铁基软磁非晶/纳米晶合金研究进展及应用前景

非晶合金通常是将熔融的金属快速冷却、通过抑制结晶而获得的原子呈长程无序排列的金属材料.由于具有这种特殊结构,铁基软磁非晶合金具有各向同性特征、很小的结构关联尺寸和磁各向异性常数,因而具有很小的矫顽力H_c,但可和晶态材料一样具有高的饱和磁感强度B_s.优异的软磁性能促进了铁基软磁非晶合金的应用研究.目前,铁基软磁非晶/纳米晶合金带材已实现大规模工业化生产和应用,成为重要的高性能软磁材料.本文回顾了软磁非晶合金的发现和发展历程,结合成分、结构、工艺对铁基非晶/纳米晶合金软磁性能的影响,介绍了相关基础研究成果和工艺技术进步对铁基软磁非晶/纳米晶合金研发和工业化应用的重要贡献.并根据结构、性能特征将铁基软磁非晶合金研发与应用分为三个阶段,指出了目前铁基软磁非晶合金研发与应用中面临的挑战和发展方向.     

Stability of (Fe-Tm-B) amorphous alloys: relaxation and crystallization phenomena

Fe-Tm-B base (TM=transition metal) amorphous alloys (metallic glasses) are thermodynamically metastable. This limits their use as otherwise favourable materials, e.g. magnetically soft, corrosion resistant and mechanically firm. By analogy of the mechanical strain-stress dependence, at a certain degree of thermal activation the amorphous structure reaches its limiting state where it changes its character and physical properties. Relaxation and early crystallization processes in amorphous alloys, starting already around 100°C, are reviewed involving subsequently stress relief, free volume shrinking, topological and chemical ordering, pre-crystallization phenomena up to partial (primary) crystallization. Two diametrically different examples are demonstrated from among the soft magnetic materials: relaxation and early crystallization processes in the Fe-Co-B metallic glasses and controlled crystallization of amorphous ribbons yielding rather modern nanocrystalline Finemet alloys where late relaxation and pre-crystallization phenomena overlap when forming extremely dispersive and fine-grained nanocrystals-in-amorphous-sauce structure. Mössbauer spectroscopy seems to be unique for magnetic and phase analysis of such complicated systems.     

Soft Magnetic Materials in a Bulk Form Prepared by Powder Compaction

The amorphous, nanocrystalline and polycrystalline ferromagnetic alloys are known as materials with excellent soft magnetic properties. These attractive magnetic properties are challenge for researchers to extend investigation of these materials with the aim to broaden their technical exploitation. The shape in which amorphous, nanocrystalline and polycrystalline materials are usually prepared, is in many cases not suitable shape for application, therefore it is logical to attempt to prepare such material in a more “bulk” form, for example in the form of a cylinder or a ring, that would be more convenient for industrial applications. One of the ways to prepare material in bulk form is to compact the powder. There is rational assumption that the non-magnetostrictive alloys (amorphous Co-Fe-Si-B, nanocrystalline Fe-Nb-Cu-Si-B, and polycrystalline Ni-Fe) may be suitable for the preparation of bulk samples by high-pressure compression, because mechanical stress does not induce magnetic anisotropy in ferromagnetic material during preparation process.We observed that milling of ribbons prepared by rapid quenching method leads to the increase of coercivity, which is caused by the increase of the fraction of magnetization vector rotation in the magnetization processes (the fraction of domain wall motion decreases). After long milling the powder particles become single-domain and can be magnetized by the magnetization vector rotation only, exhibiting maximum value of coercivity.Consolidation of powder with high value of coercivity leads to the “magnetic contact” between powder particles resulting in the decrease of coercivity to the value comparable with that for as-spun ribbons.     

The influence of ball-milling on structural and magnetic properties of Co-based powders

The melt-spun Co- and Fe-based amorphous alloys have been investigated extensively for applications in magnetic devices, which require magnetically soft materials. Although these alloys exhibit excellent soft magnetic properties, their thin sheet shape, which is a consequence of the low glass forming ability, limits significantly their engineering applications. A powder metallurgy is thus an alternative way of producing bulk and, at the same time, soft magnetic materials, having desired shape. In our case, Co₅₆Fe₁₆Zr₈B₂₀ and Co_70.3Fe_4.7Si₁₀B₁₅ amorphous ribbons have been ball-milled for a short time and subsequently compacted (by hot pressing) into disc-shaped specimens with the aim to achieve samll values of resulting coercivity. This work is focused only on the first preparation step i.e. on structural and magnetic properties of ball-milled powders obtained by ball-milling of Co-based melt-spun ribbons at different conditions. Two different ways of milling were employed in order to obtain a powder form of the material: the ribbons were either continuously ball-milled for up to 12 hours or, after each half an hour of ball-milling, the vials were cooled in liquid nitrogen bath for half an hour. Mössbauer spectroscopy, X-ray diffraction and differential scanning calorimetry were employed to compare and to present the differences between these two different ways of milling.     

