arXiv subjects

Konstantin P. Skokov

Publications and source records attributed to Konstantin P. Skokov.

15 recordsLinked to original sources

arXiv2026

Influence of Ni substitution on the phase transitions and magnetocaloric effect of NdCo2 at cryogenic temperatures

We have investigated NdCo2-xNix cubic Laves compounds with 0 <= x <= 1 using neutron diffraction and bulk magnetization measurements to study the influence of partial Ni substitutions of Co on the phase transitions and the magnetocaloric effect. Upon cooling, NdCo2 undergoes a cubic to tetragonal transition at 100 K, and a tetragonal to orthorhombic transition at 42 K. The transitions are associated with long-range ferromagnetic ordering of the magnetic moments along the c axis and spin reorientation into the ab plane, respectively. Both transitions shift to lower temperatures as the Ni content x increases. For x >= 0.5, the orthorhombic phase is suppressed. Additionally, there was a reduction in the magnetic moment upon increasing the Ni substitution of Co. The magnetocaloric effect was determined both indirectly and directly, with good agreement between the methods. NdCo2 exhibits an adiabatic temperature change of 6.3 K for a field of 20 T, which is decreased to 4.9 K for NdCoNi for the same field strength due to the reduced magnetic moment upon Ni substitution.

cond-mat.mtrl-sci↗

arXiv2025

Identifying grain boundary and intragranular pinning centres in Sm2(Co,Fe,Cu,Zr)17 permanent magnets to guide performance optimisation

Permanent magnets draw their properties from a complex interplay of chemical composition and phase, each with their associated intrinsic magnetic properties. Gaining an understanding of these interactions is the key to deciphering the origins of a permanent magnets' magnetic performance and facilitate the engineering of much improved-performing magnets. Here, we use advanced multiscale microscopy and microanalysis on a bulk Sm2(Co,Fe,Cu,Zr)17 pinning-type high-performance magnet with outstanding thermal and chemical stability. Comparison of the microstructure in regions of different composition, we demonstrate that the pinning of magnetic domains, imaged by nanoscale magnetic induction mapping, is controlled by the composition and atomic arrangement of copper. This is confirmed by micromagnetic simulations. Contrary to the belief that grain boundaries are "weak links" in magnetic materials, we demonstrate grain boundaries undergo magnetization reversal at relatively low fields (0.1-0.3 T), but this remains confined to these regions and does not significantly impact the magnet's coercivity. Our results showcase that it is the optimal microstructure within the grain itself that is crucial for achieving the desired magnetic properties.

cond-mat.mtrl-sci↗

arXiv2024

Formation of cellular/lamellar nanostructure in Sm$_2$Co$_{17}$-type binary and ternary Sm-Co-Zr magnets

2:17 SmCo magnets with a quinary composition of Sm(Co,Cu,Fe,Zr)$_{7+δ}$ are industrially relevant hard magnets used in high temperature and corrosive environments. Their complex cellular/lamellar nanostructure, consisting of ordered 2:17 phase cells, 1:5 phase cell boundaries and Z-phase (Zr-rich) lamellae, is essential for their high coercivity. However, the system's complexity makes it challenging to determine the contribution of each element or microstructural feature to coercivity. To disentangle the microstructure-property relationships, we simplified the system to binary and ternary SmCo$_{7.7-x}$Zr$_x$ (with $x = 0$ and 0.1) magnets and conducted detailed micro- to atomic-scale analyses. Only Zr-containing magnets formed a cellular/lamellar nanostructure akin to industrial magnets, in Zr-rich regions with at least 1 at.% Zr, but without achieving high coercivity due to low elemental gradients in absence of Cu across cell boundaries. Data from Zr-poor areas of SmCo$_{7.6}$Zr$_{0.1}$ suggests that 2:17 phase twin boundaries facilitate cellular nanostructure formation by providing inhomogeneities for heterogeneous nucleation.

cond-mat.mtrl-sci↗

arXiv2023

Microstructure of a spark-plasma-sintered Fe2VAl-type Heusler alloy for thermoelectric application

