(6-3-2) NPTEL - Properties of Materials at Cryogenic Temperature

6
1
Properties of Materials
Sr. No. Property

1 Mechanical From Mech Engg.
2 Thermal perspective
3 Electrical From SC
4 Magnetic perspective
2
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
Earlier Lecture
• Introduction to material properties
• Structure of Metals and Plastics
• Stress – strain relationship
• Mechanical properties of Metals at low

temperature
• Mechanical properties of Plastics at low

temperature
3
Outline of the Lecture
Title : Material Properties at Low Temperature
(contd)
• Introduction
• Thermal properties
• Electric and Magnetic properties
4
Introduction
• The properties of materials change, when cooled
to cryogenic temperatures (demo video).
• The electrical resistance of a conductor decreases

as the temperature decreases.
• Shrinkage of metals occur when cooled to lower

temperatures.
• Systems cool down faster at low temperatures due

to decrease in the specific heat.
• Hence, a study of properties of materials at low

temperatures is necessary for the proper design.
5
Material Properties
Sr. No. Thermal Properties

1 Thermal Expansion/Contraction
2 Specific Heat of Solids
3 Thermal Conductivity
6
Thermal Expansion
• Reduction (contraction) in the dimensions of a
material occur when cooled to low temperatures.
A B 300 K
A B 80 K
Contraction Contraction
of A of B
7
Thermal Expansion
• The linear coefficient of thermal expansion (λt)
λt =
( δ L / L)
K −1
δT
• is the fractional change in length per unit change
in temperature while the stress is constant.
• Similarly, the volumetric coefficient of thermal

expansion (β) is the fractional change in volume
per unit change in temperature while the
pressure is constant.
• For isotropic materials

β = 3λt
8
Thermal Expansion
32
2024-T4 Aluminum • The variation of λt for
28
304 Stainless Steel
few of the commonly
Nickel
used materials is as
X 106, per K
C1020 Carbon Steel

shown.
24
Titanium
20
• In general, the
coefficient of thermal
16
12 expansion decreases
with the decrease in
temperature.
8
• Most contraction
0 50 100 150 200 250 300 350 occurs till 80 K.
Temperature, K
9
Thermal Expansion
• The variation of
Equilibrium
Molecular Internal Energy
Molecular Internal
Spacing
Energy (U) with the
intermolecular
U2 distance (r) is as
Energy at shown. Here, ro is the
T2>T1 intermolecular
U1 distance at 0 K.
Energy at T1
• The equilibrium
U0 Zero Point spacing depicts the
Energy T=0 mean position of the
r0 r atoms about which it
oscillates.
10
Thermal Expansion
• With the rise in the
Equilibrium
temperature, the
Spacing
increased thermal
agitation leads to
U2 increased inter
Energy at molecular distance.
T2>T1
U1 • The energy curve is
Energy at T1
asymmetric about the
point ro, stating that
U0 Zero Point the atomic vibration
Energy T=0 is asymmetric.
r0 r
11
Thermal Expansion
• The rate of increase
Equilibrium
of intermolecular
Spacing
distance increases
with the increase in
U2 the temperature.
Energy at
T2>T1 • Hence, the coefficient
U1 of thermal expansion
Energy at T1
(λt) increases with
the increase in
U0 Zero Point temperature.
Energy T=0
r0 r
12
Mean Linear Thermal Exp.
• Mean linear thermal
expansion is defined
as
∆L LT − L0
=
X 105
L0 L0
• Here L0 is the length
at 0 K and LT is length
at any temperature T.
• Slope of curves is very

Temperature, K high upto 80 K, and
thereafter flattens.
13
• Mean linear thermal
expansion can also be
evaluated between two
different temperatures.
• If LT1 & LT2 be the

X 105
lengths of the
specimen at T1 and T2
respectively. Then
change in length is
given by
∆L LT 1 − LT 2
=
Temperature, K L0 L0
14
32
2024-T4 Aluminum L280 − L80 5 L80 − L20 5
304 Stainless Steel
.10 .10
28 L0 L0
Nickel
X 106, per K
24 C1020 Carbon Steel 360 24

