Invar effects of laves phase untermetallic compounds

The magnetovolume effects in Laves phase compounds such as AFe₂ and ACo₂ are received. In particular, Invar like behaviour which is found in (Zr_1-xNb_x)Fe₂ and Zr(Fe_1-xCo_x)₂ systems is reported. Comparing the present results with the classical Invar such as Fe-Ni and Fe-Pt alloys, it is proposed that so-called Invar anomalies should be classified into two type, i.e. the giant spontaneous volume magnetostriction, which is the essential characteristic of the Invar effect and the other anomalies which are observed in Fe-Ni and Zr(Fe_1-xCo_x)₂ systems but not in Fe-Pt and (Zr_1-xNb_x)Fe₂ systems.     

Elastic and magnetoelastic effects in invar alloys

A review of the elastic behaviour of Invar alloys is given. This includes (a) ferromagnetic alloys (Fe-Ni, Fe-Pt, stainless Invar); (b) antiferromagnetic alloys (Fe-Mn, Mn- and Cr-based alloys); (c) very weak ferromagnets (ZrZn₂, Ni₃Al, Ni-Pt); (d) amorphous alloys (Fe-B). It is shown that elastic anomalies (ΔE effects) can but need not occur simultaneously with a large thermal expansion anomaly. Various magnetoelastic contributions exist (ΔE_λ, ΔE_ω, ΔE_m) which are discussed in terms of existing theoretical models. The effect associated with a volume distortion, i.e. the bulk modulus anomaly, is shown to fit into the framework of the itinerant electron model.     

The Invar behaviour of iron-nickel-platinum alloys

The ordering temperatures of alloys in the quasi-binary section Fe₃(Ni_xPt_1−x) have been determined experimentally, and are found to be consistent with theoretical predictions. Lattice constants and expansion coefficients vary smothly between Fe_0.75Ni_0.25 and Fe_0.75Pt_0.25 and are basically in agreement with the predictions of the Weiss 2_γ state theory except in a region very close to Fe_0.75Pt_0.25. The effect of heat treatments below the ordering temperature is placed in an overall context of competing phase transformations, which can also be used to rationalise conflicting views on the existence of Fe₃Ni, and the role of ordering on the Invar effect in general.     

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.     

高压下有序晶态合金Fe3Pt的低能声子不稳定性及磁性反常

有序晶态Fe₃Pt因瓦合金处于一种特殊的磁临界状态, 这种磁临界状态下体系的晶格动力学稳定性对压力极为敏感. 基于密度泛函理论的第一性原理的投影缀加平面波方法研究了不同晶态合金的Fe₃Pt的焓和磁性随压力的变化规律, 结果表明, 在压力小于18.54 GPa下, P4/mbm结构是热力学稳定的相. Pm3m结构、I4/mmm结构、DO₂₂结构的Fe₃Pt在铁磁性坍塌临界压力附近体系的总磁矩急剧下降并具有振荡现象, 且I4/mmm结构和DO₂₂结构的Fe₃Pt 在临界压力附近出现了Fe1原子磁矩反转现象. 在43 GPa下, DO₂₂结构的Fe₃Pt出现了亚铁磁微观磁特性突然增强且伴随着体积突然增大的现象. 在高压下, 对Pm3m结构Fe₃Pt的晶格动力学计算表明, 压力小于26.95 GPa的铁磁态下体系的自发磁化诱导了体系横向声学支声子软化, 表明体系中存在很强的自发体积磁致伸缩. 特别是在铁磁性坍塌临界压力41.9 GPa至磁性完全消失的57.25 GPa压力区间, 晶格动力学稳定性对压力更加敏感. 压力大于57.25 GPa时, 压力诱导了体系声子谱的稳定.     

