ternary dy-er-al magnetic refrigerants · 2020. 2. 6. · ternary dy-er-al magnetic refrigerants...
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Iowa State University Patents Iowa State University Research Foundation, Inc.
7-25-1995
Ternary Dy-Er-Al magnetic refrigerantsKarl A. Gschneidner Jr.Iowa State University, [email protected]
Hiroyuki TakeyaNational Institute for Materials Science, Ibaraki, Japan
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Recommended CitationGschneidner, Karl A. Jr. and Takeya, Hiroyuki, "Ternary Dy-Er-Al magnetic refrigerants" (1995). Iowa State University Patents. 170.http://lib.dr.iastate.edu/patents/170
Ternary Dy-Er-Al magnetic refrigerants
AbstractA ternary magnetic refrigerant material comprising (Dy.sub.1-x Er.sub.x)Al.sub.2 for a magnetic refrigeratorusing the Joule-Brayton thermodynamic cycle spanning a temperature range from about 60K to about 10K,which can be adjusted by changing the Dy to Er ratio of the refrigerant.
KeywordsMaterials Science & Engineering, Ames Laboratory
DisciplinesEngineering | Materials Science and Engineering
This patent is available at Iowa State University Digital Repository: http://lib.dr.iastate.edu/patents/170
United States Patent [191 Gschneidner, Jr. et a1.
US005435137A
[11] Patent Number: 5,435,137 [45] Date of Patent: Jul. 25, 1995
[54] TERNARY DY-ER-AL MAGNETIC REFRIGERANTS
[75] Inventors: Karl A. Gschneidner, Jr., Ames, Iowa; Hiroyuki Takeya, Ibaraki, Japan
[73] Assignee: Iowa State University Research Foundation, Inc., Ames, Iowa
[21] Appl. No.: 88,882 [22] Filed: Jul. 8, 1993
[51] Int. C1.6 ............................................ .. F25B 21/00 [52] US. Cl. .......................................... .. 62/3.1; 62/6;
148/301; 148/304; 420/416 [58] Field of Search .................... .. 62/31, 6; 148/301,
148/304; 420/416
[56] References Cited U.S. PATENT DOCUMENTS
4,107,935 8/1978 Steyert, Jr. .. 62/3.1 4,332,135 6/1982 Barclay 62/3.1 4,459,811 7/ 1984 Barclay 62/3.1 4,507,927 4/1985 Barclay ...... .. 62/3.1 4,829,770 5/1989 Hashimoto .. .... .. 62/3.l
4,849,017 7/1989 Sahashi et al. 148/301 X 5,060,478 10/1991 Fukamichi . . . . . . . . . . . .. 62/3.l
5,186,765 2/1993 Arai et a1 62/3.1 X 5,213,630 5/1993 Hashimoto .... .. 148/301
5,249,424 10/ 1993 DeGegoria et a1 ................. .. 62/3.l
OTHER PUBLICATIONS
“Materials for Regenerative Magnetic Cooling Span ning 20K to 80K”; Adv. Cryogenic Eng. 37, 1992, pp. 883-890; Zimm, Ludeman, Severson, Henning. “Heat Capacity in Superconducting and Normal-State LaSx (1.333éxé 1.500) Compounds”; Phys. Review B,
40000 r
vol. 25, No. 7, Apr. 1, 1982, pp. 4604-4617; Ikeda, Gschneidner, Jr., Beaudry, Atzmony. “Comptes Rendus Herbdomadaires Des Séances” De L’académie Des Sciences, 247, pp. 1836-1838 (1958). “Thermodynamic Analysis of Magnetically Active Re generator From 30 to 70K with a Brayton-like Cycle”; Cryogenics, 1990, vol. 30, Oct., pp. 840-845; Matsu moto, Hashimoto. “An Ericsson Magnetic Refrigerator For Low Temper ature”; Adv. in Cryo. Eng, vol. 33, pp. 743-450; Matsu moto, Ito, Hashimoto. “Investigations on the Possibility of the RAlz System as a Refrigerant in an Ericsson Type Magnetic Refrigera tor”; pp. 279-286; Hashimoto, et a1. “Binary Alloy Phase Diagrams”, 2nd Edition, vol. 1, (1990), pp. 144-145. “Investigation of the Magnetic Refrigerant for the Er icsson Magnetic Refrigerator”; Jap. J. App. Phy., vol. 26 (1987), pp. 1673-1674; Hashimoto, et al. “New Application of Complex Magnetic Materials to the Magnetic Refrigerant in an Ericsson Magnetic Re frigerator”; J. Appl. Phys. 62(9), Nov. 1, 1987, pp. 3873-3878; Hashimoto, et al.
