arXiv subjects

Tino Gottschall

Publications and source records attributed to Tino Gottschall.

12 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↗

arXiv2024

A matter of performance & criticality: a review of rare-earth-based magnetocaloric intermetallic compounds for hydrogen liquefaction

The low efficiency of conventional liquefaction technologies based on the Joule-Thomson expansion makes liquid hydrogen currently not attractive enough for large-scale energy-related technologies that are important for the transition to a carbon-neutral society. Magnetocaloric hydrogen liquefaction has great potential to achieve higher efficiency and is therefore a crucial enabler for affordable liquid hydrogen. Cost-effective magnetocaloric materials with large magnetic entropy and adiabatic temperature changes in the temperature range of 77 $\sim$ 20 K under commercially practicable magnetic fields are the foundation for the success of magnetocaloric hydrogen liquefaction. Heavy rare-earth-based magnetocaloric intermetallic compounds generally show excellent magnetocaloric performances, but the heavy rare-earth elements (Gd, Tb, Dy, Ho, Er, and Tm) are highly critical in resources. Yttrium and light rare-earth elements (La, Ce, Pr, and Nd) are relatively abundant, but their alloys generally show less excellent magnetocaloric properties. A dilemma appears: higher performance or lower criticality? In this review, we study how cryogenic temperature influences magnetocaloric performance by first reviewing heavy rare-earth-based intermetallic compounds. Next, we look at light rare-earth-based, "mixed" rare-earth-based, and Gd-based intermetallic compounds with the nature of the phase transition order taken into consideration, and summarize ways to resolve the dilemma.

cond-mat.mtrl-sci↗

arXiv2024

The role of Debye temperature in achieving large adiabatic temperature changes at cryogenic temperatures: a case study on $Pr_2In$

The excellent magnetic entropy change ($ΔS_T$) in the temperature range of 20 $\sim$ 77 K due to the first-order phase transition makes $Pr_2In$ an intriguing candidate for magnetocaloric hydrogen liquefaction. As an equally important magnetocaloric parameter, the adiabatic temperature change ($ΔT_{ad}$) of $Pr_2In$ associated with the first-order phase transition has not yet been reported. In this work, the $ΔT_{ad}$ of $Pr_2In$ is obtained from heat capacity measurements: 2 K in fields of 2 T and 4.3 K in fields of 5 T. While demonstrating a $ΔT_{ad}$ that is not as impressive as its remarkable $ΔS_T$, $Pr_2In$ exhibits an unusual low Debye temperature ($T_D$) of around 110 K. Based on these two observations, an approach that combines the mean-field and Debye models is developed to study the correlation between $ΔT_{ad}$ and $T_D$. The role of $T_D$ in achieving large $ΔT_{ad}$ is revealed: materials with higher $T_D$ tend to exhibit larger $ΔT_{ad}$, particularly in the cryogenic temperature range. This discovery explains the absence of an outstanding $ΔT_{ad}$ in $Pr_2In$ and can serve as a tool for designing or searching materials with both a large $ΔS_T$ and a $ΔT_{ad}$.

cond-mat.mtrl-sci↗

arXiv2023

Designing magnetocaloric materials for hydrogen liquefaction with light rare-earth Laves phases

Magnetocaloric hydrogen liquefaction could be a "game-changer" for liquid hydrogen industry. Although heavy rare-earth-based magnetocaloric materials show strong magnetocaloric effects in the temperature range required by hydrogen liquefaction (77 ~ 20 K), the high resource criticality of the heavy rare-earth elements is a major obstacle for upscaling this emerging liquefaction technology. In contrast, the higher abundances of the light rare-earth elements make their alloys highly appealing for magnetocaloric hydrogen liquefaction. Via a mean-field approach, it is demonstrated that tuning the Curie temperature ($T_C$) of an idealized light rare-earth-based magnetocaloric material towards lower cryogenic temperatures leads to larger maximum magnetic and adiabatic temperature changes ($ΔS_T$ and $ΔT_{ad}$). Especially in the vicinity of the condensation point of hydrogen (20 K), $ΔS_T$ and $ΔT_{ad}$ of the optimized light rare-earth-based material are predicted to show significantly large values. Following the mean-field approach and taking the chemical and physical similarities of the light rare-earth elements into consideration, a method of designing light rare-earth intermetallic compounds for hydrogen liquefaction is proposed: tunning $T_C$ of a rare-earth alloy to approach 20 K by mixing light rare-earth elements with different de Gennes factors. By mixing Nd and Pr in Laves phase $(Nd,Pr)Al_2$, and Pr and Ce in Laves phase $(Pr,Ce)Al_2$, a fully light rare-earth intermetallic series with large magnetocaloric effects covering the temperature range required by hydrogen liquefaction is developed, demonstrating a competitive maximum effect compared to the heavy rare-earth compound $DyAl_2$.

