Porosity Defects in Gray and Ductile Iron Castings

from Mold Metal Interface Reactions

by Dr. R. L. (Rod) Naro, ASI International, Inc.

October 21, 2000

Introduction: Surface and subsurface gas defects have always been

common and troublesome defects in gray and ductile iron castings poured in
green sand molds. During the past 30 years, innovations in synthetic binder
technology have resulted in movement away from green sand molding and
toward total no-bake molding and core making processes and accompanying
new types of casting defects. In the year 2000, it is estimated that phenolic
urethane binders, in both the cold box and no bake versions, will account for
over 60% of all chemical binders used by the U.S. foundry industry. Although
millions of tons of gray and ductile iron castings are cast using these resins for
both core and mold binders, casting defects stemming from mold-metal
reactions continue to pose problems for foundry men.
Generally speaking, there are three major sources that may contribute to
porosity formation in gray iron castings. These are: 1) high initial gas content of
the melt originating from either the charge ingredients, melting practice or
atmospheric humidity, 2) reaction of carbon and dissolved oxygen under certain
melt conditions, and 3) mold-metal reactions between evolved mold and core
gases at the solidifying casting surface.1-16 In addition, any combination of
these three sources may have a cumulative effect on promoting porosity
formation. However, the gases normally held responsible for subsurface
porosity defects are nitrogen and hydrogen.
The appearance of the subsurface porosity defects resulting from the preceding
sources may take numerous shapes but usually form as either small, spherical
holes (sometimes elongated or pear- shaped) and called pinholes, or larger,
irregularly rounded holes or irregularly shaped fissure type defects.1,8,13,15,16
The internal surfaces of the resultant holes may be 1) oxidized, 2) lined with a
shiny graphite film, or 3) contain slag or manganese sulfide inclusions.1, 5, 8
The phenolic urethane resin system consists of no-bake and gas cured resins;
both systems consisting of two resin components. Part I is a phenolic resin
(poly-benzylic-ether-phenolic resin) diluted approximately 50% by solvents. Part
II is a polymeric di-isocyanate resin diluted with approximately 25% solvents.
The solvent can be either aliphatic and aromatic in composition. The primary
purpose of the solvents is to reduce binder viscosity. Typically, the viscosity of
the Part I and Part II resins are adjusted to 200 cps or lower to provide good
pump ability, rapid and efficient sand coating qualities and good flow ability of
mixed sand. A second purpose of the solvents is to enhance resin reactivity. An
amine-based catalyst is used as the curing agent for the no-bake binder while a
gaseous amine (triethylamine or dimethylethyl amine) is used for the gas-cured
binder.
The general chemistry of phenolic urethane binders remains essentially the
same as when the binders were developed in the late 1960 to early 1970's.
There have been some changes in basic resin formulations involving the
solvent systems as well as base phenolic resin system. The Part I phenolic
resin has been modified to reduce odor by reduction in the level of free
formaldehyde, and this becomes especially apparent when hot foundry sands
are used. In addition, because of efforts to reduce solvent evaporation into the
atmosphere, the solvent system has been modified extensively to incorporate
higher boiling point solvents or new solvents systems having improved
environmental properties.
Being organic based systems, the phenolic-urethane family of binders are
composed of only four basic elements: 72% carbon (C), 8.5% hydrogen (H),
3.9% nitrogen (N) and 15.5% oxygen (O).
With phenolic urethane systems, the nitrogen component is associated solely
with the polyphenyl polyisocyanate (Part II) binder component. Part I, or the
hydroxyl containing phenolic binder component, contains no nitrogen. The
gases typically responsible for subsurface porosity in iron castings are nitrogen
and hydrogen; carbon and oxygen from binder decomposition usually present
no problem because the high silicon content of gray iron acts to suppress the
formation of carbon monoxide porosity.
Hydrogen, nitrogen, oxygen and carbon, may react or combine in numerous ways to provide the
necessary conditions that favor porosity formation. The following gaseous reactions are
thermodynamically possible and under the right conditions may occur at the mold-metal
interface:

Binder ----------- > H (nascent) -> H2 (g)

Binder ----------- > N (nascent) ---> N2 (g)
Fe + H2O vapor (binder) --------> FeO + 2H (nascent)
3 H2 (binder ) + N2 (binder) > 2NH3(g) -------->
6H(nascent) + 2N(nascent)
FeO + C (binder) ---------> CO (g) + Fe

While the first four reactions are likely to provide both surface and subsurface
porosity defects, the last reaction usually results only in surface defects, such
as pock marking or more frequently, lustrous carbon laps and surface
wrinkles17. When an organic binder thermally degrades, hydrogen and nitrogen
are liberated in the nascent or atomic form. In this mono-atomic state, they are
readily soluble in molten iron, and if present, dissolve quite easily in both molten
gray and ductile irons. If ammonia forms, it also may dissociate into both
nascent hydrogen and nitrogen. Since the solubility of hydrogen and nitrogen in
liquid iron is far greater than in solid iron, these gases will precipitate out of
solution as gas bubbles during solidification if they are present in amounts
greater than the solid solubility limits. The shapes of the resulting gas holes may
vary from small, widely dispersed spherical shaped holes lying just under the
surface to numerous fissure type holes, often resembling shrinkage defects and
are usually perpendicular to the casting surface. In either case, absorption of
nitrogen and\or hydrogen by the molten iron, either individually or jointly, may
result in subsurface porosity defects.
Clearly, many factors are involved in the development of binder-associated
defects; neither they nor the various core making parameters and foundry
melting variables that have a direct influence on the occurrence of such defects
were well understood in the early 1970's. Recognizing this situation, the object
of this investigation was aimed at determining how such variables influence the
occurrence of porosity defects. Also, the development of remedial techniques to
alleviate these problems was also extensively studied.

