Crystallization behaviors of Al-Ni-La amorphous alloys with trace Ti and B

Effects of the single or simultaneous addition of trace Ti and B (?1 at.%) on the glass-forming ability (GFA) and crystallization behaviors of Al₈₈Ni₆La₆ and Al₈₉Ni₆La₅ amorphous alloys were investigated by X-ray diffraction and differential scanning calorimetry. The addition of trace Ti and B deteriorates the GFA, but improves the thermal stability especially if Ti is added singly. The crystallization onset temperature T_x1 of the first exothermic peak increases by 29.5 and 18.0 K when 1% of the Al atoms in Al₈₈Ni₆La₆ and Al₈₉Ni₆La₅ are replaced by Ti, respectively. However, the primary phase during annealing remains unchanged.     

Dense amorphous packing of binary hard sphere mixtures with chemical order: The stability of a solute ordered approximant

Recently, Miracle proposed that the intermediate structure in metallic glasses could be usefully characterized as an ordered face centered cubic packing of solute-centered coordination clusters. In this paper we examine the stability of such solute ordered arrangements in binary hard sphere mixtures subject to density maximization through local particle moves.     

The structure and optical properties of GeO2-GeS2 glasses

Oxy-chalcogenide glasses with compositions of xGeO₂-(100 − x)GeS₂, where 0 ? x ? 100 mol%, have been prepared and studied in terms of their structures and optical properties. X-ray fluorescence spectroscopy shows that Ge:S ratio can deviate from GeS₂ by ∼10 at.%, depending critically upon the preparation conditions. Raman scattering spectroscopy suggests that stoichiometric GeO₂-GeS₂ glasses have a heterogeneous structure in the scale of 1-100 nm. The optical gaps are nearly constant at 3.0-3.5 eV for glasses with 0 ? x ? 80 mol% and abruptly increase to ∼6 eV in GeO₂. This dependence suggests that the optical gap is governed by GeS₂ clusters, which are isolated and/or percolated. Composition-deviated glasses appear as orange and brown, and these glasses seem to have more inhomogeneous structures.     

Theoretical prediction of bulk glass forming ability (BGFA) of Ti-Cu based multicomponent alloys

The bulk glass forming ability (BGFA) of Ti-Cu based multicomponent alloys has been evaluated via theoretical modeling and computer simulation studies based on a combination of electronic theory of alloys in the pseudopotential approximation and the statistical thermodynamical theory of liquid alloys. The magnitude of atomic ordering energies, calculated by means of the electronic theory of alloys in the pseudopotential approximation, was subsequently used for calculation of the key thermodynamic parameters such as enthalpy, entropy and Gibbs free energy of mixing, viscosity, and critical cooling rate of the binary Ti-Cu and ternary Ti-Cu-X alloys. The potential alloying elements (X) can be divided in two groups defined by their effect on the variation of the negative heat of mixing and their influence on the critical cooling rate. Most of the predicted candidate alloying elements from either X_I (Al, Si, Ag) or X_II (Co, Ni, Fe, Sn, Be) and/or both groups have already been used successfully for the fabrication of new Ti-Cu based bulk metallic glasses. It was also shown that the critical cooling rate appears to be a more important parameter rather than the change in the negative heat of mixing for the prediction of candidate alloying elements improving BGFA.     

Doping-induced formation of bulk nanocrystalline alloy from metallic glass with controllable microstructure and properties

We report the formation of bulk nanocrystalline alloys from a Pr-based bulk metallic glass-forming alloy by doping iron. The microstructure of the alloys can be tuned progressively from full glassy state to composite with nanocrystalline particles in the glassy matrix, and finally into nanostructured state accompanying with the gradual magnetic and mechanical changes. The role of the addition in the control of microstructure and magnetic property, the mechanism for the nanocrystalline formation induced by addition, and the relation between the microstructure and properties are discussed.     

Preparation of amorphous composites with polymer-derived silicon nitride matrix reinforced by three-dimensional silica fiber

Perhydropolysilazane, a low viscosity preceramic polymer with good infiltration efficiency and high char yield, was used to prepare amorphous composites with polymer-derived silicon nitride matrix reinforced by three-dimensional silica fiber, and the mechanical properties and microstructures were investigated. The composites without fiber coating showed a typical brittle fracture behavior with a smooth fracture surface, and a flexural strength of just 33.5 MPa. While the composites with fiber coating exhibited a non-brittle fracture behavior with distinct fiber pull-out in the fracture surface, and a high flexural strength of 144.9 MPa. It was the controlled fiber/matrix interface by precoating treatment that contributed to the high mechanical property of the composites.     

