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, cagey@ameslab.gov

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