Supplemental Requirement S23 in ASTM A703

materials_q_and_a_graphicQ: A customer has asked whether we can supply carbon and alloy steel valve
bodies meeting Supplemental Requirement S23 in ASTM A703. What is the purpose of this requirement?

A: The macroetch test specified in Supplemental Requirement S23 in ASTM A703 is designed to detect the
occurrence of aluminum nitride embrittlement in castings.

When steel is melted, oxygen and nitrogen can be dissolved in the molten steel. When the metal is poured
into the casting mold, the oxygen can come out of the solution and form gas porosity in the castings. In order
to avoid castings with excessive gas porosity, the foundry may add deoxidizing elements to the melt. The
presence of these elements results in the formation of oxide compounds, which mitigates the formation of
oxygen gas bubbles during solidification.

One of the elements that is sometimes added as a deoxidizer is aluminum, which creates a potential for the
formation of aluminum nitride. This compound tends to precipitate in the prior austenite grain boundaries and
can result in castings that display loss of ductility that could result in brittle failure of the casting if it is shock-
loaded in service. If fracture occurs, it has a rock-candy appearance due to fracture along the prior austenite
grain boundaries. The fracture is often very shiny due to the presence of aluminum nitride platelets on the
surface.

Variables That Influence Embrittlement

There are a number of variables that influence the potential for this type of embrittlement:

1) The steel must contain enough aluminum and nitrogen to support the formation of enough aluminum
nitride to cause a significant embrittling effect. Most foundries have the equipment necessary to analyze and
report aluminum content. However, the specifications for the common cast steels used in valve bodies do not
require analysis or reporting of aluminum as a standard requirement, so some foundries do not monitor
and/or report the aluminum content.
Although some foundries monitor nitrogen levels in their steel, many do not have the necessary equipment to
do this. The specifications for the common cast steels used in valve bodies do not require analysis or
reporting of nitrogen as a standard requirement. Therefore, the nitrogen content of the steel is often not
known or reported, and it is possible that enough nitrogen is present to form aluminum nitride.

2) Other elements that inhibit the formation of aluminum nitride must be present in low enough quantities that
the reaction can occur. Certain elements are known to inhibit the formationof aluminum nitride. Additionsof
titanium and/or zirconium, addedeither along with or after the additionof aluminum, can inhibit the formationof
aluminum nitride by forming titaniumnitride and/or zirconium nitrideinstead. It has also been found thathigher
levels of phosphorus, sulfur,boron, molybdenum and copper inhibitaluminum nitride embrittlement.

3) The cooling rate in the mold must be slow enough through the critical temperature range to allow the
formation of the aluminum nitride phase. The thickness of the casting (orportion of the casting) is an
obviousfactor influencing whether embrittlementoccurs, since thicker casting sectionswill cool more slowly
through thecritical temperature range than thinsections.

The casting configuration can also influence the cooling rate. A complex casting with relatively thin walls may
experience slower cooling rates than a simple casting with the same wall thickness because the complex
casting will lose heat through the mold less effectively.

The mold material can also influence the cooling rate. For example, air-set sand is known to inherently
produce molds that cool slower than green-sand molds.

Reporting Aluminum Content

When Supplemental Requirement 23 in ASTM A703 is imposed on steel castings produced under ASTM
A216, A217 and A352, aluminum is required to be reported. For heats with aluminum content greater than
0.08%, a macroetch must be performed on one of the following:

•A cross-section of the heaviest section of a sacrificial casting

•A coupon attached to the heaviest section

•A coupon removed from directly under a riser or

•A coupon from the same heat of material removed from a separately cast test block with a thickness
representative of the heaviest section of the casting.
The resulting etched specimen is compared with 10 reference macrographs. Heats with severity levels 4 and
lower are acceptable. Heats exhibiting higher levels are dispositioned by a number of means, including
examination of etch structures on individual castings, fracture testing to determine the degree of “rock candy”
appearance, mechanical testing, weld crack susceptibility testing and/or high-temperature solution heat
treatment, as agreed upon by the supplier and purchaser.

Aluminum Nitride (AlN) embrittlement is a problem in

heavier section (>4”) steel castings. AlN precipitates at
higher residual aluminum and nitrogen levels and slow
cooling rates. In load critical components, the formation
of AlN will embrittle the casting, reducing the impact

strength and ductility of the steel.

