Chapter 3

相變態 Chapter 3 魏茂國
Crystal Interfaces and Microstructure
 Interfacial free energy

 Solid / vapor interfaces
 Boundaries in single-phase solids
 Interphase interfaces in solids
 Interface migration
1
相變態 Interfacial Free Energy 魏茂國
 Introduction
Basically three different types of interface are important in metallic systems.
- Free surfaces of a crystal (solid/vapor interface)
All crystals possess this type interface.
The solid/vapor interface is important in vaporization and condensation transformations.
- Grain boundaries (/ interfaces)
This interface separates crystals with the same composition and
crystal structure, but a different orientation in space.
Grain boundaries are important in recrystallization, i.e., the transformation of a highly deformed
grain structure into new undeformed grains.
- Interphase interfaces (/ interfaces)
The interface separates two different phases that can have different crystal structures and/or
compositions and therefore also includes solid/liquid interfaces.
 Definition of surface free energy
The free energy of a system containing an interface of area A and free energy  per unit area is
given by
G  G0  A (3.1)
G0: free energy of the system assuming that all material in the system has the properties of the
bulk.
2
 : the excess free energy arising from the fact that some material lies in or close to the interface.
相變態 Interfacial Free Energy 魏茂國
 Surface tension
- If one bar of the frame is movable it is found that a force F per unit length must be applied to
maintain the bar in position. If this force moves a small distance so that the total area of the
film is increased by dA, the work done by the force is FdA.
G  G 0  A
 dG  dA  Ad
 FdA  dA  Ad
 d 
 F    A  (3.2)
 dA 
- In the case of a liquid film, the surface energy is independent
Fig. 3.1 A liquid film on a
of the area of the interface and d/dA = 0.
wire frame.
F  (3.3)
F: surface tension (N/m), : surface energy (J/m2).
 d/dA
- Since a liquid is unable to support shear stresses, the atoms within the liquid can rearrange
during the stretching process and thereby maintain a constant surface structure.
- Solids are much more viscous and the transfer of atoms from the bulk to the surface, which is
necessary to maintain an unchanged surface structure and energy, will take much longer. If
this time is long in comparison to the time of the experiment, then surface free energy and
3
surface tension will not be identical.
相變態 Solid / Vapor Interfaces 魏茂國
 Surface free energy of FCC crystal {111} planes

- The origin of the surface free energy is that atoms in the layers nearest the surface are without
some of their neighbors.
- The atoms on a {111} surface (FCC structure) are deprived of three of their twelve neighbors.
If the bond strength of the metal is , each bond can be considered as lowering the internal
energy of each atom by /2. Therefore every surface atom with three ‘broken bonds’ has an
excess internal energy of 3/2 over that of the atoms in the bulk.
- For a pure metal,  can be estimated from the heat of sublimation LS. The latent heat of
sublimation is equal to the sum of the latent heat of melting (or fusion) and the latent heat of
vaporization.
If 1 mol of solid is vaporized, 12Na broken bonds are formed.
 L
LS  12N a   6N a     S 4
2 6N a
- Assume that the strengths of the remaining bonds in the surface are unchanged from the bulk
values.
The surface energy, Esv, of a {111} surface (FCC structure) should be given by
 1 L
E SV  3   3  S
2 2 6N a
L 
 E SV  0.25   S  (3.4)
 Na 
- Different crystals should have different values for depending on the number of broken bonds.
5
 Real surface free energy

- The surface atoms will have more freedom of movement and therefore a higher thermal
entropy compared to atoms in the bulk. Extra configurational entropy can be introduced into
the surface by the formation of surface vacancies. The surface of a crystal should be
therefore be associated with a positive excess entropy which will partly compensate for the
high internal energy of Equation (3.4).
- Experimental values of SV of pure metals indicate that near the melting temperature the
surface free energy averaged over many surface planes is given by
L 
 SV  0.15   S  (J/surface-atom) (3.6)
 Na 
Table 3.1 Average surface free
energies of selected metals.
Metals with high melting temperatures have high
values for LS and high surface energies.
6
 ‘Broken-bond’ model for surface energy

- Broken bond number 1 1
cos  1 sin  1 cos   sin 
N  N   N //      
a a a a a2
 cos  sin    1
 E SV  N   2
(3.8) 1 sin
2 2a
- The close-packed orientation ( = 0) lies at a 
cos
cusped minimum in the energy plot.
1.6
1.2
Esv
0.8
0.4
Fig. 3.3 The ‘broken-bond’ model for
0 surface energy.
-90 -60 -30 0 30 60 90
 ()
Fig. 3.4 Variation of surface energy as a function of . 7
 Wulff construction
- If  is plotted versus , similar cusps are found, but as a result of entropy effects they are less
prominent than in the E- plot, and for the higher index planes they can even disappear.
- For an isolated crystal bounded by several planes A1, A2, etc. with energies 1, 2, etc. the
total surface energy will be given by the sum Aii. The equilibrium shape has the property
that Aii is a minimum and the shape that satisfies this condition is given by the Wulff
construction.
Fig. 3.5 (a) A possible (110) section through the

-plot of an fcc crystal. The length OA represents
the free energy of a surface plane whose normal
lies in the direction OA. Thus OB = (001),
OC = (111), etc. Wulff planes are those such as
that which lies normal to the vector OA. In this
case the Wulff planes at the cusps (B, C, etc.)
give the inner envelope of all Wulff planes and
thus the equilibrium. (b) The equilibrium shape
in three dimensions showing {100} (square faces)
and {111} (hexagonal faces).
8
 Wulff construction
- A plane is drawn through the point and normal
to the radius vector OA (Fig. 3.5a). The
equilibrium shape is then simply the inner
envelope of all such planes. Therefore when
the -plot contains sharp cusps the equilibrium
shape is a polyhedron with the largest facets
having the lowest interfacial free energy.
- Equilibrium shapes can be determined

experimentally by annealing small single
crystals at high temperatures in an inert
atmosphere, or by annealing small voids
inside a crystal. FCC crystals usually assume
a form showing {100} and {111} facets as shown in Fig. 3.5b.
9
相變態 Boundaries in Single-Phase Solids 魏茂國
 Low-angle and high-angle boundaries

 Special high-angle grain boundaries
 Equilibrium in polycrystalline materials
 Thermally activated migration of grain boundaries
 The kinetics of grain growth
10
相變態 Boundaries in Single-Phase Solids 魏茂國
 Boundaries in Single-Phase Solids

- The nature of any given boundary depends on the misorientation of the two adjoining grains
and the orientation of the boundary plane relative to them.
- A tilt boundary occurs when the axis of rotation is parallel to the plane of the boundary,
Fig. 3.6a.
- A twist boundary is formed when the rotation axis is perpendicular to the boundary.
Fig. 3.6 The relative orientations of the crystals and the boundary forming (a) a tilt
boundary (rotation // GB), (b) a twist boundary (rotation  GB).
11
物理冶金 Burgers Vectors 魏茂國
 Burgers vectors
The procedure can be used to find the Burgers vectors of any dislocation if the following rules
are observed:
1. The circuit is traversed in the same manner as a rotating right-hand screw advancing in the
positive direction of the dislocation.
2. The circuit must close in a perfect crystal and must go completely around the dislocation in
the real crystal.
3. The vector that closes the circuit in the perfect crystal (by connecting the end point to the
starting point) is the Burgers vector.
12
物理冶金 Burgers Vectors: Edge Dislocation 魏茂國
Fig. 4.22 The Burgers circuit for an edge dislocation:

(A) Perfect crystal and (B) Crystal with dislocation.
13
物理冶金 Burgers Vectors: Screw Dislocation 魏茂國
Fig. 4.23 The Burgers circuit for a dislocation in a screw orientation.

(A) Perfect crystal and (B) Crystal with dislocation.
14
相變態 Low-angle and high-angle boundaries 魏茂國
 Low-angle boundary
- The low-angle tilt boundary is an array of parallel edge dislocations, whereas the twist
boundary is a cross-grid of two sets of screw dislocations (Fig. 3.7). In each case the atoms in
the regions between the dislocations fit almost perfectly into both adjoining crystals whereas
the dislocation cores are regions of poor fit in which the crystal structure is highly distorted.
- The energy of a low-angle grain boundary is the total energy of the dislocations within unit
area of boundary. This depends on the spacing of the dislocations.
b
b  D sin b
b b
D  (3.9)
sin  D
D
D: spacing of the dislocations, b: Burgers vector of the dislocations,
: the angular misorientation across the boundary.  
- The grain boundary energy  for simple tilt boundary is approximately
b  D tan  b  D sin
proportional to the density of dislocations in the boundary (1/D).
b  D sin
1
   (3.10)
D
: the grain boundary energy, : the angular misorientation across the tilt boundary.
15
Fig. 3.7 (a) Low-angle tilt boundary, (b)

(b) low-angle twist boundary:
○ atoms in crystal below boundary,
● atoms in crystal above boundary.
16
(a)
- As  increases the strain fields of the dislocations progressively cancel out so that  increases
at a decreasing rate (Fig. 3.9).
- In low-angle boundaries, most of the atoms fit very well into both lattices so that there is very
little free volume and the interatomic bonds are only slightly distorted.
Fig. 3.9 Variation of grain boundary energy with misorientation.
17
 Tilt low-angle boundary