Titanium 259 13
20
201 12
177 10
16
SS(280 – 80)  dL=2.59

12
•
8 mm.
SS(80 – 20)  dL=0.13

4
•
0 50 100 150 200 250 300 350
mm.
Temperature, K • when L0 = 1m.
15
Specific Heat of Solids
• It is the energy required to change the
temperature of a unit mass of substance by 1o C,
holding the volume or pressure as constant.
dU dH
Cv = Cp =
dT dT
• In 1911, Dulong and Petit observed that the heat
capacities of the solids are independent of
temperature. Each lattice point absorbs same
energy as the every other lattice point. Therefore,
by the principle of equipartition of energy.
U = 3RT ∴ Cv = 3R
16
Einstein & Debye Theory
• Einstein treated the solid as a system of simple
harmonic oscillators. It was assumed that, all the
oscillators are of same frequency.
• However, Debye treated solid as an infinite

elastic continuum and considered all the possible
standing waves in the material.
• A parabolic frequency distribution was derived for

the atoms vibrating in lattice.
• He presented a model to compute lattice heat

capacity per mole, which accounts for all the
vibration frequencies of all the lattice points.
17
Debye Theory
• The Debye model gives the following expression
for the lattice heat capacity per mole.
θD
3
T  T
x 4 e x dx 3
T  T 
cv = 9 R   ∫ = 3R   D  
 θD  (e − 1)
2
 θD   θD 
x
0
hυ Debye
x is a dimensionless variable. x=
kT function
•
• In the equation, only the value of θD changes

from material to material.
• θD is called as Debye Characteristic Temperature.

18
Debye Theory
• At high temperatures (T > 2θD), specific heat
obtained from the above equation approaches
3R. This is called as Dulong and Petit Value.
• At low temperatures (T < θD/12), the Debye

function approaches a constant value of D(0) =
4π4/5.
3
12π R  T 
4
cv =  
5  θD 
• The variation is a cubic equation in absolute

temperature at very low temperatures.
19
Specific Heat Curve
The variation of Cv/R
3.2
•
2.8 with T/θD is as shown.
2.4
• In general, the
2.0 specific heat
decreases with the
Cv/R
1.6
decrease in
1.2 temperature.
0.8
0.4
0
T/θD
1 2 3 4 5
20
Debye Characteristic Temp.
Material θD Material θD
Aluminum 390 Mercury 95
Argon 85 Molybdenum 375
Beryllium 980 Neon 63
Calcium 230 Nickel 375
Copper 310 Platinum 225
Diamond 1850 Silver 220
α-Iron 430 Titanium 350
γ-Iron 320 Tungsten 315
Lead 86 Vanadium 280
Lithium 430 Zirconium 280
21
Calculation of Cv
• The calculation of Cv for a particular material at
a particular temperature, T, involves the
following procedure.
• Refer the table and find the θD.
• Calculate T/θD and interpolate the value on the

graph to obtain Cv/R.
• Cv can be known by multiplying it with R.
• If the value of T/θD is less than 1/12, correlation

can be used to evaluate the Cv value directly.
22
Thermal Conductivity in Solids
• In a cryostat, the solid members made of a
metal or a non metal conduct heat from high
temperature to low temperature.
• For these members, the thermal conductivity,

kT, should be as low as possible to minimize the
heat loss.
• On the other hand, for achieving best heat

transfer of cold generated, copper can be used
as a medium due to its very high thermal
conductivity.
23
Thermal Conductivity in Solids
• Thermal conductivity,
Thermal Conductivity, W/m-k
kT, is the property of a

10000
material which
1000
indicates its ability to
Pure Copper conduct heat. In
100 2024-T4 Aluminum general, kT decreases
C1020 Carbon Steel with the decrease in
304 Stainless Steel
the temperature.
10
• However, for pure

1 metals the variation is
slightly different from
0.11
10 100 200 400 that of impure metals
Temperature, K and alloys.
24
Conduction in Pure Metals
Pure Metals
• The Electron and

10000
Phonon motion cause

1000
heat conduction.
Pure Copper
100 2024-T4 Aluminum • The contribution of

C1020 Carbon Steel electron motion to
304 Stainless Steel
heat conduction is
10 predominant above
LN2 temperature.
1
• At temperature below
0.11
10 100 200 400 LN2, phonon motion is
Temperature, K predominant.
25
• Conduction depends
on the product of
10000
electronic specific
1000
heat and mean free
Pure Copper path.
100 2024-T4 Aluminum
C1020 Carbon Steel • This product being a
304 Stainless Steel
constant above LN2,
10 the kT remains
constant above LN2.
1
0.11
10 100 200 400
Temperature, K
26
• As the temperature is
lowered, phonon
10000
contribution increases
1000
and kT varies as 1/T2.
Pure Copper
100 2024-T4 Aluminum • It reaches a high

