Magnetocaloric alloys useful for magnetic refrigeration applications

Abstract

Disclosed herein are magnetocaloric materials comprising alloys useful for magnetic refrigeration applications. The disclosed alloys include Dysprosium, Erbium, Holmium, Yttrium, or Terbium, and Cerium, Neodymium, and / or Gadolinium components that are fairly inexpensive. In certain embodiments, the materials exhibit second-order magnetic phase transitions near their Curie temperatures with negligible thermal and structural hysteresis losses, making them attractive for magnetic refrigeration. Surprisingly, the performance of the disclosed materials is comparable to or better than that of other expensive, rare-earth-based magnetocaloric materials.

Description

GERES.008WO PATENTMAGNETOCALORIC ALLOYS USEFUL FOR MAGNETIC REFRIGERATION APPLICATIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No.63 / 760,415 filed on February 19, 2025, entitled “MAGNETOCALORIC. ALLOYS USEFUL FOR MAGNETIC REFRIGERATION APPLICATIONS”, and U. S. Provisional Patent Application No. 63 / 941,404 filed on December 15, 2025, entitled “MAGNETROCALORIC ALLOYS USEFUL FOR MAGNETIC REFRIGERATION. APPLICATIONS”, the contents of each of which are incorporated herein by reference in their entirety for all purposes.BACKGROUNDField

[0002] Embodiments of the present invention relate to magnetocaloric materials comprising alloys useful for magnetic refrigeration applications. In certain embodiments, the disclosed alloys exhibit second-order magnetic phase transitions characterized by negligible thermal or structural hysteresis losses, making them attractive for magnetic refrigeration applications. In some embodiments, the disclosed compositions provide performance comparable to or exceeding other magnetocaloric materials.Description of the Related Art

[0003] Magnetic Refrigeration utilizes the magnetocaloric effect (MCE), which is the temperature variation of a magnetic material in response to a change in a magnetic field. The magnetocaloric effect (MCE) is an intrinsic property of magnetic solids that has been utilized for a variety of applications. The thermal response of the MCE material is typically maximized when the material is near its magnetic ordering temperature.

[0004] Various magnetocaloric compositions have been reported, including silicides and substituted silicides with rare-earth components at different substitution levels. The present disclosure provides materials and embodiments that are distinct in composition and / or performance characteristics.

[0005] For example, U. S. Patent 11,225,703, issued January 18, 2022, entitled “MAGNETOCALORIC ALLOYS USEFUL FOR MAGNETIC REFRIGERATION APPLICATIONS”, which is hereby incorporated by reference herein in its entirety for all purposes, discloses a magnetocaloric material comprising (CexNdi-x)Si wherein x is in the range of about 0.1 to about 0.9. Also, U. S. Patent 11,728,074, issued August 15, 2023, entitled “MAGNETOCALORIC ALLOYS USEFUL FOR MAGNETIC REFRIGERATION APPLICATIONS”, which is hereby incorporated by reference herein in its entirety for all purposes, discloses a magnetocaloric material comprising (AxBi-X) Si i (DyEz) wherein A and B are selected from the group consisting of Ce, Nd, or Gd, wherein D is selected from the group consisting of Cr or Mn, and E is selected from the group consisting of Cr, Mn, Fe, Al, Ni, Co, Cu, or Zn, wherein x is in the range of about 0 to about 1.0, wherein y is in the range of about 0.05 to about 0.3, wherein z is in the range of about 0 to about 0.3, and wherein 0.05 < y+z < 0.3.SUMMARY

[0006] Some embodiments of the present invention provide a magnetocaloric material comprising (Ax Bi-X) Si1-y-z(DyEz) wherein A is selected from the group consisting of Dy, Flo, Er, Y, or Tb, and wherein B is selected from the group consisting of Ce, Nd, or Gd, and wherein D is selected from the group consisting of Cr or Mn, and wherein E is selected from the group consisting of Fe, Al, Ni, Co, Cu, or Zn, and wherein x is in the range of about 0.05 to about 1.0, and wherein y is in the range of 0 to 0.3, and wherein z is in the range of 0 to 0.3, and wherein 0.0 < y+z < 0.3.

[0007] In some embodiments of the magnetocaloric material, y + z = 0. In some embodiments of the magnetocaloric material, y + z = 0.1. In some embodiments of the magnetocaloric material, y + z = 0.2. In some embodiments of the magnetocaloric material, y + z = 0.3. In some embodiments of the magnetocaloric material, y = 0.1 and z = 0. In some embodiments of the magnetocaloric material, y = 0.2 and z = 0. In some embodiments of the magnetocaloric material, y = 0.3 and z = 0. In some embodiments of the magnetocaloric material, y = 0.05 and z = 0.1. In some embodiments of the magnetocaloric material, y = 0.05 and z = 0.2. In some embodiments of the magnetocaloric material, y = 0.05 and z = 0.15.

[0008] In some embodiments, the magnetocaloric material comprises (DyxBnx)Sio.sCro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation, Dyi.oSio.sCro.2, Dyo.iGdo.oSio.sCro.2, Dyo.2Gdo.8Sio.sCro.2, Dyo.3Gdo.7Sio.sCro.2, Dyo.4Gdo.6Sio.8Cro.2, Dyo.5Gdo.5Sio.8Cro.2, Dyo.6Gdo.4Sio.sCro.2, Dyo.7Gdo.3Sio.8Cro.2, Dyo.8Gdo.2Sio.8Cro.2, Dyo.9Gdo.1Sio.8Cro.2, Dyo.iCeo.9Sio.8Cro.2, Dyo.2Ceo.8Sio.sCro.2, Dyo.3Ce.7Sio.8Cro.2j Dyo.4Ceo.6Sio.sCro,2, Dyo.5Ceo.5Sio.8Cro.2, Dyo.6Ceo.4Sio.sCro.2, Dyo.7Ceo.3Sio.sCro.2, Dyo.8Ceo.2Sio.sCro.2, Dyo.9Ceo.iSio.8Cro.2, Dyo.iNdo.9Sio.sCro.2j Dyo.2Ndo.sSio.8Cro.2, Dyo.3Ndo.7Sio.8Cro.2, Dyo.4Ndo.6Sio.8Cro.2, Dyo.5Ndo.5Sio.8Cro.2j Dyo.6Ndo.4Sio.sCro.2j Dyo.7Ndo.3Sio.sCro.2j Dyo.sNdo.2Sio.8Cro.2, Dyo.9Ndo.1Sio.8Cro.2-

[0009] In some embodiments, the magnetocaloric material comprises (DyxBi- x)Sii.o wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation. Dyi.oSii.o, Dyo.iGdo.9Sii.o, Dyo.2Gdo.8Sii.o, Dyo.sGdo.rSil.o, Dyo.4Gdo.6Sii.o, Dyo.sGdo.sSil.o, Dyo.6Gdo.4Sii.o, Dyo.7Gdo.3Si1. Oj Dyo.8Gdo.2Sii.o, Dyo.9Gdo.iSii.o, Dyo.iCeo.oSii.o, Dyo.2Ceo.8Sii.o, Dy0.3Ce0.7Si1.0, Dyo.4Ceo.6Sii.o, Dyo.sCeo.sSil.o, Dyo.eCeo / iSii.o, Dy0.7Ce0.3Si1.0, Dyo.sCeo.2Si1. Oj Dyo.oCeo.iSii.o, Dyo.iNdo.gSil.o, Dyo.2Ndo.sSi1. Oj Dyo.3Ndo.7Si1. Oj Dyo.4Ndo.6Sii.o, Dy0.5Nd0.5Si1.0, Dyo.6Ndo.4Sn. Oj Dyo.7Ndo.3Sn. Oj Dy0.8Nd0.2Si1.0, Dyo.9Ndo.1Si1.o-

[0010] In some embodiments, the magnetocaloric material comprises (HoxB1-x)Sio.8Cro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation, Hoi.oSio.sCro.2, H00.1 Gd0.9Si0.sCr0.2, Hoo.2Gdo.sSio.8Cro.2, Hoo.3Gdo.7Sio.8Cro.2j Hoo.4Gdo.6Sio.sCro.2, Hoo.5Gdo.5Sio.sCro.2j Hoo.6Gdo.4Sio.sCro.2, Hoo.7Gdo.3Sio.sCro.2, Hoo.8Gdo.2Sio.8Cro.2, Hoo.9Gdo.1Sio.sCro.2, Hoo.1Ceo.9Sio.8Cro.2, Hoo.2. Ceo.8Sio.8Cro.2, Hoo.3Ceo.7Sio.8Cro.2j Hoo.4Ceo.6Sio.8Cro.2-, Hoo.5Ceo.5Sio.8Cro.2j Hoo.6Ceo.4Sio.sCro.2, Hoo.7Ceo.3Sio.8Cro.2, Hoo.sCeov. Sio.sCro.2, Hoo.9Ceo.1Sio.sCro.2, Hoo.iNdo.9Sio.8Cro.2, Hoo.2Ndo.8Sio.8Cro.2, Hoo.3Ndo.7Sio.sCro.2j Hoo.4Ndo.6Sio.8Cro.2, Hoo.5Ndo.5Sio.sCro.2j Hoo.6Ndo.4Sio.8Cro.2, Hoo.7Ndo.3Sio.8Cro.2j Hoo.sNdo.2Sio.sCro.2, Hoo.9Ndo.1Sio.sCro.2-

