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Cryogenic Engineering
Magnetic Work and the Magnetocaloric Effect
Mech 445 Cryogenic Engineering  Lecture 19 1
Magnetic Cycles
If we have a way of altering entropy, we have a way of
creating a cooling cycle.
For gases, entropy is a function of temperature and
pressure
( ) , s s T p =
1
4
2
3
a significant entropy change can be induced by a pressure
variation.
If the total entropy is constant (ds = 0)
( ) , s s T p
s
T A
p T
s s
ds dT dp
T p
  c c  
= +
 
c c \ . \ .
p
T
c
s
ds dT dp
T p
  c
= +

c
\ .
s
T s
dT dp
  c
= ÷

c
\ .
2
p
s
T s
T dp
  c
A = ÷
} 
c
\ .
Mech 445 Cryogenic Engineering  Lecture 19 2
When we magnetize a substance, we alter entropy
(magnetic entropy change)
How can we use this to create a magnetic cycle?
s
p
T
c p

c
\ .
( ) ,
e
s s T B =
1
p p T
c p

c
\ .
2
Magnetism Review
Maxwell’s eqn for magnetic flux:
Flux lines have no beginning or end – there are no magnetic monopoles (unlike charge.)
0 B V· =
The functional form of the permeability as a function of H defines different
magnetic materials.
i.e.
The concept of “magnetization”, M, arises from the impact of specific materials on
flux density
Can be explained by applying BiotSavart to atoms
Electrons are charges in motion and, therefore, generate magnetic moments just as a coil of wire
carrying a current will generate a magnetic moment
Moment is determined when placed in external field measure Lorentz force
0 B V
( ) H µ µ =
Mech 445 Cryogenic Engineering  Lecture 19 3
Moment is determined when placed in external field – measure Lorentz force
Magnetic Phenomena
The magnetic moment arising from the current loop is,
An electron orbiting an atom will generate a moment due to orbital angular
dipole moment Area of loop I = ×
g g g
momentum
In addition, a moment is generated by the “spin” moment of the electron
The magnetic moment due to electron spin is defined as a Bohr magneton, β
The net magnetic moment, J, is found by summing the spin, S, and orbital, L,
moments,
27 2
9.27 10 A m
2
e
e h
m