Introduction
Aluminum Nitride (AlN) embrittlement is the result of a
solid state precipitant in heavy section steel castings. Embrittlement
can lead to failure of sections with little loading,
even during assembly.1 The AlN phase is a brittle
phase which precipitates to primary grain boundaries.2 The
resulting fracture surface is dull, intergranular, and described
as “rock-candy” fracture. It is also known that the
AlN phase will not be dissolved by ordinary commercial
heat treatment.3 Theoretical treatment of the problem by
Hannerz produced some equations that show the relationship
between the cooling rate, aluminum content, nitrogen
content, and precipitation of the AlN phase. For known
cooling rate and composition, the embrittlement by AlN
phase can be predicted.
First presented is the background on controlling section
size and composition as well as a discussion on the influence
of macro-segregation. Second, the Hannerz theoretical
model is shown and the calculation is compared
to historical data. The equations are used on slab castings
to present a relationship of feeding modulus to the
maximum aluminum content. Finally, the calculation is
applied to the simulation of a three dimensional casting
geometry, including any section size increases due to rigging
determining the embrittled volume for an average
steel chemistry.
Background
Special care should be taken to avoid the precipitation
of any AlN phase in heavy section steel castings.
As discussed in the introduction, the two factors that
control AlN embrittlement is the cooling rate and the
composition. The cooling rate is strongly determined
from the casting section size and the shape of the casting
geometry. It is not sufficient to assume the cooling
rate of a flat plate with equivalent section thickness as
the shape of the casting can greatly reduce the cooling
rate. Often the section size or shape in the casting geometry
cannot be modified to substantially change the
cooling rate. However, the addition of a heavy rigging
system can substantially increase the effective section
thickness in the casting and decrease the cooling rate.
Also, chills may increase the cooling rate locally. Similarly,
the change in a sand system from green sand to
chemically bonded sand can decrease the cooling rate.
Thus a borderline, heavy section casting can also be at
risk for embrittlement if the rigging/sand properties are
not properly considered. Both the composition and cooling
rate through proper rigging design should be used as
tools for avoiding AlN embrittlement. Once the rigging
has been determined, control of the aluminum and nitrogen
content in the steel is the best prevention of AlN
embrittlement.1 Where does the aluminum and nitrogen

in steel originate?

Aluminum in steel castings may come from two primary

sources. First, aluminum is introduced to the steel during
the deoxidation process. Before pouring into the mold, the
steel must be deoxidized to reduce the oxygen content of
the melt. If the oxygen levels remain high, then the oxygen
will react with carbon to generate CO creating small porosity
or pinholes in the casting. Although several elements
which have a higher oxidation potential than carbon can be
used, aluminum is the most common choice. Upon the introduction
of aluminum in a liquid steel melt, the oxygen
binds to it forming alumina, Al2O3, and floats to the surface to be removed as slag. Excess
aluminum is required to prevent porosity during solidification and to counteract the
additional pickup of oxygen through pouring.Aluminum may
be picked up from exothermic insulating binder sleeves surrounding
risers or exothermic riser topping. This additional
aluminum pickup in risers is found in the cast material close
to the sleeve material.
Nitrogen dissolves into the steel on any exposed surface to
the air. The total amount of nitrogen pick up is directly related
to the time that the liquid metal is exposed to the air.
In longer melting practices with no oxygen boil, such as in
induction melting, the nitrogen content can be as high as
200 ppm.4 For an electric arc furnace melting practice with
an effective oxygen blow the average nitrogen is 80 ppm.5
Nitrogen is difficult to tightly control.
One additional complicating factor in the formation of AlN
precipitate is macro-segregation. Macro-segregation is the
movement of element species due to the micro-segregation
and convective flow in the casting during solidification.
Micro-segregation is the local rejection of elements from
the solid to the liquid during solidification. Macro-segregation
may have an important influence on the final composition
locally of the aluminum and nitrogen. This effect is
not considered in the work to follow and instead only the
average composition of the aluminum and nitrogen is used
in the calculation of the potential formation of AlN phase.
Further consideration of the influence of macro-segregation
on AlN precipitation is left for future work.
Method
The theoretical Hannerz chart shows the relationship of
the maximum aluminum content and maximum nitrogen
content for different cooling rates before embrittlement.
This chart allows the user to determine whether the casting
is at risk of embrittlement based on known casting
conditions. But this chart faces several limitations. First,
the temperature range in which the cooling rate is calculated
is not specified. The cooling rate can vary as much
as an order of magnitude in the temperature range during
the precipitation of AlN phase. Second, the Hannerz chart
given in his original work was based on an approximate
evaluation of the Temperature-Time-Transformation
(TTT) diagram. The paper itself records that “To obtain
the more exact values every value on the curves should
be multiplied by 1.35”.3 The original chart based on the
approximate evaluation of the TTT has been shown to be
not conservative enough in the prediction of AlN phase in

heavy section castings.1