铝基非晶合金微观结构的特点与演变

选择Al90Fe5Ce5和Al83Zn7Ce10非晶合金来研究铝基非晶合金的微观结构的特点和微观结构的演变.在Al90Fe5Ce5非晶合金中,发现亚稳Al6Fe相与被铝相包裹的二十面体准晶相共存.在Al83Zn7Ce10非晶合金中,金属间化合物Al2ZnCe2为凝固过程中的初生相.金属间化合物Al2ZnCe2可以伴随纳米晶粒铝的晶化而析出.抑制在冷却过程中所形成的各种晶核的成长是铝基合金具有很强的非晶形成能力的主要原因.多种相的竞争形核和有限生长导致了铝基合金具有复杂的结构特点 关键词： 铝基非晶合金 二十面体准晶 预峰 化学短程序     

Glass formation and microstructure evolution in Al–Ni–RE (RE = La,Ce, Pr,Nd and misch metal) ternary systems

Glass formation has been systematically studied in melt-spun Al-rich Al–Ni–RE (RE?=?La, Ce, Pr, Nd and Mm; Mm?=?misch metal) alloys by navigating the compositions following the observation of microstructure evolution in the resulting ribbons. The optimum glass-forming regions are similarly located around Al₈₅Ni₁₀RE₅ and found in the centre of the composites with primary phase α-Al, Al₁₁RE₃ and Al₃Ni. The similarities in the critical cross-section below which a component is fully amorphous and the optimum compositions in these Al–Ni–RE systems are interpreted in terms of their competing crystalline phases and thermodynamic properties. Interestingly, it is indicated that Ni content is markedly higher than RE content in the best glass-forming alloys, which may be associated with strong interaction between Ni–Al atom pairs and the dense packing due to Ni-centred clusters.     

Origin of tweed in Au–Cu–Al alloys

The premartensitic tweed in Au–Cu–Al alloys, contrary to previous thought that resort to defects, is confirmed to be associated with the coherent embryos of an intermediate phase (I phase) embedded in parent phase. The parent?→?I phase transformation temperature was measured by differential scanning calorimeter and dynamic mechanical analysers, which shifts from 82.3 to 557.6?°C depending on the alloy composition. X-ray diffraction and transmission electron microscopes (TEM) results show that the parent?→?I phase transformation is a charge density wave transition that cannot be suppressed even by melt-spun method, which shows obvious compositional inhomogeneity between I phase and parent. The results imply that the parent?→?I phase transition is a fast displacive transformation coupled with diffusion. Moreover, accompanying the parent?→?I phase transformation, alloys demonstrate diversified microstructure revealed by TEM observation, from tweed to chessboard nanowires or twins. These findings provide the experimental evidence for that parent?→?I phase transformation in Au–Cu–Al alloys is originated from pseudospinodal decomposition as theoretically predicted.     

HRTEM and TEM studies of amorphous structures in ZrNiTiCu base alloys obtained by rapid solidification or ball milling

Amorphous structure of Ti(25)Zr(17)Ni(29)Cu(29) composition was studied. Alloys were prepared either by rapid solidification using melt spinning or by high-energy ball milling. The composition of multi-component eutectic in slowly cooled samples of ZrNiTiCu alloy was determined using EDS measurements in scanning microscope of slowly cooled cast samples. The alloys of eutectic composition were melt-spun or ball-milled. Transmission electron microscopy (TEM) studies of melt-spun ribbons from alloys near eutectic composition did not show presence of nanocrystals within the amorphous structure. TEM studies of ball-milled powders showed presence of nanocrystallites of size 2-5 nm. The electron diffraction pattern showed intense diffused ring due to the presence of the amorphous phase and a weak spot due to crystalline phases which were difficult to identify. The high temperature high-pressure compaction in vacuum of amorphous ball-milled powders resulted in a similar structure like in the powders showing nanocrystals embedded in the amorphous matrix. The crystallites were imaged using HREM. Interplanar distances were measured in pictures obtained by inverse fast Fourier transform (IFFT) of atomic planes to obtain better contrast. Analysis of the IFFT from high-resolution micrographs allowed to identify Cu(10)Zr(7) phase. Point analysis and elemental mapping performed using nondispersive X-ray energy spectroscopy showed uniform elements distribution indicating that chemical segregation to nanocrystals is within measurement error.     

