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Introduction                                                 Results                                                  Conclusions




           Enhancing the working temperature span and refrigerant
             capacity of two-phase composite systems based on
                         amorphous FeZrBCu ribbons


                 P. Alvarez1     J.L. Sánchez-Llamazares2                       P. Gorria1             J.A. Blanco1

                                                     1 University of Oviedo, Spain
                               2 Instituto Potosino de Investigación Científica y Tecnológica, Mexico




               International Symposium on Metastable, Amorphous and Nanostructured
                                            Materials
Introduction                                       Results   Conclusions




Outline




         1     Introduction
                  Magnetocaloric Effect
                  Improving the Relative Cooling Power



         2     Results
                 Magnetocaloric Properties
                 Combined System



         3     Conclusions
Introduction                                              Results   Conclusions


Magnetocaloric Effect

The Magnetic Entropy Change and the Relative Cooling Power


        Temperature dependence of
        Magnetization for GdAl2 and its
        relation with the MCE




        Maxwell Relation
        Isothermal Magnetic Entropy Change
                                     H2   ∂M
               ∆S (T , H2 )P,∆H =                    dH
                                    H1    ∂T   P,H
Introduction                                              Results                                                Conclusions


Magnetocaloric Effect

The Magnetic Entropy Change and the Relative Cooling Power


        Temperature dependence of                                   Relative Cooling Power (RCP)
        Magnetization for GdAl2 and its
        relation with the MCE




                                                                    Estimation of RCP
                                                                                      Peak
        Maxwell Relation                                            RCP1 (H) = |∆SM          (H) | × δTFWHM
                                                                                 TH
        Isothermal Magnetic Entropy Change                          RCP2 (H) =         |∆SM (T , H)| dT .
                                                                                 TC
                                     H2   ∂M
               ∆S (T , H2 )P,∆H =                    dH             RCP3 (H) = max      ∆Smag (T1 , H) × (T2 − T1 )
                                    H1    ∂T   P,H
Introduction                                           Results                Conclusions


Improving the Relative Cooling Power

Composite Compounds: an Effective way to Improve the RCP via the ∆SM (T ) Broadening

          Past: Low Temperature
          Magnetic Composites




          T. Hashimoto et al., J. Appl. Phys. 62 (9)
                    (1987) 3873-3878
Introduction                                            Results                                                    Conclusions


Improving the Relative Cooling Power

Composite Compounds: an Effective way to Improve the RCP via the ∆SM (T ) Broadening

          Past: Low Temperature                        Recent: RCP Improvement around RT by
          Magnetic Composites                          Using Magnetic Composites




          T. Hashimoto et al., J. Appl. Phys. 62 (9)
                    (1987) 3873-3878                   R. Caballero-Flores et al., Appl. Phys. Lett. 98 (2011) 102505
Introduction                                            Results                                                      Conclusions


Improving the Relative Cooling Power

Composite Compounds: an Effective way to Improve the RCP via the ∆SM (T ) Broadening

          Past: Low Temperature                        Recent: RCP Improvement around RT by
          Magnetic Composites                          Using Magnetic Composites




          T. Hashimoto et al., J. Appl. Phys. 62 (9)
                    (1987) 3873-3878                   R. Caballero-Flores et al., Appl. Phys. Lett. 98 (2011) 102505


         Further Comments
          RCP Optimization for a Two-Phase
          Magnetic Composite                                      The Maximum Refrigeration Efficiency is
                                                                  attained with Constant Magnetic Entropy
                 Shape of ∆SM (T )                                Change curves.
                 δTC
                                                                  A.M. Tishin and Y.I. Spichkin. Magnetocaloric Effect
                 Weight Fraction of Both Phases                   and Its Applications. Series in Condensed Matter
                                                                  Physics, 1 edition (2003).
                 Applied Magnetic Field
Introduction                                  Results                      Conclusions


FeZrBCu amorphous alloys

Nanoperm Alloys



                           ∆SM (T ) for Nanoperm alloys




                             P. Alvarez et al., Intermetallics 18 (2010)
                                             2464-2467
Introduction                                               Results                      Conclusions