Evidence of new high-pressure magnetic phases in Fe–Pt Invar alloy

To investigate the magnetic properties of disordered Fe₇₀Pt₃₀ Invar alloy under high pressure, measurements of the real part of the AC susceptibility (χ) were made under pressure up to 7.5 GPa in the temperature range 4.2–385 K using a cubic anvil high-pressure apparatus. The Curie temperature (T_C) decreased with increasing pressure, and then, two new high-pressure magnetic phases appeared. These results show that the ferromagnetism of Fe–Pt Invar alloy becomes weaker, and the antiferromagnetic interaction becomes dominant with increasing pressure.     

A contribution to the invar problem by hyperfine field distribution analyses

The Mössbauer spectra of Invar type Fe₆₅(Ni_1-xMn_x)₃₅ alloys (0 x 0.3) were analyzed to yield hyperfine field distribution (P(H)) curve. The P(H) curves of the alloy with x = 0, that is the “classical” Invar alloy, at 4.2 K is character ized by a relatively sharp main peak at 350 kOe and a weak low field component around 50 kOe. With increasing x, the low field component grows and the high field main peak spreads toward a low field. By raising temperature, the main peak exhibits a remarkable broadening as well as a decrease in the average internal field and a growth of the low field component has not been detected. On the basis of these observations, models of the Invar alloy so far proposed are discussed.     

Shape memory and associated properties in Fe–Mn–Si-based ribbons produced by melt-spinning

Four Fe–Mn–Si alloys, Fe₆₂Mn₃₂Si₆, Fe₆₂Mn₂₀Si₅Cr₈Ni₅, Fe₆₂Mn₁₆Si₅Cr₁₂Ni₅ and Fe₆₅Mn₉Si₇Cr₁₀Ni₉, were obtained by the melt-spinning method. The samples were structurally, magnetic and shape memory effect (SME) investigated, both “as quenched” and thermally treated. The Mn-rich compositions show different phase, magnetic behavior and SME in comparison with Mn-poor compositions. The thermal treatments generate transformation between the two existing majority phases ( and γ), related magnetization and SME behavior. The features are derived from the corroboration of structural, magnetic interaction and magnitude of SME data.     

Magnetic excitations in invar alloys, Fe65Ni35 and Fe3Pt

Magnetic excitations in Fe₆₅Ni₃₅ and ordered Fe₃Pt have been studied by neutron scattering. It has been found that both alloys show common anomalous dynamical properties. At 5 K, well defined magnon groups could be detected up to 80 meV, but the temperature variations of the magnetization M(T) cannot be explained only by the magnon excitations. The integrated intensity measurements of the magnon spectra suggest that no other excitations take part in M(T). The magnons dampen significantly with the linewidth Γ(q, T) obeying a relation Γ(q, T) = (Γ₀+aT)q² with 1. The results suggest that the magnetic excitations with volume change occur in a slow relaxation process.     

Influence of magnetization on lattice constants of 3d transition metal alloys

A simple relation is found in 3d transitional metal alloys between the lattice constant and the magnetization, which can be described with an equation: a(x) = a₀^A· (1 − x) + a₀^B. x + C μ(x). It is proposed that studies of lattice constants at high temperatures may serve as an experimental method to detect the existence of localized moments above T_c. The anomalous thermal expansion of the Invar alloy is explained as a result of the collapse of localized moments above T_c.     

Magnetic and microstructural investigations of melt-spun Fe(NdPr)B

The magnetic behavior of rapidly solidified FePrB was investigated in the composition range Fe_77+χPr₁₅B_8−χ (0 ≤ χ ≤ 4). Furthermore, the magnetic and microstructural properties of Fe(NdPr)B were analyzed in the range Fe₇₈(Nd_χPr_1−χ)₁₅B₇ (0 ≤ χ ≤ 1). The temperature dependence of the critical field was analyzed with a modified form of Brown's expression for the nucleation field. From this analysis the values for the microstructural parameters, _K and N_eff, were determined which describe the deteriorating effects of the non-ideal microstructure on the coercivity.     