[0011] In some embodiments, the magnetocaloric material comprises (HoxBnx)Sii.0 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation,Hoi.oSii.o, Ho0.1Gd0.9Si1.0, Hoo.2Gdo.sSi1. O5 Hoo.3Gdo.7Sii.o, Hoo.4Gdo.6Sii.o, Hoo.sGdo.sSii.o, Hoo.eGdt Sii.o, Hoo.rGdo.sSii.o, Hoo.8Gdo.2Sii.o, Hoo. Gdo.iSii.o, Hoo.iCeo. Sii.o, Hoo.2Ceo.sSi1. O5 Hoo.3Ceo.7Si1. O5 Hoo.4Ceo.6Sii.o, Hoo.sCeo.sSil.o, Hoo.eCecuSii.o, HoovCeo.sSil.o, Hoo.sCeovSii.o, HoovCeo.iSii.o, Hoo.iNdo. Sii.o, Hoo.2Ndo.8Sii.o, Hoo.3Ndo.7Sii.o, Hoo.4 do.6Sii.o, Hoo.sNdo.sSii.o, Hoo.6Ndo.4Sii.o, Hoo.vNdo.sSil.o, Hoo.sNdovSii.o, HoovNdo.iSii.o.

[0012] In some embodiments, the magnetocaloric material comprises (ErxBi-x)Sio.sCro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation, En.oSio.sCro.2, Ero.iGdo.9Sio.8Cro.2, Ero.2Gdo.sSio.sCro.2, Ero.3Gdo.7Sio.sCro.2, Ero.4Gdo.6Sio.sCro.2, Ero.5Gdo.5Sio.sCro.25 Ero.6Gdo.4Sio.sCro.2, Ero.7Gdo.3Sio.sCro.25 Ero.sGdo.2Sio.8Cro.2, Ero.9Gdo.iSio.8Cro.2, Ero.1Ceo.9Sio.8Cro.2, Ero.2Ceo.sSio.8Cro.2, Ero.3Ceo.7Sio.sCro.2, Ero.4Ceo.6Sio.sCro.2, Ero.sCeo.sSio.sCro.2, Ero.6Ceo.4Sio.sCro.2, Ero.7Ceo.3Sio.8Cro.25 Ero.8Ceo.2Sio.8Cro.2, Ero.9Ceo.1Sio.sCro.2, Ero.iNdo.9Sio.sCro.2, Ero.2Ndo.sSio.8Cro.2, Ero.3Ndo.7Sio.sCro.25 Ero.4Ndo.6Sio.sCro.2, Ero.sNdo.5Sio.sCro.2, Ero.6Ndo.4Sio.8Cro.2, Ero.7Ndo.3Sio.8Cro.2- Ero.sNdo.2Sio.sCro.2, Ero.9Ndo.1Sio.8Cro.2-

[0013] In some embodiments, the magnetocaloric material comprises (ErxBi-x)Sii.o wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation, Er1.0Si1.0, Er0.1Gd0.9Si1.0, Ero.2Gdo.8Sii.o, Ero.3Gdo.7Si1.c1, En Gdo.eSii.o, Ero.sGdo.sSii.o, Ero.6Gdo.4Sii.o, Ero.7Gdo.3Si1. O5 Ero.sGdo.2Si1. O5 Ero.oGdo.i Sii.o, Er0.1Ce0.9Si1.0, Er0.5Ce0.5Si1.0, Ero.3Ceo.7Sii.o, EnuCeo.eSn.o, Er0.5Ce0.5Si1.0, Ero.6Ceo.4Sii.o, Ero.7Ceo.3Sii.o, Er0.5Ce0.5Si1.0, Ero. Ceo.iSit.o, Ero.tNdo.oSii.o, Ero.2Ndo.sSi1. O5 Ero.sNdo.vSii.o, EnwNdo.eSii.o, Ero.sNdo.sSii.o, Ero.6Ndo.4Sii.o, Ero.vNdo.sSil.o, Ero.sNdov. Sn.o, Er0.9Nd0.1Si1.0.

[0014] In some embodiments, the magnetocaloric material comprises (YxBi-x)Sio.sCro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation, Y1.0Si0.8Cr0.2, Yo.1Gdo.9Sio.sCro.2, Yo.2Gdo.sSio.sCro.2, Yo.3Gdo.7Sio.sCro.25 Yo.4Gdo.6Sio.sCro.2, Yo.sGdo.sSio.sCrov, Yo.6Gdo.4Sio.8Cro.2, Yo.7Gdo.3Sio.sCro.2, Yo.8Gdo.2Sio.8Cro.2, YovGdo.iSio.sCro.2, Yo.1Ceo.9Sio.sCro.2, YovCeo.sSio.sCro.2, Yo.3Ceo.7Sio.sCro.2, Yo.4Ceo.6Sio.sCro.2, Yo.5Ceo.5Sio.sCro.25 Yo.6Ceo.4Sio.8Cro.2, Yo.7Ceo.3Sio.8Cro.25 Yo.8Ceo.2Sio.8Cro.2, Yo.9Ceo.iSio.8Cro.2, Yo.iNdo.9Sio.8Cro.2, Yo.2Ndo.8Sio.8Cro.2, Yo.3Ndo.7Sio.sCro.25 Yo.4Ndo.6Sio.sCro.2,Yo.sNdo.5Sio.8Cro.2, Yo.6Ndo.4Sio.sCro.2, Yo.7Ndo.3Sio.8Cro.2, Yo.8Ndo.2Sio.8Cro.2, Yo.9Ndo.1Sio.8Cro.2-

[0015] In some embodiments, the magnetocaloric material comprises (YxBi-x)Sit.o wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation, Yi.oSn.o, Yo.iGdo.oSii.o, Yo.2Gdo.8Sii.o, Yo.sGdo Sii.o, Yo^Gdo.eSii.o, Yo.sGdo.sSii.o, Yo.6Gdo.4Sii.o, Yo.rGdo.sSii.o, Yo.sGdovSii.o, Yo.sGdo.iSii.o, Yo.iCeo.9Sii.o, Yo.2Ceo.8Sii.o, Yo.3Ceo.7Si1.o- Yo.4Ceo.eSii.o, Yo.sCeo.sSii.o, Yo.6Ceo.4Sii.o, Yo.vCeo.sSii.o, Yo.8Ceo.2Sii.o, Yo.oCeo.iSii.o, Yo.iNdo.oSii.o, Yo.2Ndo.8Sii.o, Yo.sNdo.rSn.o, Yo.4Ndo.6Sii.o, Yo.sNdo.sSii.o, Yo.6Ndo.4Sii.o, Yo.7Ndo.3Si1.c1, Yo.sNdo / zSii.o, Yo.9Ndo.1Si1.o-

[0016] In some embodiments, the magnetocaloric material comprises (TbxBi-s)Sio.8Cro.2, wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the ranee of about 0.05 to about 1.0. In some embodiments, the material is Tb1.oSio.8Cro.2- Tbo.iGdo.9Sio.sCro.2, Tbo.2Gdo.sSio.8Cro.2, Tbo.3Gdo.7Sio.sCro.2, Tbo.4Gdo.6Sio.8Cro.2, Tbo.5Gdo.5Sio.8Cro.2- Tbo.6Gdo.4Sio.sCro.2, Tbo.7Gdo.3Sio.sCro.2, Tb.8Gdo.2Sio.8Cro.2, Tbo.oGdo.iSio.sCro.2, Tbo.1Ceo.9Sio.sCro.2, Tbo.2Ceo.sSio.sCro.2, Tbo.3Ceo.7Sio.8Cro.2, Tbo.4Ce.6Sio.8Cro.2, Tbo.5Ceo.5Sio.8Cro.2, Tbo.6Ce.4Sio.8Cro.2, Tbo.7Ceo.3Sio.8Cro.2, Tbo.8Ceo.2Sio.sCro.2, Tbo.9Ceo.iSio.8Cro.2, Tbo.1Ndo.9Sio.sCro.2, Tbo.2 do.8Sio.8Cro.2, Tbo.3Ndo.7Sio.sCro.2- Tbo.4 do.6Sio.8Cro.2, Tbo.sNdo.sSio.sCro^, Tb.6Ndo.4Sio.8Cro.2, Tbo.7Ndo.3Sio.8Cro.2, Tbo.s dovSio.sCro.?., Tbo.9Ndo.1Sio.sCro.2.

