Chapter 3: Polycrystalline Microstructures

3.1 Interfacial Tension and Microstructure

Microstructure after sintering is determined by the

interfacial tension.

If we consider an equilibrium between three

interfacial tensions:

ij = interfacial tension force per unit length between

phases i and j.

sine law

a/sin A=b/sin B=c/sinC 1

 3.1.1 Wetting Angle

Wetting angle: the angle between

solid/liquid and liquid/vapour interfaces
when a liquid drop is placed on a solid
substrate

 = wetting angle
 > 90  < 90  = 0 s = solid surface energy
l = liquid surface energy
sl = solid/liquid interfacial energy
 > 90: nonwetting
 < 90: wetting Assume interfacial tension = interfacial
 = 0: spreading energy 

The smaller  (higher wettability) N.b. force balance only satisfied in x

 enhanced densification in liquid phase sintering direction  real equilibrium not maintained
 improved bonding in soldering/brazing
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 3.1.2 Dihedral Angle

Dihedral angle: the angle at the junction between

two grains

• Solid/solid, solid/liquid and solid/vapour

systems also reach an equilibrium defined by the
surface energies.
• If a polycrystalline solid is immersed in a liquid
or vapour, grooves form where grain boundaries
meet the surface.
•  is determined only by  i.e. is independent of
pressures in the phases. b = grain boundary energy of  phase
• If  is a vapour,  is > 120, because s > b  = interfacial energy between  and 
phases
• Usually s  2 - 3  b and   150  = dihedral angle

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Dihedral angles also exist Solid grain
at internal inclusions.

Solid grain

Solid grain

A range of dihedral angles will exist:

b (ss) varies with grain misorientation

sv and sl vary with crystal orientation

For ceramics,  can be < 120 i.e. s (sv)< b

May be due to:

bond distortion at grain boundaries;
differences in impurity adsorption. Distribution of dihedral angles where grain
boundaries meet the surface 4
 3.2 Single-Phase Microstructures

Microstructure is determined by grain boundary energy b.

For an equilibrium grain shape (i.e. all grains have same shape, size and b is constant), the
microstructure must:
1. Minimize total interfacial area under interfacial tension equilibrium
2. Completely fill space without voids (holes)
In 3D, no equilibrium grain shape
For constant b,  = 120. exists.
Closest shape is a tetrakaidecahedron
(truncated octahedron)
In 2D, equilibrium grain shape is a hexagon.

When packed in bcc lattice, space is completely

filled but interfacial tension equilibrium is not met.
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However, in reality:

b changes with crystallographic orientation between grains.

 b is not constant and microstructure can vary locally. d

Grain Boundary as Dislocation Array:

Small (Low)-angle grain boundary

e.g. Tilt (: misorientation) boundary

with edge dislocations
at intervals of d

sin (θ/2) = b/(2d)

sin x  x for small x
θ/2  b/2d
θ  b/d

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All microstructures satisfy Euler's law

e.g.) Tetrahedron
C-E+P-B=1 C=4
E=6
C = corner P=4
B=1
E = edge
P = polygon 4-6+4-1=1
B = body (i.e. 3D shape)

e.g.) Hexagon
C=6
E=6
For a 2D figure, C - E + P = 1
P=1

6-6+1=1

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 3 polygons meet at each point:

3C   nPn  EC

Pn = no. of polygons with n edges

EC = no. of partially shared corners at edge of figure

2 polygons meet at each edge:

2E   nPn  EB

EB = no. of unshared edges at edge of figure Schematic 2D microstructure

If we put these equations into Euler's law:  (6  n)P  E

n B 6

If P = total no. of polygons and pn = fraction of n-sided polygons, then:  (6  n) pn  (6  EB ) / P

If P is large, then:  (6  n) p
n 0

The average grain is a hexagon and polygons are distributed to satisfy this e.g. if a 3-sided grain
is present, there must also be a 9-sided grain or two grains with 7 and 8 sides. 8
Polygons with > 6 sides have concave boundaries
Polygons with 6 sides have flat boundaries
Polygons with < 6 sides have convex boundaries

Concave boundaries migrate outwards  grain grows

Convex boundaries migrate inwards  grain shrinks

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 3.3 Multiphase Microstructures

More than one phase e.g. solid + liquid,

solid + gas (pore), solid + liquid + gas

Microstructure determined by
equilibrium among interfacial tensions.

Shape of second phase at 3-grain

junction (triple junction) depends
on dihedral angle .
 = 150?  = 90?  = 60?

Distribution of 2nd phase in a 2D microstructure

 = 30?  = 0?
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In a 3D microstructure:

 > 60: isolated second phase.

  60: continuous network along
grain edges.  > 60   60

As  , grain boundary (i.e. solid/solid) area 

W(Ni, Fe) grains

Ni-Fe-W 2nd phase

W-Ni-Fe heavy alloy

Matrix network after sintering
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 If  = 0:
liquid phase at all grain boundaries:
all grains are separated.

Some (low energy) grain boundaries remain.

anisotropy in gb & sl

W-Ni-Fe heavy alloy

Wet and dry boundaries can coexist.

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 Thickness of liquid films  1-2 nm.
1350C, 5 hrs
Liquid films can form at dry grain boundaries and
thicken during grain growth.

BaTiO3
1350C, 20 hrs

BaTiO3

1350C, 50 hrs

Causes: accumulation of segregated impurities

penetration of liquid phase at triple
junctions into grain boundaries.

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 For given values of  and 2nd phase volume fraction, the grains
change shape to obtain minimum interfacial energy.

1
E   g Ag   m Am
2

E = total interfacial energy per grain

Ag = grain boundary area
Am = grain-matrix interface area
g = grain boundary energy
m = grain/matrix interfacial energy

Park and Yoon* calculated E as a function of matrix

volume fraction Vm and .

For  > 90, m >> g and E  as Vm 

For  = 0, m << g and E  as Vm 
For 0 < < 90, E vs. Vm curve has a minimum.
As E , grain shape becomes more rounded. Vm

Minimum
*H.H. Park and D. Y. Yoon, Metall. Trans. A, 16, 923-28 (1985) 14
If  is > 90, the 2nd phase will exude from (come out
of) the sample. All boundaries will be solid/solid
grain boundaries.

For 0 < < 90, the sample will contain solid/solid

grain boundaries and solid/matrix interfaces. Any
excess liquid (beyond the minimum point of the E vs.
Vm curve) will remain outside the sample during and
after sintering.

For  = 0, all boundaries will be solid/matrix

interfaces.

Exuded liquid phase after liquid

phase sintering a system with
high 

N.b. matrix phase can be liquid or vapour

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If E vs. Vm curve isn't at minimum point:

• there will be a driving force to reach the

minimum point
• the grains will try to change shape to
reduce E.

For const. Vg and variable Vm:

1  Vm  
2

E 
Pe   V 
Vg  m V g

Pe = effective pressure
Vm = volume fraction of matrix
Vg = volume of grain
E = total interfacial energy of grain

Pe pushes grains to achieve minimum E by

changing shape. Vm

If  is small, there is a limiting porosity in solid state systems.

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