Relationship between dielectric properties and structural long-range order in (x)Pb(In1/2Nb1/2)O3:(1 − x)Pb(Mg1/3Nb2/3)O3 relaxor ceramics

The dielectric and structural order–disorder properties of as-sintered complex perovskite (x)Pb(In_1/2Nb_1/2)O₃:(1 − x)Pb(Mg_1/3Nb_2/3)O₃ ceramics are highly influenced by the quantity of Pb(In_1/2Nb_1/2)O₃ (PIN). A high PIN quantity causes the relative permittivity maxima (ε_max) to decrease and the temperature (T_max) to increase. Also, strong frequency dispersion is dominant in the relative permittivity when plotted against the temperature. In ferroelectric hysteresis loop measurements, the maximum values of electric displacements (D_max) decrease with increasing PIN. The ceramics in the composition range x = 0.1–0.8 behave as ferroelectric relaxors and exhibit very slim hysteresis loops for all these compositions. Transmission electron microscopy (TEM) studies show that the size of the 1:1 structural ordered domains is influenced by the PIN quantity. The relationship between the dielectric properties and the long-range 1:1 order in these relaxors appear to be in conflict with the commonly accepted order–disorder behavior in complex perovskite ferroelectrics, in which large structural domains correspond with the tendency to depart from the relaxor state. TEM observations show that individual 1:1 ordered domains in (x)PIN:(1 − x)PMN ceramics are composed of numerous nano-sized ordered domains, separated by fine antiphase boundaries.     

Nanoindentation characteristics of Zr69.5Al7.5 − xGaxCu12Ni11 glasses and their nanocomposites

This work deals with the indentation behavior of Zr_69.5Al_7.5 − xGa_xCu₁₂Ni₁₁ (x = 0, 1.5, 7.5 at.%) alloys. A comparison between their nanohardness and reduced elastic modulus values of the as-synthesized glassy phase with their nanocomposites has been made. The indentation characteristics of a novel Ga substituted glass composition corresponding to x = 7.5 have shown significant improvement in regard to hardness and elastic modulus. The evidence of pile up has been observed in case of as-synthesized glassy ribbons. The load (P) versus depth (h) curves for as-synthesized melt-spun ribbons displayed the presence of displacement burst, which are known as pop-ins. The amount of energy per unit volume required for the shear band formation in glassy state has been estimated based on the pop-ins observed in P-h curve. This seems to decrease with Ga addition. Based on transmission electron microscopic observations of indented glassy specimen, the possibility of nanocrystallization has been ruled out.     

Solute and vacancy segregation to a/4<1 1 1> and a/2<1 0 0> antiphase domain boundaries in Fe3Al

Segregation of solute atoms and vacancies to antiphase domain boundaries (APDBs) in Fe–Al alloys near the stoichiometry Fe₃Al (Fe–22–28 at.% Al) was studied using a phase-field model based on the Bragg–Williams approximation. Local equilibrium vacancy concentration was determined from experimental data for vacancy formation enthalpy and the configurational entropy of vacancies assuming that the formation enthalpy is independent of long-range order and chemical composition. Fe atoms and vacancies segregate to APDB with the phase-shift vector a/2<1 0 0>(D0₃-APDB) in crystals with stoichiometric composition (Fe–25 at.% Al) and with the Fe-rich composition, whereas both of them tend to be depleted in Al-rich crystals. On the other hand, Fe atoms and vacancies both segregate on APDBs with the phase-shift vector a/4<1 1 1>(B2-APDB) in all compositions studied. The effects of vacancy segregation on APDB energy and thickness is negligibly small; however, the vacancy concentration at the center of APDBs can be up to 80% larger than in the bulk, and therefore it is anticipated that the mobility of APDBs can be significantly affected by the segregation of vacancies as well as by that of solute atoms.     

