Martes cuntico Zaragoza 26 de enero, 2016

Marco Evangelisti
Instituto de Ciencia de Materiales de Aragn
CSIC and Universidad de Zaragoza
50009 Zaragoza, Spain
WWW: http://molchip.unizar.es/

Nearly-quantumless
magnetic cooling
using molecules

magnetic cooling
MCE

+
quantum

Marco
Evangelisti

Cr

2000
2004
2006
2007
2008
2009
2010
2011

2012

2013

and many, many, many more...

icma

As of December 2012

Ideal materials
with designer
properties,
defined at the
molecular scale

From Molecule-based
magnetic coolers,
M. Evangelisti, in Molecular
nanomagnets: physics and
applications, Eds. J.
Bartolom, J. F. Fernndez
and F. Luis, Springer-Verlag

Marco
Evangelisti

icma

Definition and history

Magnetocaloric effect

Theoretical framework
Experimental determination

&

Suitable refrigerant materials

Magnetic refrigeration

Adiabatic demagnetization refrigerators

o Magnetically dense Gd-MOF

Molecular coolants
with examples

o Quantum signatures in {Gd7}

o Cooling by rotating {Dy2-ac}

only if we
have time

Magnetocaloric effect (MCE) is

Marco
Evangelisti

icma

heating produced in
magnetic materials
following an increase
of the applied
magnetic field,
and cooling when
the applied magnetic
field is removed.

Or just the opposite

in the inverse MCE.
4

Marco
Evangelisti

icma

Misconception
(it was
hysteresis
Emilirreversible,
Gabriel Warburg
(1846-1931)heat)
discovered the Magneto-Caloric Effect (MCE) in an iron sample,
which heated a few millikelvin when moved into a magnetic field
and cooled back when removed out of it.
[at Freiburg in 1881]
5

Marco
Evangelisti

icma

Nickel above room-T :

observation of heating
of 0.7 C for 1.5 T.

J. Phys. (Paris), 5th Ser. 7, 103-109

(1917)

Marco
Evangelisti

icma

William Francis Giauque (1895-1982)

Nobel laureate for his studies on the properties
of matter at temperatures close to absolute zero

[at University of California, Berkeley]

61g of Gd2(SO4)38H2O for 0.8 T, 1.5 K

0.25 K

Phys. Rev. 43, 768 (1933)

Student!

No. of degrees of freedom for a spin s

Marco
Evangelisti

(vase martes cuntico)

Tad = adiabatic
temperature change

ln(2s + 1)

magnetic entropy, Sm

icma

Sm = magnetic
entropy change

Tad

Sm

H1

H2

temperature,

T1

T2

Magnetic
entropy Sm vs
temperature
for paramagnet
under applied
fields H1 and
H2 > H1

The larger Sm and Tad, the better magnetic refrigerant

8

Marco
Evangelisti

icma

Differential
of entropy

where C is specific heat

For adiabatic process

at constant pressure

Next, we consider
the Maxwell relation

Marco
Evangelisti

icma

Maxwell
relation

Adiabatic temperature change:

Magnetic entropy change:

10

icma

Marco
Evangelisti

Experimental determination of MCE

indirectly from magnetization data: only

90 %
ln(2s + 1)

magnetic entropy, Sm

indirectly from specific heat data:+ magnetization

Tad

Sm

Hi

9.9 % + 90 %

temperature,

Hf

Ti

Tf

both specific heat and magnetization can be easily measured

11

Marco
Evangelisti

icma

Experimental determination of MCE

direct method (home-made):
Controlled non-adiabaticity, down to << 1 K
Known: thermal conductance ( ) of wires

T0 = bath temperature

and

Unpublished w/ E. Palacios

12

Marco
Evangelisti

icma

Suitability of refrigerants depends on target temperatures

Very-low temperatures (10 mK < T < 1 K): paramagnetic salts (e.g., cerium
magnesium nitrate, CMN); molecular nanomagnets (so-so).
Low temperatures (1 K < T < 10 K): magnetic nanoparticles; lanthanide
alloys; molecule-based magnetic materials (good).
Intermediate temperatures:
intermetallic and lanthanide alloys
(second-order phase transitions),
magnetic nanoparticles; moleculebased magnetic materials (bad).
Near-room temperature:
Gd and lanthanide-alloys
(first-order phase transitions).
13

ADR

Marco
Evangelisti

icma

Adiabatic
Demagnetization
Refrigerator

Analogy between magnetic refrigeration and vapor cycle or conventional refrigeration.

