In-situ time-resolved small-angle neutron scattering (SANS) experiments were conducted on homogenised cold-rolled ternary Fe-Au-W alloys during aging for 12 h at temperatures of 650 to 700 °C in order to study the kinetics of the nanoscale precipitation. For comparison the precipitation kinetics in the binary counterparts Fe-Au and Fe-W alloys were also studied. In the ternary Fe-Au-W alloy nanoscale Au-rich precipitates were observed by both transmission electron microscopy (TEM) and SANS, while no significant W-rich precipitation was observed. The SANS pattern of the cold-rolled Fe-Au-W alloy clearly reveals a preferred orientation for the plate-shaped nanoscale Au-rich precipitates. As these Au-rich precipitates have a fixed orientation relation with the matrix lattice this preferred orientation originates from the texture of the bcc matrix grains, as confirmed by X-ray diffraction (XRD) pole figure measurements. The effect of texture on the nuclear and the magnetic SANS signal during the precipitation kinetics was included in the data analysis. This enables us to monitor the temperature dependence of the precipitation kinetics for the Au-rich precipitates in the Fe-Au-W alloy during aging at temperatures of 650, 675 and 700 °C. It is found that an increase in aging temperature results in a faster kinetics and a lower final precipitate fraction.

Solid-state caloric effects as intrinsic thermal responses to different physical external stimuli (magnetic-, uniaxial stress-, pressure-, and electric-fields) can achieve a higher energy efficiency compared with traditional gas compression techniques. Among these effects, magnetocaloric energy conversion is regarded as the best available alternative and has been exploited extensively for promising application scenarios in the last decades. This review systematically introduces the magnetocaloric effect and its applications, and summarizes the corresponding representative magnetocaloric materials, as well as important progress in recent years. Specifically, the review focuses on some key understandings of the magnetocaloric effect by utilizing state-of-the-art technical tools such as synchrotron X-ray, neutron scattering, muon spin spectroscopy, positron annihilation spectroscopy, high magnetic fields, etc., and highlights their importance toward advanced materials design and development. An overview of the basic principles and applications of these advanced techniques on magnetocaloric materials is provided. Finally, the challenges and perspectives on further developments in this field are discussed. Further in-depth understanding and manufacturing technology advancement combined with fast-developed artificial intelligence and machine learning are expected to advance the magnetocaloric energy conversion technology closer to real applications.

Zero thermal expansion (ZTE) materials with the advantage of an invariable length with varying temperatures are in high demand for modern industry but are relatively rare for metals. Fe-based Laves phases attract significant attention due to the rich and intriguing physical properties resulting from the coupling between crystal, electric, and magnetic structures. In this work, the structural, magnetic transition, thermal expansion, and magnetocaloric effect of single-phase Fe_2-xHf_0.80Nb_0.20 Laves phase alloys were investigated by means of macroscopic magnetic measurements, Mössbauer spectroscopy, and X-ray diffraction at the temperature range of 4.2-400 K. With the introduction of Fe vacancies, the ZTE coefficient of −1.2 ppm/K is smaller than that (1.7 ppm/K) of stoichiometric Fe₂Hf_0.80Nb_0.20 alloy. Meanwhile, the magnetic entropy change experiences an enhancement from 0.39 to 0.50 J/kg K at a magnetic field change of 2 T. These improved properties are attributed to the vacancy-induced coexistence of ferromagnetic and antiferromagnetic phases, as evidenced by variable-temperature X-ray diffraction and Mössbauer spectroscopy. This work unveils a promising avenue for new zero thermal expansion materials by controlling the vacancies at magnetic atom positions in Fe-based Laves phase alloys.

Cycling stability of the photochromic effect in rare-earth oxyhydride thin films is of great importance for long-term applications such as smart windows. However, an increasingly slower bleaching rate upon photochromic cycling was found in yttrium oxyhydride thin films; the origin of this memory effect is yet unclear. In this work, the microstructural changes under six photodarkening-bleaching cycles in YHxOy and GdHxOy thin films are investigated by in situ illumination Doppler broadening positron annihilation spectroscopy, complemented by positron annihilation lifetime spectroscopy (PALS) investigations on YHxOy films before and after one cycle. For the first three cycles, the Doppler broadening S parameter after bleaching increases systematically with photodarkening-bleaching cycle, and correlates with the bleaching time constant extracted from optical transmittance measurements. This suggests that the microstructural evolution that leads to progressively slower bleaching involves vacancy creation and agglomeration. PALS suggests that during a photodarkening-bleaching cycle, divacancies are formed that are possibly composed of illumination-induced hydrogen vacancies and preexisting yttrium monovacancies, and vacancy clusters grow, which might be due to local removal of hydrogen. If bleaching is a diffusion-related process, the formed vacancy defects induced by illumination might affect the diffusion time by reducing the diffusion coefficient. Hydrogen loss could also be a key factor in the reduced bleaching kinetics. Other microstructural origins including domain growth, or formation of OH- hydroxide groups, are also discussed with respect to the slower bleaching kinetics. During the fourth to sixth photodarkening-bleaching cycle, reversible shifts in the Doppler S and W parameters are seen that are consistent with the reversible formation of metallic-like domains, previously proposed as a key factor in the mechanism for the photochromic effect.