The influence of microstructure on thermoelectricity is increasingly recognized. Approaches for microstructural engineering can hence be exploited to enhance thermoelectric performance, particularly through manipulating crystalline defects, their structure, and composition. Here, we focus on a full-Heusler Fe2VAl-based compound that is one of the most promising thermoelectric materials containing only Earth-abundant, non-toxic elements. A Fe2VTa0.05Al0.95 cast alloy was atomized under a nitrogen-rich atmosphere to induce nitride precipitation. Nanometer- to micrometer-scale microstructural investigations by advanced scanning electron microscopy and atom probe tomography (APT) are performed on the powder first and then on the material consolidated by spark-plasma sintering for an increasing time. APT reveals an unexpected pick-up of additional impurities from atomization, namely W and Mo. The microstructure is then correlated with local and global measurements of the thermoelectric properties. At grain boundaries, segregation and precipitation locally reduce the electrical resistivity, as evidenced by in-situ four-point probe measurements. The final microstructure contains a hierarchy of structural defects, including individual point defects, dislocations, grain boundaries, and precipitates, that allow for a strong decrease in thermal conductivity. In combination, these effects provide an appreciable increase in thermoelectric performance.

cond-mat.mtrl-sci↗

arXiv2023

Reactive single-step hot-pressing and magnetocaloric performance of polycrystalline Fe$_2$Al$_{1.15-x}$B$_2$Ge$_x$Ga$_x$ ($x=0, 0.05$) MAB phases

Reactive single-step hot-pressing at 1473 K and 35 MPa for 4 h produces dense, bulk, near single-phase, low-cost and low-criticality Fe$_2$Al$_{1.15}$B$_2$ and Fe$_2$Al$_{1.1}$B$_2$Ge$_{0.05}$Ga$_{0.05}$ MAB samples, showing a second-order magnetic phase transition with favorable magnetocaloric properties around room temperature. The magnetic as well as magnetocaloric properties can be tailored upon Ge and Ga doping, leading to an increase of Curie temperature $T_C$ and spontaneous magnetization $m_S$. The maximum isothermal entropy change $Δs_{T,max}$ of hot-pressed Fe$_2$Al$_{1.15}$B$_2$ in magnetic field changes of 2 and 5 T amounts to 2.5 and 5 J(kgK)$^{-1}$ at 287.5 K and increases by Ge and Ga addition to 3.1 and 6.2 J(kgK)$^{-1}$ at 306.5 K, respectively. The directly measured maximum adiabatic temperature change $ΔT_{ad,max}$ is improved by the composition modification from 0.9 to 1.1 K in magnetic field changes of 1.93 T. Overall, we demonstrate that hot-pressing provides a much faster, more scalable and processing cost reducing alternative compared to conventional synthesis routes to produce heat exchangers for magnetic cooling devices. Therefore, our criticality assessment shows that hot-pressed Fe-based MAB phases provide a promising compromise of material and processing cost, criticality and magnetocaloric performance, demonstrating the potential for low-cost and low-criticality magnetocaloric applications around room temperature.

cond-mat.mtrl-sci↗

arXiv2023

Influence of Gd-rich precipitates on the martensitic transformation, magnetocaloric effect and mechanical properties of Ni-Mn-In Heusler alloys -- A comparative study

A multi-stimuli cooling cycle can be used to increase the cyclic caloric performance of multicaloric materials like Ni-Mn-In Heusler alloys. However, the use of a uniaxial compressive stress as an additional external stimulus to a magnetic field requires good mechanical stability. Improvement of mechanical stability and strength by doping has been shown in several studies. However, doping is always accompanied by grain refinement and a change in transition temperature. This raises the question of the extent to which mechanical strength is related to grain refinement, transition temperature, or precipitates. This study shows a direct comparison between a single-phase Ni-Mn-Sn and a two-phase Gd-doped Ni-Mn-In alloy with the same transition temperature and grain size. It is shown that the excellent magnetocaloric properties of the Ni-Mn-In matrix are maintained with doping. The isothermal entropy change and adiabatic temperature change are reduced by only 15% in the two-phase Ni-Mn-In-Heusler alloy compared to the single-phase alloy, which is resulting from a slight increase in thermal hysteresis and the width of the transition. Due to the same grain size and transition temperature, this effect can be directly related to the precipitates. The introduction of Gd precipitates leads to a 100% improvement in mechanical strength, which is significantly lower than the improvement observed for Ni-Mn-In alloys with grain refinement and Gd precipitates. This reveals that a significant contribution to the improved mechanical stability in Gd-doped Heusler alloys is related to grain refinement.