FeZrBCu amorphous alloys

Nanoperm Alloys



                                       ∆SM (T ) for Nanoperm alloys




                                          P. Alvarez et al., Intermetallics 18 (2010)
                                                          2464-2467


                                 FeZrBCu Amorphous Alloys Produced
                                  Fe90 Zr10 - Fe90 Zr9 B1 - Fe91 Zr7 B2 - Fe90 Zr8 B2

                                   Fe88 Zr8 B4 - Fe86 Zr7 B6 Cu1 - Fe87 Zr6 B6 Cu1

                           Arc-melting Bulk alloy → Melt-spinning → Amorphous Ribbons
Introduction                                   Results                      Conclusions


Advantages

Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems

               Advantages
                  Easy to produce (Melt
                  spinning technique)
                  Low Cost (Fe-Based
                  alloys)
                  Large MS values
                  Second Order Magnetic
                  Phase Transition
                  Tunable TC in a wide range
                  Broad ∆SM (T ) curves
Introduction                                   Results                               Conclusions


Advantages

Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems

               Advantages                                Magnetization Isotherms
                  Easy to produce (Melt
                  spinning technique)
                  Low Cost (Fe-Based
                  alloys)
                  Large MS values
                  Second Order Magnetic
                  Phase Transition
                  Tunable TC in a wide range                MS ≈ 125 − 135 emu g−1
                  Broad ∆SM (T ) curves
Introduction                                    Results                               Conclusions


Advantages

Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems

               Advantages                                 Magnetization Isotherms
                   Easy to produce (Melt
                   spinning technique)
                   Low Cost (Fe-Based
                   alloys)
                   Large MS values
                   Second Order Magnetic
                   Phase Transition
                   Tunable TC in a wide range                MS ≈ 125 − 135 emu g−1
                   Broad ∆SM (T ) curves

               Typical Arrott Plot
Introduction                                    Results                               Conclusions


Advantages

Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems

               Advantages                                 Magnetization Isotherms
                   Easy to produce (Melt
                   spinning technique)
                   Low Cost (Fe-Based
                   alloys)
                   Large MS values
                   Second Order Magnetic
                   Phase Transition
                   Tunable TC in a wide range                MS ≈ 125 − 135 emu g−1
                   Broad ∆SM (T ) curves
                                                          TC vs Fe Content
               Typical Arrott Plot
Introduction                                    Results                               Conclusions


Advantages

Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems

               Advantages                                 Magnetization Isotherms
                   Easy to produce (Melt
                   spinning technique)
                   Low Cost (Fe-Based
                   alloys)
                   Large MS values
                   Second Order Magnetic
                   Phase Transition
                   Tunable TC in a wide range                MS ≈ 125 − 135 emu g−1
                   Broad ∆SM (T ) curves
                                                          TC vs Fe Content
               Typical Arrott Plot
Introduction                                       Results   Conclusions


Magnetocaloric Properties

Magnetic Entropy Change

               A general view to ∆SM (T ) curves
               for amorphous FeZrCuB alloys
Introduction                                       Results   Conclusions


Magnetocaloric Properties

Magnetic Entropy Change

               A general view to ∆SM (T ) curves
               for amorphous FeZrCuB alloys
Introduction                           Results                                  Conclusions


Magnetocaloric Properties

Typical RCP and δTFWHM values of amorphous FeZrCuB alloys


               RCP-1


                                                 Metallic Gd
                                                 RCP1(µ0 H = 5 T) = 687 Jkg−1
                                                 RCP2(µ0 H = 5 T) = 503 Jkg−1




               RCP-2
Introduction                           Results                                  Conclusions


Magnetocaloric Properties

Typical RCP and δTFWHM values of amorphous FeZrCuB alloys


               RCP-1


                                                 Metallic Gd
                                                 RCP1(µ0 H = 5 T) = 687 Jkg−1
                                                 RCP2(µ0 H = 5 T) = 503 Jkg−1


                                                 Width of the ∆SM (T ) Curves


               RCP-2
Introduction                                    Results                  Conclusions


Combined System

A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 1




    ∆SM (T ) curves of Component
    A (Fe90 Zr9 B1 ) and B (Fe87 Zr6 B6 Cu1 )
Introduction                                    Results                                 Conclusions


