FACTORS AFFECTING THE DEGREE OF HOMOGENEITY OF GLASS*

The rate of homogenizing of soda-lime-silica glass under conditions of minimum convection mixing and in the absence of refractory materials was measured by the centrifuge density spread technique developed by Turnbull and Ghering. Measurements on melts prepared in pure platinum containers at 2550°F. showed that the density spread decreases rapidly during the first 16 hours of melting following which further decrease occurs at a much slower rate. The portion of glass responsible for the major part of the density spread was a light fraction, which tended to form or accumulate at the surface of the melt.     

EFFECT OF IRON OXIDE ON MELTING OF GLASS*

The addition of small amounts of iron oxide (0.1 to 0.2%) to soda-lime-silica glass batches exerts a profound influence in increasing the output of glassmelting tanks as well as in favoring the production of higher quality glass. The color produced by this addition, moreover, is not objectionable for many uses of the ware. The accelerated melting rate probably is the result of a chemical effect of iron oxide in the batch and a physical property possessed by such glass to absorb radiation from the flames more efficiently. Attempts to measure these effects were made by rioting the melting rate of glasses which contain varying additions of iron oxide and by determining the temperature gradient that exists in glass when it is melted in a miniature tank. The presence of iron oxide aids melting and fining in crucible melts at 1200°C., but no effect was observed at higher temperatures. The measurement of temperature gradients in a pot holding 45 lb. of glass and heated by flames passing over the glass surface showed that the temperature gradient increases with iron oxide content.     

INFLUENCE OF BATCH MIXING TIME AND BATCH GRAIN SIZE ON HOMOGENEITY OF A SODA-LIME-SILICA GLASS*

Density-spread determinations were made on a series of melts of a soda-lime-silica glass employing batches compounded from raw materials varying in particle size from 20- to 60-mesh to minus 200-mesh, which had been mixed by tumbling for one, ten, or thirty minutes. The two melting techniques employed were (1) melting for sixteen hours in a stationary platinum crucible at 1400°C. under conditions of even temperature distribution and consequently a minimum of convection mixing and (2) melting for four hours at 1400°C. in a rotating tilted crucible; this condition was intended to simulate convection mixing Under the experimental conditions employed, it was found that (1) batch mixing time has relatively little effect on the homogenizing rate, (2) homogenization increases rapidly with decrease in grain size, and (3) in all cases the 4-hour melting treatment with moderate mixing gives better homogeneity than sixteen hours melting time in a stationary crucible, this effect increasing with decrease in grain size. No significant difference in glass homogeneity resulted from three different methods of mixing, namely, tumbling, ball milling, and mixing in a muller-type mixer, although the homogenizing influence imposed probably was sufficient to mask any differences in uniformity of mixing that might have existed.     

The influence of temperature and cyclic loading on adhesion in polycarbonate-polyurethane-glass adhesive joint

The paper deals with the influence of temperature and cyclic loading on adhesion and transparency of the adhesive joint consisting of soda-lime-silica glass and polycarbonate (PC) bonded with polyurethane (PU) adhesive film. The tested joint represents critical part of transparent armored glass used in vehicles. Dynamic tension creep tests were performed at temperatures to which armored glass is commonly exposed (25, 50, 60, 70, and 80?°C). Sawtooth loading mode was performed to 650?N and the sine loading in the force range 0–1550?N. The aim of the paper was to discover conditions causing delamination of the adhesive joint and glass milky appearance during the use. Delamination of soda-lime-silica glass/PU adhesive interface occurred at 25?°C after load to 1550?N without the change of transparency. Both dynamic and static tension creep tests performed to 400?N led to plastic deformation of PU adhesive at and above 70?°C, in preference at both ends and circumference edges of adhesive joint, and thus, to loss of transparency, but extent of deformation differed. Milky maps observed after sawtooth load to 650?N at 80?°C reflected delaminated areas of highly deformed PU adhesive. Temperature of 70?°C was found out to be the critical parameter being in synergy effect with different thermal expansion of PC and PU adhesive.     

