Critical parameters in the processing of engineered stress profile glasses

A new approach to chemical strengthening is to move the maximum residual compression below the glass surface. With appropriate processing, this approach leads to strengthening and a decrease in the strength variability. This improvement in mechanical reliability is accomplished by introducing stable crack growth into the glass, which leads to multiple cracking of the glass surface prior to failure. In the current study, a fracture mechanics analysis is presented that uses a simple form for the stress profile. By determining the effect of this stress profile on the apparent fracture toughness of the material, it is possible to identify the conditions when spontaneous cracking occurs, the stress for the onset of multiple cracking and the ultimate strength of the glass. In particular, it is shown there is an important interplay between the depth of the maximum compression, the stress gradient and the magnitude of the maximum compressive stress. The current analysis is then used to define a strategy for the processing of glasses with engineered stress profiles.     

Morphological control and in vitro bioactivity of nanoscale bioactive glasses

In this study, nanoscale bioactive glasses with different morphologies were prepared through sol-gel process using lactic acid as hydrolysis promoter. The effect of lactic acid concentration on the morphology of bioactive glass was characterized. The influence of the morphology on the in vitro bioactivity of samples was investigated in simulated body fluid and examined by various methods. The results showed that nanoscale surface morphologies with high roughness, created by addition of lactic acid, greatly enhanced the in vitro bioactivity of as-prepared samples. It was found that the morphology with nanoscale surface feature and pore size distribution, in addition to specific surface area and pore volume, plays an important role in accelerating the formation of carbonated hydroxyapatite. According to our results, bioactive glasses possessing surface morphology with significant numbers of nanoscale bioactive glass particles and a narrow unimodal or bimodal mesopore structure, exhibit the best in vitro bioactivity.     

Layer contribution model for layer-by-layer self-assembly oxygen barrier film

Although layer-by-layer self-assembly (LbLSA) method has gained a great interests by their high oxygen barrier level below 10^?3 cc/m²day, theoretical approaches have been limited to analyze the physical properties of the coating layer. In addition, there is a conceptual problem to apply hybrid composite model based on particle distribution because the coating layer is constituted by individually concentrated substances. In this study, oxygen permeability model for LbLSA film was developed by considering the each layer contributions to the oxygen barrier level and compared with the typical models. In particular, it can be demonstrated that the layer contribution model (LCM) is depended on the qualitative factors by numerical analysis for the results of dip coating and spray-assisted spin (SAS) fabrication. As a result, it was confirmed that free volume space and surface density of the inorganic particles are strongly associated with the gas permeability of LbLSA film.     

Inline deposited thin-film silicon solar cells on imprinted foil using linear PECVD sources

The standard way to improve the light management of thin film solar cells is to introduce a light scattering structure, either on the front window or at the back reflector. Usually, growth conditions of TCO layers are adjusted to get random surface roughness on the front window. In this paper we present an alternative method, which can be applied both on the front window and at the back reflector. It involves imprinting a UV curable coating layer allowing full control on the texture (random or periodic) to fully optimise the light trapping. Light trapping is even more important for microcrystalline Si solar cells. We have fabricated thin film nip Si solar cells with sputtered Ag/ZnO back contacts on embossed barrier layers on steel foil. We show that the UV curable coating is well-suited as imprintable barrier layer between the steel foil and the active layers. For nip a-Si cells we can obtain light trapping, as measured by the short-circuit current, that is almost as good as that of nip a-Si cells made on Asahi U-type glass, covered with a Ag/ZnO back reflector. Furthermore, we show that dynamically processed a-Si nip cells on foil realised efficiencies of over 7%, which are only slightly less than for cells made in a UHV lab-scale cluster tool in static processing. Finally, a-Si/a-Si tandems and μc-Si/a-Si tandems have been fabricated. Initial efficiencies of around 8% on textured barrier layer on steel foil have been achieved.     

Acetic acid derived mesoporous bioactive glasses with an enhanced in vitro bioactivity

In this paper, a novel mesoporous bioactive glass (MBG) with a nanoscale surface feature in the SiO₂–CaO–P₂O₅ system has been synthesized by means of the acetic acid-assisted sol–gel process. As a comparison, the normal sol–gel derived bioactive glass (NBG) with the same composition was also synthesized. The structure and in vitro bioactivity of as-prepared samples were characterized using various methods. The results indicated that using acetic acid as a structure-assisted agent and hydrolysis catalyst is in favor of preparing the bioactive glass with nanoscale surface morphology, larger specific surface area, relatively homogeneous sized mesopore distribution. Depending on this novel structure, MBG presented an enhanced formation of hydroxyl-carbonate apatite layer and high in vitro bioactivity.     