Primary Examiner-Christopher Kilner Attorney, Agent, or Firm-Edward J. Timmer
[57] ABSTRACT A ternary magnetic refrigerant material comprising (Dy1_.xErx)Al2 for a magnetic refrigerator using the Joule-Brayton thermodynamic cycle spanning a tem perature range from about 60K to about 10K, which can be adjusted by changing the Dy to Er ratio of the refrig erant.
6 Claims, 27 Drawing Sheets
35000 _
3m _
251110
211300
15000
10000
TEMPERATURE S (mJ/mol K) E NTROPY
REVERSED BRAYTON CYCLE
2b 3b 4b 56 eb 70 TEMPERATURE (K)
ENTROPY 0FDya5Era5WZFRM 0T0 70K AT FIVE DIFFERENT FlElDS.
US. Patent July 25, 1995 Sheet 1 of 27 5,435,137
w 4 % Lu 1 4 '52 1 2% E 3 $ 5 ' ‘é (- 2 Q’ 2 3
ENTROPY VOLUME
REVERSED BRAYTON CYCLE REVERSED BPAYTON CYCLE
FIG. IA FIG. IB
US. Patent July 25, 1995 Sheet 2 of 27 5,435,137
(D3105 Eras) A12: AS'CA'ER 80X
FIG. 2
US. Patent 0 July 25, 1095 Sheet 3 of 27 5,435,137
Dyo?fro‘sAl2 40000 I I I I I
o O T 35000 ' v 2.46T
D 5.32 T A 30000 » A 7.53T
f O 9.85T ° 25000 -
i E 20000 ~
I E 10000 -
‘5s’ 2 _
§ 5000 -
0 '10 20 30 40 50 60 70 TEMPERATURE (K)
I-IEAT CAPACITY 0F(I)yo_5IEr05)AI2 FROM~2K T070K AT FIVE DIFFERENT MAGIIEIIC FIELDS
FIG. 3
US. Patent July 25, 1995 Sheet 4 of 27 5,435,137
W05 Eras A'2 I
TTTTT 6235 045108. 2579 O V O A O
30 40 5o 60 7o TEMPERATURE (K)
.TPLOTFOP( Er )Al ASAFUNCTION 0F TEMPERATURE 70K AT Dy“ 5E 2
IO 20
FIVE 'MAE‘? TIC FIELDS
F IG. 4
U.S. Patent
8 (mJ/mol K)
July 25, 1995 Sheet 5 of 27 5,435,137
§ 8
""" -
2b 3b 4b 5b 60 TEMPERATURE (K)
70
ENTROPY 0F (Dyo?Erai-wMl2 FROM 0T0 70K AT FIVE DIFFERENT FIELDS.
FIG. 5*
US. Patent July 25, 1995 Sheet 6 of 27 5,435,137
TEMPERATURE CHANGE (K) o M 4h- 0 co 5 F3 3 E; 35 8
20 30 40 TEMPERATURE (K)
THE CALCULATED MAGNETOCALORIC EFFECT FOR FOUR DIFFERENT MAGNETIC new CHANGES AS A ruucnou 0F TEMPERATURE FOR (Dy0_5Er0_5)A12.
FIG. 6
US. Patent July 25, 1995 Sheet 7 of 27 5,435,137
W5 595“? 40 I I I I I
O TEMP=Z2K 30 _ V TEMP=426K E In‘ I“ _
U TEW=Z5K ' ’ ' ' '
20 __ A _
D TEMP=20K V TEMP=25K
10 * m TEMP'SOK '
; <> TEMP=35K ‘g 0 - -
g 40 _ _
-20 _ _
...3O ... £1 _
...40 | 1 |
45000 -1oooo ~5o0o o 5000 10000 15000 MAGNETIC FIELD (05)
FIG. 7
US. Patent July 25, 1995 Sheet 8 of 27 5,435,137
DyasE'asAlz SAMPLE wasm=omaa
5D I I l I I I | I I
40 _ wrimpgmgun _ v I5 K . ' L
3°" “ 321i ‘
,5 _ . 5 1o - I .
