Simulation and Experiment in X-ray Topography and Diffractometry

X-ray double crystal topography and high resolution diffractometry reveal very small deformations of the crystal lattice. However, this information can be directly obtained from the topographs or diffractometer curves only if certain conditions are fulfilled. Generally a deformation model has to be used, that is compared to the measurements by simulation calculations based on the dynamical diffraction theory. Trial and error allow to adapt the parameters of the model. An example illustrates that with a few parameters an automatic fit is possible.     

Aging and drying of gels

This review describes the chemical and physical processes occurring during the aging and drying of an inorganic gel. The chemical reactions that lead to gelation are shown to continue long after the solution gels, causing changes in the composition, structure, and properties of the gel. The formation of new crosslinks produces shrinkage (syneresis) and increases the modulus and viscosity of the gel, so that aging reduces the subsequent shrinkage during drying. If the solubility of the solid phase is drying, the small pores of the gel develop high capillary pressures that results in shrinkage. If the exterior surface shrinks much faster than the interior, the differential strain can cause warping and cracking; very slow drying is generally required to prevent such catastrophes. Fracture is most likely at the moment that shrinkage stops and the liquid/vapor meniscus moves into the gel; after that point, the meniscus may remain smooth or may become unstable and ragged. The theory of drying is reviewed and shown to account for the observed behavior. Several strategies are described that minimize the tendency of the gel to crack.     

Science for the small and the tall,the young and the old

Public engagement becomes increasingly important for scientists. One reason is the demand of the taxpayer to know what her or his money is being spent on, and why. The other one is that in a world that increasingly relies on technology, student engagement even at a very young age becomes a target to assure the needed supply of well-educated and especially motivated scientists for the decades to come. And it falls on the older generation of current researchers to leave the comfort of their lab once in a while, to awaken the interest for science among the population. Many people may know that there is a ‘liquid crystal’ in their mobile (cell) phone display, but when prompted, no one really knows what that liquid crystal actually is, let alone how the display they use many times every day, actually works in principle. It is part of our job to change this. In this contribution Valentina Domenici and Ingo Dierking would like to report on two recent Science Festival events in which they took part, one held in Genoa, Italy, and the other in Manchester, UK.     

Non-equilibrium viscosity and activation energy

This article considers the break in viscosity curves that appears in the glass transition region. It demonstrates that the only possibility to interpret properly the break within the frameworks of the activation energy theory is to assume that at least several independent processes are taking place. Single process cannot explain the break. This assumption was already developed in details in the jump frequency model of Avramov and Milchev.     

CIS and CIGS nanomaterials prepared by solvothermal method and their spectral properties

Uniform CIS and CIGS nanomaterials were successfully synthesized by a simple amino‐based assisted solvothermal technique using PVP‐30 as the surfactant. The influence of surfactant, temperature and Ga amount on the structure, morphology, phase and spectral property was analyzed in detail. The results show that CIS and CIGS nanomaterials with 40∼70 nm in diameter can be gained at 200 °C for 24 h. PVP‐30 surfactant can greatly improve the dispersion characteristics of particles. XRD pattern shows that the “three peaks” obviously shift to bigger 2θ after gallium implantation because of lattice contraction. EDAX and Raman show that the final product is close to CuIn_0.7Ga_0.3Se₂. The possible reaction mechanism has also been explained in detail. UV‐vis‐NIR spectra show that the absorption peak and absorption edge of CIGS with 1.278 eV bandgap obviously shift to a lower energy compared to CIS with 1.051 eV bandgap, which shows the potential application in enhanced conversion efficiency.     

Thermodynamic and Structural Studies of Polymorphism in 1,1,1-trichloroethane and 2,2-dichloropropane

Optical birefringence measurements have been made on the different solid phases of 1,1,1-trichloroethane and 2,2-dichloropropane with the object of establishing their ranges of stability and their interrelationships. The nature of the solid phase that is contiguous to the liquid seems to depend upon the amount of impurities present in the specimens. This result is confirmed by an extensive calorimetric investigation of two specimens of 1,1,1-trichloroethane containing 0.31 and 0.82 mol° of impurity respectively. A comparison of the calorimetric data with results published in the literature suggests that one or the other of two distinguishable phases I of solid 1,1,1-trichloroethane is stable in the phase I region. While some apparently conflicting results obtained previously are thus rationalized, it is not certain that still other phases I cannot be formed.     

