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SOLUTIONS FOR CHAPTER 8

1. FIND: When a phase transformation occurs such as a liquid phase transforming to a solid
below its melting temperature, what are the two steps involved in the process? Briefly
describe each.
SOLUTION: During a phase transformation such as a liquid transforming to solid, there
are two steps involved in the process. They are:

1. nucleation of the new phase, and


2. growth of the phase.

Nucleation relates to the formation of the new phase and the development of the interface
seperating the two phases. Nucleation can either occur randomly throughout the structure
- termed homogeneous nucleation or at specific sites such as interfaces - termed
heterogeneous nucleation.

Growth - Once the phases has nucleated, it begins to grow. The growth process is
controlled by diffusion and undercooling. As in the nucleation step, there may be
competing processes that lead to a maximum growth rate at an intermediate temperature.

2. FIND: We presented a derivation in Section 8.2.3 showing that the barrier for nucleation,
G*, decreases with increasing undercooling following the proportionality

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By starting with an expression for the free energy of a distribution of spherical particles of
radius r, derive equation 8.2-9a. Explain each step in the derivation. Explain any
assumptions that are made.
SOLUTION: To determine the barrier to the nucleation process, G* we begin by noting
that the free energy as a function of particle size for homogeneous nucleation has two
terms, one that increases with r2, the interfacial energy per unit volume term, and one that
decreases with r3. A maximum occurs in G(r) at some r*. These graphical relationships
are sketched below.
The dependence of the various free energy terms associated with nucleation as a function
of temperature: (a) the relationship between cluster radius and surface energy of a
growing spherical solid phase in liquid, (b) the relationship between the cluster radius and
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(c) the sum of (a) and (b). click here to view equation.

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The change in free energy can be written as:


In this equation we assume that the nuclei can be considered as a random distribution of
spheres. To locate the maximum of a function we equate the first derivative of the
function with respect to the parameter which is the variable to zero. Here we assume that

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r is the only variable. The is SL is independent of size and orentation.


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Using equation 8.2-4 for click here to view equation. we have:

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In writing
we have assumed that the heat capacity difference between the liquid and solid phases is
zero. (Note: Although this may be a reasonable assumption at small undercoolings, i.e.
small T’s, at the large undercoolings that are typical for homogeneous nucleation that
approximation may not be valid and a more complex term is required. But for a first order
approximation this assumption is reasonable.)

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In order to determine the value of G(r) at r*, we introduce the expression


into

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Rearranging,

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If all the terms in parentheses are constant then,


3. FIND: Explain the simultaneous influence that undercooling has on the barrier to
nucleation and the atomic rearrangements necessary to initiate the transformation. Show
how these competing effects lead to classical C-curve behavior in the nucleation of
diffusional transformations.
SOLUTION: Equation 8.25 gives the change in free energy as a function of r when a
liquid transforms to a solid, for example. In the development of that equation it was
assumed that the transforming phase was spherical and the interfacial energy, SL, was
isotropic. That equation consists of two terms on the right hand side, i.e.

G(r) = (4r2) SL + 4/3 r3 (Gv)

Since SL > 0 and GV < 0 for T > 0, the first term increases with radius, and the second
decreases. Figure 8.2-3 illustrates that there is a maximum that occurs at some r we
designated as r* and a corresponding G, we designated as G* where

r* = (-2SL)/Gv

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and
Both the critical radius, r*, and the barrier to the nucleation process contain SL in the
numerator. Thinking in terms of the barrier to nucleation, G*, there is a cubic
dependence on interfacial energy. The larger the S-L interfacial energy, the larger the
barrier to nucleation and hence the more difficult. The use of nucleating agents is based
on the principle of introducing particles with lower interfacial energies to stimulate
nucleation.

5. FIND: Compare homogeneous nucleation and heterogeneous nucleation.


SOLUTION: The process of homogeneous nucleation occurs at random locations in the
parent phase. The distribution of the transforming phase occurs without regard to specific
sites, such as mold walls in solidification. Heterogeneous nucleation occurs at specific
sites. In the case of solidification they can be at mold walls, unintentional additions such
as ceramic inclusions from crucibles or it may occur at nucleating agents which are
intentionally added to control the solidification microstructure.

6. FIND: What is the difference between the following interfaces?


a. coherent
b. partially coherent, and
c. incoherent
SOLUTION: A coherent interface is one in which there is a one-to-one correspondence
of atomic planes across the interface. This type of interface occurs when the lattice
parameters in the two phases are the same or very close. When the lattice parameters are
different in the two phases, the increase in strain energy that will occur as the particle
grows necessitates the periodic insertion of dislocations at the interface to accommodate
the misfit. This type of interface is referred to as partially coherent. An incoherent
interface occurs between two phases of different crystal structures and sufficiently
different atomic spacings that can not be accommodated by dislocations.

7. FIND: How does interfacial energy vary with coherency?


SOLUTION: Interfacial energy is sensitive to the nature of the interface separating the
two phases. The interfacial energy increases going from coherent to partially coherent to
incoherent, i.e. incoh. > part.coh. . coh..

8. FIND: Based upon your answer to question 7, explain how the probability for
heterogeneous nucleation changes as the type of interface changes from coherent
to partially coherent to incoherent.
SOLUTION: Since the barrier to nucleation, G*, is related to / in the following way:
G*  /3

increasing / would increase the barrier to homogeneous nucleation. Consequently, the
probability for heterogeneous nucleation would increase as interfacial energy increases.

9. FIND: Figure 5.3-5 contains a schematic illustration of a twin boundary in a crystal.


From the point of view of coherency, what is the nature of the type of twin boundary
illustrated in the figure? Comment on the relative energy of a twin boundary compared
with a random grain boundary in a polycrystalline material.
GIVEN: Figure 5.3-5 illustrates a schematic of a twin in a matrix showing the two twin
boundaries separating the matrix from the twin and Figure 8.2-10 illustrates an incoherent
interface separating the matrix from a precipitate.
Schematic of a twin

M a tr ix

P r e c ip ita te

Schematic of an incoherent boundary


SOLUTION: Atoms that are on the twin plane are part of the stacking sequence in the
matrix above the twin plane as well as the stacking of atoms below the twin plane. Since a
coherent interface is an interface that occurs when there is a one-to-one correspondence
across the interface, then the twin illustrated in this figure would be classified as a
coherent twin boundary.

The incoherent boundary illustrated above occurs in a system when there is not a match
across the boundary separating two phases. Since a general grain boundary represents a
situation where the orientation of two grains across a boundary are not the same, we
would therefore expect that there would not be a match of atoms across the boundary.
Thus, a coherent twin plane would have lower interfacial energy than the interfacial energy
associated with grain boundary separating two randomly oriented grains.

10. FIND: In certain nickel-base superalloys, a second phase can precipitate coherently from
the matrix during aging because the lattice parameters of the two phases are very close
and both phases are cubic. For a coherent precipitate in this system, what is the most
likely relationship between the crystallographic axes in the matrix phase and that of the
precipitate? Explain, using sketches.
GIVEN: The matrix and precipitate are both cubic with similar lattice parameters.
y
m

x
z m
m

M a tr ix

C o h e r e n t in te r fa c e

P r e c ip ita te

y
p

z xp
p

SOLUTION: The best match between two similar cubic structure with similar lattice
parameters occurs when the two cubes are aligned with the two sets of orthogonal axes
parallel to one another. Thus, the x-axis in the matrix, xm, would be parallel to the x-axis
in the precipitate, xp, and the y-axis in the matrix, ym, parallel to the y-axis in the
precipitate, yp. This orientation relationship is sometimes referred to as cube//cube
orientation. That is, the two cubes defining the two crystal structures are oriented x-axis
to x-axis and y-axis to y-axis.

Furthermore, because the lattice parameters of the two phases are very close, the distances
A A A A A

B B B B B
fc c
C C C C C
In te r fa c e b e tw e e n th e
A A A A A
fc c a n d h c p p h a s e s

B B B B B
hcp
A A A A A
between the atoms in the matrix and the precipitate match very closely.

11. FIND: The transition precipitate (Al2Ag) in the aluminum-silver system is a hexagonal
close-packed structure. The a axis of the HCP phase is 0.2858 nm, and the c axis is
0.4607 nm. What crystallographic plane and direction in the aluminum matrix defines the
coherent interface between matrix and precipitate?
GIVEN: Crystal structure of aluminum is fcc and that for  is hcp. Atomic radius for
aluminum is 0.143 nm from Appendix C and the a and c lattice parameters for  are
0.2858 nm and 0.4607, respectively.
SOLUTION: Both structures are close-packed structures. The two structures have the
same packing factor and coordination number. Both have sets of planes with the highest
possible planar density, the close-packed planes. In the fcc structure these are the {111}
and in the hcp they are the {0001}. Both structures have directions with the highest
possible linear density. In the fcc the highest linear density is in the 110 and in the hcp
structure 1000 . The best potential match between the two structures is across the two
highest packing planes. Thus the {0001} of the precipitate and the {111} of the aluminum
matrix would form a boundary.
Recall that the packing sequence for an fcc structure is ......ABCABCABC....., and that for
the hcp structure is .....ABABABABAB...... . A schematic of the two structures with a
common plane would be:

To complete the analysis, the atomic spacings in a 111 direction of the fcc aluminum
matrix must be calculated to determine if a match can be made with these planes and those
of the dense packed planes in the 0001 directions in the hcp structure of .

