Structure of the amorphous phase of pyrolisates of lanthanum diphthalocyanine according to X-ray scattering data

Data on X-ray diffraction in lanthanum diphthalocyanine pyrolysates synthesized at temperatures of 800–1800°С demonstrate the formation of an amorphous carbon phase with embedded lanthanum atoms. Low-temperature pyrolysis (800–900°С) creates layered carbon structures. Due to annealing at 1000°С, carbon integrates into globules whose number of atoms is m ~ 100. Such structures with gyration radii of R _g ~ 0.4–0.5 nm on the order of the precursor molecule size are synthesized in the temperature range of 1000–1800°С, and are stable in terms of size and mass. In this case, their density approaches that of graphite.     

Structural evolution of ZrO2–mullite nanocomposites from the Si–Al–Zr–O amorphous bulk

ZrO₂–mullite nanocomposites were fabricated by in-situ-controlled crystallization of Si–Al–Zr–O amorphous bulk at 800–1250°C. The structural evolution of the Si–Al–Zr–O amorphous, annealed at different temperatures, was studied by X-ray diffraction, infrared, Laser Raman spectroscopy, field emission scanning electron microscopy, and high-resolution transmission electron microscopy. The materials consisted of an amorphous phase up to 920°C at which phase separation of Si-rich and Al, Zr-rich clusters occurred. The crystalline phases of t-ZrO₂ and mullite were observed at 950°C and 1000°C, respectively. Mullite with a tetragonal structure, formed by the reaction between Al–Si spinel and amorphous silica at low temperature, changed into an orthorhombic structure with the increase of temperature. It was the phase segregation that improved crystallization of the Si–Al–Zr–O amorphous bulk. The anisotropic growth of mullite was observed and the phase transformation from t-ZrO₂ to m-ZrO₂ occurred when the temperature was higher than 1100°C.     

Fe73.5Cu1Nb3Si13.5B9非晶合金的激波纳米晶化速率和晶化度的对比研究

对Fe735Cu1Nb3Si135B9等非晶合金进行了退火和激波诱导两种方式的晶化实验以及XRD和DSC分析.着重对合金的晶化速率和晶化度等特性展开了研究和讨论.进一步证实了激波纳米晶化是一种包含着新机理的寓意丰富的晶化现象.也再次验证了作者曾经提出过的“激波流化相变”模型的合理性. 关键词： 非晶合金 激波 纳米晶化     

Crystallization behaviour of ALD-Ta2O5 thin films: the application of in-situ TEM

The microstructure of Ta₂O₅ thin films, deposited onto Si substrates by atomic layer deposition (ALD), was investigated, using in situ transmission electron microscopy (TEM). As-deposited amorphous films crystallize as the orthorhombic phase L-Ta₂O₅ upon heating at 750°C. Two dominant crystallographic orientations are found, one with (0?0?1) and (1?11?0) planes perpendicular to the substrate, while the other has (0?0?1) planes parallel to the substrate. The grains consist of subgrains which are rotated a few degrees with respect to each other. The kinetics of the crystallization were studied by in-situ TEM heating experiments carried out at nominal temperatures of 790°C, 820°C and 850°C. They reveal that the growth and crystallization activation energies are about 4.2?eV and 6.3?eV, respectively. Tilted subgrains keep forming during growth until they come in contact with neighbouring grains. The crystallization behaviour can be approximated by the Kolmogorov–Johnson–Mehl–Avrami (KJMA or Avrami) equation, giving mode parameters of 2.5, 1.9, and 1.7 at 790°C, 820°C and 850°C, respectively. A small value of mode parameters is attributed to decreasing growth and nucleation rates with time.     

高超声速条件下7°直圆锥边界层转捩实验研究

在Ma=6低噪声风洞中开展了半锥角7?的直圆锥边界层转捩相关实验研究.利用响应频率达到MHz量级的高频压力传感器对圆锥壁面脉动压力进行了测量,研究了高超声速圆锥边界层中扰动波的发展过程.结果表明:高超声速圆锥边界层中第二模态扰动波产生的位置以及扰动波特征频率和波长等参数受雷诺数影响较大,当单位雷诺数从2×106m~(-1)增加到8×106m~(-1)时,第二模态波的特征频率从55 k Hz增加到226 k Hz;随着单位雷诺数增加,边界层中扰动增长速度加快,第二模态波出现在圆锥表面更靠近上游的位置;相同单位雷诺数条件下,随着第二模态波的向下游传播,其特征频率逐渐减小.通过对比发现自由来流湍流度对边界层中扰动波的发展同样有较大影响,自由来流湍流度降低,边界层中的第二模态波的特征频率明显减小.利用互相关分析得出第二模态扰动波在边界层中的传播速度大约为当地主流速度的0.8—0.9倍.在1?小攻角条件下,圆锥迎风面和背风面边界层发展呈现出明显的差异,背风面边界层中扰动发展提前,第二模态波出现在更靠近上游的位置,而迎风面中扰动发展受到抑制,第二模态波特征频率更大.     