A brief discussion: Thermodynamic and dynamic fragilities,non-divergent dynamics and the Prigogine–Defay ratio

This article brings together some of the work performed by the present author and collaborators that is related to the glass transition event and to some of its entropy aspects. The purpose of the work and discussion was motivated by a view that some of the frameworks in which we currently look at glassy behavior, while potentially useful, may also have limitations that we often do not fully consider. Discussion focuses on isochoric glass formation paths, thermodynamic and dynamic fragilities and how dynamic fragility in many systems (especially polymers, metals, ionic liquids and hydrogen bonding systems) seems to vary primarily with the glass transition temperature itself. This leads to the conclusion that such systems have an apparent activation energy that varies as the square of the glass temperature. The work then discusses evidence for a non-diverging relaxation time or viscosity as the glass temperature is approached and ends with a discussion of the Prigogine–Defay ratio.     

Fragility measures and mode-coupling theory

The pressure-dependence of the elastic moduli of a Lennard-Jones (LJ) system is studied within mode-coupling theory (MCT). Assuming a recently proposed link between these quantities and Angell’s fragility to hold, this implies that the fragility of the LJ system increases with pressure, and that this increase is mainly connected to a change in the equation of state of the liquid, and not glassy dynamics as such.     

Optical and electrical properties of chlorinated and hydrogenated amorphous silicon prepared by glow discharge

Chlorinated and hydrogenated amorphous silicon films were prepared by glow discharge of a SiCl₄/H₂ mixture. Infrared spectra of these films show that, in addition to the hydrogen induced bands, two new modes appear at 545 cm^?1 (SiCl stretching) and 500 cm^?1 (Si TO modes induced by chlorine). Observation of the 545 cm^?1 band proves that chlorine is able to act as a dangling bond terminator in an amorphous silicon matrix. A good agreement is found between the total amount of chlorine determined by electron microprobe analysis and the value estimated from the integrated strength of the SiCl stretching mode. The relatively high value of the optical band gap (1.80 eV) of our material containing only 5 at.% bonded hydrogen shows that chlorine plays a major role in the optical gap value. Electrical conductivity, photoconductivity and luminescence properties are qualitatively similar to that of a: SiH films.     

Europium environment and clustering in europium doped silica and sodium silicate glasses

The local environment and distribution of rare earth ions are important to the optical properties of rare earth doped oxide glasses. In this paper, we report studies of the structures of europium doped (around 1 mol% Eu₂O₃) silica and sodium silicate glasses using molecular dynamics simulations. By using effective partial charge potentials, systems with over 24,000 atoms were modeled in order to obtain better statistics of rare earth ion distribution. The simulated glass structures were validated by comparing the calculated neutron and X-ray structure factors with experimental data. It was found that europium ions have higher coordination number (5.9 versus 4.8) and more symmetric environments in sodium silicate glasses than in the silica glass. Rare earth ion clustering has been characterized in detail and it was found that the clustering probability of europium ions in sodium silicate glass is consistently less than that predicted from a random distribution, while the probability of clustering in pure silica glass is higher than that of random distribution at the 1 mol% doping level.     

Electrolytic Oxidation of Thiocyanate and Selenocyanate Salts and the Photoelectrochemical Effect.

New photosensitive materials can be obtained by electrochemical oxidation of thiocyanate and selenocyanate salts. Using (K,Na)SCN eutectic melt, the formation of an electrodic deposit, with photoelectrochemical properties, has already been reported by us. To improve the photoelectrochemical characteristics of the deposit, futher investigations were carried out in the following sistems: selenocyanate ammoniate, KSCH-Acetamide eutectic mixture and KSCN ethylene carbonate solution:. Attempts to obtain a massive deposit in the ammoniate solution were unsuccessful due to ammonia oxidation. Measurements performed on the other KSCN systems show that temperature is a parameter of remarkable importance. In fact, lowering the temperature one obtains a decrease on formation of parathiocyanogen on behalf of the polytrithiocyanogen, the species that gives rise to the photoeffect.     

