Defect configurations in Ge-S chalcogenide glasses studied by Raman scattering and positron annihilation technique

Defect configurations of Ge-S binary glasses have been studied systemically by Raman scattering technique and positron annihilation lifetime spectra (PALS). The correlations between the positron lifetime data, structural features, and chemical compositions of Ge-S binary glasses have been established, and also the identification of open volume originated from coordination defects has been carried out. The cognizance of defect configuration will be very helpful to further understand the unique photosensitivity of chalcogenide glasses.     

Positron annihilation in thermally treated metallic glasses

The positron lifetime dependence on the annealing temperature has been studied for two transition metal-metalloid glasses (FeNi-based and Co-based). Small variations of the lifetime observed after annealing below crystallization temperature are attributed to elimination of the structural defects inherent in the as-quenched metallic glasses. More abrupt changes at higher temperatures are ascribed to crystallization processes which lead to polycrystalline phases. Differences in positron lifetime between annealed FeNi-based and Co-based metallic glasses are discussed.     

Crystallization of Li2OSiO2 glass studied by positron annihilation

The crystallization of 34 Li₂O65 SiO₂1 P₂O₅ glass has been studied by positron annihilation. The changes in the positron lifetime spectra have been correlated to the magnitude of the amorphous X-ray scattering. A linear relationship has been found for heat-treatment temperatures less than 700°C, above which non-linear phenomena in the lifetime spectra set in. The volume crystallinity reaches a saturation value, which varies from 70% at the heat-treatment temperature of 535°C to 80% at 700°C because of the phase separation. The dimensionality of the crystal growth in this glass is found to be n = 1.5 ± 0.1. The effect of the phase separation on the rate and dimensionality of the crystallization is discussed. The results show that positron annihilation is a sensitive and accurate method to follow crystallization in vitreous materials.     

Crystallization and phase-separation of Li2OSiO2 glass

The crystallization and phase-separation phenomena in the Li₂OSiO₂ glass are studied by positron lifetime and annihilation lineshape measurements. Analysis of the kinetic data shows three-dimensional morphology of growing crystals. Phase-separation is seen to increase the density of crystal nuclei and the rate of volume crystallization, but it does not affect the morphology. In addition, surface crystallization is detected in glasses with small degrees of phase-separation. The results are consistent with scanning electron and optical micrographs.     

Characterization of plasticity-induced structural changes in a Zr-based bulk metallic glass using positron annihilation spectroscopy

Changes in the free volume distribution in Zr_58.5Cu_15.6Ni_12.8Al_10.3Nb_2.8 bulk metallic glass with inhomogeneous plastic deformation and annealing were examined using positron annihilation spectroscopy. Results indicate that the size distribution of open volume sites is at least bimodal prior to deformation. The size and concentration of the larger sites, identified as flow defects, changes with processing. The size of the flow defects initially increases with deformation. More extensive deformation shifts the distribution, with a third group of much larger sites forming at the expense of flow defects. This suggests that a critical strain is required for the growth of nanovoids observed elsewhere by HRTEM. Although these observations suggest the presence of three open volume size groups, further analysis indicates that all groups have a similar distribution of chemical species around them as evidenced by the same line shape parameter. This may be due to the disordered structure of the glass and the positron affinity to particular atoms surrounding the open volume regions.     

Post-irradiation relaxation in vitreous arsenic/antimony trisulphides

Instability caused by high-energy γ-irradiation was studied in (As₂S₃)_1−x(Sb₂S₃)_x glasses (x = 0, 0.1, 0.2 and 0.3) using positron annihilation lifetime spectroscopy, the obtained results being treated within a two-state trapping model. The observed decrease in the positron trapping rate of the glasses tested just after irradiation was explained due to renovation of destroyed covalent chemical bonds. This process was governed by monomolecular relaxation kinetics agreed well with corresponding changes in fundamental optical absorption edge.     

Structural aspects of volume nucleation in silicate glasses

An interrelationship between parameters of short and intermediate range order in silicate glasses and the tendency to nucleate homogeneously in the volume is tested. Changes in the average coordination number and metal-oxygen distance of network modifying cations as well as changes in the concentration of constitutive silica tetrahedra accompanied with the crystallization of 18 stoichiometric glass compositions into their crystalline analogs are determined. The intermediate range structure of the glasses is investigated by configurational entropy and flow birefringence. The changes in structural parameters are analyzed in terms of the reduced glass transition temperature T_rg, which is negatively correlated with the maximal rate of volume nucleation. The results indicate that the short-range structure in stoichiometric glasses is, in general, very similar to the corresponding crystal structure but independent of the T_rg-scale and for this reason independent of nucleation properties. In contrast to the short range of the glass structure, birefringence induced by a forced flow above the glass transition temperature and configurational entropy are positively correlated with increasing T_rg. The results indicate increased structural order in the intermediate range for melts with a high supercool limit (T_rg < 0.58). It is concluded that this order phenomena may promote nucleation events and may help to explain the tendency to volume nucleation of silicate glasses with T_rg < 0.58.     