Experimental Procedure
The experimental program used in this investigation was divided into two
phases. The first phase was devoted to 1.) the development of a suitable test
having the capability to produce porosity defects and 2.) the delineation of core
making and metal processing variables having an effect on porosity generation.
The cylindrical test casting shown in Figure 1 was developed for these tests to
observe the extent of porosity formation under various test conditions. This
"stepped cone" configuration was selected because its design was such that
core decomposition gases would be generated rapidly while the casting was still
in the molten state. Also, this design easily lent itself to the study of section size,
re-entrant angle (hot spot) and other geometric effects (see Figure 2).
The majority of molds used for the production of test castings were made with a
zero nitrogen no-bake furan binder. The base core sand mix used for most of
the experimental work consisted of the phenolic urethane no-bake binder (PUN)
mixed with a high purity, washed and dried, round grained, silica (W/D) sand.
The core making procedure used throughout most of this work consisted of
adding the phenolic polyol resin component (Part I) and the catalyst to the sand
and mixing for two minutes, followed by the addition of the polyisocyanate
component (Part II) and mixing for an additional two minutes. The mix was
immediately hand rammed into the core box and the stepped cone cores were
stripped within five minutes.
Gray and ductile irons of the compositions shown in Table I were utilized in the
investigation, although the bulk of the experimental work was conducted with a
high carbon equivalent iron (4.3 C.E) inoculated with standard foundry grade
(0.75% minimum calcium) ferrosilicon in the ladle. Inoculant addition levels were
0.25% silicon, based on the pouring weight.
All heats were prepared with virgin charge materials to insure low initial gas
content and were poured at selected temperatures as measured with a Pt-Pt
10% Rd immersion pyrometer and a high speed, strip chart recorder. Variables
studied during this phase of the investigation included binder ratio, binder level,
pouring temperature, sand type and permeability, mixing effects, metal
composition and core age. Within each series of tests, the conditions were
controlled as carefully as possible and individual variables altered to determine
their effect on porosity.
The second phase of the experimental work was devoted to developing
remedial techniques to prevent porosity. To a great extent, this effort was very
dependent upon the first phase of the work in that conditions that were found to
promote porosity were used exclusively. Therefore, it was a prerequisite to
develop the capability to produce binder-associated gas defects at will. The
same melting and core making procedures previously described were likewise
used at this time. Techniques studied in attempt to eliminate defects included
1.) Investigation of various grades of iron oxide, 2.) Ladle additions of
ferrotitanium, as well as titanium and zirconium based ferroalloy inoculants, 3.)
Use of core sand additives, 4.) Core baking, and lastly, 5.) A study of
experimental core coatings. During this phase of the work, variables found
responsible for porosity formation were held constant during the preparation of
test castings.
The extent of porosity formation in all castings was determined by careful
sectioning at several locations. To determine whether any metallurgical
changes resulting from porosity formation had occurred, metallographic
investigations of the cast structure in the mold-metal interface area were also
carried out. To observe the nature of the internal surfaces of gas porosity
defects, a scanning electron microscope was utilized.

Results

Parameters Affecting Formation of Binder Related Porosity Defects

It is of great importance to the foundry man to fully understand the nature of and
fundamental chemistry of no-bake binder systems in order to assure their
correct usage. This is particularly true with phenolic urethane no-bake (PUN)
systems. Generally, any one of a number of minor operating variables can exert
a cumulative effect on the performance of no-bake binders. Some of these
factors which contribute to binder misuse are: 1) infrequent calibration of binder
pumps and sand flow rates on continuous mixers, 2) general equipment
malfunctions related to binder pumps, worn mixer auger screws or blades, poor
housekeeping practice, etc, 3) intentional unbalancing of binder components to
facilitate stripping, or 4) general misunderstanding of possible potential
consequences resulting from any of the preceding. To determine how these
effects and other variables may affect porosity formation, numerous
experimental heats were poured to study their effect on casting integrity.

Effect of Binder Part I to Part II ratio -- The effect of the ratio of Part I to Part
II resin components for PUN binders on porosity propensity is shown in Table 2.

Binder ratios of 60 : 40 (Part I : Part II) provided sound test castings in every
case under the test conditions used. As this ratio became balanced (50 : 50),
trace amounts of porosity were found in a few test castings but the majority of
test castings made with balanced ratios were sound. In those cases where
porosity was found, a substantial portion was as surface porosity or semi-
rounded holes (pock marking). As the binder ratio was unbalanced again in
favor of excess Part II (40 : 60 and 35 : 65), greater amounts of subsurface
porosity formed in the test casting. The types of defects observed and
described as varying in intensity from nil to very severe are shown in Figure 3.
Although the recommended ratio for running PUN binders varies between a
55:45 to 60:40 ratio, in actual practice, extreme ratios favoring excess Part II or
polyisocyanate are often encountered. Such problems often arise from worn or
defective binder pumps, air in binder lines, changes in binder viscosity from
temperature, inefficient mixing, and numerous other less incidental, but often
overlooked sources. For example, in the early 1970's, it was not unusual to
foundries to run binder ratios favoring excess polyisocyanates to facilitate the
stripping of difficult cores or to increase fully cured core strengths.
New resin formulations (1998 versions) showed very little difference in casting
performance compared to early 1970 versions. Binder ratios in which
unbalanced ratios of 60 : 40 were employed produced sound castings.
Unbalanced binder ratios favoring excess Part II or the isocyanate component
once again were very susceptible to severe subsurface porosity.
Effect of Binder Level -- To determine the effect of binder level on porosity
susceptibility, test castings were poured with test cores made with binder levels
ranging from 1.25% to an extreme of 3.0%. At some of these levels, the ratio of
Pt I: Pt II was again varied to determine effect on porosity formation. (It should
also be noted that although these higher levels may never be encountered in
actual practice, they were intentionally selected to magnify the effect of binder
level or the effect of reclaimed sands having high "LOI" values.) The results
obtained from these tests showed that as the binder level increased at the same
Pt I : Pt II ratio, the severity of the porosity defects likewise increased. At the
highest binder level tested, porosity tended to form at even balanced ratios as
shown in Table 3.
These results show that if sufficient amounts of evolved hydrogen and / or
nitrogen decomposition gases are made available to the solidifying irons,
porosity will generally occur even with favorable binder ratios and using
relatively high pouring temperatures. These same phenomena can be
extrapolated to include what the consequences will be when using reclaimed
core or molding sands having high loss on ignition values. Excessive amounts
of dissolved gases stemming from inappropriate charge materials or liquid metal
processing will likewise be more susceptible to core gas defects from
absorption of hydrogen and / or nitrogen.

Effect of Casting Temperature -- Although the previously reported results

have shown significant effects of both binder ratio and level on porosity
formation, their effect was very temperature dependent. Results obtained from
test castings poured at several casting temperatures and incorporating
unbalanced binder component ratios favoring excess Part II are shown in Table
4.
These results demonstrate the temperature dependency of porosity formation
with PUN binders. Pouring temperatures of 2700oF and higher (as measured in
the pouring ladle) produce severe subsurface defects when unbalanced ratios
are used. Such pronounced behavior is not observed when these ratios are
balanced or when excess Part I is used. Reducing the pouring temperature at
both binder levels resulted in lesser amounts of porosity until at the lowest
temperature sound castings were achieved.
Pouring temperature effects were further demonstrated by pouring experimental
test step cores that were coated with the polyisocyanate binder component
(Part II). For these tests, pouring temperatures of 2500oF were employed and
test cores were bonded with an unbalanced (35:65 ratio) binder system
containing 3.0% total resin. Sectioned test castings obtained under these
conditions were entirely sound.
The porosity-temperature dependency can best be illustrated in Figure 4. In this
figure, pouring temperature is plotted against binder ratio. It is interesting to
note that there appears to be a definite region in which porosity seems to form
and also another definite region where sound castings are obtained. In between
these two areas, porosity may or may not occur depending on other liquid metal
processing factors. Similar findings on the effect of pouring temperature with
other binder systems have been reported by other investigators.4, 16
Effect of Section Size -- In those castings containing porosity, it occurred in
preferential locations. Deep seated, subsurface porosity was usually located
adjacent to the 90o re-entrant angle or "step" and most often occurred in
section thickness' ranging between 7/8 in. and 1-3/8 in. These locations act as
localized hot spots since a small volume of the core is heated from both sides
by the solidifying iron. In thinner sections, varying degrees of surface porosity or
pock marking were often found. From the appearance of these defects, it
appears probable that they were formed late in the solidification process by
gaseous decomposition products pushing away the semi-skinned over casting
surface.17 Since these bubbles are formed late in the solidification process at
the mold-metal interface, not enough time was available for their dissolution.
Consequently, a depression is left in the surface when final solidification
commences. The extent of this surface porosity varied between somewhat
large, semi-rounded holes extending at most only 1/8 in. into the surface to very
small surface pores having no appreciable depth.

