铀基非晶合金的发展现状

铀基非晶合金是非晶家族中的特殊成员,受限于铀元素的高活性与放射性特点,目前这类非晶材料的研究极不充分.本文结合非晶合金的最新发展动态简要介绍了铀基非晶发展历史,较系统地总结了本团队的最新铀基非晶研究工作:首先较详细地介绍了新型铀基非晶的制备技术、成分体系、形成规律与晶化行为,澄清了其形成机制与热稳定性;结合高分辨电镜分析展示了其微观结构特点;采用纳米压痕技术揭示了这类非晶的微纳力学性能;利用电化学测试方法评估了其耐腐蚀性能.这些结果丰富了非晶材料的内涵,有助于深化对非晶物理基础科学问题的理解,并推动新型铀合金材料的发展,为这种材料的潜在工程应用奠定了基础.     

Processing and properties of some II–IV–V2 amorphous and crystalline semiconductors

Experimental investigations on the preparation, characterization, and properties of several bulk and thin-film ternary alloys based on the chalcopyrite II–IV–V₂ semiconductors are presented. Rapid melt solidification in vacuum-sealed fused-silica tubes resulted in amorphous alloy formation in almost all compositions in the system CdGeAs₂-CdSiAs₂. ZnGeAs₂-CdGeAs₂ alloys showed very limited tendency toward amorphous phase formation. Phase separation, crystallization and electrical properties were studied for amorphous Cd-Ge-Si-As alloys by thermal analysis, transmission electron microscopy, X-ray diffraction, and Hall measurements. Rapid crystallization resulted in a reversal of conductivity type (p-to-n or vice versa). Crystallized glassy alloys showed room-temperature mobility of 64 cm²/V s, and a hole concentration of 1020 cm^–3. The p-to-n change in conductivity type upon amorphous-to-crystal transformation suggests that these alloys can be used to fabricate p-n junction devices by surface crystallization of the amorphous phase.     

A high-modulus metastable phase in Mg-Ni-Y alloys

The evolution of the elastic properties and the character of the structural changes occurring during the crystallization of amorphous Mg-Ni-Y alloys are investigated. The process of crystallization is shown to proceed in two stages with formation of an intermediate metastable phase at the first stage. This phase has higher elastic characteristics than those of the stable crystalline phases of this system.     

铸锭凝固组织对相应非晶合金晶化过程中二十面体准晶相形成动力学的影响

通过在真空电弧熔炼炉内对合金铸锭进行反复熔炼处理，获得到了凝固组织不同的Zr₆₅Al_7.5Cu_12.5Ni₁₀Ag₅合金铸锭.在相同的制备条件下，由凝固组织不同的合金铸锭通过吸铸法制备得到了薄片非晶合金.利用差示扫描量热法(DSC)对非晶合金的晶化动力学进行了分析.x射线衍射谱表明，在Zr₆₅Al_7.5Cu_12.5Ni₁₀Ag₅非晶合金晶化过程中，二十面体准晶相(I相)作为初生相析出.Kissinger分析结果表明，合金铸锭的凝固组织细化，相对应的非晶合金发生晶化时，I相形成与分解的有效激活能都增大，说明非晶合金及析出的I相的热稳定性都提高.从结构的遗传性角度就合金铸锭凝固组织对相应非晶合金晶化过程中二十面体准晶相的形成动力学的影响进行了讨论. 关键词： 二十面体准晶相 晶化动力学 凝固组织     

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.     

Crystallization and magnetic properties of melt-spun neodymium-iron alloys

The magnetic and crystallization properties of melt-spun Nd_1?xFe_x alloys are reported. By using high purity constituents and an extremely fine orifice (100–150 μm), amorphous alloys were prepared over the interval 0.4 ? x ? 0.8. Their magnetic properties, taken between 20–850 K in fields up to 95 kOe, are interpreted on the basis of a sperimagnetic structure; at high field the alloys from collinear ferromagnetic structures. Room temperature coercivities of the amorphous alloys are relatively low (1.5–2.0 kOe) but increase substantially at reduced temperatures; at 20 K, a maximum coercivity of 52 kOe was found for a Nd_0.4Fe_0.6 alloy. X-ray diffraction indicates that the melt-spun alloys crystallize by the precipitation of Nd metal and an unidentified Nd-Fe phase. Changes in magnetization and coercivity during crystallization are reported.     

