as moisture of charge materials in general, in particular fine-grained, unprotected ferro-
alloys, which often accumulate water, highly rusty charge materials (accumulated OH
groups), oils and emulsions releasing hydrocarbons, and ultimately by the impact of an
increased humidity itself
Excessive nitrogen content in the melt which may be introduced by nitrogen carriers such
as scrap steel (up to 130ppm N, max. 200ppm N), rail steel (up to 170ppm N), pig iron
(10 to 60ppm N), carburization agents (from 0.11 x 104ppm to 1675 x 104ppm N)

The nitrogen content in the casting is within the range of 40 to 140ppm, thus making it
possible for degassing to occur in case of externally excited bubble formation, e.g. by
inductive stirring. The critical limit for the formation of pin holes is often indicated with 80 to
100ppm, although lower contents in connection with CO precipitations can already be
critical.

In comparison with cast steel, cast iron has a lower tendency to gas absorption as carbon and
silicon decrease the solubility and thus the readiness to absorb hydrogen and nitrogen.
Consequently, a cast iron melt with a lower degree of saturation is significantly more
sensitive, which is also reflected in the frequency of defects in malleable cast iron, which
naturally must have a lower degree of saturation

Chromium, molybdenum, manganese, vanadium, and titanium increase the solubility of

hydrogen and nitrogen whereas it is reduced by aluminum, phosphorous, silicone, and
carbon. An examination revealed that castings with the same gas content were completely
intact at 70ppm Al whereas the same castings with 380ppm Al revealed severe pin hole
formation. Increased aluminum contents can cause a transformation of the aluminum in the
iron with the water vapor of the mold gas to aluminum oxide and hydrogen. This hydrogen
then leads to bubble formation. This is where the line between purely metallurgically caused
gas bubbles and the interfacial reaction between mold (core) should be drawn.

Molding material-related causes:

Too high nitrogen contents in the mold sand with too high moisture contents.
Unfavorable gas atmosphere in the mold cavity the causes of which originate in the type
and amount of lustrous carbon formers added.
Too high nitrogen content in core sands and/or too high nitrogen-hydrogen compounds in
core mold material binders.
Particularly in the pyrolysis of Croning core binders, large amounts of gas are released at
the time where no stable marginal shell has formed yet.

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The mechanism is explained as follows:

Under reduced atmosphere, ammoniac breaks down according to the eq. 1

Eq. 1: 2NH3 N2 + 3H2

At approximately 600C and atmospheric pressure, the ammoniac is almost completely

dissociated. During this process, the gas volume is doubled, 2mol ammoniac transform into
1mol nitrogen and 3mol hydrogen. This hydrogen gas may also react with the separated
carbon monoxide according to the following eq. 2:

Eq. 2: CO + H2 H2O + C

Insufficient degree of conditioning of the bentonite-bound mold material and therefore

presence of free water, not bound in the bentonite (in the three-layer mineral
montmorillonite) which increases the risk of hydrogen formation.

In addition to the iron composition and the mold material structure, there are other factors for
the occurrence of pin holes. For example, incomplete removal of the slag can lead to slag
inclusions , which may act as nuclei for bubble formation. Numerous oxides are present in
nodular graphite cast iron, even if the slag has been removed, and these oxides can contribute
to the formation of pin holes. The slag produced during magnesium treatment also has an
impact, although it is not clear whether it purely mechanically causes a surface defect or
promotes gas formation.

The casting and gate technology can also have an impact on pin hole formation. A gate
system with non-turbulent flow and short runners reduce the tendency for pin holes to form.

Splash balls can also be a cause for pin holes. They are oxidized and then enveloped by the
casting flow. This can lead to a reaction where CO is produced which results in the formation
of gas bubbles.

Measures for prevention (acc. to S. Hasse, FT&E):

1. Reduce hydrogen carriers reduce, i.e. use dry charge materials, avoid highly rusty, oily
charge materials.
2. Reduce the nitrogen carriers (e.g. scrap steel) in the charge, for GJL, observe minimum
titanium content (0.02%), if applicable. Use recirculation material in blasted condition,
where possible.
3. If possible, increase degree of saturation, adjust manganese to maximum 0.4% Si, reduce
aluminum content (not ? 100ppm). In the presence of titanium, the negative effect of
aluminum is further reinforced, with Ti contents of 0.02% and Al contents from 0.01 to
0.2% increased pin hole formation occurrs.
4. Use material with reduced aluminum contents and ensure that casting temperatures are
adequately high. Low casting temperatures reinforce the tendency towards defects which
is considered an indicator that pin hole formation is caused by surface oxidation of the
melt during casting and solidification.
5. Change the gate system such that the melt is given few opportunities for oxidation,
shorten flow paths, avoid turbulences.

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6. In case of cast steel, keep the hydrogen content of the melt as low as possible by means of
intensive cooking during the refining period. Ensure thorough pre-deoxidation and short
casting times, avoid long flow paths.
7. Reduction of slag formation.
8. Reduce humidity content in the mold material, reduce quantity of core sand addition
(nitrogen, urea), refresh with new sand, if required.
9. Check the lustrous carbon content of the mold material and optimize, if required, change
lustrous carbon formers, if required.
10. Reduce binder quantity in resin-bonded molds and cores, if required or use other binder
and/or catalysts.
11. Face coat molds and cores (nitrogen-absorbing barrier face coatings), thoroughly dry
water face coatings, check and optimize vents.
12. Avoid inclusion of auxiliary riser materials into the mold material system.

Foundry Technologies & Engineering GmbH (FT&E)

Rheinweg 9, CH 8200 Schaffhausen, Schweiz
Phone: +41 52 620 10 56
Fax: +41 52 620 10 57
E-mail: info(at)fte-foundry.com
CEO: Dipl.-Ing. Dr. Stephan Hasse
registration office: GmbH, Kantonsgericht Schaffhausen
registrations number: CH-290.4.014.430-8
UID-number: CHE-110.126.519