Formation and structure of nanocrystals in an Al86Ni11Yb3 alloy

The formation and structure of the nanocrystalline phase in the Al₈₆Ni₁₁Yb₃ alloy are investigated using differential scanning calorimetry (DSC), transmission electron and high-resolution electron microscopy, and x-ray diffraction. The nanocrystalline phase is formed upon controlled crystallization of the amorphous alloy prepared by quenching of the melt on a rapidly moving substrate. It is revealed that the nanocrystalline alloy consists of aluminum nanocrystals (5–12 nm in size) randomly distributed in the amorphous matrix. The maximum fraction of the nanocrystalline phase does not exceed 25%. The nanocrystal size substantially increases at the initial stage of isothermal treatment (at 473 K) and then changes insignificantly. It is found that nanocrystals are usually free of defects. However, some nanocrystals have a more complex microstructure with twins and dislocations. The size distributions of nanocrystals are determined at several durations of isothermal treatment. It is demonstrated that the nucleation of nanocrystals predominantly occurs through the heterogeneous mechanism. The experimental distributions are compared with those obtained from a computer simulation. The activation energy of crystallization, the time-lag, and the coefficient of ytterbium diffusion in the alloy are estimated     

Structural transformations in the Al<Subscript>85</Subscript>Ni<Subscript>6.1</Subscript>Co<Subscript>2</Subscript>Gd<Subscript>6</Subscript>Si<Subscript>0.9</Subscript> amorphous alloy during multiple rolling

The effect of multiple rolling at room temperature on the structure and crystallization of the Al₈₅Ni_6.1Co₂Gd₆Si_0.9 amorphous alloy has been studied using transmission electron microscopy, differential scanning calorimetry, and X-ray diffraction. The total plastic strain is 33%. It has been shown that the deformation results in the formation of aluminum nanocrystals with the average size that does not exceed 10–15 nm. The nanocrystals are formed in regions of localization of plastic deformation. The deformation decreases the thermal effect of nanocrystallization (∼15%) as compared to the heat release at the first stage of crystallization of the unstrained sample. The morphology, structure, and distribution of precipitates have been investigated. Possible mechanisms of the formation of nanocrystals during the deformation have been discussed.     

Nanocrystallization of an amorphous Fe<Subscript>80</Subscript>B<Subscript>20</Subscript> alloy during severe plastic deformation

The structural evolution of an amorphous Fe₈₀B₂₀ alloy subjected to severe plastic deformation at room temperature or at 200°C was studied. Deformation leads to the formation of α-Fe nanocrystals in an amorphous phase. After room-temperature deformation, nanocrystals are localized in shear bands. After deformation at 200°C, the nanocrystal distribution over the alloy is more uniform. Possible causes of the crystallization of the amorphous phase during severe plastic deformation are discussed.     

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     

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.     

The fine structure of FCC nanocrystals in Al-and Ni-based alloys

The structural perfection of nanocrystals in alloys of different chemical composition is studied by x-ray diffraction and high-resolution electron microscopy. In all the alloys studied, crystallization of the amorphous phase produces a nanocrystalline structure. The nanocrystal size depends on the chemical composition of the alloy and varies in aluminum-based alloys from 5 nm in Al₈₉Ni₅Y₆ to 12 nm in Al₈₂Ni₁₁Ce₃Si₄. Nanocrystals in nickel-based alloys vary in size from 15 to 25 nm. Al nanocrystals are predominantly defect-free, with microtwins observed only in some nanocrystals. The halfwidth of the diffraction lines is proportional to sec θ, which implies the small grain size provides the major contribution to the broadening. Nanocrystals in nickel alloys contain numerous twins, stacking faults, and dislocations.     

Formation mechanism of Ge nanocrystals embedded in SiO2 studied by fluorescence x-ray absorption fine structure

This paper reports that the Ge nanocrystals embedded in SiO2 matrix are grown on Si（100） and quartz-glass substrates, and the formation mechanism is systematically studied by using fluorescence x-ray absorption fine structure （XAFS）. It is found that the formation of Ge nanocrystals strongly depends on the properties of substrate materials. In the as-prepared samples with Ge molar content of 60%, Ge atoms exist in amorphous Ge （about 36%） and GeO2 （about 24%） phases. At the annealing temperature of 1073 K, on the quartz-glass substrate Ge nanocrystals are generated from crystallization of amorphous Ge, rather than from the direct decomposition of GeO2 in the as-deposited sample. However, on the Si（100） substrate, the Ge nanocrystals are generated partly from crystallization of amorphous Ge, and partly from GeO2 phases through the permutation reaction with Si substrate. Quantitative analysis reveals that about 10% of GeO2 in the as-prepared sample are permuted with Si wafer to form Ge nanocrystals.     