Surface growth mechanisms and structural faulting in the growth of large single and spherulitic titanosilicate ETS-4 crystals

Morphological, surface and crystallographic analyses of titanosilicate ETS-4 products, with diverse habits ranging from spherulitic particles composed of submicron crystallites to large single crystals, are presented. Pole figures revealed that crystal surfaces with a-, b- and c- axes corresponded to 110, 010 and 001 directions, respectively. Thus, technologically important 8-membered ring pores and titania chains in ETS-4 run along the b-axis of single crystals and terminate at the smallest crystal face. Height of the spiral growth steps observed on 1 0 0 and 0 0 1 surfaces corresponded to the interplanar spacings associated with their crystallographic orientation, and is equivalent to the thickness of building units that form the ETS-4 framework. Data suggest that the more viscous synthesis mixtures, with a large driving force for growth, increased the two- and three-dimensional nucleation, while limiting the transport of nutrients to the growth surface. These conditions increase the tendency for stacking fault formation on 1 0 0 surfaces and small angle branching, which eventually results in spherulitic growth. The growth of high quality ETS-4 single crystals (from less viscous synthesis mixtures) occurred at lower surface nucleation rates. Data suggest that these high quality, large crystals grew due to one-dimensional nucleation at spiral hillocks, and indicate that under these conditions un-faulted growth is preferred.     

Experimental and theoretical correlation between low-field power absorption and magnetoimpedance in amorphous materials

We present measurements of low-field power absorption (LFA) at 9.45 GHz on an amorphous ribbon of nominal composition (Fe_0.06Co_0.94)₇₅Si₁₅B₁₀, at room temperature. These results show an anti-symmetrical shape around zero magnetic field that peaks at ±34 Oe. We also present measurements of magnetoimpedance (MI) at 60 MHz and 3 GHz. In order to make a proper comparison between these experiments, the real part of magnetoimpedance, Re(Z_s), was numerically derived to obtain dRe(Z_s)/dH; leading also to an anti-symmetrical plot that peaks at the same fields that LFA. By using the complex Poynting vector, we show that LFA and MI are very similar processes and conclude that both measurements are a manifestation of the same response to electromagnetic absorption, in which the same physical processes take place.     

Quasi-localized vibrations and phonon damping in glasses

There is ample evidence both from computer simulation and experiments that the structural disorder characterizing glasses and amorphous materials leads to quasi-localized vibrations (QLVs). The effect of these modes on low temperature properties such as heat capacity and conduction or tunnelling can be calculated in the framework of the soft potential model. Recently it has been shown that this concept can be extended to describe the boson peak (BP). By interaction, the density of states of the QLVs is changed to a characteristic shape corresponding to the boson peak in inelastic scattering. The QLVs interact with the sound waves and dampen them. We show that resonant scattering between QLVs and sound waves can describe the strong damping observed experimentally.     

Free energy profiles of Al and La cation distribution in silica and soda silicate glasses

The factors that control the distribution of Al³⁺ and La³⁺ cations in silica and soda silicate glasses is examined by using molecular dynamics (MD) simulations. In particular, the response of the glass network to the presence of metal oxide is probed using a liquid state theory that treats the glass network as a solvent and the metal cation as a solute. MD simulations are used to obtain the mean solvent-solute and solute-solute force. The trajectory used to determine the free energy is analyzed to determine the stable configurations of a cation pair. Details of determining the potential of mean force for an Al cation pair in silica and silicate glass is presented. A comparison of these results with those previously calculated for a La cation pair in the same glass systems is given. The results reveal that there are differences in how the network accommodates the two different size cations. It is found that for the potential used here, based on the Vessal potential, the network wraps itself around the larger La cation forming a solvent shell, whereas, the smaller Al cation is incorporated into the network backbone. In silica and soda silicate glasses, La ion pairs cluster to form La-O-La linkages. In contrast, the glasses favor a separated state of the Al ion pair.     

