The influence of Sb on glass‐forming ability of Ga‐containing As2Se3 glasses

Effect of As to Sb substitution on glass‐forming ability of As₂Se₃ glass under Ga additions was comprehensively studied using optical spectroscopy in visible and IR regions, differential scanning calorimetry, X‐ray diffraction as well as Raman scattering techniques. The crystallization processes enhanced by Ga additions to As₂Se₃ glass were significantly suppressed under such As to Sb substitution. Following conventional synthesis, it was possible to substitute up to 50% of As by Sb within Ga_y(As_0.40?xSb_xSe_0.60)_100?y cut‐section without essential impact on glassy state, thus improving optical properties in the IR region by lowering the phonon energy. In the case of Ga_y(As_0.28Sb_0.12Se_0.60)_100?y cut‐section, up to 8 at.% of Ga can be introduced without crystallization, whereas in case of Ga_y(As_0.40Se_0.60)_100?y system, glass‐forming ability is limited just up to 3 at.% of Ga. The prepared Ga₅(As_0.28Sb_0.12Se_0.60)₉₅ glass composition was shown to be the richest in Ga keeping its vitreous state, good optical and thermodynamic properties allowing further rare‐earth doping and fiber drawing.     

Viscosity of glass‐forming systems

As one of the most important properties of glass‐forming liquids, viscosity has drawn significant attention in both glass manufacturing and fundamental research. We review the recent scientific progress in viscosity of glass‐forming systems, including both the liquid and glassy states. After the Vogel‐Fulcher‐Tammann (VFT) equation was introduced, many more efforts have been made to develop more accurate models to describe the temperature dependence of viscosity. In addition to the VFT equation, we also discuss three other viscosity models, viz., the Adam‐Gibbs, Avramov‐Milchev, and Mauro‐Yue‐Ellison‐Gupta‐Allan models. We compare the four viscosity models in terms of their theoretical underpinnings and ability to fit measured viscosity curves. The concept of fragility and the universality of the high‐temperature viscosity limit are also discussed. Temperature‐dependent constraint theory is introduced in detail as a powerful tool for predicting the composition dependence of viscosity. Some examples of the application of this approach to predict the glass transition temperature and fragility of various glass systems are shown. Topological constraint theory is not only of scientific interest, but also has important industrial applicability. We also discuss the thermal history dependence of viscosity in the glassy state. Some phenomenological models are briefly reviewed, while the main focus is given to the modified Mauro‐Allan‐Potuzak model, which can accurately predict the nonequilibrium viscosity as a function of temperature, thermal history, and composition. The correlation of viscosity with elasticity is described in terms of the shoving model. Some theoretical implications of the various viscosity models are discussed, including the concepts of the Kauzmann paradox and the ideal glass transition. Some of the evidence against the existence of these phenomena are discussed. We also review the link between glass relaxation and viscosity, that is, emphasizing that the viscosity equations presented in this review can also be used to model different types of relaxation effects based on the Maxwell relation.     

Effects of glass‐fiber content and coolant temperature on temperature and crystallinity profiles of PP melt during cooling

This investigation studied the temperature gradients and degree of crystallinity of polypropylene melt across a circular duct during the cooling process, where the coolant used was chilled water. The effects of glass‐fiber content, varying from 0 to 44 wt %, and coolant temperature, varying from 5 to 20°C, were our main interest. The results suggested that the rate of cooling of the polymer of each position across the duct was not significantly affected by the temperature of the coolant and glass‐fiber contents, although the rate of cooling was influenced by the size of the duct. The crystallization temperature and degree of crystallinity of the polymer increased with increasing glass fiber contents and the coolant temperature. These phenomena were associated with the heat transfer between the coolant and the polymer, crystallization temperature, exothermic crystallization process, and thermal properties of the polymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2087–2097, 2001     

Alternative methacrylate‐tethering methods for resin‐modified glass‐ionomer cements