The tilt boundary need not be symmetrical with
respect to the two adjoining crystals. If the
boundary is unsymmetrical dislocations with
different Burgers vectors are required to
accommodate the misfit (Fig. 3.8).
Fig. 3.8 An unsymmetric tilt boundary. Dislocations

18
with two different Burgers vectors are present.
 High-angle boundary
- In general, when  exceeds 10~15 the
dislocation spacing is so small that dislocation
cores overlap, and it is impossible to
physically identify the individual dislocations
(Fig. 3.10). At this stage the grain-boundary
energy is almost independent of misorientation
(Fig. 3.9).
Fig. 3.10 Disordered grain boundary structure.
- When  > 10~15 the boundary is a random
high-angle grain boundary.
Fig. 3.11 Rafts of soap bubbles showing several

grains of varying misorientation. Note that the
boundary with the smallest misorientation is made
up of a row of dislocations, whereas the high-angle
boundaries have a disordered structure in which 19
individual dislocations cannot be identified.
- High-angle boundaries contain large areas of poor fit and have a relatively open structure. The
bonds between the atoms are broken or highly distorted and consequently the boundary is
associated with a relatively high energy.
- Measured high-angle grain boundary energies b are found to be roughly given by

1
 b   SV (3.11)
3
Table 3.2 Measured grain boundary free energies.
20
相變態 Special High-Angle Grain Boundaries 魏茂國
 Twin boundary (a)

- If the twin boundary is parallel to the twinning plane the atoms in the
boundary fit perfectly into both grains (Fig. 3.12a). The result is a
coherent twin boundary.
- The energy of a coherent twin boundary is extremely low in

comparison to the energy of a random high-angle boundary.
- If the twin boundary does not lie exactly parallel to the (b)
twinning plane, the atoms do not fit perfectly into each
grain (Fig. 3.12b) and the boundary energy is much
higher. This is an incoherent twin boundary.
- The energy of a twin boundary is very sensitive to

the orientation of the boundary plane. If  is plotted
as function of the boundary orientation, a sharp (c)
cusped minimum is obtained at the coherent
boundary position (Fig. 3.12c).
Fig. 3.12 (a) A coherent twin boundary. (b) An

incoherent twin boundary. (c) Twin-boundary energy as
a function of the grain boundary orientation. 21
Table 3.3 Measured boundary free energy for crystals in twin relationships (mJ/m2).
(3.4%) (80.0%)
(2.1%) (33.4%)
(2.3%) (25.0%)
22
 Special grain boundary (in fcc metals)

- When the two grains are related by a rotation about <100> axis, Fig. 3.13a, the most high-
angle boundaries have about the same energy and should have a relatively disordered
structure characteristic of random boundaries.
- When the two grains are related by a rotation about a <110> axis, there are several large-
angle orientations which have significantly lower energies than the random boundaries,
Fig. 3.13b.  = 70.5 corresponds to the coherent twin boundary discussed above, the reasons
for these special grain boundaries are not well understood. It seems that the atomic structure
of these boundaries is such that they contain extensive areas of good fit, Fig. 3.14.
Fig. 3.13 Measured grain boundary energies for symmetric

tilt boundaries in Al (a) when the rotation axis is parallel to Fig. 3.14 Special grain boundary.
23
<100>, (b) when the rotation axis is parallel to <110>.
相變態 Equilibrium in Polycrystalline Materials 魏茂國
 Microstructure of polycrystalline materials

- Fig. 3.15 shows the microstructure of an annealed
austenitic stainless steel (fcc). The material
contains high- and low-angle grain boundaries as
well as coherent and incoherent twin boundaries.
- When looking at 2-dimensional microstructures, it

is important to remember that in reality the grains
fill three dimensions.
- Two grains meet in a plane (a grain boundary),

three grains meet in a line (a grain edge), and
four grains meet at a point (a grain corner).
Fig. 3.15 Microstructure of an annealed
crystal of austenitic stainless steel.
24
 Torque of grain boundary (a)

- The boundaries are all high-energy regions that increase
the free energy of a polycrystal relative to a single crystal.
Therefore a polycrystalline material is never a true
equilibrium structure.
- The grain boundaries in a polycrystal can adjust themselves (b)
during annealing to produce a metastable equilibrium at the
grain boundary intersections.
- Let us consider a grain-boundary segment of unit length OP,
Fig. 3.16. If the boundary is mobile, the force Fx and Fy must
act at O and P to maintain the boundary in equilibrium.
Fig. 3.16 (a) Equilibrium forces Fx
Fx   (from Equation 3.3)
and Fy supporting a length l of
If P is moved a small distance y while O remains boundary OP. (b) The origin of Fy.
stationary, the work done will be Fyy. This must be balance the increase in boundary energy
caused by the change in orientation .
 d 
Fy y  l     
 d 
 y  l (y is very small)
d
 Fy  25(3.12)
d
- This means that if the grain-boundary energy is dependent on the orientation of the boundary
(Fig. 3.16b), a force d/d must be applied (from adjacent grains) to the ends of the boundary
to prevent it rotating into a lower energy orientation. d/d is known as a torque term.
- If the boundary happens to be at the orientation of a cusp in the free energy, e.g. as shown in
Fig. 3.12(c), there will be no torque acting on the boundary since the energy is a minimum in
that orientation.
Fig. 3.12(c) Fig. 3.16(b)
26
 No torque at grain boundary

If the boundary energy is independent of orientation, the
torque term is zero and the grain boundary behaves like
a soap film. The boundary tensions 12, 23 and 13 must
balance.
 13 sin180   3    12 sin180   2 
 
  13 sin 3   12 sin 2  13  12 13sin(180-3) 13
sin 2 sin 3
3-90
  23   12 cos180   2    13 cos180   3 
  23   12 cos  2   13 cos  3 90 180-3  cos(180- )
23 13 3
180-2 12cos(180-2)
 sin 2  90
  23   12 cos  2    12  cos  3
 sin 3  2-90
12
   12sin(180-2)
  23   12   cos  2 sin 3  sin 2 cos  3 
 sin 3
Fig. 3.17 The balance of grain

boundary tensions for a grain
     
  23   12   sin 2   3    12   sin360   1  boundary intersection in
 sin 3   sin 3  metastable equilibrium.
      23  
  23   12   sin 1  23  12   13  12
 sin 3  sin 1 sin 3 (3.13)
sin 1 sin 2 sin 3 27
 Measuring grain-boundary energy

- One method of measuring grain-boundary energy is to anneal a specimen at a high
temperature and then measure the angle at the intersection of the surface with the boundary,
Fig. 3.18.
- In this case, the presence of any torque terms has been neglected, though an approximation
may introduce large errors.
If the solid-vapor energy (SV) is the same for both grains, balancing the interfacial tensions
gives
 
2 SV cos    b (3.14)
2
Therefore if SV is known, b can be calculated.
Fig. 3.18 The balance of surface and grain boundary tensions at the intersection of a grain
boundary with a free surface.
28
 Balance between coherent and incoherent twin boundaries

- If the boundary is constrained to follow a
macroscopic plane that is near but not parallel
to the twinning plane, the boundary will usually
develop a stepped appearance with large risers,
as shown in Fig. 3.19. Although this configuration
does not minimize the total twin boundary area, it
does minimize the total free energy.
- At the coherent/incoherent twin junction, the

incoherent twin boundary tension i must be
balanced by a torque term. Since the maximum
value of the resisting force is dC/d, the condition that the
configuration shown in Fig. 3.19 is stable is
d c
i  (3.15)
d
Fig. 3.19 (a) A twin boundary in a thin foil specimen as imaged in the
transmission electron microscope. (b) and (c) the coherent and incoherent
segments of the twin boundary. 29
- Likewise the incoherent facet must also be a special boundary showing rather good fit in order
to provide a force resisting C.
d i
c  (3.16)
d
- Since C is usually very small, the incoherent interface need only lie in a rather shallow energy
cusp.
30
相變態 Thermally Activated Migration of Grain Boundaries 魏茂國
 Balance of boundaries
- For simplicity, if all grain boundaries in a polycrystal are assumed to have the same grain-
boundary energy independent of boundary orientation, Equation 3.13 predicts that
1 = 2 = 3 = 120. The grain-boundary edges meeting at a corner formed by four grains will
make an angle of 10928’.
- If a boundary is curved in the shape of a cylinder, Fig. 3.20a, it is acted on by a force of

magnitude /r towards its center of curvature. Therefore, the only way the boundary tension
forces can balance in 3 dimensions if the boundary is planar (r = ) (Fig. 3.20b) or it is curved
with equal radii in opposite directions (Fig. 3.20c).
Fig. 3.20 (a) A cylinder boundary with a radius of curvature r is acted on by a force /r. (b) A
planar boundary with no net force. (c) a double curved boundary with no net force.
31
- The effect of different boundary curvatures in 2 dimensions is shown in Fig. 3.21. If a grain has
6 boundaries, they will be planar and the structure metastable.
However, if the total number of boundaries around a grain is less than 6, each boundary must
be concave inwards, Fig. 3.21. These grains will therefore shrink and eventually disappear
during annealing.
60
60 60
Fig. 3.21 Two-dimensional grain boundary of configurations. The arrows indicate the
directions boundaries will migrate during grain growth.
On the other hand, large grains will have more than 6 boundaries and will grow. The overall
result of such boundary migration is to reduce the number of grains, thereby increasing the
mean grain size and reducing the total grain boundary energy. This phenomenon is known
32
as grain growth or grain coarsening.
 Grain growth in a soap solution

