Magnetic Refirgeration

Magnetocaloric effect
materials for magnetic refrigeration
Ekkes Brck
Introduction Magnetic cooling Giant magnetocaloric effect Outlook

Review: E. Brck, Magnetic refrigeration near room temperature, Handbook of magnetic materials Vol 17 chapt. 4 (2007) ed. K.H.J. Buschow
1
Basic magnetocalorics Two energy reservoirs
spins
lattice
Basic magnetocalorics
spins
lattice
Domain movement
Magnetic cooling: Debye and Giauque 1926
61g Gd2(SO4)38H2O, B=0.8T, 1.5K 0.25K
Nobel prize 1949

5
Zeeman effect for state with total moment J
Ground state J is 2J+1 times degenerated: J =-J, -J+1, J

Splits in magnetic field into sublevels
z
J
E = g L B
Jz 2 1 0 -1 B -2
z
H P = B = z B E =< H P >= g Lande B J z B z

g Lande =
3 2
L (L + 1) S (S + 1)
2J (J
+ 1)
Spectroscopic splitting factor gLandee depends on L, S, and J Splitting at B=1 Tesla in the order of meV Atom behaves as if it has effective moment: eff=-gLBJ
6
Statistical physics description

When a system, in contact with a heat bath at temperature T can be in a state with energy E, the probability for this is given by the Gibbs rule:
where k is Boltzmann's constant. Z is called the partition sum,
Z is needed to have the proper normalization
The strength of statistical physics is that by calculating Z a lot of information about the system can be derived. The Helmholtz free energy is:
while the Gibbs free energy is:
Thermodynamic relations:
Differential of Gibbs free energy
S (T , B, p ) =
G T B ,p
,
M (T , B , p ) =
G B T , p
V (T , B , p ) =
G p T ,B
Entropy
Magnetization Differential of entropy
Volume
S S S dS = dp dT + dB + T B,p B T ,p p T ,B
9
Identification of terms
S dS = dT + dB Vdp T B T p CB p
, ,
S M Maxwell relations = B T
Magnetic entropy
Adiabatic process at constant pressure
T S dT = dB C B p B T p
, ,
T B
S m =
B
M dB T B
10
From definition of specific heat
S0 can be set to zero because it is not depending on field
Easy measurable
11
Experimental determination from magnetic measurements
M +1 (T +1 , B) M (T , B) S (T , B) = B T +1 T
i i i i m i i i
12
Continuous phase transition

In the absence of an external field, H=0, the system with exchange interaction J/k=1may spontaneously order.
1 1 1 1 1 2 F = NJm - NHm+NT ( -m) ln ( -m)+( +m) ln ( +m) 2 2 2 2 2 T=0.2J/k

T=0.25J/k T=0.3J/k
13
First order phase transition

If interactions with quartets play a role this may result in local minima in the free energy.
1 1 1 1 1 4 F = NJm - NHm+NT ( -m) ln ( T=0.0225 -m)+(J/k +m) ln ( +m) 2 2 2 2 2
T=0.02 J/k
T=0.025 J/k
14
MCE in iron 10 6T 0T
Cp [J/mol K] T [K]
3T
3T 0.8T 0
T [K]
15
Magnetic ordering T
T [ C]
MCE in gadolinium
Total entropy vs reduced temperature of gadolinium in low field (blue) and high field 9T (purple) (Gschneidner et al)
16
MCE in gadolinium
Magnetic entropy change (green left scale) and Temperature change (red right scale) Derived from specific heat data. (Gschneidner et al)
17
The magnetocaloric properties of selected binary intermetallic compounds
TC (K) Compound Gd4Bi3 Gd4(Bi2.25Sb0.75) Gd4(Bi1.5Sb1.5) Gd4(Bi0.75Sb2.25) Gd4Sb3 Gd2In Gd2In
aTemperature
-SM (mJ/cm3K) 0-2T 0-5T 27 47 47 49 55 37 -4 0-2T 2.2 3.7 3.1 3.2 3.2 2.0 -0.7
Tad (K) 0-5T 4.2 6.8 6.5 6.4 6.4 4.4 -0.2
Dens. (g/cm3)
332 308 289 273 265 194 ~50a
15 27 24 26 29 18.5 -12
10.073 9.679 9.259 8.834 8.414 8.316 8.316
at which SM has the largest positive value and Tad has largest negative MCE value
Ilyn M I, Tishin A M, Gschneidner K A Jr, Pecharsky V K and Pecharsky A O 2001 Cryocoolers 11 ed R G Ross Jr (New York: Kluwer Academic/Plenum) p 457 Niu X J, Gschneidner K A Jr, Pecharsky A O and Pecharsky V K 2001 J. Magn. Magn. Mater. 234 193
18
The magnetocaloric properties of selected binary intermetallic compounds
TC (K) Comp. Nd2Fe17 Gd7Pd3 TmAg TmAg TmCu TmCu
aTemperature bMaximum
-SM (mJ/cm3K) 0-2T 0-5T 46 57 74c -55c 118c -131c 0-2T 1.9 3.0 0.8 -0.4 0.6 -0.4
Tad (K) 0-5T 4.0 8.5 4.2c -0.9c 3.6c -1.8c
Density (g/cm3)
325 323 ~12b ~ 7a ~10b 6.7d
25 22 11 -26 25 -68
7.797 8.707 10.169 10.169 9.692 9.692

