Metal Casting
Metal Casting
METAL CASTING
QUICKEST
LEAST EXPENSIVE
ROUTE
TO A
NEAR NET SHAPE PRODUCT
-3
TABLE OF CONTENTS
Page
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7.
10.
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53.
53.
I. INTRODUCTION
Metal Castings, Metal Casting Process
Metal Casting Design
Pattern Design
Rapid Prototyping
II. SAND CASTING PROCESSES
Sand Size Distribution
Strength of Green Sand
Permeability and Compactibility
Temperature Dependence of Green Strength
Chemically Bonded Molding and Core Sand
Reclamation of Foundry Sand
Sand Life Cycle
Reclamation Systems
III. OTHER CASTING PROCESSES
Precision Casting; Cosworth Process
Rheocasting & Thixocasting
Lost Foam Casting
Die Casting
Squeeze Casting
Investment Casting
IV. MELTING OF METALS AND ALLOYS
Energy and Material flow in Cupola Melting
Cold Blast Cupola
Heat of Combustion and Iron/Coke Ratio in Charge
Energy of Melting and Energy Balance in Cupola
V. FLUID FLOW AND GATING DESIGN
Laws of Mass and Energy Conservation (Bernoullis Law)
Velocity at Efflux Point (Mold Filling Time)
Pressure at Intermediate Point in Gating System (Gas Aspiration)
Number of Gates in System
Fluidity of Molten Metals
VI. SOLIDIFICATION AND PROCESSING OF METAL CASTINGS
Intrinsic and Extrinsic Factors
Microscale-Dendritic Solidification
Solidification on a Macroscale - Defect Production
Controlled Thermal or Mechanical Treatment after Casting
Latent Heat of Solidification, Cooling Curves
Steady State Heat Transfer Processes - Ficks First Law
VII. HEAT TRANSFER AND SOLIDIFICATION IN INSULATING MOLDS
VIII. SHRINKAGE, RISER DESIGN
Shrinkage in Metals During Solidification
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55.
55.
56.
57.
58.
60.
61.
62.
63.
69.
69.
71.
72.
73.
73.
73.
74.
76.
77.
77.
77.
79.
80.
81.
83.
84.
85.
91.
95.
101.
103.
104.
106.
110.
114
114.
115.
117.
120.
122.
122.
123.
125.
126.
128.
130.
Macroshrinkage
Microshrinkage
Riser Design
Calculation of Modulus of Riser and Casting
Location of Riser, Size and Shape of Riser
Number of Risers
Casting Yield
IX. HEAT TRANSFER AND SOLIDIFICATION IN PERMANENT MOLDS
Finite Element Analysis of Solidification - Die Casting
X. CONTINUOUS AND SEMI-CONTINUOUS CASTING
Continuous Casting of Steel
Semi-Continuous Casting of Al Alloys, Free Machining Brass
Microstructure of Continuous and Semi-Continuous Castings
XI. SOLIDIFICATION, BINARY SYSTEM
Equilibrium Solidification
Non-equilibrium Solidification
The Scheil Equation and Coring in Dendrites
XII. ALUMINUM ALLOYS
Aluminum Casting Alloys Processing
Processing and Microstructure of Several Selected Al Si Base Alloys
Alloy 356.2, Modification & Age Hardening
Alloy 319.1, Grain Refinement with TiB
Alloy KS281, Phosphorous as a Nucleation Agent for Proeutectic b.
XIII. ADDITIVES TO MOLTEN METAL
XIV. CAST IRON
Phase Equilibria in Fe - C- Si System, Stable and Metastable Diagrams
Gray Cast Iron, Section Size Effects and Inoculation, Chill Wedges
Mechanical Properties of Gray Cast Iron
Ductile Cast Iron, Production
Microstructures of Hypereutectic Ductile Cast Irons
Alloying of Cast Irons
Mechanical Properties of Ductile Cast Irons
Austempered Ductile Cast Iron
Compacted Graphite Iron and Malleable Cast Iron
XV. DEFECTS IN CASTINGS
Gases in Metals
Hot Tears
Residual Stresses in Castings
Residual Stress Measurements
XVI. CAST STEEL
Peritectic Reaction, Segregation of Alloy Elements During Solidification
Segregation of Alloying Elements During Solidification of Steel
Melting and Refining Steel
Mechanical Properties of Cast Steel
Weldability of Cast Irons and Steels
Selective Surface Hardening of Cast Steels and Irons
-1
131.
131.
134.
139.
140.
148.
I. Introduction
Metal Castings
Metal castings form integral components of devices that perform useful functions for
human beings, an idea shown schematically below:
DEVICE
ENERGY
USEFUL
FUNCTION
Casting
MATERIALS
INFORMATION
Design
Engineer
Pattern
Maker
Casting
Engineer
Manufacturing
Engineer
The cast component has a shape, size, chemical composition and metallurgical microstructure
which is determined by engineering decisions arrived at by:
A. Design Engineers (Mechanical Engineers)
B. Pattern Makers (Skilled craftsman, CAD)
C. Casting Engineers ( Metallurgical Engineers)
D. Manufacturing Engineers (Mechanical, Metallurgical Engineers)
The engineering professionals that carry out this process work together, sharing information so
that the casting will perform as intended in a timely and cost effective manner. It should be noted
that the casting may only be a small part of the useful device (usually in more sophisticated
devices like an automobile where there may be hundreds of components), or it may be the entire
device (simple device like a frying pan).
ducer of industrial castings makes use of these same skills, but supplements them with an understanding of the fundamental principles of fluid flow, heat transfer, thermodynamics and
metallurgical microstructural development.
MOLTEN METAL
COPE (Upper half of sand mold)
POURING
CASTING CAVITY
BASIN
LADLE
CORE
RISER
Q
Q
SPRUE
PARTING LINE
DRAG
(Lower half of sand mold)
RUNNER
These latter engineering skills are used to help design a system which will allow the metal caster
to produce a sound (pore free) casting, free from defects (sand inclusions, slag, cracks, etc.), with
the correct dimensions and combination of mechanical properties to satisfy the designers requirements for the intended application.
Producing a good casting requires a design effort to:
1. Create a gating system (pouring basin, sprue, runner) to bring molten metal into
the mold cavity free from entrapped slag, sand or gases.
2. Provide a riser which feeds liquid metal into the casting cavity as the liquid is
cooling and solidifying (all liquid metals will shrink as they cool and most liquid
metals will shrink as they solidify). The riser may have to provide up to 5 - 7% by
volume for the casting as it solidifies.
3. Control heat flow, Q in the above figure, out of the casting so that the last liquid
to solidify is in the riser.
4. Control the rate of heat flow so as to control the nature of the solidified product.
Modern industrial castings are produced by a wide variety of processes, processes which
are broadly defined in terms of: I. The type of mold material (sand, permanent, etc.); II. The manner in which the molten metal is introduced into the cavity (gravity, pressure, vacuum); III. The
state of the metal (percent which is liquid); IV. The state of the mold cavity itself (air, vacuum,
solid, gas).
There are many examples of processes incorporating different combinations of the above
which are illustrated in Table 1 below. Each process illustrated in this table can have many different variations within each category. For example sand casting can involve molds bonded with clay
and water (so-called green sand mold) or the sand grains can be bonded with a chemical resin of
some type(so-called chemically bonded sand); die casting can be high pressure, low pressure, etc.
In addition, combinations of two different processes can be present in a given process, i.e. it is
common to utilize semi-permanent molds in some processes, where the molds contain both metal
and sand components. The combination selected for a given application depends upon the availability of processes, limited only by the creativity and engineering capability of the metal caster.
Table 1: Casting Processes, Mold and Metal Details
II.
Manner of Entry
III.
State of Metal
IV.
State of Mold
Cavity
Casting
Processes
I.
Mold Material
Sand Casting
Sand( Bonded
with clay and
water or chemicals)
Gravity
100% Liquid
Air
Permanent Mold
Metal
Gravity
100% Liquid
Air
Die Casting
Metal
Pressure
100% Liquid
Air
Investment
Ceramic
Gravity
100% Liquid
Air, Vacuum,
Gas
Lost Foam
EPC
Sand
(Unbonded)
Gravity
100% Liquid
Styrofoam,
PMMA
Thixocasting
Rheocasting
Metal
Pressure
>50% Liquid
Balance Solid
Air
Cosworth
Sand
Vacuum
100% Liquid
Air
V Process
Sand(Unbonded
with Vacuum
and Enclosing
Plastic Film)
Gravity
100% Liquid
Air
Centrifugal
Metal, Graphite
Centrifugal
Forces
100% Liquid
Ingot - NOT
Cast to Shape
Gravity
100% Liquid
Air or Gas
Shroud
Evaluation
(Mechanical & Physical Properties)
Final Part
stand the fundamental material properties of the casting, its limitations as a material, and the
limitations on the potential processes needed to produce that casting. General considerations by
designers include: Minimize Section Size Changes; Eliminate Sharp Corners; Understand the
Mechanical Property Requirements of the Casting, the Machining Requirements, Tolerancing, the
Locating Requirements, the Handling Requirements, the Process Limitations, and How Statistical
Methods Can Be Used in Process Control. It is important for the design engineer to always question the old way of making parts, to be aware of new technology so that the design envelope
can be stretched to its ultimate. Once the material to be cast has been selected and the casting process chosen, the designer will send drawings (CAD) to the foundry to answer the question, Can
this part be produced in a cost effective way as a casting? Experienced pattern makers with the
help of fluid flow and heat transfer experts (often metallurgical engineers) will proceed to lay out
the requirements for the molds and the cores necessary to produce the part. At this point in the
process, or even in the design stage, simulation of the solidification of the proposed part is a
desirable activity. Modern computers are currently being used with powerful software
packages to give a preview of solidification, illustrating in color and in real time the path of
solidification in the casting. This methodology is important in reducing the time between
design and prototype castings, in providing valuable insight to the designer and the person
who does the gating and risering. Clearly a dialogue is needed between the pattern maker, the
casting engineer, and the designer to produce tooling to make acceptable castings. This dialogue
is illustrated as dashed lines on the above schematic. After the designer and pattern maker are satisfied that a viable casting is possible (a process enhanced by the ability of the participants to talk
in the same computer language, and for each to have a working knowledge of the others problems), the foundry planning people will provide a cost estimate for the designer. Assuming that
the cost estimate is within the realm of reality, patterns are produced for prototype castings. (If
the cost is too high it will be necessary to return to the drawing board and ask more hard questions.) General considerations applied to the prototype castings by the casting engineer include:
Evaluate Dimensional Accuracy; Quantify Microstructural Integrity (presence of required
microconstituents, casting defects, porosity, shrinkage, other); Understand Response to Machining, Heat Treatment or Welding; Determine Mechanical Properties in Critical Sections. Rapid
protoyping of castings is currently being used to reduce the time between design and cast
parts. Stereolithography, Selective Laser Sintering, Fused Deposition Modeling, Laminated
Object Manufacturing, Solid Ground Curing, and Direct Shell Production Casting are some
of the methods used to produce patterns very quickly from the CAD models of the designer.
These methods are described in a following section of this set of notes. It is also crucial that
the casting engineer learn that dimensional tolerances are important and that he/she understand
the source of the dimensional changes resulting from the casting process as well as the basic differences in achievable tolerances attained by different casting processes (i.e. lost foam vs green
sand vs investment,etc.). Improvements in design can be suggested at this stage of the process as
illustrated in the above schematic, improvements which produce a better casting while at the same
time minimizing and reducing the cost and difficulty of production.
Time Required to Complete the Design Process
The time required to take a casting from the design stage through to satisfactory production will obviously depend upon many factors, but times ranging from 18 months (e.g., a new part
produced by conventional processes or a minor change in an existing casting) to 5 years (e.g., a
new part or combination of parts produced by a new process) is not uncommon. Clearly it is to
everyones advantage to minimize this time, an effort aided by good communication between the
various players in the drama, and in these times, wise use of solidification and fluid flow simulation, and rapid prototyping techniques. Two examples contrasting a new design with a redesign
are given below.
EXAMPLE: New Engine Design - Kohler - TH1416 Overhead Cam Engine (14 - 16 hp)
Old Engine - Sand Castings (Green Sand); 7 Castings in Upper Half (2 cylinder
Heads, 2 Cylinders, Upper Half of Block, Intake Manifold, Cam Housing), 4 in
Lower Half (Lower Half of Block - Crank Housing, Stud Mounting Bosses, Oil
Pump and Filter, Starter Housing). 319 Aluminum alloy (See section on kAl alloy
castings for microstructure description)
This engine had been produced for a number of years as 11 different sand castings and assembled to make a satisfactory engine.
The need to reduce cost and still improve the product led the design team to
consider new ways to produce castings. Enter the LOST FOAM process.
New Engine - Replace the seven castings in the old design with one Lost Foam
Casting. Replace the four castings in the old design with one Lost Foam Casting.
In this process, 7 foam patterns are glued together to make one pattern for casting
the upper half, and 4 foam patterns are glued together to make the lower half.
These assemblies together with a sprue (the entry point for molten metal) then
have sand compacted and vibrated around them prior to pouring the casting. This
change from 11 separate castings to 2 castings eliminates many manufacturing
steps, from machining to assembly. All of the gaskets and seals previously needed
are eliminated. In this process even the oil passages are cast-in thereby eliminating
the need to drill holes. 319 Aluminum alloy
Time Line - There is a significant learning curve for the design team and the
foundry which is producing the castings. This new design has been in process for
about 3.5 years. Prototype castings have been produced and are being tested.
EXAMPLE: Redesign of the Existing Head for a 3500 Series Caterpillar Engine, so that
the engine would run cooler. Gray Cast Iron (See sections in these notes on gray
iron describing the microstructure and properties)
The designer came to the pattern shop with new ideas requiring larger water passages so that the engine would run cooler (Late 1994). Modifications of the pattern
were made and prototype castings have been produced, with a very large reduction
in the temperature at which the engine would run. It is expected that the new heads
will be in production by late 1996.
In this example the basic casting and the casting process remained the same, gray
iron poured into green sand with suitable coring; thus a more rapid turn around
time than the example of the change in casting process from green sand to lost
foam.
Pattern Design
Pattern making is a time - honored skill which is an integral part of the casting process.
Patterns are routinely produced from wood, plastics, and metals depending upon the complexity
of the casting being produced, on the number of castings required and obviously on the capability
of the pattern shop that is involved. The design of patterns must include the following components:
1. An allowance for the solid state shrinkage that will always accompany the casting
as it cools from the melting temperature to room temperature. This will depend upon the
metal being cast, each of which will have its own unique coefficient of thermal expansion, . For
example, for aluminum at 20 oC is 23.9 x 10-6 in/inoC, for iron is 11.7 x 10-6 in/inoC and that
for copper is 16.5 x 10-6 in/in oC (see page 50 - 51). Thus the linear dimensions of the pattern will
always be larger than the casting by an amount determined by the linear expansion coefficient. Of
course the expansion coefficients for each of the above materials will change somewhat with temperature and so the pattern maker will usually give a generous allowance to cover the temperature
dependence of the expansion coefficient.
2. Inclusion of a draft angle so that the pattern can be removed from the mold (or in
the case of die casting or permanent mold casting, so the casting can be removed from the metal
die) after the molding sand has been rammed around the pattern. These draft angles can vary from
one casting to another but angles in the range 1 - 2 degrees are quite common.
3. Inclusion of enough extra stock to allow for variations in casting dimensions due to
mold preparation, pattern wear, etc. This amount will depend greatly upon the casting process
being employed. For example the amount of extra stock will be typically greater for a sand casting than for a die casting. Machining and process tolerances are typically greater for sand castings
than for permanent mold castings.
Details on pattern making can be found in several publications form the American
Foundry Society (AFS).
Rapid Prototyping
(Based on Dean Peters article in Foundry Management and Technology, June 1996)
Rapid prototyping is a technology that allows the building of 3-D models (patterns or
molds) by producing additive layer-by-layer CAT scan type slices of a pattern in plastics, waxes,
or paper , or of CAT scan type slices of a mold in ceramics. Perhaps no other technology since
the invention of interchangeable parts and automated assembly lines has held as much promise for
the compression of lead times for newly designed parts.
Some methods of accomplishing such useful work are described below:
Stereolithography
Stereolithography is the process by which three dimensional plastic objects are
created directly from CAD data.
A. Data received from a CAD file is sliced into thin, horizontal cross sections.
B. Next, an ultraviolet, software-guided laser (HeCd), draws the first cross-section of the
CAD design on the surface of a vat of ultraviolet sensitive photopolymer,or liquid
plastic. Where the laser light touches the liquid photopolymer, it solidifies to the precise dimensions of the cross section.
C. When the first layer is completed, an elevator within the system lowers the first solid
plastic layer so the next layer can be applied, recoating the the solid layer with liquid
photopolymer in preparation for the drawing of the next cross-section.
D. The thickness of each layer ranges from 0.003 - 0.015 in.
E. The process continues until the entire CAD file has been transformed into a solid
model, prototype, or casting pattern.
F. It is then removed from the vat and begins a brief final curing process after which it can
Scanning Mirror
Cured Resin
(Model)
Resin
Support
Lattice
Build
Platform
X-Y Positioning
Device
Platform
Built-Up
Part Block
Molten Metal
Mold Production
Casting
Operation
Clay
Used Sand Molds
Spent Sand
Dust
Returns
Solid Metal
Casting
Clearly in a foundry which is at steady state (produces the same weight castings day in and day
out) the amount of new sand added in cores must equal the spent sand and dust lost due to attrition
or for other reasons. In fact in most foundries, perfectly good sand is landfilled every day so as to
balance the flow of material into and out of a facility. In Michigan in 1991, approximately
1,000,000 tons of sand was landfilled to produce about 1,000,000 tons of cast product. A little
reflection by the reader will bring the realization that what comes into a volume (the Plant) must
also leave, otherwise it is likely to get very crowded in a hurry (the law of continuity on a large
scale).
10
While silica is the molding media which is used in largest quantity, other sands are also utilized in the foundry for special applicatons, including chromite, olivine, garnet, carbon sands (petroleum cokes) and other refractory materials that can be obtained with a reasonable cost. Additives
commonly used in molding sands includes cereal (finely ground corn flour) and wood flour (cob
flour, cereal hulls) for improved flowability of sand and collapsibility after casting, sea coal (a finely
ground coal) for improved surface finish, and many other materials which find use in special applications. Details on sand, additives, and testing of sands can be found in Principles of Metal Casting by
Heine, Loper, and Rosenthal (1967), chapters 5 and 6, and in the AFS Sand and Core Testing Handbook.
30
25
20
Silica Sand
15
10
5
0
10
100
1000
Details on desirable sand size distributions for specific casting situations and details on measurement
of the size distributions can be found in the AFS literature.
lonite clay with adsorbed Ca++). The data points represent actual measured data in the MY 4130
laboratory. It can be seen that the green compressive strength goes through an apparent maximum
at about 3 wt % moisture.
40
35
"Four Screen Silica Sand"
7 % Western Bentonite
7 % Southern Bentonite
30
25
20
15
10
5
1
Shear strength measurements are also used as an indicator of a green sands strength,
where the 2 x 2 standard sample is sheared along the axis of the cylinder. Typically shear
strength data is about one fourth that of compression results. This can be seen in the following
laboratory data in which both green compression and green shear are plotted vs the number of
rams:
12
Sand Data, 98
30
Green Compression
Green Shear
25
20
15
10
5
0
1
10
100
Number of Rams
Perhaps the most sensitive strength measurement is the tensile measurement, because it is the
binder which is being tested, pulled apart. The other strength tests, the compression and shear test,
reflect not only the binder strength but also the interference of sand grains as they attempt to slide
past one another under the shear stresses which are developed during the test. Unfortunately, the
tensile test is a very difficult test to do in a consistent manner and is subject to very large scatter
because of experimental inconsistencies. A careful study by Boenisch on the tensile strength of
green sands as a function of the above variables has given a better perspective on the importance
of the adsorbed species, especially where the warm strength (strength in the range 70 to 100oC)is
13
concerned. A schematic of the tensile strength vs moisture content for sand at room temperature
containing 6% clay is given below.
6% CLAY
40
Density
30
Strength
20
10
Permeability
0
2
4
6
8
Weight Percent Moisture
14
50
45
40
35
30
25
20
15
2
2.4
2.8
3.2
3.6
Percent Moisture
Permeability is a measure of the ease with which air can pass through the sand aggregate, a property which is very sensitive to the sand size distribution, mosture and clay content and degree of
compaction. Again, details about this measurement can be obtained form the AFS Mold and Core
Sand Handbook. Typical data for permeability vs % moisture and permeability vs number of rams
for a four screen sand obtained at MTU are given below:
180
160
140
120
100
80
Four Screen Silica Sand
60
40
2.5
3.5
4.5
Percent Moisture
It can be seen in the permeability vs. % moisture graph that as water is added, the permeability
increases in a nearly linear manner due to the swelling action of the clay particles, thereby pushing the sand particles further apart and making more room for air passage. On the other hand,
15
increasing the number of rams required to attain a 2 high specimen results in dramatic decrease
in permeabillty, an apparent result of the closing off of some of the continuous air passages.
Sand Data, 98
180
160
140
120
100
80
60
1
10
100
Number of Rams
16
up when in contact with the molten metal during casting, the strength properties will change dramatically as is illustrated in the schematic diagram below.
Room Temperature
Adsorbed Sodium
No Sodium
80 oC
o
95 C
Percent Moisture
The room temperature curve is typical of a sand bonded with Western Bentonite, whose clay mineral is predominantly montmorrilonite (Al2Si5 O5(OH)2). In addition the montmorrilonite has a
significant quantity of adsorbed Na. It is thought that this adsorbed species plays an important role
in maintaining the warm strength of green sand, a very important property in the short time that a
casting is filling with molten metal and in the time before significant solidification has occurred.
Boenisch and others have surmized that the bonding mechanism needed to explain the above temperature dependence requires two separate and distinct models of how the water is involved with
the sand and the clay, a low moisture model involving polarized water molecules on both clay and
sand and a high moisture model involving ionic bonds between the Na ions and the water molecules. The polar bonding at low moisture is referred to as rigid water bonding and the ionic water
bonding at high moisture is referred to as bridge bonding. The polar bonds are thought to be quite
weak and are very temperature dependent, while the ionic bonds are relatively strong and therefore less temperature dependent. Confirmation of the model comes when the adsorbed ionic species are removed from the clay by an ion exchange process; the result is the room temperature
17
properties at high moisture dropping rapidly to zero as shown above.The two bonding models
proposed are simply represented below:, where F represents a shear force
Sand
Grain
Rigid Water
Bonding
Velcro Effect
Ionic Water
Bonding
Bridge
Polar Bonds
Rigid Water
F
F
Clay
Sand
Grain
F
Na+
+
Clay
Implications of the bonding in green sand molds for the quality of castings relates to events that
occur in the short time while the metal is still molten, when any cracks or spalls in the sand surface could be filled with molten metal thereby resulting in defects on the surface of the casting.
Defects produced at this time are affectionately called rattails, buckles and scabs. The scenario
that promotes this situation is shown below:
Dry Sand
In Compression
Molten Metal
When the molten metal hits the green sand surface, drying of the sand and evaporation of the
water begins immediately.Water vapor is driven out into the cool green sand and condenses, raising the mean moisture content of the sand in the layer next to the dry warm sand. Of course, the
dry sand is expanding as a result of the heating thereby putting the wet warm sand in tension. If
the warm sand has no or little tensile strength the sand will fail making conditions ripe for buckling of the dry sand layer. If this happens before the molten metal has solidified the molten metal
will penetrate the resulting buckle very quickly producing a surface defect on the casting.
Surface defects on castings are, therefore, more prevalent when the warm wet strength of the sand
is low. This condition occurs when the clay binder has insufficient quantity of the adsorbed spe-
18
cies which account for ionic bridge bonding, that portion of the bonding mechanism which is so
important at high moistures and temperatures (see the Figure on the top of page 18).
