Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on...
Transcript of Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on...
![Page 1: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/1.jpg)
Magnetocaloric properties of
reactively sintered La(Fe,Co,Si)13
M. Katter, V. Zellmann, G.W. Reppel, K. Uestuener
Vacuumschmelze GmbH & Co. KG
Delft Days on Magnetocalorics
![Page 2: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/2.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 2
overview magnetic materials
Pure Fe,
FeCo
C-Steels
Fe
Powder cores
Ni-Fe
Hard ferrites
Cu Ni Fe
AlNiCo
AmorphousCo-based
Nanocrystalline
FeNi (medium)
FeNi 80%(Permalloys)
FeSiAl
Cr-, Co- Steels
CoFeNiFeCoCrFeCoVFeMnNiTi
FeCoVCr
NdFeBRE-Co
MnAlC
Pt Co
Fe Cr Co
2.5
2.0
1.5
1.0
0.5
0
Sat
urat
ion
mag
netiz
atio
nJ
s/ T
soft magnetic hard magneticsemi hardmagnetic
Soft ferrites
Coercivity Hc /(A/cm)
2.5
2.0
1.5
1.0
0.5
00.1 1 10 100 103 1040.010.001
Rapid Solidification Rolling Process Powder Route
FeNiAlTi
3%FeSi
Rem
anec
eB
r/ T
NdFeBbonded
SMCPure Fe,
FeCo
C-SteelsC-Steels
Fe
Powder cores
Ni-Fe
Hard ferrites
Cu Ni Fe
AlNiCo
AmorphousCo-based
Nanocrystalline
FeNi (medium)
FeNi 80%(Permalloys)
FeSiAl
Cr-, Co- Steels
CoFeNiFeCoCrFeCoVFeMnNiTi
FeCoVCr
NdFeBRE-Co
MnAlC
Pt CoPt Co
Fe Cr Co
2.5
2.0
1.5
1.0
0.5
0
Sat
urat
ion
mag
netiz
atio
nJ
s/ T
soft magnetic hard magneticsemi hardmagnetic
Soft ferrites
Coercivity Hc /(A/cm) Coercivity Hc /(A/cm)
2.5
2.0
1.5
1.0
0.5
00.1 1 10 100 103 1040.010.001 0.1 1 10 100 103 1040.010.001
Rapid Solidification Rolling Process Powder Route
FeNiAlTi
3%FeSi
Rem
anec
eB
r/ T
NdFeBbonded
SMC
![Page 3: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/3.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 3
new magnetocaloric materials
K. Gscneidner (2007)
accessable withNd-Fe-B magnets
![Page 4: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/4.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 4
magnetocaloric materials
target operating range
most promising at the moment: La-Fe-Si
Spe
cific
etr
opy
dens
ity (
∆S/l/
∆H)
poisonous
expensive, limited temperature range
poisonous
small effectGdLaMnO3
MnFePAs
MnAsLaFeSi (…)
GdSiGe
Cooltech Applications (2008)
![Page 5: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/5.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 5
- casting- anneal, e.g. 1080°C/140 h- optionally load with hydrogen
⇒ long annealing times, ⇒ with hydrogen only powder
- melt spinning- short anneal, e.g. 1000°C/2 h
⇒ only flakes or powder, no shaped parts for heat exchangers
conventional preparation of La(Fe,Si)13
-30
-25
-20
-15
-10
-5
0
180 210 240 270 300 330 360
T (K)
∆∆ ∆∆S
m (
J/k
g K
)
La(Fe0.88Si0.12)13Hy
y = 0.0 0.5 1.0 1.5
S. Fujieda et al. 2005F.X. Hu et al. 2005 (with Co)
O. Gutfleisch et al. 2005S. Hirosawa et al. 2006
![Page 6: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/6.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 6
Designs for active magnetic regenerators
J.A. Barclay and S. Sarangi 1984 in A.M. Tishin and Y.I. Spichkin 2003
large pressure dropsin powder beds?
