338 Chapter 9 Principles of Solidification

Riser An extra reservoir of liquid metal connected to a casting. If the riser freezes after the casting,
the riser can provide liquid metal to compensate for shrinkage.
Sand casting A casting process using sand molds.
Secondary dendrite arm spacing The distance between the centers of two adjacent s­ econdary
dendrite arms.
Second-phase strengthening See dispersion strengthening.
Secondary processing Processes such as rolling, extrusion, etc., used to process ingots or slabs
and other semi-finished shapes.
Shrinkage Contraction of a casting during solidification.
Shrinkage porosity Small pores between the dendrite arms formed by the shrinkage that
accompanies solidification. Also known as microshrinkage or interdendritic porosity.
Sievert’s law The amount of a gas that dissolves in a metal is proportional to the square root of
the partial pressure of the gas in the surroundings.
Skin-forming alloys Alloys with a microstructure that shows an outer skin of small grains in the
chill zone followed by dendrites.
Soldering Soldering is a joining process in which the filler has a melting temperature below 450°C;
no melting of the base materials occurs.
Solidification front Interface between a solid and liquid.
Solidification process Processing of materials involving solidification (e.g., single crystal
growth, continuous casting, etc.).
Solid-state phase transformation A change in phase that occurs in the solid state.
Specific heat The heat required to change the temperature of a unit mass of the material one
degree.
Spherulites Spherical-shaped crystals produced when certain polymers solidify.
Stainless steel A group of ferrous alloys that contain at least 11% Cr, providing extraordinary
­corrosion resistance.
Superheat The difference between the pouring temperature and the freezing temperature.
Thermal arrest A plateau on the cooling curve during the solidification of a material caused by
the evolution of the latent heat of fusion during solidification. This heat generation balances the
heat being lost as a result of cooling.
Total solidification time The time required for the casting to solidify completely after the
casting has been poured.
Undercooling The temperature to which the liquid metal must cool below the equilibrium
freezing temperature before nucleation occurs.

Problems
Section 9-1 Technological Significance 9-5 What is the difference between homoge-
9-1 Give examples of materials based on nous nucleation and heterogeneous nucle-
inorganic glasses that are made by solidi- ation?
fication. 9-6 From the thermodynamic point of view,
9-2 What do the terms “primary” and what two things must occur for solidification
“secondary” processing mean? from liquid to solid to proceed?
9-3 Why are ceramic materials not prepared 9-7 Does water freeze at 0°C and boil at 100°C?
by melting and casting? Explain.
9-8 Does ice melt at 0°C? Explain.
Section 9-2 Nucleation 9-9 Derive the formula for the rate of change
9-4 Define the following terms: nucleation, in total energy change (i.e., the derivative
embryo, heterogeneous nucleation, and of DG with respect to r) as a function of
homogeneous nucleation. the radius r of the solid nucleus. Begin

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 Problems 339

with Equation 9-1. Numerically, how is (a) 