From Appendix C the atomic radius for aluminum is 0.143 nm, since the atoms touch
along 110 directions, see accompanying figure, in a fcc structure the lattice parameter,
ao, for aluminum is:

ao = 0.4045 nm.

Schematic showing the dense packed arrangement of atoms in an fcc material like aluminum.
For fcc stacking ( .....ABCABCABC.....) the distance between equivalent positions A
positions can be determined using the above sketch:

= ( 2ao2 + ao2 ) ½
= ao3 = 0.7006 nm

Thus the spacing between the adjacent dense packed layers in the fcc structure is

= 0.7006/3
= 0.2335 nm.

A schematic showing a comparison between the fcc aluminum and the hcp  structures are
shown below.

Thus the atomic spacing in the dense packed planes are similar, and the spacing between the dense
packed planes for the two structures are similar.
12. FIND: The expression: X = 1 - exp [ - (kt) n ] , equation 8.2-1, in the text, is a powerful
empirical function that is useful in describing the kinetics of diffusional transformations. In
the equation, X is the fraction transformed, k is a rate constant having units of reciprocal
time, t is time and n is a unitless constant. Sketch the behavior of this function over a
range of times that demonstrate why this expression is useful for describing
microstructural changes like recrystallization, or the decomposition of austenite to form
pearlite.

SOLUTION: At the start of the transformation, t = 0, we expect no transformed phase,


hence, X = 0. At very long transformation times, t  , we expect the
transformation to be complete, i.e. X= 1. Examining equation 9.2-1 at these two
extremes:

At t = 1
X = 1 - exp - (k  0)n
= 1 - 1 = 0, and

At t  
X = 1 - exp - (k  )n
=1-0 = 1.

Over a range of values the function would behave like the sketch shown below:

13. The value of n and k for the decomposition of a particular steel has been investigated by
following the fraction transformed versus time. From the experimental data, values for n
and k were determined at two temperatures. Plot the fraction transformed as a function of
time at 400o and 360oC.
Decomposition temperature n k
(oC) (sec-1)
400 2.0 0.085
360 2.0 0.028

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SOLUTION: Using the equation:


where X is fraction transformed, and k and n are as given in the table, to calculate the
fraction transformed as a function of time.

Typical values are summarized in the table below and the behavior of the function is
plotted and shown on the next page.

n = 2, k = 0.085 sec-1 n = 2, k = 0.028 sec-1

time time
(seconds) X (seconds) X
1 .0072 2 .0031
2 .0285 5 .0194
3 .0629 10 .0754
4 .1092 12 .1068
5 .1652 15 .1617
8 .3702 18 .2243
10 .5145 20 .2619
12 .6467 25 .3874
15 .8032 30 .5062
18 .9038 40 .7147
20 .9444 50 .8591
25 .9891 60 .9405
30 .9985 70 .9797

14. FIND: Explain how the data from problem 10 could be used to determine the location of
the start and finish times for the transformation.
SOLUTION: Since it is often difficult to decide exactly when a reaction begins and is
completed, the "start" and "finish" points on an isotherm transformation diagram are
usually chosen when, for example, 1% of the parent phase has transformed to indicate the
start of transformation, and 99% has transformed for the finish.

The start of the transformation:

At 400oC
0.01 = 1 - exp [ - (0.028) 2 ts2]

0.01 - 1 = - exp [ - (0.028) 2 ts2]

0.99 = exp [ - (0.028)2 ts2]

- 0.01 = - (0.028)2 ts2


0.01 = 0.000784 ts2
12.75 = t22 ;
t = 3.6 sec.
At 360oC

0.01 = 1 - exp [ - (0.085) 2 ts2]

0.01 = 0.007 2  ts2


ts = 1.4 Sec.

For the finish of the transformation

At 400oC
0.99 = 1 - exp [ - (0.028) 2 tf2]

4.605 = 0.0078 tf2


tf = 76.6 Sec.
At 360oC

0.99 = 1 - exp [ - 0.085)2 tf2]

4.605 = 0.0072 tf2

tf = 25.4 Sec.

15. FIND: When fraction transformed as a function of the logarithm of time, plotted at two
different temperatures, results in two curves that are parallel (same n but different k), the
mechanisms for the transformation are the same. Sometimes we refer to the process as
being isokinetic. For the kinetic data shown below, plot fraction transformed versus time
for the two temperatures. Does the process appear to be isokinetic?

Isothermal Transformation Isothermal Transformation


Temperature (415oC) Temperature (375oC)
time fraction time fraction
(sec) transformed (sec) transformed
2.0 0.032 4.0 0.025
2.5 0.048 5.0 0.037
3.0 0.072 7.5 0.084
4.0 0.129 9.0 0.124
4.5 0.157 10.0 0.151
5.0 0.189 13.5 0.262
6.0 0.272 16.5 0.369
9.0 0.518 20.0 0.502
11.0 0.669 24.5 0.653
13.5 0.813 30.0 0.799
16.5 0.921 36.5 0.912
40.5 0.950
SOLUTION: The data are plotted in the form of fraction transformed versus time and
shown below

Since the curves are parallel the processes appear to be isokinetic.


16. FIND: The value of k in equation 8.2-12, for a set of kinetic data, can be determined by
noting:

X = 1 - exp - (kt) n, and


when kt = 1
X = 1 - exp (-1) - 1 - 1/e or
X = 0.632.

What are the values for the rate constants for the data in problem 12 ?
SOLUTION: To find the value of k, we need to find the time (t*) at which kt =1. The
data is nearly linear at X = .632, therefore we can find this time by

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@ 415oC

t* = 10.5 sec.
kt* = 1
k (10.5) = 1
k = 0.095

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@ 375oC
t* = 23.9
kt* = 1
k = 0.042

17. FIND: When the mechanisms controlling a particular transformation are independent of
temperature, we can define an empirical activation energy, Q, for the process by noting:

k = A exp (-Q/RT).

Determine the empirical activation energy for the data given in problem 12 .

SOLUTION: Since we have two value of k for two different temperatures we can solve

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two equations for Q.

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from problem 13: k1 = .042


k2 = .095
T1 = 648 K
T2 = 688 K
R = 8.314 J/(moleK)

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Q = 75,600 J/mole.

18. FIND: The value of n from a set of data can be found by noting:

X = 1 - exp - (kt) n
1-X = exp - (kt) n
ln (1 - x) = - (kt) n
-ln (1 - x) = ln (1/(1-x)), then
ln (1/(1-x)) = (kt) n
ln ln (1/(1-x)) = n lnt + n lnk.

Determine n at the two temperatures from the data in problem 12.

SOLUTION: We have data for X vs t and we have already determined k at each


temperature (problem 13). Compute
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and ln(t) for each data point.

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to n.

@ 415oC n = 2.08

@ 375oC n = 2.08

19. FIND: In a diffusion-controlled transformation, the time t at different temperatures to


yield the same fraction transformed X is as follows:

T (oC) t (hr)
25 24
100 1
150 0.25
Calculate the empirical activation energy for the transformation process.
SOLUTION: By noting that the time for a given fraction transformed is inversely related
to the rate of the reaction if the processes have the same activation energy. Then using the
Arrhenius:

Rate = constant exp (-Q/RT)

where Q is the required activation energy, R the gas constant and T the absolute
temperature, the activation energy is determined graphically by plotting, ln 1/t versus 1/T.

T T 1/T t 1/t
(oC) (K) (1/k) (hr) (hr-1)

25 298 0.0036 24 0.0417


100 373 0.00268 1 1.
150 423 0.00236 0.25 4
From the graph: slope = - 3629.9
Then, Q/R = 3629.9
R = 8.314 Joules/moleK
Q = 30,180 Joules/moleK

20. FIND: Using the data from Problem 19, calculate the time required to yield the same
fraction transformed at 125C.
GIVEN: Data from problem 19.
SOLUTION: Least squares fit of the experimental data give an equation of the form

y (ln(reciprocal of the time)) = mx (1/T) + b

With the values the expression becomes:

y = -3630  ( 1/ T ) + 9.8572

To calculate the time at 125C

y = -3630  ( 1/ (125 + 273)) + 9.8572


y = 0.7366
Taking the inverse ln gives:

1/t = 2.089,
or, t = .4787 hours
21. FIND: The precipitation of carbides in certain steels can increase their strength. Shown
below are data relating time to reach peak strength and the isothermal hold temperature.
From the data, determine the activation energy for the precipitation process. Compare
your results with the activation energy for diffusion of carbon in bcc iron. Explain why the
similarities between the two activation energies are not too surprising.

T (C) Time to Peak Hardness (min.)