÷  
= = × ·

\ .
J S L = +
Mech 445 Cryogenic Engineering  Lecture 19 4
The behaviour of the magnetic dipoles of atoms or ions determines the
macroscopic behaviour of the material
Three general types
Diamagnetic, paramagnetic, ferromagnetic (many variations, ferrimagnetic,
antiferromagnetic….)
3
Magnetic Phenomena
The general constitutive relation (relating flux density to field) for any
material can be written in many ways:
( )
0
B H M µ = +
Mis due to internal currents, H is developed by internal and external currents,
M is the magnetization and is the total magnetic moment of a sample (sum of
all atomic moments) divided by the volume of the sample.
M is a function of the applied field and can be described by the susceptibility, χ
( )
0
B H M µ +
i
m
M
V
¿
÷
( ) ( ) M H H H _ =
Mech 445 Cryogenic Engineering  Lecture 19 5
Susceptibility is related to permeability by,
So,
Or, in terms of “relative permeability”,
0
(1 ) µ µ _ = +
( )
0
1 B H µ _ = +
( )
0
1
r
µ
µ _
µ
÷ = +
0 r
B H µ µ =
Magnetic Materials
The three general magnetic material behaviours
can be described by their susceptibilities or
permeabilities:
Diamagnetic material – the flux density in a
di i i l i l h ld i i
M
ferromagnetic
diamagnetic material is less than would exist in
the same region of space if the material were not
there.
Susceptibility is small and negative.
Or, equivalently,
examples – copper, bismuth, silver
superconductors are perfect diamagnets,
Paramagnetic material – the flux density is higher
than with free space, but still have small
susceptibilities,
1
r
µ <
1
r
µ >
H
paramagnetic
diamagnetic
Mech 445 Cryogenic Engineering  Lecture 19 6
Examples – aluminum, platinum, many metals
Ferromagnetic – flux density is greatly enhanced,
very high permeabilities,
Examples – iron, cobalt, nickel, rare earth metals
and alloys.
Strong coupling between microscopic moments
causes nonlinear response to applied field.
1
r
µ >>
4
Magnetic Materials
Some ferromagnetic materials will retain
their net magnetization when the field is
removed B
permanent
magnet
These are called “permanent magnets” and
the remaining flux density, is called the
remnance, B
r
When a large enough field in a direction
opposite to the magnetization vector is
applied, the bulk magnetization will return to
zero.
The field strength required for this is called
the “coercive field”
New, rareearth permanent magnets have
l d i fi ld
H
ferromagnetic
paramagnetic
diamagnetic H
c
B
r
1
r
µ >
1
r
µ <
1
r
µ >>
Mech 445 Cryogenic Engineering  Lecture 19 7
very large remnance and coercive fields.
The strength of a permanent magnet is
usually specified in terms of the energy
stored.
The area in the second quadrant is an
indication of this
g
c
Magnetic Materials
Besides being a function of H, the magnetization can
also be (is) a function of temperature:
Why?
The atomic/molecular dipoles want to align with an external field,
but thermal vibrations act to prevent full alignment (saturation.)
As temperature decreases, greater alignment is possible.
For some materials, when a critical temperature is reached, the
material will change from paramagnetic to ferromagnetic  called
the Curie temperature.
( , ) M M T H =
Mech 445 Cryogenic Engineering  Lecture 19 8
p
This phenomenon leads to the magnetocaloric effect
and allows one to create a magnetic cycle.
5
Magnetocaloric Effect
Reversible temperature change when adiabatic change of magnetic
field – discovered by Warburg ~1881.
Not to be confused with eddy current heating due to Faraday’s Law =
i ibl irreversible.
Total entropy is a function of temperature and field, s(T,H).
1 2
T
2
B
aH
T
f
Mech 445 Cryogenic Engineering  Lecture 19 9
( , , )
L
MCE T T B B ÷ A A
1 2
s
1
B
aL
T
i
Magnetic Work
First, we need to understand the concept of
magnetic work
Imagine a magnetic body inside a
superconducting solenoid.
If current is constant, then the emf across
the battery is zero
When the current is not zero a field is
created by the coil and the material inside
becomes magnetized.
Assume that the magnetization is a single
valued function of current
Ie. there is no hystersis
( ) , I = M M r
Mech 445 Cryogenic Engineering  Lecture 19 10
If the body were not inside the solenoid,
the current would produce a magnetic flux
density which is a linear function of current
This is the external magnetic field, B
e ( )
e
I = B b r
Position in
system
Depends on
shape of coil
6
Work due to field change
Want to equate work done by power supply to magnetization of the system.
If the current is increased, the external field increases and the magnetic moment
changes in response
Th b tt d k t d thi Th t f k i i b The battery does work to do this. The rate of work is give by
The voltage (back emf) arises from two sources. One is the change in magnetic flux,
B
e
for an empty solenoid the magnetic work is equal to the change in energy of the magnetic
field
current x voltage
dW
IV
dt
= =
2
1
2
e
dW d B dV
µ
 
=
} 
\ .
Mech 445 Cryogenic Engineering  Lecture 19 11
And the integral is over the entire volume of the solenoid field.
The second contribution to the work is due to the magnetization of the system inside
the solenoid.
0
2µ
\ .
Magnetic Work
Consider a an elementary dipole at some position r. A current loop
with current i and an area a. The magnetic moment of the dipole is
then
If the current in the solenoid is I, the field produced by the solenoid at
i = m a
, p y
the dipole is,
The field creates a flux linkage through the small current loop given
by
The grouping ba is the mutual inductance (by definition) and using
Faraday’s law
(Mutual inductance relates the voltage induced in one coil to the current change in
a second coil)
( ) voltage
di
dt
= · (
¸ ¸
b r a
( ) B A I u = · = · b r a
( )
e
I = B b r
2
1 12
v
di
L
dt
¦ ¹
=
´ `
¹ )
Mech 445 Cryogenic Engineering  Lecture 19 12
)
And,
We can rewrite the above as,
And the work done by the battery is,
( ) voltage
d
dt
= ·
m
b r
voltage
e
d
I dt
= ·
B m
mag
e
dW
d
vI
dt dt
= = ·
m
B mag e
dW d = · B m
7
Magnetic Work
Where does this leave us with an expression for magnetic work?
The previous result applies for any single valued magnetic body not just an
elementary dipole.
The magnetic moment of the system can be determined by integrating the
magnetization over the entire volume of the system
So,
Or
The total work done by the power supply is thus
( )
T
dV =
}
m M r
mag
T
e e
dW
d d
dV
dt dt dt
= · = ·
}
m M
B B
( )
mag e
dW d dV = ·
}
B M Magnetization
per unit mass
Mech 445 Cryogenic Engineering  Lecture 19 13
The total work done by the power supply is thus,
And, the work performed by the magnetic material is,
( )
2
0
work on magnetic
work to develop material
external field
1
2
mag e e
dW d B dV d dV
µ
 
