arXiv subjects

Leopoldo Molina-Luna

Publications and source records attributed to Leopoldo Molina-Luna.

13 recordsLinked to original sources

arXiv2025

A voltage-responsive strongly dipolar-coupled macrospin network with emergent dynamics for computing

Emergent behavior, which arises from local interactions between simple elements, is pervasive in nature. It underlies the energy-efficient computing in our brains. However, realizing such dynamics in artificial materials, particularly under low-energy stimuli, remains a fundamental challenge. While dipole-dipole interactions are typically suppressed in magnetic storage, here we harness and amplify them to construct a strongly dipolar-coupled network of SmCo5 macrospins at wafer scale, which can exhibit intrinsic interaction-driven collective dynamics in response to voltage pulses. The network combines three essential ingredients: strong dipolar coupling by large single-domain macrospin, giant voltage control of coercivity over nearly 1000-fold, and disordered network topology with frustrated Ising-like energy landscape. When stimulated by 1 V pulses, the network enters a regime where interaction-driven magnetic behaviors emerge, including spontaneous demagnetization, greatly enhanced magnetization modulation, reversible freeze and resume evolution and stochastic convergence toward low-energy magnetic configurations. All these behaviors are completely absent at the single-nanomagnet level. Furthermore, by constructing micromagnetic models of the strongly dipolar-coupled macrospin networks, we show that the resulting nonlinear, high-dimensional collective dynamics, intrinsic to strongly-interacting systems, can enable accurate chaotic Mackey-Glass prediction and multiclass drone-signal classification. Our work establishes the voltage-responsive strongly-coupled SmCo5 network as a mesoscopic platform for probing emergent magnetic dynamics previously inaccessible under ambient conditions. It also suggests a fundamental distinct route towards scalable, low-voltage computing, one rooted in native physical interaction-driven collective dynamics at the network level.

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↗

arXiv2025

Coercivity influence of nanostructure in SmCo-1:7 magnets: Machine learning of high-throughput micromagnetic data

As a pinning-controlled permanent magnet, tailoring the cellular nanostructure of samarium-cobalt-based 1:7-type (SmCo-1:7) magnets remains crucial for improving magnetic performance. Jointing forward and inverse machine learning models with the high-throughput micromagnetic simulations (42,300 runs), we identify the nanostructural and magnetic features that are most effective for coercivity, combining both nucleation and pinning mechanisms. Sensitivity analyses reveal that the 1:5-phase enhances coercivity by providing high anisotropy, and the Z-phase strengthens pinning through fluctuations in domain wall energy. Cu additions in the 1:5-phase significantly reduce coercivity, while Fe substitutions in the 2:17-phase modestly reduce coercivity but improve pinning locally and increase saturation magnetization. Among all examined features, magnetocrystalline misorientation emerges as the dominant factor. Finally, the framework enables the inverse design of nanostructures with prescribed coercivity, demonstrating a computationally cost-effective toolkit for guiding the performance tailoring of SmCo-1:7 magnets.

cond-mat.mtrl-sci↗

arXiv2025

Direct observation of nanoscale pinning centers in Ce(Co0.8Cu0.2)5.4 permanent magnets

Permanent magnets containing rare earth elements are essential components for the electrification of society. Ce(Co1-xCux)5 permanent magnets are a model system known for their substantial coercivity, yet the underlying mechanism remains unclear. Here, we investigate Ce(Co0.8Cu0.2)5.4 magnets with a coercivity of ~1 T. Using transmission electron microscopy (TEM) and atom probe tomography (APT), we identify a nanoscale cellular structure formed by spinodal decomposition. Cu-poor cylindrical cells (~5-10 nm in diameter, ~20 nm long) have a disordered CeCo5-type structure and a composition Ce(Co0.9Cu0.1)5.3. Cu-rich cell boundaries are ~ 5 nm thick and exhibit a modified CeCo5 structure, with Cu ordered on the Co sites and a composition Ce(Co0.7Cu0.3)5.0. Micromagnetic simulations demonstrate that the intrinsic Cu concentration gradients up to 12 at.% Cu/nm lead to a spatial variation in magnetocrystalline anisotropy and domain wall energy, resulting in effective pinning and high coercivity. Compared to Sm2Co17-type magnets, Ce(Co0.8Cu0.2)5.4 displays a finer-scale variation of conventional pinning with lower structural and chemical contrast in its underlying nanostructure. The identification of nanoscale chemical segregation in nearly single-phase Ce(Co0.8Cu0.2)5.4 magnets provides a microstructural basis for the long-standing phenomenon of "giant intrinsic magnetic hardness" in systems such as SmCo5-xMx, highlighting avenues for designing rare-earth-lean permanent magnets via controlled nanoscale segregation.