353 0.9
375 3.0
400 4.0
425 10.0
450 20.0

Applications to Engineering Materials (8.3)

22. FIND: Sketch an isothermal transformation (IT) diagram for a plain carbon eutectoid
steel. Label the various decomposition regions on the diagram.
SOLUTION: An IT diagram for a plain carbon eutectoid steel should contain the
following information:

1. The temperature of the eutectoid - 727oC.

2. The start and finish lines for the diffusional reactions:


  pearlite and   bainite.

3. The start and finish lines for the athermal martensite


transformation.

Shown below is the IT diagram.


23. FIND: Sketch a section of the Fe - Fe3C diagram over the composition range 0 to 2 wt%
carbon and over the temperature range from 900oC to room temperature. Label the phase
fields and compare the information that can be extracted from the phase diagram and the
IT diagram.
SOLUTION: An IT diagram such as that for a steel provides kinetic information that is,
how rapidly austenite decomposes into a particular microstructure. It also provides the
information regarding the morphology of the phases present. For example, depending
upon the quench temperature either coarse pearlite or fine pearlite may form. These are
the same microstructures except for the scale. The lower the transformation temperature,
the finer the lamellar spacing. Alternatively, rather than pearlite forming the austenite
might decompose into an alternative two phase structure of finely dispersed carbides in
ferrite.

Also noted on an IT diagram is the presence of metastable phases such as martensite. On


an IT diagram, the temperature range (Ms - Mf) of the metastable phase is presented.

In contrast, the equilibrium diagram provides no information regarding kinetics,


morphology or the the presence of metastable phases. Since the diagram is constructed on
the requirement of equilibrium, only equilibrate phases will be present.
24. FIND: Explain experimentally how you would determine an IT diagram for a particular
steel.
SOLUTION: Isothermal transformation (IT) diagrams are constructed by following the
isothermal changes in microstructure at different temperatures. Since it is difficult to
decide exactly when a reaction starts and is completed the start and finish lines on an IT
diagram are arbitrarily defined. The microstructural changes occurring can be followed by
monitoring microstructural changes directly using metallographic techniques or tracking a
property such as electrical resistivity which is affected by the amount of solute in solution
or hardness, which is controlled by the nature of the microstructure. As many
microstructure sensitive properties as possible are used to provide sufficient collaborative
information for a desired degree of accuracy.

25. FIND: Based upon the methods you outlined in question 19, explain the limitations of
using such a diagram. In particular, explain why the application of an IT diagram is
restricted and may not be applied directly to the production environment.
SOLUTION: Since an IT diagram is constructed from numerous samples transformed
under isothermal conditions, they can only be used that way. In general, the data for IT
diagrams are collected using thin specimens in order to assure that the requirement of
instantaneous quench are realized. When larger pieces are considered, especially when
considering a production environment where a variety of cross-sections are cooled,
instantaneous temperature changes can not be realized. Depending upon the mass of the
part, slow cooling may be achieved at the center, whereas rapid cooling may occur near
the surface. If the cooling rate is slow, then some microstructural changes will occur as
the sample cools down to the desired temperature. Consequently, the continuous cooling
(CC) curves were established. These curves recognize that the effects of time and
temperature must be integrated.
26. FIND: In our discussions in Chapter 7, we introduce the concept of a phase, and in this
chapter we have been concerned with the microstructure of an alloy and ultimately how a
particular microstructure affects properties. Explain the difference between the concept of
a phase and the phases that are present, and the microstructure of the material.
SOLUTION: A phase is a homogeneous portion of matter. A particular microstructure
such as 100% martensite can be a single phase microstructure. The microstructure is
composed of martensite and only martensite. However, a microstructure can be
multiphase. For example, pearlite is a two-phase microstructure which consists of
twophases that form as alternate lamellae of ferrite and cementite. So the concept of a
microstructure includes information about the phase or phases present and their
distribution.

27. FIND: Using the concepts associated with phases and microstructure, explain what is
meant by the terms:
a. austenite
b. ferrite
c. pearlite
d. bainite
e. martensite
f. cementite, and
g. spheroidite

SOLUTION:
(a) austenite - The face-centered cubic (FCC) form of iron.
(b) ferrite - The body-centered cubic (BCC) form of iron.
(c) pearlite - A two-phase microstructure of alternate ferrite and cementite lamellae
occurring in some steels. Pearlite forms by the decomposition of austenite.
(d) bainite - A two-phase microstructure of ferrite and cementite. Bainite forms when
an austenitic steel is quenched to a temperature below the pearlite region, but
above the martensite start, Ms, temperature.
(e) martensite - Metastable body-centered tetragonal (BCT) iron phase that is
saturated in carbon. Iron carbon martensite forms when austenite is rapidly
quenched to low temperatures. (Note: A wide variety of martensite-like
transformations occur in other systems. Consequently, the term martensite has
taken on a more general concept.)
(f) cementite - An iron carbide phase, Fe3C.
(g) spheroidite - A two-phase microstructure consisting of spheroidized carbide in
ferrite, which is formed by heat-treating pearlite, bainite, or martensite at a
temperature below the eutectoid temperature.

It should be noted that in this list of terms there is a distinction between single-phase
materials - austenite, ferrite, martensite and cementite and microstructures which can be
combinations of phases such as pearlite and spheroidite.

Problems 28 - 31 can be solved using Figures 8.3-6 and 8.3-11.

28. FIND: Thin specimens of a plain carbon steel having eutectoid composition are held at
800oC and have been at that temperature long enough to have achieved a complete and
homogeneous austenitic structure. Describe the phases present and the microstructures
that would occur using the quench paths given below.

a. Instantaneous quench to 650oC, hold at that temperature for 200 seconds, and
quench to room temperature.

b. Instantaneous quench to 300oC, hold for 1000 seconds, and quench to room
temperature.

c. Instantaneous quench to room temperature.

d. Instantaneous quench to 500oC, hold for 3 seconds and quench to room


temperature.
SOLUTION: When a eutectoid steel containing approximately 0.8 wt% carbon is taken
to 800oC and held, whatever microstructure was present prior to the 800oC exposure is
replaced by single phase, austenite containing 0.8% C.

(a) When austenite containing 0.8 wt% carbon is instantaneously quenched to 650oC
and held for 200 seconds it forms the two-phase pearlite microstructure. Since all
the austenite has transformed to pearlite at this temperature and time, no other
microstructures can form on the quench to room temperature. Consequently, the
microstructure consists of alternate ferrite and cementite lamellae - termed pearlite.
The microstructure contains 100% pearlite.

(b) When austenite containing 0.8% C is quenched to 300oC and held for 1000
seconds approximately 75% of the austenite has transformed to bainite. The
remaining austenite transforms to martensite when the material is quenched to
room temperature. Consequently, the microstructure contains 75% bainite and
25% martensite.

(c) When the 0.8% C alloy is quenched from 800oC to room temperature
instantaneously, all the austenite transforms to martensite. Consequently, the
microstructure is 100% martensitic.
(d) When the 0.8% C alloy is instantaneously quenched from 800oC to 500oC and held
for 3 seconds, approximately 50% of the austenite transforms to a microstructure
that consists of fine pearlite. The remaining austenite transforms to martensite
when the material is quenched to room temperature. Consequently, the
microstructure is a mixture of 50% fine pearlite and 50% martensite.

29. FIND: Using the same initial conditions outlined in problem 23, describe the phases
present and the microstructures that would occur using the quench paths given below.

a. Instantaneous quench to 650oC, hold for 15 seconds, and quench to room


temperature.

b. Instantaneous quench to 500oC hold for 60 seconds and quench to room


temperature.
c. Instantaneous quench to 170oC hold for 100 seconds and quench to room
temperature.

d. Instantaneous quench to 170oC and hold at that temperature.


SOLUTION:
(a) When austenite containing 0.8% C is instantaneously quenched to 650oC and held
for 15 seconds approximately 50% of the austenite transforms to pearlite. The
remaining austenite transforms to martensite as the temperature drops between the
Ms and Mf temperatures. Consequently, the microstructure consists of 50%
pearlite and 50% martensite.

(b) When austenite containing 0.8% C is instaneously quenched from 800oC to 500oC
and held for 60 seconds, all of the austenite transforms to fine pearlite. Since all of
the austenite has transformed to pearlite at this temperature there are no changes
that will occur to microstructure upon quenching to room temperature.
Consequently, the microstructure will consist of 100% pearlite.

(c) When 0.8% C alloy is quenched from 800oC to 170oC 50% of the austenite has
transformed to approximately 50% martensite regardless of the time at that
temperature. The martensite reaction is athermal and hence the time at
temperature does not affect the amount of transforming phase. Quenching the
material to room temperature causes the remaining austenite to transform to
martensite as the temperature is lowered. Consequently, the room temperature
microstructure is completely martensitic.