the critical radius of the nucleus
the critical point at which solidification required and
proceeds defined? (b) 
the number of iron atoms in the
9-10 Using Equation 9-2, demonstrate that nucleus.
interfacial energy (ssl) has units of J/m2 Assume that the lattice parameter of the
in SI. solid BCC iron is 2.92 Å.
9-11 Calculate the total interfacial surface 9-21 Suppose that solid nickel was able
energy for 1016 spheres of copper, each to nucleate homogeneously with an
with the critical radius r*. undercooling of only 22°C. How many
9-12 Of the ferrous elements, which has atoms would have to group together
the lowest undercooling required for spontaneously for this occur? Assume that
homogeneous nucleation? Does this have the lattice parameter of the solid FCC
any practical significance? nickel is 0.356 nm.
9-13 If the total change in free energy of a mol- 9-22 Suppose that solid iron was able to
ten metal is 5.34 3 10217 J upon forma- nucleate homogeneously with an
tion of the first stable solid and the free undercooling of only 15°C. How many
energy per unit volume is 217.7 J/cm3, atoms would have to group together
approximate the radius of the first stable spontaneously for this to occur? Assume
spherical solid. The surface free energy that the lattice parameter of the solid
of the solid-liquid interface is 100 3 BCC iron is 2.92 Å.
1027 J/cm2.
9-14 Using the densities in Appendix A, convert Section 9-3 Applications of Controlled
the heats of fusion in Table 9-1 from units Nucleation
of J/cm3 to kJ/kg. 9-23 Explain the term inoculation.
9-15 Assume that instead of a spherical nucleus, 9-24 Explain how aluminum alloys can be
we have a nucleus in the form of a strengthened using small amounts of tita-
cube of length x. Calculate the critical nium and boron.
dimension x* of the cube necessary for 9-25 Compare and contrast grain size
nucleation. Write an equation similar to strengthe­ning and strain hardening
Equation 9-1 for a cubical nucleus, and mechanisms.
derive an expression for x* similar to 9-26 What is second-phase strengthening?
Equation 9-2. 9-27 Why is it that many inorganic melts
9-16 Why is undercooling required for solidi- solidify into amorphous materials more
fication? Derive an equation showing the easily compared to metallic materials?
total free energy change as a function of 9-28 What is a glass-ceramic? How are glass-
undercooling when the nucleating solid ceramics made?
has the critical nucleus radius r*. 9-29 What is photochromic glass?
9-17 Why is it that nuclei seen experimentally 9-30 What is a metallic glass?
are often sphere-like but faceted? Why 9-31 How do machines in ski resorts make
are they sphere-like and not like cubes or snow?
other shapes? Section 9-4 Growth Mechanisms
9-18 Explain the meaning of each term in
9-32 What are the two steps encountered in
Equation 9-2.
the solidification of molten metals? As a
9-19 Suppose that liquid nickel is undercooled
function of time, can they overlap with
until homogeneous nucleation occurs.
one another?
Calculate
9-33 During solidification, the specific heat of
(a) 
the critical radius of the nucleus
the material and the latent heat of fusion
required and
need to be removed. Define each of these
(b) 
the number of nickel atoms in the
terms.
nucleus.
9-34 Describe under what conditions we expect
Assume that the lattice parameter of the
molten metals to undergo dendritic solidi-
solid FCC nickel is 0.356 nm.
fication.
9-20 Suppose that liquid iron is undercooled 9-35 What is a dendrite and why do dendrites
until homogeneous nucleation occurs. form during solidification?
Calculate

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340 Chapter 9 Principles of Solidification

9-36 Use the data in Table 9-1 and the specific 9-43 A 2-in. cube solidifies in 4.6 min. Assume
heat data given below to calculate the un- n 5 2. Calculate
dercooling required to keep the dendritic (a) the mold constant in Chvorinov’s rule;
fraction at 0.5 for each metal. and
(b) the solidification time for a 0.5 in. 3
0.5 in. 3 6 in. bar cast under the same
Metal Specific Heat [J/(cm3 ? K)] conditions.
Bi 1.27 9-44 A 5-cm-diameter sphere solidifies in
Pb 1.47 1050 s. Calculate the solidification time
for a 0.3 cm 3 10 cm 3 20 cm plate cast
Cu 3.48
under the same conditions. Assume that
Ni 4.75 n 5 2.
9-45 Find the constants B and n in Chvorinov’s
rule by plotting the following data on a
9-37 Calculate the fraction of solidification that
log–log plot:
occurs dendritically when silver nucleates
(a) at 10°C undercooling;
(b) at 100°C undercooling; and
Casting Dimensions Solidification
(c) homogeneously. (in.) Time (min)
The specific heat of silver is 3.25 J/(cm3 ? °C).
9-38 Calculate the fraction of solidification that 0.5 3 8 3 12 3.48
occurs dendritically when iron nucleates 2 3 3 3 10 15.78
(a) at 10°C undercooling; 2.5 cube 10.17
(b) at 100°C undercooling; and 13439 8.13
(c) homogeneously.
The specific heat of iron is 5.78 J/(cm3 ? °C).
9-39 Analysis of a nickel casting suggests
9-46 Find the constants B and n in Chvorinov’s
that 28% of the solidification process
rule by plotting the following data on a
occurred in a dendritic manner. Calculate
log–log plot:
the temperature at which nucleation
occurred. The specific heat of nickel is
4.1 J/(cm3 ? °C). Casting Dimensions Solidification
9-40 It is desired to increase the dendritic frac- (cm) Time (s)
tion from 0.012 to 0.025. Assuming that
the specific heat of the metal being solidi- 13136 28.58
fied is constant, determine the increase in 23434 98.30
the amount of undercooling required. 43434 155.89