The microstructure development in Fe32Cu20Ni28P10Si5B5 immiscible alloy and possibilities of formation of amorphous/crystalline composite

Durch Messungen mittels differentieller Thermal-Analyse und dazu komplementäre Untersuchungen der Mikrostrukturen an Fe-Cu Legierungen ergibt sich erstmals der Nachweis für das Auftreten von kritischer-Punkt Benetzung an einer vollständig metastabilen Mischungslücke. Die damit verbundene vollständige Benetzung tritt in dem Zusammensetzungsbereich von 50–65 at.% Fe nahe der kritischen Konzentration auf. Glaseingelagerte Proben zeigen die vollständige Benetzung des Glases durch die Cu-reiche Schmelze während des Unterkühlens bis zur metastabilen Mischungslücke. Im Zusammensetzungsbereich der vollständigen Benetzung erfolgt die Entmischung bei der zugehörigen Binodaltemperatur ohne zusätzliche Unterkühlung. Bei der Erstarrung der phasenseparierten Schmelze aus tiefer Unterkühlung führt dies zu einem grobskaligen Entmischungsgefüge. Im Gegensatz dazu zeigt die Entmischungsreaktion bei Zusammensetzungen außerhalb des Intervalls vollständiger Benetzung eine merkliche Unterkühlung unterhalb der jeweiligen Binodaltemperatur. Das zugehörige Erstarrungsgefüge zeigt die Phasentrennung auf einer deutlich kleineren Skala. Ohne Glaseinlagerung befinden sich die Proben in Kontakt zu dem Al₂O₃-Tiegel und zu einer Oberflächenschicht aus Eisenoxid. Unter diesen Bedingungen findet kritischer-Punkt Benetzung auf beiden Seiten der kritischen Zusammensetzung statt. Diese Ergebnisse demonstrieren daß kritischer-Punkt Benetzung unabhängig von der Probenumgebung erfolgt, daß jedoch die benetzende Phase oberflächenempfindlich ist und durch die Probenumgebung selektiert wird.

Structural and magnetic nanoclusters in Cu50Zr50−xGdx (x = 5 at.%) metallic glasses

It is shown that phase-separated metallic glasses on the nanoscale can be prepared by rapid quenching of Cu₅₀Zr_50−xGd_x melts with a low concentration of gadolinium (x = 5 at.%). Gd-enriched clusters of 2 nm size are formed as early stages of decomposition in the deeply undercooled melt. The key physical parameter to obtaining such a nanoclustered microstructure upon quenching is the critical temperature of liquid-liquid phase separation which has to be close to the glass transition temperature. Thus, the thermodynamic properties of the liquid phase even in the metastable deeply undercooled melt essentially determine the structure formation. Analysis of the spatial atomic arrangement by atom probe tomography after annealing in the supercooled liquid state provides direct evidence of the spinodal character of the decomposition by uphill diffusion. The Gd-enriched nanoclusters exhibit ferromagnetic ordering below 50 K and the cluster size regime derived from magnetization measurements is in good agreement with that obtained from atom probe tomography investigations. The first stage of crystallization of Cu₅₀Zr₄₅Gd₅ glass is observed to be Ostwald-type ripening on a nanoscale. The phase-separated glass acts as a precursor for the formation of a metastable nanocrystalline structure.     

Effect of amorphous–crystalline interfaces on the martensitic transformation in Ti50Ni25Cu25

A partially crystallized amorphous Ti₅₀Ni₂₅Cu₂₅ melt-spun ribbon showing spherical particles in martensite has been investigated. Microstructural observations support the hindering of the martensitic transformation as well as the production of additional autoaccommodated structures nearby the interface compared with the ones used inwards.     

Nucleation and growth of the γ′(AlAg2) precipitate in Al–Ag(–Cu) alloys

Precipitation of the γ′(AlAg₂) phase was investigated in Al–Ag(–Cu) alloys using high-resolution transmission electron microscopy and scanning transmission electron microscopy. Precipitation commenced with segregation of Ag to stacking faults, followed by thickening in steps corresponding to single unit cell height ledges. In conjunction with gradual segregation of Ag and Al into ordered layers, this yielded γ′ phase platelets with a thickness of either 2 or 3 × the AlAg₂c-lattice parameter. Plates with a thickness of 2c(AlAg₂) could not achieve self-accommodation of the shape strain for transformation. Further thickening of the precipitates was slow, despite considerable Ag segregation around the precipitates. Growth by the addition of single unit cell height ledges is expected to lead to an additional shear strain energy barrier to ledge nucleation and this may contribute to a process of nucleation-limited growth.     

