Non-Debye excess heat capacity and boson peak of binary lithium borate glasses

The non-Debye excess heat capacities of binary lithium borate glasses with different Li₂O compositions of x = 8, 14 and 22 (mol%) are investigated to understand origin of the boson peak. The low-temperature heat capacities are measured between 2 and 50 K by a relaxation calorimeter. The experimental non-Debye heat capacities with x = 14 is successfully reproduced using the excess vibrational density of states measured by inelastic neutron scattering. This finding indicates that the non-Debye heat capacities of lithium borate glasses originate from the excess vibrational density of states measureable by inelastic neutron scattering. Moreover, it is demonstrated that all of the excess heat capacity spectra lie on a single master curve by the scaling using boson peak temperature and intensity.     

The boson peak in melt-formed and damage-formed glasses: A defect signature?

We describe the preparation and characterization of a glassy form of the moderately good glassformer PbGeO₃, by mechanical damage, and compare its properties with those of the normal melt-quenched glass and the crystal. The damage-formed glass exhibits a DSC thermogram strikingly similar to that of a hyperquenched glass, implying that it forms high on the energy landscape. The final glass transition endotherm occurs within 4 K (0.006T_g) of that of the melt-quenched glass, but crystallization occurs at a lower temperature, as if pre-nucleated. In particular, we have studied the low frequency vibrational dynamics of the alternatively prepared amorphous states in the boson peak region, and find the damage-formed glass boson peak to be almost identical in shape to, but more intense than, that of the normal melt-formed glass, as previously found for hyperquenched glasses. In view of the quite different preparation procedures, this similarity would seem to eliminate equilibrium liquid clusters as a source of the boson peak vibrations, but leaves plausible a connection to force constant fluctuations or to specific vitreous state defects.     

High frequency acoustic attenuation of vitreous silica: New insight from inelastic x-ray scattering

We present new experimental results on the propagation and damping of the high frequency acoustic-like modes in vitreous silica. The new data are measured by means of the inelastic x-ray scattering technique down to an exchanged wavevector Q ∼ 0.9 nm ^− 1, at the limit of the instrument capabilities. Thanks to the continuous development of the technique, the new spectra are characterized by a very high signal to noise ratio when compared to previous experiments. The higher data quality finally allows for a reliable determination of the position and width of the inelastic excitations. The new data show that the sound damping Γ is marked by a frequency dependence compatible with the Rayleigh law, Γ ∼ ν⁴, for frequencies below the position of the excess vibrational modes at the boson peak. We show that the new data are in good agreement with estimates of the acoustic mean free path from the thermal conductivity, which take into account the peculiar plateau at a few Kelvin. The connection between the boson peak and the Rayleigh law is further confirmed by a comparison of the present data with literature data for the sound attenuation in a permanently densified silica sample.     

Optical and spectroscopic properties of germanotellurite glasses

In this work, new glass compositions in the TeO₂-GeO₂-Nb₂O₅-K₂O system have been prepared and studied. The germanotellurite glasses were prepared by melt-quenching and their density, refractive index and characteristic temperatures have been determined. The structure of these glasses has been studied by infrared and Raman spectroscopies.The progressive replacement of TeO₂ by GeO₂ led to an increase of the glass transition and crystallisation temperatures of the glasses and a simultaneous decrease of their density and refractive index. Typical density and refractive index values of these glasses ranged from 4.98 to 3.85 g cm^− 3 and 2.08 to 1.79, respectively, with increasing GeO₂ content. The infrared spectra are dominated by a band ~ 640 cm^− 1 in the tellurite glass and ~ 800 cm^− 1 in the germanate glass. The Raman spectra of the germanotellurite glasses present an intense boson peak between ~ 34 and 47 cm^− 1, together with high frequency peaks at ~ 670 cm^− 1 and ~ 470 cm^− 1 for high tellurite and high germanate glass compositions, respectively. The vibrational spectra of these germanotellurite glasses indicate that the glass network consists basically of TeO₄ and [TeO₃]/[TeO_3 + 1] units, mixed with GeO₄ and NbO₆ polyhedra.     

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.     