REACTION BETWEEN METALS AND MOLTEN GLASS *

A series of melts of soda-lime-silica glass cullet in contact with various chemical elements was made to determine by observation the extent of the reaction between metal and glass. The heat treatment consisted of a period of two hours at about 1250°C. An atmosphere of hydrogen gas was used to protect the element from oxidation during the the test period. Various colors were produced by Cu, Ag, Au, Se, C, S, and Zr. Black fogs resulted from melts containing Ba, Cr, or V; gray or black fogs with reddish zones resulted from Mg, Ca, Ti, Mn, Si, and Al. A faint blue with large reddish zones was produced by Co. Only slight attack was shown by Fe, Ni, Zn, Cd, Bi, Sn, Pb, Mo, and W.     

Microstructure evolution of CMAS glass below melting temperature and its potential influence on thermal barrier coatings

CaO–MgO–Al₂O₃–SiO₂ (CMAS) deposition significantly degrades the performance of thermal barrier coatings (TBCs). In this study, the microstructure evolution of CMAS glass at temperatures below its melting point was investigated in order to study the potential influence of temperature on the applicability of CMAS glass in TBCs. The CMAS glass fabricated in this study had a melting point of 1240 °C, became opaque, and underwent self-crystallization when the temperature reached 1000 °C. After heat treatment at 1050 °C, diopside and anorthite phases precipitated from the glass; at a higher temperature (1150 °C), diopside, anorthite, and wollastonite were formed as the self-crystallization products. An increase in the dwelling time resulted in the transformation of diopside to wollastonite and anorthite. At 1250 °C, all products formed a eutectic microstructure and melted. The results indicate that even at low temperatures, CMAS glass underwent microstructure evolution, which could influence the coating surface and stress distribution when deposited on TBCs.     

Developing a composition for fused-cast zirconia refractories

Conclusions A composition was developed for electrofused zirconia-alumina refractory possessing a high resistance to melts of refractory aluminosilicate glass at 1750°C.To test this refractory in experimental and industrial glass furnaces designed for melting glass at temperatures above 1700°C, an industrial technology should be developed for its production.     

METHOD FOR MEASURING FINING TIME OF GLASS*

A method is described for measuring the fining time of glass, and a formula is given for using the data obtained to estimate the tonnage-temperature schedules of continuous tank furnaces. Measurement of fining time at two and preferably three temperatures, in the range 1400° to 1500°C., is required to establish the fining characteristics of a glass. Data from fining-time measurements of four glasses show that fining is largely independent of the viscosity and probably also of the surface tension of glass. The use of fining-time measurements in accounting for differences in the melting efficiencies of tank furnaces and the value of systematic studies, involving fining agents and variations in composition, are suggested.     

X-ray imaging of a high-temperature furnace applied to glass melting

The dynamics of soda-lime-silica glass grain melting is investigated experimentally using a nonintrusive technique. A cylindrical alumina crucible is filled with glass cullet and placed into a furnace illuminated by an X-ray source. This glass granular bed is gradually heated up to 1100°C, leading to its melting and the generation of a size-distributed population of bubbles rising in the molten glass. An image processing algorithm of X-ray images of the cullet bed during melting allows the characterization of bubbles size distribution in the crucible as well as their velocity. The introduction of tin dioxide μ-particles in the glass matrix before melting enhances the texture of the images and makes possible the determination of the bubble-induced molten glass velocity field by an optical flow technique. The bubble size distribution can be fitted by a log-normal law, suggesting that it is closely related to the initial size distribution in the cullet bed. The liquid motion induced by the bubbles in Stokes' regime is strongly affected by the flow confinement and the determination of bubble rising velocity along its trajectory unveils the existence of local tiny temperature fluctuations in the crucible. Overall, the measuring techniques developed in this work seem to be very promising for the improvement of models and optimization of industrial glass furnaces.     

Amorphous self-glazed,chopped basalt fiber reinforced,geopolymer-based composites

Geopolymer composites reinforced with refractory, chopped basalt fibers, and low melting glass were fabricated and heat treated at higher temperatures. K₂O·Al₂O₃·4SiO₂·11H₂O was the stoichiometric composition of the potassium-based geopolymer which was produced from water glass (fumed silica, deionized water, potassium hydroxide), and metakaolin. Addition of low melting glass (T_m ~815°C) increased the flexure strength of the composites to ~5 MPa after heat treatment above 1000°C to 1200°C. A Weibull statistical analysis was performed exhibiting how the amorphous self-healing and self-glazing effect of the glass frit significantly improved the flexure strength of the geopolymer and ceramic composites after exposure for 1 hour to high temperatures. At 950-1000°C, the K-based geopolymer converted to primarily a crystalline leucite ceramic, but the basalt fiber remained intact, and the melted glass frit flowed out of the surface cracks and sealed them. 1150℃ was determined to be the optimum heat treatment temperature, as at ≤1200°C, the basalt fibers melt and the strength of the reinforcement in the composites is significantly reduced. The amorphous self-healing and amorphous self-glazing effects of the glass frit significantly improved the room temperature flexure strength of the heat-treated geopolymer and ceramic composites.     