Transport phenomena in superionic Na<Subscript><Emphasis Type="Italic">х</Emphasis></Subscript>Cu<Subscript>2 − <Emphasis Type="Italic">х</Emphasis></Subscript>S (<Emphasis Type="Italic">х</Emphasis> = 0.05; 0.1; 0.15; 0.2) compounds

The electronic and ionic conductivity, the electronic and ionic Seebeck coefficients, and the thermal conductivity of Na _x Cu_2 ? x S (x = 0.05, 0.1, 0.15, 0.2) compounds were measured in the temperature range of 20–450 °С. The total cationic conductivity of Na_0.2Cu_1.8S is about 2 S/cm at 400 °С (the activation energy ≈ 0.21 eV). Over the studied compounds, the composition Na_0.2Cu_1.8S has the highest electronic conductivity (500–800 S/cm) in the temperature range from 20 to 300 °С, and the highest electronic Seebeck coefficient (about 0.2 mV/K) in the same temperature range is observed for Na_0.15Cu_1.85S composition; the electronic Seebeck coefficient increases abruptly above 300 °С for all compounds. The thermal conductivity of superionic Na_0.2Cu_1.8S is low, which causes high values of the dimensionless thermoelectric figure of merit ZT from 0.4 to 1 at temperatures from 150 to 340 °С.     

Studying the Generation Stage of a Plasma Jet in a Plasma Focus Discharge

A dense compact plasmoid generated at the pinch collapse stage is revealed in a plasma focus discharge by laser optical methods. The initial size of the plasmoid is ~1 mm, its electron density is more than 2 × 10¹⁹ cm^–3, and the plasmoid propagates along the axis from the anode at an average velocity of more than 10⁷ cm/s. A shock wave is generated in the residual argon plasma during the motion of the bunch, its density decreases to 10¹⁸ cm^–3 at a distance of 3 cm from its place of generation, and the plasmoid expands by 3–5 times and almost merges together with the leading edge of the shock wave.     

Surface properties of Fe76Mo8Cu1B15 alloy after annealing

NANOPERM-type alloy Fe₇₆Mo₈Cu₁B₁₅ is investigated in amorphous and in partially crystallized state. Samples were prepared by 1 h isothermal annealing in vacuum at temperatures ranging from 330°C up to 700°C. Bulk and surface microstructural characteristics were studied using transmission and conversion electron Mössbauer effect techniques, respectively. Surface features were checked by the help of atomic force microscopy. Presence of nanocrystalline bcc-Fe phase was detected during the first crystallization stage. The crystallization process starts at 450°C and it is more pronounced in surface regions than in the bulk. With progressing crystallization, hyperfine parameters especially of the amorphous residual phase are altered. Distinctions in surface morphology are revealed between wheel and air side of the ribbon-shaped samples.     

Resonance attenuation of ultrasonic waves in a superconductor with a moving vortex structure

Equations describing the interaction of ultrasonic waves with a moving vortex structure are derived. The addition to attenuation and the relative change in the velocity of longitudinal ultrasonic waves due to this interaction are calculated. It is found that when a longitudinal ultrasonic wave propagates along the direction of motion of the vortex structure and the velocity V of the structure is equal to half the velocity of the wave, then anomalous acoustic attenuation occurs and the contribution from the ultrasound-vortex interaction to the velocity of the ultrasonic wave vanishes. It is shown that if the vortex structure moves at a sufficiently high velocity, then (in contrast to the case of the structure at rest) a weakly damping collective mode propagating with velocity 2V arises in the structure. It is this mode that is responsible for anomalous attenuation of longitudinal ultrasonic waves.     

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.     

