ekkes brueck at basf science symposium 2015
TRANSCRIPT
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Magneto caloric materials for energy efficient heat pumps
Ekkes Brück, Delft University of Technology,
Fundamental Aspects of Materials and Energy
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World population
year
popu
lati
on /
mill
ion
11 billion
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World population and energy use Country Population
(million) Electricity kWh/cap)
Energy (Mtoe/cap)
World 6958 2933 1.88
OECD 1241 8226 4.28
China 1351 3312 2.03
Asia 2313 823 0.69
Africa 1045 592 0.67
IEA, Key world energy statistics, 2013
data from 2011
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Last 160,000 years (from ice cores) and the next 100 years
Time (thousands of years) 160 120 80 40 Now
–10
0
10
100
200
300
400
500
600
700 CO2 in 2100
(with business as usual)
Double pre-industrial CO2
CO2 now
Temperature difference
from now °C
CO2
conc
entr
atio
n (p
pm)
Source: IPCC
CO2 concentration
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Energy Information Administration (EIA) Annual Energy Outlook, 2009
Residential energy consumption
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BSRIA Building Services Research and Information Association
World Air Conditioning market
•>10% growth •Columbia, Brazil, Nigeria, India, Vietnam and Indonesia
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Refrigerant Chemical formula
Atmospheric lifetime (years)
GWP ASHRAE safety group
ODP
R22 CHClF2 12 1810 A1 0.05 R134a C2H2F4 14 1430 A1 0 R290 CH3CH2CH3 12 3.3 A3 0
R404a 44±2% C2HF5 52±1% C2H3F3 4±2% C2H2F4
40 3920 A1 0
R407c 23±2% CH2F2 25±2% C2HF5 52±2% C2H2F4
16 1774 A1 0
R600a CH(CH3)2CH3 12 3 A3 0
Frequently used Refrigerants
GWP Global Warming Power ODP Ozone Depletion Power A1 no flame propagation, A3 highly flammable
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Nickel metal ΔB = 1.5 T ΔT = 0.7K
Magnetocaloric effect 1917 Weiss & Piccard
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Magnetic cooling: Debye and Giauque 1926
61g Gd2(SO4)3·8H2O, ΔB=0.8T, 1.5K →0.25K Nobel prize 1949
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spins lattice
Basic magnetocalorics
E
Two energy reservoirs
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E
Basic magnetocalorics
spins lattice
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Example UVic prototype μ0H ~ 1.4 T, f ≤ 4Hz
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•CES 2015 Las Vegas
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Magnetic heat pump
Which material is most suited for use? •https://www.youtube.com/watch?v=jnl9m0rSE7U
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Giant MCE Materials @ room temperature, @ ∆B = 1 T (available with permanent magnets)
toxicity cost + availability
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Figure of Merit • Refrigerant capacity RC = ΔS·ΔT Measure of net work in reversible cycle. Often used, but not a good FoM.
Wood & Potter Cryogenics 1985
• Coefficient of Refrigerant performance CRP
Dimensionless Figure of Merit which can be used to compare different materials even gas compression
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Desired Magnetization processes
Material with field induced first order phase transition.
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Replace Fe with Mn and Si for As magnetic response of MnxFe2-xP0.5Si0.5 in 1T
Mn content strong reduction in hysteresis followed by other structural transformation
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Same effect in 2T as earlier in 5T Huu Dung et. al. Adv. Energy Mat. (2011)
Partial phase-diagram
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Electronic structure
Fe (0μB)
Mn (2.6 μB)
Fe (0μB)
Mn (2.6 μB)
Fe (0μB)
paramagnetic Closer look at the layers
Fe (P,Si)
Mn (P,Si)
Fe (P,Si)
Mn (P,Si)
Fe (P,Si)
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Electronic structure
Fe (0μB)
Mn (2.6 μB)
Fe (0μB)
Mn (2.6 μB)
Fe (0μB)
paramagnetic Closer look at the layers
Fe (1.5μB)
Mn (2.8 μB)
Fe (1.5μB)
Mn (2.8 μB)
Fe (1.5μB)
ferromagnetic
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MnFe0.95P0.595B0.075Si0.33
From MB(T)
F. Guillou et. al. Adv. Mat. (2014)
B 0.075 B 0.0
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MnFe0.95P0.595B0.075Si0.33
Cyclic insertion and extraction in 1.1 T field Resulting ΔT
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Sample ∆Str = L/Tc (J kg-1 K-1)
∆M (A m2 kg-1)
dTC/dB (K/T)
Transit. Width
(K)
∆S MCE B=1T
(J kg-1 K-1)
Boron 7.5% 21.1 65 4.4 ±0.2 7.5 -10.5
Mn rich 29.8 61 3.2 ±0.2 8.0 -10.5
-36% +40%
MnFe(P,Si,B) vs Mn1.25Fe0.7P0.5Si0.5
Reminder: MnFe(P,Si,B) Mn1,25Fe0,7P1/2Si1/2
+40% !!
