Young's modulus sound velocity and Young's modulus of Ti-, Zr- and Hf-based amorphous alloys

The Young's modulus sound velocity (V_E) and the Young's modulus of amorphous ribbons for (Ti, Zr, Hf)_100?x (Si, Ge)_x binary and (Ti, Zr, Hf)_85?xM_x(Si, Ge)₁₅ (M = V ? VIII group transition metal) ternary systems were measured as a function of alloy composition. V_E increases with increasing silicon or germanium content and with the replacement of titanium, zirconium or hafnium by M elements except tantalum or hafnium, and tends to increase with the Debye temperature of the constituent elements themselves. E increases linearly with increasing σ_f and H_v, and ratios of σ_f/E and H_v/3E show a nearly constant value (? 0.018) for Zr_100?xSi_x and Zr_85?xM_xSi₁₅(M = Ti, V, Nb, Ta or Mo) amorphous alloys. Considering the compositional dependence of these mechanical properties (E, σ_f and H_v) and the strong correlation among them, it is suggested that (1) the short-range ordering due to the strong interaction among constituent atoms causes an increase in E, σ_f and H_v, and (2) all the early transition metal-based amorphous alloys possess a common mechanism for plastic flow.     

Characterization of vapor grown (001) GaAs1−xPx layers by selective photo-etching

The technique of selective photo-etching known for GaAs was successfully applied to (001)GaAs_0.6P_0.4 and it can also be used for the characterization of phosphorus-rich GaAs_1?xP_x layers and for GaP. Using this technique misfit dislocations in GaAs_1?xP_x up to now mainly examined with the transmission electron microscope (TEM) in the GaAs_1?xP_x transition layer could be examined in a density range which is hardly accessible for observation with the TEM. Misfit dislocations are also observed in GaP and GaAs_1?xP_x layers when these are heavily doped with nitrogen. The dislocation density of GaAs_1?xP_x layers of constant composition is compared with predictions from a model of Abrahams et al. for the dislocation density of GaAs_1?xP_x as a function of the rate of grading. Within this model our results can only be explained when the asymmetry factor m between the length to distance ratio of misfit dislocations in the transition layer is about two orders of magnitude greater than the value previously derived from TEM studies of GaAs_1?xP_x layers.     

Characterization of the optical properties of LPE InxGa1−xAsyP1−y thin layers grown on InP

A series of In_xGa_1?xAs_yP_1?y single-crystal thin layers have been grown on an InP substrate in a vertical liquid phase epitaxy furnace with a rotating slide boat system. The optical properties of these LPE quaternary alloys lattice-matched to InP have been investigated mainly by photoluminescence and electroreflectance measurements. Photoluminescence spectra of In_xGa_1?xAs_y P_1?y epitaxial layers are dominated by a strong luminescence line due to band-edge emission. At low temperatures, around 4.2 K, we have observed complicated luminescence bands with many fine structures. Electroreflectance spectra for the LPE In_xGa_1?xAs_yP_1?y layers are sufficiently broad to fulfil the low-field condition, and the analysis enabled us to determine precisely the band gap energy.     

Transformation behavior of PdAuSi metallic glasses

The transformation behavior of roller-quenched amorphous Pd_0.82?xAu_xSi_0.18 and Pd_0.835?xAu_xSi_0.165 alloys, where x ? 0.10, after rapid heating to temperatures near to or above T_g, is reported. The calorimetrically determined glass (T_g) and kinetic crystallization (T_c) temperatures both increased with x up to x ≈ 0.04. With increasing x, at x ? 0.04, T_c decreased rapidly while T_g varied little. Binary Pd_0.82Si_0.18 alloys crystallized to an fcc phase without apparent composition segregation. The tendency to phase separate at T near T_g, as manifested by small- (SAXS) and large-angle X-ray scattering and calorimetry, increased with increasing Au substitution. Pd_0.8Au_0.035Si_0.165 alloy apparently phase separated by a nucleation and growth mechanism, with a growth rate limited by the melt viscosity, to form an fcc phase dispersed in an amorphous phase which later crystallized. Pd_0.74Au_0.08Si_0.18 alloy phase separated initially to two melts, each of which later crystallized in turn. The initial separation behavior was generally consistent with the predictions of the spinodal theory but with some deviation from Cahn's linear relation.     