Real-time dissolution of P40Na20Ca16Mg24 phosphate glass fibers

This study characterizes the dissolution of quaternary P₄₀Na₂₀Ca₁₆Mg₂₄ phosphate glass fibers. Mass loss rate, the evolution of the surface morphology and the pH of solution were monitored. The effects of sizing and annealing on these processes were also studied. Silane coating did not slow down the fiber dissolution rate whereas annealing did. Scanning electron microscopy showed that pitting and hydration led to the peeling of surface layers from the fibers.     

Hydrogen blistering and hydrogen-induced cracking in amorphous nickel phosphorus coating

Hydrogen blistering and hydrogen-induced cracking in amorphous Ni–P coating were studied. The results showed that hydrogen blistering and hydrogen-induced cracking in Ni–P coating could form during cathodic charging. Hydrogen blister could nucleate through hydrogen atoms diffusing into free volume cavity besides preexisted void. With increasing hydrogen pressure, shear bands appeared on the surface of hydrogen blister, and then hydrogen-induced cracking initiated and propagated along the wall of hydrogen blister.     

Towards the origin of the memory effect in oxide glasses

Glass samples with same composition and properties but different thermal histories can exhibit different behavior upon a subsequent heat-treatment, a phenomenon known as the memory effect. Generally, it is considered that the memory effect is due to nanoscale density fluctuation, which exists in all glasses and causes non-exponential relaxation with more than one relaxation time. Earlier, we studied the memory effect of various silica glasses and found that some pure silica glasses did not exhibit the memory effect while some silica glasses with higher impurity contents exhibited the memory effect. Based upon this finding, we suggested that the phenomenon originated from concentration fluctuation rather than density fluctuation. In this study, the memory effect in 6 mol% K₂O-94 mol% SiO₂ glass was investigated. The K₂O-SiO₂ glass system has a metastable immiscibility below the glass transition temperature and the chosen glass composition is the critical composition corresponding to the estimated critical temperature of the immiscibility boundary. Thus, it is expected that this glass composition would exhibit large super-critical concentration fluctuation, which increases with decreasing heat-treatment temperature. Density fluctuation, on the other hand, increases with increasing heat-treatment temperature. A much larger memory effect was observed at the lower heat-treatment temperature for the present glass. This result supports our earlier contention that the origin of the memory effect is composition fluctuation rather than density fluctuation.     

Edge-strengthening of flat glass with acrylate coatings

Edge-strengthening is a novel technology used to strengthen glass by applying a coating only on the edges. In this work, edge flaws of flat glass articles were examined in detail via scanning electron microscope (SEM) imaging. Then the effect of using weatherable acrylate coatings on edge-strengthening of flat glass was determined. Four-point bending measurement showed that the coatings provided more than twofold increase of the mean flexural strength and a factor of about two increase of the tensile stress needed to reach 0.8% cumulative probability of failure. The coatings were found to cover the flaw zone at the glass edges and partially fill in the cracks. Different surface treatments led to different levels of strengthening, indicating the importance of coating adhesion. The coating’s thermal and mechanical properties affected the extent of strengthening effect. A coating formulation with a higher glass transition temperature tended to provide a better strengthening effect, indicating the importance of closure stress within cracks generated during film curing process. Challenges of applying the edge-strengthening technology are also discussed.     

Epitaxial Sn1‐xPbxS nanorods on iso‐compositional thin films

Based on SnS (Herzenbergite) – SnPbS₂ (Teallite) mixed crystals with orthorhombic layer structures, thin films and lawns of Sn_1‐xPb_xS nanorods were produced using hot wall vacuum deposition method (HWVD). The lawn was formed onto the surface of an underlying thin Sn_1‐xPb_xS film which is build by differently oriented blocks. The density of rods arranged like a lawn depends on the metal ratio and substrate temperature. X‐ray and TEM analysis of the epitaxial material showed preferential (001) orientation perpendicular to the surface of the glass substrate. The roughness of the films measured by atomic force microscopy was in the range of R_q = 49.5–86.3 nm depending on lead concentration The rods were about 500 nm high and 300 nm in diameter. As revealed by TEM‐EDX experiments the droplet at the tip of rods consists of tin. Therefore it is assumed the rods grew via a self‐consuming vapor–liquid–solid (VLS) mechanism. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crack-free high load Vickers indentation of silica glass

The surface of pure silica glass was prepared to be resistant to cracking from application of Vickers indentation loads of up to one kilogram force (1 kgf). Sample preparation, testing environment, and water content of the glass sample were found to be critical in producing crack-free indentations. Sample preparation consisted of a careful polishing and etching to remove the densified surface layer. Indentation was performed under a nitrogen environment which was also necessary to produce crack-free specimens. Water introduced into the silica glass sample mechanically as well as water introduced into the glass during melting or heat-treatment, were found to be detrimental to crack resistance.     