Effect of polymerization on the boson peak, from liquid to glass

Reactive epoxy-amine mixtures during isothermal polymerization have been characterized by Raman scattering measurements in order to follow the modification of the vibrational density of states. In the initially liquid solutions an increasing number of Van der Waals bonds are replaced by stiffer covalent bonds. During the chemical reaction, the molecular diffusion slows down and ultimately the systems are frozen in a glassy structure. The transformation from reactive liquids to chemical glasses is accompanied by microscopic structural changes driven by the bonding process. During the reaction the samples density and the sound velocity increase, both of them contribute to significantly change the Debye level. By combining Raman with Brillouin inelastic X-ray scattering measurements, we compare the relative variations of the boson peak with that of the Debye level. We find that the shift and intensity variation of the boson peak are fully explained by the modification of the elastic properties of the medium and a boson peak master curve is obtained.     

Simple correlation between mechanical and thermal properties in TE-TL (TE = Ti,Zr,Hf;TL = Ni,Cu) amorphous alloys

We provide new data for the stiffness, hardness, Debye temperatures and crystallization and glass transition temperatures for fourteen Ti-TL and Hf-TL amorphous alloys (TL = Ni,Cu) covering wide composition range (x(TL) ≤ 70). These data increase linearly with x, as was previously observed for Zr-TL glassy alloys. Thus, the strength of interatomic bonding (reflected in stiffness) in all TE-TL amorphous alloys (TE = Ti,Zr,Hf) increases with x for x ≤ 65. The actual variations of studied properties depend on TE, being feeble for TE = Ti. The approximately linear variation of mechanical, vibrational and thermal parameters with x enables one to estimate these parameters for pure amorphous TEs, but does not indicate compositions at which bulk metallic glasses (BMG) form in these alloy systems. The reduced glass transition temperature T_rg is the property which roughly correlates with the formation of BMGs in glassy TE-TL alloys.     

Origin of boson peak in glasses: Role of Ioffe–Regel crossover and atomic soft modes

A theoretical ‘complete soft-mode-dynamics’ model of the origin and properties of the boson peak accompanied by a high-frequency sound, observed in glasses of a certain type, is described. The origin is determined by interaction of non-acoustic vibrations with acoustic phonons and a Ioffe–Regel crossover for their inelastic scattering. The non-acoustic excitations are associated with vibrations of atomic soft-mode ‘defects’. Two types of boson peak can be predicted in agreement with experiments.     

Development and properties of a glass made from MSWI bottom ash

A uniform shiny black-coloured glass was obtained using bottom ash produced by a Portuguese municipal solid waste incinerator (MSWI). The bottom ash was the single batch material used in the formation of the glass, which was obtained by vitrification of the solid waste at 1400 °C for 2 h. Under these conditions, a homogeneous melt with an appropriate viscosity to be shaped was obtained, indicating the suitability of this waste material to be employed in the development of vitreous products. The characterization of the resulting glass was performed in order to assess its structural, physical, mechanical, thermal and chemical features. The glass had a density of 2.69 g cm⁻³, a hardness of 5.5 GPa, a fracture strength of 75 MPa, a thermal expansion coefficient of 9.5 × 10⁻⁶ °C⁻¹ and it exhibited a very good chemical stability. In summary, the MSWI bottom ash glass has good mechanical and chemical properties and may, therefore, be used in several applications, particularly as a construction material.     

Low-temperature specific heats of porous silica xerogels of low densities

Low-temperature specific heat measurements have been performed in porous silica xerogels with densities varying from 670 to 1730 kg m⁻³ to study the low-energy vibrational dynamics. The specific heat, C_p, shows a bump in the temperature range above 4 K, when reported in a plot of C_p/T³ against the temperature, T. The bump is almost independent of the sample density and is close to the boson peak observed in melt-quenched amorphous silica (a-SiO₂). At temperatures <4 K, an additional contribution to that predicted by the Debye theory is observed. It follows an approximately linear temperature dependence (C_exc=aT^1+v, v being equal to about 0.25). In the xerogel with the largest density, specific heat of about a factor 5 larger than that of a-SiO₂ is measured, which increases with decreasing sample density. By comparison with the corresponding properties of a-SiO₂, we conclude that the disorder introduced by the presence of pores does not measurably affect the excess density of vibrational states in a frequency range of the boson peak (BP), but increases the density of the two-level systems (TLS).     

