Invar Behavior in Fe-Ni Alloys is Predominantly a Local Moment Effect Arising from the Magnetic Exchange Interactions Between High Moments

I argue that the main models that have been advanced to explain Invar behavior in Fe-Ni alloys (the original, classical, Invar system) can all be shown to be critically deficient, except one: The local moment frustration model of Rancourt and Dang ( Phys. Rev. B , 54 , 12225, 1996). The latter model explains all the measured structural, magnetic, and magnetovolume features of the Fe-Ni alloys with 0-65 apc (atomic percent) Fe, based on the assumptions that these systems are predominantly high-moment in character at the temperatures of interest and that the Fe-Fe pairs have large inter-atomic separation dependencies of their magnetic exchange parameters. The large magnetovolume Fe-Fe couplings are understood (based on ab initio electronic structure calculations) as a precursor effect of the low-moment/high-moment (LM/HM) transition that has recently been observed to occur at larger Fe concentrations, as a continuous transition occurring in the range , 65-75 apc Fe (Lagarec, Ph.D. thesis, 2001).     

First Observation of a Composition-Controlled Low-Moment/High-Moment Transition in the Fcc Fe-Ni System: Implications Regarding Invar and Anti-Invar Behaviors

We report the first direct observation of a high-moment (HM)/low-moment (LM) transition occurring in face centered cubic (FCC) Fe-Ni alloys. 57 Fe Mössbauer isomer shifts (ISs) give local electronic densities that exhibit a large discontinuity of , 0.4 el./ $ a_{0}^3 $ at the transition that spans the concentration range ～ 65-75 apc (atomic percent) Fe, in agreement with ab initio predictions. In the most Fe-rich alloys that have LM ground states (including n -Fe), we show that thermal stabilization of the HM state occurs at high temperatures, thereby providing an experimental proof that anti-Invar behavior is due to such HM stabilization. In Invar (Fe 65 Ni 35 ) and at near-Invar compositions, we observe temperature-induced changes in electronic density that follow the spontaneous magnetization curves and find that Invar is predominantly a HM phase at all temperatures where an Invar effect occurs. We show that LM phase thermal excitation cannot cause the Invar effect and that such excitation would cause a contraction instead of the required expansion, relative to normal behavior.     

Pressure induced self-oxidation of Fe(OH)2

M?ssbauer spectroscopy, x-ray diffraction, and electrical resistance [R(P,T)] studies in Fe(OH)(2) to 40 GPa revealed an unforeseen process by which a gradual Fe2+ oxidation takes place, starting at approximately 8 GPa reaching 70% Fe3+ abundance at 40 GPa. The nonreversible process Fe2+-->Fe3++e(-) occurs with no structural transition. The "ejected" electrons form a deep band within the high-pressure electronic manifold becoming weakly localized at P>50 GPa. This process is attributed to an effective ionization potential created by the pressure induced orientationally deformed (OH) dipoles and the unusual small binding energy of the valence electron in Fe2+(OH)(2).     

High-pressure phase transition of Bi2Fe4O9

The high-pressure behaviour of Bi2Fe4O9 was analysed by in situ powder and single-crystal x-ray diffraction and Raman spectroscopy. Pressures up to 34.3(8) GPa were generated using the diamond anvil cell technique. A reversible phase transition is observed at approximately 6.89(6) GPa and the high-pressure structure is stable up to 26.3(1) GPa. At higher pressures the onset of amorphization is observed. The crystal structures were refined from single-crystal data at ambient pressure and pressures of 4.49(2), 6.46(2), 7.26(2) and 9.4(1) GPa. The high-pressure structure is isotypic to the high-pressure structure of Bi2Ga4O9. The lower phase transition pressure of Bi2Fe4O9 with respect to that of Bi2Ga4O9 (16 GPa) confirms the previously proposed strong influence of cation substitution on the high-pressure stability and the misfit of Ga3+ and Fe3+ in tetrahedral coordination at high pressure. A fit of a second-order Birch–Murnaghan equation of state to the p–V data results in K0 = 74(3) GPa for the low-pressure phase and K0 = 79(2) GPa for the high-pressure phase. The mode Grüneisen parameters were obtained from Raman-spectroscopic measurements.     

