High-performance hexaferrite magnets tailored through alignment of shape-controlled nanocomposites.

Nanoparticles of strontium hexaferrite, SrFe12O19, were prepared by two different synthesis methods: hydrothermal (autoclave) and sol-gel autocombustion (solid-salt-matrix). The two synthesis pathways yield nanoparticles with different morphologies and correspondingly different magnetic characteristics. The autoclave synthesis results in large plate-like crystallites, which spontaneously align with a preferred crystallographic orientation when applying a uniaxial pressure, but exhibit a relatively poor coercivity. Meanwhile, the solid-salt-matrix synthesis method results in smaller less anisotropic crystallites with enhanced coercivity, but with a relatively limited ability to align under a uniaxial applied pressure. The obtained nanocrystalline powders were dry or wet mixed in different ratios followed by Spark Plasma Sintering (SPS) into dense pellets. A clear correlation between mixing ratio, the level of alignment and resulting coercivity was observed for the dry mixed samples, i.e. as more solid-salt-matrix powder is added, the texture of the pellets decreases and the coercivity increases. The best performing pellet in terms of maximum energy product (BHmax = 32.1(6) kJ m-3) was obtained by dry-mixing of 75 wt% autoclave prepared powder and 25 wt% solid-salt-matrix powder. The results presented here illustrate the potential of mixing magnetic nanoparticle powders with different shape characteristics to gain improved magnetic performance.

The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth.

The nucleation, crystallization, and growth mechanisms of MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanocrystallites prepared from coprecipitated transition metal (TM) hydroxide precursors treated at sub-, near-, and supercritical hydrothermal conditions have been studied by in situ X-ray total scattering (TS) with pair distribution function (PDF) analysis, and in situ synchrotron powder X-ray diffraction (PXRD) with Rietveld analysis. The in situ TS experiments were carried out on 0.6 M TM hydroxide precursors prepared from aqueous metal chloride solutions using 24.5% NH4OH as the precipitating base. The PDF analysis reveals equivalent nucleation processes for the four spinel ferrite compounds under the studied hydrothermal conditions, where the TMs form edge-sharing octahedrally coordinated hydroxide units (monomers/dimers and in some cases trimers) in the aqueous precursor, which upon hydrothermal treatment nucleate through linking by tetrahedrally coordinated TMs. The in situ PXRD experiments were carried out on 1.2 M TM hydroxide precursors prepared from aqueous metal nitrate solutions using 16 M NaOH as the precipitating base. The crystallization and growth of the nanocrystallites were found to progress via different processes depending on the specific TMs and synthesis temperatures. The PXRD data show that MnFe2O4 and CoFe2O4 nanocrystallites rapidly grow (typically <1 min) to equilibrium sizes of 20-25 nm and 10-12 nm, respectively, regardless of applied temperature in the 170-420 °C range, indicating limited possibility of targeted size control. However, varying the reaction time (0-30 min) and temperature (150-400 °C) allows different sizes to be obtained for NiFe2O4 (3-30 nm) and ZnFe2O4 (3-12 nm) nanocrystallites. The mechanisms controlling the crystallization and growth (nucleation, growth by diffusion, Ostwald ripening, etc.) were examined by qualitative analysis of the evolution in refined scale factor (proportional to extent of crystallization) and mean crystallite volume (proportional to extent of growth). Interestingly, lower kinetic barriers are observed for the formation of the mixed spinels (MnFe2O4 and CoFe2O4) compared to the inverse (NiFe2O4) and normal (ZnFe2O4) spinel structured compounds, suggesting that the energy barrier for formation may be lowered when the TMs have no site preference.

Defect-Engineering by Solvent Mediated Mild Oxidation as a Tool to Induce Exchange Bias in Metal Doped Ferrites.

