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Amorphous precursors with the composition MnCo0.8Fe0.2Ge1-xSix, where x = 0.2, 0.3, 0.4, and 0.6, were obtained through mechanical alloying. These precursors were subsequently subjected to different thermal treatments, resulting in the formation of the austenite Ni2In-type structure for x ≤ 0.4. For the highest Si content (x = 0.6), this phase coexists with the martensite TiNiSi-type structure without apparent partitioning of the elements at the nanoscale. These structures remain stable up to their melting points, but subsequent melting processes exhibit differences compared to the initial solidification at a cooling rate of − 20 K/min. The magnetocaloric effect was investigated through thermomagnetic and heat capacity measurements and simulated using the Arrott-Noakes equation of state, revealing the presence of a distribution of Curie temperatures. Despite the absence of a martensitic transformation, these alloys exhibit a significant magnetocaloric response, which increases as the precursor system's amorphization (i.e., homogenization) is enhanced.

Ni55Fe19Ga26 ribbons obtained by melt-spinning technique exhibit a martensitic transformation from L21 cubic austenite phase to 14 M martensite phase above room temperature. We have taken advantage of the existence of thermal hysteresis of the martensitic phase transition (~ 11 K) to analyze the effect of isothermal treatments on the reverse martensitic transformation, which has been analyzed by means of interrupted heating using differential scanning calorimetry. The experimental findings clearly indicate a time-depending effect in the martensitic transformation at temperatures between the austenite start and finish temperatures. Moreover, it has been observed that two successive martensitic transformations take place after the isothermal arrest was performed.

Mechanically amorphized MnCo1−xFexGe alloys (x = 0.20, 0.06 and 0.03) were used as precursors to obtain hexagonal austenite single phase samples. Combining thermomagnetic and magnetocaloric analysis and in situ X-ray diffraction, we observed that the presence of a distribution of transition temperatures jeopardizes the first order character of the magnetoelastic transition from the ferromagnetic to paramagnetic state. Both magnetothermal and in situ X-ray diffraction identify the presence of such distribution and the first order character of the magnetoelastic transition.

An almost single phase 14 M modulated martensite is obtained in melt spun ribbon of Ni55Fe17Ga26Co2 Heusler alloy. The effect of thermal treatments on the stability of the reverse martensitic transformation from 14 M modulated martensite to austenite phase in this system has been investigated by both non-isothermal and isothermal treatments. Heating above martensitic transformation promotes a continuous reduction of the martensitic transformation temperature, which stabilizes the austenite phase at room temperature and induces the precipitation of the gamma phase. However, thermal treatments at temperatures between the austenite start and finish temperatures induce the decoupling of the austenite formation in a subsequent heating. The two successive reverse martensitic transformations could be ascribed to the untransformed martensite in the previous interrupted heating and to the new martensite formed during cooling.

In this study, the non-isothermal kinetics of the martensitic transition from 14M modulated martensite to austenite phase in Ni55Fe19Ga26 ribbons obtained by melt-spinning has been analyzed. The proximity of the martensitic transition to room temperature makes it very sensitive to pressure and subtle differences for different pieces of the ribbon (ascribed to stresses stored in the ribbon during its rapid solidification process). Despite the dispersion in the characteristic parameters of the transition, a general behavior is observed with a decreasing activation energy as the heating rate increases due to the nucleation driven character of the transition. It has been shown that a first-order autocatalysis can describe the temperature evolution of the austenite fraction using only two experimental temperatures. Predicted curves are in good agreement with experimental data.

The influence of the fabrication method on the magnetostructural properties of a Ni55Fe19Ga26 Heusler alloy, obtained both as a ribbon, by melt-spinning, and as a pellet, by arc-melting, has been analyzed. It has been found that, while the arc-melting technique leads to the precipitation of the gamma phase and to a non-modulated martensite structure, the alloy prepared by melt-spinning presents a fully 14M modulated martensitic structure at room temperature. The tetragonal non-modulated martensite in the arc-melted bulk sample transforms into the 14M structure after a long thermal treatment (at 1073 K for 24 h) and subsequent quenching. Characteristic temperatures of the martensitic transformation are higher for melt- spun ribbons than for bulk sample, due to the precipitation of the gamma phase and consequent different martensite composition. However, while the martensitic transformation temperature is practically constant in the case of the bulk sample, it changes by ~150 K in the case of the ribbon sample submitted to the same thermal treatment applied to bulk samples. Finally, it was found that the martensitic transformation occurs in the paramagnetic regime of both types of samples.