[0017] In some embodiments, the magnetocaloric material comprises (TbxBnx)Sii.0, wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. Illustrative compositions include, without limitation, Tbi.oSii.o, Tbo.iGdo.oSii.o, TbovGdo.sSii.o, Tbo.sGdovSii.o, TtxuGdo.oSii.o, Tbo.sGdo.sSn.o, Tbo.6Gdo.4Sii.o, TbovGdo.sSii.o, Tbo.sGdovSii.o, Tbo.oGdo.iSii.o, Tbo.iCeo.oSii.o, TbovCeo.sSii.o, Tbo.3Ceo.7Sii.o, Tbo.rCeo.eSn.o, Tbo.sCeo.sSii.o, Tbo.6Ceo.4Sii.o, TbovCeo.sSii.o, Tbo.sCeo.2, Sii.o, Tbo. Ceo.iSii.o, Tbo.iNdo.oSii.o, Tbo.2Ndo.8Sii.o, Tbo.3Ndo.7Sii.o, Tbo.4Ndo.6Sii.o, Tb0.5Nd0.5Si1.0, Tbo.6Ndo.4Sii.o, TbovNdo.sSii.o, Tbo.sNdovSii.o, Tbo. Ndo.iSii.o.

[0018] Another embodiment of the invention is a magnetic refrigerator comprising a magnetocaloric material as disclosed herein. In some embodiments, a magnetic refrigerator comprises a magnetocaloric material, wherein the magnetocaloric material comprises (Ax Bi-x) Sii-y-z (Dy Ez), wherein A is selected from the group consisting of Dy, Ho, Er, Y, or Tb, and wherein B is selected from the group consisting of Ce, Nd, or Gd, and wherein D is selected from the group consisting of Cr or Mn, and wherein E is selected from the group consisting of Fe, Al, Ni, Co, Cu, or Zn, and wherein x is in the range of 0.05 to 1.0, and wherein y is in the range of 0 to 0.3, and wherein z is in the range of 0 to 0.3, and wherein 0.0 < y+z < 0.3.

[0019] Another embodiment of the invention is a method of manufacturing a heat pump, comprising fabricating at least one part of the heat pump from a magnetocaloric material as disclosed herein. In some embodiments, a method of manufacturing a heat pump comprises fabricating at least one part of the heat pump from a magnetocaloric material, wherein the magnetocaloric material comprises (Ax Bi-X) Sii-y-z(DyEz), wherein A is selected from the group consisting of Dy, Ho, Er, Y, or Tb, and wherein B is selected from the group consisting of Ce, Nd, or Gd, and wherein D is selected from the group consisting of Cr or Mn, and wherein E is selected from the group consisting of Fe, Al, Ni, Co, Cu, or Zn, and wherein x is in the range of 0.05 to 1.0, and wherein y is in the range of 0 to 0.3, and wherein z is in the range of 0 to 0.3, and w'herein 0.0 < y+z < 0.3.

[0020] For purposes of summarizing aspects of the invention and the advantages achieved over the related art, certain objects and advantages of the invention are described in this disclosure. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0021] Further aspects, features, and advantages of this invention will become apparent from the detailed description of the embodiments which follow.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] A Dyi.oSio.sCrov ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 1 shows the - AS versus temperature for the alloy with a 2nd order phase transition occurring near 140K.

[0023] A Dy0.3Gd0.7Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 2 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 270K.

[0024] A Dyo.sGdo.sSio.sCrov ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 3 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 235K.

[0025] A Dyo.7Gdo.3Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 4 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 200K.

[0026] A Dyo.5Ceo.5Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 5 show's the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 70K.

[0027] A Dyo.6Ceo.4Sio.8Cro.2 ingot was prepared by arc melting m an argon atmosphere. The ingot was measured as-cast. Figure 6 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 75K.

[0028] A Dyo.5Ndo.5Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 7 shows the AS versus temperature for the alloy with a 2nd order phase transition occurring near 85K.

[0029] A DyowCeowSu.o ingot was prepared by arc melting m an argon atmosphere. The ingot was measured as-cast. Figure 8 show's the - AS versus temperature for the alloy with a 2nd order phase transition occurring near 25K.

[0030] A En.oSio.sCrow. ingot w'as prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 9 shows the - AS versus temperature for the alloy with a 2nd order phase transition occurring less than 50K.

[0031] A Gdo.sEro.sSio.sCrov. ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 10 show's the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 165K.

[0032] A Gdo.7Yo.3Sio.8Cro.2 ingot was prepared by arc melting m an argon atmosphere. The ingot was measured as-cast. Figure 11 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 23 OK.

[0033] A Gdo.9Yo.iSio.sCro.2 ingot was prepared by arc melting m an argon atmosphere. The ingot was measured as-cast. Figure 12 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 300K.

[0034] A Ho1.0Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 13 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 75K.

[0035] A Gdo.2Ero.sSio.sCro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 14 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 80K.

[0036] A Gdo.3Ero.7Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 15 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 110K.

[0037] A Gdo.5Hoo.5Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 16 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 190K.

[0038] A Tbi.oSio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 17 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 225K.

[0039] A Gdo.5Tbo.5Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 18 shows the -AS versus temperature for the alloy with a 2nd order phase transition occurring near 280K. In certain implementations, figure captions identify the applied magnetic field used for -AS determination and the sample preparation state (as-cast or annealed).DETAILED DESCRIPTION

[0040] The magnetocaloric effect (MCE) is a phenomenon in which the temperature change of a suitable material is caused by exposing the material to a changing magnetic field. The magnetocaloric effect may be quantified as follows. In some embodiments, the adiabatic temperature change under an applied magnetic field H is described by: / dM(T, H)\ad dH\ dT )Hwhere T is the temperature, H is the applied magnetic field, C is the heat capacity of the working magnet (refrigerant), and M is the magnetization of the refrigerant. The temperature change in the material is caused by a change in the entropy of the material.

[0041] As used herein, the term “magnetocaloric effect” includes any phenomenon in which the temperature change of a material is caused by exposing the material to a changing magnetic field.

[0042] In certain embodiments, the temperature of the magnetocaloric material increases when the magnetic field is applied (e.g., moved near or in contact with the magnetocaloric material) and decreases when the field is removed. The magnetocaloric effect exhibited by most magnetocaloric materials is as follows: the temperature of the magnetocaloric material increases when the magnetic field is moved near or in contact with the magnetocaloric material, and wherein the temperature of the magnetocaloric material decreases when the magnetic field is moved away from the magnetocaloric material. Materials which undergo a magnetocaloric effect with application and removal of a magnetic field include, but are not limited to, Gadolinium-based alloys. In some embodiments, the magnetocaloric material exhibits a magnetocaloric effect, wherein the temperature of the magnetocaloric material increases when the magnetic field is moved near or in contact with the magnetocaloric material, and wherein the temperature of the magnetocaloric material decreases when the magnetic field is moved away from the magnetocaloric material.

[0043] However, some magnetocaloric materials exhibit an inverse magnetocaloric effect, wherein the temperature of the magnetocaloric material decreases when the magnetic field is applied (e.g,, moved near or in contact with the magnetocaloric material), and wherein the temperature of the magnetocaloric material increases when the magnetic field is moved away from the magnetocaloric material. Materials which undergo an inverse magnetocaloric effect with application and removal of a magnetic field include, but are not limited to, Heusler alloys, which include, but are not limited to, NiMn-based alloys. In some embodiments, the magnetocaloric material exhibits an inverse magnetocaloric effect, wherein the temperature of the magnetocaloric material decreases when the magnetic field is moved near or in contactwith the magnetocaloric material, and wherein the temperature of the magnetocaloric material increases when the magnetic field is moved away from the magnetocaloric material.

[0044] The inventors have discovered novel magnetocaloric alloys with 2nd order transitions. Some embodiments provide a magnetocaloric material comprising (Ax Bl-x) Sil - y-z (Dy Ez) wherein A is selected from the group consisting of Dy, Ho, Er, Y, or Tb, and wherein B is selected from the group consisting of Ce, Nd, or Gd, and wherein D is selected from the group consisting of Cr or Mn, and wherein E is selected from the group consisting of Fe, Al, Ni, Co, Cu, or Zn, and wherein x is in the range of 0.05 to 1.0, and wherein y is in the range of 0 to 0.3, and wherein z is in the range of 0 to 0,3, and wherein 0.0 < y+z < 0.3. When y+z=0, the composition reduces to (Ax Bl ~x)Si, with no D or E substitution present.

[0045] Without being bound by theory, it was discovered that utilizing Dysprosium (Dy), or Holmium (Ho), or Yttrium (Y), or Terbium (Tb), may provide advantageous magnetocaloric properties (~AS and / or Curie temperature) in certain compositional windows.