An example of the importance of bridge bonding occurred to a German foundry which experienced a rash of casting surface defects shortly after a change was made in the water supply for the
foundry, a water supply which contained a large quantity of chloride ion content. It was eventually
discovered that the chloride ion in the water supply was leaching the Na ion out of the binder,
thereby reducing the bridge bonding capability. The sand strength was behaving in the manner
predicted by the dotted line in the Figure on page 18.
19
of resin on the tensile properties has been determined for a no-bake binder used at MTU called
Novathane, a product of Ashland Chemical. This relationship is illustrated below:
200
Novathane
160
120
0.7
1.2
1.3
The use of chemical binders for making molds has some obvious advantages; for example greater
longevity of the mold and higher strengths . Because water is not a part of the bond in chemically
bonded molds and cores, they do not have to be poured off immediately after preparation.
Green sand will lose moisture with time, thereby shrinking and significantly affecting mold
dimensions, not to mention the added possibility of having runouts on the parting line. Some
chemically bonded sand molds have excellent longevity, can be kept on the shelf for extended
periods of time and selected as needed. Unfortunately however, most chemically bonded sands
will absorb some moisture from the air with time on the shelf, and become significantly weaker in
the process. This is a much greater problem in the summertime than in the winter.
The two to three orders of magnitude difference in tensile strength between green sand and chemically bonded sand can be understood by considering the nature of those bonds. Clay and water is
extremely plastic (a result of the weak polar bonds), one sand grain sliding easily over another in
response to a shear force. On the other hand, the chemical bond involves very strong directional
bonding within the polymeric (or inorganic) chemical which has been formed in the reaction. As a
result the plasticity of these types of bonds is very low compared to the clay-water bond. Of
course, these high strengths are absolutely necessary for cores which almost always have much
larger static stresses present than is observed in molds. Obviously the more intricate and smaller
the core, the greater the need for strength. The amount of binder materials consumed in US found-
20
ries over the last 35 years (and projected to the year 2000) is shown below. This graph gives an
150,000
Core Oil
PUNB & PUCB
Shell
Other
100,000
50,000
0
Year
1960
1970
1980
1990
PUNB - Phenolic Urethane No Bake
PUCB - Phenolic Urethane Cold Box
From March, 1995 Foundry Management & Technology - Paul Carey
2000
indication of the importance of these binder materials in making cores and molds.Considering that
the amount of resin used is about 1 - 2 % of the sand weight, the total amount of binder used in
1990 (~130,000 tons) means that approximately 8.7 million tons of sand were used to bond cores
and molds. The largest fraction is used in making cores, which in turn are largely used in green
sand molds. This is consistent with the rough amount of sand delivered to landfills in 1990 of
about 10 million tons. Recalling that axiom What goes in must come out, it is clear then that the
majority of the sand ending up in landfills is a direct result of the addition of chemically bonded
cores.
The above figure illustrates the ebb and flow of technology in the relative amounts of the different
kinds of binders used. Notice that the amount of oil core binder use (which made up the bulk of all
binder used in 1960) is projected to almost disappear by the year 2000. The production of oil
cores is time consuming, energy intensive and requires great care in handling; their production
requires moving soft and easily deformed green cores into an oven to be cured. An excellent
example of this proces can be observed at the Grede Foundry in Kingsford, MI, a frequent tour
destination for the MY 4130 laboratory. The demise of oil cores has been replaced with other processes, most notably the use of phenolic urethane in cold processes (room temperature). This was
in part a response to the energy crisis in the 1970s and 80s, where foundries worked hard to
reduce their dependence on direct energy use to produce cores and molds. It is interesting to note
that the shell process, which is heat activated and was discovered in the 1950s, is still an important player in the binder business. This is because shell molds and cores are much stronger than
those produced by the cold process binders, and so have survived in many applications requiring
higher strengths and good dimensional control. The shell process and the cold box phenolic urethane binder method can also be observed at the Grede foundry.
21
22
of new sand necessary to add to maintain the desirable properties of the sand. The effects of the
above conditions on Sandy the Sand grain are shown below:
Unhappy Grain
Happy Grain
Fresh Binder
on Whole
Sand Grain
Reacted Binder
on Fractured
Sand Grain
Core Sand
Core
Molten Metal
Mold
Adhering Sand
Removed in Cleaning
Room and Sent to
23
Landfill or
Reclamation
The shaken out sand contains sand in a variety of conditions depending upon the severity of the
interactions (chemical, mechanical, thermal) within the sandhandling and prcessing system.
These various components include:
1. Green sand unaffected by the heat of the casting process (that sand removed from
the immediate vicinity of the casting). This component would likely be the largest component
and would include the warm wet sand illustrated in the sketch on page 18.
2.Core sand in which the binder has been combusted to the extent that the sand
grain is no longer bonded to its neighbors. This component will contain all degrees of combustion from sand which has been made like new by the heat of the process to grains which are still
covered with partially combusted binder, or uncombusted binder which has fractured in handling
or at shakeout. This component is likely to be the second largest component of the shaken out
sand.
3. Green sand in the immediate vicinity of the casting, the heat affected sand. This
clay bonded sand will to a large extent have had its binder destroyed by the heat from the casting
process. This component will also likely be quite large, again depending upon the casting size and
shape.
4. Core butts, those parts of the cores which have not been affected enough by the
heat or mechanical handling during and after shakout to disintegrate. These chunks can
make up a significant part of the shaken out sand, again depending upon the size of the cores, and
especially upon the temperature of the metal poured (iron is much hotter than aluminum and
therefore would be expected to better break down the cores in the casting).
5. Dust and fines resulting from thermal and mechanical stresses of the process. This
would make up a small fraction of the weight of the shakeout sand and would be removed in the
dust collection system.
In most green sand systems the core butts (No. 4 above) are screened out and sent to the landfill
and the dust (No.5 above) is removed in baghouses or wet scrubbing systems. This leaves all of
the remaining sand to reenter the green sand system for reuse where clay and water is added to
newly bond the core sand component (which has no clay binder) and the burnt green sand component (which needs new binder). Unfortunately the component of burnt core sand which has not
had the binder completely combusted does not readily accept the clay water binder and neither
does the sand containing the burnt clay. Thus, unless a significant fraction of the green sand feed
stock is removed from the system and new sand is added the properties of the green sand will
diminish with time and casting quality will decrease. Most operating foundries will therefore
simultaneously add new sand to the system and landfill a certain fraction of used system sand.
This is an expensive process, especially when it costs more to throw away sand than it does to
buy it new.
Reclamation Systems
At this point in time most foundries continue to landfill large quantities of sand,but
because of the ever rising costs to landfill are seriously considering reclamation to make their
throw away sand like new, to be used in the production of cores. This desire on the part of
foundries has spawned a large number of companies which build reclamation systems. The bulk
of these systems rely on thermal and mechanical methods to scrub or clean the sand grain surfaces. Chemical methods involve liquids, and handling large quantities of liquids simply generates a new environmental problem. As a result there are no foundries that anticipate cleaning sand
grains chemically.
24
Mechanical systems currently available involve vibrating screens, rapidly rotating impellers which throw sand against metal or rubber surfaces, and pneumatic systems which scrub sand
grains against one another in a series of tubes. The objective in all of these processes is to separate
one sand grain from another,to remove the spent binder from the surface of the grains, and to
return the sand grain to the system ready for another coat of new binder.
Thermal systems are designed to combust the sand grain surface layers (especially effective with partially or uncombusted organic core and mold binders), removing them to the atmosphere or a scrubber system to capture obnoxious combustion gases.
Combinations of mechanical and thermal systems can be used to maximize the recovery
of sand.
These systems are designed to handle that portion of the sand system which was formerly
thrown away, which includes core butts and the excess sand removed from the system to maintain
sand quality. Unfortunately this latter component contains a significant quantity of sand which
does not need reclamation, and a good fraction which does need reclamation goes merrily on its
way to green sand processing. This dilemma results from the current shakeout practice which is
designed to mix all of the above sand components together at the point of shakeout. Clearly a better way in principle would be to separate and segregate these components at shakeout. Consider
an alternate system to the one on page 23 below:
Green Sand
Core Sand
Core
Molten Metal
Mold
Sand
Unaffected Sand
Goes Direct To
Reuse in System
Burnt Sand
and Core Sand
Casting With Core
and Burnt Green Sand
Reclamation
Dust to Baghouse
or Alternate Use
This is truly an ideal system, one which design engineers should strive to develop.
25
Controlled
Bottom Filled
Mold Using
Electromagnetic
Pump
Electric
Holding
Furnace
& Pump
Inert Gas
is pumped with an electromagnetic pump up into the mold from the bottom of the mold in a very
controlled manner. Benefits include:
1.Improved levels of accuracy and integrity
2.Very little porosity
26
RHEOCASTING
In rheocasting, the alloy is
heated into the liquid phase
eld and then cooled back into
the two phase liquid plus solid
region, where it is stirred and
subsequently injected as a slurry
into a die.
l
+
l+
Solid
INJECTION
Liquid
As Solidi ed
As Stirred
Advantages of rheocasting include greatly reduced die wear because of the much lower injection
temperatures, minimum shrinkage and greatly refined microstructural scale. Practical limitations
include use with low melting point metals and those alloys with a wide freezing range. In addition
specialized stirring equipment is needed to maintain liquid properties prior to injecting.
In THIXOCASTING the alloy is heated only into the two phase region (to B)until it contains
about 50 % solid and liquid. At this point the charge can still be handled as a solid, the liquid-solid
mixture holding together by surface tension forces. This volume can then be placed into a die and
then subjected to forces which result in the solid-liquid mixture flowing in response to those
forces. It is said to be thixotropic(like catsup). Advantages include low energy costs for melting,
minimization of shrinkage problems,distortion is kept to a minimum because of reduced temperature gradients, etc.
27
Gating
Casting
and Gating
Pattern
Assembly
Refractory
Coated
Assembly
Pattern in
Vibrated Sand
Casting
in Sand
28
events that occurs when metal hits foam is quite complex, depending upon the temperature of the
molten metal and the foam being used. The two common foams used are described structurally
and chemically below. It should be noted that the polystyrene contains a relatively stable benzene
ring as a part of the monomer, a factor which inhibits combustion. On the other hand the PMMA
has less carbon, does not contain a benzene ring and in addition contains oxygen, which aids in
combustion. The net result is that the PMMA has less carbon deposition defects than the polystyrene.
POL YMETHYL METHACR YLA TE
(Plexiglass)
POL YSTYRENE
(Styrofoam)
92.3 % C
7.7 % H
H
C
H C
C
H
C
C
55.8 % C
7.0 % H
37.2 % O
O
O
H
H
H
H
Oxygen atoms aid combustion
Recently one manufacaturer of marine engines has added a pressure chamber to their lost foam
line. After pouring the casting the mold is inserted into a pressure chamber, the lid is closed and
pressure is applied during the time that the casting is solidifying. This mechanical action reduces
shrinkage porosity and refines the cast structure resulting in much improved fatigue properties.
ADVANTAGES OF LOST FOAM PROCESS
(Oct.,1990 , Foundry Management and Technology)
1. Design freedom. Just about any shape is fair game. 2. Casting configuration flexibility. Thin
walls, zero draft, backdrafts, undercuts & keyways. 3. Cast-in metal inserts are easily added to the
pattern. 4.Prototype casting development time and cost usually greatly reduced. 5.Complex parts
made in production quantities can become very cost competitive. 6.Coring required in most complex castings is no longer needed. 7.As-cast surfaces of most foam castings are quite acceptable.
8. Parting lines and associated costs to grind them off are eliminated. 9. Machining costs reduced
or eliminated because of tight tolerances and near net shape result. 10. Practically all metals and
alloys can be cast by the process. 11.Casting quality is easily controlled by use of SPC techniques.
CHALLENGES FOR LOST FOAM
1. Emission problems associated with blowing foam patterns and with gases produced in the
casting process. 2. Stability of foam patterns over time; i.e. shelf life. 3. Deformation of patterns
during compaction. 4. Uniform vaporization of foam during casting and removal of combustion
products. 5. Removal of refractory coating from casting surface.
29
DIE CASTING
Die casting is a process whereby molten metal (usually a low melting point material like
Al, Zn or Mg alloys) is injected under pressure into a permanent mold (usually a high melting
point ferrous metal, a hot worked tool steel such as H-13 [0.35C, 1.5 Mo, 5 Cr, 1 V] or H-21 [0.35
C, 9 W, 3.5 Cr] hardened to 45 - 48 RC).
The pressure die casting process had its origin in typecasting (alloys of lead, antimony and
tin) machines, which had reached a high level of automation and mechanical efficiency by the
mid 1800s {Barton, Die Casting: Past, Present, and Future. Engineers Digest, 35, 9, 53 - 59
(1974)}.
The bulk of the die castings produced today are done by the Hot Chamber Process (mostly
Zn base alloys) and the Cold Chamber Process (mostly Al base alloys). Schematic diagrams of
these processes are illustrated below and are adapted from sketches of A.J. Clegg in his text Precision Casting Processes.
COLD CHAMBER PRESSURE DIE CASTING
Aluminum, Copper Base Alloys
Die Cavity
Metal In
Plunger
Plunger
Shot Sleeve
Port
Molten
Metal
Die Set
(Tool Steel)
Fixed Platen
Holding Furnace
Moving Platen
In the hot chamber process, a significant part of the metal delivery system is in constant
contact with the molten metal, thereby creating the opportunity for solution (dissolving) of the
delivery system in the metal to be cast. Because of this tendency, the hot chamber machine is used
exclusively for the production of the low melting point zinc base alloys. In the cold chamber
machine, each shot is ladled into the shot sleeve prior to injection of the metal thereby minimizing the deterioration of the metal delivery system. Thus aluminum and copper base alloys are produced in the cold chamber machine.
Because of the intimate contact between the molten metal and the high conductivity die
sets, the castings solidify very rapidly in comparison to sand castings, often requiring only a few
seconds between shots. Cores made of a water soluble salt are occasionally inserted into the die
cavity before the shot and then dissolved in water after casting. Very complex castings (marine
engine blocks) can be produced by this process.
30
Squeeze Casting
Squeeze casting is a hybrid machine casting process which combines features of forging
and casting in one operation. Many die castings are produced in which there is no possible way to
eliminate microshrinkage, situations in which the rate of solidification and the tortuosity of the
paths available around the dendrites is such that fluid flow to feed shrinkage is nearly impossible.
In these instances the casting is then left with the microshrinkage as inevitable defects, defects
which can significantly reduce the fatigue properties and ductility of these materials.
In the squeeze casting process described schematically below, the press force effectively squeezes
out the shrinkage porosity that otherwise would not be able to be removed by risering practice, the
movable punch exerting a force on the casting while it is solidifying.
Press Movement
Press Force
During Solidi cation
Movable Punch
Squeeze - Cast
Component
Molten Metal
Stationary Die Half
Ejector Pin
Press Open
Press Closed
In addition to eliminating shrinkage porosity, the process also alters the solidification structure,
breaking up dendrites,thereby refining the structure, and even reducing the dendritic arm spacing
because of the improved heat transfer properties associated with the intimate contact between the
dies and the casting. In normal die or permanent mold castings this intimate contact is lost
because of the casting shrinking away from the die interface as cooling occurs.
31
Investment Casting (Lost Wax Process) Text from Foundry Management and Technology,(1989)
In investment casting, a ceramic slurry is poured around a disposable pattern (normally of
modified paraffin waxes, but also of plastics) and allowed to harden to form a disposable mold.
The pattern is destroyed when it melts out during the firing of the ceramic mold. Later molten
metal is poured into the ceramic shell mold, and, after the metal solidifies, the shell mold is broken up to remove the casting. The flow and process diagram schematic is shown as follows:
Wax Pattern
More Investment of
Slurry on Pattern
Investment of
Slurry on Pattern
Melting &
Removing Wax
Up to 7
Cycles of
Investment
&Drying
This
gives
Drying
7 Layers of
Investment
More Investment of
Slurry on Pattern
Firing
Drying
(Removes Moisture,
Developes Strength)
Fired Ceramic
Coating
Drying
Pouring Metal
into Hot, Fired
Ceramic Shell
Knockout
Casting &
Remove
Ceramic
Investment
Casting
32
for the spent ceramic molds, which can be crushed and reused in some of the outer layers where
precision is not required.
33
Afterburner
Natural Gas
Charge
(Ambient Temp)
Iron Units
Coke (Fuel & Carbon)
Limestone
Silicon Units
CaCO 3 -> CaO + CO 2 (EN)
Alternate I
Hot Blast
Air
Hot Air
Zone
Heat Loss
Calcination
Zone
Iron Melt
Zone
Steel Melt
Zone
KWH
Hot Blast
Tuyere
Coke
Bed
Recuperator
Preheating
C + O 2 -> CO 2 (EX)
Exhaust Gas
Cold Blast
Forced Air
Blower
Hot Blast
Hot Air
Hot Metal
2600-2800 oF
Preheater
Slag
Alternate II
Hot Blast
Natural Gas
34
Air
10
11
333
285
250
222
200
182
300
257
225
200
180
164
268
225
193
168
148
132
C* = CA / Fe (Lb C / Lb Fe)
0.134
0.1125
0.0965
0.084
0.074
0.066
1. Assuming that 32 pounds of Carbon are needed to carburize the scrap steel in the charge.
Table 3 includes the energy availability from this carbon (in million BTU per ton of iron) for combustion to CO2, to CO, and to three combinations with different CO/CO2 ratios (volume percent
of combustion gas, including nitrogen).
Table 3: Energy Availability For Different Fe/Coke and CO/CO2 Ratios
Iron/Coke Ratio
10
11
268
225
193
168
148
132
Million BTU per Ton FE: MBTU = 4350(1 + 2.344[CO2 / CO + CO2]) x CA x 10-6
C + O2 -> CO2 (14550 BTU/# Carbon)
3.9
3.27
2.81
2.44
2.15
1.92
3.13
2.63
2.25
1.96
1.73
1.54
2.66
2.23
1.92
1.67
1.47
1.31
2.13
1.79
1.54
1.34
1.18
1.05
1.16
0.98
0.84
0.73
0.64
0.57
35
The air required in CFM (cubic feet per minute) to combust the carbon to produce the above CO/
CO2 ratios and to satisfy a melt rate of 20 tons per hour is given in Table 4 below. .
Table 4: Blast Rate to Produce 20 Tons Iron Per Hour
Iron/Coke Ratio
10
11
0.134
0.112
0.096
0.084
0.074
0.066
Blast Rate in Cubic Feet Per Minute (CFM) for a Melt Rate of 20 Tons /Hour
CFM = 2.519 x 103 x ( 1 + [CO2 / CO + CO2]) x TPH x C*
CO/CO2 = 6.6/17
11587
9727
8344
7263
6398
5706
CO/CO2 = 11.6/14
10434
8760
7514
6541
5762
5139
CO/CO2 = 18.2/10
9121
7657
6402
5718
5037
4493
Table 4 above shows that the blast rate to achieve a given CO/CO2 combustion ratio necessarily
decreases as the amount of coke available for combustion decreases. Of course, most cupolas will
have a blast rate fixed by the equipment available; i.e. the electric motor present with the blast fan
may generate 7000 cfm, or perhaps 8000 cfm. A given foundry may be interested in how the CO/
CO2 ratio would change with a variation in Fe/Coke ratio for their specific situation of blast rate
and melt rate.
Energy of Melting and Energy Balance in Cupola
The minimum energy requirement of a cupola is to provide enough heat to preheat, melt, and
superheat the charge adequately. The theoretical requirement to heat a ton of iron (4.3 wt. % carbon) to 2750 oF is approximately 1.06 million BTU (See the figure below). Clearly there will be
significant energy losses in the exhaust gases, in the slag, and through the sidewalls of the cupola.
It would be the goal of the foundry to minimize these losses through proper control of blast rate,
melt rate, Fe/Coke ratio, etc. A large fraction of lost combustion energy goes into the exhaust
gases. Estimates of these losses are in the range of the amount required to heat the iron: i.e. Svobodas Foundry Energy Conservation Workbook estimates 40% in melted iron, 35% in latent heat
in stack gas (unburned CO), 13% in sensible heat in stack gas, and 12% other (slag, sidewalls).
The latent heat fraction will obviously increase as the amount of CO in the effluent increases.
Consider, for example, a foundry with a Fe/coke ratio of 8/1 and a blast rate of 6402 cfm. By
Tables 2 and 3 this corresponds to an energy production rate of approximately 1.54 MBTU / Ton
(20 Ton/Hour). The exhaust gas contains 18.2 wt. % CO, an amount which if combusted to CO2
would yield an extra 1.27 MBTU. This latent heat amounts to about 45 % of the potential energy
in the blast (approximately 2.81 MBTU/Ton); the energy in the molten metal is about 38 % of this
potential energy. The remaining 17 % then is due to sensible heat losses in the stack gases, losses
in the slag, heat losses through the sidewall, etc.
The heat needed in melting one ton of iron, the maximum amount of heat available, the
latent heat in exhaust gases for a CO/CO2 ratio of 11.6/14, and the potential waste heat lost as sensible heat in gases, slag, etc. are illustrated below for different Fe/coke ratios. It will be noted that
the efficiency of the cupola increases as the Fe/coke ratio increases; i.e. the amount of waste heat,
36
either as latent heat or sensible heat decreases. Of course, one has to remember that the blast rate
must decrease to maintain a fixed CO/CO2 ratio as Fe/coke ratio increases.
1.4
1.2
1.06 MBTU at 2750
1.0
Fe - 4.3 C Iron
0.8
Pure Fe
0.6
0.4
0.2
0
0
400
800
1200
1600
2000
2400
2800
3200
TEMPERATURE ( F)
3.5
C + O 2 -> CO 2
3.0
LATENT
HEAT IN CO
CO/CO 2
2.5
11.6/14
2.0
HEAT LOSSES
IN CUPOLA
1.5
1.0
0.5
0
5
8
9
10
TONS IRON PER TON COKE
37
11
12
38
Notes:
1. Pouring Basin Remains Full at all Times
2. Liquid Metal is Leaving at Efflux Point
3. Assume pouring Basin is Impermeable
Molten
Metal
h1
h2
*
*
3
Exit or
(Efflux Point)
Sprue
39
Ingate(Area, Ai)
AS : AR : Ai = 1 in2 : 2 in2 : 0.5 in2
Problem: Assuming Bernoullis Law holds
with no losses due to friction,etc., compute
the filling time of the casting given.
COPE
DRAG
Sprue
Base
Sprue Well
(Area, AS)
Mold Cavity
(Entirely in Drag)
6 in. x 8 in. x 2 in.
Drag Runner
(Area, AR)
The above ratio of sprue base area to runner cross sectional area to ingate area is called the gating
ratio, a common way to quantitatively describe gating systems. Filling times for just such a cast-
40
ing has been experimentally measured at Michigan Tech for a number of years in which the head
(Distance from top of pouring basin to the parting line) and the ingate cross sectional area were
independently varied to control flow rates.These data will be introduced in homework to follow.
Pressure at Intermediate Point in Gating System
It is important to keep the actual pressure within a flowing liquid in a sand mold above
atmospheric pressure. If the pressure in the molten metal drops below 1 atmosphere then air can
be draw in or aspirated into the metal stream, thereby increasing the opportunity for defects
within the casting. These defects could include the formation of metal oxides or gas porosity, a
particularly troublesome problem in aluminum alloy castings which absorb hydrogen so readily in
the liquid state. Consider the situation in the simple pouring basin sketch on page 39. Let us
assume that the downsprue has the same cross sectional area at points 2 and 3. From the law of
continuity then v2 = v3. Writing Bernoullis Law at points 2 and 3 gives:
h2 + v22/2g + P2/ = h3 + v32/2g + P3/.
Solving for P2 subject to the straight-sided sprue constraint gives:
P2 = P3 - h2 .
Thus it can be seen that the pressure at point 2 is less than 1 atmosphere; gas aspiration will occur
at this point in the system.
Problem: It will be left to the student to show that relief of gas aspiration in the downsprue
can be achieved by building a taper into the sprue.
Students in an experiment conducted in the MY423 laboratory in the fall of 1994 (term
version of MY 4130) measured filling times in 2 x 6 x 8 inch Y-block castings (The entire casting
was in the drag similar to the schematic shown on page 28) poured under conditions in which
head and ingate area were varied independently. The results of that experiment are tabulated
below
41
:
Table 5: Filling Time Data, Fall 1998 - 01 (MY423 - MY 4130)
Casting
Number
Head, h
in.
