Microstructure Control

Shantanu K Behera

Dept of Ceramic Engineering

NIT Rourkela

CR2016

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Chapter Outline

1 Thermodynamics of Pores

2 Grain Growth in Porous Solids

3 Microstructural Maps

4 Fabrication Principles for Controlled µStructure

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 Thermodynamics of Pores

Thermodynamics of Pore Stability

Thermodynamically, whether a pore shrinks or grows depends on the free

energy change. The amount of energy gained by the formation of more grain
boundaries due to pore shrinkage should be lower than the energy lost by the
disappearance of solid-vapor interface due to pore shrinkage. It is the reverse
for pore growth.

Thermodynamically, we can write:

δE = Nδrγgb − 2πδrγsv

If the pore is surrounded by too many grains, then the increase in energy due
to the extension of the grain boundaries (into the pores) would be greater than
the decrease in free energy due to the reduction of the pore surface area. As
a results the pore should grow.

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 Thermodynamics of Pores

Pore Stability
Balancing the forces we can write:
hΨi
γgb = 2γsv Cos
2
Or, hΨi γgb
Cos =
2 2γsv
For a material systems the dihedral
angle (Ψ) is unique, therefore the
critical coordination number (Nc ) is
Figure: 2.4 from Rahaman, pg. 49. also unique. Pores with more than Nc
Equilibrium shape of the pore is number of grains coordinating it would
determined by the balance of the surficial tend to grow, and vice versa.
and interfacial tensions. γsv , γgb are
solid-vapor interface energy and grain
boundary energy, respectively. Ψ is the
dihedral angle.

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 Thermodynamics of Pores

Pore Stability
Consider a system with dihedral angle 120◦ . Therefore the Nc = 6. How the
shape of the pore changes with number of grains coordinating it can be
observed from the figure below.

Figure: Stability of pores with dihedral angle 120◦ , but with different grain coordination
number. Sintering, SJL Kang.

A relation between the two important parameters (Ψ and Nc ) can be

established as follows:
180Nc − 360
Ψ=
Nc
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 Thermodynamics of Pores

Pore Stability

Figure: 3.43 from MN Rahaman. Condition for pore stability in 3D.

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 Grain Growth in Porous Solids

Grain Growth in Porous Solids

Grain growth in porous solids can be split into two parts; GG in very porous
solids, and GG in less porous solids.

Grain growth in very porous solids (referring to the initial and a major part
of the intermediate sintering stage) is generally due to surface diffusion
and evaporation-condensation phenomena.
Strategies to control grain growth at this stage is to use additives or
dopants that would hinder the surface diffusion coefficient.
Additionally, ceramic systems with high vapor pressure would have a
pronounced effect of coarsening in this stage.

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 Grain Growth in Porous Solids

Grain Growth in Porous Solids

Grain growth during the less porous state (pertaining to the final stage
densification) can be understood and modeled by having spherical pores
at the grain boundaries or triple pockets (similar to the Zener analysis of
second phase precipitates in a microstructure).
If the pore imparts sufficient drag then the boundary migration may stop.
 r
A limiting case can be defined as GL = 2α 3 P to design fabrication
parameters, where r is the pore radius, P is the porosity, α is a
geometrical factor.
If the drag is insufficient, the boundary will break away, leaving a trapped
pore inside the grain.

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 Grain Growth in Porous Solids

Pore Mobility
Surface curvature driven boundary
migration applies a force on the pore.
This force changes the shape of the pore:
the leading surface of the pore becomes
less strongly curved than the trailing
surface.
The difference in curvature leads to a
chemical potential difference that drives
matter transport from the leading surface
to the trailing surface.
Thence, the pore moves forward in the
direction of the boundary.
Various diffusion mechanisms are marked
on the figure: vapor transport, surface
Figure: Adapted from Sintering of diffusion, and lattice diffusion.
Ceramics, Rahaman, pg. 157

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 Grain Growth in Porous Solids

Pore Mobility

Figure: Pore-boundary interaction. Neglect the intergranular impurity phases. Image:

S K Behera, Lehigh University

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 Grain Growth in Porous Solids

Pore Mobility
Like boundary mobility, we can also define pore mobility as follows:

vp = Mp Fp

where, vp is the pore velocity, Mp is the pore mobility, Fp is the driving force on
the pore.

We can have mobility expressions for each type of diffusion mechanism.

Surface diffusion:
Ds δ s Ω
Mp =
kTπr4
Lattice diffusion:
Dl Ω
Mp =
fkTπr3
Vapor transport:
Dg dg Ω
Mp =
2kTds πr3
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 Grain Growth in Porous Solids

Kinetics of Pore Boundary Interaction

In the consideration of pore and boundaries, two cases may arise:

The pores may remain attached to the boundary.