![Page 7: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/7.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 7
Powder Metallurgical (PM) Processing of La-Fe-Si
P
Vacuum InductionAlloying and Casting
Crushing
Milling
Blending
Pressing:CIP - die
isostaticpressing
die-pressing
elemental powders
![Page 8: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/8.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 8
Powder Metallurgical (PM) Processing of La-Fe-Si
P
Pressing:CIP - die
die-pressing
Isostaticpressing
Reactive Sintering
Machining and Surface Finishing
![Page 9: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/9.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 9
La(Fe0.915Si0.085)13
powder blend of Fe, Si and LaHx(no melting at all)
milled to F.S.S.S. < 5 µm
isostaticallypressed
sinteredat 1120°C/4h
density = 6.6 g/cm3 sample: 4,2 x 2 x 1,2 mm
0.00
0.20
0.40
0.60
0.80
1.00
1.20
-100 -95 -90 -85 -80 -75
temperature T (°C)
pola
rizat
ion
J (T
)
17.0
15.3
13.6
11.9
10.2
8.5
6.8
5.1
3.4
1.7
Kühlrate: - 14 K/min
H (kOe)
![Page 10: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/10.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 10
La(Fe0.893Si0.107)13, sintered
-30
-25
-20
-15
-10
-5
0
180 210 240 270 300 330 360
T (K)
∆∆ ∆∆S
m (
J/k
g K
)
La(Fe0.88Si0.12)13Hy
y = 0.0 0.5 1.0 1.5
dHT
HTMS
HP
H
T,
0
),(∫
∂∂=∆
S. Fujieda et al. 2005, 0 - 2 bzw. 0 - 5 T
external magnetic field strength H (kOe)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
180 185 190 195 200 205 210
temperature T (K)
pola
rizat
ion
J (T
)
2,0
16
10
5
2
H (kOe)
0
5
10
15
20
25
180 185 190 195 200 205 210
temperature T (K)
- ∆∆ ∆∆S
mag
n (
J/kg
K) 16
12
8
4
H max (kOe)
![Page 11: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/11.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 11
0
1
2
3
4
5
180 190 200 210
temperature T (K)
∆∆ ∆∆T
adia
batic
(K
)
2,0
1423
1393
1373
1333
T s (K)
La(Fe0.915Si0.085)13, sintered
0
2
4
6
8
10
12
14
180 210 240 270 300 330 360
∆∆ ∆∆T
ad (
K)
T (K)
La(Fe0.88Si0.12)13Hy
y = 0.0 0.5 1.0 1.5
-95-93-91-89-87-85-83-81-79-77-75
1800 1900 2000 2100 2200Zeit (s)
Pro
bent
empe
ratu
r (°C
)
T ProbeT-Regel
adiabatic temperature change
S. Fujieda et al. 2005, 0 - 2 bzw. 0 - 5 T
tem
pera
ture
T (
°C)
time t (s)
∆H = 1,7 T
![Page 12: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/12.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 12
thermal hysteresis
0.0
0.2
0.4
0.6
0.8
1.0
1.2
180 190 200 210
temperature T (K)
pola
rizat
ion
J (
T)
2 kOe
5 kOe
10 kOe
16 kOe
La(Fe 0.893Si0.107)13
0.0
0.2
0.4
0.6
0.8
1.0
1.2
190 200 210 220
temperature T (K)
pola
rizat
ion
J (
T)
2 kOe
5 kOe
10 kOe
16 kOe
La(Fe 0.881Si0.119)13
temperaturechange rate: 8 K/min
hysteresis decreaseswith increasingSi contentand field strength
![Page 13: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/13.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 13
field hysteresis
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 5000 10000 15000
magnetic field strength H (Oe)po
lariz
atio
n J
(T
)
195.5 K197.8 K200.0 K202.0 K204.4 K
La(Fe 0.881Si0.119)13
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 5000 10000 15000
magnetic field strength H (Oe)
pola
rizat
ion
J (
T)
188.7 K190.7 K192.9 K195,1 K197.0 K
La(Fe 0.893Si0.107)13
temperature decreasing at –8 K/min temperature increasing at +8 K/min temperature hysteresis
field hysteresis
-∆Smagn Tpeak ∆TWHH -∆Smagn Tpeak ∆TWHH ∆Tpeak ∆H composition
(J/kgK) (K) (K) (J/kgK) (K) (K) (K) (kOe)
La(Fe0.893Si0.107)13 21.9 192.7 6.6 22.0 195.2 6.6 2.5 2.2