Electronic properties of the amorphous FeCuNbSiB alloy

Variations in the electronic properties of amorphous Fe-Cu-Nb-Si-B alloys during crystallization have been studied by methods of positron annihilation spectroscopy. The measurements of the positron lifetime in samples and the angular distribution of annihilation photons have demonstrated substantial variations during crystallization. There is a correlation of the results with the performed measurements of the thermopower. The experimental results allow the assumption that degenerate electron gas is not formed in the amorphous alloys under study, and localized electrons participate mainly in the conduction. It can be suggested that the main role in formation of the amorphous alloy structure is played by the covalent bond. The spectrum of momentum distribution of the amorphous alloy differs little from the pure iron spectrum. Irradiation induces vacancy-copper complexes in the amorphous alloy.     

Stability of amorphous alloys

The thermal stability of a number of Ti-base and Zr-base amorphous alloys was studied by means of differential scanning calorimetry. The crystallization temperatures of these amorphous alloys and those reported in the literature for a variety of other amorphous alloys (actinide-base alloys an refractory metal-base alloys) were analysed in terms of the corresponding formation enthalpies. It is shown that there is no correlation between the crystallization temperatures and the formation enthalpies. On the other hand the crystallization temperatures were found to scale more or less linearly to the corresponding formation enthalpies of a hole the size of the smaller type of atom in the binary amorphous alloys.     

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     

Aromatic poly(ester carbonate)/poly-(ethylene terephthalate) alloys

When mixtures of poly(ester carbonate) (PEC) and poly(ethylene terephthalate) (PET) containing up to two-thirds of the latter are melt extruded, they produce a single-phase amorphous “alloy.” This alloy is characterized by a sharp, single, composition-dependent glass transition temperature, T_g. When annealed below T_g, the alloy remains unaltered, but when annealed above its T_g, the alloy separates into minute pure-PET crystallites and an amorphous PEC/PET phase. The thermal and dynamic mechanical behavior, crystallization kinetics, and SAXS patterns all strongly suggest the PEC-rich alloys to be solid solutions in which the PET molecules are dispersed individually or in small aggregates containing only a few PET molecules each. Calculations of the interaction parameter and assumed interfacial layer thickness tend to support this suggestion. Use of appropriate solvents allows one to selectively dissolve the PEC and recover from the alloys both PET and PEC in the original purity and molecular weights. Diffusion constants of PET molecules through the amorphous alloys were obtained from studies of PET crystallization above T_g of the alloys. The magnitude of the constants are in the range of expectation. The mechanical properties of the amorphous alloys in the glassy state do not deviate greatly from simple additivity of the respective properties of the parent polymers. However, the melt viscosity of the PEC-rich alloys and their plateau modulus above T show drastic decreases from straight additivity. A qualitative, but not quantitative, explanation of these observations is offered.     

What we have learned from studies on chemical properties of amorphous alloys?

Amorphous alloys have many attractive characteristics including extremely high corrosion resistance if the sufficient amounts of corrosion-resistant elements are added. The superiority of amorphous alloys is based on the homogeneous single phase nature without any chemical and physical heterogeneities. Although there are processing limitations to avoid the formation of heterogeneous crystalline structure in addition to no welding technology without crystallization, the application of corrosion-resistant amorphous alloys is expected particularly to the very aggressive environments, where any conventional crystalline metallic materials cannot be used. Some amorphous bulk alloys showed zero corrosion mass loss due to spontaneous passivation even in 12 M HCl. Production of amorphous bulk alloys became possible for selected compositions. The homogeneous single phase nature is also effective to form useful catalysts with unique composition and structure. An example of catalysts is for carbon dioxide methanation useful for supply of renewable energy in the form of methane.     

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.     

Crystallization kinetics of amorphous FeB alloys by dta

The crystallization kinetics of amorphous FeB alloys was investigated by means of differential thermal analysis. The activation energy for the crystallization of amorphous FeB alloys was estimated. The concentration dependence of the activation energy, exhibiting a maximum at about 16 at.% B, has similarity to other physical properties.     