Combined System

A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 1




    ∆SM (T ) curves of Component                     ∆SM (T ) curves of the Composite System
    A (Fe90 Zr9 B1 ) and B (Fe87 Zr6 B6 Cu1 )                      0.4 A + 0.6 B
Introduction                                          Results            Conclusions


Combined System

A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 2




    ∆SM (T ) for the two-ribbon system
    0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )
Introduction                                          Results                                             Conclusions


Combined System

A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 2
                                                                Increase of δTFWHM for the Two-Phase System
                                                                0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )




    ∆SM (T ) for the two-ribbon system
    0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )
Introduction                                          Results                                                 Conclusions


Combined System

A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 2
                                                                Increase of δTFWHM for the Two-Phase System
                                                                0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )




    ∆SM (T ) for the two-ribbon system
    0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )




                                                                Resulting RCP for the Two-Phase System
                                                                0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )




                                                                         RCP ≈ 95% of Metallic Gd
Introduction                                 Results                       Conclusions


Combined System

Flattening of the ∆SM (T ) Curve


                           Flattening of ∆SM (T ) for the system
                         0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )
Introduction                                 Results                       Conclusions


Combined System

Flattening of the ∆SM (T ) Curve


                           Flattening of ∆SM (T ) for the system
                         0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )
Introduction                             Results                          Conclusions




Conclusions



         In this contribution we experimentally show that a combination
         of two Nanoperm amorphous ribbons forming a two-phase
         composite system may lead to:

               A considerably increase of the δTFWHM with the consequent
               enhancement in the RCP;

               A Flattening of the ∆SM (T ) curve which improves the
               refrigerant efficiency of the refrigerant thermodynamic cycle.

         The latter is possible due to the broad ∆SM (T ) curve shown by
         Nanoperm alloys and their combination in a proper way (i.e, the
         right selection of both, the δTC of the two alloys chosen to form
         the composite, and the relative weight fraction).
Introduction                             Results                          Conclusions




Conclusions



         In this contribution we experimentally show that a combination
         of two Nanoperm amorphous ribbons forming a two-phase
         composite system may lead to:

               A considerably increase of the δTFWHM with the consequent
               enhancement in the RCP;

               A Flattening of the ∆SM (T ) curve which improves the
               refrigerant efficiency of the refrigerant thermodynamic cycle.

         The latter is possible due to the broad ∆SM (T ) curve shown by
         Nanoperm alloys and their combination in a proper way (i.e, the
         right selection of both, the δTC of the two alloys chosen to form
         the composite, and the relative weight fraction).

                     THANKS FOR YOUR ATTENTION!

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Enhancing the working temperature span and refrigerant capacity of two-phase composite systems based on amorphous FeZrBCu ribbons

