Preparation of cast-iron-based nanocrystalline alloy with Cu and Nb addition

The effect of minor Cu and Nb addition on glass-forming ability and nanocrystallization behavior of cast-iron-based bulk metallic glass was investigated. With simultaneous Cu and Nb addition, the crystallization kinetics of the amorphous alloys adequately modified to have enlarged initial nucleation rate and reduced growth rate of the primary α-Fe phase. However, due to the increased tendency to form secondary Fe₃C and Fe₂P phase, the cast-iron-based bulk metallic glass with combined Cu and Nb addition had a reduced processing window for nanocrystallization. Also, the simultaneous Cu and Nb addition decreased glass-forming ability of the alloy. Thus, it was revealed that the classical nanocrystallization strategy introducing combined Cu and Nb addition is not a suitable alternative to facilitate nanocrystallization of cast-iron-based bulk metallic glasses.     

Magnetic and structural studies of mechanically alloyed (Fe50Co50)62Nb8B30 powder mixtures

Amorphous (Fe₅₀Co₅₀)₆₂Nb₈B₃₀ powder mixture was prepared by mechanical alloying from elemental Fe, Co, B and Nb powders in a planetary ball mill under argon atmosphere. Structural, thermal and magnetic properties were performed on the milled powders by means of X-ray diffraction, differential scanning calorimetry and magnetic measurements. The amorphous state is reached after 125 h of milling. The excess enthalpy due to the high density of defects is released at temperature below 300 °C. Crystallisation and growth of crystal domains are the dominating processes at high temperatures. The saturation magnetisation decreases rapidly during the first 25 h of milling to about 15.24 A m²/kg and remains nearly constant on further milling. Coercivity, H_c, value of about 160 Oe is obtained after 125 h of milling.     

First-principles Study on Structure and Hardness of the RuB2

采用原位法粉末装管工艺( in-situ PIT)制备了无定形碳掺杂MgB2/Nb/Cu超导线材并研究了该掺杂对MgB2微观结构及超导电性的影响.复合线材中以Nb作为阻隔层、Cu作为稳定体并采用冷拉拔工艺进行加工.研究了无定形碳掺杂对MgB2相形成、微观结构及超导电性的影响,其中掺杂量分别为MgB2-xCx(x=0.0,0.05,0.08,0.10,0.15).分别采用XRD、SQUID、SEM/EDS及传输电流测试等方法对MgB2/Nb/Cu线材进行分析测试.XRD分析结果显示,700℃热处理后的线材可以获得纯度较高的MgB2超导相;微观结果照片显示无定形碳掺杂后可以获得良好的晶粒连接性;能谱分析表明掺杂物C元素均匀的分布在MgB2基体中;通过四引线法测试了传输临界电流密度Jc,在4.2 K、5T,其Jc值高达1.4×105 A/cm2;在4.2K、10T,其Jc值为3.3×104A/cm2.     

FINEMET非晶合金激波晶化中Cu和Nb作用的失效

应用ＸＲＤ,ＤＳＣ及ＴＥＭ等技术,将ＦＩＮＥＭＥＴ非晶合金的激波晶化与退火晶化及不含Ｃｕ,Ｎｂ的Ｆｅ－Ｂ－Ｓｉ和Ｆｅ－Ｍｏ－Ｂ－Ｓｉ合金的激波晶化作了对比研究。结果表明：该合金的激波晶化除了具有极高的转变速率和转变速率相当完全的晶化度外,合金元素Ｃｕ和Ｎｂ在退火晶化时具有的细化晶粒,阻止晶粒长大和稳定非晶态的三个作用均失效了,采用激波作用下非晶固体转变成流体状态的模型可以定性地解释这一现象。     

Nanocrystallization of Zr61Al7.5Cu17.5Ni10Si4 metallic glass

The primary nanocrystallization behavior and microstructural evolution of the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ alloy during annealing were investigated by isothermal differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. During continuous heating of the 4Si and the base (contains no Si) amorphous alloys at a heating rate of 10 K/min, the saturation point of nucleation for the 4Si amorphous alloy occurs at a crystallization fraction of 78%, which is significantly higher than 65% for the base alloy, implying that these metalloid atoms would extend the nucleation stage and refine crystalline particles. The sequence of crystallization phase from the amorphous matrix for the isothermally annealed 4Si amorphous alloy at 703 K is observed to be Zr₂Cu and Zr₂Ni at the early stage, Zr₃Al at an intermediate stage, and Zr₂Si at the final stage. Moreover, enrichment of Si atoms at the interface between Zr₂Cu crystal and the amorphous matrix is detected. This may result in increasing the thermal stability of the remaining amorphous phase and retardation of the crystal growth of Zr₂Cu particles.     

