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ENERGY CONVERSION USING PHASE TRANSFORMATION IN MULTIFERROIC MATERIALS
Yintao Song
Department of Aerospace Engineering and Mechanics,University of Minnesota
Ph.D. Final Exam, August 27th, 2013
Advisor: Richard D. James
Co-advisor: Thomas W. Shield
Page 2 of 34
About me
Born (December, 1987):
• Anqing, China
College (2004 - 2008):
• University of Science and Technology of China, Hefei, China
• Fluid mechanics, underwarter robots
Graduate school (2008 - 2013):
• University of Minnesota, Minneapolis, USA
• Ferromagnetic shape memory alloys
• Energy conversion using phase transformation
• Reversibility of martensitic phase transformation
August 27, 2013 Y. Song @ PhD Final Exam
Page 3 of 34
Multiferroic Phase Transformation
Multiferroic Phase Transformation
martensite austenite
heating
cooling
Phase Transformation
ferroelasticity
change crystalline lattice
Multiferroism
non-ferromagnetism
or (and)
non-ferroelectricity
ferromagnetism
or (and)
ferroelectricity
ferroic properties depend on the lattice
Y. Song @ PhD Final ExamAugust 27, 2013
Page 4 of 34
Example: NiCoMnSn
V. Srivastava, X. Chen, R. D. James, APL, 2010
Y. Song @ PhD Final ExamAugust 27, 2013
(5M) (L21)
Page 5 of 34
Example: NiCoMnSn – Cont.
permanent magnet
Ni45Co5Mn40Sn10
Y. Song @ PhD Final ExamAugust 27, 2013
Page 6 of 34
Demonstration Device
Y. Song, et. al., Energy Environ Sci, 2013
Y. Song @ PhD Final ExamAugust 27, 2013
Page 7 of 34
Working Cycle
HeatingCooling
N
S
M
V or I
t
V. Srivastava, Y. Song et. al., Adv Energy Mater, 2011
Y. Song @ PhD Final ExamAugust 27, 2013
Page 8 of 34
Where does the energy come from?
1st order phase trans.: trans. temp. & latent heat• water - ice: 0 °C and 334 J/g
• wax (fusion): 47 °C and 200 J/g
• NiCoMnSn: 130 °C and 13 J/g
Same for heating/cooling braches.
No work output!
Q : How can we make the trans. temp. & latent heat to be different for heating and cooling branches?
A : Biasing the trans. temperature by magnetic field.• Clausius-Clapeyron relation
Temp.
Entropy
Y. Song @ PhD Final ExamAugust 27, 2013
Page 9 of 34
Three Questions
How to determine the Clausius-Clapeyron
relation of a material?
How to use it to estimate efficiency and
power output?
How to make the best device?
Y. Song @ PhD Final ExamAugust 27, 2013
Page 10 of 34August 27, 2013 Y. Song @ PhD Final Exam
Clausius-Clapeyron Relation
Clausius-Clapeyron relation
martensite
austenite
Gibbs free energy
Page 11 of 34
Gibbs Free Energy Density
Free energy functional
Minimization
Assumption: such a function exists
• Uniform external field
• Unique minimizer – single phase
August 27, 2013 Y. Song @ PhD Final Exam
Page 12 of 34
Gibbs Free Energy – Example: NiCoMnSnDSC
Y. Song @ PhD Final ExamAugust 27, 2013
Y. Song, et. al., Energy Environ Sci, 2013
Page 13 of 34
Gibbs Free Energy – Example: NiCoMnSn
SQUID - Martensite
Y. Song @ PhD Final ExamAugust 27, 2013
Y. Song, et. al., Energy Environ Sci, 2013
Page 14 of 34
Gibbs Free Energy – Example: NiCoMnSn
Y. Song @ PhD Final ExamAugust 27, 2013
SQUID - Austenite
Y. Song, et. al., Energy Environ Sci, 2013
Page 15 of 34
Clausius-Clapeyron Relation : NiCoMnSn
Y. Song @ PhD Final ExamAugust 27, 2013
Y. Song, et. al., Energy Environ Sci, 2013
Page 16 of 34
Three Questions
How to determine the Clausius-Clapeyron
relation of a material?
• Gibbs free energy
• Calorimetry & Magnetometry
How to use it to estimate efficiency and
power output?
How to make the best device?
