The effect of cerium and lanthanum surface treatments on early stages of oxidation of A361 aluminium alloy at high temperature

X-ray photoelectron spectroscopy analysis has been used to study the surface of A361 aluminium alloy after electrodeposition of cerium and lanthanum compounds followed by oxidation tests in air at 100-500 °C for 2 h. Cerium and lanthanum oxide deposits are found on the β-AlFeSi second phase particles and to a lesser extent on the eutectic Al-Si areas, while the α-Al phase is covered with a thin aluminium oxide film. This uneven deposition may be related either to a preferential nucleation and growth process on active interfaces or to the differing electrical conductivity of the phases and intermetallic compounds of the alloy. Initial stages of oxidation of A361 alloy disclosed thickening of the aluminium oxide layer and Mg enrichment at the surface, especially above 400 °C. Rare earth deposits revealed two different effects: reduced Mg diffusion and enhanced thickening of the aluminium oxide film. A distinctive behaviour of Ce oxide appears at 300-500 °C related with Ce(III) to Ce(IV) transition.     

Thermal conductivities of solid and liquid phases for neopentylglycol, aminomethylpropanediol and their binary alloy

The variations of thermal conductivities of solid phases versus temperature for neopentylglycol (NPG), 2-amino-2-methyl-1,3-propanediol (AMPD) and AMPD-42.2 mol% NPG alloy were measured with a radial heat flow apparatus. From the graphs of the solid phases thermal conductivity variations versus temperature, the thermal conductivities of the solid phases at their melting temperature and temperature coefficients for same materials were also found to be 0.22±0.01, 0.45±0.02 and 0.32±0.02 W/Km and 0.0047, 0.0031 and 0.0043 K⁻¹, respectively. The thermal conductivity ratios of liquid phase to solid phase for the same materials at their melting temperature are found to be 1.07, 1.12 and 0.74 with a Bridgman type directional solidification apparatus, respectively. Thus, the thermal conductivities of liquid phases for pure NPG, pure AMPD and AMPD-42.2 mol% NPG alloy at their melting temperature were evaluated to be 0.24, 0.50 and 0.23 W/Km, respectively, by using the values of solid phase thermal conductivities and the thermal conductivity ratios of liquid phase to solid phase.     

Acoustic and NMR investigations of melting and crystallization of indium–gallium alloys in pores of synthetic opal matrices

The paper presents the results of studying the crystallization and melting processes of Ga–In eutectic alloys, which are embedded in opal matrices, using acoustic and NMR methods. The indium concentrations in the alloys were 4, 6, 9, and 15 at %. Measurements were performed upon cooling from room temperature to complete crystallization of the alloys and subsequent heating. It is revealed how the size effects and alloy composition influence the formation of phases with α- and β-Ga structures and on changes in the melting-temperature ranges. A difference was observed between the results obtained using acoustic and NMR methods, which was attributed to different temperature measurement conditions.     

Phase evolution and microwave dielectric properties of Bi3SbO7 ceramic

The Bi₃SbO₇ ceramic was prepared by the solid state reaction method and its phase evolution at different temperatures was studied. Low temperature phase α-Bi₃SbO₇ was formed at about 890 °C and it started to transform to high temperature phase β-Bi₃SbO₇ at about 960 °C. Microwave dielectric constants of α-Bi₃SbO₇ ceramic and β-Bi₃SbO₇ ceramic were 43.2 and 37.6, Qf value were 2080 and 5080 GHz, respectively. TCF of α-Bi₃SbO₇ ceramic was near zero and TCF of β-Bi₃SbO₇ ceramic was about −120 ppm/°C. The Bi₃SbO₇ ceramic is a promising candidate for low temperature co-fired ceramic (LTCC) technology due to its large dielectric constant, low dielectric loss at microwave region, low sintering temperature and simple composition.     