In the case of the cells in a soap froth (Fig. 3.22), the higher pressure on the concave side of
the films induces the air molecules in the small cells to diffuse through the film into the larger
cells, so that the small cells eventually disappear.
Fig. 3.22 Two-dimensional cells of a soap solution illustrating the process of grain growth.
Numbers are time in minutes.
33
 Driving force on the boundary during of grain growth

- The effect of the pressure difference caused by a
curved boundary is to create a difference in free energy
(G) or chemical potential () that drives the atoms
across the boundary, Fig. 3.24. In a pure metal  and
G are identical and are given by Equation 1.58 as
2Vm
G  (1.58)
r
2Vm Fig. 3.24 The free energy of an atom
G    (3.17)
r during the process of jumping from
one grain to the other.
- The free energy difference can be thought of as a force
pulling the grain boundary towards the grain with the higher free energy. If unit area of grain
boundary advances a distance x (Fig. 3.25), the number of moles of material that enter grain
B is 1x(1/Vm) and the free energy released is given by
 1  Gx
G  1 x    
 Vm  Vm
34
- The released free energy is equal to the work done by the pulling force Fx. Thus the pulling
force per unit area of boundary is given by
Gx
F 1 x 
Vm
G 2
F  (N/m2) (3.18)
Vm r
The force on the boundary is the free energy difference per unit volume of material.
Fig. 3.25 A boundary separating grains with different free energies is

subjected to a pulling force F.
35
Dislocations and Strengthening Mechanisms
Materials Science and Engineering 魏茂國
Recovery, Recrystallization, Grain Growth

Plastic deforming a polycrystalline metal specimen at temperatures that are low
relative to its absolute melting temperature produces microstructural and property
changes that include (1) a change in grain size, (2) strain hardening, and (3) an
increase in dislocation density. Furthermore, other properties such as electrical
conductivity and corrosion resistance may be modified as a consequence of
plastic deformation.
These properties and structures may revert back to the precold-worked states by
an annealing treatment. Such restoration results from two different processes that
occur at elevated temperatures: recovery and recrystallization, which may be
followed by grain growth.
36
Recovery
During recovery, some of the stored internal strain energy is relieved by
virtue of dislocation motion, as a result of enhanced atomic diffusion at
the elevated temperature.
There is some reduction in the number of dislocations, and dislocation
configuration are produced having low strain energies. Physical
properties such as electrical and thermal conductivities and the like are
recovered to their precold-worked states.
However, even after recovery is complete, the grains are still in a
relatively high strain energy state.
37
Recrystallization & Grain Growth
Figure 7.19 Photomicrographs

showing several stages of the
recrystallization and grain growth
of brass. (a) Cold-worked (33%
CW) grain structure. (b) Initial
stage of recrystallization after
heating 3s at 580C (1075F);
the very small grains are those
that have recrystallized. (c)
Partial replacement of cold-
worked grains by recrystallized
ones (4s at 580C). (d) Complete
recrystallization (8s at 580C).
(e) Grain growth after 15 min
at 580C. (f) Grain growth after
10 min at 700C.
38
Recrystallization
Recrystallization is the formation of a new set of strain-free and equiaxed grains

that have low dislocation densities and are characteristic of the precold-worked
condition. The new grains form as very small nuclei and grow until they completely
consume the parent material, processes that involve short-range diffusion.
Recrystallization of cold-worked metals may be used to refine the grain structure.
During recrystallization, the metal become softer, weaker, yet more ductile.
39
Recrystallization
Recrystalization is a process, the extent of

which depends on both time and temperature.
Recrystallization temperature is the
temperature at which recrystallization just
reaches completion in 1 hr. Typically it is
between one-third and one-half of the
absolute melting temperature of a metal or
alloy and depends several factors, including
the amount of prior cold work and the purity
of the alloy.
Figure 7.20 The influence of annealing

temperature on the tensile strength and
ductility of a brass alloy. Grain size as a
function of annealing temperature is
indicated. Grain structures during
recovery, recrystallization, and grain
growth stages are shown schematically.
40
Recrystallization Temperature
There exists some critical degree of cold work below which recrystallization cannot be made to
occur; normally, this is between 2% and 20% cold work. Recrystallization proceeds more rapidly
in pure metals than in alloys. Plastic deformation operations are often carried out at temperatures
above the recrystallization temperature in a process termed hot working.
Recrystall. Melting
Metal
temperature temperature
Pb -4C 327C
Sn -4C 232C
Zn 10C 420C
Al (5N) 80C 660C
Cu (5N) 120C 1085C
60 Cu-40 Zn 475C 900C
Figure 7.21 The variation of recrystallization Ni (4N) 370C 1455C

temperature with percent cold work for iron. For Fe 450C 1538C
deformations less than the critical (about 5%CW), 41
W 1200C 3410C
recrystallization will not occur.
 Recrystallization
- During recrystallization, the boundaries between the
new strain-free grains and the original deformed
grains are acted on by a force G/Vm, where G is
due to the difference in dislocation strain energy
between the two grains.
- Fig. 3.26 shows a dislocation-free recrystallized

grain expanding into the heavily deformed
surroundings. In this case, the total grain-boundary
area is increasing, therefore driving force for
recrystallization must be greater than the opposing
boundary tension forces.
- Such forces are greatest when the new grain is

smallest, and the effect is therefore important in the
early stages of recrystallization. Fig. 3.26 Grain boundary migration in
nickel pulled 10% and annealed 10 min
at 425C. The region behind the
advancing boundary is dislocation-free.
42
- It is possible that the higher mobility of special grain boundaries plays a role in the development
of recrystallization textures. If a polycrystalline metal is heavily deformed, by say rolling to a 90%
reduction, a deformation texture develops such that the rolled material resembles a deformed
single crystal. On heating to a sufficiently high temperature, new grains nucleate and begin to
grow. However, those grains which are specially oriented with respect to the matrix should have
higher mobility boundaries and should overgrow the boundaries of the randomly oriented
boundaries.
Consequently, the recrytsallized structure should have a special orientation with respect to the
original ‘single crystal’. Thus a new texture results in which is called the recrystallization texture.
- The only way to avoid a recrystallization texture is to give an intermediate anneal before a
deformation texture has been produced.
43
 Kinetics of boundary migration

- In order for an atom to break away from grain 1, it must acquire
an thermal activation energy Ga, Fig. 3.24.
- If the atoms vibrate with a frequency 1, the number of times

per second that an atom has this energy is
 G a 
 1 exp  
 RT 
- If there are on average n1 atoms per unit area in a
favorable position to make a jump, there will be
 G a 
n1 1 exp  
 RT 
jumps/m2/s away from grain 1.
- Not all these atoms will find a suitable site and ‘stick’ to grain 2. If the probability of being
accommodated in grain 2 is A2, the effective flux of atoms from grain 1 to 2 will be
 G a 
A2 n1 1 exp  
 RT 
atoms/m2/s.
44
- If the atoms in grain 2 have a lower free energy than the atoms in grain 1 by G (mol-1), the flux
from 2 to 1 will be
 G a  G 
A1n 2 2 exp  
 RT 
atoms/m2/s.
- When G = 0 the two grains are in equilibrium and there should be no net boundary movement,
i.e. the rates at which atoms cross the boundary in opposite directions must be equal.
 G a   G a  G 
A2 n1 1 exp    A1n 2 2 exp  
 RT   RT 
At equilibrium  G = 0
 G a   G a 
 A2 n1 1 exp    A1n 2 2 exp  
 RT   RT 
 A2 n1 1  A1n 2 2
 G a   G a  G 
 J net  J 12  J 21  A2 n1 1 exp    A1n 2 2 exp  
 RT   RT 
 G a    G 
 J net  A2 n1 1 exp    1  exp   (3.19)
 RT    RT 
45
- If the boundary is moving with a velocity , the above flux must be equal to C (Equation 2.59).
(C is concentration which is equal to Na/Vm)
J B  v BCB (2.59)
N 
 J net  C     a 
 Vm 
 G a    G 
 J net  A2 n1 1 exp    1  exp  
 RT    RT 
N   G a    G 
    a   A2 n1 1 exp    1  exp  
 Vm   RT    RT 
 A n V   G a    G 
    2 1 1 m   exp    1  exp  
 Na   RT    RT 
If G << RT
 G  G
 1  exp  
 RT  RT
 A n V   G a   G 
   2 1 1 m   exp     
 Na   RT   RT 
 A2 n1 1Vm2   G a   G 
      exp 
     (3.20)
 N a RT   RT   m V 46
- According to Equation 3.18, F = G/Vm, Equation 3.20 can be written simply as

G 2
F  (3.18)
Vm r
 G 
  MF  M    (3.21)
 m 
V
M: mobility of the boundary.

