katter magnetocaloric · pdf filepage4 magnetic refrigeration at room temperature features no...
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Novel magnetocaloric materials formagnetic cooling applications
M. Katter Vacuumschmelze GmbH & Co. KG
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outline
• introduction
• thermodynamic basics of magnetic cooling
• LaFeSi-based alloys produced by powder metallurgy
• prototypes and applications
• conclusions
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magnetocaloric effect: discovered by Wartburg 1881magnetic cooling: Debye and Giauque 1926
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magnetic refrigeration at room temperature
Features
no compressorno green house gaseshigh efficiencynew magnetocaloric materialspermanent magnets
Applications
industrial coolingair conditioningfood refrigeration
O. Tegus, E. Brück, K.H.J. Buschow, F.R. de Boer, Nature, vol. 415 (2002) 150.
„compression“
„expansion“
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motivation for magnetic cooling
- > 180 Mio. new cooling devices every year, needing ten-thousand tonsof environmentally harmful coolants (HFCs), 28-45% of CO2 equivalent in 2050 (Velders 2009)R134a banned in newly developed cars since 2011 in Europe
magnetic cooling uses solid, environmentally friendly coolants
- alternative CO2-compressors need pressures > 100 barmagnetic cooling devices need only 1-2 bar
- gas compression cycles reach ca. 40 % of Carnot-efficencymagnetic coolers reached ca. 60% in laboratory
- compressors are noisymagnetic cooling devices are silent
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magnetic cooling cycle for a single magnetocaloric material
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COP = 90
ΔS = 15 J/kgK
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magnetic cooling cycle for a set of 10 magnetocaloric materials
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COP = 10
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„Giant“ magnetocaloric effect
K. Gscneidner (2007)
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new magnetocaloric materials
K. Gscneidner (2007)
accessable withNd-Fe-B magnets
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Designs for active magnetic regenerators
J.A. Barclay and S. Sarangi 1984 in A.M. Tishin and Y.I. Spichkin 2003
large pressure drops in powder beds?
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- 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
S. Fujieda et al. 2005F.X. Hu et al. 2005 (with Co)
O. Gutfleisch et al. 2005S. Hirosawa et al. 2006
K. Niitsu 2012
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Powder Metallurgical (PM) Processing of La-Fe-Si
P
Vacuum Induction Alloying and Casting
Crushing
Milling
Blending
Pressing:CIP - die
isostatic pressing
die-pressing
elemental powders
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Powder Metallurgical (PM) Processing of La-Fe-SiP
Pressing:CIP - die
die-pressing
Isostaticpressing
Reactive Sintering
Machining and Surface Finishing
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set of La-Fe-Co-Si parts for a magnetic regenerator
0
1
2
3
4
5
6
7
8
9
10
-20 -10 0 10 20 30 40 50 60 70 80temperatur (°C)
entr
opy
chan
ge -Δ
Sm
(J/k
gK)
ΔH = 16 kOe
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MFP-1056, TC = -14°C
-0,50
-0,40
-0,30
-0,20
-0,10
0,00
0,10
0,20
-100 -50 0 50 100 150 200
temperature [°C]
stra
in [%
]
magnetocaloric passive statea-Fe = 71 %
magnetocaloric active statea-Fe = < 2%
reversible conversion
good machinability
good magnetocaloric properties
0,0
2,0
4,0
6,0
8,0
10,0
230 240 250 260 270 280
temperature T (K)
- ∆S
m (J
/kgK
)
4,0
8,0
12,0
16,0
Hmax (kOe)
Thermally induced Decomposition and Recombination (TDR) process
difficult to machine
tensile stress=> cracks
Katter et al. 2009
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La-Fe-Co-Si blocks and platelets with thicknesses of 0.25 – 1.0 mm
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monolithic La-Fe-Co-Si regenerators with 0.2 mm slots
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Linearly graded LaFeCoSi parts
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P
1. Compaction of powderswith different Co content
2. Sintering and diffusion treatmentto generate linearly varying TC
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sintered La-Fe-Mn-Si-Hx powders
particle sizeca. 400 µm
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prototype for wine cooler, HEIG, Yverdons le Bains, CH, M. Balli (2010)
regenerator with Gd
regenerator with LaFeCoSi
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prototype of Astronautics, USA
with La-Fe-Si-Hx powder from VAC400 W cooling power at 14°C temperature span
best performance up to now!
S. Russek(2010)
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magnetocaloric cooling systemmaterials
magnet assemblies
thermo-hydraulicsmechanics
Cooltech Applications (2008)
ca. 0,3 kg La-Fe-Si +ca. 1,5 kg Nd-Fe-Bper kW cooling power
Astronautics (2001)
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room temperautre magnetic refrigeration prototypes
K. Gscneidner (2007)
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conclusion
- magnetocaloric effect is the temperature change of a material in dependence on a magnetic field change
- La(Fe,Co,Si)13 and La(Fe,Si)13Hx with tunable Curie temperaturecan be produced by powder metallurgy
- prototypes for application at room temperature under construction
- there is a huge market for magnetic cooling, also due to upcomingenvironmental legislation for HFCs