Microstructure of hard magnetic bccFe/NdFeB nanocomposite alloys

The microstructure of amorphous-phase remaining bccFe/NdFeB nanocomposite Nd_vFe_balCo₈Nb_xCu_yB_z (V = 6–8, x = 0–2.5, y = 0–0.5 and z = 6–7 at%) magnet alloys, which were prepared by melt spinning, was investigated by means of high resolution transmission electron microscopy (HR-TEM), three-dimensional atom probing (3DAP), and Mössbauer spectroscopy. It was found by HR-TEM that a small amount of amorphous phase remains in the intergranular region between crystal grains of bccFe and Nd₂Fe₁₄B₁ even after heat treatment at 740°C. The results of 3DP showed that Nb and B atoms are significantly enriched in the remaining amorphous phase. Mössbauer spectroscoopy revealed that the intergranular region is composed of not only so called amorphous phase but also several thin layered phases which have a rather strong hyperfine field distinctivity, and that the relative existing ratios of both the total intergranular phases and the Nd₂Fe₁₄B₁ phase increase with increasing Nb content. The coercivity-enhancing effect of Nb addition is discussed in this paper.     

Cu clustering and Si partitioning in the early crystallization stage of an Fe73.5Si13.5B9Nb3Cu1 amorphous alloy

Solute clustering and partitioning behavior in the early crystallization stage of an Fe_73.5Si_13.5B₉Nb₃Cu₁ amorphous alloy have been studied by employing a three-dimensional atom probe (3DAP) and a high resolution electron microscope (HREM). Results from the 3DAP have clearly shown that Cu atom clusters are present in the amorphous state after annealing below the crystallization temperature. The density of these clusters is in the order of 10²⁴/m³, which is comparable to that of the α-Fe grains in the optimum nanocrystalline microstructure. In the early stage of primary crystallization, Cu clusters are in direct contact with the α-Fe nanocrystals, suggesting that the α-Fe primary particles are heterogeneously nucleated at the site of Cu clusters. In the early stage of crystallization, the concentration of Si is lower in the primary crystal than in the amorphous matrix phase, unlike in the late stage of the primary crystallization, where Si partitions into the α-Fe phase with a composition of approximately 20 at.%.     

The kinetics of the oxidation of aluminum—copper alloys in oxygen at high temperature

The oxidation behavior of high purity aluminum—copper alloys has been studied at temperatures from 475 to 575°C in dry oxygen at a pressure of 76 torr. The oxidation product was found to be duplex in nature consisting of both amorphous and crystalline γ-Al₂O₃. Roughly cylindrical crystals of γ-Al₂O₃ of constant thickness, at any given temperature and alloy content, grow into the metal from the amorphous oxide—metal interface by inward diffusion of oxygen through the overlying amorphous film. The amorphous oxide film, growing by outward diffusion of metal ions, forms between the crystals of γ-Al₂O₃ with accurately parabolic kinetics throughout the temperature and alloy composition ranges. Above the crystalline phase the amorphous oxide forms at a lower rate because of the additional resistance conferred to cation egress afforded by the crystalline oxide. In general, it was found that increasing copper content of the alloy in the range 0·1–4 per cent Cu caused a reduction in the crystal nucleation density and in the depth of intrusion of the crystals into the underlying alloy. Conversely, increasing copper content was also found to increase the rate of formation of amorphous γ-Al₂O₃ between the crystals of γ-Al₂O₃ and to increase the rate of radial growth of the crystals. These results are explained in terms of the defect nature of the oxidation products.     