Dynamics of high-temperature plasma formation during laser irradiation of three-dimensionally structured,low-density matter

Results are presented from an experimental investigation of the properties of the plasma produced by the action of a radiation pulse at the second harmonic of a Nd laser, with average intensity ~5·10¹⁴ W/cm² in the focal spot, on flat targets consisting of porous polypropylene (CH)_x with an average density of 0.02 g/cm³ (close to the critical plasma density) and with ~50 μm pores. The properties of the laser plasma obtained with porous and continuous targets are substantially different. The main differences are volume absorption of the laser radiation in the porous material and much larger spatial scales of energy transfer. The experimentally measured longitudinal ablation velocity in the porous material was equal to (1.5–3)·10⁷ cm/s, which corresponds to a mass velocity of (3–6)·10⁵ g/cm²· s, and the transverse (with respect to the direction of the laser beam) propagation velocity of the thermal wave was equal to ~(1–2) ·10⁷ cm/s. The spatial dimensions of the plasma plume were ~20–30μm. The plasma was localized in a 200–400μm region inside the target. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 7, 462–467 (10 October 1996)     

Phase Transitions in a Mixture of Amorphous C<Subscript>60</Subscript> and C<Subscript>70</Subscript> Fullerene Phases at High Temperatures and Pressures

Phase transitions in two types of amorphous fullerene phases (C₆₀–C₇₀ (50/50) mixtures and an amorpous C₇₀ fullerene phase) are studied via neutron diffraction at pressures of 2–8 GPa and temperatures of 200–1100°C. Fullerenes are amorphized by grinding in a ball mill and sintered under quasi-hydrostatic pressure in a toroidal-type chamber. Diffraction studies are performed ex situ. It is shown that the amorphous phase of fullerenes retains its structure at temperatures of 200–500°C, and amorphous graphite is formed at 800–1100°C with a subsequent transition to crystalline graphite. This process is slow in a mixture of fullerenes, compared to C₇₀ fullerene. According to neutron diffraction data, the amorphous graphite formed from amorphous fullerene phases has anisotropy that is much weaker in a fullerene mixture.     

De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper–niobium system

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu–Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200?°C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300?°C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.     

Mössbauer study of phase separation in Ni80 57Fe1P19 amorphous alloys

Mössbauer spectroscopy, X-ray diffractometry, scanning calorimetry and electrochemical measurements were used to study the crystallization process of Ni₈₀ ⁵⁷Fe₁P₁₉ amorphous alloys kept in melt at different temperatures before quenching. Samples were heated up to 430°C and 720°C at a rate of 20°C/min, in order to reach characteristically different stages of crystallization. Even at the same crystallization, stage the room temperature Mössbauer spectra and the X-ray differactograms were different depending on the temperature (1050°C or 1400°C) at which the samples were kept before quenching the melt. The Mössbauer spectra showed a paramagnetic component and two sextets (H=267 kOe and H=245 kOe) at 430°C while at 720°C there was only one sextet (H=267 kOe) besides the paramagnetic component. The changes in the Mössbauer spectra of different samples due to crystallization are consistent with the explanation that phase separation occurs in Ni₈₀ ⁵⁷Fe₁P₁₉ rapidly quenched from the melting temperature of 1050°C.     

Acoustic anomalies and relaxation dynamics of relaxor ferroelectric Na1/2Bi1/2TiO3 single crystals studied by using Brillouin spectroscopy

Acoustic anomalies of relaxor ferroelectric Na_1/2Bi_1/2TiO₃ single crystals were investigated over a wide temperature range from −196 °C to 900 °C by using Brillouin spectroscopy. The longitudinal sound velocity, the acoustic absorption coefficient and the elastic constant C₁₁ were determined for the acoustic phonon mode propagating in the [100] direction. Two acoustic anomalies, weaker ones at the cubic-tetragonal phase transition temperature of ~540 °C and more pronounced ones at temperatures near 315 °C near the dielectric maximum temperature, were investigated and discussed in relation with the relevant order parameters coupled to the acoustic waves. The relaxation dynamics in the cubic phase were studied based on the flattening of the mode frequency and the half width, which was observed for the first time, and a modified Arrhenius law.     

First-principles study of ground- and metastable-state properties of XO (X = Be,Mg, Ca,Sr, Ba,Zn and Cd)

The evolution of the local atomic order of an amorphous Ni₄₆Ti₅₄ alloy produced by mechanical alloying as a function of temperature was studied by synchrotron X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques. XRD measurements at several temperatures (25 °C, 350 °C, 412 °C, 430 °C, 450 °C and 515 °C) were performed and analyzed using the reverse Monte Carlo (RMC) simulations method or the Rietveld refinement procedure. The experimental total structure factor for samples at 25 °C and 350 °C, which are amorphous in nature, were simulated by using the RMC method, and the local structures of the alloy at both temperatures were determined, indicating a decrease in its density as the temperature increases. At 412 °C, the XRD pattern shows a partially crystalline sample, indicating that the crystallization process is in progress. At 430 °C, 450 °C and 515 °C, the XRD measurements indicate the presence of two crystalline phases, NiTi and NiTi₂, whose structural parameters (lattice parameters, coherently diffracting domains (CDD) sizes, microstrains and relative amount of phases) were determined using the Rietveld refinement procedure. DSC measurements at different heating rates furnished the crystallization temperature, enthalpy and activation energy of the crystallization process, and these values are similar to those found in other amorphous alloys of the Ni-Ti system. They also showed the existence of a second exothermic process, which was related to diffusive processes in the crystalline phases, which could be associated with the changes in the CDD sizes happening from 450 °C to 515 °C.     