Sand Effects -- The type of sand used in experimental test cores had a
significant effect on porosity formation. Some results obtained with typical lake
sand and washed and dried silica sand are listed in Table 5.
Although several castings were poured under identical conditions and also from
the same ladle, severe subsurface porosity was very prevalent with washed and
dried silica sand while castings made with the Michigan lake sand were entirely
sound. The behavior of lake sand in eliminating gas defects may possibly be
attributed to either its significantly larger quantity of surface impurities, bulk
impurities or greater permeability.
To determine the effect of surface purity on influencing gas porosity, an acid
treatment was administered to the lake sand to remove trace surface impurities.
The acid treatment consisted of soaking the sand in a 10% solution of sulfuric
acid for 24 hours followed by a 24-hour water wash and drying. Such treatments
have been shown to be very effective in removing these impurities.18
Comparisons of casting results obtained with acid-treated versus untreated
Lake Sands are shown in Table 6. The results in Table 6 showed that removal
of surface impurities by acid leaching was not effective in promoting porosity
and no porosity was observed in the test castings.
Because of the known effect of permeability on porosity defects and the
potential chemical effect of sand type, several other sands having a wide range
of compositions, permeabilities and AFS grain fineness distributions were
selected for testing. These tests were run to determine relative porosity
susceptibilities of common core and molding sands. The results of casting tests
all run under identical conditions along with the physical properties and resultant
porosity sensitivities are summarized in Tables 7 and 8.
Based on the preceding, even though the sands tested had a wide range of
AFS grain fineness and permeabilities, there doesn't appear to be any
correlation between these parameters and porosity sensitivity. The trend in
Tables 7 and 8 is such that the lower the impurity level, and particularly the iron
oxide content of the sand, the greater the sensitivity of the system for promotion
of porosity defects. Hence, although very pure, round grained sands offer
outstanding core and mold making properties, they may not produce the best
castings, as less impure sands seem to do.
The intentional addition of impurities such as iron oxide to sand mixes is widely
recognized as an effective means of controlling porosity, veining, improving hot
strength and other less incidental properties. However, the presence of such a
small amount of iron oxide as a bulk impurity associated with the sand
mineralogy appears to have a significant effect on retarding or inhibiting porosity
formation. In addition, the type and purity of iron oxide will be shown to have an
overriding effect on porosity formation.

Binder Dispersion or Mixing Effects -- Proper dispersion of the liquid binder

components on sand surfaces is a necessary prerequisite in the production of
high quality cores and molds. Mixers which were prevalent in the early to mid
1970's often provided relatively poor blending of binders and subsequent
coating of sand grain surfaces. This was especially true of slow speed screw or
auger types, which left something to be desired where high mixing efficiency is
desired. Also, if the screw blades or paddles and trough are not cleaned
regularly to remove resin buildup, are poorly designed or wide clearances exist
due to wear, then poor mixing action will result. If proper dispersion of the
binder components is not realized, many areas of the core surface will
essentially contain varying ratios of binder components even though the bulk
core may contain the proper total amount of each component. Although high
speed, high efficiency sand mixers along with advanced resin metering
systems, often with computerized controls, have been developed in the 1990's
and have resulted in dramatically improved mixing, consideration must still be
given to properly maintaining the equipment.
To determine the effect of proper binder dispersion on mixing efficiency, several
core mixes were made in a laboratory high intensity batch mixer and mixed for
various times to simulate mixing conditions ranging from very poor to excellent.
Experimental test cores were made using mixing times of 5, 10, 20, 30 and 60
seconds for each component (double for actual total mix cycle). All of these
cores were prepared with balanced ratios of Pt. I : Pt. II (50 : 50) on the
standard washed and dried silica sand. Cores prepared with total mixing times
of 10, 20 and 30 seconds exhibited pronounced non-uniform binder dispersion
and were spotty in appearance. This was found to be most pronounced with the
10 and 20 second mix cycles. Longer mixing times of 80, 120, and 240 seconds
provided very uniform results. Physical properties such as scratch and tensile
strengths of mixes mixed for total times of 40 seconds and longer were not
impaired even though traces of inadequate mixing were apparent on the 40-
second mix.
The results obtained from casting tests using test cores prepared in the
described manner are listed in Table 9.
To briefly summarize these results, short mix cycles of 10 to 40 seconds total
time tended to promote the formation of both surface and subsurface porosity.
Only trace amounts of subsurface porosity, probably better described as
microporosity, were found in the remaining castings made with cores mixed for
intermediate times of 60 to 80 seconds total. In castings containing pronounced
defects, these defects were obviously formed where the solidifying casting was
in contact with binder-rich areas and particularly those containing excess
polyisocyanate. Sound castings were obtained when total mixing times ranged
from 2 to 4 minutes.
Effect of Metal Composition -- The type and composition of the castings poured
had a significant effect on porosity formation. Results of these tests are shown
in Table 10.
The porosity forming tendencies seemed to be greatest for the low carbon
equivalent iron and least for ductile iron. Porosity defects in all gray iron
castings formed readily when unbalanced binder ratios favoring excess
polyisocyanate were employed. Porosity defects that formed in low carbon
equivalent irons were predominantly fissure type defects, although some
rounded and irregularly shaped holes also formed. Ductile iron castings seemed
to be far less susceptible to defect formation than either composition of gray
iron. Results obtained with a high carbon equivalent iron as used throughout
this investigation have been previously reported and remain unchanged.
Although it is commonly accepted 1,19 that ductile iron is more susceptible to
porosity defects, the present investigation tends to show just the opposite.
However, most of these previous findings or observations have been with
ductile irons containing appreciable amounts of aluminum and poured in green
sand molds. 8,15 It is also generally held that ductile irons are more prone to
hydrogen defects arising from interactions with water vapor and magnesium.
This is probably related to the fact that the residual magnesium is influencing
hydrogen solubility 15,20,21 or is assisting the reduction of water vapor.
However, Dawson and Smith also showed that although high residual
magnesium contents increased hydrogen solubility in ductile iron castings
poured in green sand molds, pinholes still did not form.20 Since the chemistry
and gaseous thermal decomposition products for PUN binders are obviously
more complex than those interactions with green sand molds, the performance
of ductile iron with these binders may in actuality differ considerably. However,
one would expect porosity formation in ductile irons to be much more difficult
due to the higher melt interfacial surface energy. Other investigators have also
reported a relationship between porosity and surface tension in ductile irons.
9,22,23 Lastly, the bubbling of magnesium vapor through the metal during the
nodularizing process effectively purges most dissolved gases from the metal,
allowing for possible absorption of core gases without super saturation. 23, 24

