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APL102- Introduction to Materials

Science and Engineering

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Time Institute
Day Group name by CC
Groups

1
Monday 3:00 to 5:00 pm 1

Tuesday 3:00 to 5:00 pm 1&2 2

Thursday 3:00 to 5:00 pm 2&3 3

Friday 3:00 to 5:00 pm 3 &4 4

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Recap

• Significance of Materials Science

• Materials Tetrahedron
Structure-Processing-Properties-Performance

• Broad Classification of Materials


Engineering Materials

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Examples of Each Material Family

Our daily life uses most of them in some form or the


other!! 5
Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
Equilibrium and Kinetics:
A Review
Why imp. to review the concepts of
Equilibrium and kinetics??

Materials in unstable state??

Kinetics: rate at which processes occurring


in the material

e.g. change in shape, size, composition, structure


Equilibrium
Concept of stability and metastability

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3

1. Metastable, 2. Unstable, 3. Stable


Mechanical push to
overcome
activation barrier

System automatically
attains the stable state
Otherwise Unstable

Minimum Energy – STABLE EQUILIBRIUM

Maximum Energy – UNSTABLE EQUILIBRIUM

Global Minimum - Most STABLE

Local Minimum - METASTABLE


State of Materials

The materials which we are using in


metastable state: Al, Fe

What is the stable state (global minimum)


of Fe??

May be the most stable state may not be


of great use for engineers
Thermodynamic Properties
Thermodynamic Properties
Intensive properties: independent of mass

Pressure
Temperature

Extensive properties: dependent on mass

Internal energy
Enthalpy
Thermodynamic Properties
U = internal energy

Consider a body, which performs work w and absorbs


heat q. Thus the total change in the internal energy of
the body, U, is

ΔU = q-w

dU = dq – dw

at constant P, dw = PdV
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Thermodynamic Properties

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Thermodynamic Properties

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Demonstration of PV term in solid

Calculation basis: 1 mol. of Cu atoms at 1 atm.

PV = 0.1 x 106 N/m2 x 7.09 x 10-6 m3


= 0.716 J

U = 6 x 56.4 KJ/mole
= 338.4 KJ

Hence H and U terms can be used


interchangeably in case of solids
Can we use H or U to determine the
stability of the system??

So now we have to look at some other


stability criterion

Lets just first define entropy…


Entropy
The entropy of a system can be defined by two
components:

1.Thermal entropy: Temperature dependent

2.Configurational entropy: Temperature


independent

No. 2 is only possible in case of crystalline


solids
Thermal Entropy
Any atom can have three kinds of motion

1)Oscillatory

2)Rotational

3)Translational
Thermal Energy
Atoms in solid oscillate about mean position
with varying amplitude and directions

T , frequency

ν = 1013 s-1 around 200 K


This oscillatory energy available can be
defined as—Average energy per atom
per mode of oscillation = KT
Thermal energy
K = Boltzmann constant
1.38 x 10-23 J/K

Average thermal energy per mole of atoms per


mode of oscillation is NKT=RT
In crystalline solids, large ensemble of
atoms, some may loose energy while others
may gain

One can invoke statistics and talk about


average energy

The probability that in an ensemble a specie


has energy ≥ E* at a given T
n  E  *
 exp  
N  kT 
Maxwell-Boltzmann Distribution

n  E  *
 exp  
N  kT 

Fraction of atoms having an energy  E*


at temperature T
Configurational Entropy
Boltzmann’s
Epitaph

S  k lnW
W is the number of
configurations having the
same energy
N!
W  Cn 
N

n!( N  n)!

N=16, n=8, W=12,870


If n>>1

Stirling’s Approximation
ln n! n ln n  n
S  k ln W
N!
 k ln
n!( N  n)!
 k[ N ln N  n ln n  ( N  n) ln( N  n)]
Free Energy
Gibbs Free Energy
G  H  TS

Helmholtz Free Energy


F  U  TS

In solids since H ≈ U, G and F are used


interchangeably
The variation of G with temperature
Gibbs Free Energy
G  H  TS

Condition for equilibrium


≡ minimization of G

Local minimum ≡ metastable equilibrium


Global minimum ≡ stable equilibrium
G = GfinalGinitial

G = 0  reversible change

G < 0  irreversible or
spontaneous change

G > 0  impossible
Kinetics
Kinetics
Arrhenius plot
 Q 
rate  A exp  
 RT 
ln (rate)

Q
slope  
R

1
T
Consider a reaction between different
atomic species A, B and C:

For this reaction to go in the forward direction as indicated,


A and BC must come into contact, the bond between B and
C must be broken and the bond between A and B must be
formed. This usually involves an intermediate step through
which the reaction has to proceed:

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Q

The rate of the reaction is proportional to the number of species n with


energy equal to or greater than that of the activation barrier, as well as
to the vibrational frequency.

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