Raman study of the structure of alkali germanosilicate glasses II. Lithium,sodium and potassium digermanosilicate glasses

Polarized and depolarized Raman spectra of lithium, sodium and potassium digermanosilicate glasses of the composition 33 A₂O 67[(1 ? y)SiO₂, y GeO₂] and powder Raman spectra of crystalline Li₂O · 2 GeO₂ and K₂O · 2 GeO₂ are given. From the Raman spectra it is concluded that the structure of the glasses mainly consists of networks of SiO₄ and GeO₄ tetrahedra with one non-bridging oxygen atom, probably mixed in a random way. The structure is comparable to that of crystalline disilicates and digermanates.     

Studies of lead–iron phosphate glasses by Raman,Mössbauer and impedance spectroscopy

The effect of Fe₂O₃ content on electrical conductivity and glass stability against crystallization in the system PbO–Fe₂O₃–P₂O₅ has been investigated using Raman, XRD, Mössbauer and impedance spectroscopy. Glasses of the molar composition (43.3 − x)PbO–(13.7 + x)Fe₂O₃–43P₂O₅ (0 ⩽ x ⩽ 30), were prepared by quenching melts in the air. With increasing Fe₂O₃ content and molar O/P ratio there is corresponding reduction in the length of phosphate units and an increase in the Fe(II) ion concentration, which causes a higher tendency for crystallization. Raman spectra of the glasses show that the interaction between Fe sites, which is essential for electron hopping, strongly depends on the cross-linking of the glass network. The electronic conduction of these glasses depends not only on the Fe(II)/Fe_tot ratio, but also on easy pathways for electron hopping in a non-disrupted pyrophosphate network. The Raman spectra of crystallized glasses indicate a much lower degree of cross-linking since more non-bridging oxygen atoms are present in the network. Despite the significant increase in the Fe₂O₃ content and Fe(II) ion concentration, there is a considerable weakening in the interactions between Fe sites in crystalline glasses. The impedance spectra reveal a decrease in conductivity, caused by poorly defined conduction pathways, which are result of the disruption and inhomogeneity of the crystalline phases that are formed during melting.     

Crystallization kinetics of the tungsten-tellurite glasses

The crystallization kinetics of the (1 − x)TeO₂-xWO₃ (where x = 0.10, 0.15, and 0.20, in molar ratio) glass system was studied by non-isothermal methods using differential scanning calorimetry (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. DSC measurements were performed at different heating rates to study crystallization kinetics of the first crystallization reactions of the glasses. XRD analysis of tungsten-tellurite glasses heat-treated above the first crystallization temperatures revealed that the first crystallization peaks attributed to the α-TeO₂ and γ-TeO₂ crystalline phases for 0.90TeO₂-0.10WO₃ and 0.85TeO₂-0.15WO₃ samples and α-TeO₂ and WO₃ crystalline phases for the 0.80TeO₂-0.20WO₃ sample. Avrami constants, n, calculated from Ozawa equation, were found between 1.14 and 1.44. The activation energies, E_A, for the first crystallization reactions were determined by using the modified Kissinger equation as 379 kJ/mol, 288.1 kJ/mol and 228.8 kJ/mol, for 0.90TeO₂-0.10WO₃, 0.85TeO₂-0.15WO₃ and 0.80TeO₂-0.20WO₃ glasses, respectively.     

The defect diffusion model and the properties of glasses and liquids

Several previously unexplained relaxation phenomena are interpreted quantitatively in terms of the defect diffusion model (DDM). These include widely different pre-exponentials, exponents and consequently fragility. In addition, the DDM is used to give a qualitative explanation of many properties that glasses and liquids exhibit. This includes interpretations of the glass transition (T_g), the liquid–liquid transition (T_B), the crystalline melting temperature (T_m), and the different values of the characteristic temperature, T_C, that some materials exhibit for different types of physical measurements. Next, qualitative explanations of the origin of secondary relaxations such as the excess wing and the β relaxation are given. In addition, the boson peak is discussed in terms of the DDM. Finally, it is pointed out that in the DDM, universality is embodied in the defects i.e. free volume.     