cond-mat.mtrl-sci↗

arXiv2023

Dissipation losses limiting first-order phase transition materials in cryogenic caloric cooling: A case study on all-d-metal Ni(-Co)-Mn-Ti Heusler alloys

Ni-Mn-based Heusler alloys, in particular all-d-metal Ni(-Co)-Mn-Ti, are highly promising materials for energy-efficient solid-state refrigeration as large multicaloric effects can be achieved across their magnetostructural martensitic transformation. However, no comprehensive study on the crucially important transition entropy change $Δs_t$ exists so far for Ni(-Co)-Mn-Ti. Here, we present a systematic study analyzing the composition and temperature dependence of $Δs_t$. Our results reveal a substantial structural entropy change contribution of approximately 65 J(kgK)$^{-1}$, which is compensated at lower temperatures by an increasingly negative entropy change associated with the magnetic subsystem. This leads to compensation temperatures $T_{comp}$ of 75 K and 300 K in Ni$_{35}$Co$_{15}$Mn$_{50-y}$Ti$_{y}$ and Ni$_{33}$Co$_{17}$Mn$_{50-y}$Ti$_{y}$, respectively, below which the martensitic transformations are arrested. In addition, we simultaneously measured the responses of the magnetic, structural and electronic subsystems to the temperature- and field-induced martensitic transformation near $T_{comp}$, showing an abnormal increase of hysteresis and consequently dissipation energy at cryogenic temperatures. Simultaneous measurements of magnetization and adiabatic temperature change $ΔT_{ad}$ in pulsed magnetic fields reveal a change in sign of $ΔT_{ad}$ and a substantial positive and irreversible $ΔT_{ad}$ up to 15 K at 15 K as a consequence of increased dissipation losses and decreased heat capacity. Most importantly, this phenomenon is universal, it applies to any first-order material with non-negligible hysteresis and any stimulus, effectively limiting the utilization of their caloric effects for gas liquefaction at cryogenic temperatures.

cond-mat.mtrl-sci↗

arXiv2022

Ce and Dy substitutions in Nd$_{2}$Fe$_{14}$B: site-specific magnetic anisotropy from first-principles

A first-principles approach combining density functional and dynamical mean-field theories in conjunction with a quasi-atomic approximation for the strongly localized 4$f$ shell is applied to Nd$_{2}$Fe$_{14}$B-based hard magnets in order to evaluate crystal-field and exchange-field parameters at rare-earth sites and their corresponding single-ion contribution to the magnetic anisotropy. In pure Nd$_2$Fe$_{14}$B, our calculations reproduce the easy-cone to easy axis transition; theoretical magnetization curves agree quantitatively with experiment. Our study reveals that the rare-earth single-ion anisotropy in the "2-14-1" structure is strongly site-dependent, with the $g$ rare-earth site exhibiting a larger value. In particular, we predict that increased $f$ and $g$-site occupancy of $R=$ Ce and Dy, respectively, leads to an increase of the magnetic anisotropy of the corresponding (Nd,$R$)$_{2}$Fe$_{14}$B substituted compounds.

cond-mat.str-el↗

arXiv2021

Influence of microstructure on the application of Ni-Mn-In Heusler compounds for multicaloric cooling using magnetic field and uniaxial stress

Novel multicaloric cooling utilizing the giant caloric response of Ni-Mn-based metamagnetic shape-memory alloys to different external stimuli such as magnetic field, uniaxial stress and hydrostatic pressure is a promising candidate for energy-efficient and environmentally-friendly refrigeration. However, the role of microstructure when several external fields are applied simultaneously or sequentially has been scarcely discussed in literature. Here, we synthesized ternary Ni-Mn-In alloys by suction casting and arc melting and analyzed the microstructural influence on the response to magnetic fields and uniaxial stress. By combining SEM-EBSD and stress-strain data, a significant effect of texture on the stress-induced martensitic transformation is revealed. It is shown that a <001> texture can strongly reduce the critical transformation stresses. The effect of grain size on the material failure is demonstrated and its influence on the magnetic-field-induced transformation dynamics is investigated. Temperature-stress and temperature-magnetic field phase diagrams are established and single caloric performances are characterized in terms of $Δ{s_T}$ and $Δ{T_{ad}}$. The cyclic $Δ{T_{ad}}$ values are compared to the ones achieved in the multicaloric exploiting-hysteresis cycle. It turns out that a suction-cast microstructure and the combination of both stimuli enables outstanding caloric effects in moderate external fields which can significantly exceed the single caloric performances. In particular for Ni-Mn-In, the maximum cyclic effect in magnetic fields of 1.9 T is increased by more than 200 % to -4.1 K when a moderate sequential stress of 55 MPa is applied. Our results illustrate the crucial role of microstructure for multicaloric cooling using Ni-Mn-based metamagnetic shape-memory alloys.

