Structure of liquid SiO2: a measurement by high-energy x-ray diffraction

The x-ray structure factor for liquid SiO2 has been measured by laser heating of an aerodynamically levitated droplet. The main structural changes of the melt compared to the room temperature glass are associated with an increase in the size of the SiO4 tetrahedra, indicating a small reduction in the average Si-O-Si bond torsion angle and an expansion of the network between 5 and 9 A. Strong directional bonds with little high temperature broadening and a high degree of intermediate range order are found to persist in the liquid state.     

Local structure of supercooled liquid Ga90In10 alloy

The local structure of liquid and supercooled liquid Ga₉₀In₁₀ alloy was studied by the X-ray absorption fine-structure (XAFS), X-ray diffractometer (XRD) and the ab initio molecular dynamics (AIMD) simulation. The ab initio FEFF8 code was applied to simulate the In k-edge X-ray absorption near edge structure (XANES) spectrum of the melt. The local atomic arrangement models have been obtained. The results indicate that the structural evolution from the liquid to supercooled liquid Ga₉₀In₁₀ alloy is mainly caused by the change of the In atom local structure. As the temperature decreases, the nearest neighbor coordination number decreases and the nearest neighbor interatomic distance increases. The nearest neighbor coordination number around In atom decreases from 13 to 12, and there is obvious Ga aggregation under the undercooled condition.     

In situ surface x-ray diffraction studies of homoepitaxial electrochemical growth on Au(100)

Direct in situ x-ray surface scattering studies of growth at a solid-liquid interface are demonstrated using the homoepitaxial electrodeposition on Au(100) as an example. With decreasing potential transitions from step-flow to layer-by-layer growth, manifested by layering oscillations in the x-ray intensity, then to multilayer growth, and finally back to layer-by-layer growth were observed. This complex growth behavior can be explained by the effect of anion coadsorbates and the potential-dependent Au surface reconstruction on the Au surface mobility.     

Structural study of supercooled liquid silicon

For many years, theoretical studies using model and ab initio potentials have predicated the existence of a liquid/liquid phase transition in silicon, based on a continuous change of the liquid A5 structure to A4. In contrast, we report here a quantitative analysis of data from high-energy X-ray diffraction measurements of containerlessly-processed supercooled liquid silicon that demonstrates that the fractions of regions with A5 and A4 order instead remain essentially constant with supercooling, but that the coherence length of the A5 order increases.     

In situ powder diffraction study of belite sulfoaluminate clinkering

Belite sulfoaluminate (BSA) cements have been proposed as environmentally friendly building materials, as their production may release up to 35% less CO₂ into the atmosphere when compared with ordinary Portland cement fabrication. However, their formation mechanism has not been studied in detail so far. Here, an in situ high‐temperature high‐resolution synchrotron X‐ray powder diffraction study is reported. Two types of BSA clinkers have been characterized, both containing 50–60 wt% C₂S and 20–30 wt% C₄A₃ as main phases. One type is iron‐rich and a second type (with different phase assemblage) is aluminium‐rich. Furthermore, the C₂S phase reacts slowly with water, thus activation of this compound is desirable in order to enhance the mechanical strength development of the resulting cements. To do so, iron‐rich BSA clinkers have been doped with minor amounts of B₂O₃ and Na₂O to promote stabilization of α‐forms of C₂S, which are more reactive with water. The decarbonated raw materials were loaded into Pt tubes and heated to between 973 K and 1673 K, and patterns were collected using a high‐energy synchrotron beam of wavelength λ = 0.30 Å. The thermal stability of Klein's salt in these clinkers has been clarified. Several reactions have been followed: formation and decomposition of Klein's salt, melting of aluminates and ferrite, and polymorphic transformations of dicalcium silicate: ‐C₂S →α‐C₂S. Changes in mineralogical phase assemblages at a given temperature owing to the addition of minor amounts of selected elements have also been determined.     

Surface structure of In/Si(1 1 1) studied by reflection high-energy positron diffraction

We have investigated a quasi-one-dimensional structure of In/Si(1 1 1) surface using reflection high-energy positron diffraction (RHEPD), which is sensitive to the topmost surface structure under the total reflection condition. From the rocking curves, we found that In atoms are located at two different vertical positions, i.e., 0.99 Å and 0.55 Å from the Si zigzag chain in both 4 × 1 (210 K) and 8 × 2 (60 K) phases.     

