Manganese substitution induced magnetic transformation and magnetoelectricity in SrFe12O19.

In this study, manganese substituted strontium hexaferrite (SrFe12-xMnxO19; x = 0, 3, 5, and 7) prepared by the sol-gel auto-combustion method are studied. We observed that the substituted Mn preferentially goes to the 2a and 12k sites of Fe. Raman modes related to the 12k site suggest the stiffening of the lattice. The transformation of the grain's shape from hexagonal (x = 0 and 3) to rhombohedral (x = 7) was observed, as shown in the micrographs obtained from FESEM. The thermomagnetic curves show the shift of TC to lower temperatures with the increase in the Mn content. From x = 5 onwards, the growth of another magnetic phase (FiM2) of lower coercivity apart from the parent phase (FiM1) of higher coercivity is seen. The FiM2 phase was found to increase with the Mn content in the sample (16.4(3)% for x = 5 but 66.2(5)% for x = 7). Although the magnetization for both FiM1 and FiM2 decreases with the increase in temperature, both magnetic phases behave in contrast to each other for x = 5 and x = 7. The study suggests a transformation of the compound from high magnetic anisotropy (x = 0) to low magnetic anisotropy (x = 7). The x = 5 composition sample displays the highest value of the first-order ME coefficient (0.83(2) mV × cm-1 × Oe-1). The observed value for x = 5 composition is ∼2.5 times higher than that of the parent x = 0 composition sample (0.33(2) mV × cm-1 × Oe-1). The studies thus suggest that the x = 5 composition is one of the viable candidates for magnetoelectric applications.

Manifestation of dissimilar types of magnetism in iron- and chromium-substituted Mn2SnS4.

Mn2SnS4 belongs to the MII2AIVQ4 (M = transition metal; A = Si, Ge and Sn; Q = S, Se and Te) class of compounds that crystallizes in the orthorhombic space group Cmmm and shows complex magnetic properties. Here we report the synthesis and magnetic properties of Fe- and Cr-substituted Mn2SnS4 quaternary chalcogenides. All these compounds have been synthesized using a high-temperature solid-state route. Room temperature neutron diffraction studies on the specific compositions of chromium- and iron-substituted compounds were performed to obtain the site occupancy of different elements in the unit cell. The neutron diffraction analysis by employing the Rietveld refinement shows that for the Fe-substituted compound, most of the Fe goes to the Mn site with a small amount at the Sn site, while in the Cr-substituted sample, all the Cr occupy the Mn site. However, the Sn site almost remains intact in the case of the Fe-substituted compound, while it is significantly disordered for the Cr-substituted sample as a fraction of Mn occupies the Sn site and an equivalent amount of Sn occupies the Mn site. XPS study shows that both Cr and Fe exist in the +3 oxidation state, while Mn exists in the +2 state and Sn exists in a mixture of +2 and +4 oxidation states. Magnetic property study of these substituted compounds shows different types of magnetism, which is attributed to the variation of d-electrons of the substituent atom. The chromium-doped compounds show ferrimagnetic character along with two transitions: one transition at ∼37 K and another at ∼152 K. However, in Fe-substituted Mn2SnS4 samples, the low-temperature transition disappears and an increase in the high-temperature antiferromagnetic ordering temperature i.e. from 152 K (Mn2SnS4) to 174 K (Mn1.82Fe0.18SnS4) is observed. The increase in the antiferromagnetic ordering temperature in Mn2-xFexSnS4 may be attributed to the increase in the covalence of Mn/Fe-S-Mn/Fe bonds (shorter) with iron substitution.

Lattice assisted dielectric relaxation in four-layer Aurivillius Bi5FeTi3O15ceramic at low temperatures.

We have investigated magnetic, structural and dielectric properties of Bi5FeTi3O15(BFTO) in the temperature range 5K-300 K. Using diffraction, Raman spectroscopy and x-ray absorption fine structure measurements, iso-structural modifications are observed at low temperatures (≈100 K). The analysis of dielectric constant data revealed signatures of dielectric relaxation, concomitant with these structural modifications in BFTO at the same temperatures. Further, employing complementary experimental methods, it is shown that the distribution of Fe/Ti ions in BFTO is random. With the help of techniques that probe magnetism at various length and time scales, it is shown that the phase-pure BFTO is non-magnetic down to the lowest temperatures.