Network topological thresholds in gallium doped As–Te glasses – Electrical and thermal investigations

Electrical switching and differential scanning calorimetric studies are undertaken on bulk As₂₀Te_80−xGa_x glasses, to elucidate the network topological thresholds. It is found that these glasses exhibit a single glass transition (T_g) and two crystallization reactions (T_c1 & T_c2) upon heating. It is also found that there is only a marginal change in T_g with the addition of up to about 10% of Ga; around this composition an increase is seen in T_g which culminates in a local maximum around x = 15. The decrease exhibited in T_g beyond this composition, leads to a local minimum at x = 17.5. Further, the As₂₀Te_80−xGa_x glasses are found to exhibit memory type electrical switching. The switching voltages (V_T) increase with the increase in gallium content and a local maximum is seen in V_T around x = 15. V_T is found to decrease with x thereafter, exhibiting a local minimum around x = 17.5. The composition dependence of T_c1 is found to be very similar to that of V_T of As₂₀Te_80−xGa_x glasses. Based on the present results, it is proposed that the composition x = 15 and x = 17.5 correspond to the rigidity percolation and chemical thresholds, respectively, of As₂₀Te_80−xGa_x glasses.     

The order parameter model for structural relaxation in glass

The order parameter model assumes that the state of a glass or liquid depends on T, P and a number of order parameters Z_i. Structural relaxation is due to the kinetically impeded evolution of the order parameters following a rapid change in T or P. The linear relaxation function for the evolution of property Q (V or H) in response to a change in X (T or P) is of the form φ_QX = Σ_igⁱ_QX exp(?tτ_i). Expressions are derived for the qeighting coefficients gⁱ_QX in terms of the dependences of V and H on the various order parameters. It is shown that gⁱ_VT = gⁱ_HP and that gⁱ_VTgⁱ_HP/gⁱ_VPgⁱ_HT = II, where II is the Prigogine-Defay ratio. The corresponding relations among the relaxation functions are φ_VT = φ_HP and φ_VTφ_HP/φ_VPφ_HT ? II. The predictions of the order parameter model for structural relaxation are compared with and found generally to agree with existing literature data. A number of suggestions for future investigations to test this model are made.     

Raman line shape analysis as a mean characterizing molecular glass-forming liquids

Raman scattering spectra in glass forming toluene were studied in the temperature range 50–323 K with the goal of extracting information about homogeneous, inhomogeneous and orientational broadening. It was found that the temperature dependence of inhomogeneous line width allows one to depict two peculiar temperatures: T_A and T_g, where T_g is the glass transition temperature and T_A is the temperature of transition from an Arrhenius-like to a non-Arrhenius behavior for the α-relaxation time dependence on temperature, τ_α(T). Temperature dependence of the orientational phase loss time τ_OPL was found to correspond well to τ_α at T > T_A and continues approximately Arrhenius behavior for lower temperature in contrast to τ_α(T). Also, a comparative analysis of homogeneous broadening of polarized and depolarized lines was done, which provided an estimation of the orientational broadening γ_NL(T). The found γ_NL(T) decreases linearly as the temperature decreases and goes to zero at T ~ T_c, where T_c is the critical temperature in framework of the mode-coupling theory (note that T_c is close to other peculiar temperatures T_B and T_β, but we did not intent to distinguish among them in the present work). Thus, it was shown that the Raman line shape analysis in molecular glass forming materials allows one to extract peculiar temperatures: T_A, T_g, and, probably, T_c.The test of the possibility to use a probe molecule for the Raman line shape analysis has revealed that the extracted data for probe molecule lines do not characterize the host matrices, at least in the low-viscous state (T > T_A).     

Ionic conductivity of cold-pressed ceramics from grinding of R0.95M0.05F2.95 solid electrolytes (R = La,Nd; M = Ca,Sr, Ba) synthesized by reaction in melt

Cold-pressed ceramics of fluorine-conducting solid electrolytes La_{1 ? y} M _y F_{3 ? y} (M = Ca, Sr, Ba) and Nd_{1 ? y} Ca _y F_{3 ? y} with y = 0.95 have been synthesized in a melt of RF₃ (R = La, Nd) and MF₂ components in a fluorinating atmosphere and ground in a ball mill. The as-prepared ceramics require annealing, during which their porosity decreases and the conductivity is stably increased (by a factor of 250 for the R _{1 ? y} M _y F_{3 ? y} composition at 293 K). The Nd_0.95Ca_0.05F_2.95 and Nd_0.95Ca_0.05F_2.95 compositions have a maximum ionic conductivity σ(293 K) ～ 5 × 10^?6 Sm/cm. This value is larger (by a factor of about 10) than σ (293 K) for the R _{1 ? y} M _y F_{3 ? y} ceramics of tysonite phases prepared by mechanochemical synthesis with the cold pressing of reaction products.     