Y. Song @ PhD Final ExamAugust 27, 2013
Page 17 of 34
Y Song, et. al., Energy Environ Sci, 2013
Thermomagnetic
Carnot Cycle
Thermomagnetic
Rankine Cycle
Thermomagnetic
Ericsson Cycle
Predicted T-S Diagram: NiCoMnSn
Y. Song @ PhD Final ExamAugust 27, 2013
Page 18 of 34
Ideal Phase Transformation
Only transforms at temperature
given by the Clausius-Clapeyron relation
Only absorbs/emits heat during phase
transformation
Y. Song @ PhD Final ExamAugust 27, 2013
Page 19 of 34
Simplified Clausius-Clapeyron Relation
Dimensionless temperature ,
can be or
The dimensionless Clausius-Clapeyron coefficient
NiCoMnSn:
FeRh:
Y. Song @ PhD Final ExamAugust 27, 2013
Page 20 of 34
Rankine Cycle = Carnot Cycle
Efficiency
Power output
NiCoMnSn:
FeRh:
Y. Song @ PhD Final ExamAugust 27, 2013
Page 21 of 34
Thermomagnetic vs. thermoelectric
August 27, 2013 Y. Song @ PhD Final Exam
System = specimen only
System = the whole device
Page 22 of 34
Three Questions
How to determine the Clasius-Clapeyron
relation of a material?
How to use it to estimate efficiency and
power output?
How to make the best device?
Y. Song @ PhD Final ExamAugust 27, 2013
Page 23 of 34
The Back Field
Faraday’s law:
Ampère’s law:
ODE of current:
Y. Song @ PhD Final ExamAugust 27, 2013
Page 24 of 34
Quality Factor
Quality Factor
Heat Transfer
number of turns
height (thickness)
demagnetization factor basal area
resistance
Y. Song @ PhD Final ExamAugust 27, 2013
Page 25 of 34Y. Song @ PhD Final ExamAugust 27, 2013
Heat Transfer
Newton’s law of cooling
Solution
heat transfer coefficient
surface/volume ratio temperature of heat reservoir
Page 26 of 34
Figure of merit
Efficiency
Power output
Figure of merit
August 27, 2013 Y. Song @ PhD Final Exam
Page 27 of 34
Thermoelectric - ZT
July 17, 2013 Y. Song (UMN) @ 2013 BIRS Workshop
Curzon-Ahlborn Limit
1.8MG Kanatzidis’ research group
A Shakouri, Ann Rev Mater Res, 2011
Page 28 of 34July 17, 2013
Efficiency & Power Output
demonstration
optimization
Y. Song (UMN) @ 2013 BIRS Workshop
10
1
0.1
Carnot
C - A
TE ( )
Page 29 of 34
Maximum power output
Maximum power Carnot cycle
August 27, 2013 Y. Song @ PhD Final Exam
For our deviceFL Curzon, B Ahlborn, Am J Phys, 1975
Page 30 of 34
Small-z limit
When z is small:
August 27, 2013 Y. Song @ PhD Final Exam
Page 31 of 34
Three Questions
How to determine the Clasius-Clapeyron
relation of a material?
How to use it to estimate efficiency and
power output?
How to make the best device?
• high quality factor
• figure of merit in the order of unity
Y. Song @ PhD Final ExamAugust 27, 2013
Page 32 of 34
Conclusions• The idea of energy conversion using first order
multiferroic phase transformation is feasible
• The efficiency and power output of the demonstration device is not satisfactory. The issue can be solved by the following steps
• First, we need a material with a high Clausius-Clapeyron coefficient.
• Second, think about a design with a high Quality Factor.
• Finally, we get the figure of merit in the order of unity.
August 27, 2013 Y. Song @ PhD Final Exam
Page 33 of 34
Future Works - Similar MethodsPhase 1 Phase 2 Physics Notes
1. Ferromagnetic Nonmagnetic Faraday’s law Biasing by a permanent
magnet; external coil
2. Ferroelectric Nonferroelectric Ohm’s law Biasing by a capacitor;
polarization induced current
3. Ferromagnetic,
high-anisotropy
Ferromagnetic,
low-anisotropy
Faraday’s law Biasing by a permanent
magnet; intermediate field;
external coil
4. Ferroelectric,
high-permittivity
Ferroelectric,
low-permittivity
Ohm’s law Biasing by a capacitor;
intermediate field; polarization
induced current
5. Ferroelectric,
large near
Nonpolar Ohm’s law Second order phase trans.
biasing by a capacitor
6. Ferromagnetic,
large near
Nonmagnetic Faraday’s law Second order phase trans.
biasing by a permanent
magnet
7. Nonpolar,
nonmagnetic
Nonpolar,
nonmagnetic
Stress-
induced trans.
Faraday’s law
Shape memory engine driving
generator; biasing by stress
Y. Song @ PhD Final ExamAugust 27, 2013V Srivastava, Y Song et al., Adv Energy Mater 2011
Page 34 of 34
Acknowledgements
Advisor• Prof. Richard D. James
Collaborators• Vijay Srivastava
• Vivekandand Dabade
• Prof. Chris Leighton, Kanwal Preet Bhatti
• Xian Chen
Sponsors
• Demonstration
• Material development
• Characterization
• Functional fatigue
Y. Song @ PhD Final ExamAugust 27, 2013