锐钛矿金红石的高温原位X射线衍射研究

对TiO₂粉末进行了空气和真空条件下从室温到1200℃的加热原位X射线衍射实验, 得到了空气和真空条件下微米级锐钛矿颗粒转变为金红石的起始温度分别为850℃ 和855℃; 分别修正了空气条件下锐钛矿在(27–850℃)范围和金红石在(900–1200℃) 范围内的晶胞参数和真空条件下锐钛矿在(27–850℃)范围和金红石在(950–1200℃) 范围的晶胞参数, 从而得到了晶胞参数随温度变化的关系, 得到了锐钛矿和金红石在空气中和真空中的热膨胀系数, 并总结了热膨胀系数随温度变化的规律. 室温下锐钛矿在空气条件下的热膨胀系数为 α_a=4.55063×10^-6/℃, α_c=7.7543×10^-6/℃, β=16.85836×10^-6/℃; 真空下为 α_a=4.69429×10^-6/℃, α_c=9.02850×10^-6/℃, β=18.69688×10^-6/℃. 室温下, 金红石在空气条件下的热膨胀系数为 α_a=6.81243×10^-6/℃, α_c=8.71644×10^-6/℃, β=22.22178×10^-6/℃; 真空条件下为 α_a=6.05834×10^-6/℃, α_c= 8.39280×10^-6/℃, β=20.52362×10^-6/℃. 关键词： 2')" href="#">TiO₂ 原位X射线衍射 相转变 热膨胀     

Anisotropic local stress and particle hopping in a deeply supercooled liquid

The origin of the microscopic motions that lead to stress relaxation in deeply supercooled liquid remains unclear. We show that in such a liquid the stress relaxation is locally anisotropic which can serve as the driving force for the hopping of the system on its free energy surface. However, not all hoppings are equally effective in relaxing the local stress, suggesting that diffusion can decouple from viscosity even at the local level. On the other hand, orientational relaxation is found to be always coupled to stress relaxation.     

Extended x-ray absorption fine structure study of local structure and atomic correlations of tellurium nanoparticles

Extended x-ray absorption fine structure measurements were performed on trigonal tellurium (t-Te) and tellurium nanoparticles in very thin films. Twofold coordinated chains, much like those in t-Te, exist even in the nanoparticles, but covalent bonds or intrachain interactions are stronger than those of t-Te as shown by a shorter bond length and higher Einstein temperature. The interchain coordination number of the nanoparticles is about half that of t-Te, suggesting reduction of interchain interactions.     

In situ high-pressure X-ray diffraction study of densification of a molecular chalcogenide glass

Structural mechanisms of densification of a molecular chalcogenide glass of composition Ge_2.5As_51.25S_46.25 have been studied in situ at pressures ranging from 1 atm to 11 GPa at ambient temperature as well as ex situ on a sample quenched from 12 GPa and ambient temperature using high-energy X-ray diffraction. The X-ray structure factors display a reduction in height of the first sharp diffraction peak and a growth of the principal diffraction peak with a concomitant shift to higher Q-values with increasing pressure. At low pressures of at least up to 5 GPa the densification of the structure primarily involves an increase in the packing of the As₄S₃ molecules. At higher pressures the As₄S₃ molecules break up and reconnect to form a high-density network with increased extended-range ordering at the highest pressure of 11 GPa indicating a structural transition. This high-density network structure relaxes only slightly on decompression indicating that the pressure-induced structural changes are quenchable.     

Probing the local order of single phospholipid membranes using grazing incidence x-ray diffraction

We report the first grazing incidence x-ray diffraction measurements of a single phospholipid bilayer at the solid-liquid interface. Our grazing incidence x-ray diffraction and reflectivity measurements reveal that the lateral ordering in a supported DPPE (1, 2-Dipalmitoyl-sn-Glycero-3-Phosphoethanolamine) bilayer is significantly less than that of an equivalent monolayer at the air-liquid interface. Our findings also indicate that the leaflets of the bilayer are uncoupled in contrast to the scattering from free standing phosphatidylcholine bilayers. The methodology presented can be readily implemented to study more complicated biomembranes and their interaction with proteins.     

Neutron powder diffraction and high-pressure synchrotron x-ray diffraction study of tantalum nitrides

Tantalum nitride(TaN) compact with a Vickers hardness of 26 GPa is prepared by a high-pressure and hightemperature(HPHT) method. The crystal structure and atom occupations of WC-type TaN have been investigated by neutron powder diffraction, and the compressibility of WC-type TaN has been investigated by using in-situ high-pressure synchrotron x-ray diffraction. The third-order Birch–Murnaghan equation of state fitted to the x-ray diffraction pressure–volume(P–V) sets of data, collected up to 41 GPa, yields ambient pressure isothermal bulk moduli of B'_0= 369(2) GPa with pressure derivatives of B 0= 4 for the WC-type TaN. The bulk modulus of WC-type TaN is not in good agreement with the previous result(B_0= 351 GPa), which is close to the recent theoretical calculation result(B_0= 378 GPa). An analysis of the experiment results shows that crystal structure of WC-type TaN can be viewed as alternate stacking of Ta and N layers along the c direction, and the covalent Ta–N bonds between Ta and N layers along the c axis in the crystal structure play an important role in the incompressibility and hardness of WC-type TaN.     

