Method of making active magnetic refrigerant materials based on Gd Si Ge alloys

Iowa State University Patents

Iowa State University Research Foundation, Inc.

10-3-2006

Method of making active magnetic refrigerant

materials based on Gd-Si-Ge alloys

Alexandra O. Pecharsky

Iowa State University

Karl A. Gschneidner Jr.

Iowa State University

, [email protected]

Vitalij K. Pecharsky

Iowa State University

, [email protected]

Follow this and additional works at:

http://lib.dr.iastate.edu/patents

Part of the

Metallurgy Commons

This Patent is brought to you for free and open access by the Iowa State University Research Foundation, Inc. at Iowa State University Digital Repository. It has been accepted for inclusion in Iowa State University Patents by an authorized administrator of Iowa State University Digital Repository. For more information, please [email protected].

Recommended Citation

Pecharsky, Alexandra O.; Gschneidner, Karl A. Jr.; and Pecharsky, Vitalij K., "Method of making active magnetic refrigerant materials based on Gd-Si-Ge alloys" (2006).Iowa State University Patents. 292.

Method of making active magnetic refrigerant materials based on

Gd-Si-Ge alloys

Abstract

An alloy made of heat treated material represented by Gd

(Si

Ge

)

where 0.47

≦

x

≦

0.56 that exhibits a

magnetic entropy change (−ΔS

) of at least 16 J/kg K, a magnetostriction of at least 2000 parts per million,

and a magnetoresistance of at least 5 percent at a temperature of about 300K and below, and method of heat

treating the material between 800 to 1600 degrees C. for a time to this end.

Keywords

Ames Laboratory

Disciplines

Metallurgy

(12) United States Patent

Pecharsky et a].

US007114340B2

US 7,114,340 B2

Oct. 3, 2006

(10) Patent N0.:

(45) Date of Patent:

(54)

(75)

(73)

(21)

(22)

(65)

(63)

(60)

(51)

(52)

(58)

METHOD OF MAKING ACTIVE MAGNETIC REFRIGERANT MATERIALS BASED ON GD-SI-GE ALLOYS

Inventors: Alexandra O. Pecharsky, Ames, IA

(US); Karl A. Gschneidner, Jr., Ames,

IA (US); Vitalij K. Pecharsky, Ames,

IA (US)

Assignee: IoWa State University Research

Foundation, Inc., Ames, IA (US)

Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35

U.S.C. 154(b) by 228 days.

App1.No.: 10/413,417

Filed: Apr. 14, 2003

Prior Publication Data

US 2003/0221750 A1 Dec. 4, 2003

Related US. Application Data

Continuation-in-part of application No. 09/793,822,

?led on Feb. 23, 2001, noW Pat. No. 6,589,366.

Provisional application No. 60/ 187,713, ?led on Mar.

8, 2000.

Int. Cl.

F25B 21/00 (2006.01) H01F 1/053 (2006.01)

US. Cl. ... .. 62/3.1; 62/6; 62/4; 62/51.1;

505/889; 505/890; 505/891; 148/301; 148/101;

420/416

Field of Classi?cation Search ... .. 148/ 101,

148/102, 103, 301, 303, 302, 120, 121, 122;

62/3.1, 4, 6, 51.1

See application ?le for complete search history.

15

(56) References Cited

U.S. PATENT DOCUMENTS

5,332,029 A * 7/1994 Tokai et a1. ... .. 165/4 5,743,095 A 4/1998 Gschneidner et a1. ... .. 62/3.1 6,022,486 A 2/2000 Tokai et a1. ... .. 252/67

6,030,468 A 2/2000 Yagi et a1. 148/301

6,336,978 B1 1/2002 Tokai et a1. ... .. 148/301

OTHER PUBLICATIONS

Hansen, Constitution of Binary Alloys, 1958, pp. 772, 774, 1193

and 1205*

L. Morellon, P.A. Algarabel, M.R. Ibarra, J. Blasco, and B. Garcia

Landa, “Magnetic-?eld-induced structural phase transition in Gd5 (Si1_8Ge2_2)”, Phys. Rev. B58, 721-724 (1998).

L. Morellon, J. StankieWicZ, B. Garcia-Landa, P.A. Algarabel, and MR. Ibarra, “Giant magnetoresistance near the magnetostructural

transition in Gd5 (Si1_8Ge2_2)”, Appl. Phys. Lett. 73, 3462-3464

(1998).