A new criterion for the glass-forming ability of liquids

Based on theoretical calculations using the fragility concept and the nucleation theory for a model glass-forming system, we propose a dimensionless criterion, ?, expressed by T_rg(ΔT_x/T_g)^a, with T_rg, the reduced glass-transition temperature, ΔT_x, the width of the supercooled liquid region when heating a glass, T_g, the glass transition temperature, and a, the exponent. The application of this simple criterion to various glasses, including network, metallic, and molecular glasses (except pure water), indicates an excellent correlation between the critical cooling rate R_c and ? in a Log R_c-? single master plot with a = 0.143.     

An analysis of the radial distribution function of SIOx

A theory is presented for the short-range order (sro) in the SiO_x alloy system for 0?x?2. The parameters of the sro are taken to be fixed by the properties of amorphous Si and SiO₂, except that the probability of an Si atom having (i?1) oxygen neighbors is left as a free parameter, C_i(x), for i=1 through 5. The areas of the first three peaks in the radial distribution function (RDF) of SiO_x are calculated as a function of x and C_i(x). It is shown that the RDF can be used to differentiate between the two models proposed for the sro in SiO_x namely the SiSiO₂ mixture model and the random bonding model. In the case of SiO powder, a mixture model at the atomic level is found to be consistent with the RDF. It is suggested that accurate RDF's of SiO_x films, which are not currently available, would be useful in determining the sro of the alloy system. The present theory may be extended to analyze the GeO_x and SnO_x alloy systems.     

Occurrence of Kondo-like behavior in electrical-conductivity of Al70Pd20+xMn10−x (x = 0, 1 and 2) icosahedral quasicrystals

Zero-field and in-field (at 8 T) conductivity vs temperature (σ-T), magneto-resistance (Δρ/ρ), magnetization vs temperature (M-T) and magnetization vs field (M-H) of unannealed Al₇₀Pd₂₀Mn₁₀ and annealed Al₇₀Pd₂₀Mn₁₀, Al₇₀Pd₂₁Mn₉ and Al₇₀Pd₂₂Mn₈ quasicrystalline alloys have been studied in the temperature range of 1.4-300 K. Room temperature resistivity and the low-temperature magneto-resistance show a correlation with the corresponding magnetization. The σ-T for all the studied samples shows a pair of minima and maxima. The σ-T maxima show a correlation with the total magnetization. The analysis shows that σ-T is dominated by weak-localization effects. The minima are arising due to competing inelastic scattering times τ_i (e-ph scattering in the dirty metallic limit, τ_i ∝ T⁻²) and the Kondo-type spin-flip scattering time τ_sf whereas the maxima has been attributed to ‘Kondo-maxima’, occurring due to maxima in the spin-flip rate . The magneto-resistance of these samples shows a changeover from negative to positive where the negative component shows a correlation with the magnetization of the sample. The values of parameters derived from refinement give spin-flip scattering fields, which are found to be correlated with the total sample magnetization.     

Growth of Nd-doped YVO4 single crystals along 〈1 0 0〉tetra by the anisotropic heating floating zone method

Nd-doped YVO₄ single crystals were grown along 〈1 0 0〉_tetra by the anisotropic heating floating zone (AHFZ) method. The relationship between the lamp power ratio (P_C/P_A) and the aspect ratio (c/a-axis diameter, D_C/D_A) of the grown crystals was investigated. D_C/D_A increased from 1.01 to 1.52 with increasing P_C/P_A from 0.7 to 1.5. The crystals grown by the AHFZ method developed a cylindrical shape with decreasing P_C/P_A, whereas those grown by a conventional FZ method developed an elliptical cylinder shape.     