A critical analysis of the glass-forming ability of alloys

Several empirical rules have been proposed during the past few years to synthesize bulk metallic glasses. But, the real reasons for the improved glass-forming ability of these alloys are still not clear and the ability to design alloy compositions to enable synthesis of larger diameter rods has not improved. The present work conducts a critical analysis of the existing data in terms of the different glass-forming criteria and concludes that the available parameters cannot satisfactorily predict the GFA and explain all the observed data. Reasons for this failure have been suggested.     

Synthesis optimization of organic xerogels produced from convective air-drying of resorcinol-formaldehyde gels

Resorcinol-formaldehyde gels were produced at 50, 70 and 90 °C and with three different R/C ratios (500, 1000 and 2000). The effect of these variables combined with that of aging time was studied in order to optimize the synthesis conditions. The convective air-drying process was used, and the drying duration was studied with regard to the synthesis conditions. The aging time has no effect on the pore texture after 24 h at 90 °C or 48 h at 70 °C, whatever the R/C value. The synthesis-aging step can be shortened by increasing the temperature. Nevertheless, the pore size tends then to decrease, especially when R/C is high, but this can be counterbalanced by increasing R/C. Moreover, bubbles often appear in the gel at high synthesis temperature, which limits the temperature to about 70 °C in the case of monolithic parts. At 70 °C and with an air velocity of 2 m/s, the elimination of 90% of the solvent requires 1 h drying when the pore size reaches 400-600 nm, 2.5 h for 50 nm wide pores and 3 h when the pore size decreases to 15-20 nm. The drying duration does not exceed 8 h in all cases and could be shortened by increasing the temperature at the end of the process.     

Effect of ZnO and Bi2O3 addition on linear and non-linear optical properties of tellurite glasses

Glasses in the system TeO₂-Bi₂O₃-ZnO were studied with respect to their linear refractive indices and optical absorption in the UV-vis range. The third order non-linear refractive indices were measured using degenerated four wave mixing (DFWM). The optical Kerr susceptibilities calculated hereof were in the range from 5.49 to 6.58 × 10⁻¹³ esu and hence 34-41 times larger than that of fused SiO₂. They are roughly proportional to values theoretically calculated by the theory of Lines.     

Influence of structural relaxation on atomic mobility in a Zr41.2Ti13.8Cu125Ni10.0Be22.5 (Vit1) bulk metallic glass

The effect of an annealing at a temperature above or below the glass transition temperature in a Zr_41.2Ti_13.8Cu₁₂₅Ni_10.0Be_22.5 bulk metallic glass was investigated using dynamic mechanical analysis. Structural relaxation influences both the storage modulus (elastic component) and the loss modulus (viscoelastic component). Kinetics can be captured by a stretched exponential relaxation function. Experimental results are correctly described using a physical model based on the concept of defects for the mechanical response of amorphous materials and especially for the characteristic time relative to atomic mobility.     

Rare earth based bulk metallic glasses

Recently, the rare earth based bulk metallic glasses (REBMGs) have attracted increasing interest due to their unique properties and potential applications as functional glassy materials. These REBMGs display many fascinating properties such as heavy fermion behavior, thermoplastic properties near room temperature, excellent magnetocaloric effect, hard magnetism, and polyamorphism, all of which are of interest not only for basic research but also for metallurgy and technology. These characteristics and properties are ascribed to the unique electronic, magnetic and atomic structures of the REBMGs. In this review paper, the fabrication, glass-forming ability, polyamorphism, elastic, thermal, and physical properties are summarized and discussed. Owing to the unique electronic structure of rare earth elements, the electric and magnetic properties of the REBMGs are especially addressed. The works have implications for seeking novel metallic glasses with controllable properties and for understanding the nature of glass formation. The development of REBMGs as functional materials might promote and extend the commercial applications of metallic glasses.     