Section 9-5 Solidification Time and Dendrite 83635 306.15

Size
9-41 Write down Chvorinov’s rule and explain
the meaning of each term. 9-47 A 3-in.-diameter casting was produced.
9-42 Find the mold constant B and exponent The times required for the solid-liquid
n in Chvorinov’s rule using the following interface to reach different distances
data and a log–log plot: beneath the casting surface were measured
and are shown in the following table:

Dimensions Solidification Distance from Surface Time

Shape (cm) Time (s) (in.) (s)
Cylinder Radius 5 10, Length 5 30 5000 0.1 32.6
Sphere Radius 5 9 1800 0.3 73.5
Cube Length 5 6 200 0.5 130.6
Plate Length 5 30, Width 5 20, 40 0.75 225.0
Height 5 1
1.0 334.9

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 Problems 341

Determine 9-51 Find the constants k and m relating the

(a) the time at which solidification begins secondary dendrite arm spacing to the
at the surface and local solidification time by plotting the
(b) the time at which the entire casting is following data on a log–log plot:
expected to be solid.
(c) 
Suppose the center of the casting Solidification Time (s) SDAS (cm)
actually solidified in 720 s. Explain why
156 0.0176
this time might differ from the time
calculated in part (b). 282 0.0216
9-48 What solidification time is required for a 606 0.0282
casting of 9.5 cm3 and a mold contact area 1356 0.0374
of 10.0 cm2? The mold constant is 838 s/cm2.
9-49 An aluminum alloy plate with dimensions
20 cm 3 10 cm 3 2 cm needs to be cast 9-52 Figure 9-25 shows dendrites in a titanium
with a secondary dendrite arm spacing of powder particle that has been rapidly
1022 cm (refer to Figure 9-6). What mold solidified. Assuming that the size of
constant B is required (assume n 5 2)? the titanium dendrites is related to
solidification time by the same relationship
as in aluminum, estimate the solidification
time of the powder particle.
9-53 The secondary dendrite arm spacing
in an electron-beam weld of copper is
9.5 3 1024 cm. Estimate the solidifica-
tion time of the weld.
9-54 A zinc alloy has a SDAS of 0.01 cm and
m 5 0.40. What is the solidification time?
9-55 In Figure 9-7, what is the equation (slope
intercept form) of the tensile strength

Figure 9-6 The effect of solidification time on the

secondary dendrite arm spacings of copper, zinc,
and ­aluminum. (Repeated for Problem 9-49.)

9-50 Figure 9-5(b) shows a micrograph of an

aluminum alloy. Estimate
(a) the secondary dendrite arm spacing and
(b) the local solidification time for that
area of the casting.

Figure 9-25 Dendrites in a titanium

powder particle produced by rapid solidi-
fication processing (3 2200) (for Problem
9-52). (Springer and The Metallurgical of
Society of AIME, Metallurgical Transac-
Figure 9-5 (b) Dendrites in an tions, Vol. 15A, June 1984, pp 1117-1127,
aluminum alloy (3 50). (From ASM “Formation of Metal Carbide Powder by
Handbook, Vol. 9, Metallography and Spark Machining of Reactive Metals,”
Microstructure (1985), ASM International, J.D. Ayers and K. Moore, figure number(s),
Materials Park, OH 44073-0002. Reprinted Copyright © 1984, The Metallurgical of
with permission of ASM International. All Society of AIME. With kind permission
rights reserved. www.asminternational.org.) from Springer Science and Business Media.)

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342 Chapter 9 Principles of Solidification

line, and what SDAS would appear to 9-57 What is meant by the term recalescence?
give a tensile strength of zero if the line 9-58 What is thermal arrest?
is extrapolated? Does extrapolating the 9-59 What is meant by the terms “local” and
trend like this make sense? “total” solidification times?
9-60 In Figure 9-8, what do the slopes of
Section 9-6 Cooling Curves
the lines A-B and E-onward represent?
9-56 Sketch a cooling curve for a pure metal Do these quantities represent physical
and label the different regions carefully. properties?
9-61 A cooling curve is shown Figure 9-26.