L. Morellon, J. Blasco, P.A. Algarabel, and MR. Ibarra, “Nature of the ?rst-order antiferromagnetic-ferromagnetic transition in the

Ge-rich magnetocaloric compounds Gd5 (SiXGe1_X)4”, Phys. Rev.

B62, 1022-1026 (2000).

J. StankieWicZ, L. Morellon, P.A. Algarabel, and MR. Ibarra, “Hall

effect in Gd5 (Si1_8Ge2_2)”, Phys. Rev. B61, 12651-12653 (2000).

(Continued)

Primary ExamineriJohn Patrick Sheehan

(57)

ABSTRACT

An alloy made of heat treated material represented by

Gd5(SixGe1_x)4 Where 0472x2056 that exhibits a mag

netic entropy change (—ASm) of at least 16 J/kg K, a

magnetostriction of at least 2000 parts per million, and a magnetoresistance of at least 5 percent at a temperature of

about 300K and beloW, and method of heat treating the

material between 800 to 1600 degrees C. for a time to this

end.

8 Claims, 32 Drawing Sheets

14

-ASm(JIkg K)

o

240 250 260 270 280 290 300

T(K)

US 7,114,340 B2

Page 2

OTHER PUBLICATIONS

L. Morellon, PA. Algarabel, C. Magen, and MR. Ibarra, “Giant

magnetoresistance in the Ge-rich magnetocaloric compound, Gd5 (Si0_1Ge0_9)4”, J. Magn. Magn. Mater. 237, 119-123 (2001). EM. Levin, V.K. Pecharsky, and K.A. Gschneidner, Jr., “Magnetic

?eld and temperature dependencies of the electrical resistance near

the magnetic crystallographic ?rst order phase transition of Gd5 (Si2Ge2)”, Phys. Rev. B60, 7993-7997 (1999).

V.K. Pecharsky and K.A. Gschneidner, Jr., “Phase relationships and Crystallography in the Pseudobinary System Gd5Si4-Gd5Ge4”, J.

Alloys Compds. 260, 98-106 (1997).

V.K. Pecharsky and K.A. Gschneidner, Jr., “Tunable Magnetic

Regenerator Alloys With a Giant Magnetocaloric Effect for Mag

netic Refrigeration from ~20 to~290K”, Appl. Phys. Lett. 70, 3299-3301 (1997).

V.K. Pecharsky and K.A. Gschneidner, Jr., “Giant Magnetocaloric Effect in Gd5 (Si2Ge2)”, Phys. Rev. Lett. 78, 4494-4497 (1997).

V.K. Pecharsky and K.A. Gschneider, Jr., “Effect of Alloying on the

Giant Magnetocaloric Effect of Gd5 (Si2Ge2)”, J. Magn. Magn.

Mater. 167, L179-L184 (1997).

T.B. Massalski, Editor-in-Chief, Binary Alloy Phase Diagrams, 2nd

ed., ASM International, Materials Park, Ohio (1990).

D.H. Dennison, M.J. Tschetter and K.A. Gschneidner, Jr., “The Solubility of Tantalum in Eight Liquid Rare-Earth Metals” J. Less-Common Metals 10, 109-115 (1965).

P. Rogl, “Phase Equilibria in Ternary and Higher Order Systems

With Rare Earth Elements and Silicon” in Handbook on the Physics and Chemistry of Rare Earths, K.A. Gschneidner, Jr. and L. Eyring, eds., Elsevier Science Publishers, B.V., Amsterdam, pp. 92-94

(1984).

“Transformations in the Gd5 (Sil_95Ge2_05) alloy induced by the temperature and magnetic ?eld cycling though the ?rst-order mag netic-mantensitic phase transition”, E.M. Levin et al., Physical.

Review B, vol. 63, 064426-1 through 10, Jan. 23, 2001.

“Magnetic refrigeration materials”, K.A. Gschneidner, Jr. et al., Journal of Applied Physics, vol. 85, No. 8, pp. 5365-5368, Apr. 15,

1999.

“Uncovering the structure-property relationships is R5(SiXGe4_X)

intermetallic phases” Vitalij K. Pecharscy et al., Journal of Alloys

and Compounds, vol. 344, pp. 362-368, 2002.