Iron oxide-based adsorbents showed potential to reach ultra-low phosphorus (P) concentrations to prevent eutrophication and recover P. High affinity, high capacity at low P concentrations (<1 mg L⁻¹), good stability, and reusability of the adsorbent are key factors for economic viability. In this study, nanoparticles of goethite (α-FeOOH), a highly stable phase, have been synthesized with increasing Zn²⁺-doping, 0–20 %at. Zn/Fe, to manipulate the surface properties, following the results of a previous work. Mössbauer spectroscopy showed preserved goethite phase and increased point of zero charge (pzc) at low Zn-doping percentages, while at higher percentages (>5%at.) co-existing phases with increased specific surface area formed. Low concentrations (0.1–10 mg L⁻¹) batch adsorption tests showed increased P removal per unit mass with increasing doping. However, the highest pzc, affinity and P removal per unit area were observed for the 5%at. doped sample, suggesting this dopant concentration to provide the most effective surface. A regeneration test, performed at a lower pH than usual, showed preserved, even improved P desorption with increasing doping. Mössbauer spectroscopy showed that the nanoparticle phase and composition, up to 5%at., doping was preserved throughout the process. These results are promising to develop a stable effective Zn-doped goethite-based adsorbent for P recovery at ultra-low concentrations.

The performance of a magnetocaloric heat pump (MCHP) consisting of active magnetocaloric regenerators (AMR) of 12 layers of MnFePSi magnetocaloric materials (MCM) with a linear distribution of Curie temperatures was investigated using a 1D numerical model. The model predicted the heating power and coefficient of performance (COP) of the AMR for a fixed temperature span of 27 K, between 281 K and 308 K, and variable flow rate and AMR cycle frequency. A maximum applied magnetic field strength of 1.4 T was used. A well-insulated house with a maximum heating power demand of 3 kW (under quasi steady state conditions) was considered. Ambient temperature in The Netherlands was taken as a reference for the estimation of the seasonal heating power demand. Without optimizing the design of the AMR, the model predicts a maximum single-AMR heating power equal to 43.5 W when the AMR operates at 3 Hz and 3 L min^-1, and a maximum COP equal to 5.8 when it operates at 1.5 Hz and 1 L min^-1 Considering the maximum heating power of a single AMR, approximately 69 AMRs are needed to provide the design heating power demand of the house. It was found that it is possible to achieve an AMR seasonal COP of 5.6 by continuously adjusting the flow rate and frequency of operation of the MCHP along with the ON/OFF switching of some groups of AMRs in order to adjust the heating power of the MCHP to the heating power demand of the house.

Compared with traditional techniques, solid-state magnetocaloric phase transition materials (MPTMs), based on the giant magnetocaloric effect (GMCE), can achieve a higher energy conversion efficiency for caloric applications. As one of the most promising MPTMs, the hexagonal (Mn,Fe)₂(P,Si)-based compounds host some advantages, but the existing hysteresis and relatively unstable GMCE properties need to be properly tackled. In this study, it is found that substitutions with Ni, Pd, and Pt can maintain and even enhance the GMCE (≈8.7% maximum improvement of |Δs_m|). For a magnetic field change of Δμ₀H = 2 T, all samples obtain a |Δs_m| in the range of 20–25 J kg⁻¹ K⁻¹ with a low thermal hysteresis ΔT_hys (≤5.6 K). The performance surpasses almost all other (Mn,Fe)₂(P,Si)-based materials with ΔT_hys (<10 K) reported until now. The occupancy of substitutional Ni/Pd/Pt atoms is determined by X-ray diffraction, neutron diffraction, and density functional theory calculations. The difference in GMCE properties upon doping is understood from the competition between a weakening of the magnetic exchange interactions and the different degrees of orbital hybridization among 3d-4d-5d elements. The studies elaborate on the responsible mechanism and provide a general strategy through d-block doping to further optimize the GMCE of this materials family.