Crystal structure of monoclinic hafnia (HfO2) revisited with synchrotron X-ray, neutron diffraction and first-principles calculations.

A study on the crystal structure of monoclinic HfO2 has been performed using synchrotron X-ray and neutron diffraction data separately, as well as a combination of both. The precision of the structural parameters increases significantly due to application of the neutron diffraction technique. The experimental oxygen positions in HfO2, derived precisely, are visualized only by semi-local density functional calculations in terms of the calculated electronic band gap, but are not captured as accurately by using hybrid functionals.

Mixed-valent antimony-induced disorder in substituted antiferromagnetic Mn2SnS4.

Among MII2AIVQ4 (M = transition metal; A = Si, Ge, and Sn; Q = S, Se, and Te)-type compounds, most of which crystallize in an olivine or spinel structure, Mn2SnS4 is a unique compound that crystallizes in the orthorhombic space group Cmmm and exhibits complex magnetic properties. In this article, we report synthesis and study of the effect of Sb substitution (up to 20%) on the magnetic properties of Mn2SnS4. All the compounds were found to be in a single phase and indexed with the orthorhombic parent structure. Rietveld refinement of the room-temperature neutron diffraction data of Mn2Sn0.85Sb0.15S4 sample shows that Sb occupies the Mn site by replacing an equivalent amount of Mn. Subsequently, the replaced Mn occupies the Sn site causing disorder at both the Mn and the Sn sites, and the refined composition (Mn1.85(1)Sb0.15(1))(Sn0.85(1)Mn0.15(1))S4 is obtained. Although the purpose of incorporation of Sb(iii) was to create a mixed valence state at the Mn site, XPS study shows contrasting results. Sb exists in a mixed valence state, Sb(iii) and Sb(v), which balances the charge at the Sn(iv) site. Magnetic study of the compounds shows a very interesting trend. Pure Mn2SnS4 shows two magnetic transitions: one at 152 K that corresponds to antiferromagnetic ordering and other at 53 K corresponding to weak ferromagnetic ordering possibly due to spin canting. With antimony substitution, the temperature (152 K) of antiferromagnetic ordering remains unchanged, whereas the temperature of weak ferromagnetic ordering gradually increases with an increase in the Sb content from 53 K for the undoped compound to 88 K for 20% Sb-doped Mn2SnS4. The increase in the temperature of weak ferromagnetic ordering could be attributed to the incorporation of Sb, which induces more disorder at the Mn site, thereby making the magnetic lattice dilute with reduced frustration.

Magnetic ordering of the martensite phase in Ni-Co-Mn-Sn-based ferromagnetic shape memory alloys.

The magnetic state of low temperature martensite phase in Co-substituted Ni-Mn-Sn-based ferromagnetic shape memory alloys (FSMAs) has been investigated, in view of numerous conflicting reports of occurrences of spin glass (SG), superparamagnetism (SPM) or long range anti-ferromagnetic (AF) ordering. Combination of DC magnetization, AC susceptibility and small angle neutron scattering (SANS) studies provide clear evidence for AF order in the martensitic phase of Ni45Co5Mn38Sn12 alloy and rule out SPM and SG orders. Identical studies on another alloy of close composition, Ni44Co6Mn40Sn10, point to the presence of SG order in the martensitic phase and the absence of SPM behavior, contrary to earlier reports. SANS results do show the presence of nanometre-sized clusters but they are found to grow in size from 3 nm at 30 K to 11 nm at 300 K, and do not correlate with magnetism in these alloys.

Nonmonotonic particle-size-dependence of magnetoelectric coupling in strained nanosized particles of BiFeO3.