非晶Ti3Al合金的变形晶化机理的原子模拟

利用分子动力学方法研究了非晶Ti₃Al合金拉伸过程中的晶化行为，模拟结果表明局部塑性变形导致非晶合金晶化.从微观结构演化的角度分析了拉伸过程中的晶化机理，局部剪切导致拉伸过程中晶粒发生成核与合并，最终生成的晶粒具有面心立方结构.晶核的生长过程伴随着应力强化现象，非晶相中的纳米晶粒能提高非晶合金材料的强度. 关键词： 非晶合金 变形晶化 分子动力学     

A comparative study of the structure and crystallization of bulk metallic amorphous rod Pr60Ni30Al10 and melt-spun metallic amorphous ribbon Al87Ni10Pr3

Pr-based bulk metallic amorphous （BMA） rods （Pr60Ni30Al10） and Al-based amorphous ribbons （Al87Ni10Pr3） have been prepared by using copper mould casting and single roller melt-spun techniques, respectively. Thermal parameters deduced from differential scanning calorimeter （DSC） indicate that the glass-forming ability （GFA） of Pr60Ni30Al10 BMA rod is far higher than that of Al87Ni10Pr3 ribbon. A comparative study about the differences in structure between the two kinds of glass-forming alloys, superheated viscosity and crystallization are also made. Compared with the amorphous alloy Al87Ni10Pr3, the BMA alloy Pr60Ni30Al10 shows high thermal stability and large viscosity, small diffusivity at the same superheated temperatures. The results of x-Ray diffraction （XRD） and transmission electron microscope （TEM） show the pronounced difference in structure between the two amorphous alloys. Together with crystallization results, the main structure compositions of the amorphous samples are confirmed. It seems that the higher the GFA, the more topological type clusters in the Pr-Ni-Al amorphous alloys, the GFAs of the present glass-forming alloys are closely related to their structures.     

Melting of embedded anisotropic particles: PbIn inclusions in Al

Small particles embedded in the solid state can assume facetted shapes that indicate the anisotropy in interfacial free energy between the particle and the embedding phase. Previous in situ transmission electron microscopy (TEM) of Al–In has shown that such facetted nanoparticles with cubic symmetry embedded in a solid can produce a series of complex melt configurations. To determine the dependence of melt configuration on solid–solid facet energies, this work numerically calculates the equilibrium melt trajectory for a family of cuboctahedral particles parameterized by the ratio of matrix–particle interfacial free energies for orientations taken with respect to the crystal axes of the matrix, ??=?γ₁₀₀/γ₁₁₁. The calculations assume that equilibrium occurs with the minimization of the total interfacial free energy to determine the stable internal melt configuration for a fixed volume of melt confined within a member of the cuboctahedral family. At particular melt volume fractions, abrupt transitions in shape occur when a stable configuration reaches a touching or necking instability. In situ TEM of a dilute Al alloy containing embedded nanosized PbIn inclusions that gradually melt as the temperature is increased from 230 to 260°C is consistent with the results calculated for ??=?1.245.     

Effect of aluminum on the hyperfine field and crystallization behaviour of NANOPERM alloy

The effect of Al on the hyperfine fields and crystallization of NANOPERM alloy has been studied by introducing 2% Al for Fe in Fe₈₈Zr₇B₄Cu₁. Al is found to enhance the nucleation rate in these alloys. Mössbauer spectroscopic technique has been used to trace the effect of Al on the hyperfine interactions in the amorphous and nanocrystalline state of these alloys. The hyperfine field clearly shows the presence of Al both in the amorphous and the nanocrystalline phase. Magnetic measurements using VSM and also XRD, TEM and DSC studies have been used to support the conclusions derived using Mössbauer spectroscopy.     