 A2 n1 1Vm2   G a 
 M     exp 
 
 N a RT   RT 
 A2 n1 1Vm2   S a   H a 
 M     exp
   exp   (3.22)
 N a RT   R   RT 
- Boundary migration is a thermally activated process like diffusion.
Boundary migration and boundary diffusion are closely related processes. The only difference
is that diffusion involves transport along boundary whereas migration requires atomic
movement across the boundary.
47
 Boundary migration in real grain boundaries

- In real grain boundaries, not all atoms in the boundary are
equivalent and some will jump more easily than others. For
example, atoms may jump preferable to and from atomic
steps or ledges, like atoms A, B and C in Fig. 3.23a.
- Theoretically, as discussed above, the relatively open

structure of a random high-angle boundary should lead to a
high mobility, whereas the denser packing in the special
boundaries should be associated with a low mobility.
Indeed, the coherent twin boundary is almost entirely
immobile. However, the other special boundaries are usually
more mobile than random high-angle boundaries.
The reason for this is associated with the presence of
impurity or alloying elements in the metal.
Fig. 3.23(a)
48
- Fig. 3.27 shows data for the migration

of various boundaries in zone-refined
lead alloyed with different concentrations
of tin.
Only very low concentrations of impurity

are required to change the boundary
mobility by orders of magnitude.
However, the special grain boundaries

are less sensitive to impurities.
It is possible that if the metal were

‘perfectly’ pure, the random boundaries
would have higher mobility.
Fig. 3.27 Migration rates of special and

random boundaries at 300C in zone-
refined lead alloyed with tin under equal
driving forces.
49
 Influence of alloying
- Generally, the grain boundary energy of a pure
metal changes on alloying. Often (though not
always) it is reduced. Under these
circumstances, the concentration of alloying
element in the boundary is higher than that
in the matrix.
- For the low mole fractions of solute in the matrix

(X0), the boundary solute concentration Xb is
given by  Gb 
X b  X 0 exp  (3.23)
 RT 
Xb: grain boundary solute concentration, is
fractions of a monolayer.
Gb: free energy released per mole when a
solute atom is moved from the matrix to the
boundary.
Fig. 3.28 Increasing grain boundary
Gb is usually positive and roughly increase as enrichment with decreasing solid
the size misfit between the solute and matrix solubility in a range of systems.
increases and as the solute-solute bond strength decreases. 50
- When the boundary moves, the solute atoms

migrate along with the boundary and exert a
drag that reduces the boundary velocity. The
magnitude of the drag will depend on the
binding energy and the concentration in the
boundary.
- The higher mobility of special boundaries can

possibly be attributed to a low solute drag on
account of the relatively more close-packed
structure of the special boundaries.
- It is a general rule that GB, which measures

the tendency for segregation, increases as the
matrix solubility decreases, Fig. 3.28.
51
相變態 Kinetics of Grain Growth 魏茂國
 Normal Grain growth

- If we assume that the mean radius of curvature of all the grain boundaries is proportional to
the mean grain diameter D, the mean driving force for grain growth will be proportional to 2/D
(from Equation 3.17). 2Vm
G    (3.17)
r
 2 
F    
D
dD
   MF 
dt
: a proportionality constant of the order of unity.
dD  2 
    M  (3.24)
dt  D 
 2Dd D  4Mdt
2
 D  k 1  4Mt
At t = 0, D = D0
 k 1  D02
D0: original average grain size.
52
2
 D  D02  Kt (3.25)
 K  4M
- Experimentally, it is found that grain growth in single-phase metals follows a relationship of the
form
D  K't n (3.26)
K’: a proportionality constant which increases with temperature.
The experimentally determined values of n are usually much less than 0.5 and only approach
0.5 in very pure metals or at very high temperatures.
53
 Abnormal grain growth

- Abnormal grain growth is characterized by
the growth of just a few grains to very
large diameters. These grains then expand
consuming the surrounding grains, until
the fine grains are entirely replaced by a
coarse-grained array.
- This effect is known as discontinuous grain

growth, coarsening, or secondary
recrystallization. It can occur due to the
presence of a fine precipitate array, when
normal grain growth ceases. Fig. 3.29 Optical micrograph showing abnormal
grain growth in a fine-grained steel containing
0.4 wt% carbon. The matrix grains are prevented
from growing by a fine dispersion of unresolved
carbide particles.
54
 Normal grain growth

- The moving boundaries will be attached to the
particles, so that the particles exert a pulling
force on the boundary restricting its motion.
- The boundary will be attached to the particle

along a length 2rcos. If the boundary
Driving force
intersects the particle surface at 90, the
particle will feel a pull of (2rcos)sin.
- As the boundary moves over the particle,

surface  changes and the drag reaches a
maximum value when is a maximum, i.e. at
 = 45. The maximum force exerted by a
single particle is given by Fig. 3.30 The effect of spherical particles
2r sin cos   r sin 2 on grain boundary migration.
 r sin 2 max  r
55
- If there is a volume fraction f of particles all with a radius r, the mean number of particles
intersecting unit area of a random plane is 3f/2r2.
(Derive) Suppose all the precipitates are spherical, and distribute very uniformly in the matrix.
The matrix can be divided into N parts, Each part has a cross-sectional area of A, a height of
2r, and a volume of VT. 4 3
Vp 3 r  n 2nr 2
f   
VT 2r  A 3A
n 3f
 
A 2r 2
Vp: total volume of precipitates, VT: volume of matrix, r: radius of precipitate, n: number of
precipitate in the matrix VT, A: cross-sectional area of the matrix.
So that the restraining force per unit area of boundary is
 3f  3f
P    r  (3.27)
 2r 
2
2r 56
- The driving force for grain growth from Equations (3.17) and (3.18)
2Vm
G  (3.17)
D
G
F (3.18)
Vm
D: radius of curvature of boundary.
2Vm 1 2
F 
D Vm D
- When D is small, P will be relative insignificant. But as D increases the driving force F
decreases and when the driving force will be insufficient to overcome the drag of the
particles, grain growth stagnates. A maximum grain size will be given by
F P
2 3f
 
D 2r
4r
 D max  (3.28)
3f
57
 Dispersion strengthening effect

- The effect of a particle dispersion on grain growth
is illustrated in Fig. 3.31. It can be seen that the
stabilization of a fine grain size during heating at
high temperatures requires a large volume
fraction of very small particles.
- Unfortunately, if the temperature is too high, the

particles tend to coarsen or dissolve. When this
occurs, some boundaries can break away before
the others and abnormal grain growth occurs, Fig. 3.31 Effect of second-phase
transforming the fine-grain array into a very particles on grain growth.
coarse-grain structure.
- Example
Aluminum-killed steels contain aluminum nitride precipitates which stabilize the austenite
grain size during heating. However, their effectiveness disappears above about 1000C
when the aluminum nitride precipitates start to dissolve.
Aluminum-kill steel: Steel deoxidized with aluminum in order to reduce the oxygen content
to a minimum so that no reaction occurs between carbon and oxygen during solidification.
58
相變態 Interphase Interfaces in Solids 魏茂國
 Interface coherence
 Second-phase shape: interfacial energy effects
 Second-phase shape: misfit strain effects
 Coherency loss
 Glissile interfaces
 Solid / liquid interfaces
59
相變態 Interphase Interfaces in Solids 魏茂國
 Interphase boundaries
Interphase boundaries in solids can be divided on the basis of their atomic
structure into three classes
- Coherent
- Semicoherent
- Incoherent
60
相變態 Interface Coherence 魏茂國
 Fully coherent interfaces

- A coherent interface arises when
the two crystals match perfectly at
the interface plane, so that the two
lattices are continuous across the
interface.
- Disregarding chemical species,

coherent interface can only be
achieved if the interfacial plane has
Fig. 3.32 Strain-free coherent interfaces. (a) Each crystal
the same atomic configuration in
has a different chemical composition but the same crystal
both phases, and this requires the
structure. (b) The two phases have different lattices.
two crystals to be oriented relative
to each other in a special way.
61
- At the interface, there is usually a change in composition so that each atom is partly bonded to
wrong neighbors across the interface. This increases the energy of the interfacial atoms and
leads to a chemical contribution to the interfacial energy (ch). For a coherent interface, this is
the only contribution.
 coherent   ch (3.29)
In general, coherent interfacial energies range up to about 200 mJ/m2.
- When the distance between the atoms in the interface is not identical, it is still possible to
maintain coherency by straining one or both of the two lattices. The resultant lattice distortions
are known as coherency strains.
Fig. 3.34 A coherent interface with

slight mismatch leads to coherency
strains in the adjoining lattices.
62
 Semicoherent interfaces
- The strains associated with a coherent interface raise the total energy of the system, and for
sufficiently large atomic misfit, or interfacial area, it becomes energetically more favorable to
replace the coherent interface with a semicoherent interface in which the disregistry is
periodically taken up by misfit dislocations.
- The matching in the interface is almost perfect except around the dislocation cores where the
structure is highly distorted and the lattice planes are discontinuous.
- Definition of misfit () between  and  lattice.

d  d
  (3.30)
d
d: interplanar spacing of matching
plane in the  phase,
d: interplanar spacing of matching
plane in the  phase.
Fig. 3.35 A semicoherent interface.