We have explored two novel methacrylate‐tethering methods for resin‐modified glass‐ionomer cements using 2‐hydroxyethyl methacrylate (HEMA) and glycidyl methacrylate (GM) as a tethering agent. Both were compared with the published method using 2‐isocyanatoethyl methacrylate (IEM). The tethering reactions were monitored using FTIR spectroscopy. It was found that IEM and HEMA tethering reactions were relatively fast compared with the GM‐tethering, even though all three tethering reactions can be completed within 6 h. The cements composed of the IEM‐tethered polymer showed the highest CS, DTS, and modulus, followed by the cements composed of the HEMA‐ and GM‐tethered polymers, which was attributed to different chemical bonds introduced. It appears that both alternative tethering methods are quite equivalent to IEM‐tethering based on the strength and reaction efficiency. The results suggest that HEMA and GM can be used as promising methacrylate‐tethering alternatives for resin‐modified glass‐ionomer applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Understanding the structural origin of crystalline phase transformations in nepheline (NaAlSiO4)‐based glass‐ceramics

Nepheline (Na₆K₂Al₈Si₈O₃₂) is a rock‐forming tectosilicate mineral which is by far the most abundant of the feldspathoids. The crystallization in nepheline‐based glass‐ceramics proceeds through several polymorphic transformations — mainly orthorhombic, hexagonal, cubic — depending on their thermochemistry. However, the fundamental science governing these transformations is poorly understood. In this article, an attempt has been made to elucidate the structural drivers controlling these polymorphic transformations in nepheline‐based glass‐ceramics. Accordingly, two different sets of glasses (meta‐aluminous and per‐alkaline) have been designed in the system Na₂O–CaO–Al₂O₃–SiO₂ in the crystallization field of nepheline and synthesized by the melt‐quench technique. The detailed structural analysis of glasses has been performed by ²⁹Si, ²⁷Al, and ²³Na magic‐angle spinning — nuclear magnetic resonance (MAS NMR), and multiple‐quantum MAS NMR spectroscopy, while the crystalline phase transformations in these glasses have been studied under isothermal and non‐isothermal conditions using differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and MQMAS NMR. Results indicate that the sequence of polymorphic phase transformations in these glass‐ceramics is dictated by the compositional chemistry of the parent glasses and the local environments of different species in the glass structure; for example, the sodium environment in glasses became highly ordered with decreasing Na₂O/CaO ratio, thus favoring the formation of hexagonal nepheline, while the cubic polymorph was the stable phase in SiO₂–poor glass‐ceramics with (Na₂O+CaO)/Al₂O₃ > 1. The structural origins of these crystalline phase transformations have been discussed in the paper.     

一种研究油气藏成藏史的新方法

为了提高油气藏的成藏过程研究的准确性,G eorge,Bhu llar等在前人的基础上改进提出了使用油气藏内包裹体的化学成分来研究油藏的成藏史。通过特定的方法对包裹体内油气进行分析,并和现今的油气源进行对比就可以确定油气的成藏史。这种方法直接针对古油气,所以油气藏的成藏史恢复会更加准确有效。对某多期成藏的油气藏的包裹体成分地化分析,结合其它的分析方法很容易恢复油藏的成藏过程。     

P2O5‐Fe2O3‐CaO‐SiO2 ferromagnetic glass‐ceramics for hyperthermia

Ferromagnetic glass‐ceramics are an important kind of thermoseed material for hyperthermia treatments. In order to investigate the applications of glass‐ceramics in magnetic hyperthermia, P₂O₅‐Fe₂O₃‐CaO‐SiO₂ (PFCS) glass‐ceramics with different compositions were prepared by the sol‐gel method. The crystal phase, magnetic properties, induction heating ability, and cytotoxicity of the as‐prepared glass‐ceramics were investigated. The results show that all the samples exhibit low cytotoxicity and good induction heating ability. Moreover, it was found that the phosphorus content affected the crystal phase component of the sample, and thus influenced the induction heating ability. Results of the magnetic hyperthermia experiments showed that the PFCS glass‐ceramic samples induced significant cell death of the LoVo cancer cells. The highest cell death rate for sample B2P7 was more than 95%, which suggests good application prospects in the field of hyperthermia therapy.     

