How a liquid becomes a glass both on cooling and on heating

The onset of structural arrest and glass formation in a concentrated suspension of silica nanoparticles in a water-lutidine binary mixture near its consolute point is studied by exploiting the near-critical fluid degrees of freedom to control the strength of an attraction between particles and multispeckle x-ray photon correlation spectroscopy to determine the particles' collective dynamics. This model system undergoes a glass transition both on cooling and on heating, and the intermediate liquid realizes unusual logarithmic relaxations. How vitrification occurs for the two different glass transitions is characterized in detail and comparisons are drawn to recent theoretical predictions for glass formation in systems with attractive interactions.     

Formation of silver nanoparticles with dielectric shell on the silver-containing glass during laser evaporation and ablation

We demonstrate a new method of silver nanoparticles formation on a silver-containing glass surface due to its irradiation by a pulsed CO₂ and YAG:Nd lasers. The particles are formed as a result of reduction of silver ions from the glass at the edges of a laser torch emerging during evaporation and ablation. The settled particles are then fixed on sample surface by a shell of glass dielectric components. The method allows creating plasmonic nanostructures on the glass surface for sensing applications.     

Glass formation and local structure evolution in rapidly cooled PdNi alloy melt under high pressure

Using molecular-dynamics simulation, investigations of the local structure under high pressure and the glass formation in the PdNi alloy melt under high pressure are performed. The critical cooling rates for glass formation are reduced apparently with pressure. With increasing of pressure, a more compacted local structure with more ideal icosahedra than defected icosahedra is obtained, which may be one of the main factors for the contribution of the high pressure to the glass formation.     

Studying the structural features of oxide nanoclusters of cerium and titanium in a silicate glass by means of the small-angle neutron scattering

The features of the formation of Ce-Ti-O complex oxide nanoclusters in a silicate glass are studied by means of the small-angle neutron scattering technique. It is found that bounded regions of density fluctuation of the glass material are formed in the initial glass matrix without the addition of titanium and cerium oxides. These regions could serve as nucleation centers for oxide clusters of cerium and titanium upon their introduction into the matrix. The calculated average size of these inhomogeneities does not exceed 30 ± 1 nm, and their surface volume equals 0.72 ± 3 nm³. A structural mechanism for Ce-Ti-O oxide formation in a silicate glass, in which the nanoclusters are formed within a bounded region of glass material inhomogeneities at low concentrations of the initial cerium oxide (CeO₂), is proposed. At high cerium oxide concentrations, oxide nanocluster growth occurs predominantly on the surface of these inhomogeneities. This leads to a sharp change in the nanocluster sizes and their fractal dimension.     

Exciton absorption at the initial stages of the formation of the CuCl phase in a glass

The fundamental absorption spectra of CuCl nanocrystals in glass samples are investigated in the energy range 3–4 eV at a temperature of 300 K with the aim of elucidating the kinetics of the initial stage of the formation of the CuCl phase in the glass. The CuCl phase is grown in the glass under stepwise annealing at temperatures of 500, 615, and 707°C. The kinetics of variation in the intensity and the shift of the maximum in the exciton absorption spectra of CuCl nanocrystals are studied in the course of annealing of the glass samples. It is established that, for all the temperatures under investigation, the formation of the CuCl phase begins with the transient stage that involves the fluctuation formation of supercritical nuclei of the CuCl nanomelt. At a temperature of 500°C, the transient stage gives way to the stage of a rapid increase in the number of supercritical nuclei of the CuCl phase. At temperatures of 615 and 707°C, the transient stage gives way to the stage of an intensive growth of nuclei without a considerable increase in their number. The number of nuclei formed during the transient stage at 707°C is smaller than that observed after the transient stage at 500°C by a factor of 24. However, the sizes of the nuclei formed at 707°C are larger than those observed after the transient stage at 500°C. This difference is explained by the fact that the diffusion length of Cu⁺ ions controlling the formation of the CuCl phase increases with increasing temperature. The experimental data on the kinetics of the formation of the new phase in the glass are in good agreement with the Zel’dovich-Frenkel classical theory of the formation of a new phase, which accounts for the stage of the formation of critical nuclei.     