H = externally applied magnetic field; S = entropy; P = pressure.
14

Marco
Evangelisti

Magnetic order

icma

MCE

Magnetic phase transitions in >90% of publications on MCE

15

Marco
Evangelisti

MCE

Magnetic order

Second-order phase transition

1.0

H=0

0.8

C/R

icma

ISING - 3D ORDER
spin 1/2

0.6

0.4

Hap

0.2

0.0

0.7

T / TC

drawback:

No more entropy left below TC

Hap

0.5

Entropy / R

S m , Tad and RC
maximized at TC

H=0

0.6

0.4
0.3
0.2
0.1

Not suitable for

achieving very low T

0.0

T / TC

16

Marco
Evangelisti

Magnetic order

icma

MCE
PRL 78, 4494 (1997)

near-room tem perature

Gadolinium metal
ferromagnet at room-T

Giant
MCE

B = (9 0) T
orthorhombic < TC

monoclinic > TC

17

ADR

Marco
Evangelisti

icma

very-low tem perature

Adiabatic
Demagnetization
Refrigerator

A cryogen-free two-stage ADR using Gadolinium Gallium Garnet (GGG) and Ferric Ammonium Alum
(FAA) paramagnetic pills for the first and second stage, with Kevlar string supports for each stage. The FAA
18
stage reaches a base temperature below 50 mK, and remains @ 100 mK for more than 200 hours.

Marco
Evangelisti

ADR

Valid alternative to the use of 3He and 4He

very-low tem perature

Adiabatic
Demagnetization
Refrigerator

icma

Mcf

19

Marco
Evangelisti

ADR

icma

very-low tem perature

Adiabatic
Demagnetization
Refrigerator

ADR for
outer-space
applications
absence of gravity

e.g.,
high spectral resolution
observation of the diffuse
X-ray background in the
601000 eV energy range
using an array of 36
1 mm2 microcalorimeters
flown on a sounding rocket

D. McCammon et al., ApJ 576, 188 (2002)

20

Marco
Evangelisti

icma

High
magnetic
Ferric Ammonium
Alum,density for large MCE
as in commercial ADR
Mainstream, stiff competition and quantumless
For T between ca. 1 and 10 K

21

Marco
Evangelisti

High magnetic density for large MCE

icma

Gadolinium formate
Metal-Organic Framework (MOF)

Gd(OOCH)3

Rhombohedral lattice (R3m)

mw = 293 g/mol and = 3.86 g/cm3

Very high metal:non-metal mass
ratio among molecule-based materials
22

icma

Marco
Evangelisti

High magnetic density for large MCE

TC1

C/R

1.5

-0.5

energy / K

2.0

TC2

-1.0

-1.5

1.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0

T/K
Experiment
Monte Carlo

0.5

B0 = 0
0.0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

T/K
7

Classical Monte Carlo for a pure dipolar

system of isotropic spins arranged in a lattice
analogous to Gd formate.

5
Agrees with
experiments

Mmol / NB

Ferrimagnetic order at TC1 = 0.9 K (solid line)

made of alternating ferromagnetic 1D chains
along c axis, i.e., two up and one down.

experiment
B0 parallel to c

2
1
00.0

Unpublished magnetic ordering in progress

T = 0.4 K

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

B0 / T

23

icma

Marco
Evangelisti

High magnetic density for large MCE

150

26

100

13

50

B0 = (7 0) T
B0 = (3 0) T
B0 = (1 0) T

15

Huge cryogenic MCE

(ca. 0.5 K < T < 10 K)
even larger than GGG !