Synthesis and characterization of ferrimagnetic glass‐ceramic frit from waste

The large amount of generated waste determines the importance of their valorization. Red mud is the residue of the Bayer process, which stored cumulative value raises 2.7 Bt. This paper describes an easy way to produce a ferrimagnetic glass‐ceramic frit, using bauxite residue, fly ash and glass cullet as raw materials. The synthesized frit consists of faceted and dendritic agglomerated crystals of magnetite and titanomagnetite embedded in a glass matrix, which exhibits a saturation magnetization (M_S) of 6.3 emu/g, a remanent magnetization (M_R) of 2.7 emu/g and a coercive field (H_C) of 347 Oe. Furthermore, it presents Vickers hardness value of H_V = 5.55 ± 0.16 GPa and fracture toughness value of K_IC = 1.64 ± 0.34 MPa·m^1/2.     

Kinetics and particle nucleation mechanism of St/BA/qBVPBr emulsifier‐free cationic emulsion polymerization

Stable functional cationic latices were prepared by emulsifier‐free emulsion copolymerization of styrene (St) and butyl‐acrylate (BA) with 1‐butyl‐4‐vinylpyridinium bromide (qBVPBr) as functional comonomer and azobis(isobutyramidine hydrochloride) (AIBA) as initiator at (70 ± 1)°C. The influences of the reaction temperature, the initiator concentration, and comonomer concentration on the polymerization conversion (x %), polymerization rate (R_p) of poly(St/BA/qBVPBr) emulsions were investigated. The results indicated that x % and R_p increase with increasing qBVPBr or AIBA concentration and temperature, and R_p can be expressed as R_p = K_p[AIBA]^0.73[qBVPBr]^0.08 (r_AIBA = 0.9968; r_qBVPBr = 0.9946, both r_AIBA and r_qBVPBr are linear correlation coefficient) and the apparent activation energy (E_a) is 47.89 kJ mol^?1. In the absence of emulsifier condition, curves of R_p versus reaction time obeyed the typical behavior characterized by Intervals I, II, and III as similar conventional emulsion polymerization. The formation and growth of poly(St/BA/qBVPBr) latex particles has been studied at different reaction times. The results indicate that N_p decrease gradually with time at the early polymerization stages and then reach a constant value after about 20% conversion, but D_p by photon correlation spectroscopy grow continuously as all polymerization proceed. Both the particle size distribution and molecular weight distribution curves are of bimodal size distribution and indicate the participation of at least two mechanisms of particle formation, namely, homogeneous nucleation in the aqueous phase and micellar nucleation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hierarchical growth of BiOCl on SrO‐Bi2O3‐B2O3 glass‐ceramics for self‐cleaning applications

We have grown hierarchical structure of bismuth oxycloride (BiOCl) on SrO‐Bi₂O₃‐B₂O₃ (SBBO) transparent glass‐ceramic. SBBO glass‐ceramics were fabricated via conventional melt‐quenching technique while BiOCl was grown by etching the glass via HCl. Enhanced visible light driven photocatalytic activity and increasing hydrophobic feature were observed on BiOCl grown SBBO than as‐quenched SBBO glass‐ceramics. Contact angle analysis showed maximum contact angle of 130.7° on the surface of most BiOCl grown SBBO glass‐ceramic. Furthermore, under visible light illumination water contact angle decreased from 130.7° to 30.8°. Such photo‐induced hydrophilicity and catalytic performance in translucent glass‐ceramics lead self‐cleaning applications.     