Theoretical treatments of ultrashort pulse laser processing of transparent materials: toward understanding the volume nanograting formation and “quill” writing effect

The dynamics of ultrashort-laser-induced generation of free electron plasma inside bulk glass is analyzed. The results of modeling are presented for typical glass modification regimes, obtained on the basis of Maxwell’s equations supplemented with the equations describing electron plasma formation and the laser-induced electric current. The model has been demonstrated to allow revealing important features of laser beam propagation in the regimes of dense electron plasma generation such as strong scattering up to complete displacing of light from the plasma region followed by beam refocusing. The geometry of the laser energy absorption zone is determined, and the glass temperature is mapped which may be foreseen at the end of electron–glass matrix relaxation. This, in turn, allows estimating the laser-induced stress levels and making conclusions on the routes of glass modification. Finally, based on the modeling results, the plausible mechanisms are discussed which may be responsible for the formation of volume nanogratings in a number of transparent solids under the action ultrashort laser pulses and laser direct writing anisotropy observed for laser pulses with a tilted front.     

Soliton-induced waveguides in an organic photorefractive glass

We demonstrate optical waveguiding of a probe beam at 980 nm by a soliton beam at 780 nm in an organic photorefractive monolithic glass. Both planar and circular waveguides induced by one- and two-dimensional spatial solitons formed as a result of orientationally enhanced photorefractive nonlinearity are produced in the organic glass. Possibilities for increasing the speed of waveguide formation are discussed.     

Formation of silver nanoparticles on the silicate glass surface after ion exchange

It has been experimentally shown that water vapor thermal treatment of silicate glasses with silver ions introduced by ion exchange leads to the formation of a silver nanoparticle layer with a high packing density on the glass surface. The results of studying the morphology of samples by atomic force and electron microscopy and X-ray spectral analysis of the composition of nanoparticles, as well as the optical density and luminescence spectra in different stages of the treatment, are presented. Mechanisms explaining the processes responsible for silver nanoparticle formation upon water vapor thermal treatment on the glass surface after ion exchange are proposed.     

不透明玻璃显现出的曙光——块体金属玻璃的发现与应用

在足够高的冷却速度下，如同其他大多数物质一样，金属合金溶体在冷冷却到室温的过程中能够经过玻璃化转变过程变成非晶态固体——金属玻璃。金属玻璃因其具有许多优异和独特的物理、化学和力学性能而一直受到很大的关注。在过去，由于玻璃形成能力的限制，金属合金只能制成厚度为数十数米的薄带状金属玻璃，因而其应用范围受到极大的限制。通过对金属合金的组成、溶体的过冷与稳定性及玻璃形成能力的关系研究，人们用常规的方法在较低的冷却速度下就能在许多金属合金体系中形成三给尺度都达毫米至数厘米的块体金属玻璃，这为金属玻璃获得广泛的应用奠定了基础。     

Protection of phosphate glass by BK7 glass film in ion-exchange processing

Surface corrosion of phosphate glass during ion-exchange processing for optical waveguide fabrication is studied, and a protection method by using BK7 glass film is proposed and demonstrated in this paper. The protection coating processing is described and optical microscope and atomic force microscope observations are presented. Characteristics of the planar waveguide were measured also to show the protection coating would not introduce influence to waveguide formation in the phosphate glass. Experimental results show that the method can serve an effective protection, and will improve the performance of rare-earth-doped active phosphate glass optical waveguides.     

Initial nucleation stages and properties of CuCl nanoparticles in glasses

The time variation and temperature dependence of a CuCl phase nucleation in a glass was studied by exciton spectroscopy. The phase formation kinetics at three temperatures was measured. A time delay in attaining a stationary rate of the new phase growth was observed at all temperatures, in agreement with the Zeldovich theory. The kinetic parameters of the CuCl phase formation were determined in the initial stage, when the critical nuclei possessing a zero surface energy (and an effective radius below 1.3 nm) appear in the glass matrix. The first-order phase transition in the new phase is 200 K below the melting temperature of CuCl single crystals. The temperature dependence of the CuCl phase nucleation rate reveals the second and third stages of the new phase formation. The activation energies for diffusion of the CuCl phase components in the glass matrix are determined.     