293-K conductivity optimization for single crystals of solid electrolytes with tysonite structure (LaF3): I. Nonstoichiometric phases R 1−yCayF3−y (R = La-Lu,Y)

The systematic optimization of single-crystal fluoride-conducting solid electrolytes R _{1 ? y} Ca _y F_{3 ? y} with a tysonite type structure (LaF₃) with respect to the conductivity at room temperature, σ(293 K), is based on high-temperature measurements of σ(T) of stoichiometric fluorides of rare earth elements, RF₃ (R = La-Nd), in dependence of the radius \(R^{3 + } (r_{R^{3 + } } )\) ; two-component stoichiometric La_{1 ? y} R _y F₃ phases (R = Pr, Nd) in dependence on the average cation radius (r _cat ); and two-component nonstoichiometric phases R _{1 ? y} Ca _y F_{3 ? y} (R = La-Lu, Y) in dependence of the CaF₂ content. The optimization of the composition with respect to thermal stability is based on studying the phase diagrams of CaF₂-RF₃ systems and the behavior of R _{1 ? y} Ca _y F_{3 ? y} crystals upon heating when measuring temperature dependences σ(T). Singlecrystal samples of a number of investigated R _{1 ? y} Ca _y F_{3 ? y} compounds has σ(293 K) values high enough to be applied in solid-state electrochemical devices operating at room temperature (chemical sensors, fluorine-ion batteries, and accumulators) and in devices subjected to thermal cycling.     

Properties and structure of cesium phosphate glasses

A series of Cs-phosphate glasses, xCs₂O(1−x)P₂O₅, where 0?x?0.60, were prepared. The glass transition temperature (T_g) decreases with the initial addition of Cs₂O to P₂O₅, from 637 K at x=0 to 472 K at x=0.16. There is little change in T_g with further additions of Cs₂O up to x=0.60. The ³¹P magic angle spinning nuclear magnetic resonance (MAS NMR) spectra show that Cs₂O additions systematically convert the cross-linked ultraphosphate network of ν-P₂O₅ to a chain-like metaphosphate structure as x approaches 0.50. The ¹³³Cs MAS NMR spectra show a 90 ppm increase in isotropic chemical shift (δ_iso) with increasing Cs₂O content, which indicates a decrease in the average electron density around the Cs⁺ ions, more covalent Cs-O bonding, and a shorter average Cs-O bond length. The physical properties and spectroscopic results are interpreted using a structural model that considers the effects of composition on the average coordination environment of Cs⁺ ions.     

Electrical switching in As-Te-Ag system-composition and temperature dependence

The current-voltage characteristics related to switching phenomena in silver doped arsenic telluride glasses, As₂₀Te_80−xAg_x and As₄₀Te_60−xAg_x, have been investigated over a wide composition range (4?x?14). The samples are found to show threshold switching behavior with the number of switching cycles withstood by the samples depending on the ON state current. The switching voltages are found to decrease with increase in silver content and a sharp minimum is seen at the composition x=12 for the As₂₀Te_80−xAg_x glasses and x=11 for the As₄₀Te_60−xAg_x glasses. An effort has been made to understand the observed composition dependence on the basis of increase in the conductance of the samples with silver addition and local structural effects.     

On the compositional dependence of the optical gap in amorphous semiconducting alloys

It is found that the optical gap E_AB for amorphous A-B alloys can be determined by the energy gap E_A for element A and E_AB for the element B in the equation E_AB(Y) = YE_A + (1?Y) E_B where Y is the volume fraction of element A. Calculations based on a random bond network agree with experiments for SiGe, SbSe, and AsTe films (class A). Calculations based on a chemically ordered bond network which tends to form microscopic molecular species gree with experimental results for the AsSe, AsS, GeTe and Sb₂Se₃As₂Se₃ systems (class B). In contrast to the above systems, agreement with experiment is not obtained for the TeSe, As₂Te₃As₂Se₃ and GeTe₂GeSe₂ systems which contain atoms of both Te and Se (class C). The classification into three types (classes A, B and C) is consistent with the calculation based on effective medium percolation theory which interprets the compositional dependence of the conductivity of chalcogenide glasses.     