Ingate
Area
in2
Measured
Casting
Measured
Riser
Filling
Time
tF (sec)
Filling
Time
tF (sec)
Casting
Number
Head, h
in.
Ingate
Area
in2
Measured
Casting
Measured
Riser
Filling
Time
tF (sec)
Filling
Time
tF (sec)
1 - 98
0.049
47
91.7
19
0.049
27
34.4
0.11
15
19.6
20
6.25
0.049
32.9
42.8
0.11
24
79
21
0.11
15
15.5
0.196
12
12
22
0.09
21
21
0.196
17
33
23 - 01
0.11
28
51
0.11
17.7
19.3
24
0.196
26
29
7 - 99
0.11
19
20
25
6.25
0.196
11.5
24
0.11
17
17
26
6.25
0.11
23
42
0.196
18
46
27
0.11
15
31
10
6.25
0.196
15
32
28
6.25
0.11
20.5
42
11
0.049
47
85
29 - 02
12
6.25
0.049
38
46
30
13
6.25
0.11
21
14
0.11
21
22
32
15 - 00
0.11
49
66
33
16
0.11
16.9
18
34
17
0.196
27
35
18
6.25
0.196
12
36
11
31
Homework Problem Using the data in the above table, compute the ideal filling time of the
casting, assuming no friction or turbulence losses in the gating system. Plot measured and ideal
calculated filling times (ordinate) vs. the independent parameter (h)1/2(Ai) on the abscissa.
Include best lines through the data. Estimate from fluid flow principles the real velocity profile
across the ingate area. Discuss the magnitude of the difference observed between measured and
calculated filling times.
42
43
tal
s
20
0
Eutec
tics
Me
40
Pu
re
Fluidity (Inches)
60
g
n
i
s
rea
c
n
I
Superheat, TP - TL
It can be seen in this figure that the fluidity of pure metals and eutectics, with a freezing fange of
zero, is the greatest. Alloys with large freezing ranges have reduced fluidities. The above figure
shows that all metals and alloys will have increasing fluidity with increasing superheat. Gray cast
iron is one of the most fluid casting alloys. Empirical fluidity spiral data from many experiments
on gray cast iron gives the expression
Fluidity (in.) = 14.9 x CF + 0.05T - 155
where T is the pouring temperature in oF, and CF is the composion of the iron and is
equal to
CF = %C + 1/4 x % Si + 1/2 x % P.
Thus for a eutectic iron of composition 3.5 % C, 2.4 % Si, 0.04 %P, the fluidity is given by
Fluidity = 14.9 x 4.12 + 0.05 (2600) - 155 = 36.39 in.
As the pouring temperature increases the fluidity increases (at 2700 the fluidity is 41.39 in.) and
as the composition decreases (increasing the temperature range over which solidification occurs)
to a hypoeutectic value (say 3.2% C, 2.1% Si, 0.04 %P) the fluidity decreases to ~ 30.8 in. Again
details about the fluidity of gray cast irons can be found in Heine, Loper and Rosenthal.
Clearly the fluidity needed to fill a mold cavity will depend upon the section size of the
casting being produced. Thin sections will naturally require higher fluidities to successfully be
filled before solidification, and therefore higher superheat temperatures. Conversely chunky castings will require less fluidity and therefore less superheat for successful filling.
44
- Chemical Composition
- Cooling Rate During Solidification
- Heat and Mechanical Treatment after
Solidification
Extrinsic
Factors
- Metal cleanliness
- Additives for Microstructure Control
- Casting Design
- Riser and Gating Design
- Solidification Rate Control
- Temperature Control Subsequent to
Solidification
Illustration of the significance of intrinsic and extrinsic factors in determining the tensile properties of a casting (Ultimate Tensile Strength and Percent Elongation) is shown below:
Intrinsic
Percent Elongation
45
It can be seen in this schematic illustration that the ultimate goal is to produce a casting with a
matrix microstructure which is homogeneous and uniform throughout. Departure from homogeneity and uniformity results in reduced strength and ductility. Achievement of the optimum goal
is difficult because of the nature of solidification on a microscale and because of the complexity
of controlling the manner of solidification on a macroscale. From an engineering point of view,
optimization of microstructure and properties of a casting is more practically achieved by concentration on controlling the manner of solidification on a macroscale in addition to controlling solidification on a microscale and subsequent heat treatment.
Secondary Arms
Segregation or Coring
Within Dendrite Arms
Porosity
(Gas, Shrinkage)
SDAS
Inclusion
(Slag, Sand)
46
and into which heat is removed. Lack of directional control of heat and metal flow responding to
shrinkage during solidification, or insufficient attention to metal cleanmliness or mold design can
result in typical defects shown schematically above. Design factors such as casting shape, riser
design, and gating design are used by the engineering team to minimize defects. This text is
largely about presenting material important in helping to make informed engineering decisions
about the extrinsic factors used to control macroscale solidification events.
G lo
G so
Gs
Gl
To
Tm
Temperature ->
47
The slopes of each line represents the entropies of each phase. Note that the entropy of the disordered liquid is greater than the entropy of the orderly crystal structure of the solid. At the melting
point, Tm , the solid and liquid are in equilibrium and therefore:
Gs = Gl,
and Hs - TmSs = Hl - TmSl,
and Hs - Hl = Tm(Ss - Sl) = Latent Heat of Solidification.
Notice that for T > Tm, Gl < Gs and therefore the liquid is the stable state.
Notice that for T < Tm, Gs < Gl and therefore the solid is the stable state.
Suppose that the liquid is supercooled to To. At this temperature there will be a driving
force,(Gso - Glo), which favors the nucleation and growth of the solid. In most real systems the
solid will nucleate heterogeneously at a temperature close to Tm and then growth will proceed at
Tm until the liquid is exhausted. A thermocouple placed into such a system will experience a cooling curve similar to the one shown schematically below:
Recallescence
Tm
Undercooling
tS
Time ->
300 oC
30 cm
x
48
Assume a steady state condition, that is, at any distance x from the wall the temperature
remains constant with time. Heat will flow from the high temperature side to the low temperature
side of the wall at a rate dependent upon the following:
1. Thermal conductivity, K
2. Temperature Gradient, T/x
3. Area of Wall, A
4. Time, t
The Total Heat Flow = AKt (T/x)
Flux of Heat = Total Heat Flow/Area.Time = J = K(T/x) FICKS FIRST LAW
Example Problem:
Assume K = 1 W m-1 oC-1
Assume K is temperature independent
Therefore J = 1x1100 / 0.3 = 3666.7 (Watts / m2)
Obviously heat flow in a mold following a casting event is not a steady state process and
therefore Ficks First Law alone is not adequate to describe the situation. However, recall that at
any given point, at any time in any situation FFL will define the flux, J, at that point in time. This
knowledge will be used to define the flux at the mold-metal interface, a changing flux which can
then be integrated to determine tS in a given casting.
TP
Tm
Thermal Conductivity
Density
T0
<- - x
0
Distance From Interface
+ x ->
49
Heat Capacity
In this situation, the high thermal conductivity of the metal results in the temperature of the metal
at the interface dropping to Tm instantly upon pouring and staying there until solidification is
complete. Of course, intimate contact between the metal and mold means that the mold at the
interface will also remain at Tm until solidification is complete.
The solution to the above equation subject to the boundary conditions that T = Tm at x = 0
and T = T0 at x = oo for small t gives:
x
T ( x, t ) = T 0 + ( T m T 0 ) 1 erf -----------------
2 M t
dT
-----dx
x
d
= ( T m T 0 ) ------ 1 erf -----------------
dx
2 M t
x=0
x=0
2
u
u
u
erf ( u ) = ------- u --------- + --------- --------- +
(T
T )
The total heat, Q, through the interface of area A :(the total surface area of the casting) up to the
time , t, is given by:
t
2AK ( T m T 0 ) 0.5
Q = A J dt = ------------------------------------ t
M
0
50
The total heat liberated befofe solidification is a sum of the superheat, QS, and latent heat of solidification, QF, where:
QF = MetalHFVMetal,
QS = MetalVMetal(TP - Tm)CMetal,
where TP is the pouring temperature.
The time necessary for this amount of heat to pass through the interface would correspond to the
solidification time, tS, and therefore:
2A K
Q +Q =
S
F
M
M
(T
T )t
0.5
S
and therefore:
2
2
2
H + C
(T T )
V
F
Me ta l P
m
M Me tal M e ta l
2
2 2
4A K (T T )
M m
0
For a given metal and mold poured at a temperatureTP we can separate a mold constant BS and the
V/A ratio to give Chvorinovs Rule,
tS = BS (V/A)2
51
The Constants needed to utilize Chvorinovs Equation for a variety of materials are given below:
Table 7:
Thermal
Conduct.
Material
K
Wm
-1 oC-1
Density
g cm-3
(mg cm-3
o -1
C )
Specific Heat
Heat of
Fusion
Melt
Temp
HF
Tm
J kg-1
oC
kg-1 oC-1
Sand (SiO2)
1.5
2.32(bulk)
1.6 (Mold)
1117
Al (liq)
94.03
2.385
9-.280
1080
Al (sol) 20C
238
2.7
917
7.015
(-.883)
795
Fe (liq)
Solidif.
Volume
Change
Expansion
Coeff. (68F)
10-6 oC-1
22.2
395995
660
-6.5
23.9
272090
1536
-3.5
Fe (sol) 20C
78.2
7.87
456
11.7
Cu (Liq)
165.6
8.0
(-0.801)
495
Cu(Sol)20C
397
8.96
386
16.5
Notes
W = Watts
m = meter
mg = milligrams
J = Joules
kg = kilogram
Assume
Temp Independent
211812
1085
-4.2
Problem
1.Using Chvorinovs Rule determine the solidification times of sand castings of Al, Cu, and Fe
poured into molds with mold cavity dimensions of 10 cm x 10 cm x 10 cm and then of 20 cm x 20
cm x 2.5 cm, with superheats of 10, 100, and 200 Co.
2. Discuss the practical implications of the results in 1. above. Any surprises?
52
Shrinkage
COPE
Parting Line
CASTING
RISER
DRAG
SHRINKAGE COMPONENTS
Pouring Temperature
Liquidus Temperature
I. Thermal Contraction of L
from TP to TL
TL
TS
TL to TS and at TS
The total amount of shrinkage experienced during solidification may be quite large, especially for
aluminum alloys, which can shrink 6.5% during the change in state (See the table on pg. 52 for
more information about shrinkage for Al, Cu, and Fe in the solid and liquid).
Problems:
1. Estimate the total percentage change in volume for solidification of Al, Cu, and Fe, each
poured with 200 Co superheat. Note for pure metals that there is no contribution from component
II. (Hint; You need to use the variation in densities in the liquids (defined as mg cm-3 oC-1in
parenthesis in the density column in the table on pg. 52)).
2. Plot Total Volume Percentage Change vs. Superheat Temperature from 0 to 200 Co superheat
for all three metals in problem #1 above. Any surprises?
53
Internal Macroshrink
Casting
Casting
Casting
Surface
Primary Dendrite
External
Microshrink
Revealing
Primary Dendrite
Eutectic
Product
Eutectic
Product
Dendrites on Surface
These diagrams illustrate the nature of shrinkage porosity which is observed within castings. Ideally, of course, effective riser design would be able to eliminate or reduce the incidence of these
defects within the casting. Usually proper riser design will prevent the incidence of the macroshrinkage class, but it is possible that no amount of risering will eliminate microshrinkage.
Shrinkage porosity within the casting results in lower strengths because the effective cross sectional area of the casting is reduced, and reduced ductility because of the incidence of preexisting
voids.Understanding the reason why these types of shrinkage occur is helpful to the designer in
eliminating or minimizing this degradation caused to mechanical and physical properties. The
presence of each of these types of shrinkage can be understood by considering the process that is
involved during solidification, a process which includes the following list of events.
Solidification Begins by Dendrite Nucleation on Mold Wall
Shrinkage Associated With Liq -> Sol Results in Local Vacuum
54
Macroshrinkage
Poor Riser Design - Riser Solidifies Before Casting
Atmospheric Pressure = P
Shrinkage
(Vacuum)
Vacuum Pressure = P 0 = 0
Completely Solidi ed
Partly Solidi ed
P0
Shrinkage
(Vacuum)
P0
Liquid
Solid
Internal Macroshrinkage results when the riser does not adequately feed the casting, but the casting
has established a solid shellagainst the mold wall which is able to resist deformation due to the
stresses generated by the pressure dif
ference . The result is the retention of a lar
ge macroshrinkage within the casting.
P
Shrinkage
(Vacuum)
Partly Solidi ed
Completely Solidi ed
P0
P
Liquid
Solid
Microshrinkage
Presence of Dendrites Makes Fluid Flow Difficult
Internal microshrinkage is a very common defect in castings where there is an abundance
of dendrites, where the dendrite arms are long and intertwined. Under these conditions the ability
of the fluid to flow into these volumes to take up shrinkage as it is occurring is significantly
reduced. This problem is exaggerated as the solidification temperature range, TL - TS, increases,
and it is also usually more prevalent in castings which solidify more slowly. In these situations
where the dendritic structure makes particularly tortuous paths for fluid flow, even proper risering
will not eliminate the microshrinkage voids between the dendrite arms. External microshrinkage
is quite often observed in those situations where solidification is occurring rather uniformly
throughout the solidifying metal, and where significant fluid flow is still possible between the
55
dendrite arms. In these situations (a good example are powders formed by atomization in water or
air), the pressure gradient generated between the inside of the solidifying powder particle and the
surface results in the liquid between the dendrites being sucked into the center of the particle leaving the dendrites exposed on the surface.
In those situations where microporosity can not be avoided in the cast state, the integrity
of the casting can by increased by HIPping (Hot Isostatic Pressing), a procedure where the casting
is subjected to high pressure at an elevated temperature to physically squeeze the pores closed.
This is an expensive procedure which is used only in those situations where processing cost is of
minor concern.
Riser Design
Riser design in sand mold castings requires, as a minimum, that the riser solidify after the
casting, i.e.:
tS(Riser) > tS(Casting)
Thus by Chvorinovs Rule,
BS(R){V/A}R2 > BS(C){V/A}C2
where BS(R) and BS(C) are the mold constants for the riser and casting respectively, and (V/A)R
and (V/A)C are the volume to area ratios of the riser and casting respectively. It is useful to define
the ratio (V/A) as the modulus, M, so that,
(V/A)R = MR (Modulus of Riser), and (V/A)C = MC (Modulus of Casting)
Thus for successful riser design,
BS(R) (MR)2 > BS(C) (MC)2
It is clear on studying this equation that any of the terms present could, in principle, be varied
independently to insure that tS(R )> tS(C). However, there are two most likely situations encountered in practice, situations defined below:
I.
BS(R) = BS(C), and then MR > MC becomes the criterion that must be met to insure
that the riser solidify after the casting. This is by far the most common situation encountered in
practice, the situation in which the riser and the casting are molded into the same sand. In practice
it has been observed that MR > 1.1 MC is usually sufficient to effectively feed the solidifying casting.This situation is illustrated below:
COPE
B S (R)
B S (C)
CASTING
Parting Line
RISER
DRAG
56
B S (R) = B S (C)
II.
BS(R) > BS(C), such that MR < MC and still the inequality tS(R) > tS(C) is obeyed.
This is the situation when an insulating riser sleeve is molded around the riser cavity. This allows
a much smaller riser to be utilized thereby increasing casting yield (see page 59 for a definition of
casting yield). This is illustrated below:
Riser Sleeve (Insulator)
B S (R)
COPE
B S (C)
Parting Line
RISER
CASTING
DRAG
CUBE
a
a
A = 6a 2
L
BAR
V = Lwt
A = 2L(w + t) + 2wt
M = Lwt / [2L(w + t) + 2wt]
M = a/6
Because of the large inequalities in the bar modulus, the term 2wt is insignificant compared to
2L(w + t), and thus an estimate of the bar modulus becomes:
M = wt / 2(w + t) = Cross Sectional Area of the Bar / Perimeter of the Bar
A plate is de ned as a shape
in which the lengt,L, and
width, W, are similar and
much greater than the
thickness, t.
i.e. L = W > > t
L
PLATE
W
V = LWt
A = 2(L W + Wt + Lt)
M = LWt / 2(L W + Lt + Wt)
57
12
1/4
1/2
S
B
58
Thus a side riser on the step bar requires a riser with a modulus MR = d/5 = 1.1MC = 0.55 in.
A schematic side view of the casting would look like this.
d
2.75
h
5.5
B
C
Riser Connection
This is an adequate size riser for this casting. However it is important to make sure the riser connection is large enough so that it does not solidify before the casting. Because of the complexity
of the heat transfer situation near the gate connection, they are often arrived at by trial and error.
The effectiveness of a riser is also determined by whether the riser is considered hot or cold.
Hot and cold risers are defined in terms of their relationship to the gating system of the casting.
This is illustrated in the top view of a system containing both a hot and a cold riser.
The Molten Metal that Enters
The COLD Riser Has Already
Passed Through the Casting, is
only a portion of the Metal Entering
the Casting and is therefore Colder
Casting
Riser 2
COLD
Riser 1
HOT
Path of Metal Flow
Clearly from a fundamental heat transfer point of view the cold riser needs to be larger than the
hot riser to accomplish feeding equivalent casting section sizes. Risers are also classified as blind
or open, these varieties being defined in the sketch below:
OPEN RISER (Open to
Atmosphere)
59
Number of RisersThe number of risers needed to effectively feed a casting depends upon casting geometry
and feeding distance required. This can be illustrated by considering the two bar castings shown
below:
t = 4, w = 4
t = 4, w = 4
R RE
oooooooooooooo
EE
ooooooooooooo
100
16
The modulus of both bars is given by the estimate, MC = Cross Sectional Area (4x4) / Perimeter
(16) = 4x4 / 16 = 1 The minimum requirement is that one riser with a modulus, MR = 1.1 would
be sufficient. Using the top riser formula for a riser with h = 2d, MR = 2d / 9, gives a cylindrical
riser with d = 4.95 and h = 9.9. Common sense would tell one that the best position for the riser
in each case would be in the middle of each bar at the positions marked R on the sketch. Thus the
riser on the short bar would be required to feed all of the shrinkage in the 16 inch bar, while the
same riser on the long bar would be required to feed 100 inches. While this may be satisfactory
for the short bar, common sense again tells us that it is likely that the long bar would contain some
shrinkage along the centerline of the bar, perhaps not near the riser or at the ends of the bar but in
the mid regions indicated on the sketch with os. In fact, sectioning the bar along the centerline
would reveal a situation similar to the sketch for the long bar. Apparently each riser and each bar
end is effective at promoting a sound (NO VOIDS) casting immediately adjacent to either the bar
end or the riser. The sound distance from the riser along the bar is said to be the Riser Effect, RE
shown on the sketch, and the sound distance from the end of the bar is said to be the end effect,
EE, both of which are shown on the above sketch of the 100 bar.
Work on steel bar castings has shown that the gradient in temperature along the centerline, dT/dx,
is a critical parameter in relating to whether voids form or not. It was shown from steel bars which
60
were instrumented with thermocouples along the centerline that voids were likely when dT/dx fell
below a certain amount.. This is shown schematically below:
AT SOME TIME, t, AFTER POURING
Riser
Instrumented
Centerline
(dT/dx) 2
(dT/dx) 1
(dT/dx) 3
It can be seen in the above figure that the gradient, dT/dx, is greatest at the end of the bar in contact with the cold mold and at the riser in contact with the hot reservoir of molten metal. It was
observed that when dT/dx at any time was less than a critical minimum value, (dT/dx)C, that
shrinkage voids formed at the centerline. Of course, the longer the distance between the end of
thebar and the riser, the more likelihood of voids. This then explains in a more rigorous way why
the voids show up in the long bar on the previous page and not in the short bar.
Thus each end of the bar and each riser is responsible for producing sound material. Selection of
the number of risers needed then requires that the RE and EE for each material be known and then
the risers positioned so that the RE and EE overlap, or at least butt together. For steel bar type
castings it has been determined that RE = 1.5 t and EE = 2 t. Thus for a bar with t = 4, the RE =
6 and the EE = 8, and then the farthest distance that a riser can be placed from the end of a bar
and still result in a sound bar would be the distance RE + EE = 14. The contribution to sound bar
castings from each riser would then be the riser diameter plus 2RE (feeding in both directions).
For the 4 bar above, then, the maximum distance fed for each riser is 4.95 + 12 = 16.95. Determination of the number of risers needed for the 100 bar is determined as follows:
No. of Risers = (100 - 2EE) / (2RE + d) = 4.96, or 5 risers distributed uniformly along the
length with the end risers 14 inches from the end of the bar.
Casting Yield
The casting yield is defined as the ratio :
Casting Yield (CY) = Weight of Castings Shipped x 100%
Weight of Metal Poured
It is obvious that the goal for a metal casting plant would be to make casting yield as high as possible. It is also obvious that the riser size and number of risers has a big impact on the casting
yield. It is common practice for metal casting plants to have overall casting yields of between 40
and 80%. Maximization of the yield will involve reducing the number and size of the risers as an
61
important contributor. Of course, reducing the size of the gating system will also have a significant effect on casting yield. Two of the most common ways to increase yield are (1) to add insulating riser sleeves so that BS (R)can be increased (see earlier discussion) and (2) to add chills
to the mold to induce stronger thermal gradients (dT/dx) thereby extending the end effect, or to
actually add end effects in between risers. This effect of chills, usually blocks of iron or other
metal set into the mold, is illustrated below:
EE + t
RE
RE + EE
RE + EE
RE
EE
CHILLS
The actual increase in length of sound casting due to chills varies from one material to the next,
but for steel bars a chill on the end of the bar will increase the EE by the bar thickness,t, while
chills placed between risers will add at least an EE in either direction.
Heat transfer between liquid metal and a permanent mold can also be described mathematically in much the same way as was done for heat transfer in insulating molds. The major difference here is that the mold material has a much larger thermal conductivity than sand, and so the
solidification will be much more rapid. In the insulating mold the rate of transfer in the sand was
the rate limiting step. In permanent molds the rate limiting step is at the interface between the
metal and mold, where heat is transfered between the solidifying metal and the permanent mold, a
mold which is usually coated with a mold wash or may quickly develop an air gap. The parameter
which defines the transfer of heat between metal and mold in these cases is called the heat transfer
coefficient, h. The model describing this event is illustrated below:
Permanent Mold
Molten Metal
+x
Distance
Notice in this schematic that the temperature drops discontinuously at the mold - casting interface.
Heat flow within the casting and in the mold is very rapid (High Thermal Conductivity) compared
62
to the relatively slow transfer across the interface. Thus the rate of heat removal and therefore
solidification rate depends on the heat transfer coefficient, h, across the interface. The total heat
flow in time t is then given by integrating the above expression, giving:
Q
= Ah [ T
]t
= A h T
t
0 S
Using the relationships for Latent Heat and Superheat given earlier, and solving for tS gives:
Metal [ H + C
V Metal
F
Metal ( T p T m ) ]
-
- ---------------t S = ------------------------------------------------------------------h ( Tm T0 )
A Metal
Writing an expression which is a similar to Chvorinov gives:
tS = BS(V/A),
where BS is a mold constant and V/A is the modulus of the casting.It should be noted that, as
opposed to solidification in a sand mold in which tS varies as the square of the casting modulus,
solidification in a permanent mold varies linearly with the casting modulus.
63
the logic used in FEA to describe a simple solidification problem involving a molten aluminum
cube in a steel mold.Consider the following simple casting:
Air
At t = 0 time
TAl = 704 oC (1300 oF)
Steel Mold
4
cm
Aluminum
Casting
4 cm
Using the above simplified equation for solidification time in a permanent mold and constants
given in Table 7 gives:
tS = 2.385(g/cm3) {[395.995 + 1.080(704-660)](joule / g) / 1.3058 joule / sec cm2 oC /
(660-149) (oC)} ( 0.666 cm)=1.055 sec
Of course, this result reflects the assumption that the mold does not change temperature and there
is no indication of when solidification is complete in various places within the casting. A more
realistic representation would involve determining temperature variations within the steel and aluminum and measuring solidification times in various places within the casting. This will be done
by using the FEA method to first, divide the aluminum and steel into nodes, and second to
determine the rate of heat transfer between nodes in discrete time intervals. This method is, of
course, amenable to doing by computer iterations from one discrete time interval to the next. Consider the following Two Dimensional Nodal Map of the aluminum and steel at time t = 0. This
map shows only one quarter of the casting and mold because symmetry conditions dictates that
the remaining three quarters will behave in exactly the same manner as the one quarter.