Strengthening of soda-lime-silica glass by surface treatment with sol–gel silica

In this study, the failure resistance of soda-lime-silica glass was increased by surface treatment with sol–gel silica. Samples annealed and ion-exchanged in KNO₃ for 24 h at 450 °C were considered. Sol–gel silica coating was carried out by dipping the glass samples into a sol suspension prepared by hydrolysis of Si(OEt)₄ in ethanol/water solution. The deposited layer was consolidated in air for 24 h and subjected to mild thermal treatment at 300 °C for 1 h. The surface treatment increased the fracture resistance of annealed glass of about 35 MPa; conversely, ion-exchanged specimens showed an average increase of about 90 MPa. The strengthening effect induced by the surface treatment was attributed to the reduction of the effective crack length generated by the silica coating. The different strength increase between annealed and ion-exchanged samples is discussed in terms of fracture toughness which, for ion-exchanged glass, is not constant, due to the presence of the surface residual stresses and thus the reduction of the crack length due to the silica coating determines a higher strength increase than for annealed glass.     

Influence of the dipping coating procedure on the mechanical strength of soda-lime glass rods

In order to investigate the effect of sol-gel coatings on the mechanical behavior of a high strength glass substrate, HF etched glass rods were used.

Coatings with different compositions (SiO₂, ZrO₂ and 20%ZrO₂---80%SiO₂) and different thicknesses were produced to study the influence of these parameters on strength.

Functions of integral probability versus strength were used to analyze data.

Coated glass rods exhibit higher strength in comparison with uncoated control rods that have undergone the same treatment. It seems evident that there is an effect of composition on strengthening. SiO₂ coated rods displayed higher strength.

A lowering in strength at thickness higher than 0.2 μ was observed, independently of composition.

The effect of a saturated Ca(OH)₂ solution was also studied.     

Color Gamut of Liquid Crystal Polysiloxanest

Polysiloxanes with suitable side-chains form a cholesteric liquid crystal phase that can be applied to a substrate to produce a durable coating which exhibits strong colours below the glass transition temperature. The peak reflectance is almost 0.5 and a nearly 1.0 peak reflectance can be obtained using a half-wave retardation plate coated on both sides with the material and viewed from one direction against a black background. Values below 0.5 and between 0.5 and 1.0 have been also obtained using suitable solvents and alignment techniques. Many desired spectral reflectance distributions can be then obtained because of the additive color properties of such cholesteric coatings. As a result it is possible to produce a larger colour gamut than with real surface colours such as pigments and dyes. Employing commercially available material experimental work was carried out demonstrating a greatly expanded colour gamut on the chro-maticity diagram. Also it is possible to modify the spectral reflectance distribution of coloured substrates by coating them with a material having a reflectance peak at the desired band of wavelength.     

A study of mechanical homogeneity in as-cast bulk metallic glass by nanoindentation

A surface softening effect induced during copper-mould suction casting of bulk metallic glass is investigated as a function of rod diameter and glass fragility index, m, by nanoindentation. A reduction in hardness and reduced modulus at the rod surface is found to be favoured in small diameter castings and in fragile systems, respectively resulting from limited in-situ annealing and from a greater diversity of metastable atomic environments in the potential energy landscape of fragile glasses. Enhanced propensity for shear transformation zone nucleation in the low moduli surface is explained in terms of reduced atomic connectivity arising from a reduction in local co-ordination number and a lowering of the shear modulus. Finally, the structure and mechanical diversity that is possible in as-cast bulk metallic glass rods is explored through a relative quantification of shear modulus and plastic zone size across the whole as-cast state and in a single rod. These findings illustrate the sensitivity of bulk metallic glass to preparation, especially in respect of thermal history, potentially making replication of mechanical data between researchers problematic.     