(d) When 0.8% C alloy is quenched from 800oC to 170oC and held at that temperature
indefinitely, the microstructure will consist of approximately 50% martensite and
50% austenite. The martensite reaction is athermal and hence the time at
temperature does not affect the amount of transforming phase. Consequently, at
170oC the microstructure is approximately 50% martensite and 50% austenite.
30. FIND: Briefly describe a heat treatment that would result in the following microstructure
for a plain carbon, eutectoid steel.

a. Coarse pearlite
b. Bainite
c. A 50-50 mixture of coarse pearlite and bainite.
d. A 50-50 mixture of bainite and martensite.
SOLUTION: Since each part of the question requires a microstructure that can form
only from austenite the first step must be a heat treatment at a temperature above the
eutectoid to form the austenite. A temperature of 800oC for 0.8%C is sufficiently above
the eutectoid temperature to ensure rapiddissolution of the starting phase resulting in only
single phase austenite.

(a) Coarse pearlite forms at the higher transformation temperatures. Consequently


choose 650oC or above as the quench temperature. Once the temperature is
established, the time is fixed by noting that the desired structure is 100% pearlite.
Consequently, heat treat at 650oC in excess of the pearlite finish time which is
about 200 seconds. A suitable heat treatment would be
1. 800oC hold to form austenite
2. Instaneously quench to 650oC and hold for at least 200 seconds, and cool
to room temperature.

(b) A distinct bainite region is below approximately 450oC. The choice of the
temperature depends on the desired microstructure. We know that the lower the
isothermal treatment temperature, the finer the microstructure. However, this was
not specified. Consequently, we can choose 400oC as the quench temperature.
The hold time is fixed by noting that we desire a 100% bainitic microstructure.
Consequently we need to hold at 400oC in excess of at least 200 seconds, the
approximate bainite finish time at 400oC. Consequently a heat treatment would be:
1. 800oC hold to form austenite
2. Instantaneously quench to 400oC and hold for at least 200 seconds, and
cool to room temperature.

(c) To achieve a 50-50 mixture of pearlite and bainite a two-step quench process is
required. At the highest quench temperature the pearlite is formed, and at the
lower temperature, the remaining austenite will transform to bainite.
Consequently, we can choose 600oC and 400oC as our two temperatures. Now
that the transformation temperatures have been selected the times for the
isothermal holds can be chosen. Since we require 50% pearlite, the time at 600oC
must be approximately 6 seconds. Quenching and holding at 400oC transforms the
remaining austenite to bainite. At this point we need to exercise some caution.
Recalling that these isothermal transformation diagrams are the result of quenching
to a specific temperature and holding to a specific time, using these diagrams
differently than the way they were produced may give erroneous results. We are
certain that if we were to quench the specimen from 800oC and held at 400oC for
200 seconds we have a 100% bainitic structure. To be conservative, we should
adopt the 200 second hold here as well. Consequently, the heat treating steps to
produce a 50-50 mixture of pearlite and bainite are:
1. 800oC hold to form austenite
2. Instantaneously quench to 600oC for approximately 6 seconds to form 50%
pearlite and 50% austenite.
3. Instantaneously quench from 600oC to 400oC and hold for 200 seconds to
transform the remaining austenite to bainite and cool to room temperature.

Note that we quench first to the high temperature to form pearlite, then quench to
the lower temperature to form the bainite. If we would have done the reverse, that
is low temperature followed by high temperature, the bainite that we formed at the
low temperature would begin to spheroidize at the higher temperature.

(d) To achieve a 50-50 mixture of bainite and marteniste, we need only to quench from
800oC to a temperature in the bainite region, hold until 50% of the austenite has
transformed to bainite, then quench to room temperature, the remaining austenite
will transform to martensite passing through the Mf temperature. We can choose
any temperature in the range where bainite will form. Choosing 400oC, as an
appropriate temperature we will need to hold for approximately 20 seconds in
order to transform 50% of the austenite to bainite. Cooling to room temperature
will result in the formation of martensite from the remaining austenite.
Consequently, a heat treatment to produce a 50-50 mixture of bainite and
martensite is:
1. 800oC hold to form austenite.
2. Instantaneously quench to 400o C and hold for approximately 20 seconds
and instantaneously quench to room temperature to transform the
remaining austenite to martensite.

31. FIND: Describe the heat treatments that would be required to transform the following
microstructure of a eutectoid steel from one microstructure to another.
a. Pearlite to bainite
b. Bainite to pearlite.
c. Coarse pearlite to a mixture of pearlite and bainite.
d. Martensite to pearlite.
SOLUTION: Since each part of the question requires a microstructure that can form
only from austenite the first step must be a heat treatment at a temperature above the
eutectoid to form the austenite. A temperature of 800oC for 0.8%C is sufficiently above
the eutectoid temperature to ensure rapid dissolution of the starting phase resulting in only
single phase austenite.
a. At the 800oC soak, the initial pearlite is dissolved and the microstructure becomes
100% . According to Figure 8.3-6 bainite can form at 300oC. The  begins
transforming to bainite in about 100 seconds, and is complete in about 2000
seconds. Cooling to room temperature does not affect the microstructure. The
heat treatment is thus:
1. 800oC hold to form austenite.
2. Instantaneously quench to 300oC and hold for 2000 seconds.
3. Cool to room temperature.

b. At the 800oC soak, the initial bainite is dissolved and the microstructure becomes
100% . Quenching a eutectoid steel to 600oC and holding results in a pearlite
structure. Austenite begins transforming to pearlite according to Figure 8.3-6 in
approximately 1 second. All the austenite has transformed to pearlite in about 7
seconds. Consequently, holding beyond that time transforms all the austenite to
pearlite, and cooling to room temperature does not alter the microstructure. The
heat treatment is thus:

1. 800oC hold to form austenite.


2. Instantaneously quench to 600oC and hold for 10 seconds.
3. Cool to room temperature.

c. At the 800oC soak, the initial course pearlite transforms to austenite. Quenching
to 600oC will result in the austenite transforming into pearlite. Holding to the
50%, approximately 5 seconds, results in the required pearlite. Instantaneously
quenching to 300oC and hold for 2000 seconds transforms the remaining austenite
to pearlite. We would like to stress that these diagrams are isothermal and care
must be exercised when using them to analyze step quench paths. Therefore, to be
conservative, hold at the lower temperature past the bainite finish time to make
sure that the remaining austenite is transformed. The heat treatment is:

1. 800oC hold to form austenite.


2. Instantaneously quench to 600oC and hold for 5 seconds.
3. Instantaneously quench to 300oC and hold for 2000 seconds.
4. Cool to room temperature.

4. At the 800oC soak, the initial martensitic microstructure


will transform to austenite. Quenching to 600oC and holding
results in a pearlite structure. Austenite begins transforming
to pearlite according to Figure 8.3-6 in approximately 1 second.
All the austenite transforms to pearlite in about 7 seconds.
Consequently, holding beyond that time transforms all the
austenite to pearlite and cooling to room temperature does not
alter the microstructure. The heat treatment is thus:

1. 800oC hold to form austenite.


2. Instantaneously quench to 600oC and hold for 10
seconds.
3. Cool to room temperature.

Recall that the pearlite spacing is controlled by the


transformation temperature. Thus, the scale of the
pearlite depends on the soak temperature. The higher
the soak temperature the coarser will be the pearlite
lamellae. However, it will take a longer time
depending on the temperature. Consequently, if we
desire a specific microstructure such as slightly
coarse pearlite, we will need to quench to 650oC and
hold for at least 200 seconds to transform all the
austenite. Because of the asymptotic behavior of the
start and finish lines, as we get closer to the
eutectoid temperature it will take much longer.

32. FIND: Sketch an IT diagram for a hypoeutectoid,


eutectoid and hypereutectoid alloy. Compare the decomposion
regions on the three diagrams with respect to proeutectoid
phases and the martensite start and finish temperatures.
SOLUTION: For a eutectoid steel the decomposition of
austenite to pearlite (  P) begins below the eutectoid
temperature (727oC). However, if the alloy is off-eutectoid
depending upon cooling rate, a proeutectoid phase can form
just below the  -  phase boundary for the hypoeutectoid
steel, or just below the  - Fe3C boundary. These
reactions are all diffusion controlled and hence follow C-
curve kinetics, that is, at low undercoolings the reaction
is slow due to high barrier to nucleation, and large
undercoolings, low due to limited diffusion rates.

The athermal transformation start and finish lines are


horizontal. Also, we know that as the carbon content
increases, the Ms and Mf temperatures decrease. Hence, our
sketches must include these issues. Included are the
sketches for the hypoeutectoid, eutectoid, and
hypereutectoid compositions.
Shown in Figure HP8-1 are IT diagrams for a hypoeutectoid,
eutectoid, and hypereutectoid steel. Questions 33 - 39 pertain
to these diagrams.

33. FIND: Which diagram is associated with a composition


that is hypoeutectoid, eutectoid and hypereutectoid and why?
SOLUTION: To differentiate between steels which are
eutectoid from those which are not, you need only look at
whether the diagram contains region over which proeutectoid
phase would form. Alloy I has no such region hence it must
be eutectoid.

Alloy III, contains a proeutectoid phase which is labeled on


the figure as , hence Alloy III is hypoeutectoid.

Alloy II must therefore be the hypereutectoid steel and the


proeutectoid phase must be Fe3C (cementite).