Influence of pressure on fast dynamics in polyisobutylene

Influence of pressure on fast dynamics and elastic properties in polyisobutylene is studied using Raman, Brillouin and neutron scattering spectroscopy. Analysis of the results shows that the boson peak frequency increases with pressure stronger than the longitudinal sound velocity measured by Brillouin scattering. Moreover, the boson peak intensity decreases under pressure stronger in Raman scattering than in neutron scattering suggesting a decrease in the light-to-vibrations coupling coefficient C(ν). The strong decrease of the microscopic peak intensity under pressure in Raman spectra supports this suggestion. We argue that variations in C(ν) might be related to amplitude of structural fluctuations. We speculate that change in disorder and/or overall density under pressure is the main cause for the observed variations.     

Nanomechanical properties of commercial float glass

The float process produces flat glass with a tin-rich surface due to contact with the molten metal bath. The incorporation of tin into the glass network is expected to modify the mechanical properties of the surface and the relative durability of the two sides of the material. In this work nanoindentation was used to evaluate the elastic modulus and hardness of a 2 mm thick commercial float glass. The near-surface elastic modulus (depths < 400 nm) of both sides of the glass was elevated by up to 10%, and could not be attributed solely to the presence of tin. However, slight differences in hardness (<10%) between the air and tin sides of the float glass were observed. These results suggest that tin may alter the flow properties of the glass, but the elastic modulus changes are masked by other structural and chemical differences between the air and tin sides of the float glass.     

Tantalum based bulk metallic glasses

Ta-based bulk metallic glasses with high strength (2.7 GPa) and hardness (9.7 GPa), high elastic modulus (170 GPa) and high density (12.98 g/mm³) were developed. The best glass forming ability so far for a Ta-Ni-Co system reaches a critical diameter of 2 mm by the copper mold casting method. It shows an exceptionally high glass transition temperature of 983 K and a high crystallization temperature up to 1023 K. The unique mechanical and physical properties make them a promising high strength material.     

A molecular dynamics study on vibration spectra of a-SiO2 surface

The charge equilibration (QEq) method was used in the molecular dynamics study of the vibration spectra on the a-SiO₂ surface. The vibrational density of states (VDOS) of a silica glass surface and partial contribution of Si and O atoms were compared with those obtained from the fixed-charge (FQ) model. The VDOS in each of the samples has two groups of vibrational bands, i.e., wide-lower-frequency band (WB) between 0-25 THz and narrow-higher-frequency band (NB) between 25 and 40 THz, which is similar to the bulk VDOS obtained experimentally. The QEq surface exhibits a peak and two shoulders while two peaks are found for the FQ surface. At the surface, an excess peak (at 1-2 THz) was observed by substracting the Debye VDOS from the calculated VDOS, which is regarded as the experimentally observed the boson peak (BP). The position of the BP is shorter than that in the case of the bulk. In the FQ surface, the VDOS consists of narrower bands, while in the QEq sample, wider bands exist due to charge variation.     

Chemical vapor transport of zinc sulfide

Crystals of cubic zinc sulfide with different isotopic compositions have been grown by iodine vapor transport for basic research purposes (vibrational, electronic, and thermodynamic properties). The synthesis reaction in sulfur vapor was found to be controlled by solid-state diffusion of zinc atoms through a ZnS passivation layer. Crystals up to 5 mm in length were grown from small amounts of source material. The presence of argon reduced the nucleation density and favored the formation of facets.     

Preparation and optical properties of titania-doped hybrid polymer via anhydrous sol-gel process

Incorporation of metal alkoxides (Ti, Zr, etc.) for tuning the optical properties of silica glasses by the sol-gel process is of significant interest for optical applications. In this paper, we report an anhydrous sol-gel process for preparation of photosensitive titania-doped hybrid glassy polymer with good homogeneity and high doping concentration (TiO₂ up to 40 mol%). The process consists of two steps: in the first step methacryloxypropyltrimethoxysilane (MPS) is hydrolyzed by boric acid through ligand exchange reaction (OH↔OR) under anhydrous conditions; and in the second step dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPhDMS) and titanium ethoxide (TET) were added to condense with the silanols formed in the first step. The optical properties of the synthesized hybrid polymer were studied, and results showed that the hybrid material has low OH absorption, low optical losses (0.45 dB/cm at 1550 nm and 0.16 dB/cm at 1310 nm respectively), and good thermo-optical linearity with tuneable refractive index. The effect of TiO₂ doping in reducing the OH concentration of the hybrid material was observed, and the mechanism for this effect is discussed.     