Thermal behavior and nucleation kinetics of 1,5-dimethyl-2-nitroimino-1, 3, 5-triazinane crystal

Nitroguanidine derivatives have increasingly gained attention because of their high insecticidal activities and wide spectrum. In this paper, nitroguanidine derivative 1,5-dimethyl-2-nitroimino-1, 3, 5-triazinane was synthesized, and its crystal structure was determined by X-ray technique. The thermal behaviors of 1, 5-dimethyl-2-nitroimino-1, 3, 5-triazinane in a nitrogen atmosphere were also studied under non-isothermal conditions by thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. The TG and DSC studies showed that the sample started to melt at 408.1 K with high melting enthalpy of 121.3 J/g and was stable up to at least 423.2 K, which indicated that the sample could be effectively utilized for various devices below 423.2 K. The melting entropy of 1,5-dimethyl-2-nitroimino-1, 3, 5-triazinane calculated from melting point and melting enthalpy using Eq. (1) was 51.476 J mol⁻¹ K⁻¹. In addition, the nucleation parameters of 1,5-dimethyl-2-nitroimino-1, 3, 5-triazinane in ethanol, such as the radius of critical nucleus and the Gibbs free energy barrier, had also been investigated based on classical nucleation theory.     

Investigations of meta-stable and post-spinel silicon nitrides

Since the discovery of post-spinel Si₃N₄, its fundamental physical properties are highly required. In this paper, theoretical calculations are performed to investigate the structural and elastic properties of the β-, γ-, wII- and post-spinel Si₃N₄ polymorphs. The calculated ground-state properties compare well with available experiments. The phase transformations of the β-, γ-, wII- and post-spinel phases are investigated by the famous plane-wave pseudo-potential density functional theory. From the elastic constants obtained, we find that β-, γ- and wII-Si₃N₄ are stable at 0 GPa and the post-spinel phase is unstable/stable at 0 GPa/160 GPa. When the high-temperature β→γ transformation is bypassed due to kinetic reasons, β-Si₃N₄ is predicted to undergo a first-order phase transition to a new phase (wII-Si₃N₄). It is found that the transition pressures of β→wII and γ→post-spinel transitions are 20.8 GPa and 152.5 GPa, respectively. The phase boundary of the γ→post-spinel transition can be described as P=152.3631−6.39×10⁻³T+2.01062×10⁻⁵T²−1.93962×10⁻⁹T³. Through the quasi-harmonic approximation, the dependences of heat capacity, entropy, thermal expansion coefficient and the Debye temperature on temperature, are also successfully predicted.     

Temperature-induced particle self-assembly

Agglomeration of monodisperse thiol-stabilized gold particles with diameters of 6 nm, suspended in organic solvents, was induced by the cooling of the suspension. A sharp transition between the stable suspension and agglomeration resulted. The temperature of the transition depends on the concentration and the compatibility of the solvent. The morphology of the formed particle structures upon agglomeration implies that the used metal colloid can be described as a van der Waals-gas. The particles undergo phase transitions from a stable fluid phase to a metastable phase, in which nucleation and growth occur, or to an instable phase, in which spinodal decomposition occurs. The results will direct research on routes to nanostructured materials using nanoparticles as building blocks.     

Phase transitions in femtosecond laser ablation

In this study we simulate an interaction of femtosecond laser pulses (100 fs, 800 nm, 0.1-10 J/cm²) with metal targets of Al, Au, Cu, and Ni. For analysis of laser-induced phase transitions, melting and shock waves propagation as well as material decomposition we use an Eulerian hydrocode in conjunction with a thermodynamically complete two-temperature equation of state with stable and metastable phases. Isochoric heating, material evaporation from the free surface of the target and fast propagation of the melting and shock waves are observed. On rarefaction the liquid phase becomes metastable and its lifetime is estimated using the theory of homogeneous nucleation. Mechanical spallation of the target material at high strain rates is also possible as a result of void growth and confluence. In our simulation several ablation mechanisms are taken into account but the main issue of the material is found to originate from the metastable liquid state. It can be decomposed either into a liquid-gas mixture in the vicinity of the critical point, or into droplets at high strain rates and negative pressure. The simulation results are in agreement with available experimental findings.     