cond-mat.mtrl-sci↗

arXiv2021

Microstructure engineering of metamagnetic Ni-Mn-based Heusler compounds by Fe-doping: A roadmap towards excellent cyclic stability combined with large elastocaloric and magnetocaloric effects

Ni-Mn-based metamagnetic shape-memory alloys exhibit a giant thermal response to magnetic fields and uniaxial stress which can be utilized in single caloric or multicaloric cooling concepts for energy-efficient and sustainable refrigeration. However, during cyclic operation these alloys suffer from structural and functional fatigue as a result of their high intrinsic brittleness. Here, we present based on Fe-doping of Ni-Mn-In a microstructure design strategy which simultaneously improves cyclic stability and maintains the excellent magnetocaloric and elastocaloric properties. Our results reveal that precipitation of a strongly Fe-enriched and In-depleted coherent secondary gamma-phase at grain boundaries can ensure excellent mechanical stability by hindering intergranular fracture during cyclic loading. In this way, a large elastocaloric effect of -4.5 K was achieved for more than 16000 cycles without structural or functional degradation, which corresponds to an increase of the cyclic stability by more than three orders of magnitude as compared to single-phase Ni-Mn-In-(Fe). In addition, we demonstrate that the large magnetocaloric effect of single-phase Ni-Mn-In-(Fe) can be preserved in the dual-phase material when the secondary gamma-phase is exclusively formed at grain boundaries as the martensitic transformation within the Heusler matrix is barely affected. This way, an adiabatic temperature change of -3 K and an isothermal entropy change of 15 $Jkg^{-1}K^{-1}$ was obtained in 2 T for dual-phase Ni-Mn-In-Fe. We expect that this concept can be applied to other single caloric and mutlicaloric materials, therewith paving the way for solid-state caloric cooling applications.

cond-mat.mtrl-sci↗

arXiv2021

Intrinsically weak magnetic anisotropy of cerium in potential hard-magnetic intermetallics

Cerium-based intermetallics are currently attracting much interest as a possible alternative to existing high-performance magnets containing scarce heavy rare-earth elements. However, the intrinsic magnetic properties of Ce in these systems are poorly understood due to the difficulty of a quantitative description of the Kondo effect, a many-body phenomenon where conduction electrons screen out the Ce-4f moment. Here, we show that the Ce-4f shell in Ce-Fe intermetallics is partially Kondo screened. The Kondo scale is dramatically enhanced by nitrogen interstitials completely suppressing the Ce-4f contribution to the magnetic anisotropy, in striking contrast to the effect of nitrogenation in isostructural intermetallics containing other rare-earth elements. We determine the full temperature dependence of the Ce-4f single-ion anisotropy and show that even unscreened Ce-4f moments contribute little to the room-temperature intrinsic magnetic hardness. Our study thus establishes fundamental constraints on the potential of cerium-based permanent magnet intermetallics.

cond-mat.str-el↗

arXiv2020

Tailoring magnetocaloric effect in all-d-metal Ni-Co-Mn-Ti Heusler alloys: a combined experimental and theoretical study

Novel Ni-Co-Mn-Ti all-d-metal Heusler alloys are exciting due to large multicaloric effects combined with enhanced mechanical properties. An optimized heat treatment for a series of these compounds leads to very sharp phase transitions in bulk alloys with isothermal entropy changes of up to 38 J kg$^{-1}$ K$^{-1}$ for a magnetic field change of 2 T. The differences of as-cast and annealed samples are analyzed by investigating microstructure and phase transitions in detail by optical microscopy. We identify different grain structures as well as stoichiometric (in)homogenieties as reasons for differently sharp martensitic transitions after ideal and non-ideal annealing. We develop alloy design rules for tuning the magnetostructural phase transition and evaluate specifically the sensitivity of the transition temperature towards the externally applied magnetic fields ($\frac{dT_t}{μ_0dH}$) by analyzing the different stoichiometries. We then set up a phase diagram including martensitic transition temperatures and austenite Curie temperatures depending on the e/a ratio for varying Co and Ti content. The evolution of the Curie temperature with changing stoichiometry is compared to other Heusler systems. Density Functional Theory calculations reveal a correlation of T$_C$ with the stoichiometry as well as with the order state of the austenite. This combined approach of experiment and theory allows for an efficient development of new systems towards promising magnetocaloric properties. Direct adiabatic temperature change measurements show here the largest change of -4 K in a magnetic field change of 1.93 T for Ni$_{35}$Co$_{15}$Mn$_{37}$Ti$_{13}$.