= + ·
} } 
\ .
B M
m e
dw dm = ÷ · B
Work per
unit mass
Internal Energy
For a simple magnetic substance (only work mode is magnetic) we can
write the the fundamental thermodynamic relation as
du q w o o = ÷
m e
du Tds dm = + · B
Therefore using Maxwell’s relations,
m s
u u
du ds dm
s m
c c    
= +
 
c c \ . \ .
m e e
dh u m Tds m d = ÷ · = ÷ · B B
m e
du Tds dm = + · B
( ) , u u s m =
u u
   
c c c c    
e
e B
s
T m
B s
  c c  
= ÷
 
c c \ .
\ .
m m
du q w o o
Magnetic energy ( ) ,
e
h h s = B Magnetic enthalpy
m e
du Tds dm + B
Mech 445 Cryogenic Engineering  Lecture 19 14
m s
s m
u u
m s s m
   
c c c c    
=
   
c c c c \ . \ .
\ . \ .
e
s m
B T
m s
c c    
=
 
c c \ . \ .
( ) ,
e
g g T = B
m e
dg h Ts sdT m d = ÷ = ÷ ÷ · B
e
e B
T
s m
B T
  c c  
=
 
c c \ .
\ .
Magnetic gibb’s energy
8
Magnetic Entropy
For a material with entropy as a function of temperature and field,
( , )
e
s T B e
e B
T
s s
ds dT dB
T B
  c c  
= +
 
c c \ .
\ .
Using the definition of heat capacity
And Maxwell’s relations
Therefore, for an isentropic field change
e
e B
T
\ .
\ .
B
e
e
T
c s
ds dT dB
T B
  c
= +

c
\ .
B
e
B
c m
ds dT dB
T T
c  
= +

c \ .
0
B
c m
dT dB
c  

T m
dT dB
c  

Mech 445 Cryogenic Engineering  Lecture 19 15
Integrating from initial field strength to final gives the magnetocaloric effect,
MCE
0
B
e
B
dT dB
T T
 
= +

c \ .
e
B B
dT dB
c T
= ÷

c \ .
f
i
B
e
B B B
T m
MCE dB
c T
c  
÷ ÷
}

c
\ .
Magnetocaloric materials
Where would MCE be
highest?
Paramagnets have a
e B B
d T T m
dB c T
A c  
÷ ÷