dNel
at which SM has the largest positive value and Tad has largest negative MCE value cInterpolated in MCE (no magnetic ordering observed at this temperature)
temperature
Dankov S Yu, Ivtchenko V V, Tishin A M, Gschneidner K A Jr and Pecharsky V K 2000 Adv. Cryog. Engin. 46 397 Canepa F, Napoletano M and Cirafici S 2002 Intermetallics 10 731 Rawat R and Das I 2001 J. Phys.: Condens. Matter 13 L379
19
The magnetocaloric properties of selected ternary intermetallic compounds.
T Ca
-SM (mJ/cm3K) 0-2T 0-5T 79 80 125 142 171 0-2T ------3.2 ---
Tad (K) 0-5T ------8.6 ---
Dens. (g/cm3)
Compound GdCoAl TbCoAl DyCoAl GdPd2Si HoCoAl 100 70 37 17 10
37 41 70 42 100
7.575 7.649 7.619 9.358 7.961
Zhang X X, Wang F W and Wen G H 2001 J. Phys.: Condens. Matter 13 L747

20
dimensionlless lattice heat capacity of three solids with different Debye temperatures, D, vs. temperature
1.0
D = 150 K
Lattice heat capacity, CL/R
0.8
D = 350 K
0.6
D = 250 K
0.4
0.2
0.0 0 50 100 150 200 250 300

21
Temperature, T (K)
Rules for magnetocaloric effect
Larger moment larger S & T Smag J Lower temperature larger S & T Lower thermal agitation Lower heat capacity
22
Magnetic refrigeration:
External magnetic field changes entropy of magnetic moments
No CFCs, easy scalable, high efficiency, permanent magnets

23
Chubu and Toshiba Refrigerator 2003
Gd metal Rotating magnet 0.76 T Cooling power 60 W T span 20 K

24
25
Other AMR prototypes
Name Ames Laboratory/ Astronautics Barcelona University of Victoria Lab. Electric Grenoble Astronautics AMR Type reciprocatin g rotary reciprocatin g reciprocatin g rotary rotary reciprocatin g reciprocatin g AMR Material Gd spheres Gd foil Gd , Gd Tb
.74
Magnetic Field (T) 5 (S) 0.3 (P) 2 (S) 0.8 (P) 1.5 (P) 1 (P) 2.18 (E) 2.0 (S)
Remarks COPT 10 Olive oil epoxy bonded pucks COPR 2.2 4 Hz Torque 10 Nm COPT 25
T 50K
Ref.
(Zimm et al. 1998) (Bohigas et al. 2000) (Richard et al. 2004) (Clot et al. 2003) (Zimm et al. 2006)
(Vasile et al. 2006) (Gao et al. 2006)
.26
Gd foil Gd, Gd-Er, spheres LaFeSiH particles Gd plates Gd spheres; Gd5(Si,Ge)4 pwdr. Gd , Gd Tb
Natl Inst. Appl. Sci. / Cooltech Xian Jiaotong Univ.