Al
1
(704)
2
(704)
5
(149)
6
(149)
3
(704)
4
(704)
7
(149)
8
(149)
9
(149)
11
(149)
13
(149)
15
(149)
10
(149)
12
(149)
14
(149)
16
(149)
Air = (22)
Steel
Initial T = 149 oC
Initial T = 704 oC
ASSUME:
1. Temperature within each Node is uniform and
2. Temperature changes by conduction between
nodes of similar material, where
dQ/dt = KA (T n1 - Tn2) / x.
3. Temperature changes by interfacial transfer
between nodes of dissimilar material.
dQ/dt = hA (T n1 - Tn2)
4. Heat ows perpendicular to the node walls.
5. Heat does not ow in or out of the page.
64
In the above equations, Q is heat in joules, K is the appropriate thermal conductivity of the metallic materials (either Al or Steel), the Tns are the temperatures of the nodes, A is the cross sectional area of each node face (1cm2), x is the distance between node centers (1 cm), and h is the
heat transfer coefficient that applies.Integrating the above equations over the time step t gives
the relationships shown below for heat flow due to conduction and interface transfer. The final
temperature of a node, Tf, resulting from the sum,Q, of the heat components into or out of a node
during the time interval t is also given below, where Ti is the initial temperature, V is the volume
of the node, is the density of the node material, and C is the heat capacity of the node material.
Q = [ KA ( T n1 T n2 ) ( ( t ) x ) ] and Q = hA ( T n1 T n2 )t
+
i
Q
V C
The appropriate constants for computation of the Qs and Tf for each node after each time increment can be obtained from the above numbers for heat transfer coefficients on page 63 and the
data in Table 7 on page 50 of these notes.
5
(149)
Q
In the first time increment t = 0.1 sec, 72.21 joules of heat flows across the node boundary, leaving the liquid Al and entering the solid steel mold. This is the only heat flow for either nodes 2 or
5 in the first time increment because there are no other temperature gradients to which these nodes
can respond.(Recall that this is only two dimensional heat flow. We are not allowing heat flow
into or out of the page for simplicity.) Clearly then after 0.1 sec the temperature of node 2
decreases and the temperature of node 5 increases by an amount determined by the heat capacity
(specific heat) of each unit and the mass of the unit. Removing 72.21 joules from node 2 results in
a temperature decrease after 0.1 sec from T2 = 704 to :
65
66
temperatures (rounded off to the nearest degree) in the 16 nodes after the first 0.1 sec of the FEA
is given below:
AFTER TIME 0.1 SEC
Steel
Al
1
(704)
2
(677)
5
(169)
6
(149)
3
(677)
4
(660)
7
(169)
8
(149)
9
(169)
11
(169)
13
(149)
15
(149)
10
(149)
12
(149)
14
(149)
16
(149)
Initial T = 704 oC
Initial T = 149 oC
Notes:
1. Node 4 has partially solidi
Shown as dark shaded area.
ed, ~ 3.2%
Air (22)
The Second Time Increment, t = 0.1 sec (Total Time = 0.2 sec)
The next iteration in the FEA involves more of the nodes in the system because of the temperature
changes resulting in the first time increment. Consider node 1, which now has thermal gradients
between itself and nodes 2 and3.
(704)
1
(677)
2
3
(677)
Consider node 2 once again. Node 2 has three inputs to heat flow in the second time increment,
illustrated below:
Thus the net heat change in node 2 is given by:
Q = Q 1->2 + Q 2->5 + Q 2->4
Q = + (0.9403) (1) (704 - 677) (0.1) / (1)
4
+(1.3058) (1) (169 - 677) (0.1)
+(0.9403) (1) ( 660 - 677) (0.1) / (1)
=2.539 - 66.334 - 1.598 = - 65.394 joules
From knowledge of heat content of
Al, only 41.65 joules of superheat remain in node 2,
therefore node 2 will begin to solidify in time increment 2, having a fraction of:
(65.39 - 41.65) / 944.45 = 2.5% solid, the temperature decreasing to and remaining at 660
1
67
C.
Q = 1.3058 (1) (667 - 169) (0.1) + [0.782 (1) (149 - 169) (0.1) / (1)] = 64.77 joule
Tf = 169 + 64.77 / [ (1) (7.87) (0.456)] = 187.05
68
The temperature distribution (rounded off to the nearest degree) after 2 increments of 0.1 sec time
is illustrated below:
AFTER TIME 0.2 SEC
Al
1
(702)
2
(660)
3
(660)
4
(660)
9
(187)
10
(149)
Initial T = 704 oC
Steel
Initial T = 149 oC
5
(187)
6
(149)
7
(186)
8
(149)
11
(186)
13
(150)
15
(149)
12
(149)
14
(149)
16
(149)
Notes:
ed, ~ 16.5%
ed, ~2.5%
Air (22)
Thus solidification and the temperature distribution in the entire casting - mold configuration can
be observed by systematically:
I Summing the Heat Flows into Each Node During Each Time Increment
II. Computing the Change in Nodal Temperature As a Result of That Heat Flow
Problem:
Continue the heat flow scenario described above until solidification is complete in node 1.
Report your results at critical periods in the process by:
a. Including distributions like the above showing the progress of solidification
b. Including cooling and heating curves for nodes 1,2,4,5,7,13, and 16 on one graph.
Clearly the best way to do this work would require a computer program to carry our your iterations. IT WILL BE ACCEPTABLE FOR GROUPS OF UP TO THREE PEOPLE TO TURN IN
ONE PAPER.
69
ingot casting to 95% in continuous casting. The growth of continuous casting of steel in the
United States as well as the demise of ingot casting is shown in the Figure below:
100
80
60
Continuous
Ingot
United States
Steel Production
Data From Making, Shaping,
and Heat Treating of Steel, 10th Ed.
& 1995 AISI Statistical Report
40
20
0
1960
1968
1976
1984
Year
1992
2000
The continuous casting process is illustrated below together with a schematic of a conventional
ingot mold.
Tundish
Conventional
Ingot
Saw or Shear
Solid Steel
The process of continuous casting involves supplying a tundish (storage and transfer vessel) with
molten steel and then metering that steel into a water-cooled mold whose bottom is the steel billet
or slab. This slab or billet is bent as it moves and large conveniently sized pieces are cut or
sheared for further processing. It should be noted that the liquid sump can extend a significant distance down into the casting. The operators must be careful so that remelting doesnt occur and
cause a runout. Other advantages over conventional ingot casting in addition to increased efficiency include higher production rates, and finer microstructures (smaller dendrite arm spacings)
due to water cooling the smaller cross-section castings. The finer dendrite arm spacing is a structure which is more easily deformed and less likely to fail during that mechanical processing. In
addition, the larger section ingot castings are more likely to be plagued by macrosegregation, in
which segregation due to gravity differences produce significant change in chemical composition
from one point to another on a macroscale.
70
Tundish
Water Cooled Mold
Water Spray
Liquid Sump
Solid Casting
Base Block
Continuous casting is clearly the most efficient way to produce stock for further mechanical processing of metals. However the casting of non-ferrous alloys based on aluminum or copper is
most often done in a semi-continuous mode, a schematic of which is indicated in the above figure.
Initially the base block is snug up against the water-cooled mold. Casting commences by pouring
directly onto the base block and then moving the base block downward as solidification
progresses. There is no attempt to bend the casting. Rather the casting extends down into a well,
typically 20 to 30 feet deep. When the base block reaches the bottom of the well the casting process is over. Most aluminum alloys produced for wrought applications are made this way, producing ingots about 20 feet long by 3-4 feet wide by 1.5-2 feet thick. Free machining brasses (Cu35Zn-3Pb) are produced in a similar way with three cylindrical logs produced simultaneously
with dimensions of about 12 inches by 20 - 30 feet long. Advantages of this technique over static
cast ingots are the same as given above for the continuous cast steel. Continuous casting of some
non-ferrous products does occur but the relative proportion is quite small.
71
Plane of
Weakness
Q = Heat
Q
Typical Continuous Cast Billet Grain Structur
e, As-Solidi ed
This schematic illustrates the basic process of grain (dendrite) nucleation and growth in a continuous cast billet. The above cross section illustrates the three common grain structures observed in
these types of castings. The outer chill layer is made up of a very fine equiaxed grain structure
which has nucleated as a result of the large undercooling present at the surface. This quickly
changes to a columnar structure which extends from the chill layer in towards the center of the
casting, the columnar (long and narrow) grains (dendrites) being extensions of chill grains (in
favorably oriented [100] directions) which grow parallel to the direction of heat flow. During the
columnar growth time, nucleation of new grains (dendrites) occurs in the remaining liquid volume
in the center of the billet, grains which grow in an equiaxed manner into the remaining liquid.
Solidification is complete when the columnar grains encounter the growing equiaxed grains. It is
thought that the nuclei which ultimately end up as the equiaxed grains in the center come from the
growing columnar dendrites, where secondary arms have broken off of the columnar dendrites (as
a result of chemical, mechanical or thermal instabilities in the melt) and have been swept out into
the liquid. These nuclei then either survive and grow giving the equiaxed grains, or are remelted
in the remaining liquid allowing the columnar grains to grow to the center of the casting. The
occurrence of the columnar zone is not a favorable structure for hot working processes, the contact area between columnar zones at right angles to each other being a dumping ground for segregants, porosity, inclusions, etc. which become effectively planes of weakness (see the above
schematic) in the casting. It is therefore desirable to produce castings which have no columnar
zone, a situation which is favored by reducing the superheat (increasing the chances of nuclei survival in the center), or by stirring the liquid thereby mechanically removing some dendrite arms
for transport to the central part of the casting. Stirring can be accomplished in certain instances
72
electromagnetically, and in other cases by shaking or moving the casting to generate shock waves
which affect the arms of the growing dendrites. The idea of chemical, thermal, or mechanical
forces dislodging dendrite arms to send them into other parts of the solidifying casting can be better understood when the physical shape of these dendrite arms is considered.This reality is
described in the schematic below:
Photographs of dendrites in real crystals inevitably reveal situations which look remarkably like
the above sketch. There is no direct proof that these released arms are in fact the source of the
equiaxed grains in the center of the castings, but the circumstantial evidence is almost overwhelming.
Temperature
Equilibrium solidification in a binary system assumes that diffusion occurs within the solid
and adequate mixing occurs in the liquid so that the
compositions described by the phase diagram are
Liquid, L
obeyed. The attached schematic phase diagram is
TL
used in the description of both equilibrium and
T0
L+
non-equilibrium solidification. During equilib
+
L
TE
rium solidification the first phase to appear is the
terminal solid solution of composition kCo at the
temperature TL, where k is the equilibrium distri+
bution coefficient and Co is the alloy composition.The equilibrium distribution coefficient is
defined as the ratio of the composition of the solid
CE
Co CM
to that of the liquid at a given temperature, a value
kCo
Wt. Pct Solute
which can be determined from the phase diagram.
Solidification is complete at temperature T0 and
the composition of solid reaches Co. The lever rule can be used to compute the weight percentage
of the phases & present in the temperature range TL to T0.
In real situations involving solidification, the largest departure from equilibrium results
from the fact that diffusion in solids usually cannot maintain equilibrium in the solid state during
solidification. In alloys with substitutional solute atoms which diffuse by a vacancy mechanism,
the number of vacancies and the statistical nature in which they move preclude the solid phase
maintaining the composition required by the phase diagram during the time available to the solidifying casting. Only those solutes which are interstitial and have mostly empty neighboring sites
(carbon in iron for example) can even hope to keep up with the dictates of the phase diagram. In
the above figure, then, the composition kCo of the initial solid to form remains at or near that
value during and after casting. With cooling below TLthe new solid to form will obey the phase
diagram and be richer in solute than the first to form. The net result of this is that when the temperature T0 is reached THE AVERAGE COMPOSITION OF THE SOLID IS LESS THAN Co
and there is still some liquid left; the casting must go to lower temperatures before solidification is
73
complete. In eutectic systems like the one shown above, the final temperature of solidification
will in fact be the eutectic temperature, TE. The practical result of this situation is that real castings are not homogeneous in composition throughout, with alloy segregation occurring on a
microscopic scale.
Solid
t = t1
t = t2
Solid
t = t3
T = TE
Q
Solute Composition (Weight %)
t=0
T = TL
Liquid Composition
Solid Composition
CE
CM
Co
kCo
0
Fraction Solid, f
In the above sketch it can be seen that the solid composition starts at kCo on the left and then
gradually increases in a non-linear fashion as solidification progresses to the right increasing until
the maximum solubility of solute in is reached , CM at TE. At the same time the liquid composition increases overall until the eutectic composition is reached at the eutectic temperature. At
this point the remaining liquid will undergo a eutectic reaction forming + . It can be shown
74
that the equation describing the non-linear solid composition, CS, from left to right is known as
the Scheil equation, given below:
CS = kCo {1/(1- f)}1-k
This variation in composition describes quantitatively the segregation of solute in a binary alloy
which has solidified under these one dimensional conditions of planar interface movement. Of
course most real solidification events involve the formation and growth of dendrites, which is not
a planar solidification event on a macroscale. However on a microscale during solidification
between dendrite arms, the planar front description is a fairly accurate representation of dendrite
arm fattening after the dendrite has already been established.
This is shown in the following schematic representation of dendritic growth.
d, Dendrite Arm Spacing
Solute Composition
Cored
Solid
Eutectic
Liquid
Cored
Solid
CE
CM
Co
kCo
It can be seen in the above sketch that the fattening of dendrite arms mirrors on a microscale the
one dimensional growth pictured on page 74. Even though the conditions of solidification on a
macroscale is definitely not planar front solidification (dendritic growth is quite the opposite of
planar front solidification in which the dendrite arms race out into the liquid in response to compositional and thermal fluctuations at the solid - liquid interface) the conditions for growth (fattening) in between dendrite arms approximate the conditions of no solid state diffusion and
complete mixing in the liquid required to develop the Scheil Equation. This is because the dendrite arm spacing is quite small, on the order of 10 to 100 microns (0.01 to 0.1 millimeters), and
liquid state diffusion is rapid enough to accomplish mixing in the microvolume between dendrite
arms. Typically liquid state diffusion coefficients are on the order of 10-6 cm2 / sec. Using the
time tested relationship between the distance an atom can move x, and the diffusion coefficient
D, and time t, [x = (Dt)1/2] , gives x = 0.1 mm for a reasonable solidification time of 100 seconds.
This means that atomic diffusion of solute within the liquid is sufficient to maintain a reasonably
uniform composition in those microvolumes. In the schematic above the final product consists of
75
dendrite arms (the center of which represents the first to freeze (FTF) part of the casting) with a
gradient of solute perpendicular to the dendrite arm (coring) and a volume of eutectic product
between the dendrite arms representing the last to freeze (LTF) part of the casting. This is a very
common configuration in commercial cast microstructures. Of course most commercial cast
materials are multicomponent alloys in which there may be several major solute species added for
one reason or another. Those solutes with equilibrium distribution coefficients, k, less than 1 (Cu
in Al) will segregate in the manner shown above, solutes described as positive segregants. Solutes with an equilibrium distribution coefficient greater than 1 (Ni in Fe) will segregregate in the
opposite way, with decreasing solute content as the dendrite fattens. These solutes are said to segregate negatively.
Aluminum is a very important metal because of its low density and excellent mechanical
properties, properties which stem largely from its face centered cubic crystal structure. It is
alloyed with elements like Mg, Si, Cu, Mn, Fe, etc. to produce a variety of wrought products from
beverage cans to aircraft structural parts, to cast products like engine blocks and steering knuckles
for automobiles. The figure below illustrates the amounts of primary and secondary aluminum
produced and the amount shipped in the year 1989 for beverage can and casting production:
U.S. Production of Al
Primary
Aluminum
4.03 Secondary
Aluminum
2.05
Wrought
New
1.04
& Cast
Old
1.01
Products
Beverage
Cans
1.37
Castings
Permanent
& SemiSand Permanent Die
0.690
0.196
0.112
It can be seen that the bulk of the aluminum produced in the U.S. goes into the production of
wrought products. An example of the largest single product tonnage-wise is the production of
beverage cans; more aluminum is used in the production of beverage cans in a given year than is
used in the production of castings for all applications. Another significant industrial fact is that a
large fraction of the secondary aluminum production comes as a result of the recycling of bever76
age cans; about 60 percent of the material used to produce beverage cans in 1989 were recycled
through the secondary market, a good source of material for casting production.
660.4 0C
Proeutectic
Liquid, L
+ L
L +
577 0C
1.65
12.6
Eutectic +
+
7
Time
Weight Percent Si
77
Schematic microstructures similar to this alloy are shown in the first laboratory handout. The
presence of Mg and Fe in this alloy gives an opportunity for the formation of a chinese-script
eutectic of + Mg2Si and platelets of Fe2Si2Al9 in addition to the Si platelets. These plate-shaped
phases produced in typical sand castings provide easy crack nucleation sites and propagation
paths , thereby resulting in relatively low strengths and ductility.
Modification of 356.2
In applications where strength and ductility are not important, the sand castings with the plateshaped second phase morphology is considered acceptable. However, higher strengths and ductilities can be realized by the addition of small amounts of Na or Sr to the melt (a process called
modification) just prior to pouring the castings (See section on additives in these notes). This
additives effectively changes the shape of the silicon from plates to rods thereby reducing the
crack nucleation and propagation potential. See the schematic modified microstructure in the laboratory handout #1. This process has the potential to double the ductility and increase the strength
by 25 %.
Age Hardening 356.2
Following solidification, the 356.2 alloy castings can be further strengthened by precipitation of
the Mg2Si as fine coherent particles within the a matrix. [The student is urged to consult an appropriate physical metallurgy text for a basic description of the fundamentals of precipitation hardening.] The heat treatment schedule needed for this process is given below together with a quasibinary phase diagram for the aluminum - Mg2Si system:
660 0 C
+L
1.85
595 0C
520 - 530
13
Water Quench
+ Mg 2Si
65 - 100 0C
150 - 155
Wt Pct Mg 2 Si
Aging Treatment
3 - 5 hours
Time
The solution treatment time of 12 hours at 525 OC is designed to dissolve the eutectic Mg2Si particles in the a solution (which formed as a result of segregation, coring, during solidification) and
to redistribute the Mg and Si uniformly throughout. It is known that up to 1.85 wt. pct. Mg2Si (see
above phase diagram) is soluble in the a matrix at 595 OC. If it is assumed that all of the Mg
which is present in the alloy (0.35 %) can be taken into solution, this gives ~ 0.52 wt. pct. Mg2Si
as potential precipitates on aging. Quenching into hot water is followed by aging at 155 for 3 - 5
hours during which time the coherent tiny strengthening precipitates of Mg2Si are formed in the a
78
solid solution.The effect of aging time on the tensile properties of A 356.2 alloys is illustrated
below:
45
Yield Strength
40
Percent Elongation
35
30
25
0
4
6
8
Aging Time (Hours)
10
10
4
2
0
12
Alloy 319.1 (Nominal Composition 6 Si, 3.5 Cu, 0.1 Max Mg, 1.0 Max Fe, 0.1 Max Ni)
This is an important alloy used to produce castings in permanent molds, a hypoeutectic
alloy which, because of the presence of Cu, is also age hardenable. The major elements, Si and
Cu, are present in an amount so that solidification proceeds in a similar way to alloy 356.2,
namely by the production of proeutectic dendrites of followed by a eutectic reaction in which
both Si and Al2Cu can form in eutectic products surrounding the dendrites of . A microstructure
of this alloy could look like the schematic below:
Fe - Containing Platelets
Fe2Si2Al9
Al2Cu
Si ()
Eutectic
Section
Through
Proeutectic
Dendrite
Arm
Composition
SDAS
Cu
Si
Distance
79
Segregation of
Cu and Si
within dendrite
due to Coring
In this schematic micrograph the position of the proeutectic dendrites are shown by dashed lines
to indicate the imaginary boundary between dendritic and eutectic . The eutectic Si () is
shown as platelets, the eutectic Al2Cu as individual particles, and the Fe-rich platelets all share
the interdendritic volume with the eutectic . In addition the segregation of Cu and Si within the
dendrites (as a result of solidification) is shown as a positive segregation event; i.e. the composition of both Si and Cu increases with increasing distance from the center of the dendrite. Like the
356.2 alloy, attaining the optimum in mechanical properties will involve a precipitation hardening
treatment, solutionizing at about 500 0C (put the Al2Cu into solution and redistribute the Cu uniformly in the dendrite arms) followed by hot water quenching and an aging treatment in the range
130 - 190 0C. Mechanical properties are in the same range as alloy 356.2. Further refinement of
this material can be accomplished by modifying the eutectic with Na or Sr, like alloy 356.2, or by
the addition of a grain refining agent such as TiB; the TiB additive is effective at providing more
nucleation sites for the dendritic product.
Alloy KS 281 (German ) [Nominal 18 Si, 1.2 Cu, 1.1Mg, <1.3 Ni, <0.7Fe, <0.3 Mn, < 0.2 Ti]
This hypereutectic Al - Si base alloy represents a modern material used for the production
of automotive pistons by a permanent molding technique, an application which requires good
wear resistance and reasonable high temperature strength. In this alloy, the high silicon content
ensures the formation of the hard, wear resistant proeutectic (see the partial phase diagram on
page 58) prior to the eutectic reaction in which the remaining liquid transforms to the Si and
Al2Cu phases in the eutectic matrix. The as - cast microstructure is illustrated schematically
below:
Proeutectic Si ()
Eutectic
Eutectic Al2Cu
Eutectic Si ()
The dominant feature of this microstructure are the blocky proeutectic Si - rich particles, the
remaining structure being composed of the eutectic products mentioned above.
Processing KS 281
Processing this material involves a special effort to refine the proeutectic product; a finescale distribution of the proeutectic product is more desirable than a coarse distribution. This is
accomplished by the addition of 60 - 80 ppm (parts per million) of phosphorous, added to the melt
80
in the form of a Cu - P alloy after the degassing operation (Degassing is an important step in the
production of Al alloy castings, a process described elsewhere in these notes).The addition of the
phosphorous creates conditions for more nucleation of the proeutectic during cooling of the
casting. Strengthening of this material is accomplished by the same precipitation hardening process described for alloys 356.2 and 319.1. The details of this heat treatment include a solutionizing step of ~ 1 hour at 510 0C, a hot water quench (70 0C for 8 minutes), and a 5 hour aging
treatment at 230 0C.
Molten metal processing often involves a procedure where additives are introduced to the
molten metal at some stage in the sequence of operations shown schematically below:
A. Charging
B. Tapping
C. Mold Pouring
Mold
Furnace
Ladle
D. In-Mold
Points of addition in the sequence include during charging, tapping, mold pouring, and in the
mold.The reasons for additions are many and varied, a number of these being listed below:
A. Alloying additions for control of chemical composition - these can be made in the
furnace charge (A above) or at some point after the metal is molten. Amounts from 0 to
several % are typically added. The choice of at what stage the alloy is added depends primarily upon the ease with which the alloy melts or goes into solution.