Homoepitaxial growth and electrical characterization of GaN-based Schottky and light-emitting diodes

Homoepitaxial growth of GaN epilayers on free-standing hydride vapor phase epitaxy (HVPE) GaN substrates offered a better control over surface morphology, defect density, and doping concentration compared to conventional heteroepitaxial growth. The FWHM of the (0 0 0 2) X-ray diffraction (XRD) rocking curve from homoepitaxial GaN was measured to be as low as 79 arcsec, much smaller than 230 arcsec for GaN grown on sapphire. Schottky diodes grown on GaN substrates exhibited sharper breakdown characteristics and much lower reverse leakage than diodes on sapphire. However, the homoepitaxial devices had poor scalability due to the presence of yield-killing defects originating from the substrate surface. Vertical InGaN/GaN light-emitting diodes (LEDs) on GaN substrates showed reduced series resistance and reverse leakage compared to lateral LEDs on sapphire. Wafer mapping demonstrated that the distribution of leaky homoepitaxial devices correlated well with that of macroscopic defects in the GaN substrates.     

Effect of X-ray irradiation on solarization and crystallization of photosensitive glasses containing Ce, Sb, Sn and Ag

The effect of X-ray irradiation on the solarization and crystallization of a lithium silicate glass was investigated in this research. The results showed that the X-ray power has a significant effect on the amount of solarization, and the crystallization temperature of the glass. Applying an X-ray power of 2400 W on glass containing the photosensitive elements of Ce, Sb, Sn and Ag led to reduction of the DTA crystallization peak temperature from 704 to 590 °C. UV spectroscopy showed that solarization of irradiated glasses containing Ce, Sb and Sn ions was responsible for formation of Ag clusters and reduction of crystallization temperature of glasses. Microstructural analysis also showed that the solarized glasses had a finer microstructure relative to that of the non-irradiated one. These differences attributed to changes in crystallization mechanism observed in the non-irradiated glass.     

Advancements (and challenges) in the study of protein crystal nucleation and growth; thermodynamic and kinetic explanations and comparison with small-molecule crystallization

This paper reviews advancements and some novel ideas (not yet covered by reviews and monographs) concerning thermodynamics and kinetics of protein crystal nucleation and growth, as well as some outcomes resulting therefrom. By accounting the role of physical and biochemical factors, the paper aims to present a comprehensive (rather than complete) review of recent studies and efforts to elucidate the protein crystallization process. Thermodynamic rules that govern both protein and small-molecule crystallization are considered firstly. The thermodynamically substantiated EBDE method (meaning equilibration between the cohesive energy which maintains the integrity of a crystalline cluster and the destructive energies tending to tear-up it) determines the supersaturation dependent size of stable nuclei (i.e., nuclei that are doomed to grow). The size of the stable nucleus is worth-considering because it is exactly related to the size of the critical crystal nucleus, and permits calculation of the latter. Besides, merely stable nuclei grow to visible crystals, and are detected experimentally. EBDE is applied for considering protein crystal nucleation in pores and hydrophobicity assisted protein crystallization. The logistic functional kinetics of nucleation (expressed as nuclei number density vs. nucleation time) explains quantitatively important aspects of the crystallization process, such as supersaturation dependence of crystal nuclei number density at fixed nucleation time and crystal size distribution (CSD) resulting from batch crystallization. It is shown that the CSD is instigated by the crystal nucleation stage, which produces an ogee-curve shaped CSD vs. crystal birth moments. Experimental results confirm both the logistic functional nucleation kinetics and the calculated CSD. And even though Ostwald ripening modifies the latter (because the smallest crystals dissolve rendering material for the growth of larger crystals), CSD during this terminal crystallization stage retains some traces of the CSD shape inherited from the nucleation stage. Another objective of this paper is to point-out some biochemical aspects of the protein crystallization, such as bond selection mechanism (BSM) of protein crystal nucleation and growth and the effect of electric fields exerted on the process. Finally, an in-silico study on crystal polymorph selection is reviewed.