University of Victoria
Gd Er
.74 .85
.26
.15
(Rowe et al. 2006)

26
Replace Gd with material with large MCE
1990 FeRh (Nikitin et al.) 1997 Gd5Si2Ge2(Percharsky & Gschneidner Jr.) 1998 RCo2 (Foldeaki et al. ) 2000-2002 La(Fe,Si)13 (Zhang et al., Fukamichi et al.) 2001 MnAs1-xSbx (Wada et al.) 2002 MnFe(P,As) (Tegus et al.) 2003 Co (S1-xSex)2 (Yamada & Goto)
27
Giant magnetocaloric effect in Gd5Ge2Si2
Magnetically dilute yet higher effect double transition?
Pecharsky & Gschneidner PRL 78 (1997) 4494
28
Crystal growth
D=4mm Sphere was cut by spark erosion from as grown rod
Crystal was grown in a mirror furnace by means of traveling solvent floating zone method
29
Unusual behavior
Extraordinary magnetic behavior: first-order character of the paramagnetic-ferromagnetic transition.
3.0 2.5
Gd5Si 1.65Ge 2.35 Crystal Sphere d=4mm B=0.05T Stepwise heating mode
2.0
M (B /f.u.)
1.5
a b c
40
1.0
0.5
30
0.0 0 50 100 150 200 250 300
600 350 550
400
M (B/f.u)
20
T (K)
a b c
500 450 400
C (J/molK)
10
Gd5Ge2.35Si1.65 crystal Sphere d=4mm at 5K

0 0 1 2
350 300 250 2003
150 B (T) 100 50 0 0 20 40 60 80 100 120 140 160 180 200 220 240 260
T (K)
30
Unusual behavior
The high temperature paramagnetic monoclinic phase transforms to the low temperature ferromagnetic orthorhombic phase. The low temperature phase has a higher symmetry than the high temperature, which is the opposite of what is normally observed for other polymorphic systems.
<Tc: Pnma, No.62
>Tc: P1121/a, No.14

31 Crystallographic data comes from W Choe PRL v84, n20, p4617, 2000
Unusual behavior
Volume decreases when cooling through the transition, i.e., the cell volume in the low-temperature ferromagnetic phase is smaller ( v>0.4%) than in the high-temperature paramagnetic one. This is in contrast with the general physical picture of the magnetovolume effects which are transtions from a lowvolume low-moment to a high-volume high-moment state.
Normal:
Unusual:
32
Unusual behavior
Gd5Si4 based orthorhombic Pnma Ferro magnet Q.L.Liu et al.
Recent XRD investigation reported that Gd5(SixGe1-x)4 alloys form a completely miscible solid-solution crystallized in the Gd5Si4-type Pnma structure below TC regardless of the composition. Ground state is low temperature (Gd5Si4based) orthorhombic ferromagnet
Temperature of structural phase transition always coincides with Curie temperature TC.
33
What is responsible for the unusual behaviors?
b a
x > 0.5 Gd5Si4 type Pnma
0.4 < x < 0.5 Gd5Si2Ge2 type P1121/a (Gd3+)5(T26-)1.5(T4-)(2e-)
x < 0.3 Gd5Ge4 type Pnma (Gd3+)5(T26-) (T26-)2 (1e-)
T=Si, Ge (Gd3+)5(T26-)2(3e-)
Breaking Breaking and and making making bond bond
RKKY RKKY or or superexchange superexchange
V. K. Pecharsky and K. A. Gschneidner, Jr., J. Alloys Compd. 260, 98-106 (1997) 34
Summary Gd5Ge2Si2
Magnetically driven 1st order structural transition below 270 K. Gd5Ge2Si2 monoclinic above magnetic transition orthorhombic below. Anisotropy on X-tals. Exceptional coupling of lattice with s-state 4f-magnetism.
Hysteretic transition: locking of structure? Mechanical stability?