[0046] In some embodiments of the magnetocaloric material, y + z = 0.0. In some embodiments of the magnetocaloric material, y + z = 0.1. In some embodiments of the magnetocaloric material, y + z = 0.2. In some embodiments of the magnetocaloric material, y + z = 0.3. In some embodiments, the optimal performance is achieved when y+z=0.2. In some embodiments of the magnetocaloric material, y + z = 0.2. In some embodiments of the magnetocaloric material, y = 0.1 and z = 0. In some embodiments of the magnetocaloric material, y = 0.2 and z = 0. In some embodiments of the magnetocaloric material, y = 0.3 and z = 0. In some embodiments of the magnetocaloric material, y = 0.05 and z = 0.1. In some embodiments of the magnetocaloric material, y = 0.05 and z = 0.05. In some embodiments of the magnetocaloric material, y = 0.05 and z = 0.15.

[0047] Exemplary compositions are set forth below' for A selected from Dy, Ho, Er, Y, or Tb and B selected from Ce, Nd, or Gd. The listed compositions are illustrative and non-limiting. In some embodiments, the magnetocaloric material comprises (DyxBi-x)Sio.sCro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Dyi.oSio.sCro.2, Dyo.lGdo.9Sio.8Cro.2, Dyo.2Gdo.8Sio.sCro.2, Dyo.3Gdo.7Sio.sCro.2, Dyo.4Gdo.6Sio.sCro.2, Dyo.5Gdo.5Sio.8Cro.2, Dyo.6Gdo.4Sio.8Cro.2, Dyo.7Gdo.3Sio.8Cro.2, Dyo.8Gdo.2Sio.8Cro.2, Dyo.9Gdo.lSio.8Cro.2, Dyo.lCeo.9Sio.sCro.2, Dyo.2Ceo.8Sio.sCro.2, Dyo.3Ceo.7Sio.sCro.2,Dyo.4Ceo.eSio.8Cro.2, Dyo.5Ceo.5Sio.sCro.2, Dy0.eCe0.4Si0.sCr0.2, Dyo.7Ceo.3Sio.8Cro.2- Dy0.sCe0.2Si0.sCr0.2, Dyo.9Ceo.1Sio.sCro.2, Dyo.1Ndo.9Sio.sCro.2, Dyo.2Ndo.sSio.sCro.2, Dyo.3Ndo.7Sio.8Cro.2, Dyo.4Ndo.eSio.8Cro.2, Dyo.5Ndo.5Sio.sCro.2, Dyo.6Ndo.4Sio.8Cro.2, Dyo.7Ndo.3Sio.8Cro.2, Dyo.8Ndo.2Sio.sCro.2, Dy0.9Nd0.1Si0.8Cr0.2.

[0048] In some embodiments, the magnetocaloric material comprises (DyxB1-x)Sii.o wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Dy1.0Si1.0, Dy0.1Gd0.9Si1.0, Dyo.2Gdo.8Sii.o, Dy0.3Gd0.7Si1.0, Dy0.4Gd0.6Si1.0, Dyo.sGdo.sSii.o, Dy0.6Gd0.4Si1.0, Dy0.7Gd0.3Si1.0, Dyo.8Gdo.2Sii.o, Dy0.9Gd0.1Si1.0, Dy0.1Ce0.9Si1.0, Dyo.2Ceo.8Sii.o, Dy0.3Ce0.7Si1.0, Dy0.4Ce0.6Si1.0, Dyo.sCeo.sSil.o, Dyo.6Ceo.4Sii.o, Dy0.7Ce0.3Si1.0, Dy0.8Ce0.2Si1.0, Dy0.9Ce0.1Si1.0, Dy0.1Nd0.9Si1.0, Dyo.2Ndo.8Sii.o, Dy0.3Nd0.7Si1.0, Dyo.4Ndo.6Sii.o, Dy0.5Nd0.5Si1.0, Dy0.6Nd0.4Si1.0, Dyo.7Ndo.3Sii.o, Dy0.8Nd0.2Si1.0, Dy0.9Nd0.1Si1.0.

[0049] In some embodiments, the magnetocaloric material comprises (Hox Bi- x)Sio.sCro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Hoi.oSio.sCro.2, Ho0.1Gd0.9Si0.8Cr0.2, Ho0.2Gd0.8Si0.8Cr0.2, Ho0.3Gd0.7Si0.8Cr0.2, Ho0.4Gd0.6Si0.8Cr0.2, Hoo.5 Gdo.5 S io.8 Cro.2, Hoo. e Gdo.4 S io.8 Cro.2, Ho0.7Gd0.3Si0.8Cr0.2, Ho0.8Gd0.2Si0.8Cr0.2, Hoo.9Gdo.1Sio.8Cro.2, Hoo.iCeo.9Sio.8Cro.2, Hoo.2Ceo.8Sio.8Cro.2, Hoo.3Ceo.7Sio.8Cro.2j Ho0.4Ce0.6Si0.8Cr0.2, Hoo.5Ceo.5Sio.8Cro.2j Hoo.6Ceo.4Sio.8Cro.2, Hoo.7Ceo.3Sio.8Cro.2, Hoo.8Ceo.2Sio.8Cro.2, Hoo.oCeo.i Sio.8Cro.2, Hoo.iNdo.9Sio.sCro.2, Ho0.2Nd0.8Si0.8Cr0.2, Hoo.3Ndo.7Sio.sCro.2j Hoo.4Ndo.6Sio.sCro.2j Hoo.5Ndo.5Sio.sCro.2j Hoo.eNdo.4Sio.sCro.2j Ho0.7Nd0.3Si0.8Cr0.2, Hoo.sNdo.2Sio.8Cro.2j Hoo.9Ndo.1Sio.8Cro.2-

[0050] In some embodiments, the magnetocaloric material comprises (Ho B1-x)Sii.o wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Hoi.oSii.o, Ho0.1Gd0.9Si1.0, Ho0.2Gd0.8Si1.0, Hoo.3Gdo.7Sii.o, Ho0.4Gd0.6Si1.0, Hoo.sGdo.sSii.o, Hoo.6Gdo.4Sii.o, Ho0.7Gd0.3Si1.0, Hoo.sGdo.2Sii.o, Ho0.9Gd0.1Si1.0, Ho0.1Ce0.9Si1.0, Hoo.2Ceo.sSii.o, Ho0.3Ce0.7Si1.0, Ho0.4Ce0.6Si1.0, Hoo.sCeo.sSii.o, Ho0.6Ce0.4Si1.0, Ho0.7Ce0.3Si1.0, Ho0.8Ce0.2Si1.0, Ho0.9Ce0.1Si1.0, Ho0.1Nd0.9Si1.0, Ho0.2Nd0.8Si1.0, Ho0.3Nd0.7Si1.0, Hoo.4Ndo.6Sii.o, Ho0.5Nd0.5Si1.0, Hoo.6Ndo.4Sii.o, Ho0.7Nd0.3Si1.0, Ho0.8Nd0.2Si1.0, Ho0.9Nd0.1Si1.0.

[0051] In some embodiments, the magnetocaloric material comprises (ErxBnx)Sio.sCro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Er1.0Si0.8Cr0.2, Ero.1Gdo.9Sio.sCro.2, Ero.2Gdo.8Sio.sCro.2, Er0.3Gd0.7Si0.8Cr0.2, Ero.4Gdo.6Sio.sCro.2, Er0.5Gd0.5Si0.8Cr0.2, Ero.6Gdo.4Sio.sCro.2, Ero.7Gdo.3Sio.sCro.2, Ero.sGdo.2Sio.8Cro.2, Ero.9Gdo.1Sio.sCro.2, Ero.iCeo.9Sio.sCro.2, Ero.2Ceo.sSio.sCro.2, Ero.3Ceo.7Sio.sCro.2, Ero.4Ceo.6Sio.sCro.2, Ero.sCeo.5Sio.sCro.2, Ero.6Ceo.4Sio.sCro.2, Er0.7Ce0.3Si0.8Cr0.2, Er0.8Ce0.2Si0.8Cr0.2, Ero.9Ceo.iSio.sCro.2, Ero.iNdo.9Sio.sCro.2, Ero.2Ndo.sSio.sCro.2, Ero.3Ndo.7Sio.sCro.2, Ero.4Ndo.6Sio.sCro.2, Er0.5Nd0.5Si0.8Cr0.2, Ero.6Ndo.4Sio.sCro.2, Ero.7Ndo.3Sio.sCro.2, Ero.sNdo.2Sio.sCro.2, Er0.9Nd0.1Si0.8Cr0.2.

