Effect of Heat Treatment on Rapidly Quenched AgI-Based Silver Orthoborate Glasses Containing Large Amounts of AgI

The effect of heat treatment on the twin-roller rapidly quenched 75AgI·18.7Ag₂O6.3B₂O₃ glass was investigated by differential scanning calorimetry (DSC), high-temperature X-ray diffraction (XRD), and field-emission-type scanning electron microscopy. The glass had an inhomogeneous microstructure with dispersed particles 40-60 nm in diameter at room temperature. On the other hand, island regions of several hundred nanometers with fine dispersed particles about 20-30 nm in diameter were observed in the glass after heating to 120°C. DSC and high-temperature XRD measurements revealed that crystallization occurred at around 120°C, which is lower than the α-β phase transformation temperature (147°C), to form α-AgI in the glass. The crystallization of α-AgI from the glass below the α-ß phase transformation temperature strongly supports the possibility of the existence of α-AgI nuclei in AgI-based silver orthoborate glasses. Validating the existence of AgI microcrystals supports the microdomain model for superionic AgI-based glasses.     

Effect of heat treatment on AgI-rich chalcogenide glasses with enhanced ionic conductivity

The glass-ceramics of AgI-based electroconductive chalcogenide system was realized using an appropriate heat treatment at a fairly high temperature (T_g + 40°C) and different times ranging from 4 to 20 hours. The crystallization behavior and electroconductive properties of the heat-treated samples were studied in detail. Transmission study was performed, and the results show that the cut-off edge of the short wavelength is red-shifted at prolonged annealing time but remains an excellent transmittance in the mid-infrared (IR) region. XRD and scanning electron microscopy results indicated that the precipitated crystalline phases are mainly β-/γ-AgI. Moreover, a small amount of α-AgI, which rarely existed at room temperature, is precipitated in the AgI-rich chalcogenide glass-ceramics. The ionic conductivity of all glass-ceramics was enhanced by heat treatment in contrast to that of base glass. Raman analysis exhibited the structure variation in the glass sample after heat treatments. This study provided an observation of crystallization in chalcogenide glass containing large amounts of AgI and be of good guidance to fabricate novel AgI-based chalcogenide glass-ceramics that can be candidates in infrared optics and solid electrolyte applications.     

Heterogeneous Plantinum Nucleation and Crystallization of a Heavy-Metal Fluoride Glass

The effect of controlled heterogeneous nucleation by platinum on the crystallization of a ZrF₄-BaF₂-LaF₃-AlF₃-NaF (ZBLAN) glass was studied. Various levels of platinum were incorporated into this glass by a combination of PtCl₂-doping and melting-atmosphere variation. The effect of doping levels and melting conditions on the incorporation of platinum and the subsequent nucleation of crystals was studied by optical microscopy, scanning electron microscopy, differential scanning calorimetry (DSC), and X-ray diffraction. Increased platinum in the glass resulted in an increased number of nucleation sites for the growth of β-ZrF₄-BaF₂ crystals. Analysis of isothermal and ramp-rate DSC measurements indicated that the crystallization of this glass changed from surface controlled to bulk controlled with an increased number of nuclei. This was confirmed by optical microscopy. In addition, Avrami analysis of the isothermal crystallization data gave an accurate approximation of the number of nuclei in the glass.     

Kinetics of Nonisothermal Crystallization of Bi2Sr2CaCu2Ox Glasses with Different Copper Valence States