Time-resolved X-ray diffraction study of the transition of an amorphous TiCu alloy to the crystalline state

The transition of the TiCu alloy from an amorphous state to the crystalline state has been studied by time-resolved X-ray diffraction. An analysis of the diffraction pattern has shown that the crystallization of the amorphous TiCu alloy upon heating occurs for a short time (no longer than 0.5 s). A sharp transition is observed at the instant of crystallization, at which the intensity of the total diffraction pattern background decreases and diffraction lines of the crystalline phase γ-TiCu arise. No intermediate crystalline phases are observed. The change in the alloy structure is accompanied by the exothermic thermal effect. The kinetics of the change in the total intensity of the diffraction spectrum in the period preceding the crystallization is nonmonotonic. Ten seconds before the occurrence of diffraction lines of the γ-TiCu phase at 300°C, the integrated spectral intensity decreases. The effect observed is related to the relaxation processes in the amorphous state and the onset of formation of long-range structural order.     

Crystallization behaviour in a new multicomponent Ti16.6Zr16.6Hf16.6Ni20Cu20Al10 metallic glass developed by the equiatomic substitution technique

A new amorphous Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ alloy has been developed using the novel equiatomic substitution technique. Melt spinning Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ forms an amorphous phase with a large supercooled liquid region, ΔT=70°C. After isothermal annealing within the supercooled liquid region for 3 h at 470°C, the amorphous alloy crystallizes to form a fine-scale distribution of 2–5 nm nanocrystals, and the supercooled liquid region increases to ΔT=108°C. Atomic-scale compositional analysis of this partially crystalline material using a three-dimensional atom probe (3DAP) is unable to detect any compositional difference between the nanocrystals and the remaining amorphous phase. After annealing for 1 hr at 620°C, the amorphous alloy crystallizes to form 20–50nm equiaxed grains of a hexagonal-type C14 Laves phase with lattice parameters a = 5.2Å and c = 9.0 Å. 3DAP analysis shows that this Laves phase has a composition very close to that of the initial amorphous phase, suggesting that the alloy crystallizes via a polymorphic rather than a primary crystallization mechanism, despite the complexity of the alloy composition.     

Formation and structure of nanocrystals in bulk Zr<Subscript>50</Subscript>Ti<Subscript>16</Subscript>Cu<Subscript>15</Subscript>Ni<Subscript>19</Subscript> metallic glass

The possible formation of a nanocrystalline structure in controlled crystallization of a bulk Zr₅₀Ti₁₆Cu₁₅Ni₁₉ amorphous alloy has been studied using differential scanning calorimetry, transmission and high-resolution electron microscopy, and x-ray diffraction. It was established that crystallization of the alloy at temperatures above the glass formation point occurs in two stages and brings about the formation of a nanocrystalline structure consisting of three phases. Local spectral x-ray analysis identified the composition and structure of the phases formed.     

Effect of annealing under tensile loading on the structure of nanocrystals in the Finemet alloy

The effect of nanocrystallization annealing under tensile loading on the structure of nanocrystals in the soft magnetic alloy Fe-Si-Nb-B-Cu (Finemet) has been investigated. It has been shown that the body-centered cubic (bcc) lattice of α-FeSi nanocrystals is extended along the direction of the application of the load upon annealing and is compressed in the transverse direction. Nanocrystals in the Finemet alloy have a higher degree of anisotropy of mechanical properties as compared to bulk crystals of α-FeSi, so that agreement between the measured and calculated values of the elongation is achieved only with a significant increase in the elastic moduli. Substantial changes in mechanical properties of the crystals with a decrease in their size to the nanometer scale are caused by the influence of the rigid amorphous matrix of the Fe(Nb)-B phase surrounding the nanocrystals.     

Phase segregation and crystallization in the amorphous alloy Ni70Mo10P20

Structural evolution of the amorphous alloy Ni₇₀Mo₁₀P₂₀ has been studied by x-ray diffraction, and by following transmission and high-resolution electron microscopy annealing both above and below the glass-transition temperature. When annealed above this temperature, the amorphous phase undergoes segregation into regions about 100 nm in size having different chemical composition. Diffraction from such samples produces diffuse rings, and the scattering vector corresponding to the maximum intensity varies from point to point within the interval of 4.88 to 4.78 nm⁻¹. When occurring between the glass-transition and crystallization temperatures, crystallization produces groups of nanocrystals, 20–30 nm in size, which are in direct contact with one another and form a polymorphic mechanism. The crystallization mechanism changes when the annealing temperature is brought below the glass-transition point. At these temperatures the amorphous matrix crystallizes entectically with formation of eutectic colonies. Fiz. Tverd. Tela (St. Petersburg) 40, 1577–1580 (September 1998)     

Size effect on the structure of Al-and Ni-based nanocrystals

The structure of nanocrystals formed upon crystallization of amorphous alloys of the Ni-Mo-B and Al-Ni-RE systems (RE = Y, Yb, Ce) was studied using x-ray diffraction and high-resolution transmission electron microscopy. It is shown that the lattice parameters and the existence of structural defects depend on the alloy composition and heat treatment conditions. At the beginning of crystallization, all nanocrystals are defectless. After the first stage of crystallization is completed, the aluminum nanocrystals remain perfect, whereas the nanocrystals of molybdenum solid solution contain numerous defects. It is revealed that the nanocrystals of the same size in different systems are either defectless (Al₈₂Ni₁₁Ce₃Si₄, Al₈₈Ni₁₀Y₂, etc.) or contain numerous defects (Ni₇₀Mo₃₀)₉₀B₁₀.     