B. Additions for the purpose of providing nucleation sites for a phase or phases these are usually made at some point after charging. Amounts are usually small, and may
be as small as 0.02 % to be effective. A classic example of this type of addition is the inoculation process in gray and ductile cast irons. This process, where a ferrosilicon alloy is
added for the purpose of nucleating graphite, varies from plant to plant and from casting to
casting. Most plants inoculate at the tapping stage (B above) when the metal flows into the
ladle, but may add insurance inoculant when the mold is poured (C above) or they may
actually put a small amount of inoculant into the gating system (The so-called In-Mold
Stage D above). In this process it has been shown that the later the addition point the more
effective is the inoculant. It is also true that the later the addition the more expensive the
process; it costs nothing extra to deliver a paper bag filled with inoculant at point B but
may be quite expensive to deliver a controlled amount at points C and D. This class will
experience the relative complexity of inoculation in the gating experiment on gray cast
iron, in which we will attempt to deliver a controlled amount using Hickman - Williams
commercial unit (The Post Inoculant Feeder PIF). The fact that lateness is important for
effective inoculation implies that time in the metal is detrimental to the formation of
nuclei. The inoculant is said to fade with time. Most processing requirements, for example, specify that the casting be poured no later than 10 minutes after inoculation if inoculation occurs at point B. If the time is exceeded then the molten metal is usually pigged to
81
avoid pouring castings of uncertain quality. The detailed effects of inoculant additions of
processing in gray cast irons will be covered later on in these notes.
C. Additions for the purpose of changing the shape of the phases that form during
solidification - these can be made at all of the above points in processing, depending upon
the material and the goal of processing. Amounts again are quite small, usually on the
order of 0.01 to 0.05 wt.%. Good examples of this processing are I.,the addition of sodium
(Na) or strontium (Sr) to aluminum - silicon alloys to force a change in shape of the eutectic silicon from plate-shape to rod-shape and II., the addition of magnesium (Mg) to a cast
iron liquid to accomplish a shape change from plate-like to spheroidal. The addition of Na
to aluminum-silicon alloys is termed modification and the addition of Mg to cast iron is
termed treatment. Both of these additions result in significant enough microstructural
change that mechanical properties are impacted greatly. This is especially true for cast iron
where the ductility changes from essentially zero for the flake-shaped eutectic graphite
(Gray Iron) to values in the range 0 to 20 % Elongation for the spheroidal shaped graphitic
iron (Ductile Iron).The details of processing ductile cast iron will be discussed at a later
place in these notes.
D. Additions for the purpose of refining grain size during solidification or for limiting grain growth in the solid state after solidification is complete. These additions are
usually made in the charge or on tapping the furnace into the ladle, and again the amounts
added are often quite small, in the range of 0.01 to 0.04 %. An example cited here would
be that of adding titanium to aluminum alloy semi-continuous castings, where the titanium
is often wire-fed into the tundish feeding the large vertically descending ingots. The mechanism by which the refinement occurs is thought to be a result of the formation of titanium
oxides which then hinder grain boundary movement during subsequent annealing operations.
E. Additions for the purpose of removing gaseous impurities in a melt. These additions may be made either by purging a melt with a gas or by adding compounds which will
react chemically with the impurity, forming an oxide or some solid compound which then
goes into the slag and is removed. The most common example of the former is the degassing of aluminum alloys (removing hydrogen) by purging with argon containing SF6, as
demonstrated in the laboratory and described earlier in these notes. Of course, since this
operation requires a significant amount of time to carry to completion, it is necessarily
completed in the melting or holding furnaces. An example of the latter is the degassing
operation (removing oxygen) in copper alloys where a compound containing phosphorous (often CuP3) is added and the phosphorous reacts with the oxygen andthe resulting
compound goes into the slag. A similar deoxidizing step is used in the production of steel,
where elements like silicon, aluminum, or magnesium are used to form oxides which then
can be removed in the slag.
All of these additives with the exception of A above result in microstructural change to a
degree which is out of proportion to the amount of the additive used. It is useful to point out that
the additives are invariably fairly active elements chemically, elements for example that oxidize
readily in comparison to the other elements present. These are important control rods which the
materials engineer had at his/her disposal to ensure that a quality product is produced consistently
from one day to the next. Even though the quantity of the additive is very small, the presence of
these active elements within the melt at the critical time of solidification is sufficient to affect and
direct either the nucleation event and/or the growth events in the solidification process. For exam-
82
ple it is thought that inoculation in cast iron results by the formation and growth of nuclei within
the melt, nuclei which provide crystallographically convenient sites for nucleation of the graphite.
In the case of modification of Al - Si alloys and treatment of cast irons, the presence of the active
elements at the growing phase interfaces is likely responsible for altering the crystallographic
manner in which growth occurs.
Cast iron is a useful engineering material which has been known in some form for several
thousand years. The cast irons that we use today are primarily alloys of iron, carbon and silicon in
which the carbon is present in either graphitic form (pure C, hexagonal structure) or as an intermetallic iron carbide compound (the most common one being cementite or Fe3C, an orthorhombic
crystal structure). Cast irons represent by far the largest tonnage of cast-to-shape products produced in the world. (Of course the largest tonnage of a cast material is steel which is subsequently
mechanically formed into wrought products.) The ranges of compositions and the respective carbon forms and distinctive microstructural features for the common cast irons are given in Table 8:
Table 8: Cast Iron Composition and Microstructures
Range of C
Weight %
Range of Si
Weight %
Gray Iron
2.5-4.0
1.0-3.0
Graphite
Platelets
Ductile Iron
3.0-4.0
1.8-2.8
Graphite
Spheres
Malleable Iron
2.0-2.6
1.1-1.6
Cementite, Fe3C
Popcorn
White Iron
1.8-3.6
0.5-1.9
Cementite, Fe3C
Compacted Iron
3.0-4.0
1.8-2.8
Graphite
Type of Iron
Eutectic Product
Graphite vs. Carbide
Graphite
Shape
Rods
Wt
Pct
Sil
ico
n
It is generally accepted that the composition of these materials be described in terms of both the
composition of carbon and silicon. Thus the term carbon equivalent, CE, has been adopted
where:
CE = %C + 1/3 %Si
The above relationship between CE = 4.3, C,
Surface of Ternary
and Si represents the equation of the eutectic
valley on the Fe - C - Si ternary phase diagram Fe - C - Si Phase
Diagram
4.3 = %C + 1/3%Si
shown. Alloys whose CE is greater than 4.3
are said to be hypereutectic and alloys whose
Eutectic
CE is less than 4.3 are said to be hypereutectic.
Valley
Most gray cast irons are hypoeutectic and
most ductile cast irons are hypereutectic for
reasons which are associated with the cast
Hypo
Hyper
(Graphite)
microstructure predicted by this diagram.In
(Pro - Austenite)
Fe
the hypoeutectic gray cast irons the proeutecWt Pct Carbon 4.3
tic austenite dendrites are the first constituent
to form. On the other hand graphite spheroids
83
Temperature
are the first constituent to form in ductile cast irons. White irons and malleable irons are always
hypoeutectic. In malleable irons graphite spheroids (so - called popcorn shape) form from the
eutectic cementite during a solid state heat treatment. This material has similar properties to ductile iron in its heat treated state.
Phase Equilibria in Cast Iron Systems, Stable and Metastable Diagrams
The microstructure of cast
3.
irons depends upon the composition,
Liquid, L
processing and thermal history of the
material. The starting point for
+L
understanding the basics of cast iron
metallurgy requires a working
L + Gr
84
Assuming that this equilibrium reaction does indeed occur, then when solidification is complete
the structure will consist of austenite dendrites surrounded by a eutectic product of austenite plus
graphite. In reality, however, this eutectic reaction may not occur depending upon the cooling rate
(section size), and processing history, the system instead preferring to solidify by another mechanism completely. This other possibility for solidification exists because of the presence of a metastable phase diagram as well as a stable phase diagram. The metastable phase diagram (dashed
lines illustrated along with the stable phase diagram in the figure below) represents metastable
equilibrium between the phases , , L and cementite,Fe3C, instead of the stable graphite.
Cooling Curve
Liquid, L
+L
L + Fe3C
Temperature
L + Gr
+ Gr
( + Fe3C)
TG
TC
+ + Gr
Solidification
Complete
TL = Liquidus
( + + Fe3C)
TL
TG = Graphite Eutectic
+ Gr
( + Fe3C)
4.0
Carbon Equivalent, CE
Fe3C
4.3
TC = Carbide Eutectic
Time
Given enough time for reactions the stable phase diagram will always be obeyed. However, reality will often intercede with the result that the system will obey the metastable phase diagram just
to complete the transformations in the time dictated by the mold. It is important to notice that the
metastable diagram is essentially shifted to lower temperatures than the stable diagram. The
extent of the shift is proportional to the amount of silicon. For example in binary Fe - C alloys the
temperature difference between stable and metastable eutectics, T, is approximately 4 Co. In a
ternary alloy with 2% silicon, T is approximately 30 Co. Similar effects are recorded in the
eutectoid reaction range. These s are exaggerated in the above figure for illustration purposes.
The presence of the stable and metastable phase diagrams provides an opportunity for
every heat of iron to choose between stable and metastable transformations during the solidification event, and even after solidification during the solid state reactions in the eutectoid range.
Thus the microstructures observed can be extremely complex. Thermal analysis offers an excellent way to monitor the transformations during the solidification and cooling of cast iron . Ther-
85
mal analysis is most often accomplished using a small chemically bonded sand containeer which
has a thermocouple traversing the cavity of the cup. A sketch of such a device is shown below.
Molten Metal
~2.5 in.
Thermocouple Wires
To Data Analyzer
A schematic cooling curve for the 4.0 CE alloy is shown together with the above phase diagram
which is typical of a material solidifying as gray cast iron. The first arrest at TL corresponds to the
formation of austenite dendrites and the second the formation of the eutectic ( + graphite) at TG.
Note that there is significant undercooling below TG before recallescence (heating back up to TG
due to the latent heat of the eutectic reaction) occurs. An actual cooling curve from a 2 inch diameter cylinder of gray cast iron is shown below.
Gray Cast Iron (2 Inch Diameter bar)
1300
Austenite Liquidus
1200
1100
1000
Austenite -> Pearlite
900
800
700
600
0
500
1000
1500
2000
Time (Seconds)
86
2500
3000
3500
The actual cooling curve shows two thermal arrests at temperatures exceeding 1100oC. The first
one represents the formation of austenite dendrites from the liquid. The second arrest (with
undercooling) represents the eutectic reaction, liquid -> austenite + graphite. The third arrest in
the temperature range 720 - 730 oC represents the solid state reaction of austenite transforming to
pearlite. This transformation will be discussed later in this set of notes. Undercooling of the eutectic liquid below the gray iron eutectic temperature, TG results because the energy requirements
of nucleation of the graphite + austenite eutectic are large. It is understood that nucleation of the
graphite phase is required first, followed by nucleation and growth of austenite with the graphite
phase. Unfortunately if the graphite nucleation event does not occur before the temperature of the
melt reaches the iron carbide eutectic,TC, then the melt will solidify as the so-called white iron
eutectic, the metastable austenite + cementite product. Thus the solidification microstructure will
be very sensitive to the cooling rate of the casting and thus to the section size. Small section sizes
will have a greater tendency to solidify white than the larger section sizes. This tendency is illustrated with the chill wedge and associated cooling curves below:
Gray Iron (Gray, Graphite, Fracture)
Nucleation of
Austenite Dendrites
Chill Wedge
Temperature
Thermocouples
at these locations
Fracture Plane
TL
3
TG
1
Nucleation of
Graphite
TC
*
1
Nucleation of
Iron Carbide
Time
If thermocouples were placed within the chill wedge at locations as shown, the cooling curves
resulting could have the appearance given. Thermocouple #3 recorded a cooling rate so fast that
the equilibrium graphite eutectic product did not have time enough to nucleate and grow. The
result was that when the undercooling liquid reached the white iron eutectic, TC, the metastable
eutectic reaction took place. In contrast to the large energy requirement of graphite nucleation, the
energy requirement to form Fe3C is small and so little undercooling is required below TC to form
the metastable product. In fact, cooling curves in white iron do not exhibit a noticeable undercooling whereas undercooling in gray iron always occurs (see curves 2 and 3 above). In positions 2
and 3 in the wedge there is sufficient time (heavier sections cool more slowly) to nucleate the
graphite eutectic product which is then followed by recalescence as the latent heat of the solidifying + graphite is released. The reality of the possibility of white iron forming in the fast cooling
parts of gray iron castings is cause for much concern for the foundry producing the castings
because of the negative effects of the iron carbide. Iron carbide is very hard and brittle, and does
not machine readily. One of the advantages of gray cast iron is its excellent machinability due to
the presence of the graphite, but if iron carbide is present it will rapidly cause cutting tools to dull
87
or to fracture. It is thus necessary to do everything possible to ensure that the white iron does not
form at any point in the gray iron casting. The steps that can be taken to prevent the formation of
iron carbide (or chill) within gray cast iron are listed below:
1. Change the casting design to eliminate any sections which would cool rapidly enough to form
eutectic iron carbide. This is not usually a practical solution because of the high cost of tooling
(pattern making, mold making, gating design, etc.).
2. Increase the T between the stable and metastable eutectics. This would require significantly
increasing the silicon content of the alloy, a practice which would not be practical because of the
potentially negative effects on mechanical properties. An increase in silicon will result in a tendency to form ferrite in the final product rather than pearlite, which will decrease the strength and
hardness of the gray iron.
3. Make an addition to the melt to provide heterogeneoous nucleation sites for the graphite, so that
the extent of the undercooling required to form graphite is not as great. This is the practice known
as inoculation, which was described earlier in these notes. Inoculants usually contain silicon,
which will obviously increase T, but the amount is usually too small to have a significant effect
in this way. Rather, the inoculant provides nuclei for graphite which has an effect all out of proportion to the amount added. The most direct result of this process can be seen in the effect of the
inoculant on the chill wedge and on the response of the cooling curves as shown below.
Chill Wedge Curve 2
Nucleation of
Austenite Dendrites
TL
Nucleation of
Graphite
TG
1I
TEMPERATURE
TEMPERATURE
Nucleation of
Austenite Dendrites
TL
TUC
Nucleation of
Graphite
TG
2I
TC
TC
Nucleation of
Iron Carbide
TIME
TIME
Inoculation
CD
*
1
White
at position 1
Gray
at position 1
*
CD
88
It can be seen from the schematic above that inoculation has reduced the chill depth in the wedge,
CD, and reduced the magnitude of the undercooling, TUC, below the graphite eutectic TG. It is
useful to consider in detail what has happened at both thermocouple positions 1 and 2 as a result
of inoculation.
Thermocouple Position 1.
The cooling rate at position 1 in the uninoculated iron was rapid enough that there was not
time enough for the nucleation of the graphite to take place. Thus the cooling continued with the
result that the metastable eutectic white iron formed. However, in the inoculated iron enough
nuclei for graphite were produced so that, even though the cooling rate did not change as a result
of inoculation, the time available between TG and TC was sufficient for the gray iron eutectic to
form and grow. This result is equivalent to insuring that thinner section sized castings could be
made succesfully gray with effective inoculation.
Thermocouple Position 2.
The cooling rate at position 2 in the uninoculated iron was slow enough that there was
enough time for the nucleation of graphite to take place. However the undercooling below the
graphite eutectic, TUC, was quite large and there was a large recallescence observed. This implies
that the number of nuclei producing eutectic cells (the two phase austenite + graphite eutectic)
was quite small, a result which produces a graphite structure which is not always desirable. This
point will be emphasized later in this discussion. However, inoculation was effective at reducing
TUC very significantly as shown in the figure and the eutectic reaction occurred at a much higher
temperature than in the case of no inoculation. This observed behavior occurred because the
number of nuclei present in the melt was much higher due to the inoculation event, promoting
growth of more eutectic cells sooner thus avoiding the severe undercooling observed in the situation with no inoculation. The higher eutectic reaction temperature promotes a more desirable graphitic structure, and therefore a higher quality iron.
The consideration above illustrates the point that effective inoculation will do two very
important things to the structure and therefore properties of gray cast iron; First the likelihood of
chill occurring will be greatly diminished and Second, the graphitic structure that is produced will be much superior for most applications. Understanding this latter point requires
understanding that the rate of the eutectic reaction is proportional to the degree of undercooling.
Greater undercooling results in faster growth of the eutectic. Faster growth requires more rapid
diffusion and therefore smaller and more numerous eutectic graphite particles. This type of structure is characteristic of the highly undercooled uninoculated iron. On the other hand the inoculated iron solidifies with very little undercooling, thus each eutectic cell grows relatively slowly
resulting in rather large graphite flakes spaced much farther apart. However, both structures will
solidify in the same period of time as dictated by the mold. The slow growing more numerous
eutectic cells in the inoculated iron will complete the solidification in the same time as the rapidly
growing sparsely populated eutectic cells in the uninoculated iron. This result can be better appre-
89
Slow Growing
Small Undercooling
Fast Growing
Large Undercooling
Relative amounts and sizes of eutectic cells in equivalent volumes of inoculated and uninoculated
Liquid
Liquid
1.0 mm
0.3 mm
90
Austenite Grains
Cooling
Graphite Flake
Graphite Flake
Ferrite
If the casting cools slowly enough the ferrite nuclei shown can continue to grow into the austenite,
the excess carbon diffusing through the ferrite into the waiting arms of the graphite flake. Were
this to occur to completion the final structure would be ferrite and graphite, the equilibrium
microstructure predicted by the stable phase diagram. If on the other hand, the casting was cooling quite rapidly, or if there were significant amounts of alloy, the austenite may find it easier to
transform the remainder of the austenite to pearlite ( + Fe3C).This scenario is shown schematically below:
Austenite Grains
Ferrite
Cooling
Pearlite
Graphite Flake
91
Fracture
Path
Fracture
Path
Eutectic Cell
(Austenite +
Graphite)
3000kg.)
Gray cast irons have relatively low tensile strengths and almost nonexistent ductilities.
This combination of tensile properties is due primarily to the nearly continuous nature of the
graphite flakes. Since all of the graphite in a given cell is interconnected, the only break in this
continuity comes at the eutectic cell boundary. Since graphite is a very soft and weak material,
tensile stresses will easily cleave the graphite plates internally or will separate the graphite from
the adjacent matrix. Once a crack nucleates in this inherently brittle material, it will propagate
readily through the cell structure, cut across cell boundaries and result in failure. The association
of the fracture surface with the graphite flakes is responsible for the name, gray iron. The appearance of a fracture is a gray color because of the exposed graphite on the interface. Similarly white
iron is named because of the white appearing fracture, a fracture in which there is no graphite,
only the white-appearing eutectic carbide. Tensile fracture stresses in gray cast irons range from
15 to 70 ksi depending upon matrix microstructure, alloy content and carbon equivalent. The
nature of these effects and their relative magnitudes are described in the material to follow.
Effect of Carbon equivalent.
The carbon equivalence of a cast iron is an important contributor to the strength of those
irons primarily because of its direct effect upon the amount of the proeutectic austenite dendrites
present. This relationship (with a sketch illustrating a dendrite and the eutectic cell) and ballpark estimates of tensile strength are given in the figure below. The tensile strength of a eutectic
iron (4.3 CE) is typically around 20 ksi. As the amount of the proeutectic austenite increases with
decreasing CE the tensile strength increases in the manner shown. It is surmised that the dendrites
Tensile Stress
Increasing Proeutectic
80
Austenite Dendrite Fraction
Austenite
Dendrite
60
Ausferrite Matrix
40
Pearlite Matrix
20
Ferrite Matrix
0
3.8
act as strengthening entities in much the same manner as adding stiffeners in a composite; i.e. silicon carbide is added to aluminum to increase strength and stiffness (the elastic modulus). It can
be seen from the above sketch also that the dendrite would effectively break or interrupt the
easy fracture path along the graphite thereby increasing the fracture stress.
Effect of Matrix Microstructure
The matrix microstructure plays a major role in determining the strength of gray cast
irons. Ferritic irons have relatively low strengths, where if the matrix is pearlite the strength
92
increases dramatically. This can be seen in the above figure, where the effect of the pearlite / ferrite ratio is illustrated. Clearly the strength of the pearlitic irons is greater because of the presence
of the fine plates of iron carbide, which impede crack propagation and local yielding.
In recent years it has been learned that the tensile strength of gray irons can be markedly
increased by the austempering process, a heat treatment in which the iron is isothermally reacted
at a temperature in the range 300 - 400 oC after austenitizing. This heat treatment produces a
matrix of austenite with fine ferrite laths, the so-called ausferrite structure. Increased strengths
above the pearlitic matrix results as shown above. This process will be discussed for ductile cast
irons at a later point in this set of notes.
Effect of Alloy Elements
Alloy elements are added to gray cast irons for the purpose of increasing the strength of
the irons. This is accomplished by the effect those alloy elements have on the matrix microstructure. Two important mechanisms contribute to strengthening in the as-cast grades of gray cast
iron, pearlite refinement (pearlite spacing gets smaller as a result of the alloy depressing the pearlite reaction to lower temperatures) and solid solution strengthening of the ferrite. As an example,
an addition of 0.5 % Mo to gray cast iron will increase the tensile strength by about 5 - 7 ksi for
all carbon equivalent irons.
Cooling Curves and Solid State Reactions During Cooling after Casting
The transformations to pearlite or ferrite during cooling after casting is observed with
cooling curves in much the same way as is done during solidification. In the solid state a thermal
arrest resulting from the latent heat given off during the transformation of austenite is shown
below for a gray iron with a CE = 4.0. In this schematic the dashed cooling curve represents the
thermal response to the nucleation and growth of the equilibrium ferrite phase on the graphite, and
the solid cooling curve represents the result when the austenite transforms to the metastable carbide-containing pearlite microconstituent (see page 86 for an actual cooling curve). In those situations where both ferrite and pearlite appear in the casting, the cooling curve will lie somewhere
93
Liquid, L
+L
TL
TG
TC
Temperature
TL = Liquidus
TG = Graphite Eutectic
TC = Carbide Eutectic
Equilibrium
+ Gr
( + Fe3C)
Eutectic Austenite
Plus Graphite
(Eutectoid Ferrite)
( + + Fe3C)
+ Gr
( + Fe3C)
4.0
Carbon Equivalent, CE
(Eutectoid Pearlite)
Metastable Equilibrium
4.3
Time
94
iron which had been heat treated to produce various combinations of pearlite and ferrite.
300
250
200
150
100
50
80
20
40
60
100
Volume Percent Pearlite
It should be pointed out that higher hardnesses can be obtained in irons which are austempered (in
the range 250 - 350 BHN), a result which produces the higher tensile strengths shown schematically above.
It is generally true that as the Brinell hardness increases, so does the tensile strength. In
fact there is a fairly consistent relationship between UTS and BHN. This is illustrated in the data
shown below for a range of gray cast irons produced at MTU. It should be noted in this data that
the austempered irons are much harder and therefore much stronger than the as-cast variety.
0
95
55
50
45
40
As Cast
35
Austempered
30
25
150
200
250
300
BHN (kg/mm
350
400
96
Furnace
Tundish
Molten iron at ~ 2800oF is
tapped into the tundish which
is clamped to the top of the
treatment chamber. The iron
drops through a hole in the
tundish filling an empty pocket
in the front of the chamber.
Eventually the iron spills over
the dam and covers the Mgcontaining material in the rear
pocket, at which point the
Mg-reaction begins.
Treatment Chamber
Pocket Containing
MgFeSi
Dam
There are many methods that have been developed to add the magnesium to the melt.
More recently many foundries are using processes in which pure magnesium is added instead of
the master alloys containing silicon and iron. The advantage of this method lies in the reduced
cost of the magnesium units as well as certain benefits resulting from the ability to have a much
more flexible charge makeup. This advantage will become obvious when the mass balances are
considered for production of ductile iron in our laboratory.
Composition of Ductile Iron, Magnesium Fade and the Shape of Graphite
The base composition of ductile cast irons usually is hypereutectic (see Table 8 on page
82), where the carbon and silicon contents are typically 3.7 and 2.4 respectively (CE = 4.5). Thus
the first constituent to appear during solidification are graphite nodules, which nucleate and grow,
first without any austenite, but eventually with austenite enclosing the graphite nodule.