The presence of a distribution of transition temperatures (DTT) is ubiquitous in materials science. It is common to ascribe deviations from theoretical pure-phase behavior to this fact. To adapt the different pure phase models to systems with a DTT, the parameters of such distribution must be known or at least estimated. In this review, the different sources for the existence of such distributions and their effects on magnetothermal properties are summarized. In addition, different models proposed to extract the parameters of the corresponding DTT are discussed and extended, starting from Weiss model, to account for other phenomenologies. Experimental results on amorphous Fe-Nb-B and intermetallic MnCo(Fe)Ge systems are also reported.

Production of the intermetallic MnCo0.8Fe0.2Ge phase, interesting as magnetocaloric material, is obtained by using an almost fully amorphous mechanically alloyed precursor. Thermal treatment to develop the intermetallic phase has been reduced in time (from several hours or even days to few minutes), and temperature (from 1123 K to 723 K). Thermomagnetic measurements allow us to analyze the magnetocaloric effect and to compare the results with those obtained from conventional annealing treatments. Close relationship between magnetocaloric properties and crystal size provides further optimization of the system preserving the advantages of the production method proposed.

Devitrification of mechanically alloyed amorphous Fe70Zr30 at. % compound consists on a two-step process: amorphous → amorphous + bcc Fe + Fe2Zr → Fe2Zr + Fe23Zr6. This sequence is inferred from the evolution of the Mössbauer spectra, the thermomagnetic experiments and the X-ray diffraction (XRD) patterns. Hyperfine parameters for both intermetallics have been obtained from Mössbauer spectroscopy in correlation with the phase identification from XRD results. The broadening of the stable compositional range of Fe2Zr intermetallic above 1000 K is responsible for a strong dependence of the phase fractions on heating and cooling rates. Despite the overlapping of the two processes involved in the devitrification, the individual Avrami exponents of each one have been estimated.

Ribbons of a Ni55Fe19Ga26 Heusler alloy were prepared by melt spinning technique. The effect of pressure on magnetostructural transitions was studied comparing as-spun ribbons to ribbons previously submitted to an axial pressure and to powder obtained from manually grinded as-spun ribbons. The martensitic transformation present in the as-spun ribbon almost vanishes after pulverization. The structural change driven by mechanical treatment is a stress-induced intermartensitic transformation from a 14 M modulated to a non-modulated tetragonal (NM) structure. There is a progressive change from the structure of as-spun samples to that of the pulverized one in samples submitted to axial pressures as it increases.

Mechanical alloying using a planetary ball mill allowed us to obtain two homogeneous systems formed by units with nanometer size and MnCo0.8Fe0.2Ge1−xSix stoichiometry (x = 0 and 0.5). The phase evolution of the systems with the milling time was analyzed using X-ray diffraction. Thermal stability of the final products was studied using differential scanning calorimetry. Room temperature 57Fe Mössbauer spectroscopy was used to follow the changes in the Fe environments. A paramagnetic Co-based amorphous phase developed in both alloys as milling progressed. However, while the presence of Si stabilized the Mn-type phase, mechanical recrystallization was observed in a Si-free composition leading to the formation of a MnCo(Fe)Ge intermetallic (Pnma space group) with a crystal size of 7 ± 1 nm. Mössbauer results indicate that Fe atoms migrate from the initial bcc phase to the amorphous and intermetallic phases.