The misfit parallel to the interface is
accommodated by a series of edge 63
dislocations.
- In one dimension, the lattice misfit can be completely accommodated without any long-range
strain fields by a set of edge dislocations with a spacing D.
d d   d
D   (3.31)
 d
In other words, in a unit length, there are 1/d and 1/d arrays of  and  respectively.
Therefore, there are (1/d - 1/d) vacant arrays of  in a unit length, which is equal to the
number of misfit dislocation in a unit length.
The spacing of edge dislocation equals to 1/(1/d - 1/d)
1 1
 1 1   d   d  d d  d
D     
d   d d  d   d 
  d     
- For small 
d  d 
d  d 
 d  b
2
b: Burgers vector of the dislocations.
b
D (3.32)

64
- In practice, misfit usually exists in two dimensions and the

coherent strain fields can be completely relieved if the interface
contains two non-parallel sets of dislocations with spacings
D1 = b1/1 and D2 = b2/2.
If the dislocation spacing is greater than b/ (3.32), the

coherency strains will have been only partially relieved by
the misfit dislocations and the residual long-range strain
fields will still be present. Fig. 3.36 Misfit in 2 directions (1 and
2) can be accomdated by a cross-grid
- Interfacial energy of a semicoherent interface of edge dislocations with spacings
It can be considered as the sum of 2 parts: (a) a D1 = b1/1 and D2 = b2/2.
chemical contribution, ch, as for a fully coherent
interface, and (b) a structure term st, which is the extra energy due to the structural distortions
caused by the misfit dislocations.
 semicoherent   ch   st (3.33)
- For small values of , the structural contribution to the interfacial energy is approximately
proportional to the density of dislocations in the interface.
1
 st   (D  b/) (3.34)
D 65
- However,  increases less rapidly as  becomes larger and it levels out when   0.25. It is very
similar to the relationship between boundary energy and .
~0.25
Misfit-strain
energy 
Fig. 3.9
Misfit strain
As the misfit dislocation spacing decreases, the associated strain fields increasingly overlap
and annul each other.
- The energies of semicoherent interfaces are generally in the range 200-500 mJ/m2.
66
 Incoherent interfaces
- When the interfacial plane has a very different
atomic configuration in the two adjoining phases,
there is no possibility of good matching across
the interface. The pattern of atoms may either be
very different in the two phases or the interatomic
distances may differ by more than 25%.
- Very little is known about the detailed atomic

structure of incoherent interface, but they have
many features in common with high-angle grain
boundaries.
Fig. 3.37 An incoherent interface.
- They are characterized by a high energy
(~500-1000 mJ/m2) which is relatively insensitive to the orientation of the interface plane.
67
 Complex semicoherent interfaces

- Semicoherent interfaces can also form
between phases when good lattice
matching is not initially obvious.
- Example: (111)fcc and (110)bcc

Nishiyama-Wasserman (N-W)
relationship
110 bcc // 111fcc
001bcc // 101fcc
Kurdjumov-Sachs (K-S) relationship
110 bcc // 111fcc

111 //011
bcc fcc
Fig. 3.38 Atomic matching across a (111)fcc/(110)bcc
interface bearing the NW orientation relationship for
The only difference between these two lattice parameters closely corresponding to the case
is a rotation in the close-packed planes of fcc and bcc iron.
of 5.26.
- A coherent or semicoherent interface between the two phases is impossible for large
interfaces parallel to {111}fcc and {110}bcc. Such interfaces would be incoherent. 68
Physical Metallurgy Principles Coincidence Site Boundaries 魏茂國
Kronberg and Wilson demonstrated that the rotation could produce surfaces,
separating the new crystal from the old, that contained a number of positions where
the atoms in both crystals were in coincidence. These were called coincidence sites.
Net A corresponds to the atomic

arrangement on the (111) plane
of the fcc parent crystal. Net B
corresponds to the (111) plane
in a secondarily recrystallized
crystal. The two nets are
rotated relative to each other by
22 about [111] pole.
Fig. 6.25 A coincident site boundary

obtained by a 22 rotation across a
(111) plane. The reciprocal density,
, of the coincident sites, known as
large open circles, is 7. 69
Physical Metallurgy Principles Ranganathan Relations 魏茂國
 Density of coincidence sites

- The fraction of atoms in coincidence at a boundary is generally known as the density of
coincidence sites.
- The reciprocal of the density is more commonly used as a parameter to describe a
coincidence site boundary. This is usually designated by the Greek symbol .
 Ranganathan relations
- Not only could rotational symmetry operations bring a lattice back into complete self-
coincidence, but also partial self-coincidence might be attained with specific rotations
about other axes.
- These latter rotations not only were able to produce a coincidence site net at a boundary
between two crystals, but they were also capable of yielding the concept of a coincidence
site three-dimensional lattice.
- Four basic factors: (1) rotation axis [hkl], (2) rotation angle , (3) coincidence net on
plane (hkl) normal to the rotation axis, (4) reciprocal  of the density of coincidence sites
in the (hkl) net. Actually these four factors are not all independent.
- If the coordinates (x,y) of a coincidence site is in the plane (hkl),
y
N  h2  k 2  l 2   x 2  y 2N   2 N tan 1
x
- If  is even it should be divided by multiples of 2 until an odd number is attained. 70
Examples Involving Twist Boundaries
Physical Metallurgy Principles 魏茂國
Simple cubic structure

Plane: (100)
Rotation: [100]
x: [010]
y: [001]
N = h2 + k2 + l2
= 12 + 02 + 02 = 1
(x, y) = (2, 1)
 = x2 + y2N
= 22 + 121 = 5
y
  2 N tan 1
x
1
   2 1 tan 1  53.1
2
Lattice constant
(2a ) 2  (a ) 2  5a
Fig. 6.26 A rotation of 53.1 about <100> axis of a simple cubic crystal gives this coincident site
boundary with  = 5. The coincident sites also form a lattice with a unit cell whose sides are
equal to 5a in the boundary. The cell size of the reciprocal lattice is thus five times larger
71 than
that of the primitive lattice.
Examples Involving Twist Boundaries
Physical Metallurgy Principles 魏茂國
Simple cubic structure

Plane: (100)
Rotation [100]
N = h2 + k2 + l2
= 12 + 02 + 02 = 1
(x, y) = (3, 1)
 = x2 + y2N
= 32 + 121 = 10
’ = 10  2 = 5
y
  2 N tan 1
x
1
   2 1 tan 1  36.9
3
Lattice constant
(2a ) 2  (a ) 2  5a
Fig. 6.27 A 36.9 rotation about a <100> axis also produces a coincident site boundary with
72
 = 5 due to the symmetry of the simple cubic lattice.
Physical Metallurgy Principles Tilt Boundary 魏茂國
Fig. 6.29 The coincident site boundaries in

Fig. 6.25 to 6.27 are twist boundaries. This
figure illustrates a coincident site boundary
formed by a tilt of 53.1 about a <100> axis
of a simple cubic crystal.  also equals 5
for this boundary and its structural
periodicity, p, is equal to an edge of the
coincident site lattice.
Structure: S.C., Plane: {100}
Rotation: <100>, (x, y): (2, 1)
Fig. 6.30 A tilt of 53.1 about <100>

of a simple cubic lattice also yields a
coincident site boundary,
but in this case the structural
periodicity, p, is equal to the diagonal
Structure: S.C., Plane: {100} of the coincident site unit cell.  again
73
Rotation: <100>, (x, y): (3, 1) is equal to 5.
Physical Metallurgy Principles Tilt Boundary 魏茂國
Fig. 6.31 If the atoms of the diagram in

Fig. 30 are drawn as hard balls instead of
points, one finds that there is an overlap
of the atoms just to the right of the
coincident sites on the boundary.
If one considers the atoms as touching spheres, the
illustrated boundaries would contain a pair of overlap-
ping atoms just to the right of each coincident site on
these boundaries. The problem of this overlap could
be relieved by removing an atom from
each of these pairs or by a relative
translation of the lattices above and
below the grain boundary.
Fig. 6.32 As suggested by Aust, the

overlapping of the atoms at the
boundary could be relieved by a
Structure: S.C., Plane: {100} relative translation of the lattices
Rotation: <100>, (x, y): (3, 1), shifted above and below the boundary.74
相變態 Second-Phase Shape: Interfacial Energy Effects 魏茂國
 Fully coherent precipitates (a)

- If the precipitate () has the same crystal structure and a similar
lattice parameter to the parent  phase, the two phase can form
low-energy coherent interfaces on all sides - provided the two
lattices are in a parallel orientation relationship.
This situation arises during the early stages of many precipitation
hardening heat treatments, and the  phase is termed a fully
coherent precipitate or a GP zone. (GP for Guinier and Preston
who first discovered their existence) (b)
- Since the two crystal structures match more or

less perfectly across all interfacial planes, the
zone can be any shape and remain fully
coherent. Thus -plot of the / interfacial energy
would be largely spherical and the equilibrium
shape of a zone would be a sphere (ignoring
coherency strains).
Fig. 3.39 (a) A zone with no misfit (O: Al, : Ag).