It is critical in making ductile iron that the amount of magnesium present in the melt during solidification be in the range 0.03 to 0.05 weight percent. Magnesium contents less than this
amount will result in graphite flakes, and amounts more than this results in the appearance of socalled exploded graphites. Either type contributes to a degradation in the ductility of the cast iron
produced. Because of the high vapor pressure of Mg and the extreme reactivity with oxygen, the
magnesium content in the melt will rapidly fade with time. Thus it is critical that the treated iron
be poured into the molds as quickly as possible after treatment. This fading of magnesium and its
97
Magnesium, Wt.%
Exploded
20
24
Flake
Spheroidal
The processing scheme utilized in the production of ductile iron using a magnesium ferrosilicon alloy (MgFeSi) involves the following steps:
1. Build a charge from scrap steel, returns (risers, gates, etc.)and pig iron.
2. Melt charge and superheat to 2800oF.
3. Pour into treatment vessel, covering MgFeSi and reacting Mg.
4. Transfer into pouring ladle, inoculating with ferrosilicon.
5. Pour castings
A common MgFeSi treatment alloy contains approximately 5 wt % Mg, about 45 wt % Si, with
the balance Fe. About twice as much Mg needs to be added during treatment than is required in
the casting (this represents a 50 % recovery) because of the losses from oxidation during the violent treatment reaction. This presents a problem because of the large amount of Si also present in
the treatment alloy, a fact which requires that the Si content in the base charge be kept quite low,
~1.4 wt%, or about 1 wt % lower than the Si content in the final casting. This necessarily means
that the charge will have to contain a significant component with a low Si content, a requirement
met by both pig iron (a virgin blast furnace product with high carbon,4.8 wt %, and low Si, 0.1
wt.%) and scrap steel (typically containing 0.2 wt % Si and 0.2 wt % C). Of course a foundry
would like to use all of their returns and minimize the cost of their other additions. In previous
years this has meant maximizing the use of inexpensive scrap steel and minimizing the use of relatively expensive pig iron. However in recent months the supply of scrap steel has tightened due
to the increasing requirements of the steel minimills, which use the same charge stock as gray and
ductile iron foundries, thereby raising the price of scrap. The change in silicon content over the
processing cycle is useful in defining the critical processing steps described above. This is shown
98
schematically below:
3
2
Final Casting
Charge
Inoculation (Add FeSi to Nucleate Graphite)
Time
The objective is to produce an iron within the chemical specifications and having the required
amount of Mg to create nodules. A mass balance is used to determine the charge makeup as well
as the amounts of treatment and inoculant . The chemical composition of charge materials is
given in Table 9.
Table 9: Chemical composition of Charge Components
Material
Wt % C
Wt % Si
Wt % Mg
Wt % Fe
Steel Scrap
0.2
0.2
99.6
Ductile Returns
3.7
2.4
0*
93.9
Pig Iron
4.2
0.2
95.6
Magnesium Treatment
45
50
75
25
50
50
Graphite
100
99
Homework Problem: Develop a plan to specify the ongoing charge makeup at a minimum
cost for producing the above grade of ductile cast iron subject to the following constraints:
1.Your foundry has the enviable experience of having an overall casting yield of 70%.
Thus,on average, only 30% of the iron units charged can come from returns.
2. Minimize the cost: The battle here is between fluctuating unit costs for scrap steel
(X$), pig iron (P$), foundry grade ferrosilicon (FS$), and graphite (G$). Obviously
the unit cost for the returns is zero. Current costs can sometimes be obtained from the
Metal Market News at the MTU library, or from operating foundries.
3. Carbon recovery by graphite additions is not 100%, but may be as low as 70%.
4. Optional homework.Look on as Extra Credit Goodie
5. Due: End of term by as many as three in a group. Four page limit, complete report.
100
Temperature
L
+L
Barely
Noticeable
Graphite
Arrest
L+G
A
TG
Fe3C Eutectic
Nucleation of
Graphite Nuclei
and Growth of
Graphite
Spheroids
B
Nucleation of Austenite
on Graphite Spheres and
Simultaneous Nucleation
and Growth of Austenite Dendrites
4.3 4.5
Carbon Equivalent, CE
Time
The sequence of events which likely occurs during the solidification of ductile cast iron is
described with reference to the above diagram:
1. Nucleation of proeutectic spheres of Graphite
2. Growth of spheres with liquid composition following arrow A.
3. As the temperature drops below TG, nucleation of austenite occurs on
the graphite and soon encloses the graphite in a shell of austenite. In
addition conditions are good for the nucleation of austenite dendrites,
whose subsequent rejection of carbon moves the liquidus composition
along arrow B.
4. Supersaturation of carbon in the liquid adjacent to the dendrites can
provide conditions to allow more nucleation of new graphite nodules,
which in turn can grow and be enveloped in austenite.
5. Finally the solidification reaction is complete.
The sequence of events is illustrated schematically below:
1.
2.
3.
4.
Austenite Shell
Austenite Dendrite
101
Because of the surrounding of the graphite nodules with the austenite shell, this is not a typical
eutectic reaction where both phases are simultaneously in contact with the liquid . Therefore this
is sometimes called a neoeutectic, where growth of the graphite occurs by diffusion of carbon
across the austenite shell into the graphite. The final as cast microstructure, of course, depends
upon the combination of section size, alloy content, and processing history. Measurement made
on the plane of polish to characterize these materials include:
1. Nodule Count - No. of nodules per square cm
2. Nodularity - sphericity of nodules, described by aspect ratio of nodules.
3. Matrix microstructure - ferrite, pearlite, ausferrite, combinations
4. Extent of segregation and defects - carbides, inclusions,shrinkage, etc.
A typical as-cast microstructure consists of a bullseye structure of ferrite surrounding graphite
which in turn is surrounded by pearlite. The development of this structure and relationship to a
cooling curve is shown below:
Austenite Grains
Graphite Liquidus
Graphite nodules
forming & growing
TG
Ferrite Shell
Ferrite begins to form
on graphite (carbon sinks)
Reaction progresses by
diffusion of C through
ferrite.
Ferrite Formation
Upper Critical Temp
Pearlite Reaction Temp
TF
TP
Pearlite
Colonies
BULLSEYE
STRUCTURE
102
The relative amount of ferrite present depends upon alloy content, nodule count, and the rate at
which the casting is cooled through the transformation where ferrite and pearlite can form and
grow, i.e. the same factors as those promoting ferrite in gray cast iron.
Continuous
Cooling
or
Isothermal
The particular austenite transformation product or products observed will depend upon the section
size of the casting, the size of the graphite flakes (surface area per unit volume), and the manner in
which the casting was cooled (i.e. continuously cooled or isothermally reacted) in addition to the
amount and type of alloying elements that are present. The microstructural results of continuous
cooling are best described by the continuous cooling diagram (CCT) for a given cast iron, a schematic of which is illustrated in the attached figure below.
Ferrite + Graphite
Pearlite
Unstable
Austenite
F+P
Ausferrite
Martensite Start
Martensite
Martensite Finish
A+ M
F+P +A
T - t space
Cooling curves passing through the specific transformation product regions (TPR) in temperature
103
- time (T - t) space in the above figure illustrate a variety of microstructures depending upon the
cooling rate. The slowest cooling specimen (largest section size) passed through the TPR of Ferrite + Pearlite (F + P). As the cooling rate increases the transformation products change as shown
until the product for the highest cooling rate is 100% martensite (M).
The shape of the various TPR and their position in the CCT diagram illustrated above will
depend most strongly upon the chemical composition of the austenite which is transforming. Of
course, the matrix austenite carbon content is an important variable which will in turn depend
upon the identity and amount of the other alloying elements present.
The position in temperature - time space of the TPR within CCT diagrams for the transformation of austenite in steel is determined primarily by the composition and the austenite grain
size. Thus the so-called hardenability of steels is primarily dependent upon the alloy content, the
carbon content and the austenite grain size.
This dependence of the TPR in T - t space on carbon content, alloy content and austenite
grain size is also true for gray and ductile cast irons. However a complicating factor for cast irons
results from the presence of graphite and the variability of matrix carbon content with temperature
in equilibrium with that graphite. Thus very fine D and E type graphites in gray cast irons (and the
high nodule count irons characteristic of well inoculated ductile irons), with their much higher
surface area per unit volume on which nucleation of ferrite can occur, would be expected to have
more ferrite present than an iron in which the graphite were present as the larger, more random Atype flakes; i.e. the ferrite + graphite TPR in the above figure would be shifted to shorter times.
The nucleation and growth of ferrite is the only transformation product shown in which requires
the presence of graphite, the growing ferrite resulting from relatively long range diffusion of carbon to graphite flakes. The other diffusional products (P, A) have the same composition as the
matrix austenite and therefore require only short range carbon diffusion (interlamellar spacings in
pearlite and the small space between the acicular plates of ferrite in ausferrite)to grow, depending
for nucleation upon the presence of surfaces (austenite grain boundaries, graphite surfaces, ferrite
boundaries, etc.). Martensite formation requires no diffusion, only requiring surfaces upon which
to nucleate.
In addition to their effect upon hardenability (position of the TPR in T-t space) substitutional alloy additions (Cu, Ni, Mo, Mn, Cr, etc) will have an important effect upon the final
mechanical properties as a result of where they finally reside within the cast microstructure. An
overview of the details of the effects of alloying elements in gray cast iron can be found in the literature (1 Angus, 2 Iron Castings Handbook, 3 ASM Cast Irons).
Mechanical Properties of Ductile Cast Iron
The mechanical properties of ductile cast iron are significantly different than that of gray
iron because of the difference in shape between the graphites in these cast irons. In ductile irons
the matrix is the continuous entity so that there are no easy crack paths to propagate fracture. As a
result, ductile cast irons have significant ductility and toughness, properties which place this
unique material in competition with other ferrous materials such as cast steels, forged steels, and
even wrought steels.
Tensile Properties
As a result of the continuity of the matrix, the tensile properties of ductile cast iron depend
almost completely upon the microstructure of the matrix, a microstructure which can be con-
104
trolled by heat treatment. An overview of the tensile properties of ductile iron is given below:
200
TM = Tempered
Martensite
P = Pearlite
F = Ferrite
ADI = Austermpered
Ductile Iron
xx-yy-zz(Grade)_
ADI
180
3
ASTM
Grades of ADI
(Guaranteed
Minimums)
160
140
UTS YS %EL
(Guaranteed Minimums)
TM
120
120-90-2
P
100
100-70-3
P+F
80
80-55-6
F+P
65-45-12
60
40
8
10
12
Percent Elongation
F
60-40-18
14
16
18
20
UTS v. % Elongation -Summary of Common As-Cast and Austempered Grades of Ductile Iron
105
section size. The grade 120-90-2 is a heat treated grade in which the iron has been austenitized,
Table 11: Typical Chemical Compositions(Wt Percent), Matrix Micro, BHN
Grade
60-40-18
Element
Grade
65-45-12
Grade
80-55-6
Grade
100-70-3
Grade
120-90-2
Carbon
3.5 - 3.9
3.5 - 3.9
3.5 - 3.9
3.5 - 3.8
3.5 - 3.8
Silicon
2.2 - 3.0
2.5 - 2.8
2.2 - 2.7
2.2 - 2.7
2.2 - 2.7
Manganese
0.30 max
0.40 max
0.2 - 0.5
0.6 max
0.6 max
Chromium
0.06 max
0.10 max
0.10 max
0.10 max
0.10 max
Copper
0.2 - 0.4
0.2 - 0.5
0.2 - 0.5
Microstructure
Ferrite
Mostly
Ferrite
Mostly
Pearlite
Pearlite
Tempered
Martensite
Brinell
Hardness
130 - 170
150 - 220
170 - 250
241 - 300
270 - 550
quenched to martensite and tempered. Typical chemical compositions for these irons are given in
Table 11. There are no chemical specifications for a specific grade. Each foundry and casting
application will determine the combination needed to obtain the minimum mechanical property
specifications. It will be noted in the above table that the ferritic grades contain a minimum of the
alloy elements Cu and Mn, both of which promote the formation of pearllite when the casting is
cooling. On the other hand the grades with pearlite commonly have a specification with a minimum of copper. The elements Mn and Cr come from the steel component of the charge; these are
both common and important elements in the production of steel. Many ferritic matrix castings are
obtained by annealing, a heat treatment where the casting is austenitized and then slowly cooled,
giving a large amount of time for the formation of ferrite. This heat treatment, of course, adds significantly to the cost of production and is not usually desired. Low residuals of Mn and Cr can be
achieved by melting larger quantities of pig iron, a charge material which is usually more expensive than scrap steel.
106
the as-cast grades, yet retaining excellent ductility. The primary cause of this dramatic improvement in mechanical properties stems from the presence of the face centered cubic matrix together
with a fine scale dispersion of ferrite. The ASTM grades represent guaranteed minimums in tensile strength and ductility; the cross hatched region located to higher strengths and ductilities from
the ASTM grades represents more typical ADI. Clearly ADI offers an entire new opportunity for
applications of ductile cast iron. Indeed ADI, with comparable strengths and ductilities, is making
inroads into markets once dominated by steel forgings and steel castings.
The Metastable Phase Diagram and Stabilized Austenite
The concept of austempered ductile iron with an austenitic matrix can be understood with
reference to a portion of the metastable Fe - C - 2.4 Si phase diagram schematic shown below:
+ Graphite
Temperature (Ko)
ar
t en +
sit
eS
tar
t,
M
+ Graphite
Room Temperature
0.8
3.6
This diagram shows the low temperature portion of the Fe - C - 2.4 Si isopleth. The amount of 2.4
Si was chosen to correspond to a typical ductile cast iron. Note that the metastable Fe - Fe3C diagram is not a part of this diagram but that other features are present, including the martensite start
temperature (that temperature below which austenite must be quenched to obtain the hard, brittle,
body centered tetragonal martensite phase), and the metastable extension of the
+ / phase boundary. These features are necessary to understand the presence of austenite at
room temperature which is stable. Consider now the heat treatment which is used to produce
austempered ductile iron.
1. Casting is heated into the austenite + graphite field and held at T until fully austenitized. At this point the structure consists of austenite of 0.8 wt. % C and graphite nodules.
2. Cool rapidly to TA, the austempering temperature and hold, allowing the reaction:
(0.8 C) -> (0 C) + (2.0 C) [AUSFERRITE]
107
This reaction usually requires about 1 - 2 hours to complete and gives a structure shown
schematically below.
After Reaction
Before Reaction
Austempering
1 - 2 Hours at TA
Graphite Nodules + (0 C) + (2 C)
In a piece of steel heat treated the same way, the austenite would transform to bainite, a
two phase mixture of ferrite and iron carbide (Fe3C). However, in cast irons, the presence
of silicon prevents the formation of carbides initially. The system takes the path of least
resistance and obeys (once again) the metastable phase diagram.
3. If given enough time the austenite will eventually transform to bainite. However, before
that happens the casting will be cooled to room temperature, a move which will retain the structure created at TA. The austempering reaction is said to have stabilized the austenite. By virtue
of the high carbon present in the ausferrite (reflecting the absence of carbon from the ferrite), the
martensite start temperature has been reduced to near absolute zero degrees Kelvin (see the diagram on page 104). The martensite start temperature is a very strong function of carbon content.
Since the carbon must be retained in the martensite in this diffusionless transformation and it
tends to want to expand the lattice, more driving force (undercooling) becomes necessary as carbon content increases. Therefore as the austenite becomes richer in carbon during the ausferrite
reaction it becomes stabilized to the notion of transforming to martensite. This allows cast irons to
be austenitic at room temperature, an accomplishment made in commercial grades of steel only by
adding large quantities of nickel or manganese. Of course, this is what makes ADI a unique material and what gives it the remarkable properties shown in the diagram on page 105.
There are a number of problems associated with the production of ADI, problems which
are concerned first with the production of a quality grade of ductile cast iron, and secondly with
the control of the heat treatment parameters necessary to convert austenite to ausferrite. It goes
without saying that the heat treated product cannot overcome basic deficiencies in the cast state.
A list of these deficiencies includes porosity (shrinkage and gas), slag, sand, inclusions from
impurities, low nodularity, low nodule count, etc. All of these extrinsic deficiencies can be minimized by good foundry practice and adhering to tight processing schedules, i.e. control of all
temperatures in the sequence, establishing a rigorous schedule for treatment, inoculation, and
pouring the castings. Some deficiencies that cannot be overcome are intrinsic to the process of
solidification, including microsegregation in the casting and limitations in the nodule count that is
attainable, a limitation defined primarily by the cooling rate (section size) of the casting. It is true
that inoculation can increase nodule count, but not usually beyond a maximum for the given section size and mold type. Microsegregation is in principle capable of being eliminated by a homogenization step, where the casting is brought to a temperature close to its melting point and soaked
at the high temperature until solid state diffusion has eliminated the problem. Unfortunately
homogenization processes are very expensive and while it is cost effective for some materials it is
108
just not a practical thing to do with cast irons . It is then necessary to live with the intrinsic deficiencies and adjust the heat treating parameters to accomodate any problems that may arise as a
result.
Austempering Ductile Iron and the Isothermal Transformation Diagram
A grasp of the important parameters defining the process in heat treating these materials
requires a basic understanding of the isothermal transformation diagram that describes what is
necessary to produce ADI successfully, and also what is necessary to avoid so that the desired
structure is attained. A schematic ITT diagram is given below for a ductile cast iron which is
Austenitize (1)
Cool to TA (2)
Upper Critical Temperature
Pearlite
Nose
Temperature
Pearlite ( + Fe3C)
99%
1%
TA
Bainite
( + Fe3C)
Hold at TA
Austemper (3) Ausferrite
( + )
Cool to Room Temperature (4)
Time
Isothermal Transformation Diagram for a Hypothetical Ductile Iron
being austenitized at T and austempered at TA. There are four steps in the heat treatment scheme
which are numbered on the ITT diagram.These four steps and the considerations associated with
each are given below:
Step (1) - Austenitize for a time so that the matrix is completely austenite with a fairly
homogeneous carbon composition. A rule of thumb for time is one hour per inch of section, with
allowance for heat up time as well. The temperature selected will depend upon the alloy compositon; it is necessary that the so-called upper critical temperature be exceeded, that temperature
below which ferrite is a stable phase.
Step (2) - Cool to the austempering temperature at a rate sufficient to miss the Pearlite
Nose on the ITT diagram. This is most often accomplished in salt baths so that the rate of heat
transfer is maximized. In heavier section castings it is necessary to alloy them quite heavily (usually with various combinations of Cu, Ni, and Mo); this has the effect of moving the entire ITT
109
diagram to greater times thereby allowing the cooling from T to TA without generating pearlite
within the casting.
Step (3) - Hold at the Austempering Temperature for a time until the ausferrite reaction
[ (0.8 C) -> (0 C) + (2 C)] is complete, but not so long a time that the bainite reaction
[ (2 C) -> (0 C) + Fe3C] occurs. The time is selected using a combination of information
including primarily alloy content and austenitizing temperature. Obviously it would be helpful to
have ITT diagram information for each alloy produced.The diagram defines the beginning of the
ausferrite reaction with a note indicating that the reaction has progressed 1 %, and similarly the
end of the reaction with a note at 99% transformed.
Step (4) - Cool to room temperature for shipment to the customer. It is not necessary to
cool rapidly; rather the castings are allowed to cool uniformly so as to minimize any residual
stresses which could arise were castings to cool nonuniformly.
It is important that the above steps be carried out in a consistent manner time after time, so
that quality ADI is produced time after time.
Control of Mechanical Properties of ADI
The four ASTM grades of ADI illustrated on page 102 can in principle be created from the
same cast alloy. The major factor controlling these tensile properties in ADI which has been produced from quality ductile iron and heat treated in a quality manner is the choice of the austempering temperature. This parameter is primarily responsible for defining the scale of the ausferrite
product, where the term scale refers to the size and number of the ferrite particles in the austenite
matrix. It is generally true that high austempering temperatures give course microstructures with
relatively low strengths but higher ductility. On the other hand low austempering temperatures
give very fine microstructures with high strengths but lower ductility. High austempering temperatures are in the range 400 - 425 oC giving ASTM grade 1 ADI,while low austempering temperatures are in the range 275 - 300oC giving ASTM grade 4 ADI.
Examples of potential applications for ADI include gears, automotive crankshafts, digger
teeth for front end loader applications, automotive camshafts, railroad car wheels, etc. Many
applications require resistance to sliding wear, a property enhanced by the presence of the austenite which transforms to martensite in service.
unique mechanical and physical properties determined in large part by the shape of the graphite.
These irons are produced in much the same way as ductile cast iron, except the objective is to
have the molten iron dissolve a lesser amount of Mg, usually ~ 0.01 - 0.015 Wt. %. This amount
of Mg is enough to guarantee that no flakes are formed, yet not high enough to allow full nodularity . A typical CG iron might contain 25% nodularity, the rest of the graphite having a twisted rodshaped structure. The mechanical and physical properties of compacted graphite irons, for a
given matrix microstructure, will reside in between the properties of flake graphite irons and
spheroidal grahite irons as shown schematically below. .
CG
Irons
Thermal Conductivity
Damping Capacity
High
Strength
Ductility
High
Ductile
Irons
Low
Low
0
Percent Nodularity
80%
100
111
Liquid, L
+L
Temperature
L + Gr
TL
L + Fe3C
TSSG
+ Gr
( + Fe3C)
TUC
+ + Gr
( + + Fe3C)
TG
TC
Solidification
Complete
TL = Liquidus
TG = Graphite Eutectic
+ Gr
( + Fe3C)
Fe3C
TC = Carbide Eutectic
2.8
Time
Carbon Equivalent, CE
Temperature
It can be seen in the cooling curve that the temperature has reached TC before nucleation of graphite has occurred thus resulting in the eutectic austenite plus carbide formation. The low silicon
content, 1.5, and low carbon, 2.3, results in a smaller T than for gray or ductile cast iron thus
promoting the formation of white iron. After the casting has cooled to room temperature, the heat
treatment to produce solid state formation of graphite, and therefore the popcorn graphite structure of malleable iron begins and is illustrated below. The castings are heated slowly into the +
TSSG
TR
Ferritic Malleable
Pearlitic
Malleable
Time
24 hours
Fe3C two phase field to a temperature TSSG where it is soaked for as long as 24 hours. During this
soaking time graphite will nucleate on the eutectic carbide particle surfaces and grow at their
expense. Eventually all of the carbide will be replaced by popcorn graphite and the structure left
behind will be quite similar to ductile cast iron except for the shape of the graphite. Like ductile
cast iron the matrix is the continuous phase and so the final structure will have similar properties to ductile cast iron, excellent strength, ductility and toughness. The strength and ductility of malleable irons would overlap the as-cast properties of ductile iron shown on page 105.
112
Pearlitic malleable irons would be stronger but less ductile than ferritic malleable cast irons for
the same reasons as for ductile iron. The temperature - time diagram on the previous page illustrates the heat treatments responsible for the production of ferritic malleable iron (by slow cooling through the upper critical temperature, TUC) and pearlitic malleable iron (by more rapid
cooling, even cooling in air) after the malleablizing treatment.
Malleable cast iron has been produced by human beings for thousands of yesrs, but it is
slowly but surely being replaced by ductile cast iron. Two important reasons why malleable iron
is decreasing in favor, is cost and limitations on section size that can be produced in the malleable state. Clearly it is less costly to produce nodules in the as-cast condition than to require an
additional long time heat treatment step. In addition ductile cast iron can be produced in very
large section sizes, while the requirement to start with white iron limits malleable to practical section sizes on the order of 1 - 2 inches. Malleable iron section sizes larger than this will solidify
with graphite flakes and would therefore have severely reduced ductility. A comparison of the
United States production of malleable, ductile, and gray cast irons in the figure below illustrates
the unmistakable trends. Malleable iron is a dying breed, and most of its former applications have
been replaced by ductile cast iron.
Ductile Iron
Gray Iron
Malleable Iron
1.2 12
1.0 10
0.8
0.6
0.4
0.2
Malleable
Gray &
Ductile
Projected
1970
Year
1980
Recession
1990
2000
The data in this plot shows scatter which is a result of fundamental change (decreasing gray and
malleable iron and increasing ductile iron production) as well as a reflection on the economics of
the times.It is interesting to note the dip in production of all three of these materials in 1982, a
recession which hit the casting and manufacturing industry very hard. Indeed the production of
steel in the U.S. plummeted from ~ 140 million tons in 1980 to about 80 million tons in 1982.