Formation and structure of crystalline inclusions in As2S3–SbSI and As2Se3–SbSI systems glass matrices

The main aim of the study presented in this paper is the investigation of the structure of (As₂S₃)_100?x(SbSI)_x and (As₂Se₃)_100?x(SbSI)_x (0 ≤ × ≤ 40) glasses by Raman spectroscopy and X-ray methods, also the nature of the crystalline inclusions which arise up in their matrix at heat treatment. We have found that in conditions of continuous heating in the interval “glassforming temperature–crystallization temperature” a crystallization with predominant mechanism of stable phase SbSI separation is taking place. The formation mechanism of crystalline inclusions of antimony sulphoiodide in glass matrix is discussed in the light of our results. It was established that all investigated glasses have a nano-heterogeneous structure.     

Sintering and crystallization of titanium-containing lead borate glasses

The sintering and crystallization of glass powders with chemical composition 47 PbO—38 B₂O₃—15 TiO₂ (mole %) was investigated under non-isothermal conditions by shrinkage measurements, differential thermo-analysis (DTA), X-ray diffraction (XRD), dielectric measurement and positron annihilation (Doppler broadening). The correlation between changes of macroscopic properties and positron annihilation results recommends this method for the detection of structural changes in glasses.     

Properties and structure of AsTe glasses: (I). Glass-forming ability and related properties

AsTe glasses have been investigated for determining the molecular mechanisms of glass formation and of crystallization. Stable and homogeneous bulk glasses are prepared throughout the range of concentration from 20 to 65 at % As, by using an improved quenching method. GFA (glass-forming ability) is determined with respect to the rate of cooling. Density, microhardness, T_g and ΔC_p at T_g are measured in the whole range of glass formation. Finally a quantitative analysis of the kinetics of crystallization is carried out. It appears that most properties which involve molecular motions exhibit anomalies for As₄₀ Te₆₀ composition (As₂Te₃ is the unique definite compound of the system). So GFA shows a sharp depression for this critical composition; similarly enthalpy and kinetics of crystallization are drastically modified at As₄₀Te₆₀. For Te-rich glasses, crystallization occurs at low temperature by homogeneous nucleation with a small energy of activation. For As-rich glasses, crystallization occurs at much higher temperatures. Above 200°C it is controlled by growth with an high activation energy which indicates deep rearrangements of the relative positions of the atoms by chemical diffusion. A coherent analysis of all the data is developed which shows that important differences of local order exist between amorphous and crystalline states and also between the two well-distinct types of glasses we are dealing with. The aim of paper II is to determine these differences from diffraction data.     

Thermal and optical properties of TeO2–BaO–SrO–Nb2O5 based glasses: New broadband Raman gain media

We systematically added WO₃ (up to 10 mol%) and P₂O₅ (up to 16 mol%) in TeO₂–BaO–SrO–Nb₂O₅ (TBSN) glass system and studied thermal and optical properties of the resultant glasses. The dependences of the additive concentration on glass transition (T_g) and crystallization (T_x) temperatures are presented. The TBSN glass added with ⩾4 mol% WO₃ and P₂O₅ showed high stability against crystallization. The changes in optical band gap energy due to WO₃ and P₂O₅ addition was studied using UV–VIS–NIR absorption spectrometry. The WO₃ addition shifted the optical band gap to longer wavelengths, whereas P₂O₅ addition shifted that to shorter wavelengths. Effects of the WO₃ and P₂O₅ addition on the Raman spectra of TBSN glass are clarified. New Raman bands due to WO₄ and PO₄ tetrahedra formed in the resultant glasses broadened their Raman spectra. Present glasses are characterized by higher thermal stability and wider Raman spectra, therefore, they are promising candidates for fiber Raman amplifiers in photonics systems.     

The structure of lithium,sodium and potassium germanate glasses,studied by Raman scattering