Synthesis, structural and microwave dielectric properties of Al2W3−xMoxO12 (x = 0-3) ceramics

Low dielectric ceramics in the Al₂W_3−xMo_xO₁₂ (x = 0-3) system have been prepared through solid state ceramic route. The phase purity of the ceramic compositions has been studied using powder X-ray diffraction (XRD) studies. The microstructure of the sintered ceramics was evaluated by Scanning Electron Microscopy (SEM). The crystal structure of the ceramic compositions as a result of Mo substitution has been studied using Laser Raman spectroscopy. The microwave dielectric properties of the ceramics were studied by Hakki and Coleman post resonator and cavity perturbation techniques. Al₂Mo_xW_3−xO₁₂ (x = 0-3) ceramics exhibited low dielectric constant and relatively high unloaded quality factor. The temperature coefficient of resonant frequency of the compositions is found to be in the range −41 to −72 ppm/°C.     

Novel photoluminescent properties of LiGaO2 nanoflakes

The luminescence properties of LiGaO₂ microflakes synthesized using the sol-gel process are investigated. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) and absorption spectra. The PL spectra excited at 325 nm have a broad and strong emission band with a peak at 383 nm, which corresponds to the self-activated luminescence of the tetrahedral gallium group. The optical absorption spectra of the sample annealed at 600 °C exhibited a band-gap energy of 3.38 eV.     

Crystallographic relationship of orthorhombic φ-Al5Mg11Zn4 phase to icosahedral quasicrystalline phase

The orthorhombic φ-Al₅Mg₁₁Zn₄ phase is known to be related to quasicrystalline phases, but the exact relationship has not been shown yet. In this study, the relationship of this phase to the icosahedral quasicrystalline phase is explored through analysis of the electron diffraction patterns. It is shown that icosahedral coordinations in three orientations occur in the unit cell - one with three mutually perpendicular twofold axes along 〈1 0 0〉 of the unit cell, and two with a twofold axis along [1 0 0] and a fivefold along [0 0 1]. In this, this phase is similar to aluminum and zinc based hexagonal phases which are related to quasicrystals.     

Determination of the composition of InxGa1−xN from strain measurements

The use of incorrect GaN and InN anisotropic elastic constants and unstrained lattice constants, or the erroneous interpolation of InGaN elastic coefficients, have led to several errors in the calculations of compositions of ternary alloys based on strain measurements. To avoid this, statistically estimated elastic constants are used to calculate the correct coefficients at any composition assuming they follow Vegard’s law as happens for relaxed lattice constants. In consequence, a general equation to extract x from experimentally determined a and c cell parameters in biaxial strained wurtzite In_xGa_1−xN is proposed. The validity of this equation is confirmed: inputting structural parameters deduced from fine electron diffraction of non-phase-segregated epilayers (0.4 < x < 0.8) gives outputs that are in agreement with compositions directly measured by energy-dispersive X-ray analysis in a scanning transmission electron microscope; high-resolution X-ray diffraction analysis also supports these findings. The proposed elastic behavior of InGaN correlates well with other experiments in the literature.     

Fatigue crack propagation in an aluminium alloy at 223 K

The fatigue crack growth behaviour of a naturally aged aluminium alloy has been investigated at 223 K. Crack growth rates in a cold environment are shown to be slower than in ambient air, which is associated with a crystallographic crack path. Results are discussed on the basis of work previously proposed [Petit J, Hénaff G, Sarrazin-Baudoux C. Fracture of materials from nano to macro. In: Milne I, Ritchie RO, Karihaloo B, editors. Comprehensive Structural Integrity, vol. 6. Oxford: Elsevier; 2003. p. 211.].     