Noncollinear itinerant-electron magnets: ground- and excited states simulations

The Heisenberg model cannot uncritically be applied to itinerant-electron magnets, including those that show noncollinear order. Density functional theory is, therefore, generalized to apply to noncollinear itinerant-electron magnets. The appropriate Kohn-Sham equations are discussed and the total energy of Spiral Magnetic Order (SMO) is found to describe the ground states of those magnets that possess a high-moment to low-moment transition such as, e.g., INVAR. Concerning excited-states properties, the energy spectrum of transverse and longitudinal spin fluctuations can be estimated with the total energy of SMO and allows a determination of thermal properties of itinerant-electron magnets. As an example calculated results for bcc-Fe are discussed in detail and compared with experimental results. Furthermore, results for Co, Ni and FeCo are collected. This revised version was published online in July 2006 with corrections to the Cover Date.     

Novel pressure-induced magnetic transition in magnetite (Fe3O4)

Fe K-edge x-ray magnetic circular dichroism of magnetite (Fe3O4) powders was measured with synchrotron radiation under variable pressure and temperature conditions in diamond anvil cell. The magnetic dichroism was observed to decrease discontinuously by approximately 50% between 12 and 16 GPa, independent of temperature. The magnetic transition is attributed to a high-spin to intermediate-spin transition of Fe2+ ions in the octahedral sites and could account for previously observed structural and electrical anomalies in magnetite at this pressure range. The interpretation of x-ray magnetic circular dichroism data is supported by x-ray emission spectroscopy and theoretical cluster calculations.     

The effect of iron spin transition on electrical conductivity of (Mg,Fe)O magnesiowüstite

We measured the electrical conductivity of Mg_0.81Fe_0.19O magnesiowüstite, one of the important minerals comprising Earth’s lower mantle, at high pressures up to 135 GPa and 300 K in a diamond-anvil cell (DAC). The results demonstrate that the electrical conductivity increases with increasing pressure to about 60 GPa and exhibits anomalous behavior at higher pressures; it conversely decreases to around 80 GPa and again increases very mildly with pressure. These observed changes may be explained by the high-spin to low-spin transition of iron in magnesiowüstite that was previously reported to occur in a similar pressure range. A very small pressure effect on the electrical conductivity above 80 GPa suggests that a dominant conduction mechanism changes by this electronic spin transition. The electrical conductivity below 2000-km depth in the mantle may be much smaller than previously thought, since the spin transition takes place also in (Mg,Fe)SiO₃ perovskite.     

High‐pressure studies of the micro‐Raman spectra of iron cyanide complexes: Prussian blue (Fe4[Fe(CN)6]3), potassium ferricyanide (K3[Fe(CN)6]), and sodium nitroprusside (Na2[Fe(CN)5(NO)]·2H2O)

The pressure dependences of the peaks observed in the micro‐Raman spectra of Prussian blue (Fe₄[Fe(CN)₆]₃), potassium ferricyanide (K₃[Fe(CN)₆]), and sodium nitroprusside (Na₂[Fe(CN)₅(NO)]·2H₂O) have been measured up to 5.0 GPa. The vibrational modes of Prussian blue appearing at 201 and 365 cm⁻¹ show negative dν/dP values and Grüneisen parameters and are assigned to the transverse bending modes of the Fe C N Fe linkage which can contribute to a negative thermal expansion behavior. A phase transition occurring between 2.0 and 2.8 GPa in potassium ferricyanide is shown by changes in the spectral region 150–700 cm⁻¹. In the spectra of the nitroprusside ion, there are strong interactions between the FeN stretching mode and the FeNO bending and the axial CN stretching modes. The pressure dependence of the NO stretching vibration is positive, 5.6 cm⁻¹ GPa⁻¹, in contrast to the negative behavior in the iron(II)‐meso‐tetraphenyl porphyrinate complex. Copyright © 2011 John Wiley & Sons, Ltd.     

Coexisting antiferromagnetism and ferromagnetism in mechanically alloyed Fe-rich Fe–Ni alloys: implications regarding the Fe–Ni phase diagram below 400°C

Fe–Ni alloys below the Invar region with compositions Fe_100−xNi_x (x=21, 24, and 27 at%) were prepared by high-energy ball milling technique (mechanical alloying). The as-milled samples, characterized by X-ray diffraction and Mössbauer spectroscopy, contain a mixture of (BCC) and γ (FCC) phases, whereas the samples annealed at 650°C for 0.5 h show a single γ (FCC) phase displaying a single line Mössbauer spectrum at room temperature (RT). At low temperature, the Mössbauer spectra of annealed Fe₇₆Ni₂₄ and Fe₇₃Ni₂₇ alloys show the existence of a magnetically split pattern together with a broad singlet, which are ascribed to a high-moment ferromagnetic Ni-rich phase and a low-moment Fe-rich phase, respectively. The Fe-rich phase in annealed Fe₇₆Ni₂₄ alloy, which is paramagnetic at RT, undergoes antiferromagnetic ordering at 40 K, estimated from the dramatic line broadening of its spectrum, giving rise to a small hyperfine field (e.g. 2 T at 6 K). The coexistence of these phases is attributed to phase segregation occurring in these alloys as a result of enhanced atomic diffusion. The stability of these alloys towards martensitic (FCC→BCC) transformation at low temperatures is discussed in connection with the Fe–Ni phase diagram below 400°C.     