The crystal site occupancy of different divalent ions and the induction of lattice defects represent an additional tool for modifying the intrinsic magnetic properties of spinel ferrites nanoparticles. Here, the relevance of the lattice defects is demonstrated in the appearance of exchange-bias and in the improvement of the magnetic properties of doped ferrites of 20 nm, obtained from the mild oxidation of core@shell (wüstite@ferrite) nanoparticles. Three types of nanoparticles (Fe0.95 O@Fe3 O4 , Co0.3 Fe0.7 O@Co0.8 Fe2.2 O4 and Ni0.17 Co0.21 Fe0.62 O@Ni0.4 Co0.3 Fe2.3 O4 ) are oxidized. As a result, the core@shell morphology is removed and transformed in a spinel-like nanoparticle, through a topotactic transformation. This study shows that most of the induced defects in these nanoparticles and their magnetic properties are driven by the inability of the Co(II) ions at the octahedral sites to migrate to tetrahedral sites, at the chosen mild oxidation temperature. In addition, the appearance of crystal defects and antiphase boundaries improves the magnetic properties of the starting compounds and leads to the appearance of exchange bias at room temperature. These results highlight the validity of the proposed method to impose novel magnetic characteristics in the technologically relevant class of nanomaterials such as spinel ferrites, expanding their potential exploitation in several application fields.

Controlling the magnetic structure in W-type hexaferrites.

W-type hexaferrites with varied Co/Zn ratios were synthesized and the magnetic order was investigated using neutron powder diffraction. In SrCo2Fe16O27 and SrCoZnFe16O27 a planar (Cm'cm') magnetic ordering was found, rather than the uniaxial ordering (P63/mm'c') found in SrZn2Fe16O27 which is common in most W-type hexaferrites. In all three studied samples, non-collinear terms were present in the magnetic ordering. One of the non-collinear terms is common to the planar ordering in SrCoZnFe16O27 and uniaxial ordering in SrZn2Fe16O27, which could be a sign of an imminent transition in the magnetic structure. The thermomagnetic measurements revealed magnetic transitions at 520 and 360 K for SrCo2Fe16O27 and SrCoZnFe16O27, and Curie temperatures of 780 and 680 K, respectively, while SrZn2Fe16O27 showed no transition but a Curie temperature at 590 K. This leads to the conclusion that the magnetic transition can be adjusted by fine-tuning the Co/Zn stoichiometry in the sample.

Texture formation in W-type hexaferrite by cold compaction of non-magnetic interacting anisotropic shaped precursor crystallites.

Crystallites of the W-type hexaferrites, Sr(Ni1-xZnx)2Fe16O27 (x = 0, 0.5, 1) have been aligned without applying magnetic field nor hot compaction, but through a simple synthesis process taking advantage of easy alignment of non-magnetic interacting, anisotropic-shaped precursor crystallites of goethite. The goethite precursor was prepared through a simple hydrothermal synthesis route, forming lathlike crystallites with apparent dimensions of 23.3 × 40.1 × 11.0 nm3 as extracted from powder X-ray diffraction along the a-, b- and c-axis, respectively. The calcined pellets consisted of almost phase pure W-type hexaferrites with relative small impurities of spinel ferrite (≤9.02(3) wt%). The high synthesis temperature resulted in large crystallites, which in turn caused low coercivities (Hc ≤ 5.4(1) kA m-1) and a squareness ration (Mr/Ms, remanence (Mr) over saturation magnetisation (Ms)) close to zero for all samples. The vanishing coercivity makes Mr/Ms an unsatisfying measure of preferred orientation. Quantitative texture analysis of the samples was carried out based on 2D transmission synchrotron diffraction data collected at different orientations of the samples. The texture investigations revealed alignment of the crystallites with the c-axis normal to the pressing surface of the pellets. The SrNi2Fe16O27 sample showed the highest texture index of 7.5 m.r.d.2.

In-depth investigations of size and occupancies in cobalt ferrite nanoparticles by joint Rietveld refinements of X-ray and neutron powder diffraction data.