Crystallization behavior and microstructure of Fe75Co6Zr9B10 alloy

Fe₇₅Co₆Zr₉B₁₀ amorphous alloy prepared by melt-spinning was annealed at various temperatures. The crystallization behavior and microstructure were investigated by differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The three exothermal peaks in the DTA curve of Fe₇₅Co₆Zr₉B₁₀ amorphous alloy correspond to the formations of α-Fe and α-Mn type phases, the growth of BCC-Fe volume fraction at the expense of α-Mn and residual amorphous phase and the precipitations of Fe₃Zr, etc. intermetallic compounds, respectively. The second exothermic peak is not influenced by heating rate, but it shifts to a higher temperature region with increasing preannealing temperature of Fe₇₅Co₆Zr₉B₁₀ alloy. The α-Mn type phase is metastable and its lattice parameter determined by TEM is 0.8830 nm. AFM images show the development of surface morphology of alloy after annealing. The particle size increases with increasing annealing temperature.     

Microstructure and hard magnetic properties in bulk rods of Nd60Fe30Al10 glass forming alloys

The Nd₆₀Fe₃₀Al₁₀ alloy exhibits a large glass forming ability which allows to obtain relatively thick cast rods containing large volume fractions of amorphous phases. In this work the microstructure and the hard magnetic properties of as-cast rods are characterized. The alloy is processed by suction casting into a chilled copper mould to obtain cylinders 5 mm diameter and 50 mm length. This diameter is selected because it is an upper limit for this processing route, beyond which the hard properties largely deteriorate. A room temperature coercivity of 0.34 T is obtained. The sample microstructure is heterogeneous, with very different size scales near the surface and along the central zone. However, in both regions a large fraction of an amorphous ferromagnetic phase is observed; it is found that paramagnetic nanocrystalline phases – mainly Nd or Nd-rich particles, embedded in the amorphous matrix – are somewhat coarser in the central zone. These larger nanocrystals, less efficient to pin domain walls, are proposed to be responsible for the lower coercive fields observed, as compared with those found in cylinders 1–3 mm diameter where no inhomogeneities are found. This conclusion is supported by microstructure, calorimetric and magnetic observations.     

Al-Mn-Ce quasicrystalline composites: Phase formation and mechanical properties

Aluminium-based composites with quasicrystalline particles as reinforcements were synthesized via the powder metallurgy processing route. In order to obtain bulk samples with a nanoscale microstructure most equivalent to that resulting from rapid solidification, powders of Al-Mn-Ce alloys were prepared by pulverization of melt-spun ribbons using a planetary ball mill. Significant differences in the phase formation upon quenching, composite microstructure and thermal stability of the microstructure were found for different alloy compositions. Severe grain growth during the subsequent consolidation by hot extrusion caused the formation of a micrometre-scale composite instead of the nanoscale phase mixture initially existing after rapid solidification. After hot extrusion, the specimens were deformed by compression at a constant compression rate at room temperature. With an ultimate strength of up to 975 MPa and a ductility of more than 4% the material yields excellent properties compared with conventionally produced aluminium-based alloys.     

Microstructure and soft magnetic properties of Finemet-type ribbons obtained by twin-roller melt-spinning

Soft magnetic ribbons of Finemet-type (Fe_73.5Cu₁Nb₃Si_13.5B₉) alloys are synthesized by the twin-roller melt-spinning technique directly from the melt, at tangential wheel speeds of 15, 18, 19 and 20 m/s. The microstructure and the magnetic properties are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), differential thermal analysis (DTA), thermo-gravimetric analysis (TGA) and hysteresis loops measurements. Samples cooled at 20 m/s are amorphous, while those quenched at lower wheel speeds are partially crystalline. All samples studied present saturation magnetization values (150-160 A m²/kg) higher than the commercial Finemet alloys (∼135 A m²/kg), obtained by controlled crystallization of amorphous single-roller melt-spun alloys. Optimal soft magnetic properties - σ_S=(154±8) A m²/kg and H_C=(6.9±0.9) A/m - are found in samples quenched at 19 m/s, consisting of size-distributed bcc Fe-Si nanograins (∼18 nm in average) embedded in an amorphous residual matrix. A minority nanocrystalline magnetic phase (≤10 nm) is also detected.     

