From magneto-elastic impedance model to accurate magneto-mechanical coefficient measurements.

The measurement of the magneto-elastic impedance enables the magneto-mechanical coefficient of amorphous tapes, for example, to be accurately estimated. We first propose an analytical model describing the principle of a resonator based on magnetostrictive ribbons. We show how, from the impedance described by a circle in the complex plane, the characteristics of a magnetostrictive resonator can be established and estimated from the evolution of the impedance as a function of frequency. This method, which is entirely implemented with an amorphous metal ribbon (Metglas™ 2826), is perfectly adapted to estimate the magneto-mechanical coupling coefficient k33 and thus establish the magnetostriction curves λ(H) of amorphous ribbons. However, application to thick nickel foil shows that the current method is restricted to magnetic materials in a thin ribbon form (<∼100 µm). It should also be noted that this technique has serious advantages over those commonly used: it is non-destructive, inexpensive, and very easy to use.

Strong magnetic exchange and frustrated ferrimagnetic order in a weberite-type inorganic-organic hybrid fluoride.

We combine powder neutron diffraction, magnetometry and 57Fe Mössbauer spectrometry to determine the nuclear and magnetic structures of a strongly interacting weberite-type inorganic-organic hybrid fluoride, Fe2F5(H taz). In this structure, Fe2+ and Fe3+ cations form magnetically frustrated hexagonal tungsten bronze layers of corner-sharing octahedra. Our powder neutron diffraction data reveal that, unlike its purely inorganic fluoride weberite counterparts which adopt a centrosymmetric Imma structure, the room-temperature nuclear structure of Fe2F5(H taz) is best described by a non-centrosymmetric Ima2 model with refined lattice parameters a = 9.1467(2) Å, b = 9.4641(2) Å and c = 7.4829(2) Å. Magnetic susceptibility and magnetization measurements reveal that strong antiferromagnetic exchange interactions prevail in Fe2F5(H taz) leading to a magnetic ordering transition at TN = 93 K. Analysis of low-temperature powder neutron diffraction data indicates that below TN, the Fe2+ sublattice is ferromagnetic, with a moment of 4.1(1) µB per Fe2+ at 2 K, but that an antiferromagnetic component of 0.6(3) µB cants the main ferromagnetic component of Fe3+, which aligns antiferromagnetically to the Fe2+ sublattice. The zero-field and in-field Mössbauer spectra give clear evidence of an excess of high-spin Fe3+ species within the structure and a non-collinear magnetic structure. This article is part of the theme issue 'Mineralomimesis: natural and synthetic frameworks in science and technology'.

Understanding the element segregation and phase separation in the Ce-substituted Nd-(Fe,Co)-B based alloys.

Ce substituted Nd2Fe14B (2:14:1)-type permanent magnets have shown increasing potential in the applications due to their high properties/cost ratio. However, the element segregation and phase separation in the Ce substituted magnets have not been fully understood yet. In this work, (Nd1-xCex)25Fe40Co20Al4B11 alloys with high coercivities were prepared by copper mold casting. Based on detailed microstructure and composition analysis, the segregation of rare earth (RE) elements was observed in the as-cast alloys. Nd element prefers to enter into the 2:14:1 phase and the Ce element enter into the 1:2 phase. The existence of the 1:2 phase can promote the element segregation. The alloy shows an abnormal increase of coercivity from 641 kA/m for x = 0.2 to 863 kA/m for x = 0.3. This increase could be attributed to the phase separation of the 2:14:1 phase, which has been confirmed by the microstructural characterization. The present data provides useful information for exploring Ce-containing Nd-Fe-B magnets.

New insights into the degradation mechanism of metal-organic frameworks drug carriers.

A versatile method based on Raman microscopy was developed to follow the degradation of iron carboxylate Metal Organic Framework (MOF) nano- or micro-particles in simulated body fluid (phosphate buffer). The analysis of both the morphology and chemical composition of individual particles, including observation at different regions on the same particle, evidenced the formation of a sharp erosion front during particle degradation. Interestingly, this front separated an intact non eroded crystalline core from an amorphous shell made of an inorganic network. According to Mössbauer spectrometry investigations, the shell consists essentially of iron phosphates. Noteworthy, neither drug loading nor surface modification affected the integrity of the tridimensional MOF network. These findings could be of interest in the further development of next generations of MOF drug carriers.

A magnetisation and Mössbauer study of triazole (M1-x2+Mx3+)M3+F5(Htaz)1-x(taz)x weberites (M = Fe, Co, Mn, Zn, Ga, V).