Solubility of glasses in the system P2O5-CaO-MgO-Na2O-TiO2: Experimental and modeling using artificial neural networks

Phosphate glasses in the system P₂O₅-CaO-MgO-Na₂O-TiO₂ for use as degradable implant materials were produced. In order to classify their solubility behavior, dissolution experiments were performed in deionized water for 60 min at 98 °C. Resulting solutions were analyzed using ICP-OES. In addition, pH measurements were carried out in physiological NaCl solution. With increasing phosphorus oxide content, the glasses showed a higher solubility and gave lower pH values in aqueous solution. This was caused by changes in the glass structure, as long phosphate chains are more susceptible to hydration than smaller phosphate groups. These changes in glass structure were followed by ³¹P MAS-NMR experiments. Increasing sodium oxide concentrations in exchange for calcium or magnesium oxide also increased the glass solubility by disrupting ionic cross links between chains. By contrast, addition of titania made the glasses more stable towards dissolution by cross linking smaller phosphate groups. The aim of this study was to find a relationship between glass composition and solubility behavior. As classical linear methods of data analysis were unsuitable due to the complexity of the relationship, preliminary artificial neural networks analyses were performed and were found to be an interesting tool for modeling the solubility behavior of phosphate glasses.     

Crystallization behavior of glasses in the system of Na2O-CaO-MgO-Fe2O3-Al2O3-SiO2 with high contents of nickel oxide

The structural behavior of nickel oxide in glassy and glass-ceramic materials, obtained in the system of Na₂O-CaO-MgO-Fe₂O₃-Al₂O₃-SiO₂, was investigated. The influence of the NiO content on the vitrification, crystallization, structure and exploitation properties of two model compositions, with different ratios [CaO]/[MgO] was analyzed. On the basis of DSC and XRD data, it is shown that NiO promoted the formation of bunsenite crystals, as nuclei for crystallization. On the other hand, NiO promoted formation of pyroxenes even for compositions with low MgO contents, which formed gehlenite without NiO admixtures. It is shown that in the composition with relatively high MgO contents, NiO could participate in the formation of two types of pyroxenes with the structure and chemical composition similar to (MgO_0.4NiO_0.6)(CaO_0.9NiO_0.1)Si₂O₆ and diopside-hedenbergite solid solutions. The optimal contents of NiO in both model compositions was about of 7 wt%, since higher contents reduced the exploitation properties. The glass-ceramics with optimal contents of NiO were also produced using Ni bearing galvanic slurry and coal ash; the resulting materials showed similar exploitation properties to those mentioned above.     

Icosahedral and dense random cluster packing in metallic glass structures

It has recently been shown that metallic glass structures can be idealized as inter-penetrating solute-centered atomic clusters that are packed with essentially periodic symmetry. The present work applies the same methodology to explore whether experimental observations can be matched by inter-connected solute-centered clusters that are organized in space via dense random cluster packing, Bergman icosahedral cluster packing or Mackay icosahedral cluster packing. Idealized partial pair distribution functions are developed where the symmetry of the solute positions in the structure is derived from the cluster-packing symmetry and the solute concentration, which establishes occupation of inter-cluster sites, especially β structural sites enclosed by an octahedron of solute-centered clusters. While each of the three models matches major features of the measured solute-solute partial pair distribution functions, the arrangement of clusters with Mackay icosahedral ordering provides the best fit. However, this model is not able to match an essential feature in solute-lean glasses and does not provide the same overall agreement as does periodic cluster packing for solute-rich glasses. Strong similarities between the structure factors in the Mackay icosahedral and periodic cluster-packing models, along with expected deviations from the idealized solute positions studied here, are likely to hinder an unambiguous distinction between these two models.     

Fluorescent porphyrins covalently bound to silica xerogel matrices

We study the influence of the nature and ring positioning of amino, hydroxy, and carboxy substituent groups on the fluorescence and some other physicochemical properties of free (H₂TPP) and metalled tetraphenylporphyrins (MTPP). Furthermore, we have studied the feasibility of covalently bonding TPP species on the surface of the pores of a silica matrix prepared by the sol-gel method through the bridging action of either one of the following functionalized alkoxides: 3-isocyanatopropyltriethoxysilane, (IPTES) or 3-aminopropyltriethoxysilane (APTES). Importantly, the red fluorescence observed in free porphyrin solutions is preserved even after the macrocyclic species is covalently bound to the silica matrix. The formation of a chemical union between the porphyrin substituting groups and the organic groups of the IPTES or APTES alkoxides render the H₂P-f precursory species has been proved successful by FTIR spectroscopy; likewise, the bond between Si-OH groups on the silica surface and the H₂P-f has been made evident. The best results, in terms of fluorescence preservation, are obtained by using a TPP substituted with -NH₂ groups in the ortho position of the phenyl rings, i.e. H₂T(o-NH₂)PP. A comparative fluorescence study of xerogels physically grafted or covalently bound with the latter TPP species confirm that, in the first case, the interaction of the molecule with the silanol groups of the silica surface of the gel inhibits fluorescence; while in the second case fluorescence is preserved.     