Creep of FINEMET Ribbons during Crystallization

The application of FINEMET-type materials with specific magnetic properties prepared by the crystallization of amorphous alloys is often limited by their brittleness. The structure of these materials consists of nanosized Fe-based grains surrounded by an amorphous phase. Then the final macroscopic mechanical properties are considerably influenced by the properties of this amorphous phase. Direct creep measurements during the crystallization of FINEMET alloys were performed and the creep properties of the residual amorphous phase formed during the nanocrystallization were described. It was shown that due to relatively high temperatures, the residual amorphous phase undergoes intensive structural relaxation resulting in the obvious embrittlement of these materials.     

The structure and magnetic properties of amorphous magnetic thin films

A review of the structural and magnetic properties of amorphous ferromagnetic and ferrimagnetic thin films is presented. An attempt is made to report structural information on atomic and microstructural scales, and to stress its relevance to the magnetic properties of these materials. The more obvious microstructural features of deposited films are not present in the other important type of amorphous magnetic material prepared by rapid quenching from the melt, and present opportunities for differences in structure dependent magnetic properties. In the main, three classes of amorphous magnetic films are considered. Ferromagnetic transition metal (TM) films which are metastable only at temperatures well below room temperature are discussed. Their importance lies in the fact that they clearly represent the most fundamental amorphous phase. Ferromagnetic transition metal-metalloid (TM-Me) alloys have potential applications as magnetically soft materials. These alloys are, perhaps, the most studied amorphous magnetic materials both in deposited thin film and rapidly quenched ribbon forms. Finally, amorphous rare earth-transition metal (RE-TM) films are reviewed. They exhibit a wide variety of magnetic properties encompassing both extremely low and very high coercivities and also perpendicular magnetic anisotropy. The possible application of these materials in various types of device has encouraged much detailed research into their magnetic properties. This has highlighted the importance of preparation conditions and microstructure in defining their properties.     

Amorphous nanoparticles — Experiments and computer simulations

The data obtained by both experiments and computer simulations concerning the amorphous nanoparticles for decades including methods of synthesis, characterization, structural properties, atomic mechanism of a glass formation in nanoparticles, crystallization of the amorphous nanoparticles, physico-chemical properties (i.e. catalytic, optical, thermodynamic, magnetic, bioactivity and other properties) and various applications in science and technology have been reviewed. Amorphous nanoparticles coated with different surfactants are also reviewed as an extension in this direction. Much attention is paid to the pressure-induced polyamorphism of the amorphous nanoparticles or amorphization of the nanocrystalline counterparts. We also introduce here nanocomposites and nanofluids containing amorphous nanoparticles. Overall, amorphous nanoparticles exhibit a disordered structure different from that of corresponding bulks or from that of the nanocrystalline counterparts. Therefore, amorphous nanoparticles can have unique physico-chemical properties differed from those of the crystalline counterparts leading to their potential applications in science and technology.     

Magnetic properties and magnetic entropy change of amorphous and crystalline GdNiAl ribbons

The structure and magnetic properties of amorphous melt-spun and subsequently crystallized GdNiAl ribbons were investigated. An amorphous phase was formed after the quenching process by melt spinning with a copper wheel having a surface speed of 30 m/s. A hexagonal phase with lattice parameters a=7.023 ? and c=3.916 ? was formed in the GdNiAl ribbon after annealing above its crystallization temperature. Magnetic entropy change was calculated directly from isothermal magnetic measurements. The results show that both the amorphous and annealed samples have a high magnetocaloric effect, indicating that these alloys can be considered as candidates for magnetic refrigeration applications. Received: 14 August 2001 / Accepted: 18 September 2001 / Published online: 23 January 2002     

非晶态合金薄带与膜的巨磁电阻抗效应理论及计算

通过建立具有平面近横向各向异性场的非晶态合金薄带及膜的磁畴结构模型，利用线性化Maxwell方程组及Landau-Lifshitz方程，推出了在高频交变磁场及外加面内轴向直流磁场H_ex作用下的铁磁材料的与取向相关的磁导率表达式，得到了对方位角平均的相对磁导率及阻抗的计算式，导出了磁导率与张量磁化率分量间的关系，对材料磁导率的实部及虚部随H_ex的变化进行了计算，并给出了对应的磁谱图.建立的磁导率与外磁场的理论关系可将Panina及Kraus给出的理论结果统一起来. 关键词： 非晶态合金薄带及膜 取向相关磁导率 GMI效应理论与计算 近横向各向异性场     