c
\ .
Paramagnets have a
constitutive relation of the
following form
Ferromagnetic materials near
the Curie temperature show a
large variation in M as a
f ti f t t d
, C "Curie constant"
e
CB
m
T
= =
μ
0
M
Gd
Mech 445 Cryogenic Engineering  Lecture 19 16
function of temperature and
applied field strength.
Much more complicated
expression to determine
magnetization
9
Magnetocaloric Effect
Rare earth elements and alloys demonstrate high
magnetocaloric effects. g
05 T
Mech 445 Cryogenic Engineering  Lecture 19 17
V. Pecharsky and K. Gschneidner, Adv. Cry. Eng. 43 (1998)
p. 1729
V.K. Pecharsky, K.A. Gschneidner Jr. / Journal of Magnetism and
Magnetic Materials 200 (1999) 44}56
Firstorder materials
Previous materials have secondorder phase change (2
nd
derivative of Helmholtz
energy is discontinuous) – heat capacity is continuous, but has a peak
Some new alloys undergo a firstorder magnetic ordering (phase change) (1
st
derivative of Helmholtz energy is discontinuous) heat capacity becomes infinite derivative of Helmholtz energy is discontinuous) – heat capacity becomes infinite
They all have hysteresis – not good.
Mech 445 Cryogenic Engineering  Lecture 19 18
10
Heat Capacity
Magnetic materials have an
additional energy storage mode
(mode of ordering). ( g)
The total entropy is a function
of lattice (vibration +
expansion), electronic, and
magnetic.
For materials that magnetically
( ) ( ) ( ) ( ) , ,
tot e latt elec mag e
s T B s T s T s T B = + +
Mech 445 Cryogenic Engineering  Lecture 19 19
For materials that magnetically
order at low temperatures, the
magnetic heat capacity can be
much larger than all other
components.
Materials
Disadvantages:
MCE small (~2 K/T)
Localized near magnetic phase transition
H t it f ti f T d B Heat capacity function of T and B
Gd
3
4
5
6
M
C
E
(
K
)
Gd
Tb
Gd
0.74
Tb
0.24
Gd
0.85
Er
0.15
(Dan'kov)
02 T
Mech 445 Cryogenic Engineering  Lecture 19 20
200 220 240 260 280 300 320
0
1
2
Temperature (K)
M
(UQTR)
(G&P)
(Tishin)
11
Single shot cooling
MCE has been used
for a long time to
achieve very low achieve very low
temperatures.
Precool paramagnetic
material in a high
field, thermally isolate
(thermal switch) then
remove the field
Mech 445 Cryogenic Engineering  Lecture 19 21
e ove e e d
~10
5
K possible
“Batch” Magnetic Cycles
Can imagine different
cycles analogous to
traditional gas cycles.
T B
H
Carnot
T B
H
Ericsson
Like gas cycles,
recuperation can increase
temperature span.
Advantages:
Solid refrigerant
(compact)
Reversible materials
(efficiency)
Inherent work recovery
T B
H
Brayton
s
B
L
s
B
L
T B
H
RBrayton
Mech 445 Cryogenic Engineering  Lecture 19 22
y
(efficiency x 2)
Benign materials
(sustainable)
s
B
L
s
B
L
i. antiferromagnetic…. dipole moment I Area of loop An electron orbiting an atom will g g generate a moment due to orbital angular g momentum In addition. β e h 27 2 9. ( H ) The concept of “magnetization”. is found by summing the spin. J. moments.27 10 A m me 2 The net magnetic moment. J SL The behaviour of the magnetic dipoles of atoms or ions determines the macroscopic behaviour of the material Three general types Diamagnetic. paramagnetic. and orbital. S.Magnetism Review Maxwell’s eqn for magnetic flux: Flux lines have no beginning or end – there are no magnetic monopoles (unlike charge.e. ferrimagnetic. therefore.) Mech 445 Cryogenic Engineering .Lecture 19 3 Magnetic Phenomena The magnetic moment arising from the current loop is. L.) B 0 The functional form of the permeability as a function of H defines different magnetic materials. a moment is generated by the “spin” moment of the electron The magnetic moment due to electron spin is defined as a Bohr magneton. ferromagnetic (many variations.Lecture 19 4 2 . arises from the impact of specific materials on flux density Can be explained by applying BiotSavart to atoms Electrons are charges in motion and. M. generate magnetic moments just as a coil of wire carrying a current will generate a magnetic moment Moment is determined when placed in external field – measure Lorentz force Mech 445 Cryogenic Engineering .