Effect of Core Age -- The effect of test core age within the first 24 hours after
strip had no effect on porosity formation. Test castings poured with cores used
immediately after strip or after overnight aging performed in a similar manner.
Results obtained from aging tests poured at three pouring temperatures are
listed in Table 11.
If test cores made with unbalanced systems were aged over several days under
ambient conditions, the severity of the defects increased slightly. This
phenomenon appears to be related to moisture from atmospheric humidity
combining with unreacted NCO groups in the polyisocyanate and forming urea
structures. 25,26 The porosity forming tendencies of this latter group of
substances is well known.1,2,8 They are reported to readily break down into
ammonia derivatives at high temperatures that later dissociate into nascent
hydrogen and nitrogen,1,27 both of which are highly soluble and dissolve very
readily in molten irons.
Elimination of Porosity Defects
Numerous methods, both metallurgical and chemical, were investigated as
potential remedial techniques to eliminate defects in castings poured under
somewhat adverse conditions. Most of these techniques were straightforward in
approach; however, those techniques that may have resulted in reduced melt
quality, such as trace element additions of tellurium, selenium or bismuth, were
not examined in the original research work since it was felt that these methods
would not be very feasible. Any potential gains in porosity elimination may have
been overshadowed by chilling and/or poor metal quality. New techniques
incorporating the use of proprietary inoculants containing carefully controlled
additions of surface active elements as well as elements that neutralize nitrogen
(by forming stable nitride compounds) were examined and are reported herein.

Effect of Titanium and Zirconium Additions -- Additions of titanium have long

been recognized as helpful additives in reducing subsurface porosity defects
related to nitrogen.1,3 To determine if such additions were effective in
controlling porosity in test castings poured with PUN test cores, varying levels of
70% ferrotitanium (20 mesh x down) were added in the ladle prior to pouring.
Besides using 70% FeTi, two commercial gray iron inoculants containing
titanium were also examined. The effect of zirconium on porosity reduction was
evaluated by adding 0.05% zirconium as ferrosilicon zirconium as well as
incorporating zirconium into a high potency proprietary inoculant. The casting
results obtained from these tests are listed in Table 12.
In almost all cases, the addition of small amounts of titanium as a ladle addition
was effective in eliminating subsurface porosity in castings made with cores
bonded with excessive Part II polyisocyanate levels. In the case of 70%
ferrotitanium additions, titanium additions of 0.05% were effective in removing
subsurface porosity defects, a considerable amount of surface porosity or small
pores remained.
Since it is well known that 70% ferrotitanium may be difficult to dissolve at
temperatures below 2,700oF, resulting in erratic recoveries and results, two
proprietary titanium containing gray iron inoculants were also investigated.
Proprietary Inoculant A was effective in eliminating porosity when the titanium
addition level was 0.03%. Inoculant B is based on 75% ferrosilicon, and since
inoculants based on 75% FeSi dissolve more rapidly than those based on 50%
FeSi 28 , Inoculant B appeared to be more effective at somewhat lower titanium
addition rates.29 No porosity was found when titanium addition levels of 0.025%
were employed with Inoculant B. Ferrosilicon zirconium was almost as effective
in eliminating porosity but somewhat higher levels of 0.05% zirconium had to be
added. This was not unexpected because of the higher atomic weight of
zirconium. Inoculant C is a potent proprietary gray and ductile iron inoculant30
containing 30 to 33% oxy-sulfide forming elements that was modified by the
addition of 9.0% zirconium ( in the form of ferrosilicon zirconium). With
zirconium additions of 0.025%, trace to no subsurface porosity was found.
Since zirconium forms much more stable nitrides than titanium, more zirconium
must be added because of its higher atomic weight. Hence, it is likely that
higher levels of zirconium need to be added to Inoculant C for complete porosity
elimination. Although Inoculant C did not entirely eliminate porosity, it was the
most effective of the three inoculants tested in reducing chill and produced the
most uniform microstructure, consisting of 100% Type A graphite flakes.
Metallographic inspection of the castings made with 70% ferrotitanium showed
that higher addition rates of titanium (0.05% and greater) were effective in tying
up nitrogen as titanium compounds (TICN or TiN) and preventing re-
precipitation as gas holes during solidification. Similar results were observed
with the proprietary inoculants. The ferrotitanium additions were not, however,
effective in preventing surface reactions associated with lustrous carbon pock
marking reactions from the high pouring temperatures employed during this
phase of the investigation. The proprietary inoculants also showed some signs
of lustrous carbon related surface porosity.

Effect of Zirconium and Selenium Inmold Additions -- Addition of selenium

to stainless steel castings poured in green sand molds is very effective in
eliminating porosity.31 Selenium is a surface-active element and can result in
degenerate graphite forms. To evaluate the effect of controlled amounts of
zirconium and selenium on porosity elimination in gray iron, very small amounts
were added (8.0% zirconium as FeSiZr) to a proprietary 9-gram inmold
inoculating tablet. A second experiment was also run with a supplemental
addition of 3.3% selenium to a 8.0% zirconium modified proprietary inmold
inoculating tablet. The casting results obtained from these tests are listed in
Table 13.
Castings made with either zirconium by itself or with both selenium and zirconium contained
subsurface porosity. The presence of porosity in the above castings is probably the result of
addition of insufficient treatment alloy. It is interesting to note that the microstructures of both
castings treated with the 9 gram inoculating tablets were somewhat improved, containing 100%
Type A graphite, compared to the standard ladle inoculation with 75% foundry grade ferrosilicon
containing 0.75% calcium, which contained some Type B and D graphite. Additional
experimental work remains to be conducted in this area using larger inserts with greater
amounts of zirconium and selenium additions.