La producción de materiales en los últimos años ha cobrado gran importancia en el campo de la ciencia. Por ello se han desarrollado múltiples técnicas que permiten obtener materiales metaestables con propiedades superiores a los que se obtienen por técnicas convencionales. Una de estas técnicas es el aleado mecánico en molinos planetarios de alta energía. Se pretende fabricar muestras de aleaciones de gadolinio, hierro y manganeso en diferentes proporciones con la finalidad de caracterizarlas microestructuralmente, así como sus entornos atómicos, y poder usarlas como materiales magnetocalóricos, los cuales se emplean en lo que se conoce como refrigeración magnética. La caracterización de una muestra metálica puede realizarse mediante múltiples técnicas conocidas. Las elegidas para este estudio son la difracción de rayos X, la cual permitirá la identificación de cada una de las fases y mediante el uso de un método cuantitativo, concretamente el método Rietveld, se podrán obtener las fracciones en peso y la evolución de múltiples propiedades (tamaño de partícula, microdeformaciones y parámetro reticular). Por otro lado, se empleará la espectroscopía Mössbauer, con la que se podrán estudiar los entornos de los átomos de Fe presentes en las diferentes fases formadas, así como establecer relaciones entre el área de las distintas contribuciones a los espectros y la composición del hierro en los entornos considerados y el tamaño del cristal.

The kinetics of amorphization during ball milling is generally analyzed using two different approaches: the classical Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory and Delogu and Cocco’s model for which a region deterministically transforms after it reaches a certain number of collisions. The application of JMAK analysis to the latter model predicts Avrami exponents to be higher than the experimental ones (typically close to one). We develop simulations based on the probabilistic character of the nucleation phenomenon and concave growth of the amorphous phase in the core of a nanocrystal. The predictions of our simulations are in good agreement with the low Avrami exponents and with the size evolution of the remaining crystallites found experimentally. From these values, the parameters involved in the simulated model (growth rate and probability of nucleation) can be estimated.

The magnetocaloric effect and its most straightforward application, magnetic refrigeration, are topics of current interest due to the potential improvement of energy efficiency of cooling and temperature control systems, in combination with other environmental benefits associated to a technology that does not rely on the compression/expansion of harmful gases. This review presents the fundamentals of the effect, the techniques for its measurement with consideration of possible artifacts found in the characterization of the samples, a comprehensive and comparative analysis of different magnetocaloric materials, as well as possible routes to improve their performance. An overview of the different magnetocaloric prototypes found in literature as well as alternative applications of the magnetocaloric effect for fundamental studies of phase transitions are also included.

Amorphous Fe-Zr and Fe-Nb alloys with 70 at.% Fe have been prepared by ball milling a mixture of elemental powders. The combination of Mössbauer spectroscopy, X-ray diffraction, scanning electron microscopy and differential scanning calorimetry techniques supplies detailed information about the composition as well as microstructural parameters of remaining crystalline and amorphous phases developed during milling. Detailed analysis of the Fe environments allows us to distinguish Fe atoms in paramagnetic sites between those incorporated to crystalline Zr or Nb rich phases and those Fe atoms in amorphous phase.

In this work, we present an investigation of the magnetic and magnetocaloric properties of Mn0.98Cr(0.02-x)FexAs compounds with x = 0.002, 0.005 and 0.010. Our findings show that as Fe content increases the unit cell volume decreases, which indicates that Fe doping emulates the pressure effect on the crystalline structure. The transition temperature TC decreases as x increases and it can be set at approximate value of room temperature by changing the doping level. In addition, the magnetic entropy change ΔSM was determined using a discontinuous measurement protocol, and realistic values from the magnetocaloric effect presented by MnAs-type compounds under pressure (emulated pressure) could be obtained. The values of ΔSMMAX are very large, around −11 Jkg−1K−1 with ΔH = 15 kOe, which is higher than that observed for most compounds with TC around room temperature. However, ΔSM is confined to a narrow temperature range of 11 K. To overcome this drawback, the composition of a theoretical composite formed by our samples was calculated in order to obtain a table-shaped ΔSM curve. The simulated composite showed a high value of full width at half maximum δTFWHM of 33 K, which is much higher than that of single sample.