Determine
(a) the pouring temperature;
(b) the solidification temperature;
(c) the superheat;
(d) the cooling rate, just before solidifica-
tion begins;
(e) the total solidification time;
(f)   the local solidification time; and
(g) the probable identity of the metal.
(h) If the cooling curve was obtained at
the center of the casting sketched in the
figure, determine the mold constant,
assuming that n = 2.
9-62 A cooling curve is shown in Figure 9-27.
Determine
(a) the pouring temperature;
(b) the solidification temperature;
Figure 9-7 The effect of the secondary dendrite (c) the superheat;
arm spacing on the properties of an aluminum (d) the cooling rate, just before solidifica-
casting alloy. (Repeated for Problem 9-55.) tion begins;

B–C: Undercooling is
necessary for homogeneous
nucleation to occur

Figure 9-8 (a) Cooling curve for a pure metal that has not been well-inoculated. The liquid cools
as specific heat is removed (between points A and B). Undercooling is necessary (between points B
and C). As nucleation begins (point C), latent heat of fusion is released causing an increase in the
temperature of the liquid. This process is known as recalescence (point C to point D). The metal
continues to solidify at a constant temperature (Tmelting). At point E, solidification is complete.
The solid casting continues to cool from this point. (b) Cooling curve for a well-inoculated, but
otherwise pure, metal. No undercooling is needed. Recalescence is not observed. Solidification
begins at the melting temperature. (Repeated for Problem 9-61.)

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 Problems 343

Figure 9-28 Cooling curves (For Problem 9-63).

the local solidification times and the

SDAS at each location, then plot the
tensile strength versus distance from the
casting surface. Would you recommend
that the casting be designed so that a
Figure 9-26 Cooling curve (For large or small amount of material must
Problem 9-61). be machined from the surface during
finishing? Explain.

Section 9-7 Cast Structure

(e) the total solidification time;
9-64 What are the features expected in the
(f) the local solidification time;
macrostructure of a cast component?
(g) the undercooling; and
Explain using a sketch.
(h) the probable identity of the metal.
9-65 In cast materials, why does solidification
(i) If the cooling curve was obtained at the
almost always begin at the mold walls?
center of the casting sketched in the
9-66 Why is it that forged components do not
figure, determine the mold constant,
show a cast ingot structure?
assuming that n 5 2.
9-63 Figure 9-28 shows the cooling curves Section 9-8 Solidification Defects
obtained from several locations within a 9-67 What type of defect in a casting can cause
cylindrical aluminum casting. Determine catastrophic failure of cast components
such as turbine blades? What precautions
are taken to prevent porosity in castings?
9-68 In general, compared to components
prepared using forging, rolling, extrusion,
etc., cast products tend to have lower
fracture toughness. Explain why this may
be the case.
9-69 What is a riser? Why should it be designed
so as to freeze after the casting?
9-70 Calculate the volume, diameter, and
height of the cylindrical riser required to
prevent shrinkage in a 1 in. 3 6 in. 3 6 in.
casting if the H/D of the riser is 1.0.
9-71 Calculate the volume, diameter, and height
of the cylindrical riser required to prevent
shrinkage in a 4 in. 3 10 in. 3 20 in.
casting if the H/D of the riser is 1.5.
9-72 Figure 9-29 shows a cylindrical riser
attached to a casting. Compare the
solidification times for each casting section
Figure 9-27 Cooling curve (For and the riser and determine whether the
Problem 9-62). riser will be effective.

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344 Chapter 9 Principles of Solidification