Effect of Iron Oxide Additions -- The addition of even small amounts of red
iron oxide had an overwhelming effect on porosity elimination. The results of
additions of varying amounts of 200 mesh red iron oxide (Fe2O3 or hematite) to
PUN core sand mixes are shown in Table 14.
Additions of as little as 0. 25% red (hematite) iron oxide were sufficient to inhibit
the formation of all traces of porosity in test castings poured under adverse
testing conditions. It must be noted that since commercial foundry grades of red
iron oxide occur naturally, not all grades may work like the grades used in the
experiments. Further, it has been shown that additions of Fe3O4 (magnetite)
are not nearly as effective as hematite in controlled casting tests.32,33 Casting
tests run comparing hematite to magnetite are shown in Table 15.
These results clearly show the effects of iron oxide mineralogy and chemistry.
Although two of the iron oxides had similar mesh sizes (325 mesh x down), the
325 mesh red iron oxide (hematite) clearly outperformed the black iron oxide
(magnetite) as well as a coarser (100 mesh) European hematite ore of relatively
high purity. It can be concluded that iron oxide purity doesn't appear to be a
determining factor in the performance of an iron oxide and its subsequent effect
on porosity elimination. Although black iron oxide additions are commonly in
use today, much of the acceptance of black oxides is more likely related to
reduced surface area considerations. Sand additives with reduced surface area
allow for reduced resin consumption and improved core making economics.
However, careful consideration must be given to the superior effectiveness of
red oxide in preventing porosity when choosing an oxide addition.
It should be noted that although some iron oxides may contain various
percentages of TiO2 (titanium dioxide) in their mineralogy, it is doubtful whether
sufficient time or quantities of the element titanium could be reduced and be
available to react with nitrogen during the casting process. Hence, the presence
of titanium dioxide in iron oxide would not impart any beneficial effect on
minimizing porosity susceptibility of nitrogen bearing resins. All of these findings
illustrate that red iron oxide almost always outperforms black iron oxide in
producing sound, porosity free castings as well as minimizing other resin related
defects such as lustrous carbon. 34
To determine the effect of iron oxide granularity, other grades of hematite
(Fe2O3) were tested using the conditions outlined in Table 15. At 1.5% and
4.00% levels, a much coarser grained hematite addition was also was effective
in eliminating defects even though it was relatively randomly distributed in the
core due to its large particle size. This behavior, coupled with how effective
0.25% red iron oxide was in eliminating porosity, appears to preclude the long
accepted role of iron oxide in preventing defects. The role of iron oxide in
preventing porosity has long been linked with its ability to react with silica to
form fayalite which in turn forms a "physical" barrier preventing gas solution. At
the low levels investigated and because of the behavior of the coarse grained
hematite, it appears probable that iron oxide is somehow affecting the kinetics
of gas absorption by the solidifying metal. Regardless, such small additions
could certainly not be effective barrier formers at the levels employed.
To further establish if the formation of a slag-type barrier at the mold-metal
interface is a viable mechanism responsible for porosity elimination, additions of
sodium fluoroaluminate (or cyrolite) were employed as sand additives. Cryolite
has a melting point of 1,825oF and does not rely on reacting with silica as does
iron oxide to form a slag; cryolite will liquefy in-situ to form such a barrier.
Additions of 0.5%, 1.0% and 2.0% were evaluated in exactly the same manner
as the previously reported iron oxide additions. The results obtained from these
tests are shown in Table 16. In these castings, veining defects were minimized
but considerable burn-on was present which appeared to be the result of severe
sand fluxing. However, in all cases, severe subsurface porosity was found in the
test castings.

Core Washes -- A considerable number of experimental core washes were

applied to test cores to determine effectiveness as porosity inhibitors. Most of
the washes were proprietary formulations but contained varying amounts of red
iron oxide. Others were made by incorporating additives to a base gel. Casting
tests were run using those conditions previously described that promoted
porosity. Results of these tests indicated that proprietary red iron oxide (Fe2O3)
bearing washes provided very slight or no reduction in porosity defects.
Experimental washes composed of aluminum powder and titanium powder
provided similar performance. However, a 100% red iron oxide (Fe2O3) wash,
and another prepared with sodium silicate and iron oxide (Fe2O3) completely
prevented the formation of porosity. This achievement was accomplished but at
the expense of severe surface finish degradation. The sodium silicate red iron
oxide wash deteriorated the casting surface only slightly but the 100% red iron
oxide wash had a very deleterious effect on the surface. Overall results tended
to indicate that adequate amounts of iron oxide were not employed in
proprietary washes; however, in experimental washes with red iron oxide, too
much was added with a resultant loss in surface smoothness. Apparently, a
delicate balance exists between the amount of iron oxide needed for porosity
elimination compared to the amount that results in deteriorated surface finish.

Core Post-Baking -- To determine the effect of core baking on porosity

elimination, several test cores were subjected to post-baking or curing for three
different times. The results of these tests are summarized in Table 17.
Castings made with test cores baked at 450oF but for only one hour contained
severe porosity defects. Intermediate times of 2 hours significantly reduced the
extent of porosity. Baking for 4 hours at 450oF produced a distinctive core color
change to chocolate brown and had a significant effect on porosity elimination.
For thorough baking to occur, it has been found that a color change usually
accompanies such a treatment and up to 55% of the binder is volatilized.
Although such lengthy times may be impractical, higher baking temperatures or
short times at high temperatures might be effective in reducing overall binder
level in the core surface layers. Baking also demonstrates that some free
hydrocarbons are undoubtedly volatilized and nitrogen components from the
Part II resin may undergo further reactions to form more stable compounds.

DISCUSSION
Although several variables have been identified that either exaggerate or
promote the formation of porosity defects in PUN binders, these variables are in
one way or another related to the gaseous decomposition products generated
by the resin during casting. Decomposition gases consisting of both hydrogen
and nitrogen are readily liberated during casting pouring and during subsequent
solidification. High pouring temperatures further enhance both the breakdown
rate and amount as well as favor increased gas solubility in the liquid metal.
High pouring temperatures also have a significant effect on liquid metal surface
tension, which has been shown to have a significant effect on porosity
formation. 9,11 Because both hydrogen and nitrogen are readily available and
extremely soluble at the casting temperatures employed, their effect on
potential porosity defects is often additive.
Numerous chemical analyses taken during this investigation showed that
considerable pickup of both hydrogen and nitrogen occurred in the immediate
subsurface layers when conditions favoring porosity were employed. At depths
of 0.25 in. and more below the cored surface, hydrogen and nitrogen levels
tended to be quite low and representative of the base metal. It is probable that
just before solidification, momentary super saturation of both hydrogen and
nitrogen exist just under the casting surface. This complex nitrogen/hydrogen
effect has long been recognized by other investigators. 6,27,35 Further, if a
considerable amount of nascent nitrogen is dissolved in a casting from
unbalanced binder ratios favoring excessive polyisocyanate components, the
presence of even a small amount of hydrogen will serve to lower the overall
solubility of nitrogen. Stated another way, hydrogen may be exerting a catalytic
effect on nitrogen to enhance porosity formation.
The same effect of alloying elements on gas solubility is well known and acts in
a similar manner. To further aggravate conditions, if the melt initially has a high
gas content resulting from the use of poor charge metallics or carbon additives,
36 then the tolerance for additional solution of nascent mold or core gases is
reduced considerably and porosity formation becomes extremely favorable.
Microstructures of sound and porosity containing castings taken in the
immediate vicinity of the mold-metal interface were identical. In all cases, no
differences in either matrix structure or graphite morphology were found. Both
microstructures contained the same ferritic type matrix with Type A graphite.
The solidification rate and composition of all base gray iron heats favored this
type of structure. Although it is widely recognized that hydrogen and nitrogen
are carbide stabilizers and favor formation of pearlite as well as alter graphite
structure,37-41 it appears that insufficient time was available during
solidification and subsequent cooling through the transformation temperatures,
for such phases to form.
Although most gas holes exhibited a bright or shiny interior of a graphitic nature,
no such films were observed during optical metallography. Further examination
of these areas with a scanning electron microscope showed distinct layers of
what appeared to be a crystalline graphitic coating lining the interior of the gas
holes. The presence of this crystalline film has been reported by numerous
other investigators. 1,8
The morphology of gas holes that formed took many shapes, even in the same
casting. Both fissure type gas holes as well as small spherical and pear shaped
holes were very often observed in the same casting. Although for the most part,
gas holes that formed were located just underneath the surface, and most
extended no more than 0.25 in. into the casting, a few castings contained gas
fissures almost 0.50 in. long (see Figure 5). Because of the sub-surface nature
of the defects, the incorporation of large amounts of alloying elements that form
stable nitrogen compounds may not be needed since only these sub-surface
layers are affected. Incorporation of proprietary nitrogen stabilizing elements or
"scavengers," which include both titanium and zirconium based ferroalloys, may
offer additional possibilities for treating binder induced porosity defects.
Likewise, inmold inoculating tablets incorporating zirconium for nitrogen control
and small amounts of selenium for hydrogen control also offer promise for
defect elimination.
Although the porosity studies focused on using ladle additions of nitrogen
stabilizing ferroalloys, the use of beneficiated ilminite ore has also been shown
to be a very effective method of introducing the element titanium. Mikelonis 42
reported that ilmenite ore was the most cost effective method of introducing
0.04 to 0.07 percent titanium levels to cupola melted irons. The ilmenite was
added as 3 in. x 2 in. ilmenite ore to the cupola charge. In this research, it was
reported that titanium recovery levels were 30 to 40 percent of the total amount
of titanium in the ore. Other developments aimed at improving titanium
recoveries are based on using beneficiated ilmenite ore that incorporate a
proprietary blend of halide containing fluxes.43 Such products are available in
the form of a briquette or tablet and can be used either as a furnace addition or
ladle addition. These products may also provide improved melt quality by
coalescing liquid and / or solid slags with the mild fluxing agents incorporated in
the tablet or briquette.
It is not well understood how small amounts of red iron oxide (0.25% addition
rates) were so effective in eliminating subsurface porosity in the test castings. It
has been suggested that the red iron oxide is exerting some type of "catalytic
effect" on binder decomposition products that minimize or alter the generation
of nitrogen and hydrogen gases. One such theory is that when exposed to the
sudden high temperatures of iron casting, red iron oxide (Fe2O3) readily
releases oxygen. This released oxygen immediately reacts with nitrogen
decomposition products from the binder to form stable NOX compounds 44.
Since hematite (red iron oxide) has a much higher concentration of oxygen
compared to magnetite (black iron oxide), and based on the improved
performance of red iron oxide compared to black, this mechanism certainly
appears to be very feasible.