A series of triazole fluoride weberites (M1-x2+Mx3+)M3+F5(Htaz)1-x(taz)x is obtained by hydrothermal synthesis. All phases are found to be isostructural to ZnAlF5(Htaz) by powder X-ray diffraction. Weberite structures are prone to induce the magnetic frustration of antiferromagnetic interactions originating from the cationic topology of HTB layers. The (nD) magnetic properties of (0D) Co-Ga, (1D) Zn-Fe, (3D) Fe-Ga, Mn-Fe, Co-Fe and Co-V couples are thus reported. Co2+ or Fe2+ magnetic anisotropy induces a negative magnetisation below TN and compensation temperatures for Mn-Fe and Co-Fe couples. All iron 3D magnetic phases exhibit high Néel temperatures, between 81 K and 102 K, and large |θP/TN| ratios, signalling strong magnetic frustration. Their cation site occupancies and the deduced (de)protonation states of the amine are accurately determined by 57Fe Mössbauer spectrometry. In addition, this spectroscopy evidences a subtle effect of the atmosphere that surrounds the samples: the magnetic ordering temperatures TN decrease significantly when the samples are cooled under vacuum with respect to samples that are cooled at ambient pressure. This novel phenomenon, which is highlighted for all studied (3D) triazole iron weberites, is reversible, and thus provides promising perspectives for understanding the underlying mechanism.

Gold-iron oxide dimers for magnetic hyperthermia: the key role of chloride ions in the synthesis to boost the heating efficiency.

With the aim of producing Au-Fe x O y dimers with outstanding heating performances under magnetic hyperthermia conditions applicable to human patients, here we report two synthesis routes, a two-pot and a one-pot method. The addition of chloride ions and the absence of 1,2-hexadecanediol (HDDOL), a commonly used chemical in this synthesis, are the key factors that enable us to produce dimers at low temperature with crystalline iron oxide domains in the size range between 18-39 nm that is ideal for magnetic hyperthermia. In the case of two-pot synthesis, in which no chloride ions are initially present in the reaction pot, dimers are obtained only at 300 °C. In order to lower the reaction temperature to 200 °C and to tune the size of the iron oxide domain, the addition of chloride ions becomes the crucial parameter. In the one-pot method, the presence of chloride ions from the start of the synthesis (as counter ions of the gold salt precursor) enables a prompt formation of dimers directly at 200 °C. In this case, the reaction time is the main parameter used to tune the iron oxide size. A record value of specific absorption rates (SARs) up to 1300 W gFe-1 at 330 kHz and 24 kA m-1 was measured for dimers with an iron oxide domain of 24 nm in size.

Synthesis engineering of iron oxide raspberry-shaped nanostructures.

Magnetic porous nanostructures consisting of oriented aggregates of iron oxide nanocrystals display very interesting properties such as a lower oxidation state of magnetite, and enhanced saturation magnetization in comparison with individual nanoparticles of similar sizes and porosity. However, the formation mechanism of these promising nanostructures is not well understood, which hampers the fine tuning of their magnetic properties, for instance by doping them with other elements. Therefore the formation mechanism of porous raspberry shaped nanostructures (RSNs) synthesized by a one-pot polyol solvothermal method has been investigated in detail from the early stages by using a wide panel of characterization techniques, and especially by performing original in situ HR-TEM studies in temperature. A time-resolved study showed the intermediate formation of an amorphous iron alkoxide phase with a plate-like lamellar structure (PLS). Then, the fine investigation of PLS transformation upon heating up to 500 °C confirmed that the synthesis of RSNs involves two iron precursors: the starting one (hydrated iron chlorides) and the in situ formed iron alkoxide precursor which decomposes with time and heating and contributes to the growth step of nanostructures. Such an understanding of the formation mechanism of RSNs is necessary to envision efficient and rational enhancement of their magnetic properties.

Evolution of the magnetic structure with chemical composition in spinel iron oxide nanoparticles.

Magnetic properties of iron oxide nanoparticles with spinel structure are strictly related to a complex interplay between cationic distribution and the presence of a non-collinear spin structure (spin canting). With the aim to gain better insight into the effect of the magnetic structure on magnetic properties, in this paper we investigated a family of small crystalline ferrite nanoparticles of the formula CoxNi1-xFe2O4 (0 ≤x≤ 1) having equal size (≈4.5 nm) and spherical-like shape. The field dependence of magnetization at low temperatures indicated a clear increase of magnetocrystalline anisotropy and saturation magnetization (higher than the bulk value for CoFe2O4: ∼130 A m(2) kg(-1)) with the increase of cobalt content. The magnetic structure of nanoparticles has been investigated by Mössbauer spectroscopy under an intense magnetic field (8 T) at a low temperature (10 K). The magnetic properties have been explained in terms of an evolution of the magnetic structure with the increase of cobalt content. In addition a direct correlation between cationic distribution and spin canting has been proposed, explaining the presence of a noncollinear spin structure in terms of superexchange interaction energy produced by the average cationic distribution and vacancies in the spinel structure.