Hybrid Al + Al3Ni metallic foams synthesized in situ via laser engineered net shaping

A hybrid, Al?+?Al₃Ni metallic foam was synthesized in situ via laser engineered net shaping (LENS®) of Ni-coated 6061 Al powder in the absence of a foaming agent. During LENS® processing, the Ni coating reacted with the Al matrix, resulting in the simultaneous formation of a fine dispersion of Al₃Ni, and a high volume fraction of porosity. As a reinforcement phase, the intermetallic compound formed particles with a size range of 1–5?µm and a volume fraction of 63%, with accompanying 35–300?µm pores with a 60% volume fraction. The microstructure of the as-deposited Al?+?Al₃Ni composite foams was characterized using SEM, EDS, XRD and TEM/HRTEM techniques. The evolution of the microstructure was analyzed on the basis of the thermal field present during deposition, paying particular attention to the thermodynamics of the Al₃Ni intermetallic compound formation as well as discussing the mechanisms that may be responsible for the observed porosity. The mechanical behavior of the as-deposited material was characterized using compression and microhardness testing, indicating that the yield strength and hardness are 190?MPa and 320 HV, respectively, which represents an increase of over three times higher than that of annealed Al6061, or similar to heat-treated Al6061 fully dense matrix, and much higher than those of traditional Al alloy foams, and with a low density of 1.64?g/m³.     

Influence of crystallization treatment on structure,magnetic properties and magnetocaloric effect of Gd71Ni29 melt-spun ribbons

The influence of crystallization treatment on the structure, magnetic properties and magnetocaloric effect of Gd₇₁Ni₂₉ melt-spun ribbons has been investigated in detail. Annealing of the melt-spun samples at 610 K for 30 min, a majority phase with a Fe₃C-type orthorhombic structure (space group, Pnma) and a minority phase with a CrB-type orthorhombic structure (space group, Cmcm) were obtained in the amorphous matrix. The amorphous melt-spun ribbons undergo a second-order ferromagnetic to paramagnetic phase transition at 122 K. For the annealed samples, two magnetic phase transitions caused by amorphous matrix and Gd₃Ni phases occur at 82 and 100 K, respectively. The maximum magnetic entropy change (–ΔS_M)^max is 9.0 J/(kgˑK) (5T) at 122 K for the melt-spun ribbons. The values of (–ΔS_M)^max in annealed ribbons are 1.0 and 5.7 J/(kgˑK), corresponding to the two adjacent magnetic transitions.     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.     

Ti6Al4V合金表面激光沉积复合涂层的组织和性能

为了增强Ti6Al4V钛合金的耐磨性,采用激光沉积制造方法在其表面上制备了以原位生成的TiC颗粒和直接添加的WC颗粒为增强相的耐磨涂层,观察了各涂层的微观组织,并测量了涂层的显微硬度和涂层在室温大气条件下的摩擦磨损性能。结果表明各涂层和基体呈现冶金结合,原位自生的TiC和部分熔化的WC颗粒均能够均匀弥散分布于基体上,由于增强相颗粒的弥散强化及激光沉积组织的细晶强化作用,基材的硬度和耐磨性均得到了提高。原位自生的TiC涂层比WC涂层硬度梯度分布平缓,但耐磨性稍差。     