The magnetocaloric effect of La(Fe,Si)13 samples deteriorates with the presence of secondary phases. However, it is highly challenging to produce single phase samples by conventional procedures and purification requires long annealing time. We propose grinding and particle size selection of non-optimal starting samples as procedure to enhance the magnetocaloric response. In this study a starting multiphase LaFe11.8Si1.2 ingot was grinded and sieved to select three different particle size ranges. X-ray diffraction and Mossbauer spectrometry reveal that all samples mainly contain fcc-La(Fe,Si) € 13 and bccFe(Si) phases. Microstructural and magnetic results show that the fcc-La(Fe,Si)13 phase fraction increases for samples with the smallest average particle size, increasing their magnetocaloric response in a factor larger than three with respect to that of the bulk sample.

Ball milling (BM) is a well-established technique for producing different materials in powder shape. Dynamical analysis of BM helps to optimize the process through simple but general relations (e.g., definition of an equivalent milling time). Concerning the field of study of magnetocaloric effect (MCE), BM is used in different ways: as a single step process (mechanical alloying), as an initial step to enhance mixing of the elements (e.g., to speed up the formation of the desired intermetallic phase) or as a final step (e.g., hydriding of La–Fe–Si). In this contribution, besides a simple description of the effects of some geometrical parameters on the power released during BM and a short review of the BM contribution to the research field of MCE, we will discuss the effect of the microstructure of the starting material and the granular shape inherent to BM on magnetic materials exhibiting MCE.

Amorphous Fe75Nb10B15 and (Fe70Co30)75Nb10B15 alloys were prepared by mechanical alloying from the elemental constituents and hot compacted at different temperatures within the supercooled liquid region. After compaction, the microstructure studied by X-ray diffraction shows an increase in the crystalline fraction for both compositions. Magnetic properties and magnetic entropy change of compacted samples of the Co-free alloy were enhanced with respect to the powder sample, meanwhile, a deterioration in these properties was observed for the Co containing alloy after compaction. Both changes could be ascribed to an enrichment in boron in the amorphous phase.

We observe an enhanced magnetic entropy change ( D S M ) at cryogenic temperatures (T < 20 K) in Eu 8 Ga 16 Ge 30 clathrate (type-I) nanocrystals prepared by a ball milling method. With reduction in the crystal size to 15 nm, D S M is enhanced at low temperatures, reaching the highest value ( 10 J/kg K) at 5 K for a field change of 5 T. For all samples investigated, there is a cross-over tem- perature ( 25 K) in D S M (T) above which D S M decreases with crystal size, opposite to that observed at low temperatures. A careful analysis of the magnetic and magnetocaloric data reveals that as the crystal size decreases the magnetic interaction between Eu 2 þ ions on the Eu2 site gov- erning the primary ferromagnetic transition at 35 K becomes gradually weaker, in effect, altering the interaction between Eu 2 þ ions occupying the Eu1 and Eu2 sites responsible for the secondary ferromagnetic transition at 15 K. As a result, we have observed a strong change in magnetization and the enhancement of D S M at low temperature.

The magnetocaloric effect (MCE) has been measured for an amorphous mechanically alloyed (MA) Co62Nb6Zr2B30. It is demonstrated that sample shape must be taken into account for a correct interpretation of the results, especially to correctly determine the field dependence of magnetic entropy change and refrigerant capacity. However, although correcting the influence of the demagnetizing factor allows us to recover the theoretically predicted behavior for these field dependencies, they differ from those obtained for a rapidly quenched (RQ) amorphous alloy of the same composition. This deviation is assigned to a broader Curie temperature distribution in MA alloys with respect to RQ alloys. Theoretical simulations based on the Arrott-Noakes equation of state and a Gaussian distribution of TC support this hypothesis.

In recent years, the magnetocaloric effect is studied not only for the search of potential magnetic refrigerant materials but also for the analysis of critical phenomena. In both cases, the demagnetizing field might have a notable influence on the results. In this work, we carry out a systematic study, based on theoretical simulations, of the influence of the demagnetizing factor on the magnetocaloric properties. On the one hand, we show that demagnetizing factor affects only slightly the magnetic entropy change ( D S M ), reducing its magnitude and shifting the peak to higher temperatures. On the other hand, it dramatically affects the exponent n of field dependence ð D S M / H n Þ at temperatures below the peak. We demonstrate that scaling of the magnetocaloric curves can be used to remove the influence of the demagnetizing field and, to which extent, critical exponent determination can be affected. Results of numerical simulations are compared with experimental data from a ball milled powder alloy.