As a check we also know that increasing carbon content


decreases the Ms and Mf temperatures. The Ms temperatures
are:

Alloy III ~ 330oC


Alloy I ~ 220oC
Alloy II ~ 200oC

Confirming that the carbon content increases going from


Alloy III I II, verifying that:

Alloy III is hypoeutectoid


Alloy I is eutectoid, and
Alloy II is hypereutectoid.

34. FIND: Label the regions on each diagram.


SOLUTION:
35. FIND: Estimate the carbon content for the
hypoeutectoid and hypereutectoid steels. Explain your
reasoning.
SOLUTION: With the aid of Figure 8.3-12, we can use the Ms
temperature and the -  phase boundary temperature to
estimate the carbon content of Alloy III, the hypoeutectoid
alloy. The -  temperature is 770oC Ms is about 320oC hence
the carbon content is approximately 0.7%C.

For alloy II, the  - Fe3C temperature is 880oC with an Ms


temperature of approximately 200oC, hence the carbon content
is 1.1%C.

36. FIND: If a thin specimen of alloy II is quenched instantaneously


from 900oC to 550oC, held for 1 second, and quenched to room temperature, what phases
will be present in the microstructure?
SOLUTION: Instantaneously quenching alloy II from 900oC to 550oC and holding will
transform 50% of the austenite to pearlite. The remaining austenite will transform to
martensite when the alloy is quenched to room temperature. Consequently the
microstructure will be 50% pearlite and 50% martensite.

37. FIND: Provide two heat treatments that would result in


the maximum difference in the amount of proeutectoid phase
that would be present in the microstructure of the
hypereutectoid steel after heat treating.
SOLUTION: The maximum amount of proeutectoid phase will
occur if the alloy is held at just above 727oC to form the
mixture of Fe3C + austenite.

Then the alloy is cooled at rate to room temperature.

To produce the minimum, in this case zero, the alloy is


quenched to any temperature below 550oC and held. This will
result in no proeutectoid cementite.

38. FIND: Calculate the maximum amount of proeutectoid


phase that can form when heat treating a plain carbon steel
containing 0.4 wt% C.
SOLUTION: The maximum amount of proeutectoid ferrite in a
0.4 wt% C alloy can be estimated using the equilibrium phase

Install Equation Editor and double-


click here to view equation.

diagram for the Fe - Fe3C system.

39. FIND: Calculate the maximum amount of proeutectoid


phase that can form when heat treating a plain carbon steel
containing 1.2 wt% C.
SOLUTION: The maximum amount of proeutectoid cementite in a
1.2% C alloy can be estimated using the equilibrium phase

Install Equation Editor and double-


click here to view equation.

diagram for the Fe - Fe3C system.


IT D ia g r a m - 4 1 4 0
A
800

700
A F + C
600 P r o e u te c to id
F e r r ite A + F + C
T e m p e ra tu re , ° C

500
50%
400

300

200

100

3 4 5
1 10 100 10 10 10
T im e , s e c o n d s
(a )

Questions 40-46 pertain to the IT diagram for two important steels, 4140 and 4340, shown in
Figure HP8.2.
IT D ia g r a m - 4 3 4 0
A
800

A
700
P r o e u te c to id
A F e r r ite F + C
600
T e m p e ra tu re , ° C

500

A + F + C
400
50%
300

200

100

3 4 5
1 10 100 10 10 10
T im e , s e c o n d s
(b )
40. FIND: From the I-T diagrams shown in Figure HP8.2, are the two alloys hypo- or
hypereutectoid? Explain.
GIVEN: Figure HP8.2, the IT diagrams for, (a) 4140 and (b) 4340.
SOLUTION: The IT diagrams for both 4140 and 4340 are included and the region
showing the proeutectoid phase labeled. Since the proeutectoid phase that forms first in
both 4140 and 4340 is ferrite, the two alloys are then hypoeutectoid.

41. FIND: Which of the two alloys, 4140 or 4340, has the greater hardenability?
GIVEN: Figure HP8.2, the IT diagrams for (a) 4140 and (b) 4340. The definition for
hardenability- “Since martensite is the strongest and hardest phase in steel, an alloy that
can form extensive amounts of martensite is said to have high hardenability.”
SOLUTION: The start of the diffusion controlled austenite decomposition reactions
occur at shorter times for 4140 than 4340, hence the critical cooling rate to the martensite
start temperature is greater for 4140, therefore, 4340 has a greater hardenability than
4140.

42. FIND: What are the maximum isothermal hold temperatures that a thin piece of either
4140 or 4340 can be quenched to while avoiding the formation of proeutectoid phase?
Explain by comparing the complex 4140 and 4340 diagrams with the off-eutectoid
compositions in plain carbon steel.
GIVEN: Figure HP8.2, the IT diagrams for (a) 4140 and (b) 4340.
SOLUTION: The maximum isothermal hold temperature that a thin piece of 4140 can be
quenched to which will avoid proeutectoid ferrite phase is 500C. For 4340, the maximum
temperature to avoid proeutectoid ferrite phase is approximately 585C.

43. FIND: What phases and microstructure would be present if thin pieces of 4140 were
homogenized in the austenite phase field and given the following quench paths?

a. Instantaneous quench to 600oC, hold for 104 seconds, and quench to room
temperature.

b. Instantaneous quench to 600oC, hold for 103 seconds, and quench to room
temperature.

c. Instantaneous quench to 400oC, hold for 103 seconds and quench to room
temperature.

d. Instantaneous quench to room temperature.

SOLUTION: Before answering this series of questions regarding the phases present
when 4140 is quenched using different paths a number of important distinctions must be
made regarding the IT diagram for 4140 and the IT diagram for the eutectoid steel used in
previous problems. The 4140 diagram does not indicate exactly how much austenite is
consumed during the formation of proeutectoid ferrite. Hence, depending upon the
quench path it may not be possible to be quantitative about the relative amounts the
various phases present. Also, there is no indication on the diagrams as to whether the F &
C (ferrite and cementite) are in the form of pearlite or bainite. However, we might infer
that similar temperature ranges should result in similar morphologies of the two-phase
ferrite and cementite. With these limitations in mind the diagram can provide some
indication of the phases that will be present.

(a) Instantaneous quench to 600oC from the austenite phase field results in
1. proeutectoid ferrite that forms in the time interval between approximately 4 and
90 seconds.
2. The remaining austenite (the amount we do not know from this diagram) begins
to transform to a two-phase mixture of ferrite and cementite. Holding for 104
seconds transforms all the remaining austenite to ferrite and cementite.

Since there is no austenite left after about 4000 seconds, cooling to room temperature
should not alter the microstructure. In summary: proeutectoid ferrite and pearlite (ferrite
and cementite).

(2) Similar to part (a) except that at 103 seconds there is some
austenite that remains. Consequently, the microstructure
consists of:

proeutectoid ferrite, pearlite and martensite that


forms on quenching from 600oC to room temperature.

(3) Instantaneously quenching to 400oC and hold for 103 seconds


transforms all the austenite to a two-phase microstructure of
ferrite and cementite. Because of the low temperature this two-
phase microstructure would be bainite. Since there is no
austenite left after about 200 seconds, no martensite can form on
the quench to room temperature.

(4) An instantaneous quench of 4140 to room temperature from the


austenite range should contain 100% martensite.

44. FIND: What phases and microstructures would be present if thin pieces of 4340 were
homogenized in the austenite phase field and subjected to the following quench paths.

a. Instantaneous quench to 650oC, hold for 105 seconds, and quench to room
temperature.

b. Instantaneous quench to 350oC, hold for 104 seconds, and quench to room
temperature.

c. Instantaneous quench to room temperature.


SOLUTION: Since 4340 also contain a proeutectoid ferrite phase, it may not be possible
to be quantitative with respect to the phases that form in the temperature range where
proeutectoid ferrite forms.
a. An instantaneous quench from the austenite range to 650oC results in the
formation of proeutectoid ferrite that forms during the time interval of 200 - 3000
seconds. Between 3000 and 3 x 104 seconds, the remaining austenite transforms
to a two-phase mixture of ferrite and cementite, probably in the form of pearlite.
Since all the austenite has transformed to either proeutectoid ferrite or pearlite,
cooling to room temperature after 105 seconds, does not alter the microstructure.
Consequently, the microstructure contains proeutectoid ferrite and pearlite.

b. An instantaneous quench of 4340 to 350oC, and holding for 104 seconds results in
all the austenite being transformed to ferrite and cementite in the form of bainite.
Since all the austenite has formed bainite, cooling to room temperature will not
alter the microstructure.

5. An instantaneous quench to room temperature produces a


microstructure containing 100% marcosite.