Interaction of self‐nucleation and the addition of a nucleating agent on the crystallization behavior of isotactic polypropylene

The relationship between heterogeneous or homogeneous nucleation and self‐nucleation of polypropylene (PP) and PP nucleated by an organic phosphate salt (PPA) was studied by DSC. For pure PP, it homogeneously nucleated during cooling after melting at the selected temperature (T_s) of 170–200°C for 3 min, but at the T_s of 160–168°C self‐nucleation occurred; PPA only nucleated heterogeneously at the T_s of 168–200°C, and there existed self nucleation at the T_s of 160–168°C. The double melting peaks of PP and PPA at the T_s of 162°C were observed. Once the self‐nucleation occurred, the change of the crystallization temperature and heat of fusion of PP is more significant than that of PPA with the change of the T_s, depending upon the crystallization conditions. Results were explained by homogeneous nucleation, heterogeneous nucleation, self‐nucleation, and annealing crystallization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 78–84, 2001     

The charge state of titanium ions in Pd‐doped Ti:CMAS glass and glass‐ceramics

We have investigated the role of charge state of Ti in the electronic properties and structure of electrically conductive CMAS‐TiO₂‐Pd glass and glass‐ceramics by X‐ray photoelectron spectroscopy, electron paramagnetic resonance, positron annihilation lifetime spectroscopy, and fluorescence spectroscopy. These studies suggest the concentration of Ti³⁺ ions was, at most, ~0.1 wt% in glass‐ceramics devitrified in the reducing atmosphere of forming gas; no other glass or glass‐ceramic samples exhibited measurable levels of Ti³⁺. The observed fluorescence at liquid nitrogen temperature in parent glasses and glass‐ceramics obtained in air is explained by UV‐induced charge‐transfer processes involving Ti⁴⁺ ions and oxygen surroundings. The X‐ray photoelectron spectroscopy data are correlated with rutile, anorthite, diopside, and titanite crystalline phases identified in Pd‐free and Pd‐doped Ti:CMAS glass‐ceramics earlier.     

Crystallization,mechanical, and optical properties of transparent,nanocrystalline gahnite glass‐ceramics

This paper describes the preparation of a transparent glass‐ceramic from the SiO₂‐K₂O‐ZnO‐Al₂O₃‐TiO₂ system containing a single crystalline phase, gahnite (ZnAl₂O₄). TiO₂ was used as a nucleating agent for the heat‐induced precipitation of gahnite crystals of 5‐10 nm. The evolution of the ZnAl₂O₄ spinel structure through the gradual formation of Al‐O bonds was examined by infrared spectroscopy. The dark brown color of the transparent precursor glass and glass‐ceramic was eliminated using CeO₂. The increase in transparency of the CeO₂‐doped glass and glass‐ceramics was demonstrated by UV‐visible absorption spectroscopy. EPR measurements confirmed the presence of Ce³⁺ ions, indicating that CeO₂ was effective in eliminating the brown color introduced by Ti³⁺ ions via oxidation to Ti⁺⁴. The hardness of the glass‐ceramic was 30% higher than that of the as‐prepared glasses. This work offers key guidelines to produce hard, transparent glass‐ceramics which may be potential candidates for a variety of technological applications, such as armor and display panels.     

Synthesis of water‐glass‐based silica aerogel powder via with and without squeezing of hydrogels

The present article describes the synthesis of water‐glass‐based silica aerogel powder via coprecursor method, using with and without squeezing, in drying technique. The present research was aimed to develop a simple, cost‐effective, and rapid drying process, i.e., squeezing through sol–gel synthesis. The physical and textural properties of the aerogel powder synthesized with and without squeezing process via ambient pressure drying (APD) have been studied and compared. For characterization of aerogel powder, we employed Brunauer, Emmett, and Teller, Barrett‐Joyner‐Halenda, and field emission scanning electron microscope techniques. The experimental results showed that the properties of the aerogel powder obtained by squeezing are superior to those dried in a furnace one. The squeeze‐dried aerogel powder exhibited lower tapping density (0.126 g/cm³) than furnace dried. Furthermore, textural investigations revealed that the aerogel powder has high‐specific surface area (752.3 m²/g), high porosity, low shrinkage, and uniform pore size distribution, which is obtained by squeezing process via APD. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A crossover‐UNIQUAC model for critical and noncritical LLE calculations