Some aspects of the precipitation of Feα crystallites in the FePC amorphous alloy

The precipitation of Fe_α in some FePC amorphous alloys has been followed in situ by using neutron diffraction with a multidetector covering 80° (2θ). The quantity of Fe_α which precipitates before the final crystallization of the remaining amorphous phase is a function of the composition of the alloy but is independent of the heating rate. The alloy tends toward a mixture of Fe_α + am′ whose composition is about Fe₇₅(PC)₂₅. The crystallization of am′ occurs as soon as the excess of iron in the amorphous matrix is precipitated. We conclude that the excess of iron stabilizes the amorphous phase.     

Properties of the amorphous-nanocrystalline Gd2O3 powder prepared by pulsed electron beam evaporation

An amorphous-nanocrystalline Gd₂O₃ powder with a specific surface area of 155 m²/g has been prepared using pulsed electron beam evaporation in vacuum. The nanopowder consists of 20- to 500-nm agglomerates formed by crystalline nanoparticles (3–12 nm in diameter) connected by amorphous-nanocrystalline strands. At room temperature, the Gd₂O₃ nanopowder exhibits a paramagnetic behavior. The phase transformations occurring in the powder have been investigated using differential scanning calorimetry and thermogravimetry (40–1400°C). The amorphous phase of the nanopowder is thermally stable up to a temperature of 1080°C. It has been found that the amorphous phase has an inhibitory effect on the temperature of the polymorphic transformation from the cubic phase into the monoclinic phase. It has been revealed that, compared with the microcrystalline powder, the Gd₂O₃ nanopowder is characterized by a complete quenching of photoluminescence.     

FeCuNbBSi等多种Fe基非晶态合金激波晶化的DSC研究

 应用升温、等温和重复加热的DSC技术，对几种非晶合金的激波晶化和退火晶化作了对比研究。结果表明，尽管激波晶化时间极短，仅为退火晶化时间的10^-6～10^-8，但晶化度却极高，接近100%。激波晶化形成多种成分和结构的结晶相，形式上很像扩散性相变，然而其相变速率却是退火转变的千万倍，而且生成相十分稳定，这一现象用传统的固态扩散相变理论很难解释。激波晶化是一种新的晶化形式，是一种新的纳米合成技术。     

Effect of the concentration of a rare-earth component on the parameters of the nanocrystalline structure in aluminum-based alloys

The effect of the concentration of a rare-earth component on the parameters of the nanocrystalline structure formed during crystallization of an amorphous phase in the Al₈₈Ni₆Y₆ and Al₈₈Ni₁₀Y₂ alloys is studied using X-ray diffraction and transmission electron microscopy. It is shown that, as the yttrium concentration increases, the nanocrystal size increases and the content of the nanocrystalline component of the structure decreases. The precipitation of nanocrystals is accompanied by separation of the amorphous matrix into regions with different radii of the first coordination spheres due to the enrichment or depletion with the rare-earth element. The parameters of the nanocrystalline structure support the assumption of the heterogeneous nucleation of the nanocrystals.     

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.     

Three-dimensional atomic scale analysis of nanostructured materials

The 3-dimensional atom probe (3DAP) has been used to provide atomic-scale microcharacterisation of a number of nanostructured materials. Grain boundary segregation has been investigated in electrodeposited nanocrystalline nickel and Ni-P. In the nanocrystalline nickel, there was no observable grain boundary segregation in the as-deposited condition. After annealing, carbon and sulphur contamination was found at the boundary of an abnormally-grown grain. In the as-deposited Ni-P alloy, only limited grain boundary segregation of P is seen, but annealing produces significant segregation and the formation of Ni₃P precipitates at grain boundaries. The phase chemistry in a melt-spun amorphous Fe-Si-Cu-Nb-B-Al (FINEMET-type) alloy has also been studied, and the hetereogeneous nucleation of Fe-Si nanocrystals at Cu precipitates shown conclusively. It is found that at early stages of crystallisation, there is only limited partitioning of the Si between the nanocrystals and the amorphous matrix. Atom probe studies of thin layered films have historically been limited by specimen preparation problems, but recent advances have now yielded data on metallic multilayer films. This has allowed atomic-scale measurements of interface chemistry in these films for the first time.