“The effect of varying the crystal structure on the magnetism,

electronic structure and thermodynamics in the Gd5 (SiyGey_X)4

system near X:0.5”, V.K. Pecharsky et al., Journal of Solid State Chemistry, vol. 171, pp. 57-68, 2003.

“The room temperature metastable/stabe phase relationships in the

pseudo-binar, Gd5 Si44GdgGey System” A.O Pecharsky et al.,

U.S. Patent

0a. 3, 2006

Sheet 1 0f 32

US 7,114,340 B2

m

I 0

'1

v.

3

O

|

.U

3

O

|

9

2

O

I

8

w/ 2

I

O

l %

IN

‘TTTTT v u

-1 234 5

_ _ - - _ v i

IOOOOO .%

-HHHH H

- v = O

I I5

H _1 = 2

H v a H

___ __F\- ___\______-k- LFLF _ _ _ m

6

4

2

O

8

6

4

2

O2

U.S. Patent

0a. 3, 2006

Sheet 2 0f 32

US 7,114,340 B2

-ASm(JIkg K)

O L l I I I l l I I I [ I @I I L I I I I | I I I I J I I I I I I I I I

250

260

270

280

290

300

310

320

U.S. Patent

0a. 3, 2006

Sheet 3 0f 32

US 7,114,340 B2

43%

U.S. Patent

0a. 3, 2006

Sheet 4 0f 32

US 7,114,340 B2

=6]? ' '

—5— H=0-2T

+

H 0-3T

14

12

10

Q

9:352

320

300

290

280

250

260

270

U.S. Patent

0a. 3, 2006

Sheet 6 0f 32

US 7,114,340 B2

250

260

270

280 I 290

300

310

320

U.S. Patent

0a. 3, 2006

Sheet 7 0f 32

US 7,114,340 B2

20 r \ . . , . . . , , . . .

16 }

12 }

-ASm(Jlkg K)

3

4

I

I ‘ 7 7

2 l

w

: = = ‘

O_.,..|....|...

.'

.,

240

250

260

270

280

290

300

310

320

T(K)

U.S. Patent

0a. 3, 2006

Sheet 11 0f 32

US 7,114,340 B2

-ASm(Jlkg K)

O 1 ‘L | F ‘ l L J Y ‘ l ‘A; L l I

240

260

280

300

320

T(K)

U.S. Patent

0a. 3, 2006

Sheet 12 0f 32

US 7,114,340 B2

O

|L4l_ILllJ_llJ_IllIJ44|_ Lllllll|l,lll4llgll

240

250

260

270

280

290

300

310

320

T(K)

U.S. Patent

0a. 3, 2006

Sheet 13 0f 32

US 7,114,340 B2

12 -——0—H=0-1T

10*

-ASm(JIkg K)

03

240

260

280

300

320

T(K)

U.S. Patent

0a. 3, 2006

Sheet 15 0f 32

US 7,114,340 B2

18

.WWWWIH.

EFrom heat capacity measurements

16 Gd5(S|2Ge2)

Field change 0-5T

14 E" -—o—- As-prepared alloy

“I

; —+~ Enhanced MCE

IFIIIITIYIF‘IIIITIYFII

ATad

(K)

0

so

100

150

200

250

300

350

U.S. Patent

ATad

(K)

0a. 3,2006

Sheet 16 0f 32

US 7,114,340 B2

18v T g rm “mm-Th Direct measurements; WW. I \ . I - ‘ .

16

1

E

i

E

9

14 ;—

i

a

12 5-

§

5

i

10 g

i

i

i

8

-§

6

f

5

Field change 0“5T §

2 F

——O— As-prepared alloy ‘2

E

+

Enhanced MCE

3

O . . L . . l l .IIULLLL Ll‘ IHIILLUHUIIJLUHIL

U.S. Patent

0a. 3, 2006

Sheet 17 0f 32

US 7,114,340 B2

|"F‘F""l‘_'_'"""["‘“fTFIF""""_

From magnetization measurements

Gd5(S|2Ge2)

%

—O— As-prepared alloy;

+

Enhanced NICE

Field change 0

i

40

35?

30:

2

9:3

E2.

US 7,114,340 B2

wimwk

Oct. 3, 2006

Sheet 18 0f 32