electronic structure of magnetocaloric systems
TRANSCRIPT
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Faculty of Physics and Applied Computer Science, AGH University of Science and Technology,
Krakow, Polandemail: [email protected]
Janusz TobolaG = G0 + G0VG
Electronic structure of magnetocaloric systems
lecture II
ΔSmag+ΔS lat= 0
Chaud FroidHot Cold
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Outline1. Magneto-caloric effect MCE (brief history
and introduction), giant MCE.
2. Entropy contributions and concept of MCEcooling – analogy to thermodynamic cycle;how to measure MCE ?
3. Illustrative examples of MC materials & experimental results- Gd5Si2Ge2 - RE alloys,- MnAs, MnFe(As-P), Fe2P, Mn3Sn2 – TM alloys.
4. Electronic structure of intermetallic MC compounds (MnAs, MnFeAs-P, …)
5. Concept of DLM (disordered local moments)- simulation of paramagnetic state within KKR-CPA method.
5. Estimation of entropy jump: mean field approach for magnetic entropy.
6. Estimation of lattice entropy from phonon calculations.
7. Summary
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Brief history of MCE discovery
Chaud FroidHotCold
Adiabaticmagnetization / demagnetisation
1881 E. Warburg, iron heats up in magnetic field ~0.5-2 K/1T, Ann. Phys. (1881)
1926 P. Debye (Nobel 1936, chemistry)
1927 W. Giauque (Nobel 1949, chemistry)
cooling via adiabatic demagnetization (order-disorder transition of magnetic moments in presence (or not) of magnetic field; for cryogenic purposes, down to 0.25 K (MacDougall, 1933).
1997 K. A. Gschneider & V. Pecharsky (Ames Lab., USA), PRL (1997) - discovery of
giant magnetocaloric effect :
MCE: an intrinsic property of magnetic materials;
MCE : the largest at the transition temperature, e.g. ferro-para
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IntroductionChaud FroidHot Cold
T(K)
M(T
)
TNTC
PMAFM
PMFM
AdiabaticMagnetisation / Demagnetisation
MCE
Intrinsic property of a material
Maximal at the transition temperature
Ferromagnet, Ferrimagnet, Antiferromagnet,Inhomogeneous Ferromagnet, Amorphous,Superparamagnet….
Type of magnetic transitions:FM-PM, AFM-PM, AFM-FM (but not so large)
ΔSmag+ΔS lat= 0
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Analysis of Ericsson cycle
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A
B
C
D
V=Vmax
V=Vmin
T
S
TF TC
A
B
C
D
H=Hma
x
H=0
T
S
TF TC
Analogy to thermodynamic cycle
Adiabatic magnetization/demagnetization
Ideal Carnot cycle :
. TH
TH TC
TC
Ericsson cycle
pressure P field B
volume V magnetization M
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Important conditions for giant MCE
What model to apply for ?
It depends first on the nature of the transition, on the typeof magnetic ordering, on the nature of the material….
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EntropySlat(T)Smag(T,B)
Se(T)
T~ Troom
S tot=S el+Smag+S lat ΔSmag+ΔS lat= 0Adiabatic Process
ΔSlat=C p(B,T )ΔTT
ΔT max=−TΔSmagC p (B,T )
Calorific Capacity
C p(B,T )
Magnetic Entropy
ΔSmag
ΔSmag (T,ΔB)=∫0
B
(∂M∂T )
BdB
ΔTmax
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Okamura (2007)
Kawanami (2007)
ASTRONAUTICS
rotary device (2001)Gschneider (2007)
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B = 5 T
[8]~280267 !!MnAs (under pressure)
[1-3][4] [5][6][7][7]
283305274272294313
301823
36.42.522
MnAs0.9Sb0.1
FeMn(As,P)La(Fe0.88Si0.12)13H1
Gd5Si2Ge2
GdFe49Rh51 (B = 2T)
SCTE200631635.7Mn0.98Ti0.02As
SCTE200627424Mn0.90Ti0.05V0.05As
SCTE200628630.5Mn0.98V0.02As
SCTE2006310 34.6Mn0.99Cr0.01As
[1]31840MnAs
ReferencesT [K]-S [J*kg-1*K-1]Compound