CONCLUSIONS

1. Unbalanced PUN systems favoring excess Part II or polyisocyanates

promote the occurrence of gaseous mold-metal reactions resulting in
both surface and subsurface gas defects. High binder levels also tended
to slightly increase defect propensity even when balanced ratios were
employed. Balanced or slightly unbalanced isocyanate / polyol hydroxyl
ratios favoring excess Part I were relatively unsusceptible to such defects
although a few cases of slight porosity were found.
2. Inadequate mixing that results in poor distribution of the binder
components in the mix was also found to accentuate porosity formation.
3. The temperature of the molten iron as it contacted the core surface was
found to have a significant effect on porosity formation when castings
were poured under conditions favoring their formation. Severe porosity
defects were formed at 2700o F and higher. As the temperature was
reduced, these defects became fewer in number and intensity until none
formed at 2550o F.
4. Porosity formation was found to be very sensitive to core sand type. Lake
sands were relatively insensitive to defect formation while high purity,
round grained white silica sands were found to be very sensitive.
5. Cast iron composition had an effect on porosity formation. Ductile iron
was least susceptible to defect formation while low carbon equivalent
irons were most susceptible.
6. Addition of titanium compounds, either in the form of 70% ferrotitanium or
proprietary gray iron inoculants containing titanium were effective in
eliminating porosity defects. Zirconium additions were also somewhat
effective in eliminating defects at the addition levels employed.
Incorporation of ferrosilicon zirconium into a proprietary inoculant was
also found to reduce the incidence of defects.
7. The addition of small amounts of red iron (Fe2O3) oxide (82% minimum
purity) to silica sand mixes was extremely effective in eliminating
porosity. Sound castings were obtained with additions as small as 0.25%
red iron oxide. Black iron oxides were not anywhere as effective as red
iron oxide.
8. No metallurgical changes in either graphite morphology or matrix
structure occurred in the gas affected mold-metal interface region. A
 layer or film, probably graphitic in nature, was found lining the internal
surfaces of most gas holes.
9. Porosity defects tended to form in geometric hot spots or re-entrant
angles on the test casting. The location seems to indicate that localized
heating of the core re-entrant angles creates a condition that results in a
momentary super saturation of the surface layers. Gas analysis taken
well beneath the affected surface layers showed normal gas contents.

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16. J.M. Greenhill, "Diagnosis of Causes of Defects in Gray Iron
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17. R. L. Naro, et. al, "Formation and Control of Lustrous Carbon
Surface Defects", AFS Transactions, Vol. 85, pp. 65, 1977.
18. R. H. Toeniskoetter, "Effects of Sand Surface Characteristics on
Adhesion of Resinous Binders", AFS Transactions, Vol. 81, pp. 280,
1973.
19. D. A. Taylor, J. M. Clifford, BCIRA JI., Vol. 9, p. 632, Sept., 1961.
20. J. V. Dawson, L. W. L. Smith, "Gases in Cast Iron with Special
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Head, SC, October 20, 1998.
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Third Edition, p.339 (1966).
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in Steel", AFS Transactions, Vol 74, 1966.
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Transactions, Vol. 91, 1983, pp. 263.
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Method for Gray and Ductile Cast Irons", filed August 8, 1998.
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Steel Castings by Additions of Selenium", Battelle Memorial Institute,
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1969 Materials Engineering Exposition, 1969.
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Molds", Steel Founders Society of America, Steel Founders' Research
Journal, No. 5, First Quarter 1984, pp. 9, 1984.
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on Casting Surface Finish", AFS Transactions, Silver Anniversary Paper,
Vol. 100, pp. 797, 1992.
35. H. P. Rassbach, E. R. Saunders, W. L. Harbrecht, "Nitrogen in Stainless
Steel," Electric Furnace Steel Proceedings of the AIME, Vol. 11, 1953.
36. K. H. Caspers, "Influence of Steel Scrap and Burden Additives in
Induction Furnaces on the Tendency for Defect Formation in Cast Iron",
AFS International Cast Metals Journal, 1976 Giesserei, Vol 62, no. 8, pp.
186 - 189, 1975.
 37. R. L. Naro, J. F. Wallace, "Minor Elements in Gray Iron, " AFS
Transactions, Vol. 78, pp. 229., 1970.
38. W. A. Schmidt, H. F. Taylor, "Risering of Gray Iron Castings, AFS
Transactions, Vol. 61, pp. 131, 1953.
39. F. Brown, M. F. Hawkes, "Effect of Hydrogen on Graphitization, " AFS
Transactions, Vol 60, p. 635, 1952.
40. A. A. Ananin, V. P. Chernobrovkin, R. M. Belyakova, "Effect of the
Structure and Properties of Roll Iron of Injecting Different Gases, "
Russian Castings Production, No. 5, p. 201, ( 1971).
41. S. Morita, N. Inoyama, "Behavior of Nitrogen in Cast Iron," AFS Cast
Metals Res. Jl, pp. 109, Vol. 5, No. 3, Sept 1969.
42. P. J. Mikelonis, "The Effects and Use of Ilmenite Ore as a Titanium
Source in Cupola Melted Gray Iron", AFS Transactions, Volume 84, pp.
449, 1976.
43. U.S. Patent, "Titanium Containing Treatment Agents for Molten Ferrous
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America, December 1998.