Phosphorus recovery via vivianite extraction from digested sludge has recently gained considerable interest. The separation of vivianite was demonstrated earlier at the pilot scale, and operational parameters were optimized. In this study, we tested the robustness of this technology by changing the sludge characteristics, such as dry matter, and via that, sludge viscosity, and vivianite particle size. It was proven that the main factor influencing recovery was the concentration of vivianite in the feed. The technology can extract vivianite even when the sludge has higher dry matter (1.8% - 3.3%) and, therefore, higher viscosity. Smaller vivianite sizes (< 10 µm) can still be recovered but at a lower rate. This made magnetic separation applicable to a wide range of wastewater treatment plants.

The influence of chromium and aluminium doping on the over-reduction during activation of iron-oxide-based water-gas shift catalysts was investigated using Mössbauer spectroscopy for the first time. In situ Mössbauer spectra of catalysts exposed to industrially relevant gas compositions were recorded with increasingly reducing R factors R = [CO]*[H₂]/[CO₂]*[H₂O]. Whereas α-Fe and cementite formed during exposure of a non-doped iron-oxide catalyst to process conditions with an R factor of 2.09, such phases were only observed at R = 4.60 for a chromium-doped catalyst, showing that chromium stabilizes the catalyst. Over-reduction was enhanced to R = 2.88 in a chromium-copper co-doped catalyst. α-Fe was already observed at R = 1.64 in an aluminium-doped catalyst, while cementite formation occurred at R = 2.09, showing that over-reduction was enhanced, the presence of aluminium delaying carburization. Co-doping copper in the aluminium-doped catalyst showed cementite formation at R = 2.09, the same as a non-doped catalyst.

Recently, the all-d-metal Ni(Co)MnTi based Heusler compounds are found to have a giant magnetocaloric effect (GMCE) near room temperature and manifest different functionalities like multicaloric effects, which can be employed for solid-state refrigeration. However, in comparison to other traditional Heusler compounds, the relatively large thermal hysteresis (ΔT_hys) and moderately steep ferromagnetic phase transition provides limitations for real applications. Here, we present that fast solidification (suction casting) can sufficiently tailor the GMCE performance by modifying the microstructure. Compared with the arc-melted sample, the magnetic entropy change of the suction-casted sample shows a 67% improvement from 18.4 to 29.4 Jkg⁻¹K⁻¹ for a field change (∆μ₀H) of 5 T. As the thermal hysteresis has maintained a low ΔT_hys value (5.5 K) for the enhanced first-order phase transition, a very competitive reversible magnetic entropy change of 21.8 Jkg⁻¹K⁻¹ for ∆μ₀H = 5 T is obtained. Combining high-resolution transmission electron microscopy (HRTEM) and positron annihilation spectroscopy (PAS) results, the difference in lattice defect concentration is found to be responsible for the significant improvement in GMCE for the suction-cast sample, which suggests that defect engineering can be applied to control the GMCE. Our study reveals that fast solidification can effectively regulate the magnetocaloric properties of all-d-metal NiCoMnTi Heusler compounds without sacrificing ΔT_hys.

The transition-metal based alloy system YNi _4-xCo _xSi shows a second-order ferromagnetic-to-paramagnetic transition near room temperature. Here, the magnetic structure, the magnetocaloric properties and the magnetic anisotropy of YNi _4-xCo _xSi (x = 0–4) are investigated. For x = 3.5, 3.75 and 4.0 a Curie temperature near room temperature is observed with T _C = 250, 283 and 310 K, respectively. In orientated YNi _4-xCo _xSi powder samples the c axis of the hexagonal crystal structure is found to be the easy magnetic axis, with a large dominant K ₂ anisotropy constant (K ₂ > K ₁ > 0). The magnetic structure and the preferred atomic position for Ni are demonstrated by neutron diffraction measurements. We have found a dramatic decrease in the magnetic moment at the 3 g site in the CaCu ₅-type structure (space group P6/mmm), the saturation magnetization and the Curie temperature with increasing Ni concentration.

The emerging all-d-metal Ni(Co)MnTi-based Heusler compounds attract extensive attention because it can potentially be employed for solid-state refrigeration. However, in comparison to the abundant physical functionalities in bulk conditions, the hidden properties related to the NiCoMnTi-based Heusler nanoparticles (NPs) have not yet been investigated experimentally. Here, we present NiCoMnTi Heusler NPs that have been manufactured by spark ablation under Ar gas flow, and the related magnetic and microstructural properties have been studied. Compared with the bulk sample, it is found that the magneto-structurally coupled transition in the bulk sample has collapsed into a magnetic transition for the NPs sample. Superparamagnetic NPs with widely distributed dislocations have directly been observed by high-resolution transmission electron microscopy. For the NPs, the magnetocrystalline anisotropy constant is 3.54 × 10⁴ J/m³, while the saturation magnetization after post-treatment has been estimated to be around 26 Am² kg⁻¹. Our current research reveals that Ni-Co-Mn-Ti-based quaternary NPs could show interesting properties for future nano-application, and the produced NPs will further expand the functionalities of this material family.