Development of m-plane GaN anisotropic film properties during MOVPE growth on LiAlO2 substrates

The anisotropic film properties of m-plane GaN deposited by metal organic vapour phase epitaxy (MOVPE) on LiAlO₂ substrates are investigated. To study the development of layer properties during epitaxy, the total film thickness is varied between 0.2 and 1.7 μm. A surface roughening is observed caused by the increased size of hillock-like features. Additionally, small steps which are perfectly aligned in (1 1 −2 0) planes appear for samples with a thickness of ∼0.5 μm and above. Simultaneously, the X-ray rocking curve (XRC) full width at half maximum (FWHM) values become strongly dependent on incident X-ray beam direction beyond this critical thickness. Anisotropic in-plane compressive strain is initially present and gradually relaxes mainly in the [1 1 −2 0] direction when growing thicker films. Low-temperature photoluminescence (PL) spectra are dominated by the GaN near-band-edge peak and show only weak signal related to basal plane stacking faults (BSF). The measured background electron concentration is reduced from ∼10²⁰ to ∼10¹⁹ cm⁻³ for film thicknesses of 0.2 μm and ∼1 μm while the electron mobilities rise from ∼20 to ∼130 cm²/V s. The mobilities are significantly higher in [0 0 0 1] direction which we explain by the presence of extended planar defects in the prismatic plane. Such defects are assumed to be also the cause for the observed surface steps and anisotropic XRC broadening.     

Interaction of intrinsic point defects with dislocation stress fields in hcp zirconium crystal

The crystallographic, energetic, and kinetic characteristics of intrinsic point defects (vacancy-self-interstitial atom) in stable, metastable, and saddle configurations in hcp zirconium crystal have been calculated by the molecular-statics method. The spatial dependences of the interaction energies of intrinsic point defects and stress fields of rectilinear dislocations with Burgers vectors of 1/3[11$ \bar 2 $ \bar 2 0], 1/3 [11$ \bar 2 $ \bar 2 3], and [0001] have been found within the anisotropic linear theory of elasticity. The most likely trajectories of intrinsic point defects in dislocation stress fields (trajectories with minimum energy barriers for motion) have been constructed. Such trajectories result in dislocation only for the interaction of self-interstitial atoms with an edge dislocation that has a Burgers vector of 1/3 [11$ \bar 2 $ \bar 2 3].     

Calculation and analysis of vibrational spectra of PbCl2-Sb2O3-TeO2 glass from first principles

Ternary PbCl₂-Sb₂O₃-TeO₂ system provides promising materials for photonic applications. Glasses in this system are thermally stable, their refraction index is about 2.2 and they are transparent from 400 nm up to 6 μm. The ab initio molecular dynamics (MD) simulations of xPbCl₂-10SbO_3/2−(90-x)TeO₂ glasses (x = 10, 20, 30, 40, and 50) were carried out using density functionals, the plane-wave basis set expansion, and the projector-augment waves (PAW). The resulting glassy structures were analyzed with the help of partial radial distribution functions (RDF) and partial coordination numbers. Good agreement with the available experimental data was confirmed. The axial and equatorial oxygen atoms of TeO₄ trigonal bi-pyramids were distinguished. Vibrational frequencies and their corresponding eigen-modes were found by diagonalization of the dynamical matrix. The simulated vibrational spectra were decomposed to determine the contributions from individual atomic species and some more complex structural features and compared with experimental Raman spectra. The spectral decomposition was carried out by projecting vibrational displacement vectors onto various normal modes of typical symmetric structural units. The method proved to be able to successfully interpret the experimental Raman spectra.     

Generalized Mittag-Leffler relaxation of NH4H2PO4: Porous glass composite

In this paper the dielectric spectroscopy data of ammonium dihydrogen phosphate NH₄H₂PO₄: porous glass composite was studied at various temperatures. It was found that the investigated material exhibits the two-power-law relaxation pattern with the low- (m) and high-frequency (n-1) exponents satisfying the relation m < 1 − n, where 0 < m, n < 1. Such a relaxation behavior belongs to the class of less typical ones and cannot be fitted by any of the well-know empirical relaxation functions. In order to explain the relation between the power-law exponents of the studied sample we utilize a new relaxation function, recently derived (Stanislavsky et al. (2010) [1]) in the framework of the relaxation diffusion scenario.