List of Figures:

 Figure 1: Cylindrical test casting illustrating gating system employed.

 Figure 2: Dimensions of cylindrical test casting.
 Figure 3. Types of porosity defects encountered in test castings
 Figure 4: Effect of pouring temperature on porosity formation.
 Figure 5: Morphology of subsurface gas porosity (1.5 x magnification)

List of Tables

 Table 1: Compositions of Test Castings Poured

 Table 2: Effect of Binder Ratio on Porosity Formation
 Table 3: Effect of Binder Level on Porosity Formation
 Table 4: Effect of Pouring Temperature on Porosity Formation
 Table 5: Effect of Sand on the Formation of Porosity
 Table 6: Effect of Acid Surface Treatments on Porosity Susceptibility
 Table 7: Effect of Sand Type on Porosity Formation
 Table 8: Physical and Chemical Properties of Sands
 Table 9: Effect of Mixing Time and Mixing Efficiency on Porosity
Formation
 Table 10: Effect of Type and Composition of Castings on Porosity
Formation
 Table 11: Effect of Core Aging on Porosity Formation
 Table 12: Effect of Titanium and Zirconium Additions on Porosity
Formation
 Table 13: Effect of Selenium and Zirconium Additions on Porosity
Formation
 Table 14: Effect of red iron oxide (hematite) on Porosity Formation
 Table 15: Effect of Iron Oxide Type on Porosity Elimination
 Table 16: Results of Casting Tests with Cryolite Additions
  Table 17: Results of Casting Tests with Test Cores baked for 1, 2, and 4
hours

Tables

Table 1: Compositions of Test Castings Poured

Back to Article

High C.E. Low C.E. Ductile

%C 3.50 2.90 3.5-3.6

%Si 2.40 1.70 2.5-2.6

%Mn 0.50 0.50 0.35
%S 0.02 0.02 0.01 max
%P 0.02 0.02 0.01
%Mg -- -- 0.04
%Ni -- -- 0.80

Table 2: Effect of Binder Ratio on Porosity Formation

Back to Article

Binder Level Ratio Pt I: Pt. II Porosity Extent

1.50% (1998
60 : 40 nil
version)

1.50% 60 : 40 nil

1.50% 50 : 50 nil to trace

1.50% 40 : 60 traces to moderately severe

1.50% (1998 version) 35 : 65 severe

1.50% 35 : 65 severe

Test conditions: PUN binder with washed and dried silica sand (W/D) Iron Chemistry -
4.3 C.E. iron, Pouring temperature - 2700oF

Table 3: Effect of Binder Level on Porosity Formation

Back to Article

Binder Level Ratio: Pt I : Pt. II Porosity Extent

3.0% 60:40 nil to trace
3.0% 50:50 moderate
3.0% 40:60 severe
3.0% 35:65 very severe
1.8% 60:40 none
1.8% 50:50 trace
1.8% 35:65 severe
1.5% 60:40 none
1.5% 50:50 none to trace
1.5% 35:65 severe
1.25% 50:50 none
1.25% 35:65 moderate
 Test conditions: PUN binder on W/D silica sand 4.3 C.E. iron, Pouring temperature -
2700oF.

Table 4: Effect of Pouring Temperature on Porosity Formation

Back to Article

Binder Pouring
Level % Temperature (oF) Porosity Extent
1.50 2780 very severe - gross w/some traces of fissures
1.50 2700 severe
1.50 2625 traces
1.50 2550 none
3.0 2700 very severe
3.0 2600 moderate
3.0 2500 none
Test conditions: PUN on W/D silica sand, 4.3 C.E. Gray Iron, Pt. I : Part II ratio held
constant at 35 : 65

Table 5: Effect of Sand on the Formation of Porosity

Back to Article

Sand Type Binder Level Ratio Pt. I / Pt.II Porosity Extent

W/D Silica 1.50 % 35 : 65 Severe
Lake Sand 1.50 % 35 : 65 None, Completely Sound

Test Conditions: 4.3 C.E. iron, Pouring temperature - 2700oF

W/D - Washed and Dried Silica Sand

Table 6: Effect of Acid Surface Treatments on Porosity Susceptibility

Back to Article

Sand Treatment Binder Level Ratio Pt. I / Pt.II Porosity Extent

None 1.50% 35:65 None
Acid Treated 1.50% 35:65 None, Sound

Test conditions: 4.3 C.E. iron, Pouring temperature - 2700oF Sand Type - Michigan Lake
Sand

Table 7: Effect of Sand Type on Porosity Formation

Back to Article

Sand Binder Level Ration : Pt I / Pt II Porosity Extent

Silica Sand No. 1 1.5% 35:65 Severe

Silica Sand No. 2 1.5% 35:65 Severe

Silica Sand No. 3 1.5% 35:65 Severe

Silica Sand No. 4 1.5% 35:65 Trace to Moderate
Sand No. 5 1.5% 35:65 None
Lake Sand 1.5% 35:65 None
Test Conditions: PUN binders on above sands, 4.3 C.E. iron, Pouring Temperature,
2700oF
 Table 8: Physical and Chemical Properties of Sands
Back to Article

Sand % SiO2 %Fe203 %Al2O3 GFN Perm Sensitivity

Silica Sand No. 1 99.88 0.02 0.10 67 95 high

Silica Sand No. 2 99.88 0.02 0.10 37 225 high

Silica Sand No. 3 99.88 0.02 0.10 131 20 high

Silica Sand No. 4 99.6 0.018 0.27 54 180 moderate
Sand No. 5 99.2 0.13 0.40 55 190 none
Lake Sand 94.8 0.44 2.12 56 150 none

Table 9: Effect of Mixing Time and Mixing Efficiency on Porosity

Formation
Back to Article

Mixing Time per

Total Binder Level Pt 1: Pt II Porosity Extent
component
5 seconds 10 seconds 1.50% 50:50 very severe
10 seconds 20 seconds 1.50% 50:50 moderate
20 seconds 40 seconds 1.50% 50:50 nil to moderate
30 seconds 60 seconds 1.50% 50:50 nil to traces
40 seconds 80 seconds 1.50% 50:50 nil to traces
60 seconds 120 seconds 1.50% 50:50 none
120 seconds 240 seconds 1.50% 50:50 none
Test Conditions: PUN binders on W/D silica sands, 4.3 C.E iron, Pouring
Temperature - 2700oF