The pore may get separated from the boundary.

Figure: Microstructure evolution in alumina Figure: Microstructure evolution in alumina

ceramic: Pores attached to the boundary. ceramic: Pores separated from the
Image: SKB boundary. Image: SKB

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 Grain Growth in Porous Solids

Kinetics of Pore Boundary Interaction

Pore separation will occur when vp < vb , which can be written as:

Fp Mp < FMb

where, F is the effective driving force on the boundary. For a unit area it can
be written as: F = Fb − NFp .

Therefore,
Fp Mp < (Fb − NFp )Mb

On the condition that the pores remain attached to the boundary, vp = vb .

Therefore:

Mp Mb
vb = Fb
NMb + Mp

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 Grain Growth in Porous Solids

Kinetics of Pore Boundary Interaction

Two conditions can arise from the expression:
Mp Mb
vb = Fb
NMb + Mp

When NMb >> Mp , then

Fb Mp
vb =
N
This is a condition where many pores with low mobilities are present in
the microstructure. The boundary motion in this case is limited by pore
mobility. This is called pore control.
When NMb << Mp , then
vb = Fb Mb
This is a condition where a small number of pores with high mobility are
present in the microstructure. The presence of the pores has no effect on
boundary motion. This is called boundary control.
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 Grain Growth in Porous Solids

Grain Growth Kinetics in a Porous System

Considering grain growth by surface diffusion, we have

dG Fb h Ds δs Ω i
vb = =
dt N kTπr4

Again, Fb ∼ 1/G, Interpore distance X is approximately G, therefore

1/N ∼ 1/G2 . Again, assuming pore growth by coalescence r ∼ G. Therefore,

dG K
= 3
dt G
Upon integration, we have
G4 = G40 + K0 t

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 Microstructural Maps

Brook Model

Figure: Sir Brook’s Model: Pore boundary interaction on microstructural parameters for
pore migration by surface diffusion.

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 Microstructural Maps

Yan Cannon Chowdhary Model

This model considers a simple
analysis: More good, less bad.
Ratio of the coarsening rate (ρ̇) to the
densification rate (Ġ).

3 Ds δs γgb
Γ=
176 Dgb δgb γsv
This expression is for boundary
migration limited by surface diffusion
controlled pore drag, and sintering by
GB diffusion.

Figure: YCC Model: G ∼ ρ evolution during

the final stage of sintering for different
values of the ration of coarsening rate to
the densification rate (Γ).

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 Microstructural Maps

Harmer Model

Figure: Harmer Model: G ∼ ρ map for Al2 O3 , illustrating the effect of raising the surface
diffusion coefficient by 4 times, reducing the lattice diffusivity by 2 times, and boundary
mobility by 34 times. The G ∼ ρ trajectory has been flattened, and the separation
region has been shifted to larger grain size, thereby making it possible to achieve full
density.
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 Fabrication Principles for Controlled µStructure

Hot Pressing

Sintering with an applied pressure

ρ˙hp ∝ Σ + Pa

ρ˙s ∝ Pa
where ρ˙hp , ρ˙s are the densification rates in hot pressing and pressureless
sintering, respectively, Σ is the pressure through Hot Press, Pa is the
sintering pressure. Since, generally, Σ >> Pa , we can say that

ρ˙hp ∝ Σ

Therefore, h ρ̇ i h ρ̇ i
>>
Ġ hp Ġ s

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 Fabrication Principles for Controlled µStructure

Use of Dopants, Inclusions/ Uniform Packing

Use of additives or dopants that reduce boundary mobility (by solute
drag) and reducing the rate of grain growth (or coarsening)

Ġdoped < Ġundoped

Effectively, therefore, we have

h ρ̇ i h ρ̇ i
>>
Ġ doped Ġ undoped

Fine, inert inclusions, when used, impact the rate of grain growth by
imposing a drag force on it, thus reducing boundary mobility. This
effectively increases densification rate than coarsening.
Uniform packing of fine particulates leads to small pores with low
coordination number (N < Nc ). As a result of sintering the pores shrink in
size and disappear.
Additionally, homogeneous distribution of powders with a narrow particle
size distribution help eliminate differential sintering and abnormal grain
growth, thus ensuring more uniform development of microstructure.
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 Fabrication Principles for Controlled µStructure

Fast Firing
If, the activation energy of densification is higher than that of coarsening in a
ceramic system: fast firing can be an effective technique for consolidation to
full density.

Figure: 11.9, pg. 161, SJL Kang. Activation

energy for densification and grain growth
for a ceramic. This information can be
used to formulate a fabrication schedule.
Figure: from M P Harmer, Effects of
pressureless sintering, fast firing and hot
pressing in MgO doped Al2 O3 .

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