Density-structure correlations in Na2O-CaO-P2O5-SiO2 bioactive glasses

Relations for Na₂O-CaO-SiO₂ glasses have been developed to calculate the density of Na₂O-CaO-P₂O₅-SiO₂ bioactive glasses. The calculation makes use of NMR results of O’Donnell et al. indicating that P₂O₅ forms a separate phase, containing Na₃PO₄ and Ca₃(PO₄)₂, in the investigated glasses. The volume of the silicate units is the same as that found in Na₂O-CaO-SiO₂, Na₂O-SiO₂, and CaO-SiO₂ glasses. Similarly, the volume of PO₄ units is equivalent to that in Na₃PO₄ and Ca₃(PO₄)₂. Calculated densities are consistent with the experimental data.     

The structure of SiO2-GeO2 glasses: A spectroscopic study

Four glasses of the SiO₂-GeO₂ binary system have been synthesized via a sol-gel route followed by a heat treatment and a quench. Glass structure has been determined by Ge K-edge X-ray absorption spectroscopy (XAS) at low temperature and Raman spectroscopy. These mixed glasses present a continuous random network of interconnected GeO₄ and SiO₄ tetrahedra, with GeO₄ tetrahedra similar to the GeO₄ units in GeO₂ glass and continuous compositional variations from GeO₂-rich regions to SiO₂-rich regions. Such a random mixture is consistent with physical properties of these binary glasses as well as with the chemical dependence of their polyamorphism at high pressure. This EXAFS-derived mean Ge-O-Si angles are close to the Ge-O-Ge mean angle in GeO₂ glass, 134° and 130°, respectively. This misfit with the Si-O-Si angles might explain the ease of formation of isolated and pair defects centers, which are suspected to be at the origin of photo-induced modifications of optical properties in Ge-bearing SiO₂ glasses.     

Point defect formation and annihilation in silica glass by heat-treatment: Role of water and stress

It was discovered that E′ centers were created by heat-treatment when silica glass contains water and has residual stress. Silica glass samples were heat-treated at 1000 °C for various lengths of time in 355 torr (47 000 Pa) water vapor pressure and dry nitrogen gas atmospheres. The electron paramagnetic resonance (EPR) signal of E′ centers increased initially with heat-treatment time in both atmospheres but then decreased afterwards in the wet atmosphere. It is known that water molecules eliminate paramagnetic defects, such as E′ centers and non-bridging oxygen hole centers (NBOHCs) by reacting with these defects in the glass, transforming them to non-paramagnetic species such as Si-OH or Si-H. The present study indicates that water molecules are also capable of initially creating paramagnetic defects in the glass structure by breaking the silica network structure in the presence of stress. The present observation may be relevant to mechanical strength reduction of silica glasses, which is commonly observed in the presence of water and stress.     

Formation, mechanical properties and corrosion resistance of Ti-Pd base glassy alloys

No biocompatible Ti-based glassy alloys without a harmful element have been reported. We have examined the mechanical and chemical properties of Ti-Pd-Zr-Si glassy alloy in comparison with pure Ti metal and Ti-6Al-4V alloy which have been used so far for biomaterials. The present Ti-Pd base glassy alloys do not contain Al and Ni elements which are considered to be rather toxic. Melt-spun Ti₄₅Zr_50−xPd_xSi₅ glassy alloy ribbons (x = 35, 40, 45) exhibited good bend ductility and had higher Vickers’s hardness and lower Young’s modulus as compared to pure titanium and Ti-6Al-4V alloy. In addition, the Ti₄₅Zr_50−xPd_xSi₅ glassy alloys had higher corrosion resistance and were passivated over a wide range and at the lower passive current density of approximately 10⁻² Am⁻² than at of pure titanium and Ti-6Al-4V alloy in 1 mass% lactic acid and PBS(−) solutions at 310 K.