Reactive Compatibilization of Poly(trimethylene terephthalate)/Polypropylene Blends by Polypropylene‐graft‐Maleic Anhydride. Part 2. Crystallization Behavior

The crystallization behavior of uncompatibilized and reactive compatibilized poly(trimethylene terephthalate)/polypropylene (PTT/PP) blends was investigated. In both blends, PTT and PP crystallization rates were accelerated by the presence of each other, especially at low concentrations. When PP content in the uncompatibilized blends was increased to 50–60 wt%, PTT showed fractionated crystallization; a small PTT crystallization exotherm appeared at ～135°C besides the normal ～175°C exotherm. Above 70 wt% PP, PTT crystallization exotherms disappeared. In contrast, PP in the blends showed crystallization exotherms at 113–121°C for all compositions. When a maleic anhydride‐grafted PP (PP‐g‐MAH) was added as a reactive compatibilizer, the crystallization temperatures (T _c ) of PTT and PP shifted significantly to lower temperatures. The shift of PTT's T _c was larger than that of the PP, suggesting that addition of the PP‐g‐MAH had a larger effect on PTT's crystallization than on PP due to reaction between maleic anhydride and PTT.

The nonisothermal crystallization kinetics was analyzed by a modified Avrami equation. The results confirmed that PTT's and PP's crystallization was accelerated by the presence of each other and the effect varied with blend compositions. When the PP content increased from 0 to 60 wt%, PTT's Avrami exponent n decreased from 4.35 to 3.01; nucleation changed from a thermal to an athermal mode with three‐dimensional growths. In contrast, when the PTT content increased from 0 to 90 wt% in the blends, changes in PP's n values indicated that nucleation changed from a thermal (0–50 wt% PTT) to athermal (60–70 wt% PTT) mode, and then back to a thermal (80–90 wt% PTT) mode. When PP‐g‐MAH was added as a compatibilizer, the crystallization process shifted considerably to lower temperatures and it took a longer crystallization time to reach a given crystallinity compared to the uncompatibilized blends.     

Phase transition of nano-sized amorphous tungsten to a crystalline state

We study thermal-physical characteristics of nano-sized amorphous tungsten and of its oxide. It is shown that a nano-size amorphous metal gets into a nano-size crystalline state after heating up to temperatures much lower than the half-temperature of melting, which is typical for all nano-size amorphous materials. Phase transition of amorphous nano-size WO₂ into crystalline state occurs in the temperature range 350–520°C, while the same transition in case of W takes place in the range 1000–1370°C. The energy released at crystallization of nano-size amorphous metal amounts to 170±25 J/g coinciding practically with the value of specific melting heat of usual tungsten. Such a high additional energy of nano-size amorphous metals above the energy of nano-size crystalline metals is their main peculiarity which widens essentially the range of their practical applications.     

Comportement thermoelastique de monocristaux de Cu2O

The velocity of elastic waves in monocrystals of Cu₂O has been measured with good precision at 24° C as a contribution to turther development of lattice dynamics of this compound. There is no significant deviation of the velocity in connexion with the non-stoechiometric properties of various samples. Elastic waves behaviour has been investigated up to 700° C and will be connected to plastic properties.     

Crystallization Behavior of Amorphous Poly(l-Lactide)

Amorphous poly(l-lactide) (PLLA) was annealed in two different ways: amorphous samples were heated at a given temperature to induce crystallization (one-step annealing); and amorphous samples were first crystallized at a low temperature and subsequently annealed at a higher temperature than the crystallization temperature. Samples thus prepared were measured by DSC. The original amorphous sample exhibited an exothermic peak at about 100°C (exothermic peak I), an exothermic peak just below the melting point (exothermic peak II), and an endothermic peak when it was melted. Exothermic peak I was caused by cold crystallization. When the melting points of PLLA samples, heat-treated in various ways, were plotted as a function of annealing temperature, there was discontinuity at about 120°C. From analyses of wide-angle X-ray diffraction patterns, it was found that when amorphous PLLA was crystallized at a temperature below 120°C, crystallites of the β-form formed, and when annealed at a temperature above 120°C, crystallites of the α-form grew. Thus, exothermic peak I was attributed to cold crystallization of the β-form, and peak II was caused by the phase transition of the β-form to a more stable form.