[0052] In some embodiments, the magnetocaloric material comprises (ErxB1-x)Si1.0wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Er1.0Si1.0, Er0.1Gd0.9Si1.0, Ero.2Gdo.sSii.o, Er0.3Gd0.7Si1.0, Er0.4Gd0.6Si1.0, Ero.sGdo.sSii.o, Ero.6Gdo.4Sii.o, Er0.7Gd0.3Si1.0, Ero.sGdo.2Sii.o, Er0.9Gd0.1Si1.0, Er0.1Ce0.9Si1.0, Ero.2Ceo.8Sii.o, Ero.3Ceo.7Sii.o, Er0.4Ce0.6Si1.0, Er0.5Ce0.5Si1.0, Er0.6Ce0.4Si1.0, Er0.7Ce0.3Si1.0, Ero.8Ceo.2Sii.o, Er0.9Ce0.1Si1.0, Er0.1Nd0.9Si1.0, Ero.2Ndo.sSii.o, Ero.3Ndo.7Sii.o, Er0.4Nd0.6Si1.0,, Ero.sNdo.sSii.o, Er0.6Nd0.4Si1.0, Ero.7Ndo.3Sii.o, Ero.sNdo.2Sii.o, Er0.9Nd0.1Si1.0.

[0053] In some embodiments, the magnetocaloric material comprises (YxBi-x)Sio.8Cro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Y1.0Si0.8Cr0.2, Y0.1Gd0.9Si0.8Cr0.2,, Y0.2Gd0.8Si0.8Cr0.2,, Y0.3Gd0.7Si0.8Cr0.2,, Y0.4Gd0.6Si0.8Cr0.2,, Yo.sGdo.sSio.sCro.2, Yo.6Gdo.4Sio.sCro.2, Yo.7Gdo.3Sio.sCro.2j Y0.sGd0.2Si0.sCr0.2, Y0.9Gd0.1Si0.8Cr0.2,, Y0.1Ce0.9Si0.sCr0.2, Y0.2Ce0.sSi0.sCr0.2, Yo.3Ceo.7Sio.sCro.2, Yo.4Ceo.6Sio.8Cro.2, Y0.5Ce0.5Si0.8Cr0.2,, Y0.6Ce0.4Si0.8Cr0.2,, Yo.7Ceo.3Sio.sCro.2, Y0.sCe0.2Si0.sCr0.2, Yo.9Ceo.1Sio.sCro.2, Y0.1Nd0.9Si0.8Cr0.2,, Y0.2Nd0.8Si0.8Cr0.2,, Y0.3Nd0.7Si0.8Cr0.2,, Y0.4Nd0.6Si0.8Cr0.2,, Yo.5Ndo.5Sio.sCro.2j Yo.6Ndo.4Sio.sCro.2, Yo.7Ndo.3Sio.sCro.2, Yo.sNdo.2Sio.sCro.2, Y0.9Nd0.1Si0.8Cr0.2.

[0054] In some embodiments, the magnetocaloric material comprises (YxBi-x)Sii.o wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Y1.0Si1.0, Yo.iGdo.oSii.o,Y0.2Gd0.8Si1.0, Y0.3Gd0.7Si1.0, Yo.4Gdo.6Sii.o, Yo.sGdo.sSil.o, Yo.6Gdo.4Sii.o, Y0.7Gd0.3Si1.0, Y0.8Gd0.2Si1.0, Y0.9Gd0.1Si1.0, Y0.1Ce0.9Si1.0, Yo.2Ceo.8Sii.o, Y0.3Ce0.7Si1.0, Yo.4Ceo.6Sii.o, Y0.5Ce0.5Si1.0, Y0.6Ce0.4Si1.0, Y0.7Ce0.3Si1.0, Yo.8Ceo.2Sii.o, Yo.9Ceo.iSii.o, Y0.1Nd0.9Si1.0, Y0.2Nd0.8Si1.0, Y0.3Nd0.7Si1.0, Yo.4Ndo.6Sii.o, Yo.sNdo.sSii.o, Yo.6Ndo.4Sii.o, Y0.7Nd0.3Si1.0, Yo.8Ndo.2Sii.o, Y0.9Nd0.1Si1.0.

[0055] In some embodiments, the magnetocaloric material comprises (Tbx Bi- x)Sio.sCro.2 wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Tbi.oSio.sCro.2, Tbo.iGdo.9Sio.8Cro.2, Tbo.2Gdo.8Sio.8Cro.2, Tbo.3Gdo.7Sio.sCro.2j Tbo.4Gdo.6Sio.8Cro.2, Tbo.5Gdo.5Sio.sCro.2j Tbo.6Gdo.4Sio.sCro.2, Tbo.7Gdo.3Sio.8Cro.2j Tbo.8Gdo.2Sio.sCro.2j Tbo.9Gdo.iSio.8Cro.2, Tbo.iCeo.9Sio.8Cro.2, Tbo.2Ceo.sSio.sCro.2j Tbo.3Ceo.7Sio.sCro.2, Tbo.4Ceo.6Sio.sCro.2, Tbo.5Ceo.5Sio.8Cro.2j Tbo.6Ceo.4Sio.sCro.2, Tbo.7Ceo.3Sio.8Cro.2j Tbo.8Ceo.2Sio.8Cro.2, Tbo.9Ceo.iSio.8Cro.2, Tbo.iNdo.9Sio.8Cro.2, Tbo.2Ndo.sSio.8Cro.2j Tbo.3Ndo.7Sio.sCro.2j Tbo.4Ndo.6Sio.8Cro.2, Tbo.5Ndo.5Sio.8Cro.2j Tbo.6Ndo.4Sio.sCro.2j Tb0.7Nd0.3Si0.8Cr0.2. Tbo.8Ndo.2Sio.sCro.2, Tb0.9Nd0.1Si0.8Cr0.2.

[0056] In some embodiments, the magnetocaloric material comprises (Tbx Bi- x)Sii.o wherein B is selected from the group consisting of Ce, Nd, or Gd, wherein x is in the range of about 0.05 to about 1.0. In some embodiments, the material is Tbi.oSii.o, Tbo.iGdo. Sii.o, Tbo.2Gdo.8Sii.o, Tb0.3Gd0.7Si1.0, Tb0.4Gd0.6Si1.0, Tbo.sGdo.sSii.o, Tbo.6Gdo.4Sii.o, Tbo.7Gdo.3Sii.o, Tb0.8Gd0.2Si1.0, Tb0.9Gd0.1Si1.0, Tb0.1Ce0.9Si1.0, Tbo.2Ceo.8Sii.o, Tbo.3Ceo.7Sii.o, Tb0.4Ce0.6Si1.0, Tbo.sCeo.sSii.o, Tb0.6Ce0.4Si1.0, Tb0.7Ce0.3Si1.0, Tb0.8Ce0.2Si1.0, Tb0.9Ce0.1Si1.0, Tb0.1Nd0.9Si1.0, Tb0.2Nd0.8Si1.0, Tb0.3Nd0.7Si1.0, Tb0.4Nd0.6Si1.0, Tb0.5Nd0.5Si1.0, Tb0.6Nd0.4Si1.0, Tb0.7Nd0.3Si1.0, Tb0.8Nd0.2Si1.0, Tbo.9Ndo.1Si1.o-

[0057] In some embodiments, a magnetic refrigerator comprises the magnetocaloric material as described herein. In some embodiments, a magnetic refrigerator comprises a magnetocaloric material, wherein the magnetocaloric material comprises (Ax Bi-x) Si1-y-z(Dy Ez) wherein A is selected from the group consisting of Dy, Ho, Er, Y, or Tb, and wherein B is selected from the group consisting of Ce, Nd, or Gd, and wherein D is selected from the group consisting of Cr or Mn, and wherein E is selected from the group consisting of Fe, Al, Ni, Co, Cu, or Zn, and wherein x is in the range of 0.05 to 1.0, and wherein y is in the range of 0 to 0.3, and wherein z is in the range of 0 to 0.3, and wherein 0.0 < y+z < 0.3.

[0058] In some embodiments, a method of manufacturing a heat pump comprises fabricating at least one part of the heat pump from a magnetocaloric material as described herein In some embodiments, a method of manufacturing a heat pump comprises fabricating at least one part of the heat pump from a magnetocaloric material, wherein the magnetocaloric material comprises (Ax Bi-X) Si1-y-z(DyEz) wherein A is selected from the group consisting of Dy, Ho, Er, Y, or Tb, and wherein B is selected from the group consisting of Ce, Nd, or Gd, and wherein D is selected from the group consisting of Cr or Mn, and wherein E is selected from the group consisting of Fe, Al, Ni, Co, Cu, or Zn, and wherein x is in the range of 0.05 to 1.0, and wherein y is in the range of 0 to 0.3, and wherein z is in the range of 0 to 0.3, and wherein 0.0 < y+z < 0.3.

[0059] In certain embodiments, the response temperature (e g.. Curie temperature or transition temperature) of the magnetocaloric material may be adjusted with small changes in the composition of the material. In some embodiments, the response temperature of the magnetocaloric material is adjusted by changing the composition of the material. In some embodiments, the magnetocaloric material exhibits a magnetocaloric effect within temperature ranges including, but not necessarily limited to about IK to about 350K. In some embodiments, the magnetocaloric material exhibits a magnetocaloric effect at any temperature in the range of about 10K to about 50K. In some embodiments, the magnetocaloric material exhibits a magnetocaloric effect at any temperature in the range of about 50K to about lOOOK. In some embodiments, the magnetocaloric material exhibits a magnetocaloric effect at any temperature in the range of about 100K to about 350K. In some embodiments, the magnetocaloric material exhibits a magnetocaloric effect at any temperature in the range of about 50K to about 200K. In some embodiments, the magnetocaloric nanomaterial exhibits a magnetocaloric effect at any temperature in the range of about 10K to about 80K.