  • 1. Introduction Results Conclusions Enhancing the working temperature span and refrigerant capacity of two-phase composite systems based on amorphous FeZrBCu ribbons P. Alvarez1 J.L. Sánchez-Llamazares2 P. Gorria1 J.A. Blanco1 1 University of Oviedo, Spain 2 Instituto Potosino de Investigación Científica y Tecnológica, Mexico International Symposium on Metastable, Amorphous and Nanostructured Materials
  • 2. Introduction Results Conclusions Outline 1 Introduction Magnetocaloric Effect Improving the Relative Cooling Power 2 Results Magnetocaloric Properties Combined System 3 Conclusions
  • 3. Introduction Results Conclusions Magnetocaloric Effect The Magnetic Entropy Change and the Relative Cooling Power Temperature dependence of Magnetization for GdAl2 and its relation with the MCE Maxwell Relation Isothermal Magnetic Entropy Change H2 ∂M ∆S (T , H2 )P,∆H = dH H1 ∂T P,H
  • 4. Introduction Results Conclusions Magnetocaloric Effect The Magnetic Entropy Change and the Relative Cooling Power Temperature dependence of Relative Cooling Power (RCP) Magnetization for GdAl2 and its relation with the MCE Estimation of RCP Peak Maxwell Relation RCP1 (H) = |∆SM (H) | × δTFWHM TH Isothermal Magnetic Entropy Change RCP2 (H) = |∆SM (T , H)| dT . TC H2 ∂M ∆S (T , H2 )P,∆H = dH RCP3 (H) = max ∆Smag (T1 , H) × (T2 − T1 ) H1 ∂T P,H
  • 5. Introduction Results Conclusions Improving the Relative Cooling Power Composite Compounds: an Effective way to Improve the RCP via the ∆SM (T ) Broadening Past: Low Temperature Magnetic Composites T. Hashimoto et al., J. Appl. Phys. 62 (9) (1987) 3873-3878
  • 6. Introduction Results Conclusions Improving the Relative Cooling Power Composite Compounds: an Effective way to Improve the RCP via the ∆SM (T ) Broadening Past: Low Temperature Recent: RCP Improvement around RT by Magnetic Composites Using Magnetic Composites T. Hashimoto et al., J. Appl. Phys. 62 (9) (1987) 3873-3878 R. Caballero-Flores et al., Appl. Phys. Lett. 98 (2011) 102505
  • 7. Introduction Results Conclusions Improving the Relative Cooling Power Composite Compounds: an Effective way to Improve the RCP via the ∆SM (T ) Broadening Past: Low Temperature Recent: RCP Improvement around RT by Magnetic Composites Using Magnetic Composites T. Hashimoto et al., J. Appl. Phys. 62 (9) (1987) 3873-3878 R. Caballero-Flores et al., Appl. Phys. Lett. 98 (2011) 102505 Further Comments RCP Optimization for a Two-Phase Magnetic Composite The Maximum Refrigeration Efficiency is attained with Constant Magnetic Entropy Shape of ∆SM (T ) Change curves. δTC A.M. Tishin and Y.I. Spichkin. Magnetocaloric Effect Weight Fraction of Both Phases and Its Applications. Series in Condensed Matter Physics, 1 edition (2003). Applied Magnetic Field
  • 8. Introduction Results Conclusions FeZrBCu amorphous alloys Nanoperm Alloys ∆SM (T ) for Nanoperm alloys P. Alvarez et al., Intermetallics 18 (2010) 2464-2467
  • 9. Introduction Results Conclusions FeZrBCu amorphous alloys Nanoperm Alloys ∆SM (T ) for Nanoperm alloys P. Alvarez et al., Intermetallics 18 (2010) 2464-2467 FeZrBCu Amorphous Alloys Produced Fe90 Zr10 - Fe90 Zr9 B1 - Fe91 Zr7 B2 - Fe90 Zr8 B2 Fe88 Zr8 B4 - Fe86 Zr7 B6 Cu1 - Fe87 Zr6 B6 Cu1 Arc-melting Bulk alloy → Melt-spinning → Amorphous Ribbons
  • 10. Introduction Results Conclusions Advantages Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems Advantages Easy to produce (Melt spinning technique) Low Cost (Fe-Based alloys) Large MS values Second Order Magnetic Phase Transition Tunable TC in a wide range Broad ∆SM (T ) curves
  • 11. Introduction Results Conclusions Advantages Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems Advantages Magnetization Isotherms Easy to produce (Melt spinning technique) Low Cost (Fe-Based alloys) Large MS values Second Order Magnetic Phase Transition Tunable TC in a wide range MS ≈ 125 − 135 emu g−1 Broad ∆SM (T ) curves
  • 12. Introduction Results Conclusions Advantages Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems Advantages Magnetization Isotherms Easy to produce (Melt spinning technique) Low Cost (Fe-Based alloys) Large MS values Second Order Magnetic Phase Transition Tunable TC in a wide range MS ≈ 125 − 135 emu g−1 Broad ∆SM (T ) curves Typical Arrott Plot