113
%H
solid
0.5 ml/100 g Al
liquid
T mp
Temperature
Thus, if the gas is present in the liquid, hydrogen will be evolved as H2 during solidification. This
gas may be trapped in the casting which results in porosity or blows.
Sources of H : H2O in air, charge; H - containing compounds in combustion gases; contamination
of the charge with oil,grease,etc.
Remedy- Bubble a gas through the melt, like argon, nitrogen, chlorine, sulfur hexafluoride. These
gases cleanse the melt by action of Sieverts Law and by providing a reactant with which the
hydrogen can be chemically changed and then removed.
Sieverts Law- % H = Kp(H2)0.5
In this expression H is the concentration in liquid Al , K is the equilibrium constant, and p(H2) is
the partial pressure of H in equilibrium with a gas in contact with the melt. If new gas with low
p(H2) is continually added the H will be extracted from the melt to establish equilibrium. Thus H
will be eliminated before pouring the casting. This mechanism will work well with an inert gas
like argon; however a more potent method will include using a gas containing a reactive component like chlorine or SF6. In this situation the H reacts with the Cl or the SF6 and is removed as
another gaseous species, for example HCl . Unfortunately this is a rather dangerous product and
most aluminum foundries are working hard to eliminate the use of Cl. The gas used in our experimental foundry is argon with about 5% SF6.
114
cores or molds. Gases that find their way into castings are often trapped under the cope surface,
but can actually be found anywhere within the casting depending upon the situation.
Remedy - Proper venting, reduce binder content in core, change binder in core, increase sand permeability, control pouring temperature, etc.
Hot Tears
Hot tears are defects which occur most often in materials with a large range of solidification and with significant mold constraints. Hot tears are defects which require the presence of a
liquid. Consider the phase diagram and sand casting below:
Tensile Bar Shaped Casting
Temperature
TA
TE
L+
+L
Hot Spots
cA c0
c1
Solidifying Metal
Liquid Metal
Weight Fraction B
Alloys with compositions between 0 and c0 wt. fraction B and between c1 and 1 will, on cooling
from the liquid, pass through the shaded regions in the + L and L + two phase fields. Within
these shaded regions these alloys will experience a temperature range over which more than 50 %
solid is present. For example an alloy of composition cA will have about 50 % solid at TA, and
on cooling to TE this solid amount will increase by the lever rule to about 70 %. Thus it is anticipated that solid continuity will exist throughout the surface volume of the piece over a temperature range in which contraction of that solid due to cooling is occurring in the presence of the
liquid. Solid continuity is expected along the surface because that is where solidification usually
begins. If the contracting solid is constrained by a rigid or even an expanding mold, stresses may
build up within the solid portion of the casting which are ultimately relieved by tensile failure
along some convenient dendrite - liquid interface. The casting is literally torn apart. This failure is
known as a hot tear, an opening which may or may not be filled by the liquid that is present.
Consider the tensile bar shaped casting shown above, a sand casting with an alloy concentration of cA which in the sketch is shown as being partly solidified in the temperature range TA to
115
TE. The solidified metal is shown as being continuous on the surface of the casting, with relatively thick solid layers at the external corners (large mold volume to extract heat) and thin solid
layers at the internal corners (the so-called hot-spots where there is only a small mold volume to
extract heat). The continuity of the solid combined with the reality of this continuity over the temperature range TA - TE results in the weak solid skin wanting to contract. At the same time the
mold is heating and it wants to expand. The clash between the expanding mold and the contracting solid metal will generate tensile stresses in the solid metal and compressive stresses in the
mold. It is apparent that something will have to give. If the mold remains rigid and expanding it is
inevitable that the solid skin of the casting will tear at the weakest points in the system, the hot
spots shown on the above sketch. These tears often will extend to the surface resulting in what
appears to be cracks. The presence of the liquid during this event may allow the hot tear to be
filled as it is happening. In this case the integrity of the casting will not be lost but it is possible
that the liquid filler , because of segregation, could have a significantly different composition
than the solid and thus act as a weak point in the structure. If, on the other hand, the liquid cannot
fill the expanding tear, then the integrity of the casting is lost.
The likelihood of such an occurrence:
1. Increases as the temperature range containing more than 50% solid
increases. Thus the problem is minimized for pure elements and eutectics.
2. Increases as sand expansion increases. Thus collapsible sand molds are
helpful to avoid the production of tensile stresses in castings. Molding
sands with minimal thermal expansion will also tend to minimize this
defect.
3. Increases in designs containing coring (particularly with large cores)
and casting designs containing sharp corners or large section size changes.
Remedies:
1. If possible, stay away from specifying large freezing range alloys for
castings. Of course this is not always possible, and so the designer must be
aware of the problem and take other steps to minimize the problem.
2. If possible, use generous fillets in design to avoid hot spots (see the
examples below) and minimize section size changes.
Not This
This
116
117
sequence.
Solid State Cooling Curves
TEMPERATURE
Tm
Hat
Tm/2
tI
t0
2
Outboard Wear Plate
Cooling Fin
tH
Elastic
TR
t1
TIME
t2
118
any stresses developing within each section will be relieved by plastic flow in one section or the
other. This occurs because the temperatures are much higher than the point at which dynamic
recrystallization can occur (In cast irons this temperature, Tm/2 = 350 oC).
2. At time t1, the wear plate has cooled into the elastic range (at tI) and is still contracting
more rapidly than the hat which is still well within the plastic zone. Contraction of the wear plates
sets up tensile tangential stresses within itself and, by virtue of the connection between the two
parts, corresponding compressive stresses in the hat. Because the hat is still in the plastic zone,
these stresses can be relieved by plastic flow within the hat. Thus there is no problem yet.
3. At time t2, the wear plates are essentially at room temperature and are therefore no
longer contracting. However the heavier section hat has just entered the elastic zone at tHand is
continuing to contract. The contracting hat will then put the wear plates into residual tangential
compression (and radial tension) as it tries to pull away from the wear plates, leaving itself in a
state of tensile elastic stress.
Clearly the magnitude of the stresses present will depend upon the differences in rate at
which these sections cool and the relative section sizes through which these residual stresses can
be distributed.
Implications of Residual Stresses
1. If the stresses are large enough to cause yielding then a shape change (warping) can
occur during the cool down period of the casting. In some instances the stresses can even be large
enough to cause catastrophic failure, a documented result in large semi-continuous cast aluminum
alloy ingots which have been left to cool after casting.
2. A casting containing significant residual stress could fail or warp during the machining
operation depending on the nature of material removed during machining. For example disc brake
rotors have been known to change shape as material is removed during machining of the wear
plates to their final configuration.
3. A casting containing significant residual stress could fail in service. A classic example
of this problem is illustrated by railroad car wheels which have exploded when the full weight of
the car is brought to the individual wheel. In some instances the shrapnel resulting was enough to
punch big holes in buildings and kill people.
Solutions to Problems
1. Control Cooling After Shakeout - The straightforward solution to excessive residual
stress is to control processing so that all sections cool down uniformly. This could be done by
shaking the castings out of their molds and then putting them together in a soaking pit. This is
especially important for castings with large section size differences, like the railroad car wheel.
2. Stress Relief Anneal - In those instances in which the residual stresses are not large
enough to affect the as cast condition, but are large enough to affect the part during machining or
in service (often promoting dimensional change and/or warping), the castings may be subject to a
stress relief anneal.
For ferrous castings this involves heating to about 1000 - 1100 oF followed by slowly
cooling, usually in air. In ferrous castings this temperature range is well below the temperature
where significant microstructural change can take place; i.e. it is well below the lower critical
temperature where the ferrite begins to transform into austenite. It is also well below the temperature range where significant spheroidization of pearlite can occur.
119
For aluminum alloy castings a stress relief anneal, called the T5 treatment (also called a
stabilization treatment), is carried out in the range 400 - 500 oF followed by an air cool. In many
cast aluminum alloys this treatment also contributes to a slight increase in strengthening by age
hardening in addition to the stress relief anneal. This is a cheap way to pick up strength, because a
solution treatment process normally required before age hardening is not necessary. Apparently
there is enough supersaturation of portions of the matrix dendrites as a result of cooling following casting to allow precipitation hardening without the solution treatment. This can be understood by realizing that the coring described by the Scheil analysis of microsegregation in
dendrites results in relatively high alloy concentrations in the volumes immediately on the edges
of the dendrites, volumes which can then be coaxed to precipitate the strengthening particles at
400 - 500 oF.
Residual Stress Measurements
There are a number of techniques which are available to measure residual stresses in castings, techniques which are utilized by many companies to better understand and control their
product. These techniques can be placed into two camps, destructive and nondestructive.
The non-destructive camp utilizes electromagnetic radiation to effectively measure the
interplanar spacings in materials as a function of position, heat treatment and service conditions.
The most common technique available is the x-ray diffraction technique, where a beam of x-rays
of known wavelength, , is scattered from certain definable atomic planes in the item of interest.
These planes will have a spacing d, which can be measured using Braggs Law:
d = / 2 sin
where is the diffraction angle measured. The departure of the measured d from that of the material not experiencing residual elastic stress is used to compute that stress. This is a very common
technique to investigate surface residual stresses in carburized and induction hardened cases in
steel. Unfortunately residual stress measurements by this method are limited to measurements on
the surface of the sample. Bulk stresses are not measureable unless the internal stresses are identical to that on the surface. It is possible to remove material from the surface by etching techniques
and then by this serial technique continue to measure stresses with depth into a material. Of
course, this then ceases to be non-destructive. Another technique available to do nondestructive
testing involves the use of neutron scattering, a technique which does allow examination of the
stresses at depth. Unfortunately neutron scattering equipment is not common and measurements
are quite expensive.
Destructive measurement are often the only reliable, relatively quick methods to evaluate
the degree to which residual stresses exist. These methods can involve cutting and / or drilling
castings on which strain gages have been placed to record relief of elastic compressive or tensile
stresses after the cutting operation. These methods have been used at MTU to measure residual
120
stresses in as - cast disc brake rotors. A brief synopsis of part of that work is indicated below:
Qualitative Method - Radial Cut
Tangential Stresses
B
* A
*
-.01
-3
-.02
-6
-.03
-9
-.04
12
16
24
20
Rotor Weight (Lb)
28
-12
32
B
A **
Strain
Gage
The qualitative method above is made quantitative by adding strain gages to the wedge which is
removed. This gage, which measures both radial and tangential stresses is illustrated in the above
sketch. Rotor closure occurred in almost all cases, the extent of closure proportional to the degree
of tangential residual compressive stresses present. It can be seen that the magnitude of the residual stresses in the largest rotor (also largest difference in section size between the hat and the wear
plates) is on the order of 9000 psi, a significant fraction of the nominal 30000 psi ultimate. Radial
stresses were mostly tensile, but relatively small, in the neighborhood of 1000 psi. It can easily be
seen that machining could result in changes in shape as a result of the relief of these stresses, or
changes in how the stresses are born by the rotor. In addition, it is also clear that the heating which
results from service conditions could result in stress relief with eventual warping, a condition
which could promote brake judder, the experience of rapid and sometimes violent pulsating when
the brakes are applied.
Another method commonly used to measure residual stresses in materials is called the
blind hole method, a technique where a special strain gage is glued to the piece in question.
Then a small, precise hole is drilled in the center of the gage, and the relaxation of the stresses is
recorded at several locations around the hole. The principal stresses are computed from these
data, which can then be used to compute the residual stresses. Because this is such a small hole,
this test could be considered non-destructive. Unfortunately it too is mainly a surface stress
method. Bulk stress measurements by this method are possible but the degree of difficulty is high
and the errors in measurement are potentially quite large.
121
Temperature, oC
1400
+L
0.54
1300
AUSTENITE () fcc
1200
1100
2 % Maximum Carbon
Solubility at 1148 oC
1000
723 (Eutectoid Temperature)
900
800
700
600
FERRITE () bcc
0
Fe
0.1
0.2
0.3
+ Fe3C
0.4
0.5
0.6
0.7
+ Fe3C
1.0
0.8
0.9
Consider a steel with a composition of 0.16 wt % carbon, the peritectic alloy. A peritectic
reaction is one where liquid + solid -> new solid. In the case of plain carbon steels, this reaction
is described as:
Liquid (0.54 Carbon) + Ferrite (0.1 Carbon) -> Austenite (0.16 Carbon)
The peritectic alloy, on casting from about 1600oC, goes through the following phase changes on
solidification in order: First, nucleation and growth of dendrites of composition 0.025 C at 1525
oC; Second, growth of dendrites until 1496oC is reached at which point the dendrites of composition 0.1 C (the dendrites have no trouble maintaining the equilibrium carbon composition
122
because of the very high diffusion rate of carbon at these temperatures) react via the peritectic
reaction with the remaining liquid of composition 0.54 C to form austenite of composition 0.16
carbon. This reaction involves a long range diffusion problem for the carbon in the system; the
carbon must diffuse from the liquid through the forming austenite layer to the interface between
the austenite and the ferrite, illustrated on the schematic by points a and b. :
Liquid (0.54 C)
Liquid (0.54 C)
(0.16 C)
a
(0.1 C)
(0.1 C)
Thus the austenite layer takes on the dendritic shape of the primary delta ferrite, the interface of
the product austenite growing in both directions, into the liquid and into the solid ferrite with the
rate of the reaction governed by the rate at which diffusion of carbon can occur across the austenite layer and into the volume which is carbon poor. Fortunately the high rate of carbon diffusion at
these temperatures allows the reaction to be completed very quickly; thus the liquid and the primary delta is transformed to austenite. Further cooling of this austenite to room temperature
results in the solid state reactions to proeutectoid ferrite (between 875 and 723 oC) and finally a
significant amount of pearlite (below 723oC) as dictated by the binary phase diagram on page 74.
Segregation of Alloying Elements During Solidification of Steel
The product of the peritectic reaction, the austenite phase, is quite homogeneous in carbon
content because of the relatively high diffusion rate of interstitial carbon in the austenite. Unfortunately this is not the case for other substitutional alloy elements like manganese, chromiun,
nickel, copper, molybdenum, etc. These elements will initially be segregated during the nucleation and growth of the primary delta ferrite, and then will find a huge barrier awaiting them when
the peritectic reaction occurs. Their diffusion rate in the austenite is slow enough at the peritectic
temperature that a large fraction is left behind in the liquid which is being depleted by the growing
austenite interface. The final solid austenite product then contains regions of grossly different
alloy composition (microsegregation) which mirrors the original delta dendritic appearance. Consider for example the element manganese. The equilibrium Fe - Mn binary diagram predicts an
equilibrium distribution coefficient of about 0.6 in the range of compositions 0 to 5 weight percent manganese. This means that in the initial dendritic solidification of delta ferrite the new solid
that forms will only contain about one half of the amount included in the alloy. The remainder of
the Mn will be left out in the liquid, where it will remain until the austenite begins to form in the
peritectic reaction. Fortunately the solubility of Mn in the austenite phase is quite large, and so the
austenite interface advancing into the liquid can include those Mn atoms that it encounters in its
sweep toward the completion of solidification. However, the diffusion coefficient of the substitutional Mn atom is not rapid enough to allow the original Mn-poor delta volume to achieve equilibrium during the time of the peritectic reaction or even after solidification is complete. The
diffusion coefficient of Mn in austenite is given by the relationship:
DMn = 0.055 exp [- 29995 / T] (cm2/sec)
123
x-> 1
Manganese (Wt. %)
Where DMn is the diffusion coefficient of manganese and T is the absolute temperature in oK.
Using the simple approximation that the time required for diffusion over a distance x, is given by:
t = x2 / 2DMn,
and assuming that the distance required for Mn atoms to move is on the order of 100 microns
(10-2 cm), solving for time required at the melting point of ~ 1500oC (1777oK) gives :
t = (10-2)2 / 2 (0.055 exp[- 29995 / 1777 ]) = (19476 Sec) or 325 min.
Even with a very small distance x, of 10 microns (10-3 cm), the time is on the order of 3 minutes,
a much longer time than what is usually available during the cooling of the casting. The net result
is that significant manganese segregation will remain within the casting, segregation which has
strong implications for the microstructures and therefore mechanical properties that are attainable
in these materials. Consider a steel with a manganese concentration of 0.7 %.(A typical cast steel
will have manganese concentrations in the range 0.25 - 1.0 wt. percent.). The sketch below illustrates schematically the Mn concentration gradients that could be expected within a solidified
microstructure and therefore also at room temperature.
Original Delta Ferrite Dendrite
Solidified Austenite
2
kC0 = 0.6x0.7 = 0.42
1
C0=0.7 Mn
0
Distance x
0
1
Microprobe Trace for Manganese
Thus a solidified cast steel with such a composition variation could be expected to reflect that
variation in the microstructure of the casting. Because of the effect that Mn has in moving the
boundaries of the Fe - C phase diagram (increasing Mn reduces the carbon content of the eutectoid and reduces the eutectoid temperature) the low Mn areas corresponding to dendrite centers
will be ferritic and the remainder pearlitic in slowly cooled cast steels. These concentration variations and therefore microstructural variations will also persist in rolled steels, a situation where
the rolling operation strings out the segregated dendrites so that bands of segregation result.
This, of course, results in bands (in the rolling direction) of different microstructural products
which depends upon the subsequent heat treatment. This banding can lead to premature failure,
or reduced mechanical properties in a direction perpendicular to the bands. See the schematic rep-
124
resentation below:
Rolling Mill
Ferrite Bands in a Pearlitic Matrix
Ferrite Dendrites in
a Pearlitic Matrix
125
clean steel technology is the use of the plasma ladle furnace, or PLF, a device illustrated below:
Argon
Tightly Sealed
PROCESSING SCHEME
Cover
Graphite Electrode
Plasma Arc
Molten
Slag
Bottom Pour
Stopper Rod
Molten
Steel
Refractory
Lining
126
erties attainable in ASTM grades of cast steel are plotted with the ductile iron data below:
4
200
A148 Quenched $
Tempered
A148 Normalized
& Tempered
Normalized &
Tempered
180
ASTM
Grades of ADI
(Guaranteed
Minimums,UTS)
160
140
120
Yield UTS
TM = Temp Mart
P = Pearlite
F = Ferrite
ADI = Austem. Duct. Iron
UTS
Yield
(Guaranteed Minimums)
DUCTILE IRONS
(Guaranteed Minimums)
CAST STEEL, ASTM Grades
TM
1
A148
P
100
P+F
80
UTS
F+P
60
40
A217
Yield
0
8
10
12
Percent Elongation
14
16
18
20
A352
24
UTS v. % Elongation -Summary of Common As-Cast and Austempered Grades of Ductile Iron and Cast Steel
It can be seen in the above summary of tensile data that cast steels as a rule have excellent ductility for a given strength, in general much higher ductility than ductile cast irons. This is due to the
lack of graphite nodules in steel, which serve as nucleation sites for cracks and voids in ductile
cast iron. It can be seen that the ADI grades are very competitive, however.
It is important to emphasize that for the ASTM grades of steel plotted above, the tensile
data represent minimum values guaranteed, and that maximum values of both ductility and
strength can easily exceed the boundaries of the above scale. For example it is not unusual for
quality steel of lower strength to have tensile ductilities in excess of 40%, and tensile strengths up
to and exceeding 300 ksi are within reach for either higher alloy grades or smaller section sizes of
plain carbon grades which have been quenched and tempered at the appropriate temperatures.
Quenching and Tempering (Q & T) of steel involves the following procedure:
A. Austenitize at T for a period of time to ensure that 100% austenite is produced. This
time will depend upon the section size of the casting and whether or not the casting is put
into a hot furnace or a cold furnace. A hot furnace will accelerate heating so that shorter
austenitizing times can be realized. According to the Steel Castings Handbook of the
SFSA, the most efficient austenitization schedule would involve determining the time
required for the center of the heaviest section to reach T and then adding 15 minutes.
127
B. Quench to a temperature below the martensite finish, MF, temperature in a media which
will guarantee that in the center of the heaviest section of the casting the austenite transforms to martensite, and does not undergo any diffusional transformations to pearlite
(lamellar + Fe3C) or bainite (acicular ferrite with discrete particles of Fe3C either within
the ferrite or on the surface of the ferrite). See the schematic ITT diagram below. Alloying
elements such as Mn, Cr, Mo, Ni, V, etc.may be added to increase the hardenability of the
steel (moving the ITT diagram to longer times, thereby effectively buying time) so diffusional transformation products are avoided during quenching.
C. Heat to a temperature (tempering) to obtain the desired mechanical properties in the
casting. This will usually involve heating in an air furnace for a period of about one hours
time. The effect of the tempering process on hardness of a typical Quenched & Tempered
steel is illustrated below:
Isothermal Transformation (ITT) Diagram
Surface
MS
MF
Pearlite
99%
Bainite
Center
100% Martensite, RC 30 - 65
Rockwell C Hardnesss
1%
Temperature
Austenite
60
50
As - Cast
40 Hardness
30
20
0
Time
400
800
1200
Tempering Temperature (oF)
128
result from the response of each of these materials to the melting, rapid solidification, and rapid
cooling in the solid state that is characteristic of the welding process. The thermal and the physical
nature of weldments are described below:
Heating and Cooling Curves during Welding
Temperature
Tm
TE
Weld Metal
Melting Temp
Eutectoid Temp
Heat Affected Zone (HAZ)
Time
Application of a weld bead to the surface of either cast iron or steel would result in local melting,
creation of a weld bead, and local heating near the weld bead where the temperature will have
entered the austenitization range. Rapid cooling would follow after the heating, a period of time
when the weld metal would solidify and the austenite in the HAZ would transform to martensite
or some form of + Fe3C (pearlite, bainite, etc.).Typical scenarios for each material are given:
Steel
Weld Metal -> austenite -> + Fe3C or martensite
HAZ -> austenite -> + Fe3C or martensite
Cast Iron
Weld Metal -> Eutectic Fe3C + ; and then > + Fe3C or martensite
HAZ -> austenite -> + Fe3C or martensite
The most desirable structure to have throughout the weld bead and HAZ after welding would be a
continuous matrix of ferrite with an even distribution of Fe3C. Creation of martensite in either the
weld bead or the HAZ is not desirable because of the brittle nature of this austenite decomposition
product. Minimizing the carbon content and alloy content of the material to be welded makes it
likely that no martensite would form, a characteristic of low alloy plain carbon steels. These steels
make up the bulk of steel castings produced and are therefore highly weldable. Cast irons, on the
other hand have two strikes against them in this welding process. First, the rapidly cooling molten
iron weld bead is likely to solidify with the formation of the continuous iron carbide eutectic, the
hard and brittle white iron that gray and ductile iron processing so studiously avoids by proper
inoculation. Secondly the matrix carbon contents of cast irons are almost always greater than 0.6
wt %, making it very likely that the HAZ would transform to the hard, brittle martensite. Both the
eutectic carbide and the martensite are very detrimental to production of a successful weldment.
The problem of eutectic carbide formation in cast iron weldments have been solved by proper
choice of electrode material; high nickel alloys have been used successfully. Unfortunately these
alloys are expensive. The problem of martensite formation in the HAZ and the weld bead can be
dealt with by proper preheating and postheating schemes. However, these too are costly and cannot always be done conveniently. It is clear therefore that cast steel is a much more friendly material when it comes to welding than cast iron.
129
130
1083 oC
1455
Temperature
Temperature
1083
kNi = 1.8
oC
322oC
+L
oC
kSn = 0.15
' + T1
Cu
C C0
Wt. Percent Nickel
13.5
+
+
+
+
C
Ni
Cu
10
Wt. Percent Tin
Consider an alloy with 10 wt. pct. Sn and 5 wt. Pct Ni. Examination of the binary phase
diagrams above shows the complete solubility of Ni in Cu in the solid solution , and the solubility of about 13 % Sn also in . The Cu - Ni phase diagram contains a miscibility gap at low temperatures, where the single phase solid solution of composition C0 will separate into two
phases + of composition C and C respectively at temperature T1, phases with the identical
crystal structure of the parent but with different compositions as dictated by the tie lines on the
phase diagram. It can also be seen that the Cu - Sn phase diagram is quite complex, with a number
of intermetallic phases present in equilibrium with between melting and room temperature. It
can also be seen that the equilibrium distribution coefficients of Ni in Cu and Sn in Cu are of
131
opposite sign. The Ni atoms segregate negatively, that is there will be more Ni in the first to freeze
(FTF) part of the dendrite than at the edge of the dendrite, the last to freeze (LTF) volume; on the
other hand Sn atoms segregate positively, with less Sn in the FTF than in the LTF. Thus a composition profile across the dendrite in such an alloy would have the general appearance as is
shown in the sketch below:
12
10
8
Nickel
6
4
2
Tin
1
0
Wt.