C1020 Carbon Steel value until the mean
304 Stainless Steel
free path of the
10 electrons equals to
the dimensions of test
1 specimen.
0.11
10 100 200 400
Temperature, K
27
• When this condition is
reached, the surface

10000
exhibits a resistance
1000
causing the kT to
Pure Copper decrease with the
100 2024-T4 Aluminum further drop in the
C1020 Carbon Steel temperature.
304 Stainless Steel
10 Impure & Alloy Metals

• Electron and phonon
1 motion are of same
magnitude in impure
0.11
10 100 200 400 and alloy metals.
Temperature, K
28
Conduction in Impure Metals
• The impure metals
have imperfections
10000
like grain boundaries

1000
and dislocations.
Pure Copper
100 2024-T4 Aluminum • An additional

C1020 Carbon Steel scattering of electrons
304 Stainless Steel
occur due to grain
10 boundaries and
dislocations which is
1 proportional to T3 and
T2 respectively, at
0.11
10 100 200 400 temperatures lower
Temperature, K than θD.
29
Conduction in Impure Metals
• At low temperatures,
scattering decreases.
10000
1000
• As a result, kT
Pure Copper decreases with
100 2024-T4 Aluminum decrease in
C1020 Carbon Steel temperature in impure
304 Stainless Steel
metals and alloys.
10
• These materials do
1 not exhibit any high
maxima like that of
0.11
10 100 200 400 pure materials.
Temperature, K
30
Thermal Conductivity Integrals
• As we found that, thermal conductivity, kT, is a
strong function of temperature, the term kTdT is
very important.
• Due to this variation in kT, the calculation of

heat transfer (Q) can be very complicated.
• Therefore, a simple method is proposed in order

to simplify calculation of Q.
• This method use ∫ kdT or Thermal Conductivity

Integral, which basically sums up the effect of
variation of kT with change in temperature, dT.
31
• The Fourier’s Law of heat conduction is given by
the following mathematical expression.
dT  A( x) 
Q = −k (T ) A( x) Q = −  {k (T )dT }
dx  dx 
• In this method Q is expressed as given below.
−G (θ 2 − θ1 )
Q=
• Here, θ1 and θ2 are expressed as Thermal

Conductivity Integrals.
32
• kdT is taken as an integral called as Thermal
Conductivity Integral evaluated w.r.t a datum
temperature.
For Example
T1
θ1 = ∫ k (T )dT
Td
Td = 0 or 4.2
• If Acs is constant, G is defined as
G = Acs / L
33
100000
• The variation of kdT for few of
10000 the commonly used materials
is as shown.
1000
• In the calculations, the actual
, W/m
temperature distribution is
100 not required, but only the end
point temperatures.
1 Aluminum 6063
Phospher Bronze
304 Stainless Steel
0.011
10 100 1000
Temperature, K
34
100000
• This technique is widely used
10000 in the analysis of heat leaks.
• If the datum temperature is

1000
taken as 0 K and the two
, W/m
ends of a specimen are

100 maintained at 100 K and 10
K respectively, then the kdT
integral is given by
1 Aluminum 6063
100 100 10
Phospher Bronze
0.011
304 Stainless Steel
10 100 1000
∫ kdT = ∫ kdT − ∫ kdT
10 0 0
Temperature, K
35
Electric & Magnetic Properties
Electrical Conductivity
• It is defined as the electric current per unit cross
sectional area divided by the voltage gradient in
the direction of the current flow.
Electrical Resistivity
• It is the reciprocal of electrical conductivity.
• Decreasing the temperature decreases the

vibration energy of the ions. This results in
smaller interference with electron motion.
• Therefore, electrical conductivity of the metallic

conductors increases at low temperature.
36
Electrical Resistivity
1
2024-T4 Aluminum • Electrical resistivity ratio is
Electrical Resistivity ratio
Iron defined as R
T
Copper
R273
0.1
• The variation of electrical
resistivity ratio for some
commonly used materials
is as shown.
0.01
• This ratio for a material
decreases with the
decrease in the
0.004
20 100 200 273 temperature.
Temperature K
37
Electrical Conductivity
• Electrical and thermal conductivities are related
by Wiedemann – Franz expression.
1πk 
2
kT
=  
keT 3  e 
• It means that the ratio of kT and ke is a product
of constant and absolute temperature.
kT
= AT
ke
38
Summary
• The coefficient of thermal expansion decreases
with the decrease in temperature.
• For pure metals, kT remains constant above LN2

temperature. Below LN2, it reaches a maxima and
then after decreases steadily.
• For impure metals, kT decreases with decrease in

temperature. Integral kdT is used to calculate Q.
• Electrical conductivity of the metallic conductors

increases at low temperature.
• ke and kt are correlated by Wiedemann–Franz Law.