(b) Electron micrograph of Ag-rich zones in an 75
Al-4 atomic % Ag alloy. (GP zone ~10 nm)
 Partially coherent precipitates

- A -plot of the interfacial energy in partially
coherent precipitates could look like a sphere
with two deep cusps normal to the coherent
interface. The Wulff theorem would predict the
equilibrium shape to be a disc with a thickness/
diameter ratio of C/i, where C and i are the
energies of the (semi-) coherent and incoherent Fig. 3.40 A section through a -plot for a
interfaces. precipitate showing one coherent or
semicoherent interface, together with the
- The precipitate shapes observed may deviate
equilibrium shape (a disc).
from “disc” shape for 2 main reasons.
1. The above construction only predicts the equilibrium shape if misfit strain energy effects can
be ignored.
2. The precipitate may not be able to achieve an equilibrium shape due to constraints on how
it can grow.
For example, disc-shaped precipitates may be much wider than the equilibrium shape if the
incoherent edges grow faster than the broad faces.
76
 Incoherent precipitates
- When the two phases have completely
different crystal structures, or when the two
lattices are in a random orientation, it is
unlikely that any coherent or semicoherent
interfaces form and the precipitate is said
to be incoherent.
- The interfacial energy would be high for

all interfacial planes, the -plot and the
equilibrium inclusion shape will be roughly
Fig. 3.44 Electron micrograph showing
spherical. It is possible that certain incoherent particles of  in an Al-Cu alloy.
crystallographic planes of the inclusion lie
at cusps in the -plot, so that polyhedral shapes are also possible.
77
 Precipitates on grain boundaries

When a second-phase particle is located
on a grain boundary, it is necessary to
consider the formation of interfaces with
two different oriented grains. The
precipitate can have Fig. 3.45 Possible morphologies for grain boundary
precipitates. Incoherent interfaces smoothly curved.
1. incoherent interfaces with both grains. Coherent or semicoherent interfaces planar.
2. a coherent or semicoherent interface
with one grain and an incoherent interface
with the other.
3. a coherent or semicoherent interface with

both grains.
The first two cases are commonly encountered.
Fig. 3.46 An  precipitate at a grain boundary

triple point in an - Cu-In alloy. Interfaces A
78
and B are incoherent while C is semicoherent.
相變態 Second-Phase Shape: Misfit Strain Effects 魏茂國
 Fully coherent precipitates

- When misfit is present, the formation of coherent interfaces raises the free energy of the
system on account of the elastic strain fields that arises. The condition for equilibrium becomes
 Ai  i  GS  min imum (3.35)
i: interfacial energy, Gs: elastic strain energy.
- If the volume of matrix encircled in

Fig. 3.47a is cut out and the atoms are
replaced by smaller atoms, the cut-out
volume will undergo a uniform negative
dilatational strain to an inclusion with a
smaller lattice parameter, Fig. 3.47b.
In order to produce a fully coherent Fig. 3.47 The origin of coherency strains. The
number of lattice points in the hole is conserved.
precipitate, the matrix and inclusion must
be strained by equal and opposite force as shown in Fig. 3.47c.
- Unconstrained misfit  a   a ainclusion  amatrix

  (3.36)
a amatrix
a: lattice parameter of the unconstrained matrix,
79
a: lattice parameter of the unconstrained precipitate.
- Constrained misfit 
The stresses maintaining coherency at the interface distort the precipitate lattice. In the case of
a spherical inclusion, the distortion is purely hydrostatic, i.e. it is uniform in all directions, giving a
new lattice parameter a’.
a  'a
 (3.37)
a
If the elastic moduli of the matrix and inclusion are equal and Poisson’s ration is 1/3,
2
 (3.38)
3
- When the precipitate is a thin disc, the in

situ misfit is no longer equal in all directions,
but instead it is large perpendicular to the
disc and almost zero in the plane of the
broad faces.
Fig. 3.48 For a coherent thin disc, there is little

misfit parallel to the plane of the disc. Maximum
misfit is perpendicular to the disc. 80
- Elastic strain energy GS

In general, the total elastic energy depends on the shape and elastic properties of both matrix
and inclusion.
If the matrix is elastically isotropic and both precipitate and matrix have equal elastic moduli, the
total elastic strain energy GS is independent of the shape of the precipitate, and assuming
Poisson’s ratio  = 1/3.
GS  4  2V (3.39)
: shear modulus of the matrix, : unconstrained misfit,
V: volume of the unconstrained hole in the matrix.
- If the precipitate and inclusion have different elastic moduli, the elastic strain energy is no longer
shape-independent, but is a minimum for a sphere if the inclusion is hard and a disc if the
inclusion is soft.
81
- Influence of strain energy

In various aluminum-rich precipitation hardening alloys: Al-Ag, Al-Zn and Al-Cu.
Atomic radius (Å) Al: 1.43 Ag: 1.44 Zn: 1.38 Cu: 1.28
Zone misfit () +0.7% -3.5% -10.5%
Zone shape sphere sphere disc
(a) When  < 5%, the strain energy effects are less important than interfacial energy effects and
spherical zones minimize the total free energy.
(b) For  > 5%, the small increase in interfacial energy caused by choosing a disc shape is more
than compensated by the reduction in coherency strain energy.
82
 Incoherent inclusions
- When the inclusion is incoherent with the
matrix, there is no attempt at matching the
two lattices and lattice sites are not
conserved across the interface. Misfit
strains can still arise if the inclusion is the
wrong size for the hole it is located in Fig. 3.49 The origin of misfit strain for an
Fig. 3.49. In this case, the lattice misfit  incoherent inclusion (no lattice matching).
has no significance and it is better to consider the volume misfit .
V
 (3.40)
V
V: volume of the unconstrained hole in the matrix, V-V: volume of the unconstrained inclusion.
- For a coherent spherical inclusion, the volume misfit and the linear lattice misfit are related by
 = 3 .
- The spheroidal inclusions are described by the equation

x 2 y 2 z2
2
 2  2 1 (3.41)
a a c
83
- Nabarro gives the elastic strain energy for a homogeneous

incompressible inclusion in an isotropic matrix as
2 c 
GS  2V  f   (3.42)
3  
a
f(c/a): a factor that takes into account the shape effects.
- Function of f(c/a)
1. c/a = 1: a sphere has the highest strain energy.
2. c/a  0: a thin, oblate spheroid has a very low strain energy.
3. c/a : a needle shape lies between the above
Fig. 3.50 The variation of misfit strain
mentioned two.
energy with ellipsoid shape, f(c/a).
- If elastic anisotropy is included it is found that the same general form for f(c/a) is preserved and
only small changes in the exact values are required.
Therefore, the equilibrium shape of an incoherent inclusion will be an oblate spheroid with value
that balances the opposing effects of interfacial energy and strain energy.
- When  is small, interfacial energy effects should dominate and the inclusion should be roughly
spherical.
 Ai  i  GS  min imum (3.35)
2 2 c 
GS   V  f   84 (3.42)
3 a
 Plate-like precipitates
- Misfit across the broad faces results in large
coherency strains parallel to the plate, but no
coherency strains will exist across the edges.
- The in situ misfit across the broad faces increases

with increasing plate thickness which leads to Fig. 3.51 Coherency strains caused
greater strains in the matrix and higher shear by the coherent broad faces of ’
stresses at the corners of the plates. Eventually it precipitates.
becomes energetically favorable for the broad faces to become semicoherent.
- Thereafter the precipitate behaves as an incoherent inclusion with comparatively little misfit
strain energy.
85
相變態 Coherency Loss 魏茂國
 Coherency loss
- For a spherical precipitate with a misfit  and a radius r, the free energy of a crystal containing
a fully coherent spherical precipitate has contributions from
(i) the coherency strain energy given by Equation 3.39 (GS  42V),
(ii) the chemical interfacial energy ch.
4
G( coherent )  4  2  r 3  4r 2  ch (3.43)
3
- If the same precipitate has incoherent or semicoherent

interfaces that completely relieve the unconstrained misfit,
there will be no misfit energy, but there will be an extra
structural contribution to the interfacial energy st.
G( non coherent )  0  4r 2  ch   st  (3.44) Fig. 3.52 The total energy of
matrix + precipitate vs.
- When small, the coherent state gives the lowest total energy,
precipitate radius for spherical
while it is more favorable for large precipitates to be
coherent and non-coherent
semicoherent or incoherent (depending on the magnitude of precipitates.
). At the critical radius (rcrit), G(coherent) = G(non-coherent) giving
 G( coherent )  G( non coherent )
3 st
 4   r 3  4r 2 ch  0  4r 2  ch   st 
42 rcrit  (3.45) 86
3 4  2
- If we assume that  is small, a semicoherent interface will be formed with a structural energy
st  . 1
 st   (for semicoherent interface & small ) (3.34)
D
3 st
 rcrit  (3.45)
4  2
1
rcrit  (3.46)

- If a coherent precipitate grows during aging,
it should lose coherency when it exceeds rcrit.
Loss of coherency requires the introduction
of dislocation loops around the precipitate
and this can be rather difficult to achieve.
Consequently coherent precipitates are often
found with sizes much larger than rcrit.
Fig. 3.53 Coherency loss for a spherical
precipitate. (a) Coherent. (b) Coherency strains
replaced by dislocation loop. (c) In perspective.
87
 Mechanisms for coherency loss

- Punched-out dislocation loop
For a dislocation loop to be punched out at the interface,
this requires the stress at the interface to exceed the
theoretical strength of the matrix. The punching stress pS
is independent of the precipitate size and depends only on
the constrained misfit . If the shear modulus of the matrix
is .
pS  3  (3.47) Fig. 3.54(a) Dislocation punching
The critical value of  that can cause the theoretical from interface.
strength of the matrix to be exceed is approximately given by
 crit  0.05 (3.48)
Consequently precipitate with a smaller value of  cannot lose coherency by this mechanism,
no matter how large.
88
- Capture of matrix dislocation