Powder X-ray diffraction (PXRD) and neutron powder diffraction (NPD) have been used to investigate the crystal structure of CoFe2O4 nanoparticles prepared via different hydro-thermal synthesis routes, with particular attention given to accurately determining the spinel inversion degrees. The study is divided into four parts. In the first part, the investigations focus on the influence of using different diffraction pattern combinations (NPD, Cu-source PXRD and Co-source PXRD) for the structural modelling. It is found that combining PXRD data from a Co source with NPD data offers a robust structural model. The second part of the study evaluates the reproducibility of the employed multipattern Rietveld refinement procedure using different data sets collected on the same sample, as well as on equivalently prepared samples. The refinement procedure gives reproducible results and reveals that the synthesis method is likewise reproducible since only minor differences are noted between the samples. The third part focuses on the structural consequences of (i) the employed heating rate (achieved using three different hydro-thermal reactor types) and (ii) changing the cobalt salt in the precursors [aqueous salt solutions of Co(CH3COOH)2, Co(NO3)2 and CoCl2] in the synthesis. It is found that increasing the heating rate causes a change in the crystal structure (unit cell and crystallite sizes) while the Co/Fe occupancy and magnetic parameters remain similar in all cases. Also, changing the type of cobalt salt does not alter the final crystal/magnetic structure of the CoFe2O4 nanoparticles. The last part of this study is a consideration of the chemicals and parameters used in the synthesis of the different samples. All the presented samples exhibit a similar crystal and magnetic structure, with only minor deviations. It is also evident that the refinement method used played a key role in the description of the sample.

Alignment of strontium hexaferrite, by cold compaction of anisotropic non-magnetically interacting crystallites.

Cold compacted, anisotropic shaped non-magnetically interacting precursors are used to achieve aligned strontium hexaferrites. The simple process of dry mixing platy hematite and/or rod-like goethite with strontium carbonate removes the need for external magnetic fields or high temperatures during compaction to assist in alignment. The calcined strontium hexaferrite pellets all displayed preferred orientation and high levels of phase purity (>99 wt%). The mix of goethite and strontium carbonate achieved the highest degree of magnetic alignment with Mr/Ms reaching 0.83(1) obtained by vibrating sample magnetometry. The magnetic data were supported by examining crystallographic alignment using powder X-ray diffraction as well as 2D texture synchrotron analysis.

Local and long-range atomic/magnetic structure of non-stoichiometric spinel iron oxide nanocrystallites.

Spinel iron oxide nanoparticles of different mean sizes in the range 10-25 nm have been prepared by surfactant-free up-scalable near- and super-critical hydro-thermal synthesis pathways and characterized using a wide range of advanced structural characterization methods to provide a highly detailed structural description. The atomic structure is examined by combined Rietveld analysis of synchrotron powder X-ray diffraction (PXRD) data and time-of-flight neutron powder-diffraction (NPD) data. The local atomic ordering is further analysed by pair distribution function (PDF) analysis of both X-ray and neutron total-scattering data. It is observed that a non-stoichiometric structural model based on a tetragonal γ-Fe2O3 phase with vacancy ordering in the structure (space group P43212) yields the best fit to the PXRD and total-scattering data. Detailed peak-profile analysis reveals a shorter coherence length for the superstructure, which may be attributed to the vacancy-ordered domains being smaller than the size of the crystallites and/or the presence of anti-phase boundaries, faulting or other disorder effects. The intermediate stoichiometry between that of γ-Fe2O3 and Fe3O4 is confirmed by refinement of the Fe/O stoichiometry in the scattering data and quantitative analysis of Mössbauer spectra. The structural characterization is complemented by nano/micro-structural analysis using transmission electron microscopy (TEM), elemental mapping using scanning TEM, energy-dispersive X-ray spectroscopy and the measurement of macroscopic magnetic properties using vibrating sample magnetometry. Notably, no evidence is found of a Fe3O4/γ-Fe2O3 core-shell nanostructure being present, which had previously been suggested for non-stoichiometric spinel iron oxide nanoparticles. Finally, the study is concluded using the magnetic PDF (mPDF) method to model the neutron total-scattering data and determine the local magnetic ordering and magnetic domain sizes in the iron oxide nanoparticles. The mPDF data analysis reveals ferrimagnetic collinear ordering of the spins in the structure and the magnetic domain sizes to be ∼60-70% of the total nanoparticle sizes. The present study is the first in which mPDF analysis has been applied to magnetic nanoparticles, establishing a successful precedent for future studies of magnetic nanoparticles using this technique.