新型掺Tb3+硅酸盐发光玻璃的研制

在数字X射线成像系统中使用的X光-可见光转换屏具有相当重要的作用,其性能直接影响成像系统的性能。针对特殊用途开发了一种新型掺Tb^3 硅酸盐发光玻璃转换屏,可用于30MeV的γ光子的成像探测;在低能X光(100keV)作用下的空间分辨能力与301型发光玻璃相当,而在能量高达12MeV的X光的照射下,其空间分辨能力不低于1．5lp／mm,发光效率约为301型发光玻璃的3倍。并对其性能进行了实验研究,相应的测量结果为：SiO2的质量分数达到50％以上时才能得到玻璃性质较好的材料．并使发光性能得到提高,BaO和Cs2O的质量分数接近相等的条件下,Tb^3 离子的质量分数为10．5％时发光性能最好;适量的Gd^3 离子可以敏化Tb^3 发光,也能增加玻璃密度,而Ce^3 离子可以降低发光的余辉;其它的微量元素则主要影响玻璃的熔融温度。     

Structural Characteristics of Metal Nanoparticles in Glass Upon Irradiation-Assisted Processing

Irradiation-assisted processing, i.e. ion, electron and laser irradiation, have been applied to fabricate metal/glass nanocomposites. The particle configurations are studied by transmission electron microscopy to get some insight into the rather complex formation mechanisms. Special attention is given to spheroidally shaped particles surrounded by smaller secondary particles observed upon ion beam mixing of silica/silver/silica layer compounds as well as irradiating femtosecond laser pulses on sodium silicate glass containing spherical silver particles. Another unique type of structure are cavities observed in silver particles formed by high fluence ion implantation into silica as well as upon laser pulse irradiation of silver particles in glass. The experimental findings are discussed in terms of irradiation-induced defect formation and radiation-enhanced diffusion.     

On the Role of Supercritical Water in Laser-Induced Backside Wet Etching of Glass

The features and mechanisms of microcrater formation in optical silicate glass by laser-induced backside wet etching (LIBWE) are determined in a wide range of energy densities (Φ) from 4 to 10³ J/cm² for laser pulses of 5 ns length and 1 kHz repetition rate. The existence of two different mechanisms of laserinduced microcrater formation is revealed: (i) chemical etching in supercritical water (SCW), and (ii) cavitation. At Φ > 10² J/cm² irregular craters of 1–20 μm in depth with rough walls and distinct cracks around microcrater are formed testifying that in such mode (“hard”) laser induced cavitation plays a dominant role in glass removal. At Φ < J/cm² neat glass craters with smooth walls are formed, their size and shape are easily reproducible, cracks are not formed, and the processing area is limited to the laser spot area. In this mode (“soft mode with active cavitation”), a microcirculation of water is stimulated by cavitation without causing undesirable shock breakage. The latter is achieved thanks to the fast removal of glass etching products by microcirculation, and the inflow of “fresh” etchant (SCW) to the glass surface in the vicinity of the formed microcraters. Such mode is optimal for highly controlled laser microstructuring of glass and other optically transparent materials.     

Three-dimensional microfluidic structure embedded in photostructurable glass by femtosecond laser for lab-on-chip applications

A new technology for rapid prototyping of lab-on-chip devices is described. Direct write of a near-infrared femtosecond laser forms three-dimensional (3D) latent images inside photostructurable glass. Modified regions are developed by a post-annealing and then preferentially etched away in dilute hydrofluoric acid solution with an etching selectivity of 40–50 times, resulting in the formation of true 3D hollow microstructures inside the glass. Microfluidic structures with microcells and microchannels embedded in the glass are fabricated by this technique. PACS 42.62.-b; 47.85.Np; 81.05.Kf     

Signatures of glass formation in a fluidized bed of hard spheres

We demonstrate that a fluidized bed of hard spheres during defluidization displays properties associated with formation of a glass. The final state is rate dependent, and as this state is approached, the bed exhibits heterogeneity with increasing time and length scales. The formation of a glass results in the arrest of macroscopic particle motion and thus the loss of fluidization. Microscopic motion persists in this state, but the bed can be jammed by application of a small increase in flow rate. Thus a fluidized bed can serve as a test system for studies of glass formation and jamming.     