La(Fe0.887Si0.113)13 18.7 196.5 7.0 18.9 198.9 7.0 2.4 1.6
La(Fe0.881Si0.119)13 16.9 202.2 6.7 16.2 202.9 7.2 0.7 0.9
field sweep rate: 4.3 kOe/min
![Page 14: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/14.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 14
La(Fe0.862Co0.05Si0.085)13sintered
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 5000 10000 15000
magnetic field strength H (Oe)
pola
rizat
ion
J (
T)
250.1 K253.2 K256.7 K260.3 K263.4 K
La(Fe 0.862Co0.05Si0.085)13
0,0
2,0
4,0
6,0
8,0
10,0
230 240 250 260 270 280
temperature T (K)
- ∆∆ ∆∆S
m (
J/kg
K)
4,0
8,0
12,0
16,0
Hmax (kOe)
allmost no hysteresis at all
ρ = 7.24 g/cm3
-∆Sm @16 kOe= 67 kJ/m3KTpeak = -19 °C
∆TWHH = 14 K
![Page 15: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/15.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 15
0,00
2,00
4,00
6,00
8,00
10,00
-30,0 -20,0 -10,0 0,0 10,0 20,0 30,0 40,0 50,0 60,0 70,0 80,0
T (°C)
- ∆∆ ∆∆S
m (J
/kgK
)
x = 0.050
x = 0.058
x = 0.065
x = 0.075
x = 0.087
x = 0.099
x = 0.112
Gd
sintered La(Fe0.915CoxSi0.085)13
several kgblocks 23x19x12 mmproduced onlabscale for prototyping
∆H = 16 kOe
![Page 16: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/16.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 16
thermal expansion of sintered La-Fe-Co-Si
-0,50
-0,45
-0,40
-0,35
-0,30
-0,25
-0,20
-0,15
-0,10
-0,05
0,00
-100 -50 0 50 100 150 200
temperature T (°C)
ther
mal
exp
ansi
on
∆∆ ∆∆l/l
(%)
difficult to machine
La(Fe0,865Co0,05Si0,085)13
La(Fe0,803Co0,112Si0,085)13
![Page 17: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/17.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 17
performance in a magnetic refrigeration prototype at
Risø National Laboratory for Sustainable Energy
25% ethylene glycol / water solution K.K. NielsenJ.B. JensenK. EngelbrechtCh. Bahl
2008
![Page 18: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/18.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 18
Adiabatic temperature change measured at Risø
∆H = 1.1 T
Cast bulk samples
F.X. Hu 2005
magnetizationmagnetization
demagnetizationdemagnetization
La(Fe0,85Co0,065Si0,085)13
La(Fe0,84Co0,075Si0,085)13
La(Fe0,855Co0,06Si0,085)13
K.K. NielsenJ.B. JensenK. EngelbrechtCh. Bahl
2008
![Page 19: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/19.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 19
Hydrogenation of sintered La-Fe-Co-Si
0
1
2
3
4
5
6
7
8
9
10
-50 0 50 100 150temperature T (°C)
ent
ropy
ch
ange
- ∆S
m (J
/kgK
)
La(Fe0,865Co0,05Si0,085)13H1,9
La(Fe0,806Co0,123Si0,071)13
∆H = 16 kOe
La(Fe0,865Co0,05Si0,085)13
![Page 20: Magnetocaloricpropertiesof reactivelysinteredLa(Fe,Co,Si) 13 Science and Technology...Delft Days on Magnetocalorics2008, M. Katter, La-Fe-Co-Si sintered page2 overviewmagneticmaterials](https://reader033.fdocuments.us/reader033/viewer/2022041900/5e60493819820901900f4195/html5/thumbnails/20.jpg)
Delft Days on Magnetocalorics 2008, M. Katter, La-Fe-Co-Si sintered page 20
Conclusion
- La(Fe,Si)13 sucessfully prepared by powder metallurgy
- bulk material available after reactive sintering for a few hours
- hysteresis decreases with increasing Si and Co content
- Curie temperature controllable by Co or H substitution
- entropy change similar or better compared to Gd
- several kg with various Curie temperatures produced
- process upscalable on an industrial basis
- temperature span comparable to Gd
0,00
2,00
4,00
6,00
8,00
10,00
-30,0 -20,0 -10,0 0,0 10,0 20,0 30,0 40,0 50,0 60,0 70,0 80,0
T (°C)
- ∆∆ ∆∆S
m (J
/kgK
)
x = 0.050
x = 0.058
x = 0.065
x = 0.075
x = 0.087
x = 0.099
x = 0.112
Gd