45. FIND: Briefly describe a heat treatment that would result in the following
microstructures for 4140:

a. A 50-50 mixture of martensite and bainite (ferrite + carbide) where none of the ferrite
is in the form of proeutectoid ferrite.
b. A mixture of proeutectoid ferrite and coarse pearlite.
c. A mixture of 50% bainite, 25% austenite, and 25% martensite.
GIVEN: Figure HP8.2(a), the IT diagram for 4140.
SOLUTIONS:
(a) Homogenize above 800C in the austenite phase field to form a microstructure
containing only austenite. This step is important because pearlite, bainite and
martensite can only form from austenite. Once the steel is homogenized it is then
rapidly quenched to 450C and held for 20 seconds. The exact temperature depends
on the relative fineness of the bainite required. Finer bainitic structures would require
lower quench temperatures. The corresponding time would thus depend on the time
to reach the 50% line. This heat treatment results in a microstructure that contains
50% austenite + 50% bainite. The remaining austenite is then transformed to
martensite when the alloy is rapidly quenched below the M90 temperature to room
temperature. The final microstructure contains 50% bainite and 50% martensite.

(b) Homogenize above 800C to form microstructure containing only austenite. Rapidly
quench to 700C and hold for 2x103 seconds and cool to room temperature. Again,
the choice of temperature depends on the exact structure of pearlite desired.
Increasing the quench temperature results in a coarser pearlite micrstructure.

(c) Homogenize above 800C to form a microstructure containing only austenite. Rapidly
quench to 400C hold for 30 seconds, then quench to approximately 310C, the
resulting microstructure will contain 50% bainite, 25% austenite and 25% martensite.
The remaining austenite will not decompose to martensite unless the temperature is
reduced.
46. FIND: Briefly describe a heat treatment that would result in the following
microstructures for 4340:
a. A mixture of proeutectoid ferrite and coarse pearlite.
b. A 50-50 mixture of bainite and martensite.
c. 100% bainite.
d. A mixture of 50% bainite, 25% austenite, and 25% martensite.

Figure HP8.2(b), the IT diagram for 4340.


SOLUTIONS:
(a) Homogenize above 755C to form a microstructure containing only austenite. Rapidly
quench to 650C for 2 x 104 seconds and cool to room temperature. The resulting
microstructure is a mixture of proeutectoid ferrite and coarse pearlite.

(b) Homogenize above 755C to form a microstructure containing only austenite. Rapidly
quench to 400C and hold for 300 seconds and quench to room temperature. The
resulting microstructure is a 50-50 mixture of bainite and martensite.

(c) Homogenize above 755C to form a microstructure containing only austenite. Rapidly
quench to 350C and hold for 2 x 103 seconds. The resulting microstructure will
contain 100% bainite.

(d) Homogenize above 755C to form a microstructure containing only austenite. Rapidly
quench to 350C, hold for 2 x 103 seconds, quench and hold to the M50 line, 250C.
The resulting microstructure will contain 50% bainite, 25% austenite and 25%
martensite. The remaining austenite can only transform to martensite if the
temperature is reduced.

47. FIND: When reporting isothermal transformation diagrams, the original austenite grain
size is always reported. What effect, if any, would you expect the austenite grain size to
have on the rate of the transformation of pearlite?
SOLUTION: The decomposition of austenite to form pearlite initiates at the austenite
grain boundaries. By decreasing the starting austenite grain size, the surface area per unit
volume of austenite grain boundary increases, thus increasing the number of potential
sites available to begin the decomposition process. With increased nucleation density the
rate of the transformation decreases.

48. FIND: Figure 8.3-15 shows Jominy end quench test data for a series of steels. Explain
why these hardness results are consistent with the IT diagrams shown in Figure HP8-2.
SOLUTION: A comparison of the IT diagrams for 4140 and 4340 illustrate the
difference in the kinetics of austenite decomposition between these two alloys. The start
of each of the diffusional transformations takes longer in 4340 collaborating the Jominy
results shown in Figure 8.3-15.
49. FIND: True or False. If you believe the statement is false, please explain the error and
correct the statement.

a. The general shape of a T-T-T curve describing the start of a diffusional phase
transformation can be explained by noting that both nucleation rate and diffusion rate
increase with increasing temperature.

b. In a eutectoid steel, as the transformation temperature is lowered, the carbide phase


becomes more coarsely distributed.

c. For a plain carbon steel, increasing the carbon content increases both the martensite
start and finish temperatures.

d. IT diagrams like phase diagrams provide equilibrium information about the phases
present in a microstructure.

SOLUTION:
(a) As written the statement is false. Both nucleation and diffusion rate are a function of
temperature, but they both do not increase with increasing temperature. Nucleation
rate increases with decreasing temperature below the transformation temperature while
diffusion rate increases. The product of these two events results in the general C -
curve shape shown below.

(b) This statement as written is false. The correct statement is:


In a eutectoid steel, as the transformation temperature is lowered, the carbide phases
becomes more finely distributed.

(c) This statement as written is false. The correct statement is:


For a plain carbon steel, increasing the carbon content decreases both the martensite
start and finish temperatures.

(d) This statement as written is false. The correct statement is:


IT diagrams unlike phase diagrams provide kinetic, morphological and metastable
phase information.

50. FIND: Using the continuous cooling curve for a eutectoid steel shown in Figure 8.3-13,
calculate the slowest cooling rate that would ensure a 100% martensitic structure at room
temperature.
SOLUTION: The slowest cooling rate that would ensure 100% martensite need to
follow quench path (3) in this figure. To estimate the rate:
Install Equation Editor and double-
click here to view equation.

51. FIND: Suppose you have in a thin sheet of eutectoid steel. If you desire a microstructure
with the finest pearlite spacing achievable, without any martensite, what cooling rate
would you suggest?
SOLUTION:

Install Equation Editor and double-


click here to view equation.

52. FIND: The cooling rate along the radius of a bar fabricated from plain carbon eutectoid
steel was determined to be 35oC/sec at the center, 55oC/sec at midradius and 200oC/sec at
the surface. What microstructure would you expect at each of these locations?
SOLUTION: To determine the microstructure given a cooling rate requires a continuous
- cooling transformation (CT) curve. A CT curve for a eutectoid steel is shown in Figure
8.3-13. From the cooling rate, temperature versus time can be determined and plotted on
the CC curve. Since we determined the cooling rates that give martensite (200 oC/sec
(Problem 40)) and the cooling rate to form the finest pearlite (16oC/sec (Problem 41)), the
microstructures for this problem will lie between pearlite and martensite for 35 and
50oC/sec, and 100% martensite for 200oC/sec.

35oC/S:
t (s) T T (727 - T)
.1 3.5 723.5
.5 17.5 709.5
1.0 35.0 692
5.0 175 552
10.0 350 377
Crosses the dotted line for Figure 8.3-13 giving approximately 75% pearlite
+ 25% Martensite.

55oC/s
t (s) T T (727 - T)
.1 5.5 721.5
.5 27.5 699.5
1.0 55 672
5.0 275 452
10.0 550 117
Crosses the dotted line giving approximately 50% pearlite + 50% Martensite.

200oC/sec
t (sec) T T (727 - T)
.1 20 707
.5 100 627
1.0 200 527
This is the critical cooling rate, hence all
martensite.

53. FIND: Sketch a portion of a binary phase diagram that can be used to help define the
following terms associated with alloys that are precipitation hardenable.

a. Solution heat treating.

b. Artificial aging.
SOLUTION: In precipitation hardening alloy systems solution heat treatment and
artificial aging are two essential steps in maximizing the effectiveness of second phase
particles.

a. Solution heat treating - A high temperature heat treatment designed to take into
solution the soluble elements in an alloy. For example, alloy of composition Xo, can be
solution heat treated at temperature T1.

b. Artificial aging - the precipitation of a second phase from a supersaturated solid


solution above room temperature. The choice of artificial aging temperature is a
compromise between the acceleration of the precipitation process with increased
temperature and an increase in the volume fraction of second phase particles with
decreasing temperature. T2 on the diagram illustrates the artifical aging temperature.
54. FIND: A simple binary eutectic diagram can be very useful in defining the conditions that
are necessary for an alloy to precipitation harden. Construct such a diagram, paying
careful attention to explain specific features that would tend to optimize a potential system
for precipitation hardening. The factors that should be considered are:

a. Maximum solid solubility of the solute in the matrix phase.

b. The solubility in the matrix at room temperature.

c. Change in solubility at temperatures between room temperature and the eutectic


temperature.

SOLUTION: The sketch shown below illustrates a hypothetical system which exhibits
some of the characteristics which must be met for a system to be precipitation hardenable.
These include:
a. A high solubility at some elevated temperature. The more solute that can be dissolved,
the greater the potential for property changes when precipitates form;
b. There must be a significant decrease in solubility with decreasing temperature. The
larger the difference in solubility between high and low temperatures, the larger the
volume fraction of precipitating phase.
c. Very limited solubility a room temperature would be helpful since, the choice in
artificial aging temperature is controlled by precipitation kinetics and volume fraction
of the second phase particles.

The figure shown below has these characteristics.


55. FIND: In alloys which can be strengthened by age hardening, why is a longer time
required to reach maximum hardness at a lower temperature? Why would you expect the
maximum hardness to be higher for lower aging temperatures?
SOLUTION: Precipitation kinetics are controlled by the temperature. Increasing the
temperature increases the rate of precipitation.