添加Ti对Al-Bi难混溶合金组织和性能的影响

难混溶合金在凝固过程中极易发生液-液相分离,造成第二相的宏观偏析,失去了合金的应用价值.本文将第三组元Ti添加到Al-Bi难混溶合金中,研究了Ti的添加对合金的凝固组织和性能的影响,探索了原位生成的金属间化合物的存在形式,分析了第二相Bi颗粒的分布.研究结果表明,凝固过程中原位生成的长针状Al_3Ti化合物,均匀分布在Al基体中,穿插在Bi相颗粒之间,阻碍了Bi相颗粒的沉降及凝并,防止了Bi相颗粒的碰撞及长大,制备了Bi相弥散分布在Al基体中的难混溶合金;同时弥散分布在基体中的硬质相Al_3Ti还增强了基体的强度,提高了合金的硬度,使合金表现出优异的耐磨性能.     

Selective aluminum dissolution as a means to observe the microstructure of nanocrystalline intermetallic phases from Al–Fe–Cr–Ti–Ce rapidly solidified alloy

Rapidly solidified aluminum alloys are promising materials with very fine microstructure. The microscopy observation of these materials is complicated due to overlay of fcc-Al matrix and different intermetallic phases. A possible way to solve this problem is to dissolve the Al matrix. By this process powder formed by single intermetallic phase particles is obtained. In this paper a new aqueous based dissolving agent for Al-based alloy is presented. The influence of oxidation agent (FeCl₃) concentration on quality of extraction process was studied.     

Nanocrystal formation in gas-atomized amorphous Al85Ni10La5 alloy

An Al₈₅Ni₁₀La₅ amorphous alloy, produced via gas atomization, was selected to study the mechanisms of nanocrystallization induced by thermal exposure. High resolution transmission electron microscopy results indicated the presence of quenched-in Al nuclei in the amorphous matrix of the atomized powder. However, a eutectic-like reaction, which involved the formation of the Al, Al₁₁La₃, and Al₃Ni phases, was recorded in the first crystallization event (263°C) during differential scanning calorimetry continuous heating. Isothermal annealing experiments conducted below 263°C revealed that the formation of single fcc-Al phase occurred at 235°C. At higher temperatures, growth of the Al crystals occurred with formation of intermetallic phases, leading to a eutectic-like transformation behaviour at 263°C. During the first crystallization stage, nanocrystals were developed in the size range of 5 ～ 30 nm. During the second crystallization event (283°C), a bimodal size distribution of nanocrystals was formed with the smaller size in the range of around 10 ～ 30 nm and the larger size around 100 nm. The influence of pre-existing quenched-in Al nuclei on the microstructural evolution in the amorphous Al₈₅Ni₁₀La₅ alloy is discussed and the effect of the microstructural evolution on the hardening behaviour is described in detail.     

Kinetics of ß-phase transformation in the heat treatment of FeSi2- and Fe2Si5-based thermoelectric alloys

FeSi₂- and Fe₂Si₅-based thermoelectric alloys have been fabricated by melt spinning and levitation melting. It was found that the levitation-melted FeSi₂-based alloy must be annealed at 800°C for 10 h to complete transformation of the β phase, while an anneal for only 6 h was needed for the melt-spun alloy. On the other hand, annealing the levitation-melted Fe₂Si₅-based alloy for 4 h was enough to complete β-phase formation, whereas 14 h was required for the melt-spun alloy. Annealing temperature dependence of the Seebeck coefficient showed that the maximum rate of transformation to β phase occurred at about 800°C for all samples. Application of the Johnson-Mehl-Avrami equation revealed that grain-boundary nucleation was predominant in the levitation-melted FeSi₂-based alloy (time exponent n = 1.1), while the zero nucleation mechanism was operative in the melt-spun alloy (n = 3.1). For the eutectoid reactions in the Fe₂Si₅-based alloys, several kinds of nucleation site were active. However, nuclei formed at grain edges were dominant in the melt-spun alloy since n = 1.6.