[0060] Magnetocaloric materials can be synthesized using various methods, such as arc melting, induction melting, or any other type of metal melting process. In some embodiments, the magnetocaloric materials are synthesized using an arc melt furnace. In some embodiments, the magnetocaloric materials are synthesized using an induction melt furnace. In some embodiments, the magnetocaloric materials are synthesized using a rotating disk atomization furnace. In some embodiments, the magnetocaloric materials are synthesized using a levitation melt furnace.

[0061] Following synthesis of the magnetocaloric alloy, an annealing process may be used to homogenize the material. In some cases, the anneal improves and / or shifts the magnetocaloric properties (-AS or the Curie temperature). Anneals can be performed in a variety of furnace types, including radiation furnaces, induction furnace, tube The optimal anneal temperature and time may vary depending on the magnetocaloric material composition. In certain embodiments, the anneal temperature is between about 700°C and about 2000°C. In some embodiments, the anneal time is between about 30 minutes and about 6 weeks.

[0062] For purposes of summarizing aspects of the invention and the advantages achieved over the related art, certain objects and advantages of the invention are described in this disclosure. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0063] Further aspects, features, and advantages of this invention will become apparent from the detailed example embodiments which follow.EXAMPLES

[0064] The embodiments will be explained with respect to preferred embodiments which are not intended to limit the present invention. Further, in the present disclosure where conditions and / or structures are not specified, the skilled artisan in the art can readily provide such conditions and / or structures, in light of the teachings herein, as a matter of routine experimentation.

[0065] The object of some of the current inventions is to provide magnetocaloric materials useful for magnetic refrigeration applications.Example 1

[0066] A Dyi.oSio.sCro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 1 shows the −ΔS versus temperature for the alloy with a second-order phase transition occurring near 140K.Example 2

[0067] A Dy0.3Gd0.7Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 2 shows the -AS versus temperature for the alloy w’ith a second-order phase transition occurring near 270K.Example 3

[0068] A Dy0.5Gd0.5Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 3 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 235K.Example 4

[0069] A Dyo.7Gdo.3Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 4 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 200K.Example 5

[0070] A Dy0.5Ce0.5Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 5 shows the AS versus temperature for the alloy with a second-order phase transition occurring near 70K.Example 6

[0071] A Dy0.6Ce0.4Si0.8Cr0.2 ingot was prepared by arc melting m an argon atmosphere. The ingot was measured as-cast. Figure 6 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 75K.Example 7

[0072] A Dyo.sNdo.5Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 7 shows the -AS versus temperature for the alloy w’ith a second-order phase transition occurring near 85K.Example 8

[0073] A Dyo.5Ceo.5Si1.0 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 8 shows the - AS versus temperature for the alloy with a second-order phase transition occurring near 25K.Example 9

[0074] A Er1.0Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 9 shows the -AS versus temperature for the alloy with a second-order phase transition occurring less than 50K.Example 10

[0075] A Gdo.5Ero.5Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 10 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 165K.Example 11

[0076] A Gdo.7Yo.3Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 11 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 230K.Example 12

[0077] A Gdo.9Yo.iSio.8Cro.2 ingot was prepared by arc melting m an argon atmosphere. The ingot was measured as-cast. Figure 12 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 300K.Example 13

[0078] A Ho1.0Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 13 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 75K.Example 14

[0079] A Gdo.2Ero.8Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 14 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near SOK.Example 15

[0080] A Gd0.3Er0.7Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 15 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 11 OK,Example 16

[0081] A Gdo.5Hoo.5Sio.8Cro.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 16 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 190K.Example 17

[0082] A Tb1.0Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 17 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 225K.Example 18

[0083] A Gd0.5Tb0.5Si0.8Cr0.2 ingot was prepared by arc melting in an argon atmosphere. The ingot was measured as-cast. Figure 18 shows the -AS versus temperature for the alloy with a second-order phase transition occurring near 280K.Example 19

[0084] An example magnetic refrigerator comprising the disclosed magnetocaloric material is made by the following steps 1) preparing the magnetocaloric material into thin plates or millimeter sized spherical particles, 2) placing the magnetocaloric material into a magnetic field, where the application of the magnetic field causes the material to heat up, 3) using a heat transfer fluid to remove the heat from the magnetocaloric material, 4) thenremoving the magnetic field, causing the magnetocaloric material to cool down, 5) then exposing the cold magnetocaloric material to the desired refrigeration environment, where heat from the refrigeration environment is transferred to the magnetocaloric material, 6) then repeating steps 1 to 5 to create a refrigeration cycle which maintains a desired cold temperature within the refrigeration environment.Example 20

[0085] An example magnetic refrigerator comprising the disclosed magnetocaloric material is made by the following similar steps as in Example 9, except that a heat transfer fluid is used in step 5 to expose the cold magnetocaloric material to the desired refrigeration environment, where the heat from the refrigeration environment is transferred to the heat transfer fluid.Example 21

[0086] An example heat pump comprising fabricating at least one part of the heat pump from a magnetocaloric material is made by incorporating at least one magnetocaloric material of the disclosed invention, at least one permanent magnet, and at least one mechanical movement system; wherein the magnetic field generated by the permanent magnet enables the magnetocaloric effect of the magnetocaloric material when at least one oscillation cycle is performed by the mechanical movement system, wherein a change in temperature of the magnetocaloric material occurs when the magnetocaloric material is moved into or out of a magnetic field; and wherein the mechanical movement system performs the at least one oscillation cycle by physically moving the permanent magnet, the magnetocaloric material, a magnet shielding material, or any combination thereof; and wherein the at least one oscillation cycle comprises exposing the magnetic field to the magnetocaloric material at a predefined magnetic field ramp-up speed, holding the magnetic field near or in contact with the magnetocaloric material for a specified contact holding time, removing the magnetic field from the magnetocaloric material at a predefined ramp-down speed, and holding the magnetic field away from the magnetocaloric material for a specified removed holding time; and wherein the at least one oscillation cycle is optimized to provide cooling on one side of the heat pump device.

[0087] For purposes of summarizing aspects of the invention and the advantages achieved over the related art, certain objects and advantages of the invention are described in this disclosure. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein. It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention.Definitions. Disclaimers, and Interpretation of Terms

[0088] As used herein, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. The term “or” is intended to mean an inclusive “or” (i.e., “and / or”) unless the context clearly indicates otherwise.

[0089] Unless otherwise indicated, the terms “comprising,” “including,” “having,” “containing,” and “characterized by” are used in an open-ended sense and do not exclude additional, unrecited elements, features, steps, or components. In certain contexts, “consisting essentially of’ may be used to indicate that recited features are material to performance, while permitting the presence of other features that do not materially affect the recited performance. The phrase “consisting of” is used, where stated, to indicate a closed set.

[0090] Terms such as “about,” “approximately,” “substantially,” “generally,” and “negligible” are used to account for measurement uncertainty, manufacturing tolerances, and expected variation in material properties. Unless otherwise specified, “about” when applied to a numerical value or range should be understood to encompass values within ±10% of the stated value, or within normal experimental error for the measurement technique, whichever is greater. Unless otherwise indicated, numerical values are expressed to appropriate significant figures and may be interpreted as approximate values. Conversions between units are assumed to be exact for purposes of clarity unless otherwise specified.

[0091] Ranges disclosed herein are intended to include all values and subranges within the stated endpoints. For example, a range stated as “0.05 to 1.0” encompasses any value and subrange from and including 0.05 up to and including 1.0 (e.g., 0.05-0.10, 0.1-0.5, 0.25, 0.95-1.0). When a range is stated and referenced with “at least,” “no more than,” “greater than,” or “less than,” unless otherwise indicated, the range shall be construed to include the boundary value. Where multiple ranges are presented for a variable, any disclosed endpoints and subranges can be combined unless the context clearly indicates otherwise.

[0092] Lists of elements, material s, components, or steps identified by phrases such as “include,” “includes,” “including,” “selected from,” “chosen from,” “such as,” and “for example,” are intended to be non-limiting and illustrative. Unless expressly stated to the contrary, the listed items may be combined, may be used alternatively, and may include equivalents known to those skilled in the art.

[0093] Where formulas or compositions are expressed with variables (e.g., (Ax B1−x)Si1−y−z(Dy Ez)), the variables (x, y, z) denote atomic fractions or stoichiometric coefficients as commonly understood in the art. Unless otherwise specified, “x in the range of,” “y in the range of,” and “z in the range of’ include all values and subranges therebetween, and may be selected independently. In embodiments where y+z=0, the absence of D and E substitution shall be understood as no intentional addition of those elements, allowing for incidental impurities within standard material tolerances.