非晶态Fe90-xBxZr10合金的磁性、电性和晶化

本文研究了部分B元素替代Fe对非晶态FeZr基合金磁性、电性和晶化的影响,并与非晶态FeB合金作了比较。解释了样品中每个FeZr原子的平均磁矩μ_FeZr和居里温度T_c随B含量x的增加而增加的原因,讨论了在不同的温区样品中可能存在的散射机制对电阻率的贡献以及影响晶化温度的因素。 关键词：     

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.     

Mössbauer study of the amorphous alloy with and without ion implanted

Amorphous alloys as a new magnetic materials have very important significance for both basic researches and applications. The CO, N ion-implanted amorphous Fe?B?Si?C alloys were studied by using X-ray diffraction, magnetic measurement and Mössbauer effect. It was shown that this amorphous alloys can be crystallized in different degree and in different phases by different kind and dose of implanted ions. The crystallization process was started in surface layer and then spread into interior.     

An integral fitting method for analyzing the isochronal transformation kinetics: Application to the crystallization of a Ti-based amorphous alloy

An integral fitting method has been developed to determine the phase transformation mechanism and to extract the kinetic parameters during the crystallization of amorphous alloys. The proper kinetic function of the phase transformation was firstly deduced. Theoretical differential scanning calorimetry curves were then calculated. All the kinetic parameters can be extracted by fitting the calculated differential scanning calorimetry curves to experimental data. We applied the integral fitting method to analyze the isochronal crystallization of the Ti₅₀Cu₄₂Ni₈ amorphous alloy. Results indicate that a transformation process considering impingement is more suitable to describe the crystallization kinetics of this alloy than using the traditional Johnson-Mehl-Avrami model. Mean values of the obtained kinetic parameters show strong heating rate dependence.     

Crystalline amorphous semiconductor superlattice

A new class of superlattice, crystalline amorphous superlattice (CASL), by alternatively depositing two semiconductor materials, is proposed. CASL displays three states depending on the component materials' phase: both polycrystalline phases, both amorphous phases, and one polycrystalline phase while another amorphous phase. Using materials capable of reversible phase transition, CASL can demonstrate reversibility among three states. GeTe/Sb(2)Te(3) CASL has been synthesized and proved by x-ray reflectometry and TEM results. The reversible transition among three states induced by electrical and laser pulse was observed. The changes in the optical absorption edge, electrical resistivity, thermal conductivity, and crystallization temperature as a function of layer thickness are interpreted as quantum or nanoeffects. The unique properties of CASL enable the design of materials with specific properties.     

非晶Fe78Si9B13合金在高压下的晶化

 本文研究了压力对Fe₇₈Si₉B₁₃非晶合金晶化温度的影响。给出了常压及7.5 GPa压力下的时间－温度－相变图。结果指出：晶化温度不仅与压力的大小有关，而且还与热处理的时间因素有关。此外，高压下bcc-Fe(Si)相结晶区域明显变大。     

Effect of rare-earth elements on nanophase evolution, crystallization behaviour and mechanical properties in Al-Ni-R (R = La/Mischmetal) amorphous alloys

The crystallization behaviour and evolution of nanoparticles in amorphous Al-Ni-Mischmetal (Mm) and Al-Ni-La alloys during heat treatment have been studied. Rapidly solidified ribbons were obtained by induction melting and ejecting the melt onto a rotating Cu wheel in an Ar atmosphere. The crystallization behaviour of the melt-spun ribbons was investigated using differential scanning calorimetry and X-ray diffractometry (XRD). XRD studies confirmed that all the ribbons were fully amorphous. Al-Ni-Mm systems showed a three-stage crystallization process whereas Al-Ni-La system, in general, showed a two-stage crystallization process on annealing. Crystallization kinetics was analysed by Kissinger and Johnson-Mehl-Avrami approaches. In Al-Ni-La alloys, the crystallization pathways depend on the La concentration. Microhardness of all the ribbons was examined at different temperatures and correlated with the corresponding evolution of phases.