r B r 0 H Mech 445 Cryogenic Engineering . platinum. but still have small susceptibilities. M ferromagnetic Susceptibility is small and negative. diamagnetic Paramagnetic material – the flux density is higher than with free space. H is developed by internal and external currents. r 1 very high permeabilities. Examples – iron. χ M (H ) (H )H mi V Susceptibility is related to permeability by. r 1 examples – copper. rare earth metals and alloys. silver superconductors are perfect diamagnets.Lecture 19 5 Magnetic Materials The three general magnetic material behaviours can be described by their susceptibilities or permeabilities: Diamagnetic material – the flux density in a di diamagnetic material i l than would exist i i i l is less h ld i in the same region of space if the material were not there. in terms of “relative permeability”. nickel. Strong coupling between microscopic moments causes nonlinear response to applied field. cobalt. M M is a function of the applied field and can be described by the susceptibility. equivalently. 0 (1 ) 1 0 B 0 1 H Or. many metals Ferromagnetic – flux density is greatly enhanced. So. bismuth.Magnetic Phenomena The general constitutive relation (relating flux density to field) for any material can be written in many ways: B 0 H M M is due to internal currents. paramagnetic Or. r 1 H Examples – aluminum.Lecture 19 6 3 . M is the magnetization and is the total magnetic moment of a sample (sum of all atomic moments) divided by the volume of the sample. Mech 445 Cryogenic Engineering .
the bulk magnetization will return to zero. Mech 445 Cryogenic Engineering .Lecture 19 7 Magnetic Materials Besides being a function of H. d i fi ld Hc diamagnetic r 1 g H The strength of a permanent magnet is usually specified in terms of the energy stored.Lecture 19 8 4 . B Br permanent magnet ferromagnetic r 1 paramagnetic r 1 The field strength required for this is called the “coercive field” New. Br When a large enough field in a direction opposite to the magnetization vector is applied.) As temperature decreases. rareearth permanent magnets have very l large remnance and coercive fields. the magnetization can also be (is) a function of temperature: Why? The atomic/molecular dipoles want to align with an external field.called p the Curie temperature. is called the remnance.Magnetic Materials Some ferromagnetic materials will retain their net magnetization when the field is removed These are called “permanent magnets” and the remaining flux density. greater alignment is possible. H ) This phenomenon leads to the magnetocaloric effect and allows one to create a magnetic cycle. The area in the second quadrant is an indication of this Mech 445 Cryogenic Engineering . For some materials. when a critical temperature is reached. but thermal vibrations act to prevent full alignment (saturation. the material will change from paramagnetic to ferromagnetic . M M (T .
T Tf 2 BaH MCE T (T .H). BL . Assume that the magnetization is a single valued function of current Ie.Lecture 19 5 . the current would produce a magnetic flux density which is a linear function of current Position in system This is the external magnetic field. Not to be confused with eddy current heating due to Faraday’s Law = i ibl irreversible. B ) 1 2 BaL Ti 1 s Mech 445 Cryogenic Engineering . Total entropy is a function of temperature and field.Lecture 19 9 Magnetic Work First.Magnetocaloric Effect Reversible temperature change when adiabatic change of magnetic field – discovered by Warburg ~1881. there is no hystersis M M r. we need to understand the concept of magnetic work Imagine a magnetic body inside a superconducting solenoid. s(T. I If the body were not inside the solenoid. Be Be b(r ) I Depends on shape of coil 10 Mech 445 Cryogenic Engineering . If current is constant. then the emf across the battery is zero When the current is not zero a field is created by the coil and the material inside becomes magnetized.
voltage b r dWmag Be dm 12 Mech 445 Cryogenic Engineering . y the dipole is. The second contribution to the work is due to the magnetization of the system inside the solenoid. One is the change in magnetic flux. Be for an empty solenoid the magnetic work is equal to the change in energy of the magnetic field 1 2 dW d Be dV 2 0 And the integral is over the entire volume of the solenoid field. the field p produced by the solenoid at . A current loop with current i and an area a.Lecture 19 11 Magnetic Work Consider a an elementary dipole at some position r. dWmag dm vI Be dt dt And. voltage e I dt And the work done by the battery is. Be b(r ) I The field creates a flux linkage through the small current loop given by B A b r aI di dt The grouping ba is the mutual inductance (by definition) and using Faraday’s law voltage b r a di2 v1 L12 dt (Mutual inductance relates the voltage induced in one coil to the current change in ) a second coil) dm dt B dm We can rewrite the above as. The rate of work is give by d k t d thi Th t f ki i b dW current x voltage IV dt The voltage (back emf) arises from two sources. If the current is increased.Work due to field change Want to equate work done by power supply to magnetization of the system. The magnetic moment of the dipole is then m ia If the current in the solenoid is I. the external field increases and the magnetic moment changes in response The b tt Th battery does work to do this. Mech 445 Cryogenic Engineering .Lecture 19 6 .