Interfacial tension measurements and evidence of order in high‐density polyethylene melts

Polyethylene (PE) is a widely used product commercially. However, our knowledge is incomplete about the properties of high‐density polyethylene (HDPE) at temperatures above its melting point, where solid crystals disappear. Recently, there has been increasing evidence from rheological, differential scanning calorimetry, and NMR studies that suggests the presence of microstructural order in the bulk of PE melts. In this study, the interfacial tension of HDPE melts in contact with silicone oil was measured with a spinning drop tensiometer in the same temperature range in which phase transitions have been observed in the bulk HDPE. Anomalous temperature dependence of interfacial tension was found between 200 and 230°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4061–4067, 2003     

Sintering behavior of anorthite-based composite ceramics produced from natural phosphate and kaolin

In the present work anorthite-TCP composite ceramics was produced for the first time by the solid-state sintering process involving the mixture of local natural materials of phosphate and kaolin. Various samples were prepared by varying the kaolin content from 47 to 57 wt%. The composite ceramics were sintered in air at various temperatures ranging from 1250 °C to 1325 °C and characterized to determine the phase present, relative density, Vickers microhardness, chemical bonding of molecules and microstructural development. In general, all the samples exhibited a hybrid structure, comprising of anorthite and β-TCP as the major phases with a concomitant minor phases such as TTCP and/or gehlinite depending on the temperature and kaolin content. In addition, increasing kaolin content and sintering temperature were found to be effective in improving the densification and hardness of the sintered body. In particular, sample containing 57 wt% kaolin exhibited excellent densification at 1300 °C and 1325 °C, achieving above 97% dense bodies and highest hardness of about 6.5 ± 0.7 GPa. Microstructural investigation revealed that a dense structure was evident for these samples due mainly to enhanced particle coalescence during the liquid phase sintering, resulting in pore elimination and grain coarsening.     

RELATION OF ELECTRICAL CONDUCTIVITY TO CHEMICAL COMPOSITION OF GLASS*

The electrical conductivity of some glasses in the soda-lime-silica system was measured at 400 °C. with an apparatus which is described. The specific resistance at this temperature ranged from 0.06 to 5.0 × 10⁵ ohms per cc. Measurements were made on other glasses containing equivalent amounts of various oxides incorporated in a parent soda-lime-silica glass. It was found that an increase in resistance was produced by additions of MnO, ZnO, B₂O₃, Fe₂O₃, BaO, PbO, TiO₂, and K₂O, the resistances increasing in this order. A decreased resistance was produced by Na₂O, CaO, and Al₂O₃. Previously published data on the power factors of these glasses are reviewed.     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997     

Investigation of the high-temperature behaviour of coal ash in reducing and oxidizing atmospheres

The high-temperature behaviour of ashes from a suite of coals exhibiting a wide range of mineralogies has been investigated. Phase analysis of ash samples quenched from various temperatures under either a reducing (60% CO/40% CO₂) or an oxidizing (air) atmosphere was performed by Mössbauer spectroscopy, scanning electron microscopy (SEM)/automatic image analysis (AIA), and X-ray diffraction (XRD). It was found that significant partial melting of the ashes occurred at temperatures as low as 200–400 °C below the initial deformation temperature (IDT) defined by the ASTM ash cone fusion test. Melting was greatly accelerated under reducing conditions, for which the percentage of melted ash increased rapidly between 900 and 1100 °C, saturating at temperatures above ≈ 1200 °C. The observation of such phases as wustite (FeO), fayalite (Fe₂SiO₄), hercynite (FeAl₂O₄), and ferrous glass in samples quenched from 900 to 1200 °C indicates that ash melting in a reducing atmosphere is usually controlled by the iron-rich corner of the FeO-Al₂O₃-SiO₂ phase diagram. Ashes rich in CaS are an exception to this rule, for large quantities of iron sulphide are formed and the melting behaviour is controlled in part by the FeO-FeS phase diagram. Under oxidizing conditions, potassium appears to be the most important low-temperature fluxing element, as the percentage of glass in samples quenched from temperatures below 1100 to 1200 °C was proportional to the amount of the potassium-bearing mineral illite contained in the coal. Above 1200 °C in air, calcium and, to a lesser extent, iron became effective as fluxing elements; melting accelerated between 1200 and 1400 °C, and was near completion between 1400 and 1500 °C for most ashes. To retard ash melting, it is generally concluded that aluminium is the most desirable constituent of ash, whereas the most undesirable constituents are iron, calcium, and potassium.     