Morphology and texture evolution of FeCrAlTi-Y2O3 foil fabricated by EBPVD

An electron beam physical vapor deposition method was used to fabricate freestanding Y₂O₃ dispersive strengthened FeCrAlTi foils for high-temperature applications. The vapor incidence mode was found to have great impact on the morphology and crystallographic orientation of the foils. Under symmetric vapor incidence mode, an out-of-plane < 100> fiber texture was formed. While under asymmetric vapor incidence mode, both out-of-plane preference of < 111> direction and several in-plane preferences were developed. As the deposition proceeded, the extent of in-plane orientation increased, and the preferred out-of-plane orientation increasingly deviated from the surface normal. The vapor incidence mode played a role on the growth rate of < 100> direction and < 110> direction, by which the morphology and crystallographic orientation of grains were modified.     

Defect microstructure in heavy-ion-bombarded (0 0 0 1) ZnO

Radiation defects in oxides are complex and remain poorly understood. Here, we use transmission electron microscopy to study ZnO crystals bombarded at room temperature with heavy ions (500 keV Xe). Results reveal that the damage evolution proceeds via the formation of a band of cavities centered on ～7 nm from the sample surface. With further irradiation, a layered structure is formed, with alternating near-stoichiometric and Zn-rich layers. The anomalous intermediate peak and step in ion channeling spectra are attributed to a Zn-rich defect band and an interface between stoichiometric and Zn-rich layers, respectively. To explain these observations, we propose a damage build-up scenario involving vacancy clustering, loss of O from the surface, and peculiarities of point-defect transport through a Zn-rich defect band toward the surface.     

Structural, magnetic and electrical properties of (La0.70−xNdx)Sr0.30Mn0.70Cr0.30O3 with 0 ≤ x ≤ 0.30

The structural, magnetic and electrical properties of (La_0.70−xNd_x)Sr_0.30Mn_0.70Cr_0.30O₃ perovskites (0 ≤ x ≤ 0.30) prepared by the usual ceramic procedure were investigated. Structural Rietveld refinement revealed that these compounds crystallize in a rhombohedral perovskite structure when x = 0, 0.10 and 0.20, while for x = 0.30 the structure becomes orthorhombic (Pbnm). It was found that the substitution of La by Nd reduces the Curie temperature (T_C). The FC, ZFC, M(H) and AC susceptibility measurements show typical canted-antiferromagnetism for the Nd-doped samples, in which a ferromagnetic component coexists with predominant antiferromagnetic interactions. The values of the magnetization (M(H)) decrease very slightly when increasing the Nd content, compared to the undoped sample (M_S values at 5 T and 2 K are, respectively, 47.9, 47.3 and 47.5 emu/g for x = 0.10, 0.20 and 0.30, compared to 48.2 emu/g for x = 0), indicating that the Nd³⁺ contribution is negligible compared to the total moment of the ferromagnetic (Mn/Cr) network. The resistivity increases by several orders of magnitude with Nd-doping and the semi-conducting behaviour persists in the whole temperature range. The interaction between Mn⁴⁺–O–Cr³⁺and Cr³⁺–O–Cr³⁺ is responsible for the semi-conducting state.     

SEM and TEM characterization of magnesium hydride catalyzed with Ni nano-particle or Nb2O5

The microstructures of MgH₂ catalyzed with Ni nano-particle or Nb₂O₅ mesoporous powders are examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. For MgH₂ catalyzed with Ni, the Ni particles with the diameter smaller than 1 μm were detected on the MgH₂ particles with the diameter smaller than 5 μm by the back scattering electron (BSE) microscopy. In details, the TEM micrograph indicates that the Ni particles distribute 20 nm in diameter on MgH₂ uniformly, which was the same size as the additive doped in MgH₂ before milling. On the other hand, for MgH₂ catalyzed with Nb₂O₅, the additive particles could not be found anywhere in the BSE image. Even in the TEM micrograph by much larger magnification than the SEM micrograph, the particles corresponding to the additive cannot be observed at all. Furthermore, an energy dispersive X-ray (EDX) analysis in spots with a diameter of 20 nm indicated that the existing ratio of Mg to Nb was evaluated to 98:2, being the same as the starting ratio before milling. Therefore, the metal oxide Nb₂O₅ becomes extremely small particle that could not be observed by the present work after milling compared to metal Ni^nano.