+6%
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CRP for different compositions
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Consequences of no volume change
Mn1.3Fe0.7P0.5Si0.5 ΔV/V ≤ 0.2 %
MnFe0.95P0.587B0.078Si0.34
ΔV/V ≤ 0.05 %
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Summary: MCE materials @ 1T Room T. ∆B=1 T
∆Smax (J kg-1 K-1)
∆Tmaxad
(K) CRP
Gd ʘ 3 2.5 0.17
LaFe11.38Mn0.36Si1.26H1.52 * ~10 2.6 ~0.4
Mn1,25Fe0,7P0,51Si0,49 10.5 1.9 0.47
MnFe(P,Si,B) 10 2.8 0.62
Not toxic Not expensive (Boron only 0.5 wt%)
Good mechanical stability Easy tunability of TC
Mn/Fe + P/Si + B, from 130 K to 450 K ʘ Dankov et al Phys. Rev. 57 (1998)
* Morrison et al Int. J. Ref. 35 (2012)
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TU Delft: N.H. van Dijk, F. Guillou, L. Caron, G. Porcari, H. Yibole, X.F. Miau, N. Van Thang, M. Boeije, K.H.J. Buschow Radboud Universiteit: R.A. de Groot, P. Roy, G.A. de Wijs BASF: L. Zhang, B. Reesink
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Thank You for Your attention
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Optimisation of MnFe(P, Si, B)
Recommendations to design MnFe(P,Si,B): B content as high as possible (from 0.06 to 0.09) Si between 0.3 and 0.4 then TC adjustment with Mn and Fe from Mn1.3Fe0.7 to Mn0.7Fe1.3 -(P,Si,B)
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Control of TC
# Magnetic refrigeration: Room T.
# Regenerator: Stacking of materials with different TC
# Cryogenic operation/Gas liquefaction: as low as possible
# Thermomagnetic generator: at least up to 400 K
MnFe0.95P0.583B0.077Si0.34
Mn/Fe ~ 1 Si ~ 1/3
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Tuning the latent heat with Boron
DSC
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MnFeP1-yXy
Hexagonal Fe2P type of structure
Bacmann, JMMM 1994
Space group: P62m
Mn 3g sites
Fe 3f sites
P/As 1b & 2c sites
_
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Temperature dependence of Magnetization
Step-like
transition
first order
but very little
hysteresis
Tegus et al. Nature 415
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Comparison of magnetocaloric effect in different materials
Entropy change
concentrated in
relevant T interval
Tegus et al. Nature 415
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•0-2T
•Fujita et al Phys Rev B 67 (2003) •Hu, et al, JAP 97 (2005)
Giant MCE Materials
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Magnetocaloric material
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Sample preparation MnFe(P,x)
Starting Fe, Mn2As3, Ge, Si, Mn & P
mechanical alloying
sintering 1000oC
annealing 800oC
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Ball milled material SEM analysis
Homogeneous
Alloy formed
XRD Fe2P phase
Magn. phase trans.
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MnFe(P,Si) first samples
Large hysteresis
MnFeP0.6Si0.4
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Magnetization isotherms
Metamagnetic transition with little hysteresis
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Magnetic response in different fields
Sharp transition with little hysteresis
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Typical refrigerator and refrigeration cycle