In situ X‐ray diffraction study on the growth kinetics of NiO nanoparticles

The growth kinetics of NiO nanoparticles have been studied by in situ X‐ray diffraction using two detection systems (conventional and imaging plate). NiO nanoparticles were formed by thermal decomposition after heating of an amorphous compound formed by the coprecipitation method. It was found that the detection method using an imaging plate is more efficient than the conventional detection mode for observing changes in the crystallite growth of nanocrystalline materials. Studies have been carried out to investigate the effects of the heating rates on the particles growth. The results suggest that the growth process of the particles is accelerated when the samples are treated at low heating rates. The evolution of particles size and the diffusion coefficient obtained from X‐ray powder diffraction patterns are discussed in terms of the thermal conditions for the two types of detection.     

Observation of Si(111) and gold-deposited Si(111) surfaces using micro-probe reflection high-energy electron diffraction

Observations of clean Si(111) and gold-deposited Si(111) surfaces have been performed using micro-probe reflection high-energy electron diffraction. It was found that many atomic steps on a Si(111) surface run in nearly the same direction, about 9° off the [1̄1̄2] direction. When gold was deposited on this surface at a substrate temperature of about 800°C, 5 × 1, diffuse √3 × √3R30°, sharp √3 × √3 R30° structures and Au clusters appeared on the surface with continuation of the deposition. During the deposition process, it was found that one kind of Si(111) 5 × 1 Au domain grew selectively along these atomic steps and nearly covered the entire surface. A phenomenon of gold clusters moving during the deposition was also observed. These clusters all moved in nearly the same direction so as to climb the atomic steps.     

Recent experimental aspects of the structure and dynamics of liquid and supercooled water

Liquid water, the most familiar liquid, is still not completely understood, even less so all the processes in which it participates. The directionality of the bonds and quantum aspects make the establishment of a complete theory difficult, particularly in the case of effective potentials built with spherical electrostatic forces. Recent work has focused on the hydrogen bonds formed between water molecules or with hydrophilic substrates. We describe the present situation of research concerning the so-called anomalies of liquid water at low temperature. Although without direct applications, this problem is consistently an object of discussion, enhanced by results from molecular dynamics simulations. Conversely, because in many situations where water plays a major role, such as, for example, in biology, only a few molecules are involved, the study of confined water is extremely important, sometimes decoupled from the more fundamental studies of bulk water. A short, but far from exclusive, summary of some of the more active domains of research concerning liquid water is given, mainly concerning interactions with other media.     

In situ synchrotron diffraction studies on the formation kinetics of jarosites

This paper reports the results of time‐resolved synchrotron powder diffraction experiments where jarosites with different K/H₃O, K/Na and Na/H₃O ratios were synthesized in situ at temperatures of 353, 368 and 393 K in order to observe the effect on kinetics and species produced. The Na/H₃O sample formed monoclinic jarosite at all three temperatures, whereas the K/H₃O and K/Na samples formed as rhombohedral jarosites at 353 K, and as mixtures of rhombohedral and monoclinic jarosites at the higher temperatures. The relative amount of the monoclinic phase increased with increase in temperature. Unit‐cell parameter changes with reaction time could be explained by changes in iron stoichiometry (samples become more stoichiometric with time) together with changes in K/H₃O and Na/H₃O ratios. The reaction kinetics have been fitted using a two‐stage Avrami model, with two different Avrami exponents corresponding to initial two‐dimensional growth followed by one‐dimensional diffusion‐controlled growth. Activation energies for the initial growth stage were calculated to be in the range 90–126 kJ mol^?1.     

Neutron diffraction study of liquid iodine

A theory of molecular diffusion in liquids that takes into account the shape of intermolecular potential wells with a cosine potential produces fine spectral detail in the far infrared. The effect of a static external electric field is to shift this panoply of peaks to higher frequency, increase the number of peaks, and shift their individual relative frequencies and intensities.     

Dynamics of a supercooled liquid

The theory of collective motion in liquids suggested by the authors has been found to explain successfully the recent experimental results of temperature dependent disorder in supercooled liquid gallium. Metastability limit is exhibited through a singularity of S(k, ω = 0) and corresponds to a critical value of correlation between different particles beyond which the supercooled liquid goes to the thermodynamically stable solid state.