Fraction
Solidified
LTF
FTF
The above schematic is not quite accurate because in a 10 percent Sn alloy there will be a significant amount of the interdendritic phase which results from the non-equilibrium coring during
solidification. This interdendritic phase is a rather hard intermetallic compound which will contribute to the wear resistance of the casting; binary alloys of 10% Sn are used in gear applications
where good sliding wear resistance is necessary, wear resistance provided in large measure by the
interdendritic . The rather high level of Ni within the dendrite promotes a certain amount of solid
solution strengthening of the dendrite, but has the added potential for contributing much more
strengthening to this material by precipitation hardening. This hardening is accomplished through
formation of the coherent a + a phases on aging the casting at low temperatures. These phases
are illustrated on the phase diagram on page 128, but form in a manner quite different than a normal nucleation and growth process. Instead of the precipitates nucleating and growing individually the + phases grow as composition waves within the structure as illustrated below:
Wt. Pct Ni
C
C0
t0
t1
t2
t3
C
Distance x
In this transformation (sometimes called spinodal decomposition) a random composition variation of composition C0 at time t0 will spontaneously increase in amplitude (composition) with
132
aging time until the composition limits C and C are reached by the composition wave. This
composition variation creates barriers to defect motion and therefore strengthens the matrix.
An age hardening response for an alloy containing 10.5 Sn and 4.4 Ni in the as - cast condition is
shown in the figure below:
350 oC
425 o C
220
200
180
160
140
120
12
16
20
24
28
32
Alloy
It should be noticed that the hardness increase on aging was much greater at 350oC than at 425oC,
a consequence of the larger composition difference (C - C) at 350 than at 425oC. See the phase
diagram on pg. 128 to appreciate how this difference increases with decreasing temperature. This
increase in hardness resulted in significant increases in tensile strength as well. These results are
133
60
As-Cast
& Aged
350C
4.5 Hr
50
As
Cast
Solution
Treated
780C,8 Hr
40
Creating
30
Yield
UTS
New Ppts
20
0
10
30
20
Percent Elongation
As-Cast Ppts
into Solution
40
50
60
Treatment
This figure also illustrates the large gain in elongation following solution treatment at 780oC, a
process whereby most of the Ni and Sn available for precipitation were put back into solution. It is
interesting to note that the yield, a parameter which is very dependent on the microstructure of the
matrix, is much more sensitive to aging than the UTS.
Most alloy castings have significant segregation present in the as-cast structure, a result
which is usually detrimental to the mechanical properties of the casting. This segregation can take
the form of gradients in composition across dendrites or as interdendritic phases which would not
be present at equilibrium. Removal or elimination of this segregation requires heating to temperatures near the melting point and holding for a period of time sufficient to allow diffusion of the
atomic species involved. Singh and Flemings have analyzed the kinetics of homogenization in
cast Al - Cu alloys, alloys in which both Cu gradients and the non-equilibrium interdendritic
phase is present. A part of the Al - Cu phase diagram, microstructure and expected Cu gradient for
134
across Dendrite
Interdendritic
Cu -rich Phase
53.5 Wt % Cu
Center of
Interdendritic
Phase
53.5
5.65
Maximum Solubility of Cu
C 0 = 4.5
kC 0 = 0.77
0
+
Al
33
4.5 Wt.% Cu
Distance
53.5
It can be seen in the above sketch of the Cu concentration vs. distance that a significant fraction of
Cu is present as the phase; an eyeball estimate of the average concentration of Cu in the dendrite
is about 1.5 %. Thus the phase must contain about 3 % (4.5 - 1.5) of the Cu; this translates to
about 6 wt % of the interdendritic q phase in the as-cast condition in an alloy in which the equilibrium structure would contain none of the phase after solidification is complete (see diagram
above). The primary reason why Cu is added to Al is to take advantage of the potential for age
hardening the matrix a phase (this is the basis for the development of the 2000 series wrought aluminum alloys). Unfortunately for the cast alloy, as is seen in the above sketch, most of the Cu is
not available on direct aging for the generation of precipitates. Thus it becomes necessary to
homogenize (or solutionize) the cast material, to put the Cu atoms into solution in the aluminum
rich matrix (dissolve the phase particles) so that then the alloy can be heat treated to take advantage of the Cu that is present.
Singh and Flemings showed that the rate at which the phase would dissolve into the a
phase is a function of the diffusion coefficient of Cu in the Matrix, DCu, and the secondary dendrite arm spacing, d. Their expression for the variation of the volume fraction of the phase, X,
with time at temperature is given by:
X = Xo exp - [2Dt / d2]
where:
Xo = Volume fraction of in as-cast condition,
t = time.
Heat treatment to homogenize requires that the casting be heated up into the single phase field,
to a temperature range of about 520 to 570 oC. It can be seen in the above equation that the value
of X will decrease with time in an exponential fashion until (at an infinite time) all of the interdendritic phase will be dissolved into the dendritic matrix. Clearly this is not practically acceptable; rather it is necessary only to put most of the Cu into solution in the dendrites. Assuming that
95 percent of the phase is an acceptable amount to be dissolved into the matrix gives an
expression for the time for homogenization, tH of:
135
1000
Ingot Casting
Sand Casting
Die Casting
Gas Atomiz.
100
MY 423
Lab
10
Water Atomiz.
Laser Skin Melting
Splat Quenching
0.1
0.01
10 -2
10 4
100
10 6
10 8
136
107
106
One Week
10
10
One Day
103
10
One Hour
450o C
500o C
2
One Minute
INGOTS
10
550o C
1
10
10
-1
ATOMIZA TION
-2
10-3
0.01
0.1
10
100
1000
137
ship applies even though there may be no significant interdendritic phase, for situations in which
there are only composition variations from inside the dendites to outside of the dendrites. A
selected group of diffusion coefficient data is given in Table 12:
Table 12: Selected Diffusion Coefficients in Al, Cu and Fe
D = D0 exp [-Q/RT], (cm2 / sec)
Matrix
D0
Solute
Q/R(oK)
Al
Cu
0.29
15662
Al
Mg
4.4
16859
Al
Li
4.5
16759
Cu
Ni
1.4
27428
Cu
Sn
0.027
18762
Cu
Zn
19879
Fe, In Austenite
Mn
0.055
29995
Fe, In Austenite
Mo
0.068
29693
Fe, In Austenite
Ni
0.344
32964
Fe, In Austenite
0.91
20262
Fe, In Austenite
16.2
16575
Fe, In Austenite
Si (0 -2%)
Fe, In Austenite
Cu
3.6
32964
Data from Smithells Metal Reference Book; Shewmons Text, Diffusion in Solids
Problem: A ductile cast iron with a nominal composition 3.7 C, 1.99 Si, 0.29 Mn, 0.18 Mo, 1.33
Ni, 0.77 Cu, 0.052 Mg was produced at MTU and cast into sand molds (4 inch Y-Block). The elements Si, Ni, and Cu segregate negatively (high concentration in the center of the dendrites and
near the nodules[FTF], while Mn and Mo segregate positively (high concentrations in the interdendritic regions [LTF]). The extremes in concentration observed in this alloy is given in the table
below:
Table 13:
Location
Si
Ni
Cu
Mn
Mo
FTF
2.9
1.65
1.55
0.2
0.05
LTF
1.0
0.65
0.3
1.1
1.7
138
The SDAS observed in this heavy section casting was in the range of 200 microns (0.02 cm).
Show that homogenization of this alloy is not practical (Tm = 1150oC).
Product
Use
Product
Disposal
In this modern age of environmental concern, the product life cycle has been modified to include
closure of the life cycle and to reflect the concern for the environmental cost of producing and
using the product. This cost includes an awareness , both qualitative and quantitative, of the
energy and material inputs and outputs during the process of producing the product. The Product
Life Cycle indicated above has been updated to reflect the Environmental Cost in the figure on
page 137. In this Figure the several options of Life Cycle Closure (Recycling, Remanufacturing
or Reusing) are included together with the introduction of the Environmental Concern Envelope.
This envelope emphasizes the material and energy inputs and the solid, liquid, and gaseous out-
139
Product
Manufacturing
Resource
Extraction
Packaging
& Transport
Recycling
Landfill
Reuse or
Remanufacturing
Product
Use
Product
Disposal
140
life cycles, it is useful to look at whether or not product matter is dissipated during the lifetime of
the product and/or after it has ceased to be useful. In this discussion, dissipation implies loss of
mass external to the product. A schematic product lifedissipation diagram,shown below, illustrates product use on a scale from dissipative to non-dissipative. This figure shows that
highly dissipative products are those which are usually produced for their controlled chemical
reactions (gasoline, blast furnace coke, explosives, fertilizer, pesticides), while non-dissipative
products are most often produced for their electronic or electrical properties (TVs, computers,
batteries). In the former, the reaction products are invariably dissipated to the environment and
cannot be conveniently recovered. In the latter, the product does not dissipate matter to its surroundings but ceases to be useful by obsolescence, by nonreversible chemical reactions, or by
internal mass flow. In many of these instances, it is interesting to note that product function
ceases by atomic dissipation (diffusion) within the product and not by dissipation to the environment. The in between products shown below invariably have a component of mechanical or
chemical use in which dissipation of matter can occur to different degrees depending upon the
product. This is illustrated by automotive parts which move against other parts and lose mass by
wear, and by auto body parts which corrode. If there is enough wear or corrosion, the part will
eventually cease to function and will require replacement or repair.
Products
Chemical Uses
Gasoline
Coke
Explosives
Fertilizers
Pesticides
DecreasingTendency to Dissipate
IncreasingTendency to Dissipate
Non-Dissipative Use
Electronic or
Electrical Uses
Mechanical Uses
Automobile Brake Pads
Automobile Disc Brake Rotors
Internal Combustion Engines
Automobile Bodies
Foundry Sand
NOT RECYCLABLE
Televisions
Computers
Batteries
Copper Cable
Beverage Cans
GENERALL
Y RECYCLABLE
141
for cooling and scrubbing air, and chemicals are sometimes necessary to bind sand grains and create metal penetration resistant layers. This dynamic flow situation is illustrated schematically
below, a flow diagram which is representative of a foundry of 1950. In this schematic the solids
DUST
CHEMICALS
AIR
AIR
[IN]
[OUT]
Disposal in Landll
[IN]
CASTING
To Scrapyard
OTHER CHEMICALS
BINDERS
SAND
Consumer
Reprocessed
Sand
Metal
Returns
SCRAP
METAL
[TO LANDFILL]
[IN]
FOUNDRY
BOUNDARY
SPENTSAND
WATER [IN]
SLUDGE
CHEMICALS
WATER
[OUT]
are depicted as entering the casting process from right and left, the water enters from the bottom,
and the air enters from the top. All material input is focussed upon the casting process in the center of the figure. Note that in 1950 the only recycled material was the metal, the remaining solid,
liquid and gas being dispensable. As a result of environmental, financial, and social pressures, the
foundry industry, like most other American industry has responded by paying much more attention to the flow of materials, other than the metals which make up their product, into and out of
their manufacturing centers. Those materials, gases, solids, and liquids, which are absolutely necessary in the process of producing the product but dont appear in the product are also very important This concern is illustrated schematically in the figure on page 140, a schematic flow diagram
for a typical foundry in the year 2000, in which solid, liquid and gaseous waste problems are
142
AIR
[OUT]
FOUNDRY
BOUNDARY
AIR
[IN]
AirTreatment
Baghouse
Dust
OTHER CHEMICALS
BINDERS
SAND
[IN]
CASTING
Consumer
Reprocessed
Sand
Metal
Returns
To Disassembly
for Remanufacture
Recycle or Reuse
Sand
Reclamation
SPENTSAND
SCRAP METAL
[IN]
Water
Treatment
WATER
[IN]
Sludge
WATER
[RECIRCULA
TED]
Byproduct
from Dust
It can be seen that the solid, liquid, and gas loops have been closed by the incorporation of
devices for scrubbing and cleaning the air and water, and by sand reclamation devices which will
scrub the sand grains for reuse. These efforts to control material flow into and out of metal casting
plants have been made in response to the need to improve the environment of people. Environmental specialists within the industry respond to health concerns related to the industrial output of
solids, liquids, and gases affecting workers (close proximity to the industrial output), affecting
near neighbors (within a few blocks of the industrial setting), and all residents on earth (green
house gas emission, acid rain, etc.).
Spent Molding Media
The greatest fraction of castings produced are made in molds in which an aggregate of some
refractory material is used as molding media, most often silica sand. As described earlier in these
notes, the process of making molds requires a pattern around which sand with an appropriate
bonding medium is packed. The pattern is removed, leaving a cavity in the sand into which molten metal is poured. As indicated previously, bonding media vary from clay + H2O to complex
organic resins which, as a result of the heat from the liquid metal, burn and produce a residual
143
coating on the sand grain surfaces. This new carbon-containing surface results in difficulty in
rebonding the shakeout sand. As a result, a significant amount of this spent sand is disposed of
in landfills (1 million tons per year in Michigan and 15 million tons in the U.S., 1990 estimate).
The figure below is a schematic flow diagram for sand in a typical green sand (clay-water bond)
foundry. This figure shows that after the casting operation the shakeout sand is divided into two
components. The major component is reused for making new molds (reconditioned sand), while
the minor component is treated as waste, screened fines and lumps created by the contact with
high temperatures.
Mining of Sand
Dunes and Old Lake Beds
Washing, Screening,
and Sizing
Add Water
and clay
Reconditioned
Sand
Add Water
and clay
Molding Sand
Core Sand
Bonding Media
Production of
Molds and Cores
Pouring of
Molten Metal into
Sand Molds
Separation of Castings
from Sand
[SHAKEOUT]
CASTINGS
Shakeout Sand
1. Sand Unaffected by Heat
2. Heat Affected Sand (Lumps, Fines)
RECLAMATION
To Landfill
or Alternate Use
Fines
There are opportunities available for sand (lumps and fines shown above) which is no longer satisfactory for direct use in molding, including:
A.
Subjecting the sand grains to a cleaning process whereby the interfering layer is removed
144
so that the grains can be used again as molding medium. These cleaning processes are generically
called reclamation and are shown closing the product cycle in the above sketch. This process is an
expensive addition to the foundry handling system and has been discussed in some detail on pages
64 - 67 of these notes.
B.
Using the sand grains (lumps and fines) for an alternate use, some of which are:
1. Aggregate in asphalt
2. Aggregate in concrete
3. Charge stock in a cement kiln
4. Charge stock in glass making
5. Daily cover in a landfill
Option A is not currently in wide use in the State of Michigan because for many foundries it is not
yet cost effective; i.e., the cost of landfilling is still not high enough to offset the increased capital
cost requirement to clean these grains. However, the rate of increase in the cost of disposal is
large, and it is simply a matter of time before Option A will become attractive and become a part
or the sand system in each foundry. Option B is in its beginning stage, with B1, B3 and B5 currently in process in several locations in this country. Which option each foundry uses will depend
upon its own unique circumstances.
Environmental Concern of Metal Casting Facilities.
Metal casting facilities have long been known as recyclers because of their basic function of taking scrap metal and turning it into useful products. Unfortunately, because of the other
material needs of these processes which are described above, metal casting facilities had also
earned the reputation of being very dirty places to work at or live near. This reputation has
changed, however, with governmental pressure responding to peoples physical and health needs
as well as the drive for environmental responsibility on the part of industry. As a result of these
pressures, significant federal legislation has been passed which has been directed at forcing closure of the above loops illustrated on page 140, legislation dealing with clean water, clean air, and
the generation and disposal of solid waste, both hazardous and non-hazardous. A partial summary
of the most significant of these legislations is given below:
1963 - Clean Air Act (CAA)
1965 - Solid Waste Disposal Act - First Law dealing with safe disposal of household,
municipal, commercial and industrial waste.
1970 - Resource Recovery Act
1970 - Clean Air Act (CAA), Amendments to CAA, Most of Basic Structure of CAA
were established in these amendments - Emission Standards for industrial
plants and automobiles.
1970 - Clean Water Act (CWA)
1976 - Resource Conservation and Recovery Act (RCRA) - regulates generation, storage,
transportation, treatment and disposal of hazardous waste
1977 - Clean Air Act, Amendments to CAA
1977 - Clean Water Act, Requires at least secondary treatment of all publicly owned treatment works, stipulating that such facilities provide at least 85% BOD (biochemical oxygen demand) removal.
1980 - Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) , Requires Cleanup of sites which pose a threat to human health or
145
146
INPUTS
Scrap Metal
Sand
Chemicals
Air
Other Gases
Water
Melting
Casting
Core Making
Mold Making
Casting Shakeout
Sand Processing
Reclamation
Casting Cleaning
Casting Painting
PROCESS ENVELOPE
OUTPUTS
Volatiles (Gases)
Dusts
Sludges
Slags
Spent Sands
Castings
Foundry Boundary
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marizes the emissions from 1 pound of a phenolic No-Bake binder (This assumes that the binder
is completely combusted in a manner typical for a ferrous foundry).
Table 14: Emissions (in lbs) from One Pound of No-Bake Phenolic Resin; after Mosher
Emission
Amnt
10-6Lb
ppm
Emission
Amnt
10-6Lb
ppm
Emission
Amnt
10-6Lb
ppm
NH3
39
Benzene*
11209
Phenol*
975
Total Hydrocarbons
12159
Formaldehyde*
10
Toluene*
634
NOX
29
HCN*
29
49
SO2
15107
M-Xylene*
97
Total C2 to C5 Aldehydes*
3070
H2S
1462
Napthalene*
49
16174
Acroleine*
O-Xylene*
49
TOTALS**
44972
** Thus for one pound of binder, 0.0449 pounds of Objectionable gaseous emissions and
0.0162 pounds classified as hazardous emisssions are released to the atmosphere. Presumably
the remainder of the one pound of binder will be emitted as the combustion products of water,
CO2, and CO (The OSHA emission standard for CO is 50 ppm)
Emission Factors for 12 of the most common binders or sand additives are available for calculational purposes. Granting of an operating permit will depend upon the individual states law and
on the total amount of HAP emitted per annum.
This method is a common sense approach (What Goes In Must Come Out) and a conservative estimate of emissions, because all of the binder is assumed to be combusted during the
casting operation. However, it is common knowledge that a significant part of the binder will be
lost to solid waste streams, most notably the core butts and broken cores which never see the heat
of molten metal. Thus the foundry can be fairly confident of their air emission responsibility provided that they keep good records of the input binder purchases.
RCRA of 1976
The Resource Conservation and Recovery Act of 1976 regulates the generation, storage,
handling and disposal of toxic waste material. A toxic substance is harmful or fatal if ingested or
absorbed. Toxicity is determined using a standardized laboratory test called the extraction procedure, a process which in essence is supposed to simulate the leaching action which could occur if
the substance were allowed to be exposed to rainfall in an open landfill. A substance is designated
as being EP Toxic if an extract (the leachate from the test) contains any of the eight toxic elements or six pesticides that follow in concentrations greater than the values given (in milligrams
per liter): Arsenic (5); Barium (100); Cadmium (1); Chromium (5); Lead (5); Mercury (0.2); Selenium (1); Silver (5); Endrin (0.02); Lindane (0.4); Methoxychlor (10); Toxaphene (0.5);
2,4-D(10); 2,4,5 TP Silvex (1). It should be noted that a hazardous substance is a more allencompasing term than a toxic substance, though the two are often used interchangeably.
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According to the EPA there are over 400 listed hazardous wastes and there is more than one ton of
hazardous waste per person per year generated in the U.S. (This amounts to ~ 250 million tons
of hazardous waste generated in the U.S. Of this amount only a small portion is contributed by metal casting facilities, perhaps - as a guess - only 1 million tons at maximum.) All
of the elements in the above list are potentially present in the output from foundries. Certainly
lead and cadmium are likely to show up in ferrous materials as carry over from scrap in the
charge. This distribution of lead as an impurity is illustrated in the input - output schematic below:
INPUTS
Scrap Metal
Sand
Chemicals
Air
Other Gases
Water
Pb
or
PbO
Melting
Pb
Casting
or
Core Making
PbO
Mold Making
Casting Shakeout
Sand Processing
Reclamation
Casting Cleaning
Casting Painting
PROCESS ENVELOPE
OUTPUTS
Volatiles (Gases)
Dusts
Sludges
Slags
Spent Sands
Castings
Hazardous
Waste Landfill or
Chemical
Treatment
Foundry Boundary
Inputs and Outputs Illustrating the Flow of Lead in a Typical Iron or Steel Foundry
Sources of lead in the charge include 1. Leaded steels (lead is used to improve machinability of
steels); 2. Leaded paints on scrap (Lead was a prominent element in paints for many years); 3.
Lead included in automobile shredding products (lead-acid batteries). It can be seen from the
above schematic that the melting operation results in lead being ever more widely distributed
(entropy in action) throughout the foundry work area, perhaps to the immediate neighborhood of
the foundry, and to the landfill site through leaching action of rainfall. The foundry is required by
law to make sure that emissions of lead from their stacks is within state - accepted tolerances and
that the air within their foundry contains no more than a certain allowable maximum amount.
Clearly the solution to this problem includes careful monitoring of input charge materials and
using an air handling system within the foundry which captures effluent from the melting area by
the use of a scrubber ( a device using water to entrap particulate matter) or a baghouse (a big filter
which captures particulate matter).
Of course, the scrubber sludge and the baghouse dust may now contain lead in quantities large
enough to be classified as a toxic waste. This material will then either have to be transported to a
toxic waste site (very expensive- ~ 5 to 10 times the cost of a normal landfill fee), or the lead will
have to be rendered non-leachable by chemically combining it with another material or by coating
the lead particles in a material which will not leach (another costly operation).
While lead is of concern as an impurity in charge materials which then ends up in the baghouse or in scrubber sludge, the fraction of solid waste from metal casting plants which is classified as hazardous is quite small indeed. The largest component of waste materials from foundries
is spent sand which, for the most part, is not hazardous and can be disposed of in local landfills at
reasonable cost. In fact most of the spent sand from foundries is used for daily cover at the land-
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fill, which usually means that the foundry will pay less per ton to dispose of the spent sand. Even
in the instance of lead and cadmium containing dusts and sludges, there are industrial organizations which mine these wastes for their heavy metals, and as such will either purchase these
byproducts from the foundry or will take them at no cost. Of course the monetary exchange is
determined by the grade of the ore that is the dust or the sludge.
Pollution Prevention
The above examples of air emissions and lead emissions are only two environmental concerns which foundries face on a daily basis. Obviously there are many other examples as well,
examples which will change from one foundry to another, from one metal to another, and even
from one state to another (depending on state statutes). The challenge for the foundry industry
(and every other industrial sector which uses large quantities of materials) is to look closely at
their processes and purchases with the intent of minimizing or eliminating waste. This engineering and management strategy is referred to as pollution prevention, as opposed to the end-ofpipe treatment which has dominated the environmental area for the first 20 years of the environmental revolution.
Pollution Prevention in the future of metal casting facilities will require efforts to:
1. Take a closer look at the fundamental material handling processes with
an eye to implementing design changes which will minimize waste.
2. Explore alternate molding media (to sand) with the intent of developing
dimensionally more stable aggregates which are more resistant to the rigors of metal casting and more reclamation friendly.
3. Develop new core and mold binders which will combust more completely and produce a minimum of the hazardous combustion products.
4. Develop and use more sophisticated equipments for screening incoming
charge material to minimize problems from contaminants such as lead or
cadmium.
5. Increase the overall industry wide casting yield, by using innovative
casting techniques and developing new casting techniques which minimize
gating and risering systems.
6. Explore new sources of charge material; for example in the cast iron
industry take a serious look at direct reduced iron as an alternate to scrap.
7. Other?
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