Mech 445 Cryogenic Engineering . Be dg m h Ts sdT m dB e s m Be T T B e 14 Mech 445 Cryogenic Engineering . Be dhm u B e m Tds m dBe T m Be s s Be Magnetic gibb’s energy g g T . the work performed by the magnetic material is. m dum Tds Be dm u u du ds dm s m m s u u m s m s s m s m T Be m s s m Magnetic enthalpy h h s.Lecture 19 dwm B e dm 13 Internal Energy For a simple magnetic substance (only work mode is magnetic) we can write the the fundamental thermodynamic relation as dum q wm dum Tds Be dm Therefore using Maxwell’s relations. Magnetic energy u u s. thus And.Lecture 19 7 .Magnetic Work Where does this leave us with an expression for magnetic work? The previous result applies for any single valued magnetic body not just an elementary dipole. The magnetic moment of the system can be determined by integrating the magnetization over the entire volume of the system mT M (r ) dV So. dWmag dt Be dmT dM Be dV dt dt Magnetization per unit mass Work per unit mass Or dWmag Be dM dV 1 2 dWmag d Be dV B e dM dV 2 0 work on magnetic work to develop external field material The total work done by the power supply is thus.
for an isentropic field change c m 0 B dT dBe T T B dT Integrating from initial field strength to final gives the magnetocaloric effect. Mech 445 Cryogenic Engineering .Magnetic Entropy For a material with entropy as a function of temperature and field. s (T .Lecture 19 16 8 . MCE MCE Bf T m dBe Bi cB T B Mech 445 Cryogenic Engineering . Be ) Using the definition of heat capacity And Maxwell’s relations s s ds dBe dT T Be Be T s c ds B dT dBe T Be T c m ds B dT dBe T T B T m dBe cB T B Therefore. T C "Curie constant" d T T m dBe cB T B Gd Much more complicated expression to determine magnetization μ0M Ferromagnetic materials near the Curie temperature show a large variation in M as a function f t f ti of temperature and t d applied field strength.Lecture 19 15 Magnetocaloric materials Where would MCE be highest? Paramagnets have a constitutive relation of the following formm CBe .
Gschneidner. Mech 445 Cryogenic Engineering .Lecture 19 17 Firstorder materials Previous materials have secondorder phase change (2nd derivative of Helmholtz energy is discontinuous) – heat capacity is continuous.A. 43 (1998) p. Eng. Cry. K. 1729 V. Pecharsky and K.Magnetocaloric Effect Rare earth elements and alloys demonstrate high magnetocaloric effects. Pecharsky. but has a peak Some new alloys undergo a firstorder magnetic ordering (phase change) (1st derivative of Helmholtz energy is discontinuous) – heat capacity becomes infinite They all have hysteresis – not good.Lecture 19 18 9 . / Journal of Magnetism and Magnetic Materials 200 (1999) 44}56 Mech 445 Cryogenic Engineering . Gschneidner Jr. g 05 T V. Adv.K.
74Tb0. Be slatt T selec T smag T . Be Materials Disadvantages: MCE small (~2 K/T) Localized near magnetic phase transition Heat H t capacity function of T and B it f ti f d 6 02 T 5 Gd0.85Er0.Heat Capacity Magnetic materials have an additional energy storage mode (mode of ordering). and magnetic.24 Gd Gd Tb 4 M MCE (K) 3 (Dan'kov) (G&P) 2 (Tishin) (UQTR) 1 0 200 220 240 260 Temperature (K) 280 300 320 Mech 445 Cryogenic Engineering .Lecture 19 20 10 . the magnetic heat capacity can be much larger than all other components. Mech 445 Cryogenic Engineering .Lecture 19 19 stot T .15 Gd0. For materials that magnetically order at low temperatures. ( g) The total entropy is a function of lattice (vibration + expansion). electronic.
Like gas cycles. Advantages: Solid refrigerant (compact) Reversible materials (efficiency) Inherent work recovery y (efficiency x 2) Benign materials (sustainable) T Carnot BH T Ericsson BH BL BL s T Brayton s T RBrayton BH BH BL BL s Mech 445 Cryogenic Engineering . thermally isolate (thermal switch) then e ove e e d remove the field ~105 K possible Mech 445 Cryogenic Engineering .Lecture 19 s 22 11 .Single shot cooling MCE has been used for a long time to achieve very low temperatures.Lecture 19 21 “Batch” Magnetic Cycles Can imagine different cycles analogous to traditional gas cycles. Precool paramagnetic material in a high field. recuperation can increase temperature span.
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