Thermally induced crystallization of Fe73.5Cu1Nb3Si15.5B7 amorphous alloy

Thermally induced crystallization of Fe_73.5Cu₁Nb₃Si_15.5B₇ amorphous alloy occurs in two well-separated stages: the first, around 475 °C, corresponds to formation of α-Fe(Si)/Fe₃Si and Fe₂B phases from the amorphous matrix, while the second, around 625 °C, corresponds to formation of Fe₁₆Nb₆Si₇ and Fe₂Si phases out of the already formed α-Fe(Si)/Fe₃Si phase. Mössbauer spectroscopy suggests that the initial crystallization occurs through formation of several intermediate phases leading to the formation of stable α-Fe(Si)/Fe₃Si and Fe₂B phases, as well as formation of smaller amounts of Fe₁₆Nb₆Si₇ phase. X-ray diffraction (XRD) and electron microscopy suggest that the presence of Cu and Nb, as well as relatively high Si content in the as-prepared alloy causes inhibition of crystal growth at annealing temperatures below 625 °C, meaning that coalescence of smaller crystalline grains is the principal mechanism of crystal growth at higher annealing temperatures. The second stage of crystallization, at higher temperatures, is characterized by appearance of Fe₂Si phase and a significant increase in phase content of Fe₁₆Nb₆Si₇ phase. Kinetic and thermodynamic parameters for individual steps of crystallization suggest that the steps which occur in the same temperature region share some similarities in mechanism. This is further supported by investigation of dimensionality of crystal growth of individual phases, using both Matusita–Sakka method of analysis of DSC data and texture analysis using XRD data.     

Effect of γ-(Fe,Ni) crystal-size stabilization in Fe–Ni–B amorphous ribbon

The effect of stabilizing crystal size in a melt-quenched amorphous Fe₅₀Ni₃₃B₁₇ ribbon is described upon crystallization in a temperature range of 360–400°С. The shape, size, volume fraction, and volume density have been investigated by transmission electron microscopy and X-ray diffraction methods. The formation of an amorphous layer of the Fe₅₀Ni₂₉B₂₁ compound was found by means of atomic-probe tomography at the boundary of the crystallite–amorphous phase. The stabilization of crystal sizes during annealing is due to the formation of a barrier amorphous layer that has a crystallization temperature that exceeds the crystallization temperature of the matrix amorphous alloy.     

Microstructure and properties of Cu−2Cr−1Nb alloy fabricated by spark plasma sintering

Cu?2Cr?1Nb alloy was fabricated by spark plasma sintering (SPS) using close coupled argon-atomized alloy powder as the raw material. The optimal SPS parameters obtained using the L₉(3⁴) orthogonal test were 950 °C, 50 MPa and 15 min, and the relative density of the as-sintered alloy was 99.8%. The rapid densification of SPS effectively inhibited the growth of the Cr₂Nb phase, and the atomized powder microstructure was maintained in the grains of the alloy matrix. Uniformly distributed multi-scale Cr₂Nb phases with grain sizes of 0.10?0.40 μm and 20?100 nm and fine grains of alloy matrix with an average size of 3.79 μm were obtained. After heat treatment at 500 °C for 2 h, the room temperature tensile strength, electrical conductivity, and thermal conductivity of the sintered Cu?2Cr?1Nb alloy were 332 MPa, 86.7% (IACS), and 323.1 W/(m·K), respectively, and the high temperature tensile strength (700 °C) was 76 MPa.     

Nb、Cu金属层厚度对Si3N4/Nb/Cu/Ni/Incone l600接头组织和性能的影响

采用Nb／Cu／Ni作中间层，在连接温度为1403K、连接时间为50min、连接压力为7．5MPa的条件下，采用不同尺寸的中间层进行了Si3N4陶瓷与Inconel 600高温合金的部分液相扩散连接。通过改变Nb层、Cu层厚度，研究了Cu层、Nb层厚度变化对Si3N4／Nb／Cu／Ni／Inconel 600接头的组织和性能的影响。研究发现，当Cu层厚度小于0．05mm时，随着Cu层厚度的增加，接头中的Cu—Ni合金层厚度增加，接头强度快速增加；当Cu层厚度超过0．05mm时，接头中的Cu—Ni合金层厚度由于压力的作用不明显增加，接头强度增加缓慢。随着Nb层厚度的增加，反应层厚度增加，接头的强度先增大后减小。     