39
• A self assessment exercise is given after
this slide.
• Kindly asses yourself for this lecture.
40
Self Assessment
1. Coefficient of thermal expansion is the change in
length to original length per __________.
2. Coefficient of thermal expansion ______ with the

decrease in temperature.
3. Metals undergo most of the contraction upto ___.
4. Mathematically, mean linear thermal expansion is

defined as _______.
5. Dulong and Petit value for Specific heat is _____.
41
Self Assessment
6. Debye characteristic temperature is denoted by
____.
7. At low temperatures (T < θD/12), the Debye

function approaches a constant value of _____.
8. Expression for Q in Thermal conductivity integral

form is ___________.
9. kT decreases with the _________ in the

temperature for impure metals.
42
Self Assessment
10. Specific heat of the material __________ with
decrease in temperature.
11. Electrical conductivity of the metallic conductors

__________ at low temperature.
12. ke and kt are correlated by _________ Law.
43
Answers
1. Unit rise in temperature.
2. Decreases
3. 80 K
4. F∆L LT − L0
=
L0 L0
5. 3R
6. θD
7. 4π4/5
d=
8. Q −G (θ 2 − θ1 )
44
Answers
9. Decrease
10. Decrease
11. Increase
12. Wiedemann–Franz
45
Thank You!
46

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6

Sr. No. Property

• Structure of Metals and Plastics

• Stress – strain relationship

• Mechanical properties of Metals at low

• Mechanical properties of Plastics at low

• Electric and Magnetic properties

• The electrical resistance of a conductor decreases

• Shrinkage of metals occur when cooled to lower

• Systems cool down faster at low temperatures due

• Hence, a study of properties of materials at low

Sr. No. Thermal Properties

• Similarly, the volumetric coefficient of thermal

• For isotropic materials

C1020 Carbon Steel

• Slope of curves is very

• If LT1 & LT2 be the

24 C1020 Carbon Steel 360 24

SS(280 – 80)  dL=2.59

SS(80 – 20)  dL=0.13

• However, Debye treated solid as an infinite

• A parabolic frequency distribution was derived for

• He presented a model to compute lattice heat

• In the equation, only the value of θD changes

• θD is called as Debye Characteristic Temperature.

• At low temperatures (T < θD/12), the Debye

• The variation is a cubic equation in absolute

• Refer the table and find the θD.

• Calculate T/θD and interpolate the value on the

• Cv can be known by multiplying it with R.

• If the value of T/θD is less than 1/12, correlation

• For these members, the thermal conductivity,

• On the other hand, for achieving best heat

kT, is the property of a

• However, for pure

• The Electron and

Phonon motion cause

100 2024-T4 Aluminum • The contribution of

100 2024-T4 Aluminum • It reaches a high

reached, the surface

10 Impure & Alloy Metals

like grain boundaries

100 2024-T4 Aluminum • An additional

• Due to this variation in kT, the calculation of

• Therefore, a simple method is proposed in order

• This method use ∫ kdT or Thermal Conductivity

• In this method Q is expressed as given below.

• Here, θ1 and θ2 are expressed as Thermal

• If Acs is constant, G is defined as

• If the datum temperature is

ends of a specimen are

• Decreasing the temperature decreases the

• Therefore, electrical conductivity of the metallic

• For pure metals, kT remains constant above LN2

• For impure metals, kT decreases with decrease in

• Electrical conductivity of the metallic conductors

• ke and kt are correlated by Wiedemann–Franz Law.

• Kindly asses yourself for this lecture.

2. Coefficient of thermal expansion ______ with the

3. Metals undergo most of the contraction upto ___.

4. Mathematically, mean linear thermal expansion is

5. Dulong and Petit value for Specific heat is _____.

7. At low temperatures (T < θD/12), the Debye

8. Expression for Q in Thermal conductivity integral