Using high resolution powder x-ray and neutron diffraction experiments, we determined the off-centered displacement of the ions within a unit cell and magnetoelectric coupling in nanoscale BiFeO3 (≈20-200 nm). We found that both the off-centered displacement of the ions and magnetoelectric coupling exhibit nonmonotonic variation with particle size. They increase as the particle size reduces from bulk and reach maximum around 30 nm. With further decrease in particle size, they decrease precipitously. The magnetoelectric coupling is determined by the anomaly in off-centering of ions around the magnetic transition temperature (T N ). The ions, in fact, exhibit large anomalous displacement around the T N which is analyzed using group theoretical approach. It underlies the nonmonotonic particle-size-dependence of off-centre displacement of ions and magnetoelectric coupling. The nonmonotonic variation of magnetoelectric coupling with particle size is further verified by direct electrical measurement of remanent ferroelectric hysteresis loops at room temperature under zero and ∼20 kOe magnetic field. Competition between enhanced lattice strain and compressive pressure appears to be causing the nonmonotonic particle-size-dependence of off-centre displacement while coupling between piezo and magnetostriction leads to nonmonotonicity in the variation of magnetoelectric coupling.

Investigation of Ca substitution on the gas sensing potential of LaFeO3 nanoparticles towards low concentration SO2 gas.

The present work investigates the superior ability of LaFeO3 (LaFeO) and La0.8Ca0.2FeO2.95 (LaCaFeO) nanoparticles to detect 3 ppm SO2 gas. The influence of calcium substitution on the sensing behaviour of LaFeO has been studied. High resolution TEM images show that the particle sizes of LaFeO and LaCaFeO are less than 100 nm and SEM images show the agglomeration of interconnected nanoparticles. Both LaFeO and LaCaFeO crystallize in the orthorhombic crystal system with the space group Pbnm. Rietveld analysis of neutron diffraction data showed that LaCaFeO has lattice oxygen vacancies. In addition, magnetic refinements on both the samples have been carried out. The presence of lattice oxygen vacancies in LaCaFeO is qualitatively supported by Raman and XPS measurements. Electrical characterization showed increased conductivity for the LaCaFeO sample, influencing their sensing performance significantly. The LaCaFeO nanoparticles exhibit higher sensitivity, faster response time, rapid recovery time and good recyclability for sensing 3 ppm SO2 gas. This enhanced sensing behaviour is attributed to the increased oxygen vacancies in the lattice as well as the surface. As a consequence, increased active sites are created in LaCaFeO, promoting redox reaction between the analyte and the sensing material. The results demonstrated that while LaFeO is a good gas sensor, p-type substitution by Ca(2+) renders this material an improved resistivity based gas sensor to detect low concentration SO2.

Synthesis, Characterization and Exploration of Multiferroic Properties in Nano-Crystalline Tb1-xYxMnO3 (0 ≤ x ≤ 0.4).

We report the synthesis and electric properties of nano-crystalline Tb1-xYxMnO3 (x = 0, 0.1, 0.2, 0.3 and 0.4) compounds prepared by gel-combustion method. These samples were characterized by a number of techniques including X-ray diffraction (XRD), Raman spectroscopy, specific-heat measurement, neutron diffraction, and magnetic field dependent pyrocurrent measurement. All the samples crystallize in the orthorhombic structure with space group Pnma at room temperature. Anomalies were observed in low temperature specific-heat measurement corresponding to magnetic and electric phase transitions. The magnetic phase transitions occurred at ~35, ~22-28 and ~7 K for all the samples. Signatures of coupling between magnetic and electric order parameters were revealed by pyrocurrent measurements carried out in presence of magnetic fields.

Origin of the Spin-Orbital Liquid State in a Nearly J=0 Iridate Ba_{3}ZnIr_{2}O_{9}.

We show using detailed magnetic and thermodynamic studies and theoretical calculations that the ground state of Ba_{3}ZnIr_{2}O_{9} is a realization of a novel spin-orbital liquid state. Our results reveal that Ba_{3}ZnIr_{2}O_{9} with Ir^{5+} (5d^{4}) ions and strong spin-orbit coupling (SOC) arrives very close to the elusive J=0 state but each Ir ion still possesses a weak moment. Ab initio density functional calculations indicate that this moment is developed due to superexchange, mediated by a strong intradimer hopping mechanism. While the Ir spins within the structural Ir_{2}O_{9} dimer are expected to form a spin-orbit singlet state (SOS) with no resultant moment, substantial frustration arising from interdimer exchange interactions induce quantum fluctuations in these possible SOS states favoring a spin-orbital liquid phase down to at least 100 mK.