[0094] Performance descriptors such as “second-order transition,” “negligible hysteresis,” “enhanced,” “improved,” “advantageous,” and similar terms are intended to be qualitative and may be assessed using accepted measurement methods in the art (e.g., magnetization, calorimetry, cyclic −ΔS evaluation). Unless otherwise specified, such descriptors are not intended to impose a numerical limitation and should be construed in light of the disclosed measurement approaches.

[0095] Unless otherwise indicated, parameters (e.g., x, y, z; temperatures; times) may be selected independently and need not be correlated, except where explicitly constrained or technically incompatible. Features identified as ‘optional’ or steps identified as ‘may’ or ‘can’ are not required unless expressly stated as required for a particular embodiment. Where features or elements are disclosed in connection with any embodiment, such features orelements may be combined in any operable manner, where technically compatible and clearly supported by the present disclosure.

[0096] Headings and section titles are provided for convenience and shall not be used to limit the scope or interpretation of the disclosure. The examples and figures are illustrative and intended to aid understanding; they need not reflect optimal or exclusive configurations, and do not limit the claimed subject matter.

[0097] Such changes and modifications are intended to be covered by the appended claims and equivalents. Unless otherwise specified, properties such as magnetization, heat capacity, Curie temperature, and isothermal entropy change are measured using accepted methods in the art under standard laboratory conditions. Differences attributable to sample preparation (e.g., as-cast versus annealed), applied field strength, or measurement protocol should be considered when interpreting reported values. Any background statements or references, where provided, are presented for general context and shall not be construed as an admission that any such materials constitute prior art against the present disclosure. It will be understood that changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention. Such changes and modifications are intended to be covered by the appended claims and their equivalents.

Claims

WHAT IS CLAIMED IS:

1. A magnetocaloric material comprising:(Ax B1−x) Si1−y−z (Dy Ez)wherein A is selected from the group consisting of Dy, Ho, Er, Y, or Tb, wherein B is selected from the group consisting of Ce, Nd, or Gd,wherein D is selected from the group consisting of Cr or Mn,and E is selected from the group consisting of Fe, Al, Ni, Co, Cu, or Zn, wherein x is in a range of 0.05 to 1,0,wherein y is in a range of 0 to 0,3,wherein z is in a range of 0 to 0,3, and wherein 0,0 < y+z < 0.3.

2. The magnetocaloric material of claim 1, wherein y<z=0.2.

3. The magnetocaloric material of claim 2, wherein the material comprises: (DyxBi-x) Sio.sCro.2wherein B is selected from the group consisting of Ce, Nd, or Gd,wherein x is in the range of 0.05 to 1.0.

4. The magnetocaloric material of claim 2, wherein the material is Dyi.oSio.sCro.2, Dyo.1Gdo.9Sio.sCro.2, Dyo.2Gdo.sSio.8Cro.2, Dyo.3Gdo.7Sio.8Cro.2, Dyo.4Gdo.6Sio.8Cro.2, Dy 0.5 Gdo.5 S io.8 Cro.2, Dy 0.6 Gdo.4 S io.8 Cro.2, Dyo.7Gdo.3Sio.8Cro.2, Dyo.8Gdo.2Sio.8Cro.2, Dyo.9Gdo.1Sio.sCro.2, Dyo.1Ceo.9Sio.8Cro.2, Dyo.2Ceo.sSio.8Cro.2, Dyo.3Ceo.7Sio.8Cro.2, Dyo.4Ceo.6Sio.sCro.2, Dyo.5Ceo.5Sio.sCro.2, Dyo.6Ceo.4Sio.8Cro.2, Dyo.7Ce.3SlO. Cro.2, Dyo.8Ceo.2Sio.8Cro.2, Dyo.9Ceo.1Sio.sCro.2, Dyo.iNdo.9Sio.8Cro.2, Dyo.2Ndo.8Sio.sCro.2, Dyo.sNdo.rSio.sCro.?., Dyo.4Ndo.6Sio.8Cro.2, Dyo.sNdo.sSio.sCro.?., Dyo.6Ndo.4Sio.8Cro.2, Dyo.7Ndo.3Sio.sCro.2, Dyo.8Ndo.2Sio.8Cro.2, Dyo.9Ndo.1Sio.8Cro.2.

5. The magnetocaloric material of claim 1, wherein y+z=0.

6. The magnetocaloric material of claim 5, wherein the material is Dyi.oSii.o, Dy0.1Gd0.9Si1.0, Dyo.2Gdo.8Sn.o, Dyo.sGdo.rSii.o, Dy Gdo.oSii.o, Dyo.sGdo.sSii.o, Dyo.6Gdo.4Sn.o, Dyo.rGdo.sSii.o, Dyo.sGdo.2Sii.o, Dyo. Gdo.iSii.o, Dy0.1Ce0.9Si1.0, Dyo.2Ceo.sSii.o, Dyo.sCeo.rSii.o, Dyo.4Ceo.6Sii.o, Dyo.sCeo.sSii.o, Dyo.eCeo. Sii.o, Dyo^Ceo.sSii.o, Dyo.8Ceo.2Sii.o, Dyo.oCeo.i Sii.o, Dyo.iNdo.oSii.o, Dyo.2Ndo.sSii.o, Dyo.sNdo.rSii.o, Dyo.4Ndo.6Sii.o, Dyo.sNdo.sSii.o, Dyo.6Ndo.4Sii.o, Dyo.rNdo.sSii.o, Dyo.8Ndo.2Sn.o, Dyo. Ndo.i Sii.o.

7. The magnetocaloric material of claim 2, wherein the material comprises:(Hox Bi-x) Sio.sCro.2wherein B is selected from the group consisting of Ce, Nd, or Gd,wherein x is in a range of 0.05 to 1.0.

8. The magnetocaloric material of claim 2, wherein the material is Hoi.oSio.sCro.2, Hoo.lGdo.9Sio.8Cro.2, Hoo.2Gdo.8Sio. Cro.2, Hoo.3Gdo.7Sio.8Cro.2, Hoo.4Gdo.6Sio.8Cro.?, Hoo.5Gdo.5Sio.8Cro.2, Hoo.6Gdo.4Sio.sCro.2, Hoo.7Gdo.3Sio.sCro.2, Hoo.8Gdo.2Sio.sCro.2, Hoo.9Gdo.lSio.8Cro.2, Hoo.i Ce0.9Si0.sCr0.2, Hoo.2Ceo.8Sio.sCro.2, Hoo.3Ceo.7Sio.8Cro.2- Hoo.4Ceo.6Sio.8Cro.2, Hoo.5Ceo.5Sio.sCro.2, Hoo.6Ceo.4Sio.sCro.2, Hoo.? Ceo.3 Sio.sCro.2, Hoo.sCeo.2Sio.sCro.2j Hoo. Ceo.i Sio.sCro.2, Hoo.iNdo. Sio.sCroz, Hoo.2Ndo.8Sio.sCro.2- Hoo.3Ndo.7Sio.sCro.2j Hoo.rNdo.eSio.sCro.?, Hoo.sNdo.sSio.sCro.?, Hoo.6Ndo.4Sio.sCro.2, Hoo.7Ndo.3Sio.8Cro.2, Hoo.sNdo.2Sio.8Cro.2- Hoo.9Ndo.iSio.8Cro.2.

9. The magnetocaloric material of claim 1, wherein y+z=0.The magnetocaloric material of claim 5, wherein the material is Hoi.oSii.o, Ho0.1Gd0.9Si1.0, Hoo.? Gdo.sSii.o, Hoo.sGdo.rSii.o, Hoo. Gdo.eSii.o, Hoo.sGdo.sSii.o, Hoo.eGdo. Sii.o, Ho0.7Gd0.3Si1.0, Hoo.sGdo.2Si1. Oj Hoo.oGdo.iSil.o, Hoo.iCeo. Sil.o, Hoo.2Ceo.sSi1. Oj Ho0.3Ce0.7Si1.0, Hoo / jCeo.eSii.o, Hoo.sCeo.sSil.o, Hoo.eCeo. Sil.o, Hoo.7Ceo.3Si1. Oj Hoo.8Ceo.2Si1. Oj Hoo.oCeo.iSil.o, Hoo.iNdo.oSii.o, Hoo.2Ndo.sSi1. Oj Hoo.sNdo.rSii.o, Hoo.4Ndo.6Sii.o, Hoo.sNdo.sSii.o, Hoo.6Ndo.4Sii.o, Ho0.7Nd0.3Si1.0, Ho0.8Nd0.2Si1.0, Hoo.9Ndo.1Si1.o- 10. The magnetocaloric material of claim 2, wherein the material comprises: (ErxBi-x) Sio.sCro.2wherein B is selected from the group consisting of Ce, Nd, or Gd,wherein x is in a range of 0.05 to 1.0.