Amorphization by dislocation accumulation in shear bands

Microcrystalline γ-Y₂Si₂O₇ was indented at room temperature and the deformation microstructure was investigated by transmission electron microscopy in the vicinity of the indent. The volume directly beneath the indent comprises nanometer-sized grains delimited by an amorphous phase while dislocations dominate in the periphery either as dense slip bands in the border of the indent or, further away, as individual dislocations. The amorphous layers and the slip bands are a few nanometers thick. They lie along well-defined crystallographic planes. The microstructural organization is consistent with a stress-induced amorphization process whereby, under severe mechanical conditions, the crystal to amorphous transformation is mediated by slip bands containing a high density of dislocations. It is suggested that the damage tolerance of γ-Y₂Si₂O₇, which is exceptional for a ceramic material, benefits from this transformation.     

The effect of Cu addition on the corrosion behaviour of sintered stainless steel in H2SO4 environment

The influence of Cu addition on the corrosion behaviour of hot pressed sintered stainless steel of Type 316 in H₂SO₄ solution was investigated. It was found that Cu additions of 0.25-5 wt% enhance the passivation processes of the hot pressed sintered stainless steel. The open-circuit potential of samples containing Cu was + 200 mV(SCE) as compared to −250 mV(SCE) in the other case. The potentiodynamic measurements indicate that as a result of the Cu addition the corrosion potential is increased, and the anodic critical current density and the cathodic overpotential for the hydrogen evolution are decreased. It is suggested that the low hydrogen cathodic overpotential caused by Cu addition, combined with the active-passive basic behaviour of the 316 stainless steel matrix, arc the main factors affecting the improved corrosion resistance.     

Local chemical and topological order in Al-Tb and its role in controlling nanocrystal formation

How the chemical and topological short- to medium-range order develops in Al-Tb glass and its ultimate effect on the control of the high number density of face-centered-cubic-Al (fcc-Al) nuclei during devitrification are described. A combined study using high-energy X-ray diffraction (HEXRD), atom probe tomography (APT), transmission electron microscopy and fluctuation electron microscopy (FEM) was conducted in order to resolve the local structure in amorphous Al₉₀Tb₁₀. Reverse Monte Carlo simulations and Voronoi tessellation analysis based on HEXRD experiments revealed a high coordination of Al around Tb atoms in both liquid and amorphous states. APT results show Al-rich and Al-depleted regions within the as-quenched alloy. A network structure of Tb-rich clusters divides the matrix into nanoscale regions where Al-rich clusters are isolated. It is this finely divided network which allows the amorphous structure to form. Al-rich regions are the locus for fcc-Al crystallization, which occurs before the intermetallic crystallization. FEM reveals medium-range ordered regions ∼2 nm in diameter, consistent with fcc-Al and trigonal-like Al₃Tb crystal structures. We propose that the high coordination of Al around Tb limits diffusion in the intermetallic network, allowing for the isolated Al-rich regions to form at high density. These regions are responsible for the extremely high density of Al nanocrystal nuclei.     

Grain boundary mobility and grain growth behavior in polycrystals with faceted wet and dry boundaries

The effect of an intergranular amorphous film on grain growth behavior has been studied in a faceted model system, BaTiO₃. We prepared two kinds of samples with and without intergranular amorphous films but with the same grain size and density. During annealing the samples at 1350 °C in air, abnormal grain growth occurred in samples with intergranular amorphous films while grain growth was inhibited in samples with dry boundaries, indicating the presence of a pinning force in samples with dry boundaries. To compare the mobilities of dry and wet boundaries, single crystal and polycrystal bilayer samples with or without amorphous films were prepared and annealed at 1340 °C. In contrast to the observed grain growth behavior in polycrystals, the growth of the single crystal into the polycrystal with dry boundaries was faster than that into the polycrystal with wet boundaries, demonstrating the higher mobility of a dry boundary, unlike the conventional understanding.     