Extensional processing behavior of thermoplastics reinforced with a melt processable glass

This work was concerned with investigating the processing behavior of thermoplastics reinforced with a melt processable phosphate glass under extensional flows at temperatures used for forming and shaping operations. Injection molded blends consisting of polyetherimide (PEI) and polyphenylene sulfide (PPS) reinforced with 30‐60 wt% phosphate glass were exposed to uniaxial and planar deformation at temperatures above the T_g of the phosphate glass (234°C) to evaluate the effects on the morphology and mechanical properties of the composites. Tensile testing at elevated temperatures (250‐300°C) was used to evaluate the forming behavior and ascertain the conditions most suited for the deformation of the composite blends. A temperature approximately 35°C above the T_g of the P‐glass was found to offer conditions most conducive to the deformation of the PEI/P‐glass blends. The phosphate glass reinforced PEI was found to offer greater retention of properties and smoother surfaces than an E‐glass filled material when exposed to shearfree deformation similar to that seen in a process such as thermoforming. For PPS based composites, the application of planar shearfree deformation near the melting point of the PPS (≈︁ 283°C) resulted in the elongation of the phosphate glass phase which served to enhance the stiffness of the composite blends along the principal deformation direction.     

The eicosenoic acid of cameline seed oil

Summary The eicosenoic acid previously discovered in cameline seed oil (1) was isolated and identified. It melts at 22.5°C. and yields an elaidinated acid melting at 43.5°C. and a dioxy derivative melting at 132°C. By its hydrogenation to arachidic acid and destructive oxidation to undecanedioic acid it was shown to be normal Δ¹¹-eicosenoic acid-1 like the acid in jojoba wax.     

Influence of the method of mixing on homogeneity and crystallization kinetics of blends of linear and branched polyethylene

The influence of mixing method—solution and melt mixing—on the homogeneity and crystallization kinetics of a series of blends of single‐site materials of linear polyethylene and ethyl‐branched polyethylene was studied by differential scanning calorimetry. Data obtained for heats of melting and crystallization, melting and crystallization peak temperatures, and melting and crystallization temperature profiles were essentially the same for the samples obtained by the two mixing methods. The results obtained can be interpreted as indicating that melt mixing is capable of producing homogeneous melts of these relatively low molar mass polymers, given that solution mixing is considered to give perfectly homogeneous blends. The heat associated with the high temperature melting peak after crystallization at 125°C of the blend samples, obtained by the two preparation methods, was higher than that of the linear polyethylene included in the blends, suggesting that a part of the branched polyethylene crystallized at 125°C. The unblended branched polyethylene showed no crystallization at 125°C. Samples obtained by powder mixing showed independent crystallization and melting of the linear and branched polyethylene components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1730–1736, 2004     

MELTING OF ICE AROUND A HORIZONTAL ISOTHERMAL CYLINDRICAL HEAT SOURCE

Processes during melting from a horizontal cylindrical heat source of uniform surface temperature embedded in ice have been studied experimentally. The volume of the melt and its shape were photographed at different times for various constant temperatures of the heat source. At early times and under all conditions, the melt occupied a cylindrical annulus. At later times free convective motion caused pear-shaped melt contours which pointed downward when the temperatures of the heat source were below 7°C and upward when the temperatures were above 8°C. Instabilities in cellular natural convection motion resulted in waviness of the interface. The location and magnitude of these ripples were found to depend on the temperature of the heat source and the melt layer thickness. Shadowgraph techniques were used to determine local heat transfer coefficients at the heat source surface.