High coercivity SmCo5 synthesized with assistance of colloidal SiO2.

SmCo5 is one of the most promising candidates for achieving a hard magnet with a high coercivity. Usually, composition, morphology, and size determine the coercivity of a magnet, however, it is challenging to synthesize phase pure SmCo5 with optimal size and high coercivity. In this paper, we report on the successful synthesis of phase pure SmCo5 with spherical/prolate spheroids shape. Size control is obtained by utilizing colloidal SiO2 as a template preventing aggregation and growth of the precursor. The amount of SiO2 nanoparticles (NPs) in the precursor tunes the average particle size (APS) of the synthesized SmCo5 with particle dimension from 740 to 504 nm. As-prepared pure SmCo5 fine powder obtained from using 2 ml SiO2 suspension possesses an APS of 625 nm and exhibits an excellent coercivity of 2986 kA m-1 (37.5 kOe) without alignment of the particles prior to magnetisation measurements. Comparing with a reference sample prepared without adding any SiO2 NPs, an enhancement of 35% of the coercivity was achieved. The improvement is due to phase purity, stable single-domain (SSD) size, and shape anisotropy originating from the prolate spheroid particles.

Magnetic Property Enhancement of Spinel Mn-Zn Ferrite through Atomic Structure Control.

Temperature treatment of magnetic Mn-Zn ferrites with the composition Mn0.6Zn0.2Fe2.2O4 up to 1100 °C results in a tremendous enhancement of the saturation magnetization by more than 60%. Employing a robust combined Rietveld refinement of powder X-ray and neutron diffraction (PXRD and NPD) data, it is revealed how a reordering of the cations takes place during the annealing step, the extent of which depends on the annealing temperature. While Zn(II) exclusively occupies tetrahedral sites throughout the whole temperature range, as the annealing temperature increases up to 700 °C, the Mn(II) cation distribution shifts from 80(7)% of the total Mn content occupying the octahedral sites (partly inverse spinel) to Mn only being present on the tetrahedral sites (normal spinel). Above 700 °C, pronounced crystallite growth is observed, followed by an increase of the saturation magnetization. Complementary techniques such as energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM) confirm an even cation distribution and the particle growth with annealing temperature. The structural changes caused by annealing of spinel ferrites directly alter the magnetic properties of the materials, thus serving as an easy handle for enhancing their magnetic properties.

Elucidating the relationship between nanoparticle morphology, nuclear/magnetic texture and magnetic performance of sintered SrFe12O19 magnets.

Several M-type SrFe12O19 nanoparticle samples with different morphologies have been synthesized by different hydrothermal and sol-gel synthesis methods. Combined Rietveld refinements of neutron and X-ray powder diffraction data with a constrained structural model reveal a clear correlation between crystallite size and long-range magnetic order, which influences the macroscopic magnetic properties of the sample. The tailor-made powder samples were compacted into dense bulk magnets (>90% of the theoretical density) by spark plasma sintering (SPS). Powder diffraction as well as X-ray and neutron pole figure measurements and analyses have been carried out on the compacted specimens in order to characterize the nuclear (structural) and magnetic alignment of the crystallites within the dense magnets. The obtained results, combined with macroscopic magnetic measurements, reveal a direct influence of the nanoparticle morphology on the self-induced texture, crystallite growth during compaction and macroscopic magnetic performance. An increasing diameter-to-thickness aspect ratio of the platelet-like nanoparticles leads to increasing degree of crystallite alignment achieved by SPS. Consequently, magnetically aligned, highly dense magnets with excellent magnetic performance (30(3) kJ m-3) are obtained solely by nanostructuring means, without application of an external magnetic field before or during compaction. The demonstrated control over nanoparticle morphology and, in turn, crystal and magnetic texture is a key step on the way to designing nanostructured hexaferrite magnets with optimized performance.