"3' o - I _ s’
a? ' E "10 ‘ ii ‘
g-g-zo - _
2-30 3" v i/ - _.4Q _ -
~50 4.0 is -6.6 -o'.4 -62 do 0.2 d4 0?; 018 1.0 MAGNETIC FIELD (T)
FIG. 8
US. Patent July 25, 1995 Sheet 9 of 27 5,435,137
954E510
DY.5E¥25AL2 '
FILE DYEPAM 10811
I
TEMPERATbRE 2.2K
P5202
4000 0 1M) 2000 3000 MAGNETlC FIELD (0E)
FIG. 9
US. Patent July 25, 1995 Sheet 10 of 27 5,435,137
10 15 20 2'5 30 35 4o TEMPERATURE K
FIG. l0
_ _ _ _ ._ _
o
m m w m w G8 15.3 “63 ma?hgz
0 0 an
US. Patent July 25, 1995 Sheet 11 of 27 5,435,137
Dyas Er(15 A12 AC FIELD =I.2566 0e FREQUENCY=1Z5 Hz
0:060 I I l I
0.055 -
0.050 -
0.045
0.040 -
0.035 -
0.030
0.025
0.020 -
I
<1 0 v I 4 0 g _ P-Nr-‘DQQ OOOcn-O AC SUSCEPTIBILITY (emu/q)
0.015 -
0.010 -
0W5 -
0.000 0 so 60 7b 80 90 100
TEMPERATURE (K)
US. Patent July 25, 1995 Sheet 12 0f 27 5,435,137
DyosErasAlz AC FIELD = 1.2566 09 FREQUENCY "-125 Hz
0.030
0.025
0.020
p 2 ' u I
0.010 -
AC SUSCEPTIBILITY (emu/g) 0005 -
304'o 50610708090100 TEMPERATURE (K)
FIG. I2
0000
US. Patent July 25, 1995 Sheet 13 of 27 5,435,137
DyasErosAlz AC FIELD = 12566 0e DC F|ELD= o kOe
0.060
0102030405060708090100
0055 -
0.050 -
0.045 -
_ _ _ _ n p
5 w 5 0 5 3 ‘I m. 0 0. 0.
0 0 0 0
00 325 gazhmwgm "a
TEMPERATURE (K) FIG. l3
US. Patent July 25, 1995 Sheet 14 of 27 5,435,137
Dyoa?hsmz AC FIELD = 1.2566 09 DC FIELD =0 kOe
I I I l l I | | |
FR UE Y 0 I25 Hz v 500 Hz
0.009 — D 1000 Hz _
a
0.008 - 8% I -
3° “q: 3 O
5 v 0.001 - "o ..
E :1
Q E 0000 - ‘b - U U 0‘) 3 Cf) 6
2 O 0.005 - ,u _
° d
0.001 50 5.5 000 6.5 7.0 is 0'0 0.5 0.0 0'5 10.0 TEMPERATURE (K)
FIG. l4
US. Patent July 25, 1995 Sheet 15 of 27 5,435,137
DyasErosAlz AC FIELD= 12566 0e DC FIELD = 20 kOe
0.0030||||||| T‘
Q4070 m .0 § c
22. II §NNE2 0.0025 - 1000
00020
00015
0.0010 PC SUSCEPTIBILITY (emu/g)
0.0005
0 1b 2b 3b 4B 5b 60 TEMPERATURE (K)
FIG. IS
00000
US. Patent July 25, 1995 Sheet 16 of 27 5,435,137
DyosErasmz AC FIELD = [2566 De DC FIELD = 40 We
0.0018 ' . l I I
FREQUENCY 0.001s - 3 e155?) 3% -
u100OHZ
0.0014
0.0012 -
0.0010
0.0008 -
0.0006 —
AC SUSCEPTIBILITY (emu/g) 0.0004
0.0002
0‘00000 2'0 4'0 6b ab 160 do 140 TEMPERATURE (K) FIG. l6 .
US. Patent July 25, 1995 Sheet 17 of 27 5,435,137 j
20
HEAT CAPACITY (J/mol K)
I I I Q8I5T£SLA
0 10 20 30 4o 50 so
TEMPERATURE (K)
FIG. I?
US. Patent July 25, 1995 Sheet 18 of 27 5,435,137
800 I I I I T
600 -
C/T (mJ/mol K2)
o 0.00TESLA I
100 - i - 2.46TESLA
I‘ v _. ' 7.53TESLA
O I I I I u agsTEsLA
0 10 2o 30 40 so so TEMPERATURE (K)
FIG. l8