11. The magnetocaloric material of claim 2, wherein the material is En.oSio.sCro.2, Er 0.1 Gdo.9 S io.8 Cr 0.2, Ero.2Gdo.sSio.8Cro.2, Ero.3Gdo.7Sio.sCro.2, Ero.4Gdo.6Sio.8Cro.?, Ero.5Gdo.5Sio.8Cro.?,, Ero.6Gdo.4Sio.sCro.2, Ero.7Gdo.3Sio.8Cro.?., Ero.8Gdo.2Sio.sCro.2, Ero.oGdo.iSio.sCro.2, Ero.1Ceo.9Sio.sCro.2, Ero.2Ceo.8Sio.sCro.2, Ero.3Ceo.7Sio.8Cro.?, Ero.4Ceo.6Sio.sCro.2, Ero.sCeo.sSio.sCro.?, Ero.6Ceo.4Sio.sCro.2, Ero.? Ceo.3 Sio.sCro.2, Ero.sCeozSio.sCro.?, Ero. Ceo.i Sio.sCro.?, Ero.1Ndo.9Sio.8Cro.?, Ero.2Ndo.8Sio.sCro.?, Ero.3Ndo.7Sio.sCro.2, Ero.4Ndo.6Sio.sCro.2, Ero.5Ndo.5Sio.sCro.?, Ero.6Ndo.4Sio.sCro.2, Ero.7 do.3Sio.sCro.2, Ero.8Ndo.2Sio.sCro.2, Er0.9Nd0.1Si0.8Cr0.

2.

12. The magnetocaloric material of claim 1, wherein y+z=0.

13. The magnetocaloric material of claim 5, wherein the material is Er1.0Si1.0, Er0.1Gd0.9Si1.0, Ero.2Gdo.8Sii.o, Ero.3Gdo.7Sii.o, En Gdo.eSii.o, Ero.sGdo.sSii.o, Ero.6Gdo.4Sii.o, Ero.vGdo.sSil.o, Ero.sGdo.2Si1. Oj Ero.oGdo.i Sil.o, Ero.iCeo.oSil.o, Ero.2Ceo.sSii.o, Ero.aCeo.vSil.o, Ero.rCeo.oSii.o, Ero.sCeo.sSil.o, Ero.6Ceo.4Sii.o, Ero.7Ceo.3Si1. Oj Ero.sCeo.2Si1. Oj Ero.oCeo.iSil.o, Ero.iNdo. Sil.o, Ero.2Ndo.sSii.o, Ero.sNdo.rSil.o, Ero.4Ndo.6Si].o, Ero.sNdo.sSil.o, Ero.eNdo. Sii.o, Ero.7Ndo.3Sii.o, Ero.sNdo.2Sii.o, Er0.9Nd0.1Si1.

0.

14. The magnetocaloric material of claim 2, wherein the material comprises: (YxBi-x) Sio.sCro.2wherein B is selected from the group consisting of Ce, Nd, or Gd,wherein x is in a range of 0.05 to 1,0.

15. The magnetocaloric material of claim 2, wherein the material is Y1.0Si0.8Cr0.2, Yo.iGdo.9Sio.sCro.2j Yo.2Gdo.sSio.sCro.2, Yo.3Gdo.7Sio.sCro.2j Yo.4Gdo.6Sio.sCro.2, Yo.5Gdo.5Sio.sCro.2j Yo.6Gdo.4Sio.sCro.2, Yo.rGdo.s Sio.sCro.2, Yo.sGdo.2Sio.sCro.2, Yo.9Gdo.iSio.sCro.2j Yo.iCeo.gSio.sCroc, Yo.2Ceo.sSio.sCro.2, Yo.3Ceo.7Sio.sCro.2j Yo.4Ceo.6Sio.sCro.2, Yo.5Ceo.5Sio.sCro.2j Yo.6Ceo.4Sio.sCro.2j Yo.7Ceo.3Sio.sCro.2j Yo.sCeo.2Sio.sCro.2, Yo.9Ceo.iSio.sCro,2, Yo.iNdo.9Sio.sCro.2j Yo.2Ndo.sSio.sCro.2, Yo.3Ndo.7Sio.sCro.2j Yo. do.6Sio.sCro.2, Yo.5Ndo.5Sio.sCro.2, Yo.6 do.4Sio.8Cro.2, Yo.rNdo.3 Sio.sCro.2, Yo.sNdo.2Sio.8Cro.2, Yo.9Ndo.iSio.sCro,2.

16. The magnetocaloric material of claim 1, wherein y+z=0.

17. The magnetocaloric material of claim 5, wherein the material is Yi.oSn.o, Yo.iGdo. Sil.o, Yo.2Gdo.sSi1. Oj Yo.sGdo.rSn.o, Yo.4Gdo.6Sii.o, Yo.sGdo.sSil.o, Yo.6Gdo.4Sii.o, Yo.7Gdo.3Si1. Oj Yo.sGdo.2Sii.o, Yo.oGdo.iSil.o, Yo.iCeo. Sil.o, Yo.2Ceo.sSii.o, Yo.3Ceo.7Sii.o, Yo.4Ceo. Sii.o, Y0.5Ce0.5Si1.0, Yo.6Ceo.4Sii.o, Yo.7Ceo.3Si1. Oj Yo.sCeo.2Si1. Oj Yo.oCeo.iSil.o, Yo.iNdo.oSil.o, Yo.2Ndo.sSi1. Oj Yo.3Ndo.7Si1. Oj Yo.4Ndo. Sii.o, Yo.sNdo.sSil.o, Yo. Ndo.4Sn. Oj Yo.7Ndo.3Si1. Oj Yo.8Ndo.

2. Sii.o, Yo.9Ndo.1Si1.o- 18. The magnetocaloric material of claim 2, wherein the material comprises: (Tbx Bi-x) Sio.sCro.2wherein B is selected from the group consisting of Ce, Nd, or Gd,wherein x is in a range of 0.05 to 1.0.

19. The magnetocaloric material of claim 2, wherein the material is Tbi.oSio.sCro.2, Tbo.iGdo.9Sio.sCro.2j Tbo.2Gdo.8Sio.8Cro.2, Tbo.3Gdo.7Sio.sCro.2j Tbo.4Gdo.6Sio.sCro.2,Tbo.sGdo.5Sio.8Cro.2, Tbo.6Gdo.4Sio.sCro,2, Tbo.7Gdo.3Sio.8Cro.2, Tbo.sGdo.2Sio.8Cro.2, Tbo.9Gdo.1Sio.sCro.2, Tbo.i Ceo.9Sio.8Cro.2- Tbo.2Ceo.8Sio.8Cro.2, Tbo.3Ceo.7Sio.sCro.2j Tbo.4Ceo.6Sio.sCro.2, Tbo.5Ceo.5Sio.8Cro.2- Tbo.6Ceo.4Sio.sCro.2, Tbo.7Ceo.3Sio.8Cro.2- Tbo.8Ceo.2Sio.8Cro.2, Tbo. Ceo.i Sio.8Cro.2, Tbo.1Ndo.9Sio.8Cro.2, Tbo.2Ndo.8Sio.sCro,2, Tbo.3Ndo.7Sio.8Cro.2j Tbo. Ndo.6Sio.sCro,2, Tbo.5Ndo.5Sio.8Cro.2, Tbo.6Ndo. Sio.8Cro.2, Tbo.7Ndo.3Sio.8Cro.2, Tbo.8Ndo.2Sio.8Cro.2, Tbo. Ndo.i Sio.sCro.2.

20. The magnetocaloric material of claim 1, wherein y+z=0.

21. The magnetocaloric material of claim 5, wherein the material is Tbi.oSn.o, Tbo.1Gdo.9Si i.o, Tbo.2Gdo.8Sn.o, Tbo.3Gdo.7Si1. Oj Tbo.rGdo.eSii.o, Tbo.sGdo.sSii.o, Tbo.6Gdo.4Sii.o, Tbo.7Gdo.3Si1. Oj Tbo.8Gdo.2Sii.o, Tbo. Gdo.iSil.o, Tbo.iCeo. Sii.o, Tbo.2Ceo.8Sn.o, Tbo.3Ceo.7Si1. Oj Tbo.4Ceo.6Sii.o, Tbo.sCeo.sSil.o, Tbo.oCeo. Sii.o, Tbo.7Ceo.3Si1. Oj Tb0.8Ce0.2Si1.0, Tbo.9Ceo.1Si1.o- Tbo.iNdo. Sii.o, Tbo.2Ndo.8Sii.o, Tbo.sNdo.ySil.o, Tbo.4Ndo.6Sii.o, Tbo.5Ndo.5Si 1.0, Tbo.eNdo. Sn.o, Tbo.7Ndo.3Si 1.0, Tbo.8Ndo.2Sii.o, Tbo. Ndo.iSii.o.22, A magnetic refrigerator, comprising the magnetocaloric material of any of claims 1 to 21.

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