Table 10: Effect of Type and Composition of Castings on Porosity Formation

Back to Article

Low Carbon Equivalent Iron (3.40 C.E. - Class 50)

Binder Level Binder Ratio Temperature Porosity Extent
Subsurface microporosity and small
1.50% 60:40 2,700oF
fissures
1.50% 60:40 2,500oF nil amounts of porosity
o
1.50% 50:50 2,700 F small fissures and subsurface holes
1.50% 50:50 2,500oF nil amounts of porosity
o
1.50% 40:60 2,700 F severe fissures, subsurface porosity
o
1.50% 40:60 2,500 F trace fissures
Ductile Iron (60 - 40 - 20)
Binder
Binder Level Temperature Porosity Extent
Ration
1.50% 60:40 2,700oF none
1.50% 60:40 2,500oF none
o
1.50% 50:50 2,700 F none
o
1.50% 50:50 2,500 F none
o
1.50% 40:60 2,700 F nil to trace
1.50% 40:60 2,500oF none
High Carbon Equivalent Iron (4.30 C.E. Class 20)
 1.50% 60:40 2,700oF none
o
1.50% 60:40 2,500 F none
1.50% 50:50 2,700oF nil to trace
o
1.50% 50:50 2,500 F none
o
1.50% 40:60 2,700 F trace to moderate subsurface porosity
1.50% 40:60 2,500oF none
Test Conditions: PUN binders on W/D silica sands
High C.E. 4.3 iron, Low C.E. 3.4 iron, Ductile Iron (60 - 40 - 20)
Pouring Temperature - varied between 2700oF and 2500oF.

Table 11: Effect of Core Aging on Porosity Formation

Back to Article

Core Age Binder Level Pt. I : Pt II Porosity Extent Pouring Temperature

1 hr. 1.50% 35:65 Severe 2,700oF
24 hr. 1.50% 35:65 Severe 2,700oF
1 hr. 1.50% 35:65 Traces 2,600oF
24 hr. 1.50% 35:65 Traces 2,600oF
1 hr. 1.50% 35:65 None 2,500oF
24 hr. 1.50% 35:65 None 2,500oF
Test Conditions: PUN binders on W/D silica sands, 4.3 C.E. (Class 20) iron
Pouring Temperature - 2700 oF

Table 12: Effect of Titanium and Zirconium Additions on Porosity Formation

Back to Article

% Addition Binder Level Pt. I : Pt. II Porosity Extent

0.00% 1.50% 35:65 Very Severe
0.025% Ti as 70% FeTi 1.50% 35:65 Trace to Moderate
0.050% Ti as 70% FeTi 1.50% 35:65 None
0.025% Ti as Inoc. A 1.50% 35:65 Trace
0.030% Ti as Inoc. A 1.50% 35:65 None
0.025% Ti as Inco. B 1.50% 35:65 None
0.050% Zr as FeSiZr 1.50% 35:65 None
0.025% Zr as Inoc. C 1.50% 35:65 Trace to none

Test Conditions:
PUN binders on W/D silica sands, 4.3 C. E. iron,
Pouring Temperature - 2700oF
Inoculant A - 52% Si, 11% Ti, 1.25% Ca, 1.0% Al, Bal - Fe
Inoculant B - 75% Si, 11% Ti, 5.5% Ba, 3.5% Mn, 1.25% Ca, 1.0% Al, Bal - Fe
FeSiZr - 35% Si, 33% Zr, 2.5% Ca, 1.0% Al, Bal - Fe
Inoculant C - 47.0% Si, 33% oxy-sulfide forming elements, plus 9.0% Zr, Bal - Fe

Table 13: Effect of Selenium and Zirconium Additions on Porosity

Formation
Back to Article

% Addition Binder Level Pt. I : Pt. II Porosity Extent

0.00% (std 75% FeSi) 1.50% 35:65 Very Severe
Inoculant Tablet D
1.50% 35:65 Severe
0.0048% Zr
 Inoculant Tablet E
1.50% 35:65 Severe
0.0048% Zr and 0.0019% Se
Test Conditions: PUN binders on W/D silica sands, 4.3 C. E. iron, Pouring Temperature -
2700oF
Standard Inoculant - Foundry grade 75% FeSi with 0.75% Calcium, 0.33% addition
Inoculant D - 9 gram inoculant tablet containing 27.7% Si, 28.41 oxy-sulfide forming
elements plus 8.0%Zr, Bal - Fe
Inoculant E - 9 gram inoculant tablet containing 25.6% Si, 26.88% oxy-sulfide forming
elements plus 8.0%Zr and 3.3% Se, Bal - Fe
Zirconium and Selenium percentage levels based on the 35 lb. step cone pouring weight

Table 14: Effect of red iron oxide (hematite) on Porosity Formation

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Binder Level Binder Ration % Iron Oxide Porosity Extent

1.50% 35:65 0.00% Severe
1.50% 35:65 0.25% None
1.50% 35:65 0.50% None
1.50% 35:65 1.50% None
1.50% 35:65 2.0% None
1.50% 35:65 3.0% None

Test Conditions: PUN binders on W/D silica sands, 4.3 C.E. iron
Pouring Temperature - 2700 oF

Table 15: Effect of Iron Oxide Type on Porosity Elimination

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Binder Level % Iron Oxide Mesh Size Oxide Type Porosity Extent

1.50% 0.0% ---- None Severe

1.50% 0.25% 325 Fe2O3 (red) None
1.50% 0.25% 325 Fe3O4 (black) Severe
1.50% 0.25% 100 Hematite ore Severe
Test Conditions: PUN binders on W/D silica sands, 4.3 C.E. iron
35 : 65 Ratio of Part I to Pat II, Pouring Temperature - 2700 oF
Fe2O3 assay: 87% Fe2O3, 8.0% SiO2, 2% Al2O3, Balance not reported
Fe3O4 assay: 62% Fe3O4, 1.5% SiO2, 4% Al2O3, Balance not reported
Hematite ore: 92.5% Fe2O3, 4.75% SiO2, 1% Al2O3, Balance not reported

Table 16: Results of Casting Tests with Cryolite Additions

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Binder Level Binder Ration % Cryolite Porosity Extent

1.50% 35:65 0.0% Severe
1.50% 35:65 0.50% Severe
1.50% 35:65 1.00% Severe
1.50% 35:65 2.00% Severe

Test Conditions: PUN binders on W/D silica sands, 4.3 C.E. iron. Pouring Temperature -
2700 oF for all tests

Table 17: Results of Casting Tests with Test Cores baked for 1, 2, and 4 hours
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 Binder Level Binder Ration Temperature Time Porosity Extent
o
1.50% 35:65 450 F 1 hour Severe
1.50% 35:65 450oF 2 hours Nil to Trace
1.50% 35:65 450oF 4 hours None
Test Conditions: PUN binders on W/D silica sands, 4.3 C.E. iron
Pouring Temperature - 2700 oF for all tests

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