[1] H.Wada and Y. Tanabe, Appl. Phys. Lett. 79, 3302 (2001).[2] H.Wada, K. Taniguchi, and Y. Tanabe, Mater. Trans., JIM 43, 73 (2002).[3] H. Wada, T. Morikawa, K. Taniguchi, T. Shibata, Y. Yamada, and Y. Akishige, Physica B (Amsterdam) 328, 114 (2003).[4] O. Tegus, E. Bru¨ck, K. H. J. Buschow, and F. R. de Boer, Nature (London) 415, 150 (2002).[5] A. Fujita, S. Fujieda, Y. Hasegawa, and K. Fukamichi, Phys. Rev. B 67, 104416 (2003).[6] A.O. Pecharsky , K. A. Gschneidner, Jr.,V. K. Pecharsky, J. Appl. Phys. 93, 4722 (2003).[7] A.M. Tishin and Y. I. Spichkin, (Institute of Physics,Bristol and Philadelphia, 2003), 1st ed., Vol. 1, Chap. 11, p.351.[8] S.Gama et all, Phys. Rev. Let. 93, 237202 (2004)
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Pecharsky & Gschneider, 1997-2007
Giant MCE system
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K.Gschneider, 2007
New MCE materials
Entropy jump
Temperature jump
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Giant MCE – magnets demanded
Gschneider, 2007
0.1-100 kg / AMR
Active magnetic refrigerator(AMR), e.g. Gd, La-Fe-Si
Efficient magnetsNd-Fe-B
0.1-100 kg / AMR
Magnetic Bussiness & Technology (2007)
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Entropy contributions and relations to ab initio calculations
Phonon DOS is needed to estimate lattice contribution
BUT this can be approximativelydone e.g. from Debye model
Estimations of entropy can be made for electrons and phonons if DOS is known. Using Debye temperature, S
lat may be roughly estimated - allowing to interpret
S jump in experiment.
Stot
= Sel + S
mag+ S
lat
for hext = 0, the intergral gives Sel
Sel often sufficient
in MCE systems smaller than Smag
, Slat
de Oliveira, Eur. Phys. J. B (2004)
ΔSmag+ΔS lat= 0
adiabatic process
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Reminder: magnetic susceptibility
Free energy (Helmholtz)
Partition function
Magnetisation
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Reminder: Brillouin functions & Curie law
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Remider: magnetic ordering & molecular field theory (Weiss)
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Reminder: Heisenberg and Ising hamiltonians
Direct exchange
Super-exchange via non-magnetic ions
Indirect exchange via
conduction electrons
exchange integral (in eV)
ferro antiferro
1D in magnetic field
Magnetisation inIsing model
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Hexagonal (P-62m, #189) a = 5.872 Å, c = 3.460 Å, Z=32 Fe sites: 3f (small magnetic moment) & 3g (large magnetic moment)
Fe2P (magneto-elastic transition) at 217 K
TC increases from 217 K for Fe
2P to 235 K for Fe
1.85Ru
0.15P
Fruchart et al., Physica A (2005)Influence of electrons polarisation at E
F in
increase of TC, presence of small moment
0.4 /Ru, similar effect in Fe2-x
NixP
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Fe2P and MnFe(P-As)
Tobola et al., JMMM (1996)
Fe2P
MnFe(P-As)
Bacmann et al., JMMM (1994)
2.402.332.23Fe(3g)
0.600.800.59Fe(3f)
KKR-FPKKR-MTNeutrons
2.952.55Mn(3g)
1.251.24Fe(3f)
KKR-CPANeutrons
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Calculation of entropy contributions in Fe2-xTxP
B Wiendlocha, J Tobola, S Kaprzyk, R Zach, E K Hlil and D Fruchart, J. Phys. D: Appl. Phys. 41 (2008) 205007
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Entropy from electronic structure KKR-CPA & MFT
B Wiendlocha, J Tobola, S Kaprzyk, R Zach, E K Hlil and D Fruchart, J. Phys. D: Appl. Phys. 41 (2008) 205007
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Simulations of electronic structure above Curie temperature DLM (disordered local moments)
1. Analogy with chemical alloy within the coherent potential approximation) CPA with 2 atoms on 1 site.
2. atom A – Feup (iron with magnetic moment 'up') atom B - Fedown (iron with magnetic moment 'down')
3. A and B atoms occupy the same crystallographic site.
4. For concentration 50% the total magnetic moment per site and unit cell is zero, but the 'local' magnetic moments may be non-zero.