Phase Transition in β-nucleated Isotactic Polypropylene Induced by Combination of Annealing and High Pressure

The effects of annealing and high pressure on the microstructure of β-nucleated isotactic polypropylene (iPP) were investigated. Annealing treatment was carried out at different temperatures from 90–170°C under different pressure conditions, that is, atmospheric pressure and high pressures of 150, 250, and 350 MPa, respectively. The microstructure of the specimens was comparatively investigated through using wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). Different from the common annealing treatment under atmospheric pressure, which induces the single-phase transition from metastable β-iPP to the more stable α-iPP (β→α) depending on the annealing temperatures, the application of high pressure induces not only the phase transition of β→α but also the phase transition of β→γ. Furthermore, the thermostability of β-iPP was improved greatly under high pressure. The higher the pressure applied, the smaller was the degree of the transition from β-iPP to α-iPP and/or γ-iPP. This work reports, for the first time, a novel crystalline morphology composed of β-iPP and γ-iPP.     

Stability of bulk metastable Fe<Subscript>83</Subscript>B<Subscript>17</Subscript> eutectic alloy prepared by hypercooling method

The bulk metastable Fe₈₃B₁₇ eutectic alloy has been successfully prepared using hypercooling solidification. The bulk alloy consists of αFe and metastable Fe₃B phases, without the stable Fe₂B phase. Upon isothermal annealing, decomposition of the metastable Fe₃B phase (prepared by hypercooling) was investigated, as compared to the corresponding behaviour from amorphous Fe-B alloy. PACS 61.82.Bg; 64.60.-i; 64.60.My; 64.70.Kb; 68.60.Dv     

Effects of Ta on microstructure and microhardness of Ni based laser clad coating

Through addition of Tantalum, fine TaC particles were in situ synthesized in a NiCrBSi alloy laser clad composite coating. Microstructure, microhardness and abrasive wear resistance of the composite coating were investigated. The result showed that TaC particles were dispersed in Ni based alloy composite coating, refining the microstructure of the coating after laser cladding. Amount of coarse primary carbides such as M7C3 and eutectic of γ-Ni + M23C6 substantially decreased because the formation of TaC particles suppressed the formation of M7C3 and M23C6. On the one hand, fine TaC particles acted as hard phase, which improved the microhardness of the composite coating; on the other hand, a decrease in amount of the coarse M7C3 and eutectic of γ-Ni + M23C6 reduced the crack susceptibility of the Ni based composite coating. Also, Ta element improved the abrasive wear resistance of the Ni based coating.     

Influence of thermal degradation and saline exposure on dielectric permittivity of polyimide

This paper studies the relationship between dielectric permittivity and mechanisms of thermal degradation of polyimide (PI) film in air and saline exposure. The real permittivity and loss factor of dried PI were measured at temperatures from −140 to 180 °C and frequencies from 1 Hz to 1 MHz. Two peaks in the temperature-dependent loss factor revealed the occurrence of β- and γ-relaxations in PI. Following thermal degradation at 475 °C for 3 h, the real permittivity of PI was observed to increase by 14% because of the formation of free radicals. The intensity of β-relaxation was also greatly increased after thermal degradation due to scission of chemical bonding in imide groups. Activation energy obtained from the Arrhenius law for γ-relaxation did not change after thermal degradation. For samples exposed to either distilled water or salt water, the variation in salinity did not significantly influence the dielectric permittivity.     

Synthesis, crystal structure and blue electroluminescence of a new zinc complex based on 2,6-bis(benzimidazolyl)pyridine

A very stable and blue luminescent complex Zn(bbp)Cl₂ (bbp: 2,6-bis(benzimidazolyl)pyridine) was synthesized. X-ray crystal structural analysis for the complex revealed that there are intermolecular π?π interactions in the solid state. The fluorescence properties for this complex were studied. The similar devices with the structure of [ITO/CuPc(31 nm)/NPB(80 nm)/[Zn(bbp)Cl₂] (or L) (85 nm)/LiF15/Al] were constructed to investigate their electroluminescent performance. Both the complex and the ligand can be fabricated as blue-emitting materials. The complex shows emission peak at 555 nm, electroluminescent efficiency 0.017 cd A⁻¹ and turn-on voltage 7 V, compared to 470 nm, 0.036 cd A⁻¹ and 9 V for the ligand.     