  • 13. Introduction Results Conclusions Advantages Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems Advantages Magnetization Isotherms Easy to produce (Melt spinning technique) Low Cost (Fe-Based alloys) Large MS values Second Order Magnetic Phase Transition Tunable TC in a wide range MS ≈ 125 − 135 emu g−1 Broad ∆SM (T ) curves TC vs Fe Content Typical Arrott Plot
  • 14. Introduction Results Conclusions Advantages Advantages of FeZrBCu alloys for their use in Two-Phase Composite Systems Advantages Magnetization Isotherms Easy to produce (Melt spinning technique) Low Cost (Fe-Based alloys) Large MS values Second Order Magnetic Phase Transition Tunable TC in a wide range MS ≈ 125 − 135 emu g−1 Broad ∆SM (T ) curves TC vs Fe Content Typical Arrott Plot
  • 15. Introduction Results Conclusions Magnetocaloric Properties Magnetic Entropy Change A general view to ∆SM (T ) curves for amorphous FeZrCuB alloys
  • 16. Introduction Results Conclusions Magnetocaloric Properties Magnetic Entropy Change A general view to ∆SM (T ) curves for amorphous FeZrCuB alloys
  • 17. Introduction Results Conclusions Magnetocaloric Properties Typical RCP and δTFWHM values of amorphous FeZrCuB alloys RCP-1 Metallic Gd RCP1(µ0 H = 5 T) = 687 Jkg−1 RCP2(µ0 H = 5 T) = 503 Jkg−1 RCP-2
  • 18. Introduction Results Conclusions Magnetocaloric Properties Typical RCP and δTFWHM values of amorphous FeZrCuB alloys RCP-1 Metallic Gd RCP1(µ0 H = 5 T) = 687 Jkg−1 RCP2(µ0 H = 5 T) = 503 Jkg−1 Width of the ∆SM (T ) Curves RCP-2
  • 19. Introduction Results Conclusions Combined System A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 1 ∆SM (T ) curves of Component A (Fe90 Zr9 B1 ) and B (Fe87 Zr6 B6 Cu1 )
  • 20. Introduction Results Conclusions Combined System A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 1 ∆SM (T ) curves of Component ∆SM (T ) curves of the Composite System A (Fe90 Zr9 B1 ) and B (Fe87 Zr6 B6 Cu1 ) 0.4 A + 0.6 B
  • 21. Introduction Results Conclusions Combined System A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 2 ∆SM (T ) for the two-ribbon system 0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )
  • 22. Introduction Results Conclusions Combined System A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 2 Increase of δTFWHM for the Two-Phase System 0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 ) ∆SM (T ) for the two-ribbon system 0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )
  • 23. Introduction Results Conclusions Combined System A Concrete Two-Phase Composite based on amorphous FeZrCuB ribbons: EXAMPLE 2 Increase of δTFWHM for the Two-Phase System 0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 ) ∆SM (T ) for the two-ribbon system 0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 ) Resulting RCP for the Two-Phase System 0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 ) RCP ≈ 95% of Metallic Gd
  • 24. Introduction Results Conclusions Combined System Flattening of the ∆SM (T ) Curve Flattening of ∆SM (T ) for the system 0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )
  • 25. Introduction Results Conclusions Combined System Flattening of the ∆SM (T ) Curve Flattening of ∆SM (T ) for the system 0.5 A (Fe87 Zr6 B6 Cu1 ) + 0.5 B (Fe90 Zr8 B2 )
  • 26. Introduction Results Conclusions Conclusions In this contribution we experimentally show that a combination of two Nanoperm amorphous ribbons forming a two-phase composite system may lead to: A considerably increase of the δTFWHM with the consequent enhancement in the RCP; A Flattening of the ∆SM (T ) curve which improves the refrigerant efficiency of the refrigerant thermodynamic cycle. The latter is possible due to the broad ∆SM (T ) curve shown by Nanoperm alloys and their combination in a proper way (i.e, the right selection of both, the δTC of the two alloys chosen to form the composite, and the relative weight fraction).
  • 27. Introduction Results Conclusions Conclusions In this contribution we experimentally show that a combination of two Nanoperm amorphous ribbons forming a two-phase composite system may lead to: A considerably increase of the δTFWHM with the consequent enhancement in the RCP; A Flattening of the ∆SM (T ) curve which improves the refrigerant efficiency of the refrigerant thermodynamic cycle. The latter is possible due to the broad ∆SM (T ) curve shown by Nanoperm alloys and their combination in a proper way (i.e, the right selection of both, the δTC of the two alloys chosen to form the composite, and the relative weight fraction). THANKS FOR YOUR ATTENTION!