非晶态合金带中内应力场的形成和磁各向异性的分布

本文中分析了从高温合金熔体快速淬火形成非晶态合金带的固化过程。指出非晶态合金带的不同部位在固化过程中,具有不同的固化推进方式,从而形成不同的区域应力场。从理论上计算了非晶态薄带中不同区域的内应力场和应力磁各向导性。计算的结果及其推论能很好地解释观察到的非晶态铁滋合金带的磁畴结构和实验现象。 关键词：     

Novel trends in the study of magnetically soft Co-based amorphous glass-coated wires

An overview of the recent progress and state-of-the-art results in the investigation of the amorphous glass-coated wires with nearly zero magnetostriction is presented. These versatile microwires display enhanced soft magnetic properties, which make them suitable as sensing elements in various sensors for biomedical and automotive applications. Current results on their magnetic characteristics refer to a major refinement of their core-shell magnetic structure by taking into account the interdomain wall and to the thorough analysis of the magnetization within the outer shell. Experimental techniques such as giant magneto-impedance, magneto-resistance, and magneto-optical Kerr effect measurements are employed to prove the outcome of the theoretical calculations. The impact of the magnetic structure of the outer shell on the propagation of domain walls in bistable amorphous wires is analyzed. Very recent results on the magnetization process in nearly zero magnetostrictive amorphous glass-coated wires with submicron dimensions are also reviewed.     

Structure and magnetic properties of nanocrystalline soft ferromagnets

The structure and magnetic properties of soft magnetic nanocrystalline composites crystallised from amorphous ribbons are reviewed. The Fe-Early Transition Metal-Boron (Nanoperm-type) nanostructures are discussed in details and compared to the Si containing (Finemet) alloys. The nanocrystallization process was studied by calorimetry; the spatial dimension, the composition and the relative fraction of the bcc and the residual amorphous phases were investigated by X-ray diffraction and Mössbauer spectroscopy. A small fraction of Fe atoms (about 4%) was found which cannot be assigned either to the residual amorphous or to the bcc phase. It is suggested that the magnetic anisotropy of the bcc phase is decreased due to the dissolved Zr and B impurities. The Curie point and Fe atomic moments in the residual amorphous tissue are determined and compared to that of a macrosized amorphous phase of similar composition. The observed deviations do not scale with the average characteristic size of the amorphous phase and thus cannot be explained in the framework of the existing models. Magnetic dipolar coupling and tensile stresses between the grains of the different phases are suggested for explaining the soft magnetic behaviour of the nanostructures.     

Perspectives in magnetics: Italy

A review is given of fundamental research in magnetics pursued in Italian universities and laboratories of Consiglio Nazionale delle Ricerche. The main topics covered are in the field of soft materials, hard materials and garnets. The electronic structure of metals is investigated by polarized neutron diffraction, while studies of domain wall motion provide the basis for fully understanding power loss processes and mechanisms. Work on amorphous magnetism has focused in particular on the study of short range order in these materials. Most fundamental research on hard materials is directed toward permanent magnet applications, microwave devices and magnetic recording. Magnetization processes are a major subject of investigation in these materials, with applications both to hexagonal ferrites and rare earth-3d metal compounds. The crystal chemistry of garnets is being pursued by carrying out a variety of metal substitutions and studying site occupancies and valence states in both bulk materials and LPE films. The static and dynamic properties of domains are also investigated for display and memory applications in addition to microwave properties and materials.     

Hyperfine interaction studies of amorphous materials using NMR

Through hyperfine interactions the electronic structure of amorphous materials can be investigated by NMR. Furthermore, the local character of these interactions makes them adequate to study the local environment and the local symmetry around the probe nuclei through the measurement of hyperfine fields and electric field gradients. We review recent NMR studies of amorphous metals from the following two points of view: (1) Electronic structure: Knight shifts and spin relaxation times in paramagnetic materials and hyperfine fields in ferromagnetic materials. (2) Local amorphous structure: topological and chemical short-range order. Emphasis will be given to the comparisons between amorphous materials and corresponding crystalline materials.     