Fe75Nb10B15 alloys were prepared by mechanical alloying using different boron powders (crystalline B, commercial amorphous B, optimized amorphous B and intermetallic FeB) in the initial mixture, in order to study the boron incorporation into the Fe matrix and its influence on the amorphization of the alloys. Another composition with the same Fe/Nb ratio but whithout boron was prepared in order to differentiate between the influence of B and Nb in the evolution of microstucture and magnetic properties. Amorphization of samples was followed by X-ray diffraction and Mössbauer spectroscopy, concluding that only B-containing alloys develop an amorphous phase, while for the B-free alloy a supersaturated solid solution was observed as the final microstructure. Nb is rapidly incorporated into the matrix whereas remaining B inclusions are found at the end of the explored milling range for all B-containing samples. The amount of dissolved boron into the amorphous matrix was estimated from magnetic measurements, being the alloy prepared using FeB powder the one that most effectively dissolves this element

Microstructure and magnetic properties of metalloid-free (Fe100- xCox)90Zr10 amorphous and nanocrystalline alloys were characterized. Devitrification of these amorphous alloys occurs in two overlapped transformations leading to the formation of α-Fe(Co) and Fe(Co)Zr2 phases. Constant local Avrami exponents have been found for each individual process. Although Co-free alloy shows a larger grain size, crystalline fractions are similar for both alloys after equivalent annealing. Good soft magnetic properties at room temperature have been observed for amorphous and nanocrystalline alloy with x = 30, which exhibits an amorphous Curie temperature of 735 K. The x = 0 amorphous alloy is paramagnetic at room temperature and nanocrystalline samples exhibit a transition to superparamagnetic behavior.

Amorphous samples of nominal composition Co62Nb6Zr2B30 have been prepared using mechanical alloying (MA) and rapid quenching (RQ) techniques. Differences appear in Curie temperature and the phases developed after crystallization. Refrigerant capacity is enhanced 20% in the MA-sample with respect to that of RQ-sample. Neglecting the demagnetizing factor of powder samples significantly affects the exponent n characterizing the field dependence of the maximum magnetic entropy change

Fe75Nb10B15 amorphous ribbons were grinded via ball milling to produce powder samples preserving the amorphous microstructure. A continuous increase of the Curie temperature with the milling time is observed as well as an enhancement of spontaneous magnetization, average hyperfine field, and magnetocaloric effect. This enhancement in the magnetic character of the samples as milling progresses is ascribed to an increase of the Fe-Fe distance. However, the peak entropy change reduces after grinding the ribbon sample. This effect could be related to a broader distribution of Curie temperatures in powdered samples.

In this work, we propose a method to extract the individual parameters that describe the field dependence of magnetic entropy change of each phase in a multiphase system. This method makes use of the scaling laws of the magnetocaloric effect and can help us to determine the behavior of individual phases and to predict their critical exponents. The accuracy of the procedure is illustrated applying it to ball milled powders, in which an amorphous phase with T C around room temperature coexists with bcc-Fe type crystallites. The obtained values are in good agreement with those reported in the literature for single phase systems. The proposed method could be applied to other systems where single phase materials cannot be easily obtained in order to characterize the effect of impurities.

Nanocrystalline alloys of nominal composition Fe85Nb5B10 were produced by mechanical alloying from a mixture of elemental powders. Two commercial boron structures were used: amorphous and crystalline. In addition, a third composition Fe94.4Nb5.6 was prepared for comparison. X-ray diffraction and Mössbauer spectroscopy were used to describe the evolution of the microstructure and Fe environments as a function of the milling time. Whereas Nb is rapidly incorporated into the nanocrystalline matrix, boron inclusions remain even after long milling times. The presence of boron is found to enhance the comminuting of crystallites