cond-mat.mtrl-sci↗

arXiv2018

Thermoelectric determination of electronic entropy change in Ni-doped FeRh

The net entropy change corresponding to the charge carriers in a Ni-doped FeRh bulk polycrystal was experimentally evaluated in a single sample using low temperature heat capacity experiments with applied magnetic field, and using Seebeck effect and Hall coefficient measurements at high temperatures across the first order transition. From the heat capacity data a value for the electronic entropy change $ΔS_{el}\approx8.9$ J\ kg$^{-1}$K$^{-1}$ was extracted, whereas a value of up to 4 J\ kg$^{-1}$K$^{-1}$ was obtained form the Seebeck coefficient. Additionally, the analysis of the Seebeck coefficient allows tracing the evolution of the electronic entropy change with applied magnetic field. An increase of the electronic entropy with increasing applied magnetic field is evidenced, as high as 10 percent at 6 T.

cond-mat.mtrl-sci↗

arXiv2018

Tuning magnetocrystalline anisotropy of Fe$_{3}$Sn by alloying

The electronic structure, magnetic properties and phase formation of hexagonal ferromagnetic Fe$_{3}$Sn-based alloys have been studied from first principles and by experiment. The pristine Fe$_{3}$Sn compound is known to fulfill all the requirements for a good permanent magnet, except for the magnetocrystalline anisotropy energy (MAE). The latter is large, but planar, i.e. the easy magnetization axis is not along the hexagonal c direction, whereas a good permanent magnet requires the MAE to be uniaxial. Here we consider Fe$_{3}$Sn$_{0.75}$M$_{0.25}$, where M= Si, P, Ga, Ge, As, Se, In, Sb, Te and Bi, and show how different dopants on the Sn sublattice affect the MAE and can alter it from planar to uniaxial. The stability of the doped Fe$_{3}$Sn phases is elucidated theoretically via the calculations of their formation enthalpies. A micromagnetic model is developed in order to estimate the energy density product (BH)max and coercive field $μ_{0}$H$_{c}$ of a potential magnet made of Fe$_{3}$Sn$_{0.75}$Sb$_{0.25}$, the most promising candidate from theoretical studies. The phase stability and magnetic properties of the Fe$_{3}$Sn compound doped with Sb and Mn has been checked experimentally on the samples synthesised using the reactive crucible melting technique as well as by solid state reaction. The Fe$_{3}$Sn-Sb compound is found to be stable when alloyed with Mn. It is shown that even small structural changes, such as a change of the c/a ratio or volume, that can be induced by, e.g., alloying with Mn, can influence anisotropy and reverse it from planar to uniaxial and back.

cond-mat.mtrl-sci↗

arXiv2016

Mastering hysteresis in magnetocaloric materials

Hysteresis is more than just an interesting oddity, which occurs in materials with a first-order transition. It is a real obstacle on the path from existing lab-scale prototypes of magnetic refrigerators towards commercialization of this potentially disruptive cooling technology. Indeed, the reversibility of the magnetocaloric effect, being essential for magnetic heat pumps, strongly depends on the width of the thermal hysteresis and therefore it is necessary to understand the mechanisms causing hysteresis and to find solutions how to minimize losses associated with thermal hysteresis in order to maximize the efficiency of magnetic cooling devices. In this work, we discuss fundamental aspects, which can contribute to thermal hysteresis and we are developing strategies for at least partially overcoming the hysteresis problem in some selected classes of magnetocaloric materials with large application potential. Doing so, we refer to the most relevant classes of magnetic refrigerants La-Fe-Si-, Heusler- and Fe2P-type compounds.

cond-mat.mtrl-sci↗