Exploring the direct synthesis of exchange-spring nanocomposites by reduction of CoFe2O4 spinel nanoparticles using in situ neutron diffraction.

In situ neutron powder diffraction (NPD) was employed for investigating gram-scale reduction of hard magnetic CoFe2O4 (spinel) nanoparticles into CoFe2O4/CoFe2 exchange-spring nanocomposites via H2 partial reduction. Time-resolved structural information was extracted from Rietveld refinements of the NPD data, revealing significant changes in the reduction kinetics based on the applied temperature and H2 available. The nanocomposite formation was found to take place via the following two-step reduction process: CoxFe3-xO4 → CoyFe1-yO → CozFe2-z. The refined lattice parameters and site occupation fractions indicate that the reduced phases, i.e. CoyFe1-yO and CozFe2-z, initially form as Co-rich compounds (i.e. y > 0.33 and z > 1), which gradually incorporate more Fe as the reduction proceeds. The reduction depletes the Co-content in the parent spinel, which may end up becoming magnetically soft Fe3O4 at high temperature (T = 542 °C), while at lower temperatures there may be a co-existence of Fe3O4 and γ-Fe2O3 or CoxFe3-xO4. The macroscopic magnetic properties of the products were measured by vibrating sample magnetometry (VSM) and revealed the hard and soft magnetic domains in the nanocomposites to be effectively exchange-coupled. An increase of approximately 70% in specific saturation magnetisation, remanence magnetisation, and coercivity compared to the parent CoFe2O4 material was achieved for the best sample.

Laboratory setup for rapid in situ powder X-ray diffraction elucidating Ni particle formation in supercritical methanol.

The design and function of a custom-made Soller slit for a laboratory 2D area detector is presented through a series of demonstration images and an in situ experiment following the formation of nickel particles in supercritical methanol. The in situ experiment is performed in a capillary sample environment, modified for a laboratory scale Rigaku Smartlab diffractometer, and with a temperature range of 300-1050 K. The formation of nickel particles was followed successfully using laboratory in situ X-ray powder diffraction with a time resolution in the order of 27 s. Observations from the area detector images showed the appearance of three distinct phases during the reaction: Ni3(NO3)2(OH)4, NiO, and Ni. The images were linearly integrated and analyzed using Rietveld refinement. A reaction mechanism is proposed based on an evaluation of the weight fractions and scattering factors as a function of reaction time.

Structure and magnetic properties of W-type hexaferrites.

W-type hexaferrites (WHFs) (SrMe 2Fe16O27, Me = Mg, Co, Ni and Zn) are hard magnetic materials with high potential for permanent magnet applications owing to their large crystalline anisotropy and high cation tunability. However, little is known with regards to their complex structural and magnetic characteristics. Here, the substitution of metals (Me = Mg, Co, Ni and Zn) in WHFs is described and their crystal and magnetic structures investigated. From joined refinements of X-ray and neutron powder diffraction data, the atomic positions of the Me atoms were extracted along with the magnetic dipolar moment of the individual sites. The four types of WHFs exhibit ferrimagnetic ordering. For Mg, Ni and Zn the magnetic moments are found to be ordered colinearly and with the magnetic easy axis along the crystallographic c axis. In SrCo2Fe16O27, however, the spontaneous magnetization changes from uniaxial to planar, with the moments aligning in the crystallographic ab plane. Macromagnetic properties were measured using a vibration sample magnetometer. The measured saturation magnetization (M s) between the different samples follows the same trend as the calculated M s extracted from the refined magnetic moments of the neutron powder diffraction data. Given the correlation between the calculated M s and the refined substitution degree of the different Me in specific crystallographic sites, the agreement between the measured and calculated M s values consolidates the robustness of the structural and magnetic Rietveld model.