Polarized and depolarized Raman spectra of alkali germanate glasses are given, together with Raman powder spectra of the crystalline compounds Li₂O · 2 GeO₂; 3 Li₂O · 8 GeO₂; 2 Li₂O· 9 GeO₂; Li₂O · 7 GeO₂; 2 Na₂O · 9 GeO₂; K₂O · 2 GeO₂; K₂O · 4 GeO₂ and K₂O · 8 GeO₂.The alkali germanate glasses: xA₂O (1?x) GeO₂ are studied in the composition range 0 < x < 0.333. The vibrational modes observed in the high energy range of the Raman spectra of the crystalline compounds are interpreted in terms of symmetrical and antisymmetrical O-Ge-O and Ge-O^? stretch vibrations. The molecular structure of the germanate glasses is deduced from a comparison of the Raman spectra of the glasses with those of the crystalline compounds, together with a study of the polarization properties of the glass spectra.It is observed that 6-coordinated Ge atoms occur in a network structure which resembles the structures occurring in the crystalline compounds 2 Li₂O · 9 GeO₂ and 2 Na₂O · 9 GeO₂.In the region of 0.18 < x < 0.33 it is found that tetrahedra with one non-bridging oxygen atom are formed. These tetrahedra are probably present in a network as occurs in the crystalline digermanates Li₂O · 2 GeO₂ and K₂O · 2 GeO₂.     

Structure of lead germanate glasses by Raman spectroscopy

Lead germanate glasses of the xPbO(1−x)GeO₂ compositions with x ranging from 0.200 to 0.625 have been synthesised and their crystallisation behaviour and vibrational properties studied by differential thermal analysis (DTA) and Raman spectroscopy. Raman spectra of the Pb₅Ge₃O₁₁ ceramics also have been measured and compared to lead germanate glass spectra and literature data on β-PbO. Ge atoms in low lead glasses are supposed to be surrounded by four to six oxygen atoms, while the high-lead glass (x=0.625) corresponding to stoichiometry of the Pb₅Ge₃O₁₁ ferroelectrics contains predominantly fourfold coordinated germanium. Structural resemblence of high-lead germanate glasses to the Pb₅Ge₃O₁₁ crystal is proposed rather than to β-PbO. The `boson' peak range in the spectra of lead germanate glasses is discussed taking into account the similarities of the spectra of glassy and crystalline Pb₅Ge₃O₁₁.     

Kinetics of crystallization of titanium based binary and ternary amorphous alloys

Metallic glasses are kinetically metastable materials. These amorphous materials can be transformed into a crystalline state by both isothermal and isochronal methods. The study of this transformation, and hence the thermal stability of metallic glasses, are important from an application view-point. In the present work, the non-isothermal crystallization kinetics of two titanium-based amorphous alloys namely, Cu₅₀Ti₅₀ and Ti₅₀Ni₃₀Cu₂₀, are reported. The activation energies for crystallization, E_c for both the systems have been evaluated using different non-isothermal methods viz. derived through Kissinger, Augis and Bennet and Ozawa. The values of E_c obtained using these methods are consistent for both the metallic glasses and it is found that E_c for the ternary metallic glass is considerably higher than the binary metallic glass. The increase in the activation energy on the substitution of Ni in the Cu–Ti metallic glass suggests the increase in the thermal stability.     

Vibrational spectra and structure of chloro-fluorozirconate glasses

A series of barium chloro-fluorozirconate glasses have been prepared. Their IR absorption, IR reflectivity and Raman spectra have been measured down to 33 cm^?1. The glass transition and crystallization temperatures have also been measured. The high frequency IR absorption and Raman modes of the chloro-fluorozirconate glasses have been assigned as in fluorozirconate glasses. The IR reflection spectra of chloride-containing glasses differed from the fluorozirconates in that one band was clearly related to Cl atom motions. The structure of the glasses probably consists of zig-zag chains of ZrCl₂F₄ mixed halide octahedra plus a pure fluoride matrix whose structure is similar to that of a ZrF₄BaF₂ glass with the same composition.     

Non-isothermal crystallization kinetics study on new amorphous Ga20Sb5S75 and Ga20Sb40S40 chalcogenide glasses

Bulk glasses of the system Ga₂₀Sb_xS_80−x (x = 5 and 40) were prepared for the first time by the known melt quenching technique. Non-isothermal differential scanning calorimetric (DSC) measurements of as-quenched Ga₂₀Sb_xS_80−x (x = 5 and 40) chalcogenide glasses reveal that the characteristic temperatures e.g. the glass transition temperature (T_g), the temperature corresponding to the maximum crystallization rate (T_p) recorded in the temperature range 400-650 K for x = 5 and 480-660 K for x = 40 are strongly dependent on heating rate and Sb content. Upon heating, these glasses show a single glass transition temperature (T_g) and double crystallization temperatures (T_p1 and T_p2) for x = 5 which overlapped and appear as a single crystallization peak (T_p) for x = 40. The activation energies of crystallization E_c were evaluated by three different methods. The crystallization data were examined in terms of recent analysis developed for non-isothermal conditions. The crystalline phases resulting from (DSC) have been identified using X-ray diffraction.