Effects of substrate temperature on properties of NbNx films grown on Nb by pulsed laser deposition

NbN_x films were deposited on Nb substrate using pulsed laser deposition. The effects of substrate deposition temperature, from room temperature to 950 °C, on the preferred orientation, phase, and surface properties of NbN_x films were studied by X-ray diffraction, atomic force microscopy, and electron probe micro analyzer. We find that the substrate temperature is a critical factor in determining the phase of the NbN_x films. For a substrate temperature up to 450 °C the film showed poor crystalline quality. With temperature increase the film became textured and for a substrate temperature of 650−850 °C, mix of cubic δ-NbN and hexagonal phases (β-Nb₂N + δ′-NbN) were formed. Films with a mainly β-Nb₂N hexagonal phase were obtained at deposition temperature above 850 °C. The c/a ratio of β-Nb₂N hexagonal shows an increase with increased nitrogen content. The surface roughness of the NbN_x films increased as the temperature was raised from 450 to 850 °C.     

Surface modification of Al-20Si alloy by high current pulsed electron beam

Hypereutectic Al-20Si (Si 20 wt.%, Al balance)alloy surface was treated with high current pulsed electron beam (HCPEB) under different pulse numbers. The results indicate that HCPEB irradiation induces the formation of metastable structures on the treated surface. The coarse primary Si particle melts, producing a “halo” microstructure with primary Si as the center on the melted surface. A supersaturated solid solution of Al is formed in the melted layer caused by Si atoms dissolving into the Al matrix. Cross-section structure analysis shows that a 4 μm remelted layer is formed underneath the top surface of the HCEPB-treated sample. Compared with the matrix, the Al and Si elements in the remelted layer are distributed uniformly. In addition, the grains of the Al-20Si alloy surface are refined after HCPEB treatment, as shown by TEM observation. Nano-silicon particles are dispersed on the surface of remelted layer. Polygonal subgrains, approximately 50-100 nm in size, are formed in the Al matrix. The hardness test results show that the microhardness of the α(Al) and eutectic structure is increased with increasing pulse number. The hardness of the “halo” microstructure presents a gradient change after 15 pulse treatment due to the diffusion of Si atoms. Furthermore, hardness tests of the cross-section at different depths show that the microhardness of the remelted layer is higher than that of the matrix. Therefore, HCPEB technology is a good surface modification method for enhancing the surface hardness of hypereutectic Al-20Si alloy.     

In situ energy dispersive X-ray diffraction study of iron disilicide thermoelectric materials

The dynamic phase transformation and structure of rapidly solidified Fe_1−xCo_xSi₂ (0.02?x?0.06) thermoelectric materials were in situ investigated under high temperatures and high pressures by energy dispersive X-ray diffraction using synchrotron radiation. The FeSi₂ alloys which solidified as α-Fe₂Si₅ and ε-FeSi eutectic structures, were transformed to the semiconducting β-FeSi₂ phase upon heating by the main reaction α+ε→β and the subsidiary reaction α→β+Si. The low heating rates and Co contents were found to be beneficial for the β phase formation. The decomposition temperature of β→α+ε was weakly dependent on heating rate, but significantly suppressed by the high pressures.     

Microstructure evolution in the rapidly quenched Fe78Si9B13 ribbons

We report microstructure evolution in as-spun Fe₇₈Si₉B₁₃ ribbons under various wheel speeds (s), which was investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). With decreasing s, the volume fraction of the residual amorphous phase (V_a) in the as-spun ribbons decreases gradually, and the total exothermic heat of the crystallization in the DSC curves also decreases, but the ratio of the exothermic heat of the second crystallization to the first one is on the contrary. α-Fe is found in the ribbon with s of 32.9 m/s, while α-Fe, eutectic α-Fe+Fe₂B, and Fe₃Si phases are found in ribbons with s of 25.6 and 18.3 m/s. The phase precipitating behavior in cooling processes is well consistent with the annealing process in the literatures.     

