Structure and correlation in liquid alloys by X-ray and neutron diffraction

A method for obtaining information about correlation in a liquid or amorphous alloy is presented. The explicit structure in a binary could in principle be determined from three independent diffraction patterns. It is relatively much simpler to measure and analyse the x-ray and neutron intensity patterns and with these alone obtain considerable correlation information, even if more than two atom types are present, by calculating the ratio of the two experimental radial distributions. For the binary the relevance of the ratio derives from the fact that each distribution is a sum of the radial distributions of the three types of atom-pairs, each term being weighted by the appropriate product of scattering amplitudes. The structure of the sample can be analysed by comparing the ratio for any interatomic distance to the values it would have for pure A-A, pure B-B, pure A-B, and random pairing. In a true liquid the results are semiquantitative. In an alloy with well-defined short-range order, the correlation of these close pairings can be clearly determined. Results are shown for liquid NaK and vitreous silica. For any alloy the experimental results would serve to test structural models.     

Polymorphism and chevron layer structure of an antiferroelectric liquid crystal studied by X-ray diffraction

We report X-ray diffraction experiments performed on an antiferroelectric compound exhibiting a very rich polymorphism (). The structural study of the unknown phases only allows us to exclude some phenomenological models. The use of oriented planar samples prepared between solid glass plates generate by cooling from the phase a chevron structure of tilted layers already well characterized for the phase. The extensive analysis of the evolution of the chevron structure through the numerous smectic-smectic phase transitions provides some original information in three distinct areas: fundamental data on the important physical parameters in the chevron structure formation, detection of the smectic-smectic phases transition by small change of the chevron structure, and information on the local molecular order induced by the alignment layer (interaction with a rubbed polymer). Received: 13 November 1996 / Received in final form: 19 January 1997 / Accepted: 30 January 1998     

Surface and transport properties of Au-In liquid alloys

Thermodynamic quantities on Au-In liquid alloys have been used as the input data for the interaction parameter calculations in the framework of the complex formation model (CFM). Once the interaction energies are computed the surface (surface tension and surface composition) and transport properties (chemical diffusion and viscosity) as well as the microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) have been calculated. The concentration and temperature dependent surface tension values have been compared with our new set of experimental data, obtained by the large drop method in the temperature range of T = 1273-1493 K. The anomalous change of surface tension for some alloy compositions may be attributed to a retention of order in the Au-In melts which is similar to the atomic arrangement in solid Au-In.     

High-pressure phases of plutonium monoselenide studied by X-ray diffraction

Abstract

Plutonium monoselenide was studied under high pressure up to 47 GPa, at room temperature, using a diamond anvil cell in an energy dispersive X-ray diffraction facility. At ambient pressure, PuSe has the NaC1-type (B1) structure. The compound has been found to undergo a second-order crystallographic phase transition at around 20 GPa. This phase can be described as a distorted B1 structure, with a rhombohedral symmetry. PuSe transforms to a new phase at around 35 GPa, which can be indexed in the cubic CsCl-type (B2). The volume collapse at this phase transition is 11%. When releasing pressure, we observed a strong hysteresis to the inverse transformation down to 5 GPa. From the pressure-volume relationship, the bulk modulus has been determined to B ₀ = 98 GPa and its pressure derivative as B ₀ = 2.6. These results are compared to those obtained with other actinide monmictides and monochalcogenides.     

Structure and magnetic properties of FeMnAl alloys investigated by Mössbauer spectroscopy and X-ray diffraction

The system (Fe_0.88Mn_{0.12 1–x} Al _x has been investigated in a concentration range from 5 to 14 at.% Al. We applied Mössbauer spectroscopy in the temperature range from 4 up to 900 K and X-ray diffractometry at room temperature. The as-cast samples show a bcc phase for all concentrations and exhibit broadened six-line Mössbauer spectra typical for disordered alloys. The Mössbauer spectra during a high temperature treatment show dramatic changes. These are due to ordering processes appearing at temperatures above 700 K. As an example of the observed changes, we present results obtained for the alloy withx= 14 at.% Al.     