9-77 A 2 cm 3 4 cm 3 6 cm magnesium casting

is produced. After cooling to room
temperature, the casting is found to weigh
80 g. Determine
(a) the volume of the shrinkage cavity at
the center of the casting and
(b) the percent shrinkage that must have
occurred during solidification.
9-78 A 2 in. 3 8 in. 3 10 in. iron casting is
Figure 9-29 Step-block casting (For produced and, after cooling to room
Problem 9-72). temperature, is found to weigh 43.9 lb.
Determine
(a) the percent of shrinkage that must
have occurred during solidification
and
9-73 Figure 9-30 shows a cylindrical riser (b) the number of shrinkage pores in the
attached to a casting. Compare the casting if all of the shrinkage occurs as
solidification times for each casting section pores with a diameter of 0.05 in.
and the riser and determine whether the 9-79 If you cool an open vessel of liquid
riser will be effective. gallium until a thin solid “cake” forms, will
the cake form on the top or the bottom?
Assume that the air above the liquid
gallium is stagnant and does not cool the
surface at all.
9-80 Give examples of materials that expand
upon solidification.
9-81 What is Sievert’s Law? How can gas
porosity in molten alloys be removed or
minimized?
Figure 9-30 Step-block casting 9-82 In the context of stainless steel making,
(For Problem 9-73). what is argon oxygen decarburization?
9-83 Liquid magnesium is poured into a 2 cm
3 2 cm 3 24 cm mold and, as a result
of directional solidification, all of the
solidification shrinkage occurs along the
9-74 A hollow cylindrical mold for casting 24-cm length of the casting. Determine
aluminum ingots has a 300 mm inside the length of the casting immediately after
diameter and is 2 m high. If the mold is solidification is complete.
filled with liquid aluminum at 935 K, what 9-84 A liquid cast iron has a density of 7.65 g/
is the largest spherical cavity that may cm3. Immediately after solidification, the
form in the ingot? density of the solid cast iron is found to be
9-75 A 4-in.-diameter sphere of liquid copper 7.71 g/cm3. Determine the percent volume
is allowed to solidify, producing a change that occurs during solidification.
spherical shrinkage cavity at the center Does the cast iron expand or contract
of the casting. Compare the volume and during solidification?
diameter of the shrinkage cavity in the 9-85 Molten copper at atmospheric pressure
copper casting to that obtained when a contains 0.01 wt% oxygen. The molten
4-in. sphere of liquid iron is allowed to copper is placed in a chamber that is
solidify. pumped down to 1 Pa to remove gas
9-76 A 4-in. cube of a liquid metal is allowed from the melt prior to pouring into the
to solidify. A spherical shrinkage cavity mold. Calculate the oxygen content of
with a diameter of 1.49 in. is observed in the copper melt after it is subjected to this
the solid casting. Determine the percent degassing treatment.
volume change that must have occurred 9-86 From Figure 9-14, find the solubility
during solidification. of hydrogen in liquid aluminum just

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 Problems 345

Explain why this process is often used to

cast turbine blades.
9-93 Why is pressure a key ingredient in the
pressure die casting process?

Section 9-10 Continuous Casting and Ingot

Casting
9-94 What is an ore?
9-95 Explain briefly how steel is made, starting
with iron ore, coke, and limestone.
9-96 Explain how scrap is used for making
alloys.
9-97 What is an ingot?
9-98 Why has continuous casting of steels
and other alloys assumed increased
importance?
9-99 What are some of the steps that follow the
Figure 9-14 The solubility of hydrogen gas
continuous casting process?
in aluminum when the partial pressure of
H2 5 1 atm. (Repeated for Problem 9-86.) Section 9-11 Directional Solidification (DS),
Single-Crystal Growth, and Epitaxial Growth
9-100 Define the term directional solidification.
9-101 Explain the role of nucleation and growth
before solidification begins when the in growing single crystals.
partial pressure of hydrogen is 1 atm.
Determine the solubility of hydrogen (in Section 9-12 Solidification of Polymers and
cm3/100 g Al) at the same temperature Inorganic Glasses
if the partial pressure were reduced to 9-102 Why do most plastics contain amorphous
0.01 atm. and crystalline regions?
9-87 The solubility of hydrogen in liquid 9-103 What is a spherulite?
aluminum at 715°C is found to be 1 cm3/ 9-104 How can processing influence crystallinity
(100 g Al). If all of this hydrogen precipi- of polymers?
tated as gas bubbles during solidification 9-105 Explain why silicate glasses tend to form
and remained trapped in the casting, cal- amorphous glasses, however, metallic
culate the volume percent gas in the solid melts typically crystallize easily.
aluminum.
9-88 Review Example 9-7. The usual method Section 9-13 Joining of Metallic Materials
of measuring a vacuum in the United 9-106 Define the terms brazing and soldering.
States vacuum pump industry is in inches 9-107 What is the difference between fusion
of mercury. For example, atmospheric welding and brazing and soldering?
pressure is 29.92 inches of mercury. 9-108 What is a heat-affected zone?
Convert the pressure found in the example 9-109 Explain why, while using low intensity
to in. Hg. heat sources, the strength of the material
Section 9-9 Casting Processes for Manu- in a weld region can be reduced.
facturing Components 9-110 Why do laser and electron-beam welding
processes lead to stronger welds?
9-89 Explain the green sand molding process.
9-90 Why is it that castings made from pressure
die casting are likely to be stronger
than those made using the sand casting
Design Problems
process? 9-111 Aluminum is melted under conditions
9-91 An alloy is cast into a shape using a sand that give 0.06 cm3 H2 per 100 g of
mold and a metallic mold. Which casting aluminum. We have found that we must
is expected to be stronger and why? have no more than 0.002 cm3 H2 per 100 g
9-92 What is investment casting? What are of aluminum in order to prevent the
the advantages of investment casting?