A new model, named the crossover‐UNIQUAC model, has been proposed based on the crossover procedure for predicting constant‐pressure liquid–liquid equilibria (LLE). In this manner, critical fluctuations were incorporated into the classical UNIQUAC equation. Coexistence curves were estimated for systems having a diverse range of asymmetries. These systems included the LLE of five different mixtures, composed of nitrobenzene with one of the members of the alkane homologous family (either pentane, octane, decane, dodecane, or tetradecane), as well as an extra system having a different chemical nature, namely the mixture of n‐perfluorohexane and hexane, to further check the validity of the proposed approach. Using these nonideal mixtures, the validity of the new model was investigated within wide ranges, covering near‐critical to regions falling far away from the critical point. The graphical trends, as well as the quantitative comparison with experimental data indicated the good agreement of the proposed model results with the experimental data. A maximum AARD% value of 3.97% was obtained in calculating molar compositions by the proposed model for such challenging systems covering noncritical, as well as critical regions. In addition, to show the strength of the proposed crossover approach to describe properties other than LLE, molar heat capacities were investigated for the system of nitrobenzene + dodecane. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3094–3103, 2015     

Comparative study of the nucleation activity of third‐generation sorbitol‐based nucleating agents for isotactic polypropylene

The nucleation activity of the sorbitol derivatives 1,2,3,4‐bis(3,4‐dimethylbenzylidene sorbitol) and methyldibenzylidene sorbitol are compared with that of talc, a conventional nucleating agent for the monoclinic crystalline phase of isotactic polypropylene. The thermal parameters associated with the dynamic crystallization process are studied as a function of the cooling rate by differential scanning calorimetry, and the nucleating efficiency is assessed by comparison with self‐nucleation, the highest values being observed for 1,2,3,4‐bis(3,4‐dimethylbenzylidene sorbitol) over the whole concentration range. The nature of the polymer crystals formed in the nucleated polymer was studied by X‐ray diffraction, and the data show an increase in a preferred orientation of the polymer crystallites with increasing concentration of nucleating agent. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2440–2450, 2002     

一种新型环保、节能除湿技术——热电冷凝除湿

回顾了传统除湿技术的发展以及目前所存在的弊端。系统介绍了热电冷凝除湿技术的工作原理、理论模型、国内外研究进展。详细比较了热电冷凝除湿技术与传统除湿技术,表明随着热电技术的发展、热电冷凝装置性能的提高以及太阳能电池的成本降低,热电冷凝除湿技术作为一种节能、环保的新型除湿技术,将具有非常广阔的发展前景。     

Identification of cell‐nucleation mechanism in foam injection molding with gas‐counter pressure via mold visualization

The mechanisms of cell nucleation and growth are investigated in foam injection molding (FIM) using gas‐counter pressure (GCP). An in‐situ mold visualization technique is employed. The application of GCP suppresses cell nucleation, and prevents the blowing agent from escaping during mold‐filling. The inherent structural heterogeneity in the regular FIM can be improved because of the uniform cavity pressure when employing GCP. The cavity pressure profiles show much faster pressure‐drop rates using GCP, because the single‐phase polymer/gas mixture has a lower compressibility than the two‐phase polymer/bubble mixture. Therefore, both the cell nucleation and growth rates are significantly increased through a higher pressure‐drop rate on the removal of the GCP. The effect of GCP magnitude on the cell morphology is explored. When the GCP is lower than the solubility pressure, bimodal foaming occurs. As the GCP increases above the solubility pressure, the cell density increases because of the higher pressure‐drop rate. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4035–4046, 2016     

The critical conditions for secondary nucleation of silica colloids in a batch Stöber growth process

In this work, we determined experimentally the critical total surface area of silica seeds in the solution to avoid the formation of new particles (i.e. secondary nucleation) in a batch Stöber growth process. This critical surface area corresponded to the balance between the generation rate of reaction intermediate from the hydrolysis of TEOS and its consumption rate via the growth of existing seeds. Further calculation showed that the secondary nucleation was probably related to the average distance between seed particles. When the distance between seeds exceeded a critical value for each growth condition, i.e. for each generation rate, one would then observe secondary nucleation. Otherwise, simple growth was observed. Higher generation rate corresponded to shorter distance.