Direct accessibility of mixed-metal (III/II) acid sites through the rational synthesis of porous metal carboxylates.

The scalable and environmentally-friendly synthesis of mixed Fe(III)/M(II) (M = Ni, Co, Mg) polycarboxylate porous MOFs based on the Secondary Building Unit approach is reported. A combination of in situ infrared spectroscopy, (57)Fe Mössbauer spectrometry and adsorption microcalorimetry confirms the direct accessibility of the iron(III) and metal(II) sites under low temperature activation conditions.

Structural transition at 360 K in the CaFe5O7 ferrite: toward a new charge ordering distribution.

An efficient synthesis route is proposed to obtain single phase powder ceramic of CaFe5O7. This complex structure can be described as an intergrowth between one CaFe2O4 unit and n = 3 slices of FeO Wüstite-type structure. A detailed structural study has been carried out at room temperature combining transmission electron microscopy (TEM) observations (ED, HREM), scanning transmission electron microscopy (STEM-HAADF), and X-ray diffraction data. The analysis of these data has revealed an unexpected supercell with a monoclinic symmetry. From the hkl conditions deduced from the electron diffraction study and the analysis of X-ray diffraction data by simulated annealing, a structural model considering the centrosymmetric P21/m setting can be proposed. In addition the first magnetic and electrical transport measurements are reported showing a sharp peak in magnetic susceptibility and a strong localization around 360 K, associated to a structural change from monoclinic setting to orthorhombic one.

A new magneto-elastic resonance based technique to determine magneto-mechanical parameters of amorphous ferromagnetic ribbons.

Measurement of the magneto-mechanical parameters characteristics of amorphous ribbons often requires complex or limited methods due to their very small thickness. In this paper, it is shown how one can establish and estimate the characteristics of a magnetostrictive resonator from the experimental frequency response free of any kind of mechanical measurement (stress or elongation). This technique which is completely developed with a ribbon exhibiting good resonator properties, is suitable to estimate the magneto-mechanical coupling coefficient k33 and the Young's modulus and also to establish the magnetostriction curves λ(H) of amorphous ribbons. Results obtained from resonators made of 2605SC and 2826 from Metglas(TM) ribbons confirmed the validity of the present technique. However, measurements performed on a thin foil of nickel demonstrate that the present method cannot be extended to semi-soft magnetic materials. The technique which is proposed, has serious advantages upon others as it is non-destructive, low cost and easy to develop compared to common ones.

Cationic distribution and spin canting in CoFe2O4 nanoparticles.

CoFe(2)O(4) nanoparticles (D(NPD) ~6 nm), prepared by a thermal decomposition technique, have been investigated through the combined use of dc magnetization measurements, neutron diffraction, and (57)Fe Mössbauer spectrometry under high applied magnetic field. Despite the small particle size, the value of saturation magnetization at 300 K (M(s) Í = 70 A m(2) kg(-1)) and at 5 K (M(s) Í = 100 A m(2) kg(-1)) are rather close to the bulk values, making the samples prepared with this method attractive for biomedical applications. Neutron diffraction measurements indicate the typical ferrimagnetic structure of the ferrites, showing an inversion degree (γ(NPD) = 0.74) that is in very good agreement with cationic distribution established from low temperature (10 K) Mössbauer measurements in high magnetic field (γ(moss) = 0.76). In addition, the in-field Mössbauer spectrum shows the presence of a non-collinear spin structure in both A and B sublattices. The results allow us to explain the high value of saturation magnetization and provide a better insight into the complex interplay between cationic distribution and magnetic disorder in ferrimagnetic nanoparticles.

Water soluble dendronized iron oxide nanoparticles.

The grafting of pegylated dendrons on 9(2) nm and 39(5) nm iron oxide nanoparticles in water, through a phosphonate group as coupling agent has been successfully achieved and its mechanism investigated, with a view to produce biocompatible magnetic nano-objects for biomedical applications. Grafting has been demonstrated to occur by interaction of negatively charged phosphonate groups with positively charged groups and hydroxyl at the iron oxide surface. The isoelectric point of the suspension of dendronized iron oxide nanoparticles is shifted towards lower pH as the amount of dendron increases. It reaches 4.7 for the higher grafting rate and for both particle size. Thus, the grafting of molecules using a phosphonate group allows stabilizing electrostatically the suspensions at physiological pH, a prerequisite for biomedical applications. Moreover the grafting step has been shown to preserve the magnetic properties of iron oxide nanoparticles due to super-super exchange interactions through the phosphonate group.