Lattice dynamics in two-photon-excited CdS studied by picosecond time-resolved X-ray diffraction

Lattice dynamics and radiative processes in single-crystal cadmium sulfide induced by two-photon excitation with a femtosecond laser are investigated. The development of lattice expansion is directly observed by picosecond time-resolved X-ray diffraction. The obtained lattice dynamics are explained on the basis of a thermally induced impulsive-strain model. The model calculation indicates that two- and more-photon absorption processes occur and that reflectivity rapidly increases under laser irradiation. In photoluminescence spectroscopy, the spectra for TW cm⁻² excitation are shifted to lower energy and show an additional shoulder at 2.35 eV. Furthermore, emission due to Fabry-Perot laser modes with self-formed cavities was observed under 11 TW cm⁻² excitation. The discrepancy between carrier densities deduced from the lattice expansion and the PL spectra indicates that the predominant process at a higher carrier density is not radiative recombination, but Auger recombination followed by lattice heating.     

The optical properties and electronic structure of liquid mercury and mercury-indium alloys

Recent experimental values for the optical constants of liquid mercury are shown to differ appreciably from free electron values. An apparent violation of the sum rule by the experimental results can be explained by considering the influence of the core electrons. The optical constants of liquid mercury-indium alloys (4.9–33.4 at. % In) show some agreement with free electron theory with a suitable choice of relaxation time. The significance of these results for Mott's (1966) theory of the electronic structure of liquid mercury is discussed.     

Surface segregation in liquid Ga-In alloys studied by bombardment-induced photon emission

The surface composition in liquid Ga-In alloys bombarded by Ar⁺ ions is mostly determined by thermal segregation effects. Photon emission from sputtered atoms was successfully used to study the surface segregation. The coordination numbers characterizing the surface layer of liquid Ga-In alloys were found.     

Structure of metal nanowires in nanoporous alumina membranes studied by EXAFS and X-ray diffraction

The structure of nanowires of different metals grown within nanoporous alumina membranes has been studied by EXAFS, WAXS and high energy X-ray diffraction. Nanowires of gold, silver, copper and iron adopt the lattice structure and bond distances of the bulk metals. Cobalt nanowires on the other hand were composed of a mixture of hcp phase, stable at room temperature, and fcc phase, which in bulk cobalt is normally stable only at high temperatures, in a ratio depending on the pore size. The nanowires are non-continuous but are made of nanocrystallites whose shape and size was found to depend strongly on the metal. All the metals except gold showed the presence of a preferred orientation which was slight in the case of Ag and Cu but much stronger in the case of iron and cobalt nanowires. Received 30 November 2000     

Valence bands of aluminium noble-metal alloys studied by X-ray photoelectron spectroscopy

The valence bands of aluminium noble-metal alloys are studied by XPS using Al Kα-radiation. The alloys were prepared by evaporation followed by interdiffusion of the components under ultra-high vacuum within the analyzer chamber of the spectrometer. In the absence of surface contamination the alloys exhibit more intense spectra, with sharper features, than those observed for previously studied bulk samples.     

Precipitation in silicon wafers after high temperature preanneal studied by X-ray diffraction methods

We have investigated oxygen precipitation in Czochralski silicon wafers focusing on influence of nucleation temperature and high temperature pre-anneal during common three step treatment. Thick Si wafers were studied mainly by x-ray diffraction in Laue transmission geometry using Mo x-ray tube, but were also compared to reciprocal space maps obtained in Bragg reflection geometry. The analysis of measured diffraction scans in Laue geometry was performed by means of Takagi equations and statistical dynamical theory of diffraction. From the simulated Laue diffraction curves we find the size of the individual defect area and the fraction of strain area volume in the wafer. The results obtained from x-ray diffraction were compared to loss of interstitial oxygen according to infrared absorption spectroscopy and the size of SiO₂ precipitate core was estimated. These techniques are in agreement with transmission electron microscopy images.     

Structure and dynamics of clean and adsorbate-covered crystal surfaces studied by surface X-ray diffraction

Received: 24 March 1998/Accepted: 21 August 1998     

An X-ray diffraction study of liquid chlorine

The static structure of liquid chlorine at room temperature is investigated by means of X-ray diffraction. From comparisons with previous neutron and X-ray data, it appears that most of the discrepancies present in the liquid structure factor between neutron and X-ray studies have been removed. Some experimental difference in the two structure factors still remains and one possible explanation is that the electron density distribution of liquid chlorine differs from that derived within the independent atom approximation.     