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346 Chapter 9 Principles of Solidification

formation of hydrogen gas bubbles during

solidification. Design a treatment process
for the liquid aluminum that will ensure
that hydrogen porosity does not form.
9-112 When two 0.5-in.-thick copper plates are
joined using an arc-welding process, the
fusion zone contains dendrites having a
SDAS of 0.006 cm; however, this process
produces large residual stresses in the
weld. We have found that residual stresses
are low when the welding conditions
produce a SDAS of more than 0.02 cm.
Design a process by which we can
accomplish low residual stresses. Justify
your design.
9-113 Design an efficient riser system for the
casting shown in Figure 9-31. Be sure to Figure 9-7 The effect of the secondary dendrite
include a sketch of the system, along with arm spacing on the properties of an aluminum
appropriate dimensions. casting alloy. (Repeated for Problem 9-115.)

enthalpy of fusion ΔHf. Be sure to have the

correct prompts in the program to have
the values entered in the correct units.
9-117 Free Energy for Formation of Nucleus of
Critical Size via Heterogeneous Nucleation.
Figure 9-31 Casting to be risered When nucleation occurs heterogeneously,
(For Problem 9-113). the free energy for a nucleus of a critical
size (ΔG*hetero) is given by

9-114 Design a process that will produce a DG*hetero 5 DG*homofsd, where

steel casting having uniform properties s2 1 cos ds1 2 cos d2
and high strength. Be sure to include the fsd 5
4
microstructure features you wish to con-
trol and explain how you would do so. 163sl
9-115 Molten aluminum is to be injected into
and DG*homo is given by ,
3DGv2
a steel mold under pressure (die casting).
which is the free energy for homogeneous
The casting is essentially a 12-in.-long,
nucleation of a nucleus of a critical size.
2-in.-diameter cylinder with a uniform
If the contact angle (θ) of the phase that
wall thickness, and it must have a mini-
is nucleating on the pre-existing surface is
mum tensile strength of 40,000 psi. Based
180°, there is no wetting, and the value of
on the properties given in Figure 9-7,
the function f (θ) is 1. The free energy of
design the casting and process.
forming a nucleus of a critical radius is the
same as that for homogeneous nucleation.
If the nucleating phase wets the solid
Computer Problems completely (i.e., θ 5 0), then f(θ) = 0, and
there is no barrier for nucleation. Write a
9-116 Critical Radius for Homogeneous Nucle- computer program that will ask the user to
ation. Write a computer program that will provide the values of parameters needed
allow calculation of the critical radius for to calculate the free energy for formation
nucleation (r*). The program should ask of a nucleus via homogeneous nucleation.
the user to provide inputs for values for sl, The program should then calculate the
Tm, the undercooling (ΔT ), and the value of ΔG*hetero as a function of the

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 Problems 347

contact angle (θ) ranging from 0 to 180°. Chvorinov’s rule to calculate the time of
Examine the variation of the free energy solidification.
values as a function of contact angle.
9-118 Chvorinov’s Rule. Write a computer
program that will calculate the time of Knovel® Problems
solidification for a casting. The program
should ask the user to enter the volume of K9-1 What is chilled white iron and what is it
the casting, the surface area from which used for?
heat transfer will occur, and the mold K9-2 hat kinds of defects may exist in chilled
W 

constant. The program should then use white iron?

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