35
Transition-metal compounds
other alternative
High abundance (low price) Intermediate magnetic moment (moderate MC effect) Strong coupling to lattice (Simultaneous magnetic and structural transitions or metamagnetism)
36
La(Fe,Si)13 compound
Cubic CaZn13 type of structure stabilized by addition of 10% Si (Kripyakewich et al. 1968) Invar type of behavior and unusual magnetic transition (Palstra et al 1983) Difficult to obtain single phase.
37
Concentration dependence of Curie temperature and moment
Tc increase with dilution
Palstra et al. 1983

38
LaFe13 system
MCE decrease with dilution
APL Zhang et al 2000 Fujieda et al 2002

39
LaFe13 system with hydrogen
Tc increase with hydrogen! Sharp transition maintained!

PRB Fujita et al 2003
40
LaFe13 system with hydrogen
MCE almost not affected with hydrogen
PRB Fujita et al 2003

41
Summary La(Fe,Si)13
Field driven 1st order metamagnetic transition around 200 K . La(Fe,Si)13 cubic above magnetic transition cubic below volume change 1.5%. Low Tc can be increased by addition of Cobalt or Hydrogen. Hysteretic transition: powder after hydrogenation? Mechanical stability?
42
MnFeP1-xAsx Hexagonal Fe2P type of structure
Space group: _ P62m Mn 3g sites Fe 3f sites P/As 1b&2c sites
Bacmann, JMMM 1994 43
Sample preparation
Starting Fe2P, Mn2As3, Mn & P mechanical alloying sintering 1000oC annealing 800oC
44
Temperature dependence of magnetization with different compositions
Tc tunable
45
Temperature dependence in different fields
Strong shift of Tc with field

46
Magnetization process near Tc
Field induced transition with small hysteresis

47
Concentration dependence of TC for MnFeP1-xAsx
340 320 300 280 PM
T (K)
Somewhat higher TC compared with lit. Almost linear concentration dependence.
260 240 220 200 180 160 0.2 0.3 0.4 0.5 0.6 0.7
48
FM
Comparison with Gd metal
Step-like transition first order
but very little hysteresis

49
Comparison of magnetocaloric effect in different materials
Entropy change concentrated in relevant T interval
Tegus et al. Nature 415

50
MCE as function of composition
35 30 25
MnFeP 1-xAs x
x=0.35 x=0.45 2T 5T x=0.5 x=0.55 x=0.65
x=0.25
-Sm(J/kgK)
Broad T interval covered
20 15 10 5 0 150 200 250
300
350
51
T (K)
Adiabatic temperature-change
5
Mn1.1Fe0.9P0.47As0.53
B = 1.45 T
4
MnFeP0.47As0.53
Tad (K)
MnFeP0.45As0.55
3 2
Sample dependence need for careful 1 preparation

0 285 290 295 300 T (K) 305 310 315
Direct measurements MSU

52
Summary MnFe(P,As)
Field driven 1st order magnetoelastic transition 150 K < Tc < 450 K . MnFe(P,As) hexagonal above magnetic transition hexagonal below. Hardly any volume change( 0.1 %) but change of c/a.
Hysteretic transition: Hysteresis depends on grain size? High chemical stability allows As content?
53
Conclusions
First order magnetic transition common to the different systems! Structural transition may cause extra hysteresis. Control of hysteresis very important. Evaluation of entropy change needs care. Fe and Mn based systems with much lower materials costs. Relevant T range covered by La(Fe,Si)13Hx and MnFe(P,As,Si,Ge). Sample preparation simplest for MnFe(P,As) with As replaced by other element.
54
Outlook
Cooltech current N4 Prototype

IMPORTANT issues: 1 The AMRR Cycle (Active Magnetic Regenerator Refrigeration): with Gd inserts as cross-flow plate heat-exchangers. 2 - Amplification of by accumulation of cycles. 3 - Reduction in torque (10 Nm) obtained by ensuring a ferromagnetic continuity on the disc. 4 - Very low level of noise and vibrations (< 25 dB) 5 - Creation of magnetic fields of 0.7 to 2 Tesla with standard permanent magnets. 6 - Low thermal losses, completely separate hot and cold fluid circuits.
55
Registered Patents, Brand and Models
Availability
Limiting ingredient Gd metal Gadolinium Silicon alloys Gd4(Si1-xGex)5 Manganese alloys Gd Ge Estimated availability 1000 WW prod=90t, avail 10t ? Total availability of MC material 1000t 140t
Mn(As1-xSbx) MnFe(P1-xAsx)
Lathanum alloys
none
none
No limitation for an industrial production
La(Fe13-xMx)
Manganites
La
4000
22000t
LaMnO3
Ni0.501Mn0.227Ga0.258
La
4000 WW prod=90t, avail 10t ?
7000t
Ga
60t?
56
Data : Cooltech source and USGS.GOV
25 20 15 10 5 0 0 20 40
T (C0)
57
Increased T span with active magnetic regenerator containing different materials with tailored TC
S (J/Kkg)
60
80