Raman phonon anomalies in Sr(Fe1-xCox)2As2

Phonon anomalies have been reported in iron-pnictide superconductors indicating a diverse interplay between different orders in the materials.Here,we report Raman scattering measurements on Sr(Fe_1-xCo_x)₂As₂(x=0 and x=0.04)single crystals in the B;symmetry with respect to a 1 Fe unit cell.Upon cooling,we observe a larger split(13 cm;)of Eg Raman phonon modes pertaining to in-plane Fe and As displacements as the crystals undergo the tetragonal-toorthorhombic structural phase transition,although a considerable split(9 cm;)has been reported in BaFe_1-xCo_x)₂As₂.Furthermore,the splitting of E;phonon modes is strongly reduced upon doping.We perform an order-parameter analysis revealing a similar doping dependence of E;phonon splitting as reported in other compounds of the 122 family,indicating these phonon anomalies widely exist in 122 iron-based superconductors and might share the same mechanisms.     

正交相Fe2(MoO4)3的制备与表征及其负膨胀行为的第一性原理研究

采用水热合成法制备出Fe₂(MoO₄)₃样品, 并用高温X-射线衍射、热重和差示扫描量热同步热分析仪对其进行表征, 发现样品在510 ℃附近发生低温单斜相和高温正交相之间的可逆相变, 且正交相表现出负膨胀特征. 采用第一性原理计算了正交相Fe₂(MoO₄)₃ 的原子、电子结构以及声子谱、声子态密度, 并和可获得的实验结果进行了系统的比较. 结果显示正交相Fe₂(MoO₄)₃中MoO₄四面体较之FeO₆八面体具有更强的刚性. 发现最低频的光学支处具有最负的格林乃森(Grüneisen)系数, MoO₄四面体和FeO₆ 八面体相连的桥氧原子的横向振动、FeO₆八面体柔性扭曲转动以及MoO₄四面体的刚性翻转共同导致了Fe₂(MoO₄)₃负膨胀现象的发生.     

The anomalous behaviour of Gd atoms (Fe1−xMnx)2 compounds

The educed Gd atoms in the X-structure (Th₆Mn₂₃-type) of Gd(Fe_1−xMn_x)₂ were magnetically investigated by comparing with Gd₆(Fe_1−yMn_y)₂₃ whose structure is Th₆Mn₂₃-type. The magnetic properties of Gd(Fe_1−xMn_x)₂ (0.4≤x≤0.7) were observed to be quite similar to those of Gd₆(Fe_1−yMn_y)₂₃ (0.4≤y≤0.7).     

Low-temperature structure of Fe-Ni alloys

The Debye temperature (θ_M) of Fe-Ni alloys was obtained from measurements of the X-ray integrated intensity and the electrical resistivity at low temperatures from 4 to 300 K. A decrease of θ_M, implying a lattice softening effect, was found by lowering the temperature or increasing the iron concentration in the Invar region.     

Magnetic behaviour of some Mn.III2.VI4 compounds and their alloys

Measurement of the magnetic susceptibility χ as a function of temperature were made on polycrystalline samples from the alloy systems Cd_1−zMn_zGa₂Se₄, Zn_1−zMn_zGa₂Se₄ and Cd_1−zMn_zIn₂Te₄ which had been subjected to various heat treatments. The 1/χ versus T curves indicated that for the Zn---Se alloys, for all values of z, samples slowly cooled to room temperature were antiferromagnetic showing ideal Curie-Weiss behaviour, but for samples quenched from 700°C the behaviour was a mixture of antiferromagnetic and spin-glass. For the Cd---Se alloys, samples from the range (0.6 < z < 1.0) showed very similar behaviour, but in the range (0 < z < 0.6) even the very slowly cooled samples showed a mixture of antiferromagnetic and spin-glass behaviour. For the Cd---Te alloys, all samples, however heat-treated, showed spin-glass form. Values of the Curie-Weiss constant Ф were determined from all of the 1/χ versus T curves, and by comparison with the T(z) phase diagrams for the different alloy systems, the values of Ф were correlated with the ordering of the Mn atoms on the cation lattice. It is shown that the experimental values of Ф can give a very convenient way of determining the type of ordering and the degree of order in such alloys.     