The precipitate can attract a matrix dislocation with a suitable Burgers
vector, and cause it to wrap itself around the precipitate. But it requires
the precipitate to reach a large size than rcrit. This mechanism is difficult
in annealed specimens but is assisted by mechanical deformation.
- Nucleation at edge of plate Fig. 3.54(b) Capture

In the case of plate-like precipitates, it is possible for of matrix dislocation.
the high stresses at the edges of the plates to nucleate
dislocations by exceeding the theoretical strength of
the matrix. The process can be repeated as the plate
lengthens so as to maintain a roughly constant
interdislocation spacing.
Fig. 3.54(c) Nucleation at edge of
- Vacancy condensation plate repeated as plate lengthens.
For plate-like precipitates, the nucleation of dislocation
loops within the precipitate has been observed. Vacancies
can be attracted to coherent interfaces and ‘condensate’
to form a prismatic dislocation loop which can expand Fig. 3.54(d) Loop expansion by
across the precipitate. vacancy condensation in the
precipitate. 89
相變態 Glissile Interface 魏茂國
 Glissile interface
- Glide of the interfacial dislocations cannot
cause the interface to advance and the
interface is non-glissile.
- Under certain circumstances, it is possible

to have glissile semicoherent interfaces
which can advance by the coordinated glide
Fig. 3.55 The nature of a glissile interface.
of the interfacial dislocations.
This is possible if the dislocations have a Burgers vector that can glide on matching planes
in the adjacent lattices.
- A glissile interface between two different lattices is that which can arise between the cubic
and hexagonal close-packed lattices.
90
 Close-packed layer of atoms

If the centers of the atoms in the first layer are denoted as A-positions, the second layer of
atoms can be formed either by filling the B-positions or C-positions.
Fig. 3.56 The location of A, B and C sites in a close-packed layer of atoms. 91

 Hexagonal closed-packed arrangement

- Stacking sequence: ABABABAB…
- The close-packed plane can be indexed as (0001)
and the close-packed directions are of the type
<1120>.
Fig. 3.57 A hexagonal close-packed

unit cell and stacking sequence.
 Cubic closed-packed arrangement

- Stacking sequence: ABCABCABC…
- The close-packed atomic planes become the
{111} type and the close-packed directions the
<110> type.
Fig. 3.58 A cubic close-packed structure

showing fcc unit cell and stacking sequence.
92
Structure of Crystalline Solids
Point Coordinates
 Point coordinates in a unit cell: pqr  Atomic position: pqr
0  p/q/r  1 - 0  p/q/r < 1
- If p/q/r  1,
 p-1/q-1/r-1,
Z
 Until 0  p/q/r < 1
000 010
001 011
½½0
½½1
100 110 0½½
101 111
½0½
½0½ ½1½
000 010
000 010 Y
1½½
½½0
100 110
100 110
X 93
Share of Atoms in Unit Cells
Corner: 1/8 Edge-center: 1/4
Face-center: 1/2 Body-center: 1
94
Face-Centered Cubic Crystal Structure

Figure 3.1
For the face-centered cubic crystal
structure:
(a) a hard sphere unit cell
representation,
(b) a reduced-sphere unit cell,
(c) an aggregate of many atoms.
95

Unit cell: 4 atoms
Coordination number: 12
APF: 74%
Lattice Top view
96
(011)
110
(101) e3
e1 e2
011 101
(110)
e1 
1 1
    1
  011  110   121
3 2 6
 
1 1
3 2
    1
e2    110  101   211
6
 
1
6
 1
6
 
1
e3  e1  e2  121   211   110
2
 
97

 Atom positions
(000), (0½½), (½0½), (½½0)
 Unit cell: 4 atoms
(000): 8  1/8 = 1
(0½½): 2  ½ = 1
(½0½): 2  ½ = 1
(½½0): 2  ½ = 1
 Coordination number: 12
 APF: 74%
a Atomic radius: r 16r 3

a Edge length of unit cell: a APF  3
Volume of unit cell 16 2r 3
r+r+2r = 4r  2a = 4r  a = 2 2 r 
 APF   74.0%
a3 = (2 2 r)3 = 16 2 r3 3 2
a
Atom volume per unit cell
2a
4r 3 16r 3
4  98
3 3
Close-Packed Planes of FCC Structure
Unit cell {110}  {100} plane

2a - Area: a2
- Atoms: 1 + 4¼ = 2
- Density: 2/a2
a  {110} plane
- Area: a  2a  2a
2
- Atoms: 4¼ + 2½ = 2

- Density: 2 / 2a 2  2 / a 2
 {111} plane
{100} {111} - Area: 1/ 2  2a  3 / 2a  3a 2 / 2
- Atoms: 31/6 + 3½ = 2
a - Density: 2 /( 3a 2 / 2)  4 / 3a 2
2a
 Density
2a
4/ 3  2  2
a
{111}  {100}  {110}
2a  Close-packed directions: 3
99
 Close-packed planes {111}

- (111)  (111)
- (111)  (111)
- (111)  (111)
- (111)  (111)
- Total: 4
 Slip directions <110>

- Total: 3
 Slip system: 4 X 3 = 12
100
Figure 3.3 For the hexagonal close-packed crystal structure,

(a) a reduced-sphere unit cell (a and c represent the short and long
edge lengths, respective),
(c) an aggregate of many atoms. 101
Crystallographic Directions
Figure 3.8(a) [0001], [1100], and [1120] directions for the hexagonal crystal system
102
Crystallographic Directions
[2110]
a2
a2 = ⅓[1210]
a3
a2 a1
a3 a1 = ⅓[2110]
HCP: [uvtw]  t = -(u+v) a1
a2
[1120] [1210]
a3
a1
a3 = ⅓[1120] 103
Figure 3.15
(a) Close-packed stacking sequence for face-centered cubic.
(b) A corner has been removed to shown the relation between the stacking
of close-packed (111) planes of atoms and the FCC crystal structure; the
104
heavy triangle outlines a (111) plane.
 Shockley partial dislocation

- In fcc unit cell, the distance between the B- and C-sites
measured parallel to the close-packed planes corresponds
a
to vectors of the type  112  .
6
- If a dislocation with a Burgers vector
a
6
 
112 glides between
two (111) layers of an fcc lattice, say layers 4 and 5, all
layers above the glide plane (5, 6, 7, …) will shifted relative
to those below the glide plane by a vector
a
6
 
112 .
Therefore, all atoms above the glide plane in B-sites are
moved to C-sites. Fig. 3.56
- The type of dislocation with

a
b 112 is known as Shockley
6
partial dislocation.
a
- Since 112 vectors of the type
6
do not connect lattice points in
the structure, they are called
partial dislocations. Fig. 3.59 (a) An edge dislocation with a Burgers vector
a
 
b  112 on (111). (b) The same dislocation locally 105
6
changes
the stacking sequence from fcc to hcp.
- In thermodynamically stable fcc lattices, the stacking fault is a region of high free energy. On the
other hand, if the fcc lattice is only metastable with respect to the hcp structure, the stacking
fault energy will be effectively negative and the gliding of Shockley partial dislocations will
decrease the free energy of the system.
- A sequence of Shockley partial dislocations between every other (111) plane will create a
glissile interface separating fcc and hcp crystals.
A B C A
C A B C
B C A
A B C
C A
B C
A
C
Fig. 3.61 An array of Shockley partial dislocations forming a glissile interface between
fcc and hcp crystals.
106
 Shape change from glissile dislocation interfaces

- In the dislocation network glides into the fcc crystal,
it results in a transformation of fcc  hcp, whereas
a hcp  fcc transformation can be brought about
by the reverse motion.
- If the transformation is achieved using all three

partials in equal numbers, there will be no overall
shape change, Fig. 3.62b.
- The formation of martensite in steel and other

Fig. 3.62 Schematic representation of the
alloy systems occurs by the motion of glissile-
different ways of shearing cubic close-
dislocation interfaces.
packed planes into hexagonal close-
packed (a) using only one Shockley
partial, (b) using equal numbers of all
three Shockley partials.
107
相變態 Solid / Liquid Interface 魏茂國
 Two types of atomic structure for solid/liquid interfaces

- An atomically flat close-packed interface
The transition from liquid to solid occurs over a rather
narrow transition zone approximately one atom layer
thick. Such interfaces can be described as smooth,
faceted, or sharp.
- An atomically diffuse (rough, non-faceted) interface

The transition from liquid to solid occurs over several
layers. There is a gradual weakening of the
interatomic bonds and an increasing disorder across
the interface into the bulk liquid phase; or in
thermodynamic terms, enthalpy and entropy gradually Fig. 3.63 Solid/liquid interfaces.
change from bulk solid to bulk liquid values across the (a) Atomically smooth, (b) and
(c) atomically rough.
interface.
108
When the solid and liquid are in equilibrium (at Tm), the high enthalpy of the liquid is balanced
by a high entropy so that both phases have the same free energy. In the interface, the balance
is distributed thereby giving rise to an excess free energy SL.
G L  H L  TS L
G S  H S  TS S
G  G S  G L
  
 G  H S  H L  T S S  S L 
 G  H  TS
At equilibrium,  G = 0.
 H  TS
Fig. 3.64 The variation of H, -TmS and G across the solid/liquid interface at the equilibrium
109
melting temperature Tm, showing the origin of the solid/liquid interfacial energy .
 Latent heat v.s. solid/liquid interface