One of the characteristics of a precipitation hardening system is that there is an increase in


solubility with increasing temperature. Consequently, as artificial aging temperature is
increased, there will be a corresponding decrease in volume fraction of precipitates. If it is
the presence of the precipitates that controls strength, decreasing the amount will
decrease the maximum achievable strength.

56. FIND: Explain why you would expect the composition of a precipitation hardening alloy
to affect the choice of

a. artificial aging temperature and

b. solution heat treatment temperature.

SOLUTION: To assist in answering this question a sketch of a system that exhibits some
of the characteristics necessary for a system to precipitation harden are shown below.
Two alloys, X1 and X2 have been chosen to illustrate the effect of alloy composition on the
(a) choice of artificial aging temperature and (b) solution heat treatment temperature.

a. Artificial aging temperature for alloy X2 - more solute is available to precipitate,


consequently a slight increase in the aging temperature would compensate for a slight
reduction in the volume fraction of the alloy at a higher artificial aging temperature.

b. Solution heat treating temperature - since the solution heat treating step must be
conducted in the single phase region, increasing the alloy composition increases the
temperature required to dissolve the solute.
57. FIND: Explain why alloy composition would affect the strength of a precipitation
hardenable alloy.
SOLUTION: Increasing alloy composition increases the amount of solute that can
precipitate during artificial aging. If it is the presence of the second phase particles that
controls strength, increase their number will increase the achievable strength. In this
chapter we are only interested in introducing qualitative relationship between precipitation
and strength. These concepts will be explained more fully in the next chapter.

58. FIND: Why is it important to rapidly quench a precipitation hardening alloy from the
solution heat treatment temperature.
SOLUTION: The purpose for the rapid quench is to maintain a maximum
supersaturation of solute for the precipitation process. By rapidly quenching from the
solution heat treating temperature you are ensuring that heterogeneous nucleation is not
occurring at grain boundaries as the material cools below the solvus temperature.

59. FIND: Compare the distribution of precipitates that would form in a precipitation
hardening alloy that is slowly cooled to the distribution that would result if the alloy is
rapidly cooled, then artificially aged.
SOLUTION: Slow cooling encourages heterogeneous nucleation along grain
boundaries. The slow cooling process gives time for the precipitates that nucleate at the
higher temperature to grow more rapidly as a result of high diffusion rates at elevated
temperatures. Consequently, slow cooling results in course precipitates, heterogeneously
nucleated on grain boundaries, with less solute available to precipitate at the lower
temperatures.

Rapid cooling on the other hand tends to maintain higher supersaturation that is relieved
during artificial aging. Since artificial aging is a low temperature process, the precipitates
are fine and more numerous than those that nucleate and grow during the slow cool.

60. FIND: It takes 200 hours for an aluminum copper alloy to reach maximum hardness at
150oC and 5 hours at 190oC. Calculate the temperature to reach the maximum hardness in
8 hours.
SOLUTION: To work this problem one must assume that the microstructures that form
after 200 hours at 150oC and after 5 hours at 190oC are the same. Consequently, the rate
to reach these identical microstructures is inversely proportional to the time.
Furthermore, it is also assumed that the precipitation process is thermally activated and
can thus be described by an Arrhenius equation having the form:
rate = constant exp (-Q/RT)

The data can be plotted using this expression and the temperature required to reach the
given microstructure in 8 hours determined.

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T1 = 423k t1 = 200 hrs


T2 = 463k t2 = 8 hrs

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R = 8.314 J/(molK)
Q = 1.50 x 105 J/mol.

Now, find T3, the temperature to reach the same fraction transformed in 8 hours.
Install Equation Editor and double-
click here to view equation.

Install Equation Editor and double-


click here to view equation.

T3 = 458 k = 185oC

61. FIND: Calculate the activation energy for the precipitation process from the data given in
the previous problem.
SOLUTION: See solution to problem 49. The activation energy to reach a certain level
of hardness is the same as the activation energy for precipitation since hardness is related
to the fraction of precipitate transformed.

62. FIND: Figure 7.7-3 in Chapter 7 shows the Al-Ni phase diagram. The precipitation of
the phase  [denoted as (Ni-Al) on the figure] having composition near Ni3Al is the basis
of high-temperature nickel-base superalloys. Using the Al-Ni phase diagram, explain the
factors that are necessary for nickel alloys containing aluminum to be candidates for
precipitation hardening alloys.
GIVEN: The Al-Ni phase diagram, Figure 7.7-3 and follow the principles outlined in the
discussion for Figures 8.3-17 (a) and (b).
SOLUTION: Precipitation hardening requires a significant volume fraction of precipitate
be present in the alloy. The size and shape (morphology) must be controlled by heat
treating in the solid state. To control the size and distribution of the precipitates, there
must be a temperature where essentially all of the solute is taken back into solid solution
to precipitated at a lower temperature. For precipitation to occur the solubility of the
solute must decrease with temperature. Thus the schematic illustrated in Figure 8.3-17(a)
of the text.
A similar set of conditions exist in the Ni-Al system illustrated in Figure 7.7-3. A section
of the Ni-rich end of the NiAl diagram is included. The single phase, solid solution region
is shown in the schematic. According to the diagram, the maximum solid solubility of
aluminum in nickel is 11.2% Al at 1385 C. The sloping solvus indicates that the solubility
of aluminum decreases with decreasing temperature. The phase that precipitates during the
heat treatment is Ni3Al (shown in Figure 7.7-3 as  (Ni-Al).
Schematic of the Ni-Al phase diagram.

Figure HP8-3 shows the yield strength dependence on artificial aging response for two
precipitation hardening aluminum alloys. Although these alloys are complex in that they contain
more than one solute element, the age hardening principles that apply to binary alloys like Al-Cu
can be applied to these complex alloys.

63. FIND: Explain why the time to reach peak strength for 2014 and 6061 decreases with
increasing aging temperature.
SOLUTION: The increase in strength in these two alloys is attributed to the precipitation
of solute elements from supersaturation during artifical aging. The precipitation process is
thermally activated and controlled by the diffusion of solute to the growing particles.
Increasing temperature increases the rate of diffusion and hence, decreases the time to
reach maximum strength.

64. FIND: Why does the value of peak strength increase with decreasing artificial aging
temperature?
SOLUTION: Although the two alloys, 2014 and 6061, are complex alloys in that they
contain more than one element that precipitates during aging, the requirement of
decreasing solubility with decreasing temperature is a requirement in these alloys for
precipitation hardening just like the requirements in binary alloys like Al-Cu. Increasing
the artificial aging temperature decreases the amount of supersaturation, and consequently
the volume fraction of precipitate. Thus, just like the precipitation process in a binary
alloy, increasing aging temperature increases the rate of age hardening but decreases the
maximum achievable strength.

65. FIND: Although the precipitation process is a very complex phenomenon, it is often very
useful to apply the concept of activation energy as determined through an Arrhenius plot
to assist in interpolating data. Determine the activation energy for the artificial aging of
2014.
SOLUTION: The assumption that is to be made in this calculation is that the time
required to achieve a specific strength is inversely proportional to the rate. Consequently,
the time to reach peak strength is used to calculate the rate at each aging temperature.

log (t) T (oF) t T (K) 1/t (K-1) ln (1/t) Regression


-1.3 500 0.05 533 0.001876 2.993 2.807
-0.5 450 0.32 505 0.001979 1.151 1.331
0.25 400 1.79 477 0.002094 -0.576 -0.316
0.6 375 4.0 464 0.002157 -1.382 -1.214
0.9 350 7.94 450 0.002224 -2.072 -2.167
1.55 300 35.5 422 0.002370 -3.569 -4.262
2.3 275 200 408 0.002451 -5.300 -5.416
3.1 250 1260 394 0.002537 -7.138 -6.651

The data in the form ln (1/t) versus 1/T are plotted below. Included is the regression line
with a slope of Q = 119 kJ/mole.
66. FIND: Using the approach developed in problem 53, determine the activation energy for
artificially aging 6061.
SOLUTION: The assumption that is to be used in this calculation is that the time
required to achieve a specific strength is inversely proportional to the rate. Consequently,
the time to reach peak strength is used to calculate the rate at each aging temperature.

log (t) T (oF) t T (K) 1/t (K-1) ln (1/t) Regression


-1.35 500 0.045 533 0.001876 3.108 2.981
-0.35 450 0.445 505 0.001979 0.806 1.290
0.15 400 1.412 477 0.002094 -0.345 -0.598
0.65 375 4.476 464 0.002157 -1.497 -1.627
1.2 340 15.85 444 0.002252 -2.763 -3.176
1.8 325 63.1 436 0.002295 -4.145 -3.882
2.3 300 200 421 0.002370 -5.296 -5.120

The data in the form ln (1/t) versus 1/T are plotted below. Included is the regression line
with a slope of Q = 136 kJ/mole.

67. FIND: Determine the time to reach peak strength for alloy 2014 using an artificial aging
temperature of 210oC.
SOLUTION: To determine the time to reach peak strength for alloy 2014 use the data
plotted in problem 53.
Convert 210oC to K  483K.