Magnetism under high pressure studied by 57Fe and 151Eu nuclear scattering of synchrotron radiation

The nuclear forward scattering (NFS) of synchrotron radiation is especially suited for probing magnetism at very high pressure, here in the Mbar range, by the nuclear resonances of ⁵⁷Fe and ¹⁵¹Eu. We report on high pressure (h.p.) NFS studies with the 14.4 keV transition of ⁵7Fe on magnetic RFe₂ Laves phases of cubic C15 structure (YFe₂, GdFe₂) and hexagonal C14 structure (ScFe₂, TiFe₂) at pressures up to 100 GPa (=1 Mbar). We present also h.p. NFS studies performed with the 21.5 keV resonance of ¹⁵¹Eu, probing the magnetism in the CsCl-type h.p. phase of EuTe. This revised version was published online in August 2006 with corrections to the Cover Date.     

Superconducting properties of V/Fe superlattices

We report measurements on the superconducting properties of V/Fe superlattices with various layer thicknesses. These samples were prepared with a novel UHV evaporator which can produce up to twenty different samples in the same run. The Fe layer, a strong pair breaker, suppresses the superconducting transition temperature in a systematic way. When the V layer thickness is on the order of the BCS coherence length and the Fe layer is only a few atomic planes thick, a 2D–3D crossover has been observed in the temperature dependence of the parallel upper critical field H_C2∥. This implies the coexistence of superconductivity and ferromagnetismm. We observe three dimensional behavior for thinner Fe layers (～1 atomic plane) and two dimensional behavior for thicker Fe layers (greater than 10 atomic planes).     

钕铁硼的冲击压缩特性

 利用二级轻气炮对恒磁体钕铁硼进行冲击压缩,采用阻抗匹配法进行测量,获得了平均初始密度为7.346 g/cm³的钕铁硼Hugoniot关系数据。实验结果表明,该种钕铁硼在19~78 GPa范围内,其D-u_p满足线性变化关系,即：C₀、λ分别为3.686 km/s、1.059,是一种稳定的压缩过程,其间没有相变产生。而较小的λ值表明该种钕铁硼材料偏向于疏松体结构,且容易被压缩。同时实验结果也为其状态方程和脉冲功率源等方面的研究工作提供了可资参考的实验参数。     

First-Order Transition of Fe 2 P and Anti-Metamagnetic Transition

A fixed-spin-moment (FSM) calculation is carried out for Fe 2 P using the linear muffin-tin orbital method. It is found that the Fe atom at the 3f site shows a metamagnetic behavior, while the Fe atom at the 3g site is ferromagnetic. In order to study the magnetic properties of this compound at finite temperatures, a simple model based on the Landau-Ginzburg theory is proposed, by taking into account the effect of spin fluctuations. The Landau parameters included in this model are estimated from the results obtained by fixed-spin moment band-calculations. It is shown that the first-order transition at T C observed for Fe 2 P is attributed to the metamagnetic Fe atoms at the 3f site. The present mechanism of the first-order transition is connected with the anti-metamagnetic transition observed in some rare-earth and Co compounds.     

Stability of Ferromagnetism in Fe, Co, and Ni Metals under High Pressure with GGA and GGA+U

The stability of the ferromagnetic state in Fe, Co, and Ni metals under high pressure is investigated using generalized gradient approximation (GGA) and GGA+U within the density functional theory (DFT). It is found that the ferromagnetic state under pressure is very different for Fe, Co, and Ni metals, and is closely associated with the crystal structure. In the case of Fe, a ferromagnetic bcc ground state is obtained at ambient pressure and a nonmagnetic hcp ground state is found at pressure around 12 and 115 GPa for GGA and GGA+U, respectively. For Co, the phase transition from a ferromagnetic hcp to a nonmagnetic fcc is found around 107 GPa for GGA. In contrast to Fe and Co, a ferromagnetic fcc state in Ni is maintained even at 200 GPa. The calculated results suggest that the suppression of ferromagnetism in Fe, Co, and Ni is due to pressure-induced decrease of the density of state at the Fermi level.     