Effect of anions on the phase stability of γ-FeOOH nanoparticles and the magnetic properties of gamma-ferric oxide derived from lepidocrocite

The effect of anions such as Cl⁻, SO₄²⁻, and HPO₄²⁻ on the phase stability of FeOOH (α or γ) during precipitation is investigated. Oxidation of Fe(OH)₂·xH₂O from FeCl₂ solution with high Cl⁻ concentration ([Cl⁻]/[Fe]=R_Cl≥8) or (NH₄)₂Fe(SO₄)₂ (FAS) with [HPO₄²⁻]/[Fe]=R_P≥0.02 yields phase-pure γ-FeOOH. In the medium ranges of R_Cl and R_P, mixed phases of α-FeOOH and γ-FeOOH are obtained. Replacement of OH⁻ by Cl⁻ with the bridging cations or strongly bonded HPO₄²⁻ ions in the matrix of the intermediate phase (Fe_x²⁺Fe_y³⁺(OH)_2x+2y−nz·xH₂O(A)_zⁿ⁻, where A is anions such as Cl⁻, SO₄²⁻, HPO₄²⁻, etc.), promoted the lower density γ-FeOOH. However, the particles are less developed and have poor crystallinity as evidenced from transmission electron microscope and thermogravimetry-differential thermal analysis of the precipitates. Whereas, monophasic, uniformly sized, nano-lath shaped particles with high aspect ratio >10 are obtained when morphology-controlling cation additives such as Pt⁴⁺, Pd²⁺ or Rh³⁺ are present in FeCl₂ (R_Cl≥8) solution. Preferential adsorption of additives on (0k0) and (h00) planes limits the growth in the perpendicular directions leading to high aspect ratios. The effect of these additives are suppressed by the phosphate ion, a strong complexing ligand, giving rise to fibrous aggregate with the length of individual particles as small as 10-30 nm. While most of the Cl⁻ ion is removed from the final precipitates on washing, phosphate remained as HPO₄²⁻ as evidenced from IR absorption spectra. Maghemite obtained by dehydroxylating γ-FeOOH contains randomly distributed micropores bringing in the relaxation effects of spins on the surface atoms as deciphered from Mössbauer spectroscopy. This leads to the low σ_s (44-48 emu/g) and H_c (120-130 Oe) for γ-Fe₂O_3−δ particles. Whereas nearly pore-free single crystalline particles obtained by reduction followed by reoxidation has high value of σ_s (73 emu/g) and H_c (320 Oe), which decreases to 30 emu/g and 75 Oe, respectively, for nanoparticles obtained from phosphate stabilized lepidocrocite. The mobility of iron ions and counter mobility of vacancies during the topotactic transformation of γ-FeOOH to magnetite to γ-Fe₂O_3−δ renders the particles pore-free.     

Phase transitions in cerium at high pressures (up to 15 GPa) and high temperatures

Phase transitions in cerium have been studied by the electrical resistance method in the 15-GPa pressure range at high temperatures. At pressures above 10 GPa, cerium represents a mixture of stable and metastable phases, the composition of this mixture being dependent on the trajectory in the P-T plane that leads to a given point. Transformations in both stable and metastable components of the mixture proceeding rather independently display a complicated picture of phase transitions. It was assumed that only the α (fcc) and α′ (α-U) phases are stable at pressures above the well-known γ-α transition, the other phases being metastable. The proposed bow-shaped equilibrium phase diagram includes an extremely wide hysteresis region, where stable and metastable phases can coexist. The fcc α phase alone survives upon heating above 50°C at 15 GPa.     

Microstructure and age characterization of Cu-15Ni-8Sn alloy coatings by laser cladding

The present work has investigated the influence of direct aging treatment on the precipitation sequence and properties of the Cu-15Ni-8Sn alloy coatings prepared by laser cladding. The experimental results show that the tendency of Sn segregation in the conventional Cu-15Ni-8Sn solidification microstructure is effectively relieved. Before aging, there are only two phases in the coating: the α-Cu solid solution dendrites with 7 wt.% Sn solubility, and a small fraction of Sn-enriched δ-phase at the interdendrites in rapid solidified microstructure. After the coating was directly aged at 370 °C without traditional solution pretreatment, the α-Cu solid solution dendrites experience precipitations in the order of pure spinodal decomposition, DO₂₂-ordered structure and discontinue γ-DO₃. The microhardness of the coating treated by direct aging reached 390 HV 0.5, which was higher than that treated by conventional solution and aging process owing to the solidified fine grains and hardening effect of spinodal decomposition. In addition, the Sn-enriched δ-phase at the interdendrites also decomposes to laminar discontinuous precipitated γ-DO₃ phase after aging. Precipitation sequence and properties of the clad coatings change obviously during the direct aging treatment.