Optimization of magnetic properties in fast consolidated SrFe12O19 nanocrystallites.

The magnetic properties of SrFe12O19 nanocrystallites produced by hydrothermal synthesis and consolidated by Spark Plasma Sintering (SPS) were optimized by varying the compaction parameters: sintering time, sintering temperature, uniaxial pressure or pre-compaction in a magnetic field. Highly textured compacts with a high degree of crystallite alignment were produced. Qualitative and quantitative textural information was obtained based on X-ray diffraction pole figure measurements. The optimum sintering conditions, relating the degree of alignment and bulk magnetic properties, were identified based on the resulting magnetic properties. It was found that one must strike a balance between the degree of crystallite alignment for high saturation magnetisation and coercivity (H c) to gain the highest energy product (BHmax). It was found that the coercive field drops when the crystallite alignment increases. This was particularly pronounced in the case of magnetically pre-aligned powders prior to SPS, where H c and BHmax decreased as the pellets became increasingly textured. The best BHmax value of 29(4) kJ m-3 was found for the sample sintered at 950 °C for 2 minutes with an applied pressure of 100 MPa for a powder pre-aligned in an applied field of 0.55 T. The results presented here show the potential of SPS consolidation of SrFe12O19 with high relative densities and emphasize the effect of the degree of alignment on the decrease of coercive field and its influence on the magnetic performance.

Approaching Ferrite-Based Exchange-Coupled Nanocomposites as Permanent Magnets.

During the past decade, CoFe2O4 (hard)/Co-Fe alloy (soft) magnetic nanocomposites have been routinely prepared by partial reduction of CoFe2O4 nanoparticles. Monoxide (i.e., FeO or CoO) has often been detected as a byproduct of the reduction, although it remains unclear whether the formation of this phase occurs during the reduction itself or at a later stage. Here, a novel reaction cell was designed to monitor the reduction in situ using synchrotron powder X-ray diffraction (PXRD). Sequential Rietveld refinements of the in situ data yielded time-resolved information on the sample composition and confirmed that the monoxide is generated as an intermediate phase. The macroscopic magnetic properties of samples at different reduction stages were measured by means of vibrating sample magnetometry (VSM), revealing a magnetic softening with increasing soft phase content, which was too pronounced to be exclusively explained by the introduction of soft material in the system. The elemental compositions of the constituent phases were obtained from joint Rietveld refinements of ex situ high-resolution PXRD and neutron powder diffraction (NPD) data. It was found that the alloy has a tendency to emerge in a Co-rich form, inducing a Co deficiency on the remaining spinel phase, which can explain the early softening of the magnetic material.

Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles.

Magnetic spinel ferrite MFe2O4 (M = Mn, Co, Ni, Zn) nanoparticles have been prepared via simple, green and scalable hydrothermal synthesis pathways utilizing sub- and supercritical conditions to attain specific product characteristics. The crystal-, magnetic- and micro-structures of the prepared crystallites have been elucidated through meticulous characterization employing several complementary techniques. Analysis of energy dispersive X-ray spectroscopy (EDS) and X-ray absorption near edge structure (XANES) data verifies the desired stoichiometries with divalent M and trivalent Fe ions. Robust structural characterization is carried out by simultaneous Rietveld refinement of a constrained structural model to powder X-ray diffraction (PXRD) and high-resolution neutron powder diffraction (NPD) data. The structural modeling reveals different affinities of the 3d transition metal ions for the specific crystallographic sites in the nanocrystallites, characterized by the spinel inversion degree, x, [M2+1-xFe3+x]tet[M2+xFe3+2-x]octO4, compared to the well-established bulk structures. The MnFe2O4 and CoFe2O4 nanocrystallites exhibit random disordered spinel structures (x = 0.643(3) and 0.660(6)), while NiFe2O4 is a completely inverse spinel (x = 1.00) and ZnFe2O4 is close to a normal spinel (x = 0.166(10)). Furthermore, the size, size distribution and morphology of the nanoparticles have been assessed by peak profile analysis of the diffraction data, transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The differences in nanostructure, spinel inversion and distinct magnetic nature of the M2+ ions directly alter the magnetic structures of the crystallites at the atomic-scale and consequently the macroscopic magnetic properties of the materials. The present study serves as an important structural benchmark for the rapidly expanding field of spinel ferrite nanoparticle research.

