Non-itinerant-type ferromagnetism and the magnetocaloric response of quinary all-d-metal ribbon: Ni₃₅Mn_34.5Co₁₄Fe₁Ti_15.5

Abstract Most of the ferromagnetic shape memory (FSM) Heusler alloys, which are primarily studied in bulk form in the literature, exhibit p-d type hybridization. This study conducts a thorough multidirectional investigation of a strongly d-d hybridized quinary melt-spun annealed ribbon having the composition Ni 35 Mn 34.5 Co 14 Fe 1 Ti 15.5 (NMCFT-1). This off-stoichiometric, polycrystalline FSM, fabricated using the melt-spin technique, exhibits a highly textured microstructure, double magnetic transitions and super-mechanical features mitigating brittleness. It crystallizes in a perfectly B2-type disorder austenite (Pm-3m, space group number 221) phase at room temperature. It has been hypothesized that geometric frustration is the causative factor for this disorder. Curie temperature of austenite phase ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msubsup> <mml:mi>T</mml:mi> <mml:mrow> <mml:mtext>C</mml:mtext> </mml:mrow> <mml:mrow> <mml:mtext>A</mml:mtext> </mml:mrow> </mml:msubsup> </mml:mrow> </mml:math> ) between paramagnetic → ferromagnetic state is found to be ∼364.57 K, whereas martensite transformation temperature from weak magnetic martensite state to ferromagnetic austenite state is ∼174.74 K. Calculated moments (effective moment, <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:mrow> <mml:msub> <mml:mi>μ</mml:mi> <mml:mrow> <mml:mrow> <mml:mtext>eff</mml:mtext> </mml:mrow> </mml:mrow> </mml:msub> </mml:mrow> </mml:mrow> </mml:math> = 5.12 <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:mrow> <mml:msub> <mml:mi>μ</mml:mi> <mml:mrow> <mml:mtext>B</mml:mtext> </mml:mrow> </mml:msub> </mml:mrow> </mml:mrow> </mml:math> ; low-temperature saturation moment, <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:mrow> <mml:msub> <mml:mi>μ</mml:mi> <mml:mrow> <mml:mtext>S</mml:mtext> </mml:mrow> </mml:msub> </mml:mrow> </mml:mrow> </mml:math> (or <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:mrow> <mml:msub> <mml:mi>M</mml:mi> <mml:mrow> <mml:mtext>S</mml:mtext> </mml:mrow> </mml:msub> </mml:mrow> <mml:mrow> <mml:mo>(</mml:mo> <mml:mn>0</mml:mn> <mml:mo>)</mml:mo> </mml:mrow> </mml:mrow> </mml:math> ) = 5.08 <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:mrow> <mml:msub> <mml:mi>μ</mml:mi> <mml:mrow> <mml:mtext>B</mml:mtext> </mml:mrow> </mml:msub> </mml:mrow> </mml:mrow> </mml:math> ) yield a Rhodes–Wohlfarth ratio of ∼1, indicating the existence of the non-itinerant nature of 3d electrons, whereas the ferromagnetism and the linear or non-linear dependency of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msubsup> <mml:mi>M</mml:mi> <mml:mrow> <mml:mtext>s</mml:mtext> </mml:mrow> <mml:mn>2</mml:mn> </mml:msubsup> <mml:mo stretchy="false">(</mml:mo> <mml:mi>T</mml:mi> </mml:mrow> </mml:math> ) on T 2 around <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msubsup> <mml:mi>T</mml:mi> <mml:mrow> <mml:mtext>C</mml:mtext> </mml:mrow> <mml:mrow> <mml:mtext>A</mml:mtext> </mml:mrow> </mml:msubsup> </mml:mrow> </mml:math> indicates the presence of long-range Rudermann–Kittel–Kasuya–Yosida-type interaction. More importantly, the maximum magnetic entropy change ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:mi mathvariant="normal">Δ</mml:mi> <mml:mrow> <mml:msub> <mml:mi>S</mml:mi> <mml:mrow> <mml:mtext>m</mml:mtext> </mml:mrow> </mml:msub> </mml:mrow> </mml:mrow> </mml:math> ) obtained across the first-order magneto-structural transition and second-order magnetic transition are +18.2 J·kg −1 K −1 at 6 T and −8.8 J·kg −1 K −1 at 2 T, respectively, while a very high working temperature span (Δ T FWHM ) of 28.561 K and 6.922 K are found for the same condition. The sample exhibits a significant relative cooling power of 402.98 J·kg −1 at a magnetic field of 6 T across the FOMT and 60.19 J·kg −1 at a 2 T field across the SOMT, respectively, along with excellent mechanical features such as a Vickers hardness (HV) of 411.80 HV (∼4.04 GPa). Meanwhile, Chen’s super hard model fails to predict the ribbon’s HV value, but Miao’s hard model does, indicating that the ribbon is hard but not super hard. It also paves the way for additional investigation into innovative FSMs like this.