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

A study on rare-earth Laves phases for magnetocaloric liquefaction of hydrogen

We are witnessing a great transition towards a society powered by renewable energies to meet the ever-stringent climate target. Hydrogen, as an energy carrier, will play a key role in building a climate-neutral society. Although liquid hydrogen is essential for hydrogen storage and transportation, liquefying hydrogen is costly with the conventional methods based on Joule-Thomas effect. As an emerging technology which is potentially more efficient, magnetocaloric hydrogen liquefaction is a "game-changer". In this work, we have investigated the rare-earth-based Laves phases ${\rm R}Al_2$ and ${\rm R}Ni_2$ for magnetocaloric hydrogen liquefaction. We have noticed an unaddressed feature that the magnetocaloric effect of second-order magnetocaloric materials can become "giant" near the hydrogen boiling point. This feature indicates strong correlations, down to the boiling point of hydrogen, among the three important quantities of the magnetocaloric effect: the maximum magnetic entropy change $ΔS_{m}^{max}$, the maximum adiabatic temperature change $ΔT_{ad}^{max}$, and the Curie temperature $T_C$. Via a comprehensive literature review, we interpret the correlations for a rare-earth intermetallic series as two trends: (1) $ΔS_{m}^{max}$ increases with decreasing $T_C$; (2) $ΔT_{ad}^{max}$ decreases near room temperature with decreasing $T_C$ but increases at cryogenic temperatures. Moreover, we have developed a mean-field approach to describe these two trends theoretically. The dependence of $ΔS_{m}^{max}$ and $ΔT_{ad}^{max}$ on $T_C$ revealed in this work helps us quickly anticipate the magnetocaloric performance of rare-earth-based compounds, guiding material design and accelerating the discoveries of magnetocaloric materials for hydrogen liquefaction.

cond-mat.mtrl-sci↗

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

Quartic metal: Spontaneous breaking of time-reversal symmetry due to four-fermion correlations in Ba$_{1-x}$K$_x$Fe$_2$As$_2$

Discoveries of ordered quantum states of matter are of great fundamental interest, and often lead to unique applications. The most well known example -- superconductivity -- is caused by the formation and condensation of pairs of electrons. A key property of superconductors is diamagnetism: magnetic fields are screened by dissipationless currents. Fundamentally, what distinguishes superconducting states from normal states is a spontaneously broken symmetry corresponding to long-range coherence of fermion pairs. Here we report a set of experimental observations in hole doped Ba$_{1-x}$K$_x$Fe$_2$As$_2$ which are not consistent with conventional superconducting behavior. Our specific-heat measurements indicate the formation of fermionic bound states when the temperature is lowered from the normal state. However, for $x \sim 0.8$, instead of the standard for superconductors, zero resistance and diamagnetic screening, for a range of temperatures, we observe the opposite effect: the generation of self-induced magnetic fields measured by spontaneous Nernst effect and muon spin rotation experiments. The finite resistance and the lack of any detectable diamagnetic screening in this state exclude the spontaneously broken symmetry associated with superconducting two-fermion correlations. Instead, combined evidence from transport and thermodynamic measurements indicates that the formation of fermionic bound states leads to spontaneous breaking of time-reversal symmetry above the superconducting transition temperature. These results demonstrate the existence of a broken-time-reversal-symmetry bosonic metal state. In the framework of a multiband theory, such a state is characterized by quartic correlations: the long-range order exists only for {\it pairs} of fermion pairs.

cond-mat.supr-con↗

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↗

arXiv2020

Multicaloric effects in Metamagnetic Heusler Ni-Mn-In under uniaxial stress and magnetic field

The world's growing hunger for artificial cold on the one hand, and the ever more stringent climate targets on the other, pose an enormous challenge to mankind. Novel, efficient and environmentally friendly refrigeration technologies based on solid-state refrigerants can offer a way out of the problems arising from climate-damaging substances used in conventional vapor-compressors. Multicaloric materials stand out because of their large temperature changes which can be induced by the application of different external stimuli such as a magnetic, electric, or a mechanical field. Despite the high potential for applications and the interesting physics of this group of materials, only few studies focus on their investigation by direct methods. In this paper, we report on the advanced characterization of all relevant physical quantities that determine the multicaloric effect of a Ni-Mn-In Heusler compound. We have used a purpose-designed calorimeter to determine the isothermal entropy and adiabatic temperature changes resulting from the combined action of magnetic field and uniaxial stress on this metamagnetic shape-memory alloy. From these results, we can conclude that the multicaloric response of this alloy by appropriate changes of uniaxial stress and magnetic field largely outperforms the caloric response of the alloy when subjected to only a single stimulus. We anticipate that our findings can be applied to other multicaloric materials, thus inspiring the development of refrigeration devices based on the multicaloric effect.

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↗

arXiv2014

First-principles calculation of the instability leading to giant inverse magnetocaloric efects

The structural and magnetic properties of functional Ni-Mn-Z (Z = Ga, In, Sn) Heusler alloys are studied by first-principles and Monte Carlo methods. The \textit{ab initio} calculations give a basic understanding of the underlying physics which is associated with the strong competition of ferro- and antiferromagnetic interactions with increasing chemical disorder. The resulting $d$-electron orbital dependent magnetic ordering is the driving mechanism of magnetostructural instability which is accompanied by a drop of magnetization governing the size of the magnetocaloric effect. The thermodynamic properties are calculated by using the \textit{ab initio} magnetic exchange coupling constants in finite-temperature Monte Carlo simulations, which are used to accurately reproduce the experimental entropy and adiabatic temperature changes across the magnetostructural transition.

cond-mat.mtrl-sci↗