Nuclear magnetic resonance studies of the glasses in the system K2OB2O3P2O5

B¹¹ NMR spectra have been used to study the structure of glasses in the system K₂OB₂O₃P₂O₅. The results indicate that the glasses do not contain an appreciable number of boron atoms in BO₃ units with one or two non-bridging oxygens. The fraction N₄ of boron atoms in BO₄ units is measured and analyzed according to a structural model containing the following elements. (1) If the binary borophosphate system forms glasses, they consist of a borophosphate (BPO₄) network and a borate network for K<1, or a borophosphate (BPO₄) network and a phosphate network for K>1, where K = mol.% P₂O₅/mol.% B₂O₃. (2) The conversion rates of BO₄ units (i.e. the rate of production or destruction by added oxygens) in the borate network and the borophosphate (BPO₄) network are given as (+2) and (?0.38), respectively. (3) K⁺¹ ions are proportionally shared between the two networks; (i.e. between the borate and borophosphate (BPO₄) networks for K<1, and between the phosphate and borophosphate (BPO₄) networks for K>1).     

Investigation of the interaction of dimethyl sulfoxide with lipid membranes by small-angle neutron scattering

The influence of dimethyl sulfoxide (CH₃)₂SO (DMSO) on the structure of membranes of 1,2-dimiristoyl-sn-glycero-3-phosphatidylcholine (DMPC) in an excess of a water-DMSO solvent is investigated over a wide range of DMSO molar concentrations 0.0 ≤ X _DMSO ≤ 1.0 at temperatures T = 12.5 and 55°C. The dependences of the repeat distance d of multilamellar membranes and the thickness d _b of single vesicles on the molar concentration X _DMSO in the L _β’ gel and L _α liquid-crystalline phases are determined by small-angle neutron scattering. The intermembrane distance d _s is determined from the repeat distance d and the membrane thickness d _b. It is shown that an increase in the molar concentration X _DMSO leads to a considerable decrease in the intermembrane distance and that, at X _DMSO = 0.4, the neighboring membranes are virtually in steric contact with each other. The use of the deuterated phospholipid (DMSO-D6) and the contrast variation method makes it possible, for the first time, to determine the number of DMSO molecules strongly bound to the membrane.     

X-ray and neutron diffraction study of the defect crystal structure of the as-grown nonstoichiometric phase Y0.715Ca0.285F2.715

This work begins a series of papers aimed at studying the defect structure of nonstoichiometric phases R _{1 ? y} Ca _y F_{3 ? y} with a tysonite-type (LaF₃) structure. In the single-crystal structure of Y_0.715Ca_0.285F_2.715 with a tysonite-type small unit cell (sp. gr. P6₃/mmc, a = 3.9095(2) Å, c = 6.9829(2) Å; Z = 2; R _w = 2.16%), the displacements of Y³⁺ cations and F^2? anions from 6₃ symmetry axes were observed for the first time. The X-ray diffraction pattern shows weak satellites insufficient for structural calculations. The LaF₃ structure type is stabilized up and down on the temperature scale due to anion vacancies and the symmetrizing effect of Ca²⁺ cations lying on 6₃ symmetry axes. At 120°C the fluoride-ion conductivity in the nonstoichiometric phase Y_0.715Ca_0.285F_2.715 is five orders of magnitude higher than that in the stoichiometric phase β-YF₃. The transition to a superionic state is caused by a deviation from stoichiometry and is not associated with reconstructive phase transformation.     

Crystal growth and defect crystal structure of CdF2 and nonstoichiometric phases Cd1 − x R x F2 + x (R = rare earth element or in). 5. Crystal structure of as-grown Cd0.9R0.1F2.1 (R = La-Nd) single crystals: Nanoclusters of structural defects

As-grown Cd_0.9 R _0.1F_2.1 (R = La-Nd) crystals were assigned to the CaF₂ structure type and their structure was determined by X-ray diffraction. A new octacubic cluster of structural defects in Cd_0.9 R _0.1F_2.1 phases is proposed. The changes in the anionic motif of the Cd_0.9 R _0.1F_2.1 phase can be explained as a result of the formation of tetrahedral [Cd_{4 ? n} R _n F₂₆] and inverse octacubic [Cd_{14 ? n} R _n F₆₈] clusters with, respectively, tetrahedral and cuboctahedral anionic groups as cores. It is established that fluctuations of the La concentration in the cross section of a Cd_0.9La_0.1F_2.1 crystal boule do not exceed 2.7%.