Luminescence and mechanoluminescence of Ba4Si6O16:Eu2+, RE phosphors.

The luminescence properties of green Ba4Si6O16:Eu2+, rare-earths (RE) (RE = Sc, Y, La and Lu except Pm) phosphors are reported. Their long-lasting phosphorescence is discussed in view of trap depths and concentrations determined from thermally stimulated luminescence experiments. A second emission band centered at 439 nm was evidenced at low temperatures, which stems from the substitution of Eu2+ in the two non-equivalent Ba2+ sites of Ba4Si6O16. The mechanoluminescence properties of Ba4Si6O16:Eu2+, RE phosphors are described, and a new mechanoluminescence mechanism is proposed, in the case where RE = Ho3+, involving a trap distribution from 0.694 to 0.924 eV. Mechanical loading (post UV irradiation) induces a decrease in depth of the trap distribution, leading to an increase of the luminescence intensity, whereas a drop of the luminescence intensity is observed upon unloading, following the faster release of the charge carriers.

Molecular design of melt-spinnable co-polymers as Si-B-C-N fiber precursors.

Two series of co-polymers with the general formula [B(C2H4SiCH3(NH)x(NCH3)y)3]n, i.e., composed of C2H4SiCH3(NH)x and C2H4SiCH3(NCH3)y (C2H4 = CHCH3, CH2CH2) building blocks in a well defined x : y ratio, have been synthesized by hydroboration of dichloromethylvinylsilane with borane dimethyl sulfide followed by successive reactions with lithium amide and methylamine according to controlled ratios. The role of the chemistry behind their syntheses has been studied in detail by solid-state NMR, FT-IR and elemental analyses. Then, the intimate relationship between the chemistry and the melt-spinnability of these polymers was discussed. By keeping x = 0.50 and increasing y above 0.50, i.e., obtaining methylamine excess, the co-polymers contained more ending groups and especially more tetracoordinated boron, thus allowing tuning very precisely the chemical structure of the preceramic polymer in order to meet the requirements for melt-spinning. The curing treatment under ammonia at 200 °C efficiently rendered the green fibers infusible before their subsequent pyrolysis under nitrogen at 1000 °C to generate Si-B-C-N ceramic fibers. Interestingly, it could be possible to produce also low diameter hollow fibers with relatively high mechanical properties for a further exploration as membrane materials.

Driving force for indentation cracking in glass: composition, pressure and temperature dependence.

The occurrence of damage at the surface of glass parts caused by sharp contact loading is a major issue for glass makers, suppliers and end-users. Yet, it is still a poorly understood problem from the viewpoints both of glass science and solid mechanics. Different microcracking patterns are observed at indentation sites depending on the glass composition and indentation cracks may form during both the loading and the unloading stages. Besides, we do not know much about the fracture toughness of glass and its composition dependence, so that setting a criterion for crack initiation and predicting the extent of the damage yet remain out of reach. In this study, by comparison of the behaviour of glasses from very different chemical systems and by identifying experimentally the individual contributions of the different rheological processes leading to the formation of the imprint--namely elasticity, densification and shear flow--we obtain a fairly straightforward prediction of the type and extent of the microcracks which will most likely form, depending on the physical properties of the glass. Finally, some guidelines to reduce the driving force for microcracking are proposed in the light of the effects of composition, temperature and pressure, and the areas for further research are briefly discussed.

Towards ultrastrong glasses.

The development of new glassy materials is key for addressing major global challenges in energy, medicine, and advanced communications systems. For example, thin, flexible, and large-area glass substrates will play an enabling role in the development of flexible displays, roll-to-roll processing of solar cells, next-generation touch-screen devices, and encapsulation of organic semiconductors. The main drawback of glass and its limitation for these applications is its brittle fracture behavior, especially in the presence of surface flaws, which can significantly reduce the practical strength of a glass product. Hence, the design of new ultrastrong glassy materials and strengthening techniques is of crucial importance. The main issues regarding glass strength are discussed, with an emphasis on the underlying microscopic mechanisms that are responsible for mechanical properties. The relationship among elastic properties and fracture behavior is also addressed, focusing on both oxide and metallic glasses. From a theoretical perspective, atomistic modeling of mechanical properties of glassy materials is considered. The topological origin of these properties is also discussed, including its relation to structural and chemical heterogeneities. Finally, comments are given on several toughening strategies for increasing the damage resistance of glass products.

The boson peak of silicate glasses: the role of Si-O, Al-O, and Si-N bonds.

The role of Si-O, Al-O, and Si-N bonds on the boson peak of silicate glasses has been investigated from a study of amorphous Si, SiO(2), and two calcium aluminosilicates with 0 (Ca28-O) and 4.4 (Ca28-N) mol % Si(3)N(4). The low-frequency part of the vibrational density of states g(omega) has been calculated from inversion of literature data and new heat capacity measurements. As defined by g(omega)/omega(2), the boson peak correlates with the excess heat capacity observed with respect to Debye T(3) limiting law. That libration of SiO(4) tetrahedra represents the main source of low-frequency excitations in silica glass is illustrated by the strong difference between the anomalies of amorphous Si and SiO(2) glass and the marked decrease observed for SiO(2) phases of increasing density. When Al substitutes for Si, libration of AlO(4) tetrahedra appears hampered by the presence of a charge-compensating cation. Rigidification of the silicate network resulting from substitution of N for O causes the boson peak of Ca28-N to be smaller than that of Ca28-O and shifted toward higher frequencies as increased cross-linking hinders libration of SiO(4) or AlO(4) tetrahedra. In agreement with their universal phenomenology, the calorimetric boson anomalies of Ca28-O and Ca28-N plot on the master curve defined previously by SiO(2) and alkali silicate glasses.