Phase transitions in diglyceride monolayers studied by computer simulations,pressure-area isotherms and X-ray diffraction

Summary 1,2-sn-diglyceride monolayers exhibit unique and complex phase transitions as a function of surface pressure. The dynamical response of the layer on expanding the film has been investigated by computer simulations, (π-A) isotherms and grazing-incidence X-ray diffraction. Good agreement is found between the simulations and experiments. The Langmuir film undergoes two phase transitions occurring at 38.3 and 39.8 ?²/molecule. The transition at low surface density is associated with a tilt of ≈14° in the direction close to nearest neighbour. The first transition is unique for the diglyceride molecules and has not been observed for other amphiphilic molecules. It is driven by a competition of hydrophobic/hydrophilic and intra/intermolecular forces and can be pictured as a ?seesaw? mechanism. Due to the close packing of the chains at high surface pressure, thesn-1 ester group aligns with the alkyl chain, and only thesn-2 ester group is favoured to lay at the aqueous interface. Hydrophilic forces attract thesn-1 ester group, but its motion towards the aqueous subphase is hindered by intra- and intermolecular chain interactions. On expansion, the intermolecular interaction decreases, and at the first transition, the intramolecular interaction between the two chains is strong enough to cause a ?swelling? of the molecules. The diffraction pattern determined in the different mesophases reveals that the layer maintains its hexagonal structure up to the second phase. Concomitant with the tilt, the structure relaxed from a hexagonal to a distorted hexagonal lattice. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Mass and thermal transport in liquid Cu-Ag alloys

In this paper, the diffusion, thermodynamic and thermotransport properties in Cu–Ag liquid alloys are extensively investigated with molecular dynamics over a wide composition and temperature range. The simulations are performed with the most reliable EAM potential. The Green-Kubo formalism is employed for calculating transport properties. It is found that the reduced heat of transport in Cu–Ag is very small (about 0.10?eV in absolute value) and almost temperature independent. Further it is found that the interdiffusion coefficient together with both self-diffusion coefficients are almost composition independent. In Cu–Ag, the thermodynamic factor is found to be less than unity whereas the Manning factor is greater than unity (with significant composition and temperature dependence) and their product is very close to 1.     

Kapitza conductance of Bi/sapphire interface studied by depth- and time-resolved X-ray diffraction

We present Kapitza conductance measurements of the bismuth/sapphire interface using depth- and time-resolved X-ray diffraction, for Bi film thicknesses ranging from 65 to 284 nm. Our measurements provide complementary information about heat transport in the films; we directly observe the thinnest film to be uniformly heated within 1 ns, whereas the thickest film sustains a large near-surface temperature gradient for several ns. The deduced Kapitza conductance is 1950 W/cm²/K. This value is close to the theoretical prediction using the radiation limit.     

Short-range order structure and free volume distribution in liquid bismuth: X-ray diffraction and computer simulations studies

ABSTRACT

The structure of liquid bismuth was studied by X-ray diffraction and computer simulation methods. The contraction of the atomic structure within the first coordination sphere in the temperature interval of 575-1225?K is reported. The temperature dependencies of the coordination numbers and of the free volume are analysed. On the basis of the temperature dependencies of the free volume, the temperature dependencies of viscosity and the self-diffusion coefficient were calculated to be in the ranges from 1.17 to 0.86?mPa?s and from 2.18 × 10^?9 to 5.44 × 10^?9?m²/s, respectively. The free volume – extracted results are in fair agreement with the experimental data and with the results obtained in the molecular dynamics simulations.     

Separation of enantiomers in a diol monolayer studied by fluorescence microscopy and grazing incidence X-ray diffraction

Summary Monolayers of a racemic mixture and of the pure S- and R-enantiomers of 3-hexadecyloxy-propane-1,2-diol have been investigated by fluorescence microscopy and grazing incidence X-ray diffraction. Above the transition pressureΠ _c domains with a polygonal shape appear. On compressing the monolayers shape instabilities occur. While the spirals of the S-enantiomer turn clockwise and the spirals of the R-enantiomer turn counterclockwise, the spirals from one domain of the racemate exhibit opposite handedness. This behaviour is explained by a separation of enantiomers on the molecular level. At all pressures investigated the enantiomers exhibit an oblique lattice. The tilt angle of the molecules decreases with increasing pressure. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

CO dissociation on NiZr alloys studied by photoemission and electronic structure calculations

We present a photoemission study of the CO adsorption on amorphous NiZr alloys at various compositions. Our results indicate a distinct enhancement of dissociative adsorption even at very low Zr concentrations. These observations are supported by LCAO-type calculations of potential energy surfaces, which suggest a strong increase of backdonation into antibonding $\text{CO 2π}{}^1$ type orbitals near Zr sites.