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Magnetocaloric effect

materials for magnetic refrigeration

Introduction Magnetic cooling Giant magnetocaloric effect Outlook

Basic magnetocalorics Two energy reservoirs

61g Gd2(SO4)38H2O, B=0.8T, 1.5K 0.25K

Nobel prize 1949

Ground state J is 2J+1 times degenerated: J =-J, -J+1, J

H P = B = z B E =< H P >= g Lande B J z B z

Statistical physics description

where k is Boltzmann's constant. Z is called the partition sum,

while the Gibbs free energy is:

Magnetization Differential of entropy

Adiabatic process at constant pressure

S0 can be set to zero because it is not depending on field

Continuous phase transition

1 1 1 1 1 2 F = NJm - NHm+NT ( -m) ln ( -m)+( +m) ln ( +m) 2 2 2 2 2 T=0.2J/k

First order phase transition

1 1 1 1 1 4 F = NJm - NHm+NT ( -m) ln ( T=0.0225 -m)+(J/k +m) ln ( +m) 2 2 2 2 2

332 308 289 273 265 194 ~50a

10.073 9.679 9.259 8.834 8.414 8.316 8.316

Tad (K) 0-5T 4.0 8.5 4.2c -0.9c 3.6c -1.8c

325 323 ~12b ~ 7a ~10b 6.7d

7.797 8.707 10.169 10.169 9.692 9.692

Tad (K) 0-5T ------8.6 ---

Compound GdCoAl TbCoAl DyCoAl GdPd2Si HoCoAl 100 70 37 17 10

7.575 7.649 7.619 9.358 7.961

Zhang X X, Wang F W and Wen G H 2001 J. Phys.: Condens. Matter 13 L747

Lattice heat capacity, CL/R

0.0 0 50 100 150 200 250 300

External magnetic field changes entropy of magnetic moments

No CFCs, easy scalable, high efficiency, permanent magnets

Gd metal Rotating magnet 0.76 T Cooling power 60 W T span 20 K

Natl Inst. Appl. Sci. / Cooltech Xian Jiaotong Univ.

(Rowe et al. 2006)

Magnetically dilute yet higher effect double transition?

Pecharsky & Gschneidner PRL 78 (1997) 4494

D=4mm Sphere was cut by spark erosion from as grown rod

0.0 0 50 100 150 200 250 300

600 350 550

500 450 400

Gd5Ge2.35Si1.65 crystal Sphere d=4mm at 5K

350 300 250 2003

<Tc: Pnma, No.62

>Tc: P1121/a, No.14

Gd5Si4 based orthorhombic Pnma Ferro magnet Q.L.Liu et al.

What is responsible for the unusual behaviors?

x > 0.5 Gd5Si4 type Pnma

0.4 < x < 0.5 Gd5Si2Ge2 type P1121/a (Gd3+)5(T26-)1.5(T4-)(2e-)

x < 0.3 Gd5Ge4 type Pnma (Gd3+)5(T26-) (T26-)2 (1e-)

Breaking Breaking and and making making bond bond

RKKY RKKY or or superexchange superexchange

V. K. Pecharsky and K. A. Gschneidner, Jr., J. Alloys Compd. 260, 98-106 (1997) 34

Hysteretic transition: locking of structure? Mechanical stability?

Tc increase with dilution

Palstra et al. 1983

MCE decrease with dilution

APL Zhang et al 2000 Fujieda et al 2002

Tc increase with hydrogen! Sharp transition maintained!

MCE almost not affected with hydrogen

PRB Fujita et al 2003

Space group: _ P62m Mn 3g sites Fe 3f sites P/As 1b&2c sites

Bacmann, JMMM 1994 43

Strong shift of Tc with field