Heat capacity investigation of dopant effects on the magnetic disordering temperature in Fe3O4†

The heat capacities of ZnFe₂O₄, Zn_0.005Fe_2.995O₄, Zn_0.066Fe_2.934O₄, and Cd_0.010Fe_2.990O₄ were measured over the temperature range of 350–1000 K by means of differential scanning calorimetry. The temperatures at which the maximum in heat capacity occurs due to the ferrimagnetic anomaly in the doped-Fe₃O₄ samples were found to decrease with increasing dopant. The excess entropy associated with the ferrimagnetic anomaly was estimated using three methods. One method, used previously for Fe₃O₄, employed a calculated lattice contribution for Fe₃O₄. The other two methods used the experimentally determined heat capacity of ZnFe₂O₄, either unmodified or mass adjusted, to approximate contributions from lattice vibrations.     

Magnetostriction of Fe–Sn polycrystalline alloys

In the present work we study the magnetostriction of Fe₉₁Sn₉ and Fe₈₀Sn₂₀ polycrystalline samples produced by arc melting and heat treated at temperatures of 1153 K for 6 h and 1023 K for 24 h, looking for high values of magnetostriction as in Fe–Ga alloys. Magnetostriction, as well as saturation magnetization measurements, was carried out at temperatures close to 203 K in the magnetic field interval 0 to 1.5 T. Results of magnetostriction on sample Fe₉₁Sn₉, which has almost pure -phase, show magnitude and behavior similar to pure Fe. The two additional Fe₈₀Sn₂₀ samples have a combination of -phase plus either Fe₅Sn₃ or Fe₃Sn₂ and show a peculiar behavior of the magnetostriction. For μ₀H<0.3 T the magnetostriction grows from zero to saturation of the -phase. Following, for μ₀H>0.3 T, the magnetostriction starts again to grow linearly with the field, but saturation was not observed up to 5 T. This behavior was attributed to the presence of Fe₅Sn₃ or Fe₃Sn₂ phases in these samples that are also ferromagnetic as the -phase is.     

Low-temperature phase and magnetic interactions in FCC Fe-Cr-Ni alloys

The low-temperature (5 K < T < 300 K) magnetic properties of a set of nine isostructural fcc Fe-Cr-Ni (Fe ≈ 68 at %, Cr ≈ 20 at%, Ni ≈ 9 at%) alloys were studied by SQUID magnetometry, neutron diffraction and ultrasonic techniques. Type-1 antiferromagnetic (AF) ordering was observed below the Néel temperature, T_N. The dc susceptibility, χ(T), did not exhibit a simple Curie-Weiss dependence. Above T_N, atemperature independent component χ₀ was observed, i.e., χ(T) = χ₀ + C / (itT + θ. T_N was systematically influenced by the lattice parameter, a, decreasing from (47.9 ± 0.5) K to (35.0 ± 0.5) K as a increased by only 0.25%. The average magnetic moment of ≈ 0.6μ_B obtained from neutron scattering was lower than the ≈ 1 μ_B obtained from the SQUID data. Mean field estimates of antiferromagnetic nearest-neighbors exchange interaction (J₁) and ferromagnetic second-nearest-neighbors interaction (J₂) indicate that |J₂/J₁|≈ 1.5. We believe that this is evidence of the RKKY interaction, and self-consistently argue that only the external d electrons are responsible for the localized average moment. This may mean that s-d hybridization of the external electrons is weak in these alloys.     

Electron irradiation effects on iron-nickel invar alloys

Electron irradiation was used as a means of accelerating the diffusion in Fe-Ni alloys. Mössbauer effect, X-ray and electron microscopy experiments on samples with 28 to 50% Ni show that the Invar character disappears after irradiation up to 250°C, in particular the variation of the lattice parameter versus temperature becomes linear around room temperature. At the same time, two phases appear in the alloy, one rich in nickel and ordered with FeNi (AuCu) superstructure, the other rich in iron and probably ordered (Fe₃Ni). The Invar state is therefore shown to be a metastable state. A diagram of the Fe-Ni alloy is proposed.