cond-mat.mtrl-sci↗

arXiv2025

DFT-Guided Operando Raman Characterization of Ni-Based Phases Relevant to Electrochemical Systems

We present a phase-resolved investigation of Ni-based oxides and hydroxides relevant to the oxygen evolution reaction (OER), combining ground-state DFT+U calculations with operando and in situ Raman spectroscopy, supported by high-resolution TEM. Five crystalline phases-cubic and hexagonal NiO, monoclinic and trigonal Ni(OH)2, and NiOOH-are systematically characterized in terms of their vibrational and electronic structure. Although the DFT models are idealized (0 K, defect-free, no solvation), they serve as clean, phase-specific references for interpreting complex experimental spectra. Cubic NiO is confirmed to be dynamically and electronically stable, consistent with dominant Raman modes observed experimentally. Despite dynamic instabilities in phonon dispersions, hexagonal NiO is structurally verified via TEM, suggesting substrate- or defect-stabilized metastability. Ni(OH)2 polymorphs are both vibrationally stable semiconductors, with the trigonal phase exhibiting stronger spin polarization. NiOOH exhibits spin-polarized electronic states across the Brillouin zone, consistent with its asymmetric band structure under ferromagnetic ordering. Independently, phonon calculations reveal soft modes near the Gamma-point, indicating dynamic instability under idealized conditions, yet operando Raman spectra align closely with calculated zone-center modes. However, introducing 0.03 Angstrom symmetry-breaking displacements relaxes the NiOOH lattice off its saddle point, removing imaginary phonon modes and stabilizing the phase. This integrated framework demonstrates how idealized DFT can reveal intrinsic fingerprints that anchor the interpretation of vibrational and electronic responses in catalytically active, dynamically evolving Ni-based materials.

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↗

arXiv2024

Off-stoichiometry engineering of the electrical and optical properties of SrNbO$_3$ by oxide molecular beam epitaxy

The highly conducting and transparent inorganic perovskites SrBO$_3$ with V, Nb, Mo, and their mixtures at the B-site have recently attracted the attention of the oxide electronics community as novel alternative transparent conducting oxides. For different applications from solar cells to transparent electronics, it is desirable to tune the optical transmission window in the ultraviolet (UV), visible and infrared (IR) range. The conventional approach is substitutional design at the A- and/or B-site. Here, we suggest a method by engineering the off-stoichiometry of the perovskite, opening new pathways to broaden the range of applications without adding additional elements. For oxide molecular beam epitaxy grown SrNbO$_3$ on GdScO$_3$ substrates, we show that controlled Sr deficiency shifts the plasma edge from about 2 eV in the visible range into the near-infrared region, 1.37 eV (similar to stoichiometric SrVO$_3$). Here, epitaxial growth allows going beyond the limitations of phase stability set by thermodynamics. The suggested approach opens a new design toolbox by including controlled vacancy sites as quasi-substitutional virtual elements.

cond-mat.mtrl-sci↗

arXiv2023

Magneto-active composites with locally tailored stiffness produced by laser powder bed fusion

Additive manufacturing technologies enable the production of complex and bioinspired shapes using magneto-responsive materials, which find diverse applications in soft robotics. Particularly, the development of composites with controlled gradients in mechanical properties offers new prospects for advancements in magneto-active materials. However, achieving such composites with gradients typically involves complex multi-material printing procedures. In this study, a single-step laser powder bed fusion (LPBF) process is proposed that enables precise local adjustments of the mechanical stiffness within magneto-active composites. By utilizing distinct laser parameters in specific regions of a composite containing thermoplastic polyurethane and atomized magnetic powder derived from hard magnetic Nd-Fe-B, the stiffness of the composite can be modified within the range of 2 to 22 MPa. Various magneto-responsive actuators with locally tailored stiffness are fabricated and their magnetic performance is investigated. The enhanced response exhibited by actuators with locally adjusted mechanical properties in comparison to their homogeneous counterparts with identical geometries is shown. As a demonstration of a biomedical application, a magnetically responsive stent with localized adjustment is presented with the ability to meet specific requirements in terms of geometry and local stiffness based on an individual's anatomy and disease condition. The proposed method presents an approach for creating functionally graded materials using LPBF, not only for magneto-active materials but also for several other structural and functional materials.