Strong interface adhesion in Fe/TiC

As an aid to understanding the superior toughness of Ti-modified steels provided by fine Ti(C,?N) particles, first-principles full-potential linearized augmented plane wave (FLAPW) density functional calculations were performed on the Fe matrix/TiC particle interface. It was found that at equilibrium a strong covalent bonding between Fe–C is formed at the interface, and the magnetic moment of the interface Fe (1.98?μ _B ) is reduced from that of the tetragonally strained structure (2.51?μ_B). We then calculated with a rigid separation model the separation energy curve and the force separation law for the Fe–C debonding process at the interface, which predicts 2.45?J?m_?2 for the work of separation and 30.66 [GPa] for the force maximum. We also found that the strong Fe–C bond provides an interfacial fracture strength equal to that of the pure bcc Fe matrix. A clear picture is given for the microscopic origin of this strong metal/ceramic adhesion based on density of states (DOS) considerations. For a more realistic understanding of the Fe–C bonding, structural optimization calculations were performed at each separation distance. The effect of relaxation was found to be larger at short separation distances than in the large separation region, which leads to a crossover behavior in the separation energy curve from the elastically deformed to the clearly separated regime at a critical distance (～1.75?Å), and to a discontinuity in the force separation law. Despite this large relaxation effect, the work of separation, 2.52?J?m_?2, is not changed much from that of rigid separation.     

Magnetic transition of ferromagnetic material at high pressure using a novel system

A system for the investigation of the magnetic properties of materials under high pressure is fabricated based on diamond anvil cell （DAC） technology. The system is designed with an improved coil arranged around the diamond of a non-magnetic DAC. Using this system, the magnetic transition of ferromagnetic （Fe） sample under increasing pressure can be observed. We successfully obtain the evolution of magnetic properties as a function of applied pressure reaching 26.9 GPa in the Fe sample. A magnetic transition is observed at approximately 13 GPa, which is consistent with the theoretical prediction.     

57Fe Mössbauer study under high pressure; ε-Fe and Fe2O3

Using diamond anvil cell, the⁵⁷Fe Mössbauer spectra of pure iron foil and α-Fe₂O₃ powder under high pressure have been measured at room temperature.⁵⁷Fe Mössbauer spectra of α-Fe were measured from 15 GPa to 45 GPa. Isomer shift value decreased and the quadrupole splitting slightly increased as the pressure increased.⁵⁷Fe Mössbauer spectra of Fe₂O₃ under high pressure up to 72 GPa were observed. Above 52 GPa, the new lines appeared at the center portion of the spectrum corresponding to the new high pressure phase. The spectrum of new high pressure phase consisted of 6-line splitting and doublet, suggesting the existence of the two different kinds of iron states in it.     

Pressure-induced magnetization in FeO: evidence from elasticity and Mössbauer spectroscopy

The complete elastic tensor of Fe0.94O (wüstite) has been determined to 10 GPa using acoustic interferometry at GHz frequencies inside a diamond-anvil cell. The soft mode (C44) elastic constant of FeO is reduced by 20% over the experimental pressure range. An unusual discontinuity in the pressure derivatives of C11 and C12 at 4.7+/-0.2 GPa corresponds to the pressure at which the onset of a magnetic ordering transition is observed by high-pressure M?ssbauer spectroscopy and neutron powder diffraction. Our new results combined with literature structural high P-T data suggest that there is a magnetic, although still cubic, phase of FeO between approximately 5 and approximately 17 GPa.     

Adsorption and dissociation of CO on Fe(1 1 0) from first principles

We employ spin-polarized periodic density functional theory (DFT) to characterize CO adsorption and dissociation on the Fe(1 1 0) surface. We investigate the site preference for CO on Fe(1 1 0) at θ_CO = 0.25 and 0.5 monolayer (ML), for different functional forms of the generalized gradient approximation (GGA) to electron exchange and correlation within DFT. At 0.25 ML, we predict the existence of a new ordered structure comparable in stability to one proposed previously. At 0.5 ML, we confirm the preference of a distorted on-top adsorption configuration suggested by experiment. The calculated heats of adsorption, CO stretching frequencies, and work function changes agree well with experiment. When dissociating from the on-top site, we predict that CO first moves off the on-top site and then goes through a lying-down transition state with a barrier of 1.52 eV. Diffusion of CO on Fe(1 1 0) from the on-top site to the long-bridge site is predicted to have a very small barrier of 0.1 eV. Dissociation of CO from the long-bridge site goes through the same transition state as from the on-top site, but the former has a slightly lower barrier. After dissociation, O atoms remain on the surface while C atoms are embedded into Fe(1 1 0), indicating C atoms may readily diffuse into Fe(1 1 0).