The Fe₂P type Mn–Fe–P–Si alloys exhibit a giant magneto-elastic first-order transition, but the large hysteresis limits their performance. Crystal structure evolution and magnetocaloric performance were investigated by varying the Mn and Fe contents at a constant V substitution of 0.02 in Fe₂P-type (Mn_1.17-xFe_0.73-yV_0.02) (P_0.5Si_0.5) (where x + y = 0.02). The V substitution of Fe content shows a larger reduction of hysteresis compared with the same substitution amount of Mn content. During magnetoelastic phase transition, V-substitution reduces the volume change and the volumetric stresses, providing a superior mechanical stability. Compound with the V substitution of Fe (y = 0.02) shows the best magnetocaloric effect with a low thermal hysteresis of 0.6 K. Our developed Mn_1.17-xFe_0.73-yV_0.02P_0.5Si_0.5 alloys are excellent materials for room-temperature magnetic heat-pumping applications by using a permanent magnet.

The magnetocaloric properties of Mn₅Si_1-xP_xB₂ (0 ≤ x ≤ 1) compounds were studied for energy harvesting applications. The crystal structure and the magnetic structure were characterized by powder X-Ray Diffraction and powder Neutron Diffraction. The results indicate that these magnetocaloric materials crystallize in the tetragonal Cr₅B₃-type crystal structure. The introduction of P causes a stretching of the c axis and compression of the a-b plane, leading to a decrease in the unit-cell volume V. In the ferromagnetic state the magnetic moments align within the a-b plane, and the magnetic moment of the Mn1 atom on the 16 l site is larger than that of the Mn2 atom on the 4c site. The Curie temperature T_C can be adjusted continuously from 305 K (x = 1) to 406 K (x = 0) by replacing Si with P. The corresponding magnetic entropy change varies from 1.90 Jkg⁻¹K⁻¹ (x = 0) to 1.35 Jkg⁻¹K⁻¹ (x = 1) for a magnetic field change of 1 T. The PM-FM transition in these compounds corresponds to a second-order phase transition. Mn₅Si_1-xP_xB₂ compounds exhibit a magnetization difference of 28.1 - 31.3 Am²kg⁻¹ for a temperature span of 30 K around T_C in an applied magnetic field of 1 T. The considerable change in magnetization, the tunable T_C near and above room temperature and the absence of thermal hysteresis make these compounds promising candidates for magnetocaloric energy harvesting materials.

The development of affordable magnetocaloric materials (MCM) with a giant magnetocaloric effect (MCE) has brought magnetocaloric heat pumps a step closer to commercialization. The narrow temperature range in which these materials exhibit a large MCE demands the use of several materials with Curie temperatures covering the temperature span of the heat pump in a so-called layered active magnetocaloric regenerator (AMR). How to place these materials in the AMR in terms of distribution of Curie temperatures and thickness of each layer is still a topic of study. In this research we used a one dimensional numerical model to unveil potential benefits of either using a distribution of Curie temperatures that follows a sigmoidal shape or using thicker layers at the cold and hot ends of the AMR along with a linear distribution of Curie temperatures. We found that these AMRs are less sensitive to changes in the hot and cold reservoir temperatures compared to an AMR that uses just a linear distribution of Curie temperatures with uniform layer length, but only the one with thicker ends produces similar heating capacities and second law efficiencies. The heating capacity of the simulated AMR with a sigmoidal distribution of Curie temperatures varies only 5.6 % in a high utilization scenario, flow rate 37.5 g/s and a frequency of 0.75 Hz, when the hot side temperature changes from 308 K to 312 K and the temperature span is 18 K while the corresponding change is 8.7 % for the AMR with thicker end layers, and 37.9 % for the one with a linear distribution of Curie temperatures. For the considered geometry and operating conditions, the maximum heating capacities with temperature span 27 K in the high utilization scenario are 28.6 W, 23.0 W, and 28.5 W, whereas the corresponding second law efficiencies are 33.2%, 27.3 %, and 32.7% for the AMRs with linear distribution of Curie temperatures, sigmoid distribution, and linear distribution with thicker ends respectively.