In situ observations by magnetic resonance imaging for formation and dissociation of tetrahydrofuran hydrate in porous media

Tetrahydrofuran (THF) hydrate has long been used as a substitute for methane hydrate in laboratory studies. This article investigated the formation and dissociation characteristics of THF hydrate in porous media simulated by various-sized quartz glass beads. The formation and dissociation processes of THF hydrate are observed using magnetic resonance imaging (MRI) technology. The hydrate saturation during the formation is obtained based on the MRI data. The experimental result suggests that the third surface has an effect on hydrate formation. THF hydrate crystals lean to form on the glass beads and in their adjacent area as well as from the wall of the sample container firstly. Furthermore, as the pore size diminishes, or as the formation temperature decreases, the nucleation gets easier and the formation processes faster. However, the dissociation rate is mostly dependent on the dissociation temperature rather than on the pore size.     

Formation of silver nanoparticles in photothermorefractive glasses during electron irradiation

The formation of silver nanoparticles in photothermorefractive glasses during electron irradiation and subsequent heat treatment is experimentally studied. The optical density spectra of samples at various stages of heat treatment are compared. The formation of metallic nanoparticles is shown to occur during both electron irradiation and subsequent heat treatment. Nanoparticles are localized in layers parallel to the surface. At the initial stage of nanoparticle formation, the key role is played by the appearance of a negative bulk charge in the near-surface layer in glass, which results in the field-assisted migration of positive metal ions and a characteristic layered distribution of metallic nanoparticles in the glass volume.     

Investigation of the surface reactivity of a sol-gel derived glass in the ternary system SiO2-CaO-P2O5

A new glass formulation, with the molar composition 60% SiO₂-35% CaO-5% P₂O₅, was synthesized using the sol-gel process, for applications as biomaterial in orthopaedic or maxillo facial surgery. Pellets, made of glass powder, were uniaxially compacted and soaked in simulated body fluid (SBF) for up to 7 days at 37 °C to evaluate glass bioactivity. Ionic exchanges at the interface glass-SBF were evaluated by studying evolutions of calcium, phosphorus and silicon concentrations in SBF using ICP-OES. Changes in glass surface, and the formation of crystalline phases were analyzed using XRD, SEM, EDS and FTIR methods.Results form ICP-OES showed a high reactivity of the glass surface with a very high and continuous release of calcium, a limited glass dissolution and an uptake of phosphorous from SBF. Results from both FTIR and XRD analysis indicated that the glass surface was progressively covered by two different phases: CaCO₃ as calcite and a carbonated apatite layer. The formation of these phases, following two different schemas, was observed after 2 h of immersion and confirmed after 7 days. SEM micrographs and EDS analysis demonstrated that the main phase, a carbonated apatite, was present as micro-spheroids and the secondary phase, calcite, was materialized by agglomerates which have diameters up to 10-15 μm. These results are in accordance with a bioactive feature of the glass studied.     

Ultrafast time-resolved photography of femtosecond laser induced modifications in BK7 glass and fused silica

The dynamics of absorption after excitation of fused silica and BK7 glass with femtosecond laser radiation are visualized by transient absorption spectroscopy. Focusing laser radiation with pulse durations in the picosecond time regime in BK7 glass generates free electrons with relaxation by emission of radiation or by formation of defects. The temporal and spatial emission characteristics are observed by high-speed photography in the streak mode. The beam waist moves within the pulse duration towards the incoming laser radiation by self-focusing and with the laser radiation absorbed by multi-photon processes. The dynamics of the long lasting stress formation is visualized by time-resolved Nomarski-Photography. The modification of the glass is investigated during and after irradiation with ultra-short pulsed laser radiation (100 fs<t_p<3 ps) at the wavelength =810 nm. The formation of a sound wave in fused silica and BK7 glass is observed and the mechanical stress, depending on the excitation pulse duration, is measured. PACS 06.60.Jn; 42.50.Md; 78.47.-p; 81.16.-c; 82.53.-k