溶胶-凝胶法制备紫外及蓝光双截止润眼镀膜玻璃

采用溶胶-凝胶法,在3 mm厚的普白玻璃含锡面镀制镶嵌Ag纳米粒子的氧化硅薄膜,达到吸收蓝光的效果,在其非锡面镀制纤锌矿结构的氧化锌薄膜,达到阻隔紫外效果.通过双膜层的相互作用,达到对紫外和短波蓝光有效阻隔吸收,从而获得具有紫外蓝光防护及润眼功能的镀膜玻璃.研究了热处理温度和膜层厚度对近紫外和蓝光阻隔率的影响.结果表明:随着退火温度的升高,膜层更加致密,且退火温度越高,蓝光的吸收率也逐渐提高,吸收峰位红移.利用浮法玻璃本体的富锡表面还原AgNO3成Ag纳米粒子分散镶嵌在氧化硅薄膜的结构,能有效吸收380～450 nm的短波蓝光.实验样品呈现出美观的淡金黄色,且随着膜厚的增大,金黄色程度逐渐加深.以样品a为例,所制备的氧化锌膜层为稳定的纤锌矿结构,膜厚为438 nm,表面为球状颗粒,对380 nm以下的紫外光阻隔率为98.83;;所制备氧化硅薄膜厚为200 nm,表面致密,对380～450 nm的蓝光阻隔率为90.73;,样品整体450～780 nm可见光透过率为77.8;.     

Outer space formation of a laser host glass

Classical crystallization calculations were performed to determine the possibility of forming a particular type of laser glass with the avoidance of devitrification in an outer space laboratory. Although the laser glass in question readily crystallizes in an earth environment, it is demonstrated that under the homogeneous nucleating conditions obtainable in a zero gravity laboratory this laser glass may be easily quenched to a virtually crystal-free product. Use of this material as a host in a neodymium glass laser would result in a more than 10% increase in efficiency when compared to laser glass rods of similar composition currently commercially available.     

Improvement of the chemical resistance of zirconium fluoride glasses coated with a Tiron® modified tin oxide layer prepared by the sol–gel process

In order to improve the chemical resistance of zirconium fluoride glass a protective transparent SnO₂ layer was deposited by the sol–gel dip-coating process in the presence of Tiron^® as particle surface modifier agent. After water immersion for different periods of time, both coated and non-coated fluoride glasses were analyzed by scanning electron microscopy, mass loss evaluation, infrared spectroscopy and X-ray photoelectron spectroscopy. In contrast to the effects occurring for non-coated glass, where the surface undergoes a rapid selective dissolution of the most soluble species, the results for the SnO₂-coated glass showed that the filling of the film nanopores by dissolved glass material results in a hermetic barrier protecting the glass surface. The selective glass dissolution was confirmed by liquid chromatography measurements of the etching solution after each exposure time.     

Investigation on sol–gel silica coatings for the protection of ancient glass: Interaction with glass surface and protection efficiency

To hinder the phenomenon of weathering of ancient stained glass, the present work proposes the application of sol–gel coatings to the glass surface. Previous investigations [1], [2], [3], [4], [5] and [6], in fact, show that sol–gel silica coatings do not change the appearance of artistic glasses when deposited on their surface. Moreover, the film thickness is so small (around 200 nm) and its composition and structure so compatible with that of the original glass, that the characteristics of the coating and original glass are not distinguishable. In this work, several recipes used to produce sol–gel coatings have been tested in order to understand their behavior when adopted for covering ancient weathered glass. The coatings are made of sol–gel silica prepared with two different catalysts: H⁺, Pb²⁺ and without catalyst. All the investigated samples show a good adhesion of the coating to the glasses used to simulate the behavior of ancient artefacts. The sol–gel silica coatings have been studied before and after accelerated ageing to test the resistance of the protective coatings to weathering. Another important index to test of the efficiency of the sol–gel coatings for the protection of an ancient glass is the lead ion mobility. In ancient stained glass, in fact, this element is present in the metallic lead network, in the grisaille paintings and constitutes a main component of many glass tesserae. The action of water on this highly mobile ion involves the degradation of the glass itself and the release of the ion in the rain solution. Ageing tests show the efficiency of H⁺ and Pb²⁺ catalyzed coatings and the inefficiency of the non-catalyzed sol–gel layers.     

Incorporation of water into glasses and its influence on the diffusion of cations,including the creation of diffusion barriers

When heated to elevated temperatures, many glasses take up water from moisture-containing environments. This leads not only to changes in local water concentrations, but also to non-uniform structural changes within the glass. These structural changes impact many structure-sensitive properties, including the diffusivity of ions. Experimental data for the uptake of water by a Type I silica glass, Infrasil 302, and by an alkaline-earth boroaluminosilicate glass, Corning Code 1737, are discussed as well as the influence of the incorporation of water into these glasses on the diffusion of sodium. Furthermore, the modification of glass near the surface by the uptake of water, leading in the case of the alkaline-earth boroaluminosilicate glass to the creation of a very effective barrier layer against the diffusion of sodium, is addressed.