1/T = 0.00207.
ln (1/t)  0 -  time is 1 hour.

68. FIND: Determine the time to reach peak strength for alloy 6061 using an artificial aging
temperature of 210oC.
SOLUTION: To determine the time to reach peak strength for alloy 6061 use the data
plotted in problem 54.
Convert 210oC to K  483K.

1/T = 0.00207

then,

ln (1/t)  0
 time is 1 hour.
69. FIND: The aging response curves used in the preceding problems were constructed from
numerous tensile tests taken at each of eight aging temperatures. Explain how you might
apply the knowledge gained from these data to reduce the number of temperatures to be
investigated if small changes to the alloy compositions were made to either 2014 or 6061.
SOLUTION: The aging curves for both 2014 and 6061 were reasonably well behaved
and using the concept of an apparent activation energy, the time to achieve peak
strength as a function aging temperature could be modelled. Consequently, rather than
running numerous mechanical tests, using a temperature of 250oF and 400oF for 2014 and
275oF and 400oF for 6061 would provide the range of aging temperatures that would
permit you to pick an appropriate aging temperature. Once you have chosen an aging
temperature you could judiciously choose the appropriate aging times around the peak to
better define its location. Thus, fewer tests with the composition modification are
required.

70. FIND: Sketch a binary phase diagram containing a simple eutectic. Using this diagram,
explain what is meant by coring and why it occurs.
SOLUTION: The figure below shows a simple binary eutectic and illustrates the effect of
negligible solid state diffusion on the resulting solidified microstructure.

During normal cooling experienced with most casting processes, the time for diffusion in
the solid state is too small for the solid to reach the equilibrium solute concentration
predicted by the phase diagram.

At the start of solidification T = T1, the solid and the liquid have the compositions
predicted by the phase diagram. When the temperature is changed instantaneously to a
new temperature, the composition of the next element to solidify is once again that given
by the phase diagram at that temperature. However, since solid state diffusion is not
permitted the composition of the first element to solidify remains the same. The average
composition of the two solid elements to solidify is less than the composition of the alloy,
and given as the dotted line.

The process just described is referred to as coring. This term comes from the observation
that the composition at the center, or core, of the solid grain is different from that at the
grain surfaces.

As the temperature continues to drop, a similar event occurs.


71. FIND: If an Al-Cu alloy containing 5% by weight of copper is solidified to produce a
cored microstructure, what is the minimum local copper concentration in the
aluminum phase? What is the maximum local copper concentration in the aluminum
phase?
SOLUTION: Shown below is the aluminum rich end of the Al-Cu phase diagram. The

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local minimum content of copper in solid solution is:


The maximum local copper content is 5.7%

72. FIND: Suppose the cored Al-Cu microstructure is rapidly heated to above the liquidus
temperature. At what temperature would the first melting reaction occur and why?
SOLUTION: If the alloy is cored, the maximum amount of copper in solid solution is
5.7% copper. Rapid heating to the eutectic temperature will result in eutectic melting.
Consequently, local eutectic melting will occur at 820K.

73. FIND: Figure HP8-4 shows a hypothetical binary phase diagram for a peritectic system.
The dotted lines show the location of nonequilibrium solidus and have the same meaning
as those shown in Figure 8.3-24. For the alloy of composition X, explain why you expect
both the  an  phases to be cored.
SOLUTION: Alloy of composition X begins to solidify when the temperature reaches T 1.
At this temperature the composition of 1 is in equilibrium with liquid of composition L1.
As in the eutectic case, diffusion in the solid state lags that of the liquid and we can
assume that there is insufficient time for solid state diffusion. Hence the composition of
the solidifying alloy follows the dotted line on the figure below. When temperature T 4 is
reached (the peritectic temperature) the liquid of composition L4 is in equilibrium with 4
and 4. Because of coring the quantity of  is less and that of liquid larger than occurs
when the alloy is solidified under quilibrium conditions. As the temperature drops below
the peritectic isotherm there is some extra liquid. The average composition of solid once
again lags behind the equilibrium value in the solid and solidification follow 5, 6 and 7.
In the peritectic system both the -phase and the -phase are cored.
74. FIND: Figure HP8-5 shows percent recrystallized as a function of time at several
temperatures. Calculate the activation energy for the recrystallization process over the
temperature range of 43 to 135oC.
SOLUTION: As in the problem that involve precipitation, the rate of the transformation
is proportional to the reciprocal of time to a certain degree of recrystallization. Choosing
50% recrystallized from the data in figure HP8-5 we can determine the time and hence the
rate.

T, oC T, K 1/T, K-1 time, min rate  1/time ln rate


135.2 408.2 0.002450 9.5 0.105 -2.254
119.0 392.0 0.002551 22 0.0454 -3.092
112.6 385.6 0.002593 38 0.0263 -3.638
102.2 375.2 0.002665 80 0.0125 -4.382

X = 1 - exp (-(kt) n)
kt = constant = B for 50% transformed and a constant value
of n over the range of our data.
k = A exp (-Q/RT)
B/t = A exp (-Q/RT)
-ln(t) = ln(A/B) - Q/RT
ln(t) = -ln(A/B) + Q/RT

We plot ln(t) vs 1/T and determine the slope by linear regression. The
slope = Q/R. Q/R = 10,100K, Q = 84,000J
75. FIND: Figure HP8-6 shows the isothermal recrystallization behavior of zone-melted Fe-
0.6% Mn alloy. How would you determine the activation energy for recrystallization?
SOLUTION: Choose a fixed amount of percentage recrystallized and determine the time
to achieve that degree of recrystallization at each temperature. The rate is then inversely
proportional to time to achieve that structure. The slope of plot of ln rate versus 1/T is
Q/R, where Q is the activation energy and R is the gas constant.

76. FIND: Figure HP8-6 shows the isothermal recrystallization behavior of zone-melted Fe-
0.6%Mn alloy. Estimate the activation energy for the recrystallization process.
SOLUTION: We choose 20% recrystallized as the constant fraction transformed for our
calculations. Assume n is constant. We read the following data from Fig. HP8-6.

Temp (K) time to 20% recrystallized (min)


923 .7
868 10.8
813 100
753 1300

X = 1 - exp ((-kt) n)
kt = constant = B for 20% transformed and a constant value of n.
k = A exp (-Q/RT)
B/t = A exp (-Q/RT)
ln(t) = -ln(A/B) + (Q/RT)

We plot ln t vs 1/T and calculate the slope by linear regression. The


slope = Q/R, Q/R = 30,300K, Q = 252,000 J/mole
77. FIND: Using the data plotted in Figure 8.3-38 for the crystallization of polypropylene at
123, 128 and 132oC, determine n and k in equation 8.2-11.
SOLUTION:

123oC

lnt t x ln (-ln (1 - x))


0.6931 2 0.01 -4.6001
1.0986 3 0.05 -2.9702
1.3863 4 0.12 -2.0570
1.6094 5 0.27 -1.1561
1.7918 6 0.47 -0.4543
1.9459 7 0.59 -0.1147
2.0794 8 0.70 0.1856
2.1972 9 0.75 0.3266
2.3026 10 0.78 0.4148

ln (-ln (1 - x )) = n ln k + n ln t

n ln k = -6.5222

n = 3.1960
k = 0.1299
128oC

t x lnt ln (-ln (1 - x))


3 0.02 1.0986 -3.9019
4 0.04 1.3863 -3.1985
5 0.07 1.6094 -2.6232
6 0.10 1.7918 -2.2504
7 0.14 1.9459 -1.8916
8 0.18 2.0794 -1.6172
9 0.23 2.1972 -1.3418
10 0.28 2.3026 -1.1132
20 0.84 2.9957 0.6057
30 0.89 3.4012 0.7918
40 0.90 3.6889 0.8340
50 0.90 3.9120 0.8340

x = 1 - exp (-(kt) n)
ln (-ln (1 - x)) = n ln k + n ln t

n ln k = -5.4079

n = 1.8145
k = 0.0462
n = 1.7588
132oC

t x lnt ln (-ln (1 - x))


6 0.01 1.7918 -4.6001
7 0.02 1.9459 -3.9019
8 0.03 2.0794 -3.4914
9 0.035 2.1972 -3.3346
10 0.04 2.3026 -3.2189
16 0.10 2.7726 -2.2504
20 0.18 2.9957 -1.6172
30 0.48 3.4012 -0.4248
40 0.71 3.6889 0.2134
50 0.89 3.9120 0.7918
60 0.92 4.0943 0.9265

x = 1 - exp (-(kt) n)
n ln k + n ln t = ln (-ln(1 - x))

n ln k = -8.6492

n = 2.3807
k = 0.0264
78. FIND: Using the results from problem 77, compare the actual kinetic data with the
calculated fraction transformed using equation 8.2-11.
SOLUTION: Shown below are the generated curves using equation 8.2-11. There is
reasonably good agreement between the experimental data and the JMA formulation.
(Equation 8.2-11) This relationship has been used to model various processes and
materials systems in the problems in this chapter. At this point you should begin to see the
power in this model.

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