5. CPA medium is used to randomly distribute the magnetic moments among the sites (like in paramagnetic state)
KKR+CPA
TC =1250 K
Experiment
TC =1044 K Gyorffy et al., J. Phys. F (1985)
Fe
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Ground state properies KKR-CPA code
Total density of states DOS
Component, partial DOS
Total magnetic moment
Spin and charge densities
Local magnetic moments
Fermi contact hyperfine field
Bands E(k), total energy, electron-phonon coupling, magnetic structures, transport properties, photoemission spectra, Compton profiles, …
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Fe2P (ferromagnetic vs. 'paramagnetic' DLM state)
0.60
2.40
0.0 0.0
-2.12 +2.12
B Wiendlocha, J Tobola, S Kaprzyk, R Zach, E K Hlil and D Fruchart, J. Phys. D: Appl. Phys. 41 (2008) 205007
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Hexagonal NiAs-type structure (P63/mmc, #194) a = 3.730 Å, c = 5.668 Å, Z=2
MnAs (magneto-structural transition) at 318 K
Orthorhombic MnP-structure (Pnma, #62) a = 5.72 Å, b = 3.676 Å, c = 6.379 Å, Z=4
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MnAs in ferromagnetic state
NiAs-type MnP-type
3.10 2.96
In excellent agreement with neutron diffraction data : 3.14
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MnAs in 'paramagnetic' state
DLM (disordered local moments)
NiAs-type MnP-type
+3.02 -3.02 +2.89 -2.89
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soft mode near M point (phonon calculations)
Orthorhombic MnP-structure Hexagonal NiAs-type structure
MnAs phonon mechanism of magneto-structural phase transition
J. Lazewski, P. Piekarz, J. Tobola, B. Wiendlocha, P. T. Jochym, M. Sternik and K. Parlinski, PRL 104, 147205 (2010)
volume contration (V/V ~ 2%) near Curie temperature
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J. Lazewski, P. Piekarz, J. Tobola, B. Wiendlocha, P. T. Jochym, M. Sternik and K. Parlinski, PRL 104, 147205 (2010)
MnAs phonon mechanism of magneto-structural phase transition
Stot= -30 J/(K kg) for B = 5 Texperiment
giant coupling between the softmode and magnetic moments
theory Slat= +9.3 J/(K kg) ~ 4 THzEntropy jump mainly related to magnetic entropy
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Magnetocaloric effect in Mn3Sn2 (i) Mazet, Ihou-Mouko, and Malaman, Appl. Phys. Lett. 89, 022503 (2006)
Magnetic entropy
Magnetisation curves M(B, T)
MRC - maximum refrigerant capacity
5th Euroschool in Materials Science, Ljubljana, 24-29 May, 2010
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Magnetocaloric effect in Mn3Sn2 (ii)
Mazet, Ihou-Mouko, and Malaman, Appl. Phys. Lett. 89, 022503 (2006)
Hystheresis loops
MCE „figure of merit”
MRC = max of RC
RCP ~ 4/3 q
5th Euroschool in Materials Science, Ljubljana, 24-29 May, 2010
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Magnetocaloric effect in Mn3Sn2 (iii)
Heat capacity C(T, H)
Recour, Mazet, and Malaman J. Appl. Phys. 105, 033905 (2009)
5th Euroschool in Materials Science, Ljubljana, 24-29 May, 2010
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Adiabatic temperature change
Magnetocaloric effect in Mn3Sn2 (iv) Entropy change from magnetisation & heat capacity measurements
Recour, Mazet, and Malaman, J. Appl. Phys. 105, 033905 (2009)
5th Euroschool in Materials Science, Ljubljana, 24-29 May, 2010
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Summary
• The concept of DLM were sucessfully applied to study complex MCE systems: MnAs, MnFe(As-P), Fe2P by simulating paramagnetic state from KKR-CPA .
• MnAs - the calculated magnetic moment on Mn in DLM state (ortho) is comparable to FM state (hex), likely promoting large entropy jump near transition; phonon mechanism responsible for hex-ortho magneto-structural phase transition; giant spin-phonon coupling; Mn1-xTxAs - remarkable variation of local magnetic moments with T impurity.
• Fe2P - the magnetic moment appearing on Fe(3f) in FM state, completely vanishes in DLM state, while that one on Fe(3g) remains only slightly smaller.with respect to the FM state; MFT + KKR-CPA nicely reproduce entropy jump in disordered alloys.
• Mn3Sn2 - with two second-order magnetic transitions very interesting compound for MCE cooling ; more difficult for calculations – noncollinear magnetism.
• First principle calculations – helpful in interpretation and description of magnetocaloric materials. Best way is to combine electronic structure and phononcalculations to enabling to estimate entropy jump near transition temperature- crucial for large MC effect.
Illustrative examples