Effect of Nb content on the microstructures and mechanical properties of Zr–Ti–Cu–Be–Nb glass-forming alloys

(Zr₃₅Ti₃₀Be_27.5Cu_7.5)_100?xNb_x (x = 0, 5, 8, 10, 12, 15 at.%) glass-forming alloys were prepared by copper-mould suction casting. The alloys with different Nb contents exhibited different microstructures and mechanical properties. The proper addition of Nb (x = 5, 8 at.%) to the Zr–Ti–Be–Cu system could ensure the formation of mostly amorphous phase. And excessive amount of Nb favored the formation of the bcc β-Zr solid solution. The alloys with Nb contents of 8 at.%, 10 at.%, and 12 at.% displayed the distinguished plasticity of 11.1%, 7.6%, and 11.0%, respectively.     

First-principles study on the electronic and optical properties of F- and Nb-doped anatase TiO2

We present a comparative study on the electronic and optical properties of Nb- and F- doped anatase TiO₂ by first-principles calculations based on the density functional theory (DFT). Although both TiO₂:Nb and TiO₂:F have a similar band structure, the effective mass of TiO₂:F is larger than that of TiO₂:Nb, and the carriers density in the former is lower than that in the latter, indicating that TiO₂:Nb has better electronic conductivity than TiO₂:F. The interaction between photons and electrons in TiO₂:F is much stronger than that in TiO₂:Nb, resulting in increased photon absorption and reduced transmittance, especially in the visible and near-infrared regions. The results demonstrate that TiO₂:F is not suitable for transparent conductive oxide applications.     

Intergranular amorphous films and dislocations-promoted grain growth in SrTiO3

To investigate the effect of dislocations on grain growth in polycrystals, two sets of experiments were performed using SrTiO₃ single crystals and SrTiO₃ powder compacts. In the first set, with single crystals embedded in 2.0-mol%-TiO₂-exess powder compacts, the growth of the single crystal was not affected by dislocations at 1300 °C, below the eutectic temperature, while it was enhanced by dislocations at 1470 °C, above the eutectic temperature, where the grain boundaries are wetted by an amorphous phase. In the second set, with 0.5-mol%-Nb₂O₅-doped powder compacts, the single crystal grew considerably into the SrTiO₃ matrix grains in the presence of an amorphous film between the grains at 1470 °C both in 95N₂-5H₂ and in air, similar to the case of the TiO₂-exess samples. However, when annealed at 1470 °C in 95N₂-5H₂ after pre-annealing at 1250 °C in 95N₂-5H₂, the amorphous phase remained at triple junctions and did not penetrate the grain boundaries, implying that this boundary configuration also is thermodynamically stable above the eutectic temperature. In this case, growth of the embedded single crystal was insignificant in spite of the presence of dislocations. These experimental observations indicate that the growth of SrTiO₃ is promoted by dislocations only when an intergranular amorphous film is present at grain boundaries. The apparent ineffectiveness of dislocations on grain growth promotion without an intergranular amorphous film is discussed in terms of a low fraction of facetted grain boundaries and grain boundary drag by triple junctions.     

Ta–Rh binary alloys as a potential diffusion barrier between Cu and Si: Stability and failure mechanism of the Ta–Rh amorphous structures

Thermodynamic calculations were carried out to derive the Gibbs free energy diagram for the amorphous and crystalline phases in the Ta–Rh system. These calculations predicted that the compositional range for the amorphous Ta–Rh phase was within 37–66 at.% Ta, which was validated by X-ray diffraction (XRD) analysis, high-resolution transmission electron microscopy (HRTEM) observations and resistivity measurements of as-deposited films. The thermodynamic modeling provided a valuable guide for selecting an amorphous composition suitable for diffusion barrier applications. The stability and metallurgical failure mechanism for TaRh_x diffusion barriers in contact with Cu and/or Si were investigated by resistivity measurements, XRD analysis and detailed electron microscopy on samples annealed in 5% H₂/95% N₂ gas for 30 min at various temperatures. Amorphous TaRh_x in contact with the Si substrate was stable up to 700 °C, whereupon TaRh_x decomposed and reacted to form TaSi₂ and RhSi. Si/amorphousTaRh_x (13 nm)/Cu stacks, on the other hand, were stable only up to 550 °C. Failure occurred by reaction of Rh with the Si substrate to form RhSi at the interface. The large density of defects formed in the barrier layer as a result of outward diffusion of Rh facilitated diffusion of Cu to the Si/TaRh_x interface to form Cu₃Si particles. The formation of Cu₃Si was observed to trigger further silicidation of the barrier to form a discontinuous TaSi₂ layer.