The influence of off-stoichiometry and of doping with the 5d transition metal Ta has been studied in the quaternary (Mn,Fe)₂(P,Si)-based compound, which is one of the most promising materials systems for magnetic refrigeration. It is found that Ta substitution can decrease the transition temperature T_tr, while the thermal hysteresis ∆T_hys remains about constant. A low Ta doping enhances the magnetocaloric effect (MCE). For Mn_0.6Fe_1.27-yTa_yP_0.64Si_0.36 with y = 0.01 the magnetic entropy change ∆S_m shows and enhancement of 30.7% compared to the undoped material for a low magnetic field change of 1 T. The occupancy of substitutional Ta atoms is determined by XRD and DFT calculations. The T_tr shift and enhanced MCE upon Ta doping are ascribed to the competition between a weakening of the magnetic exchange interactions and a strengthening of the hybridization. Our studies provide a good strategy to further optimize the MCE of this material family.

Hybrid anion exchange adsorbents (HAIX) seem promising to prevent eutrophication and recover phosphate (P). HAIX consist of an anion exchange resin (AIX) backbone, promoting anion physisorption (outer-sphere complex), impregnated with iron (hydr)oxide nanoparticles (NPs), for selective P chemisorption (inner-sphere complex). In this work, for the first time, as far as we know, Zn-doped iron (hydr)oxide NPs were embedded in AIX, and the performances compared with conventional HAIX, both commercial and synthesized. Zn-doped HAIX displayed improved P adsorption performances. Mössbauer spectroscopy (MS) revealed the goethite nature of the NPs, against the “amorphous hydrous ferric oxide” claimed in literature. The P adsorption comparisons, made in synthetic solution and real wastewater, underlined the crucial role of the NPs for selective P adsorption, while improving the understanding on the competition between physisorption and chemisorption. In pure P synthetic solutions, especially at high P concentrations, physisorption can “hide” chemisorption. This depends also on the anion form of the AIX, due to their higher affinity for multivalent anions, which affects HAIX adsorption selectivity and P desorption. In fact, a mild alkaline regeneration over three adsorption–desorption cycles revealed a complex interaction between the regenerant OH⁻ and the adsorbed P. OH⁻ molecules are consumed to transform phosphate speciation, causing (stronger) P re-adsorption and preventing desorption. Finally, Mössbauer spectroscopy revealed NPs agglomeration/growth after the three cycles plus final regeneration at pH 14. This study provides further understanding on the P adsorption–desorption mechanism in HAIX, drawing attention on the choice of experimental conditions for reliable performance assessment, and questioning HAIX consistent P removal and efficient P recovery in the long-term.

In this work, the magnetocaloric effect and negative thermal expansion in melt-spun Fe₂Hf_0.83Ta_0.17 Laves phase alloys were studied. Compared to arc-melted alloys, which undergo a first-order magnetoelastic transition from the ferromagnetic to the antiferromagnetic phase, melt-spun alloys exhibit a second-order transition. For Fe₂Hf_0.83Ta_0.17 ribbons, we observed a large volumetric coefficient of negative thermal expansion of −19 × 10⁻⁶ K⁻¹ over a wide temperature range of 197 – 297 K and a moderate adiabatic temperature change of 0.7 K at 290 K for a magnetic field change of 1.5 T. The magnetic field dependence of the transition temperature (dT_t/dµ₀H = 4.4 K/T) for the melt-spun alloy is about half that of the arc-melted alloy (8.6 K/T). The origin of second-order phase transition of the melt-spun alloy is attributed to the partially suppressed frustration effect, which is due to the atomic disorder introduced by the rapid solidification.

Magnetic refrigeration (MR) is a cutting-edge technology that promises high energy efficiency and eco-friendliness, making it an exciting alternative to traditional refrigeration systems. However, the main challenge to its widespread adoption is cost competitiveness. In this context, the use of liquid metals as heat transfer liquids in the MR has been proposed as a game-changing solution. Unfortunately, the toxicity and flammability of these liquid metals have raised serious concerns, limiting their practical use. In this study, we investigate the compatibility of a nontoxic and nonflammable GaInSn-based liquid metal with a magnetocaloric material, La(Fe,Mn,Si)₁₃H_z, over a 1.5 year period. Our findings reveal nearly a 14% reduction in specific cooling energy and peak-specific isothermal magnetic entropy change for the considered magnetocaloric material. Our study provides valuable insights into the long-term stability of magnetocaloric materials and their compatibility with liquid metals, facilitating the development of more cost-effective and sustainable MR systems.