Enhanced Néel temperature in Mn ferrite nanoparticles linked to growth-rate-induced cation inversion.

Mn ferrite (MnFe(2)O(4)) nanoparticles, having diameters from 4 to 50 nm, were synthesized using a modified co-precipitation technique in which mixed metal chloride solutions were added to different concentrations of boiling NaOH solutions to control particle growth rate. Thermomagnetization measurements indicated an increase in Néel temperature corresponding to increased particle growth rate and particle size. The Néel temperature is also found to increase inversely proportionally to the cation inversion parameter, delta, appearing in the formula (Mn(1-delta)Fe(delta))(tet)[Mn(delta)Fe(2-delta)](oct)O(4). These results contradict previously published reports of trends between Néel temperature and particle size, and demonstrate the dominance of cation inversion in determining the strength of superexchange interactions and subsequently Néel temperature in ferrite systems. The particle surface chemistry, structure, and magnetic spin configuration play secondary roles.

The effect of Mn and B on the magnetic and structural properties of nanostructured Fe60Al40 alloys produced by mechanical alloying.

The effect of Mn and B on the magnetic and structural properties of nanostructured samples of the Fe60Al40 system, prepared by mechanical alloying, was studied by 57Fe Mössbauer spectrometry, X-ray diffraction and magnetic measurements. In the case of the Fe(60-x)Mn(x)Al40 system, 24 h milling time is required to achieve the BCC ternary phase. Different magnetic structures are observed according to the temperature and the Mn content for alloys milled during 48 h: ferromagnetic, antiferromagnetic, spin-glass, reentrant spin-glass and superparamagnetic behavior. They result from the bond randomness behaviour induced by the atomic disorder introduced by the MA process and from the competitive interactions of the Fe-Fe ferromagnetic interactions and the Mn-Mn and Fe-Mn antiferromagnetic interactions and finally the presence of Al atoms acting as dilutors. When B is added in the Fe60Al40 alloy and milled for 12 and 24 hours, two crystalline phases were found: a prevailing FeAl BCC phase and a Fe2B phase type. In addition, one observes an additional contribution attributed to grain boundaries which increases when both milling time and boron composition increase. Finally Mn and B were added to samples of the Fe60Al40 system prepared by mechanical alloying during 12 and 24 hours. Mn content was fixed to 10 at.% and B content varied between 0 and 20 at.%, substituting Al. X-ray patterns show two crystalline phases, the ternary FeMnAl BCC phase, and a (Fe,Mn)2B phase type. The relative proportion of the last phase increases when the B content increases, in addition to changes of the grain size and the lattice parameter. Such behavior was observed for both milling periods. On the other hand, the magnetic hyperfine field distributions show that both phases exhibit chemical disorder, and that the contribution attributed to the grain boundaries is less important when the B content increases. Coercive field values of about 10(2) Oe slightly increase with boron content. Comparison with previous results on FeAIB alloys shows that Mn promotes the structural stability of the nanostructured powders.

Structural characterization of nanostructured Fe-8P powder mixture.

Nanostructured Fe-8P (wt%) powder mixture was prepared by high energy ball milling in a planetary ball mill (Fritsch P7) under argon atmosphere. The morphology of the particles, the phase identification and the alloying evolution process as a function of milling time are studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and 57Fe Mössbauer spectrometry (MS), respectively. Refinement based on Rietveld method of the XRD patterns and the Mössbauer spectra analysis show that the Fe(x)P (1 < x < 2) and Fe2P phosphide phases are the main product after 3 h of milling (approximately 10%). From the XRD Rietveld refinement, it is observed that the Fe2P phase disappears completely after 12 h of milling, while the Fe3P nanophase appears after 9 h and remains for larger milling duration. The lattice structure distortion is evidenced by the lattice parameter changes of the milled products. A two structure state of the alpha-Fe(P) solid solution: alpha-Fe1 and alpha-Fe2 is confirmed by both the XRD and MS measurements. After milling for 21 h, a mixture of a disordered two phase alpha-Fe(P) solid solution, Fe3P nanophase and a small amount of a paramagnetic FeP phosphide phase (approximately 2%) is obtained.

[Fe2(C10O8H2)]: an antiferromagnetic 3D iron(II) carboxylate built from ferromagnetic edge-sharing octahedral chains (MIL-62).

The first three-dimensional iron(II) tetracarboxylate is built from the connection of chains of edge-sharing Fe(II) octahedra by 1,2,4,5-benzenetetracarboxylates; magnetic measurements show an antiferromagnetic coupling of ferromagnetic chains below TN = 25(1) K.