physics.app-ph↗

arXiv2023

Influence of amorphous phase on coercivity in SmCo5-Cu nanocomposites

Severe plastic deformation of powder blends consisting of SmCo5-Cu results in magnetically hardened nanocomposite bulk materials. The microstructure is continuously refined with increasing torsional deformation, yet, coercivity saturates at a certain level of strain. Transmission electron microscopy (TEM) investigation of the microstructure reveals a partial amorphization of the SmCo5 phase due to high-pressure torsion by 20 applied rotations. In this amorphous matrix nanocrystals are embedded. The effect of these experimentally observed microstructural features on the magnetic properties are investigated by micromagnetic simulations, which show that an increasing volume fraction of nanocrystals is beneficial for higher coercivities. For a fixed volume fraction of nanocrystals the simulations reveal an increasing coercivity with decreasing the size of the nanocrystals due to increasing number of interfaces acting as pinning sites. Furthermore, our micromagnetic simulations disclose the mechanisms of the saturation and decline of magnetic hardening due to the strain induced by high-pressure torsion. The calculated coercivity fits very well to the experimentally observed coercivity of Hc=1.34 T. The knowledge can also be used to develop and provide optimization strategies from the microstructure perspective.

cond-mat.mtrl-sci↗

arXiv2023

The Premartensite and Martensite in Fe50Rh50 System

Metallic/intermetalic materials with BCC structures hold an intrinsic instability due to phonon softening along [110] dirrection, causing BCC to lower-symmetry phases transformation when the BCC structures are thermally or mechanically stressed. Fe50Rh50 binary system is one of the exceptional BCC structures (ordered-B2) that has not been yet showing such transformation upon application of thermal stress, although mechanical deformation results in B2 to disordered FCC (gamma) and L10 phases transformation. Here, a comprehensive transmission electron microscopy (TEM) study is conducted on thermally-stressed samples of Fe50Rh50 aged at water and liquid nitrogen from 1150 degree C and 1250 degree C. The results show that, samples quenched from 1150 degree C into water and liquid nitrogen show presence of 1/4{110} and 1/2{110} satellite reflections, the latter of which is expected from phonon dispersion curves obtained by density functional theory calculation. Therefore, it is believed that Fe50Rh50 maintains the B2 structure that is in premartensite state. Once Fe50Rh50 is quenched from 1250 degree C into liquid nitrogen, formation of two short-range ordered tetragonal phases with various c/a ratios (~1.15 and 1.4) is observed in line with phases formed from mechanically deformed (30%) sample. According to our observations, an accurate atomistic shear model ({110}<1-10>) is presented that describes the martensitic transformation of B2 to these tetragonal phases. These findings offer implications useful for understanding of magnetic and physical characteristics of metallic/intermetallic materials.

cond-mat.mtrl-sci↗

arXiv2023

A machine learning framework for quantifying chemical segregation and microstructural features in atom probe tomography data

Atom probe tomography (APT) is ideally suited to characterize and understand the interplay of chemical segregation and microstructure in modern multicomponent materials. Yet, the quantitative analysis typically relies on human expertise to define regions of interest. We introduce a computationally efficient, multistage machine learning strategy to identify chemically distinct domains in a semi automated way, and subsequently quantify their geometric and compositional characteristics. In our algorithmic pipeline, we first coarse grain the APT data into voxels, collect the composition statistics, and decompose it via clustering in composition space. The composition classification then enables the real space segmentation via a density based clustering algorithm, thus revealing the microstructure at voxel resolution. Our approach is demonstrated for a Sm(Co,Fe)ZrCu alloy. The alloy exhibits two precipitate phases with a plate-like, but intertwined morphology. The primary segmentation is further refined to disentangle these geometrically complex precipitates into individual plate like parts by an unsupervised approach based on principle component analysis, or a U-Net based semantic segmentation trained on the former. Following the chemical and geometric analysis, detailed chemical distribution and segregation effects relative to the predominant plate-like geometry can be readily mapped without resorting to the initial voxelization.

physics.chem-ph↗

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↗

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↗