Neutron diffraction evidence for kinetic arrest of first order magneto-structural phase transitions in some functional magnetic materials.

Neutron diffraction measurements, performed in the presence of an external magnetic field, have been used to show structural evidence for the kinetic arrest of the first order phase transition from (i) the high temperature austenite phase to the low temperature martensite phase in the magnetic shape memory alloy Ni37Co11Mn42.5Sn9.5, (ii) the higher temperature ferromagnetic phase to the lower temperature antiferromagnetic phase in the half-doped charge ordered compound La0.5Ca0.5MnO3 and (iii) the formation of glass-like arrested states in both compounds. The cooling and heating under unequal fields protocol has been used to establish phase coexistence of metastable and equilibrium states, and also to demonstrate the devitrification of the arrested metastable states in the neutron diffraction patterns. We also explore the field­temperature dependent kinetic arrest line TK(H), through the transformation of the arrested phase to the equilibrium phase. This transformation has been observed isothermally in reducing H, as also on warming in constant H. TK is seen to increase as H increases in both cases, consistent with the low-T equilibrium phase having lower magnetization.

Anomalous variation of the Lamb-Mössbauer factor at the magnetic transition temperature in magnetoelectric GaFeO3.

Temperature-dependent (57)Fe Mössbauer spectroscopy (5-723 K) and neutron diffraction (2-290 K) measurements are carried out on polycrystalline magnetoelectric GaFeO(3). From the neutron diffraction data, evidence for the magnetostriction and increased disorder at Fe sites close to the ferrimagnetic Curie transition temperature (T(C)) is observed. From the Mössbauer data, it is observed that the Lamb-Mössbauer factor as a function of temperature f(T), which is related to the integral over the first Brillouin zone of the phonon spectrum, shows a unequivocal variation at the T(C). The observations are discussed in terms of spin-phonon coupling. The observed average hyperfine fields from (57)Fe Mössbauer spectra match with the bulk magnetization data. A critical exponent (ß) of 0.38 ± 0.02 and a Debye temperature (θ(D)) of ~350 K is estimated from the (57)Fe Mössbauer data.

Magnetic behavior of Ba3Cu3Sc4O12.

The chain-like system Ba(3)Cu(3)Sc(4)O(12) has potentially interesting magnetic properties due to the presence of Cu(2+) and a structure-suggested low dimensionality. We present magnetization M versus magnetic field H and temperature T, T- and H-dependent heat-capacity C(p), (45)Sc nuclear magnetic resonance (NMR), muon spin rotation (µSR), neutron diffraction measurements and electronic structure calculations for Ba(3)Cu(3)Sc(4)O(12). The onset of magnetic long-range antiferromagnetic (AF) order at T(N) ∼ 16 K is consistently evidenced from the whole gamut of our data. A significant sensitivity of T(N) to the applied magnetic field H (T(N) ∼ 0 K for H = 70 kOe) is also reported. Coupled with a ferromagnetic Curie-Weiss temperature (θ(CW) ∼ 65 K) in the susceptibility (from a 100 to 300 K fit), it is indicative of competing ferromagnetic and antiferromagnetic interactions. These indications are corroborated by our density functional theory based electronic structure calculations, where we find the presence of significant ferromagnetic couplings between some copper ions whereas AF couplings were present between some others. Our experimental data, backed by our theoretical calculations, rule out the one-dimensional magnetic behavior suggested by the structure and the observed long-range order is due to the presence of non-negligible magnetic interactions between adjacent as well as next-nearest chains.

Elephant trunk anastomosis between left carotid and subclavian arteries for aneurysmal distal aortic arch.

There is an increased risk of rupture with attempting a distal anastomosis when the distal aortic arch exceeds 5 to 6 cm. To circumvent this problem, we describe performing the anastomosis between the left common carotid and the left subclavian arteries and, at the second-stage operation, interposing a tube graft between the left subclavian artery and the descending aortic tube graft.