高密度磁记录材料——金属磁粉的穆斯堡尔效应研究

目前,制造高密度磁带的磁记录材料——金属磁粉,已被认为是较理想的材料。但是,这种磁粉有一些主要问题需要解决,才能制成实用的磁带,其中存在的主要问题是金属磁粉在空气中化学稳定性不好以及在磁浆中不易分散。所以研究金属磁粉化学稳定性不好的产生原因及解决办法是它能否实用的主要问题。我们利用穆斯堡尔效应并配合其它一些实验手段研究了金属磁粉的化学稳定性不好的原因及防护的方法。为在我国制成能实用的金属磁粉提供了科学数据。 关键词：     

非晶态合金与氢相互作用的研究进展

非晶态合金在力学性能、耐磨耐蚀性、磁性等方面比传统晶态合金具有显著优势,是一类有优良应用前景的新型结构与功能材料.非晶态合金与氢相互作用可以产生很多有趣的物理化学现象和应用.本文从物理基础和材料应用两个方面评述非晶态合金和氢相互作用的研究进展,在物理基础研究方面,从氢在非晶态合金中的存在状态出发,讨论氢在非晶态合金中的溶解、分布、占位和扩散等相关物理问题,进而分析氢对非晶态合金的热稳定性、磁性、内耗、氢脆等的影响.在材料应用研究方面,对非晶态储氢合金、非晶态合金氢功能膜、吸氢改善非晶态合金的塑性和玻璃形成能力、氢致非晶化、利用非晶态合金制备纳米储氢材料等方面的研究进展进行评述.最后总结并展望有关非晶态合金与氢相互作用的研究和应用.     

Sputtered ductile amorphous Fe80B20 foils

Ductile amorphous foils of Fe₈₀B₂₀ have been sputter-deposited. We report here the results of structural and magnetic studies on these samples. Structural analysis shows slight differences between amorphous foils and ribbons. From the high-field measurements (H<15 T) the magnetic moment of Fe is estimated as 2.1±0.02 at 4.2 K in agreement with the value reported for ribbons. However, the magnetization is less temperature dependent in the foil, as compared to the ribbon. This result would indicate a lesser fluctuation in the exchange integralJ and hence lesser variations in the local environment of Fe. Finally the thermal stability is shown to be higher in the foils. It is suggested that sputtering technique could be used to prepare amorphous foils of large area for certain applications.     

Fabrication,properties, and applications of flexible magnetic films

Flexible magnetic devices, i.e., magnetic devices fabricated on flexible substrates, are very attractive in applications such as detection of magnetic field in an arbitrary surface, non-contact actuators, and microwave devices, due to their stretchable, biocompatible, light-weight, portable, and low cost properties. Flexible magnetic films are essential for the realization of various functionalities of flexible magnetic devices. To give a comprehensive understanding for flexible magnetic films and related devices, recent advances in the study of flexible magnetic films are reviewed, including fabrication methods, magnetic and transport properties of flexible magnetic films, and their applications in magnetic sensors, actuators, and microwave devices. Our aim is to foster a comprehensive understanding of these films and devices. Three typical methods have been introduced to prepare the flexible magnetic films, by deposition of magnetic films on flexible substrates, by a transfer and bonding approach or by including and then removing sacrificial layers. Stretching or bending the magnetic films is a good way to apply mechanical strain to them, so that magnetic anisotropy, exchange bias, coercivity, and magnetoresistance can be effectively manipulated. Finally, a series of examples is shown to demonstrate the great potential of flexible magnetic films for future applications.     

Optical properties and the magnetoimpedance effect in amorphous Co-Ni-B metal alloys

A magnetoimpedance effect is observed in Co_80–xNi_xB20 (x = 4, 6, 8, 10, 12) amorphous metal alloy ribbons when an alternating current at frequencies ranging from 1–3000 kHz is passed through samples in an external magnetic field. Spectra of the permittivity and optical conductivity of the surface of ribbons of these alloys are obtained for incident photon energies of 1.0–5.0 eV. The relationships between the magnitude of the magnetoimpedance effect, and the magnetic properties, electronic structure parameters, and optical characteristics of the amorphous alloy samples are determined.     

Multiscale structures and phase transitions in metallic glasses:A scattering perspective

Amorphous materials are ubiquitous and widely used in human society, yet their structures are far from being fully understood. Metallic glasses, a new class of amorphous materials, have attracted a great deal of interests due to their exceptional properties. In recent years, our understanding of metallic glasses increases dramatically, thanks to the development of advanced instrumentation, such as in situ x-ray and neutron scattering. In this article, we provide a brief review of recent progress in study of the structure of metallic glasses. In particular, we will emphasize, from the scattering perspective, the multiscale structures of metallic glasses, i.e., short-to-medium range atomic packing, and phase transitions in the supercooled liquid region, e.g., crystallization and liquid-to-liquid phase transition. We will also discuss, based on the understanding of their structures and phase stability, the mechanical and magnetic properties of metallic glasses.