1.0

starting (Bi,Ti)

0.8
0.6

B/T

20

T / K

200

B0= (7 0) T
B0= (3 0) T
B0= (1 0) T

B
T
Tad

1.0
T/K

Sm / J kg-1 K-1

39

Sm / mJ cm-3 K-1

from: C

52

0.4

10
0.2

5
0

0.5

0.0
0

T/K

10

15

20

25

30

500

1000

tt0 / s

1500

2000

limited by TC2

A dense metal-organic framework for enhanced magnetic refrigeration, G. Lorusso et al., Adv. Mater. 25, 4653 (2013)

24

Marco
Evangelisti

icma

AF exchange interactions and MCE

Potentially quantum !
Though hardly observable w/o direct MCE measurements

25

Marco
Evangelisti

AF exchange interactions and MCE

icma

Paramagnets have linear isentropes,

giving a decrease in T as field is decreased.

Simplest interacting case:

let us consider a dimer of s1 = s2 = 1/2, i.e.,

Cooling rate:
A weakly dependent for small fields

Isentropes

B normal (paramagnet) for high fields

C drastically enhanced just above
level crossing
D heating just below level crossing

Enhanced MCE at fieldinduced level crossing

26

Marco
Evangelisti

AF exchange interactions and MCE

icma

Can be mapped onto

2D frustrated triangular
AF lattice

The [Gd7]
snowflake

27

AF exchange interactions and MCE

Marco
Evangelisti

icma

The [Gd7]
snowflake

Nat. Commun. 5, 12092 (2014)

28

= Ei E0 at B

AF exchange interactions and MCE

J1 = 0.09 K

Marco
Evangelisti

icma

J2 = 0.08 K

J1
J2

The [Gd7]
snowflake
Zeeman diagram calculated from spin Hamiltonian:

See also: Application of the finite-temperature Lanczos method for

the evaluation of magnetocaloric properties of large magnetic
molecules, J. Schnack and C. Heesing, Eur. Phys. J. B 86, 46 (2013)

Nat. Commun. 5, 12092 (2014)

29

AF exchange interactions and MCE

Marco
Evangelisti

icma

Frustration-enhanced MCE
Competing AF exchanges for J1 0 and J2 0

J1 = 0.09 K (as from experimental data)

J2 = 0.09, 0.08, 0.07, 0.06 K

J1
J2

Isentropes for S/R = 1

Non-degenerate
g.s. for J2 = 0

Expected experiments
for J2 = 0.08 K

The [Gd7]
snowflake

Low-energy states

Simulations

Nat. Commun. 5, 12092 (2014)

30

Marco
Evangelisti

AF exchange interactions and MCE

icma

The [Gd7]
snowflake
Home-made, sub-Kelvin
direct MCE
measurements

Experimental T corrected for energy dissipated via

wires (from addenda, C of sample and of wires)
and
Nat. Commun. 5, 12092 (2014)

31

AF exchange interactions and MCE

Marco
Evangelisti

icma

J1
J2
Experiments
The [Gd7]
snowflake
o Experiments no longer blind to exchange couplings.
= 0.09 K
cooling using magnetically-frustratedJ1molecules.
o Sub-Kelvin
Home-made,
sub-Kelvin
J2 = 0.08 K
direct MCE
o Feasible because of high-density of low-energy excitations,
measurements
especially in certain T-B regions.
Simulations
Nat. Commun. 5, 12092 (2014)

32

Marco
Evangelisti

icma

simulation

Isotropic or anisotropic MCE ?

simulation

33

Marco
Evangelisti

Isotropic or anisotropic MCE ?

icma

simulation

Example: magnetic specific heat, CSch,

of individual molecule with S = 10 and
anisotropy D = 0.5 or 1.5 or 3.0 K

MCE

Smaller anisotropy
Larger entropy change
Lower temperatures

Recipes for enhanced molecular cooling, M. Evangelisti and E. K. Brechin, Dalton Trans. 39, 4672 (2010)

34

Marco
Evangelisti

Cr

2000
2004
2006
2007
2008
2009
2010
2011

icma

As of December 2012

2012

2013

and many, many, many Gd more...