Enhancement of magnetic properties through morphology control of SrFe12O19 nanocrystallites.

Nanocrystallites of the permanent magnetic material SrFe12O19 were synthesised using a conventional sol-gel (CSG) and a modified sol-gel (MSG) synthesis route. In the MSG synthesis, crystallite growth takes place in a solid NaCl matrix, resulting in freestanding nanocrystallites, as opposed to the CSG synthesis, where the produced nanocrystals are strongly intergrown. The resulting nanocrystallites from both methods exhibit similar intrinsic magnetic properties, but significantly different morphology and degree of aggregation. The nanocrystallites were compacted into dense pellets using a Spark Plasma Sintering (SPS) press, this allows investigating the influence of crystallite morphology and the alignment of the nanocrystallites on the magnetic performance. A remarkable correlation was observed between the crystallites morphology and their ability to align in the compaction process. Consequently, a significant enhancement of the maximum energy product was obtained after SPS for the MSG prepared sample (22.0 kJ/m3), compared to CSG sample, which achieved an energy product of 11.6 kJ/m3.

Structural evolution and stability of Sc2(WO4)3 after discharge in a sodium-based electrochemical cell.

Sc2(WO4)3, prepared by solid state synthesis and constructed as an electrode, is discharged to different states in half-cell batteries, versus a Na negative electrode. The structural evolution of the Na-containing electrodes is studied with synchrotron powder X-ray diffraction (PXRD) revealing an increase in microstrain and a gradual amorphization taking place with increasing Na content in the electrode. This indicates that a conversion reaction takes place in the electrochemical cell. X-ray absorption spectroscopy (XAS) at the tungsten L3 absorption edge shows a reduction in the tungsten oxidation state. Variable temperature (VT) PXRD shows that the Sc2(WO4)3 electrode remains relatively stable at higher temperatures, while the Na-containing samples undergo a number of phase transitions and/or turn amorphous above ∼400 °C. Although, Sc2(WO4)3 is a negative thermal expansion (NTE) material only a subtle change of the thermal expansion is found below 400 °C for the Na-containing electrodes. This work shows the complexity in employing an electrochemical cell to produce Na-containing Sc2(WO4)3 and the subsequent phase transitions.

Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles.

Varying atomic short-range order is correlated with the ratio of the monoclinic (m) to tetragonal (t) phase in ZrO2 nanoparticle formation by solvothermal methods. Reactions from Zr oxynitrate in supercritical methanol and Zr acetate in water (hydrothermal route) were studied in situ by X-ray total scattering. Irrespective of the Zr source and solvent, the structure of the precursor in solution consists of edge-shared tetramer chains. Upon heating, the nearest-neighbor Zr-O and Zr-Zr distances shorten initially while the medium-range connectivity is broken. Depending on the reaction conditions, the disordered intermediate transforms either rapidly into m-ZrO2, or more gradually into mixed m- and t-ZrO2 with a concurrent increase of the shortest Zr-Zr distance. In the hydrothermal case, the structural similarity of the amorphous intermediate and m-ZrO2 favors the formation of almost phase-pure m-ZrO2 nanoparticles with a size of 5 nm, considerably smaller than the often-cited critical size below which the tetragonal is assumed to be favoured. Pair distribution function analysis thus unravels ZrO2 phase formation on the atomic scale and in this way provides a major step towards understanding polymorphism of ZrO2 beyond empirical approaches.