- According to Jackson, the optimum atomic arrangement depends on the latent heat of fusion
(Lf) relative to the melting temperature (Tm).
- This theory predicts that there is a critical value of Lf/Tm  4R, above which the interface
should be flat and below which it should be diffuse.
- Most metals have Lf/Tm  R and are predicted to have rough interfaces. Some intermetallic
compounds and elements such as Si, Ge, Sb as well as most non-metals have high values
of Lf/Tm and generally have flat close-packed interfaces.
110
 Solid/liquid interfacial free energy
- Comparison of Tables 3.2, 3.3 and 3.4 indicates SL  0.30b (for a grain boundary).
- More direct experiments imply that SL  0.45b.
- Empirical relationship
 SV   SL   LV
For a solid metal close to Tm, it is energetically favorable for the surface to melt and replace
the solid/vapor interface with solid/liquid and liquid/vapor interfaces.
Table 3.2 Table 3.4 Experimentally

determined solid/liquid
interfacial free energy.
Table 3.3
111
相變態 Interface Migration 魏茂國
 Diffusion-controlled and interface-controlled growth
112
 Heterogeneous phase transformation

The great majority of phase transformations in metals and alloys occur by nucleation and
growth, i.e. the new phase () first appears at certain sites within the metastable parent ()
phase (nucleation) and this subsequently followed by the growth of these nuclei into the
surrounding matrix.
 Homogeneous transformations
- There is a small class of transformations, known as homogeneous transformation.
- They do not occur by the creation and migration of an interface, i.e. no nucleation stage is
involved. Instead the transformation occurs homogeneously throughout the parent phase.
- Like spinodal decomposition and certain ordering transformations.
113
 2 types of interface
- Glissile interface
Glissile interfaces migrate by dislocation glide that results in the shearing of the parent lattice
into the product. The motion of glissile interfaces is relatively insensitive to temperature and
is known as athermal migration.
- Non-glissile interface
Most interfaces migrate by the more or less random jumps of individual atoms across the
interface in a similar way to migration of a random high-angle grain boundary. The extra
energy that the atom needs to break free of one phase and attach itself to the other is
supplied by thermal activation.
 Military transformations
- Transformations produced by the migration of a glissile interface are referred to as military
transformations.
- During a military transformation, the nearest neighbors of any atom are essential unchanged.
Therefore the parent and the product phases must have the same composition and no
diffusion is involved in the transformation.
- Like martensitic transformations and twinning.

114
 Civilian transformations
- Atoms across a non-glissile interface results in a civilian transformation.
- During civilian transformations, the parent and product may or may not have the same
composition.
- If there is no change in composition, e.g.    transformation in pure iron, the new phase
will be able to grow as fast as the atoms can across the interface. Such transformations are
said to be interface controlled.
- When the parent and product phases have different compositions, growth of the new phase
will require long-range diffusion.
If the interfacial reaction is fast, i.e. the transfer of atoms across the interface is an easy
process, the rate at which the phase can growth will be governed by the rate at which lattice
diffusion can remove the excess atoms from ahead of the interface. This is known as
diffusion-controlled growth.
If the interfacial reaction is much slower than the rate of lattice diffusion, the growth rate will
be governed by the interface kinetics. This is known as interface controlled.
The interface reaction and diffusion process occur at similar rates in which case the interface
is said to migrate under mixed control.
115
Table 3.5 Classification of nucleation and growth transformations
116
相變態 Diffusion-Controlled and Interface-Controlled Growth 魏茂國
 Diffusion-Controlled and Interface-Controlled Growth
- Consider a  precipitate of pure B growing behind
a planar interface into A-rich  with an initial
composition X0.
- As the precipitate grows, the  adjacent to the

interface becomes depleted of B so that the 
composition adjacent to the interface Xi decreases
below the bulk composition, Fig. 3.67a.
- Since growth of the precipitate requires a net flux of

B atoms from the  to the  phase, there must be a
positive driving force across the interface as shown
in Fig. 3.67b.
- The origin of the chemical potential difference can

be seen in Fig. 3.67c.
Fig. 3.67 Interface migration with long-range diffusion.
(a) Composition profiles across the interface. (b) The
original of the driving force for boundary migration into
the  phase. (c) A schematic molar free energy diagram 117
showing the relationship between  Bi , Xi and Xe.
- For growth to occur, the interface composition must be greater
than the equilibrium concentration Xe.
- The net flux of B atoms across the interface will produce an

interface velocity 
  i 
  M   (3.49)
 Vm 
 
 i   i   e
M: interface mobility, Vm: molar volume of the  phase.
- The flux across the interface

1 M i
 M i

J Bi  CB     2
(mol/m2-s) (3.50)
Vm Vm Vm
- In the  phase, there will be a flux of B atoms towards the

interface
 C 
J B  D   B  (mol/m2-s) (3.51)
 x  int erface
- If a steady state exists at the interface, these two fluxes must balance.
J Bi  J B (mol/m2-s) (3.52) 118
- Diffusion control
If the interface mobility is very high, e.g. an incoherent interface,  Bi can be very small and
Xi  Xe. In this case, there is effectively local equilibrium at the interface. The interface will move
as fast as diffusion allows.
- Mixed control
When the interface has a lower mobility, a greater chemical potential difference (  Bi ) is required
to drive interface reaction and there will be a departure from the local equilibrium at the interface.
- Interface control
In the limit of a very low mobility, it is possible that Xi  Xe and (CB/x)interface is almost zero.
There is a maximum possible driving force  Bi across the interface.
For a dilute or ideal solution, the driving force  Bi is given by
 Bi 
RT
X i  X e  (3.53)
Xe
Thus the rate at which the interface moves under interface control should be proportional to the
deviation of the interface concentration from equilibrium (Xi - Xe).
119
 Bi  GB  RT  ln ai  GB  RT  ln  i X i
 Be  GB  RT  ln ae  GB  RT  ln  e X e
 X
  Bi   Bi   Be  RT  ln i i
 e Xe
For ideal solution   i   e  1
For dilute solutions (obey Henry’s law)   i   e  cons tan t
Xi
  Bi  RT  ln
Xe
 X  Xe 
  Bi  RT  ln1  i 
 Xe 
 X i  X e  X e
 X  Xe  Xi  Xe
 ln1  i  
 Xe  Xe
 X i  X e 
RT
  Bi 
Xe
120

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相變態 Chapter 3 魏茂國

Crystal Interfaces and Microstructure

 Interfacial free energy

 Surface free energy of FCC crystal {111} planes

 Real surface free energy

 ‘Broken-bond’ model for surface energy

Fig. 3.5 (a) A possible (110) section through the

- Equilibrium shapes can be determined

 Low-angle and high-angle boundaries

 Boundaries in Single-Phase Solids

Fig. 4.22 The Burgers circuit for an edge dislocation:

Fig. 4.23 The Burgers circuit for a dislocation in a screw orientation.

Fig. 3.7 (a) Low-angle tilt boundary, (b)

Fig. 3.9 Variation of grain boundary energy with misorientation.

 Tilt low-angle boundary

Fig. 3.8 An unsymmetric tilt boundary. Dislocations

Fig. 3.11 Rafts of soap bubbles showing several

- Measured high-angle grain boundary energies b are found to be roughly given by

Table 3.2 Measured grain boundary free energies.

 Twin boundary (a)

- The energy of a coherent twin boundary is extremely low in

- The energy of a twin boundary is very sensitive to

Fig. 3.12 (a) A coherent twin boundary. (b) An

 Special grain boundary (in fcc metals)

Fig. 3.13 Measured grain boundary energies for symmetric

 Microstructure of polycrystalline materials

- When looking at 2-dimensional microstructures, it

- Two grains meet in a plane (a grain boundary),

 Torque of grain boundary (a)

Fig. 3.12(c) Fig. 3.16(b)

 No torque at grain boundary

 Measuring grain-boundary energy

Therefore if SV is known, b can be calculated.

 Balance between coherent and incoherent twin boundaries

- At the coherent/incoherent twin junction, the

- If a boundary is curved in the shape of a cylinder, Fig. 3.20a, it is acted on by a force of

 Grain growth in a soap solution

 Driving force on the boundary during of grain growth

Fig. 3.25 A boundary separating grains with different free energies is

Recovery, Recrystallization, Grain Growth

Recrystallization & Grain Growth

Figure 7.19 Photomicrographs

Recrystallization is the formation of a new set of strain-free and equiaxed grains

Recrystalization is a process, the extent of

Figure 7.20 The influence of annealing

Al (5N) 80C 660C

Cu (5N) 120C 1085C

60 Cu-40 Zn 475C 900C

Figure 7.21 The variation of recrystallization Ni (4N) 370C 1455C

- Fig. 3.26 shows a dislocation-free recrystallized

- Such forces are greatest when the new grain is

 Kinetics of boundary migration

- If the atoms vibrate with a frequency 1, the number of times

- According to Equation 3.18, F = G/Vm, Equation 3.20 can be written simply as

M: mobility of the boundary.

 Boundary migration in real grain boundaries

- Theoretically, as discussed above, the relatively open

- Fig. 3.27 shows data for the migration

Only very low concentrations of impurity

However, the special grain boundaries

It is possible that if the metal were

Fig. 3.27 Migration rates of special and

- For the low mole fractions of solute in the matrix

- When the boundary moves, the solute atoms