From Molecule-based
magnetic coolers,
M. Evangelisti, in Molecular
nanomagnets: physics and
applications, Eds. J.
Bartolom, J. F. Fernndez
and F. Luis, Springer-Verlag

35

Marco
Evangelisti

icma

36

Marco
Evangelisti

icma

Ideal rotocooler or rotoheater

Constant
applied field,
B

Magnetically
anisotropic
single-crystal

T decreases upon rotating from an easier to a harder magnetization direction.

T increases upon rotating from a harder to a easier magnetization direction.
37

Isotropic cooler:

Marco
Evangelisti

[{Gd(OAc)3(H2O)2}2]4H2O

icma

Parent molecule

First time: use of light ligands (carboxylates)

Larger magnetic density (but low TC)
Good for cryogenic MCE
Cryogenic magnetocaloric effect in a ferromagnetic molecular dimer,
M. Evangelisti et al., Angew. Chem. Int.-Ed. 50, 6606 (2011)

38

Anisotropic cooler:

Marco
Evangelisti

[{Dy(OAc)3(H2O)2}2]4H2O

icma

P-1 triclinic
View along the c axis

As expected,
significantly smaller
MCE (ca. 1/3) w.r.t.
Gd-analogue
but
Cooling by rotating a magnetically anisotropic molecular dimer,
G. Lorusso, O. Roubeau and M. Evangelisti, Angew. Chem. Int.-Ed. (2016, in press)

39

Anisotropic cooler:

Marco
Evangelisti

[{Dy(OAc)3(H2O)2}2]4H2O

icma

P-1 triclinic
View along the c axis
Single-crystal photograph

Magnetic anisotropy
easier to harder

B bc
B // b
No ordering

B // c

Cooling by rotating a magnetically anisotropic molecular dimer,

G. Lorusso, O. Roubeau and M. Evangelisti, Angew. Chem. Int.-Ed. (2016, in press)

a forms 300 w.r.t.

cristal plane

40

Anisotropic cooler:

Marco
Evangelisti

[{Dy(OAc)3(H2O)2}2]4H2O

icma

Dy3+ ion has ground state 6H15/2 (4f9)

C / J kg-1 K-1

100

Sm / J kg-1 K-1

Zero-field specific heat, C, from which: entropy

14
12
10
8

B=0

6
4

10

10

T/K

B=0
1

T3

T 2

10

T/K

Relatively high-T magnetic entropy, Sm, to 2Rln(2)

Cooling by rotating a magnetically anisotropic molecular dimer,
G. Lorusso, O. Roubeau and M. Evangelisti, Angew. Chem. Int.-Ed. (2016, in press)

effective spin s = 1/2

41

Anisotropic cooler:

[{Dy(OAc)3(H2O)2}2]4H2O

Marco
Evangelisti

icma

From
and zero-field
entropy, S(T,0)

field-dependent
S(T,B)

Magnetization measurements
on single-crystal
Cooling by rotating a magnetically anisotropic molecular dimer,
G. Lorusso, O. Roubeau and M. Evangelisti, Angew. Chem. Int.-Ed. (2016, in press)

42

Anisotropic cooler:

[{Dy(OAc)3(H2O)2}2]4H2O

Marco
Evangelisti

icma

Anisotropic MCE

easier

harder

TR = Tad(easier) Tad(harder)
Cooling by rotating a magnetically anisotropic molecular dimer,
G. Lorusso, O. Roubeau and M. Evangelisti, Angew. Chem. Int.-Ed. (2016, in press)

43

Anisotropic cooler:

[{Dy(OAc)3(H2O)2}2]4H2O

Marco
Evangelisti

icma

From ca. 4 to 1.5 K, by 900 in 5 T

Cooling by rotating a magnetically anisotropic molecular dimer,

G. Lorusso, O. Roubeau and M. Evangelisti, Angew. Chem. Int.-Ed. (2016, in press)

44

Marco
Evangelisti

Experimental rotocooler or rotoheater

icma

Right now (!)

implementing it
by recycling an
old rotator

Will allow direct

measurements of
the rotating MCE

Hoy a las 13hr !!

45

Marco
Evangelisti

icma

46