The kinetics of the nonisothermal crystallization process in Bi₂Sr₂CaCu₂O_x glasses with different copper valance states, R(Cu⁺) = Cu⁺/(Cu⁺+ Cu²⁺) = 0.79–0.99, were examined by using differential scanning calorimetry. Four different kinetic equations were used for the data analyses. It was found that the values of activation energy for crystal growth, E _a, decreased with increasing Cu⁺ content. The value of E _a, which was estimated from the modified Ozawa equation, for the glass with R(Cu⁺) = 0.79 was 483 kJ·mol^-1 and for the glass with R(Cu⁺) = 0.99 was 353 kJ·mol^-1. In the former glass, the number of crystal nuclei was almost independent of the heating rate. But, in the latter glass, the number of crystal nuclei varied significantly with the heating rate. The crystallization mechanism in the glasses was closely related to the thermal stability and viscosity of glasses: the glass with R(Cu⁺) = 0.99 showing a high thermal stability and a low activation energy for viscous flow had a small value of E _a. The plot of In ( T _p²/α) against 1/ T _p, where T _p and α are crystallization peak temperature and heating rate, respectively, gave a reasonable value of E _a for the glass with R(Cu⁺) = 0.79 but was unsuitable for the evaluation of E _a for crystal growth of the glass with R(Cu⁺) = 0.99.     

Structural–chemical features and mechanism of crystallization of TlAsX<Subscript>2</Subscript> glasses (X = S,Se)

The vibrational IR spectra of polymer-chain glasses and single crystals of TlAsX₂ (X = S, Se) have been studied. The results of the kinetic study of the surface isothermal crystallization of glasses are theoretically anlayzed in different ways, taking into account the peculiarities of their structure. The semiempirical calculation of the temperature dependence of nonreconstructive crystal growth rate is performed. It is shown that the layered stationary growth of crystals in the TlAsS₂ glass occurs on screw dislocations. In the TlAsSe₂ glass the transition from a dislocation mechanism to two-dimensional nucleation and the layered growth of crystals is possible at supercooling of more than 120°C.     

Structure,crystallization, and performances of alkaline-earth boroaluminosilicate sealing glasses for SOFCs

We study the structure, crystallization, and performances of the sealing glasses with the composition (mol.%) of 12Al₂O₃·8B₂O₃·40SiO₂·40RO (R = Mg, Ca, Sr) for solid oxide fuel cells (SOFCs) before and after isothermal treatment at 700°C, which is within the operation temperature range (600-800°C) of SOFCs. The crystallization behavior has been investigated by differential scanning calorimetry and X-ray diffraction under both dynamic and isothermal conditions. The structural evolution is probed using the Raman and nuclear magnetic resonance spectroscopies. The performances of the sealing glasses are characterized in terms of the coefficient of thermal expansion, the crystallization-induced stress at glass–steel interface. We find that strong crystallization occurs at the operation temperature (700°C) far below the crystallization onset temperature measured by DSC. The structure origin of this anomalous crystallization is discussed in terms of structural heterogeneity of the three studied glasses. We determine the residual stress at the interface between the Ca-containing glass and the steel after isothermal treatment at 700°C for 48 h, but this stress does not lead to falling off the glass layer from the steel. This indicates that this glass is a good candidate to be applied in SOFCs.     

Microstructural Development on Crystallizing Hot-Pressed Pellets of Cordierite Melt-derived Glass Containing B2O3 and P2O5

Comparing the crystallization mechanism of stoichiometric and B₂O₃ and P₂O₅ containing glass reveals that the additives extend the gap between the glass transition and crystallization temperatures and suppress formation of μ, cordierite while promoting direct crystallization of α cordierite. Detailed TEM analysis of nucleation and growth of crystals in hot-pressed pellets of B₂O₃/P₂O₅-containing glass particles shows that nucleation occurs on unidentified heterogeneous nuclei at the sites of the previous particle surfaces. Growth of α cordierite with a cellular morphology or μ cordierite with a dendritic morphology is most likely controlled by the glass composition directly ahead of the growth front.     

Microstructural Evolution in Fast-Heated Cordierite-Based Glass-Ceramic Glazes for Ceramic Tile

The crystallization mechanism of α-cordierite from a B₂O₃- and TiO₂-containing glass submitted to fast heating in the cordierite primary phase field of the CaO–MgO–Al₂O₃–SiO₂ quaternary system was investigated. Addition of B₂O₃ to a SiO₂-rich glass suppressed the formation of μ-cordierite. This suppression facilitated densification by viscous flow before crystallization. Powder X-ray diffractometry, field-emission electron scanning microscopy, and energy-dispersive X-ray analysis revealed that α-cordierite nucleated directly from glass on the boundaries of original particles and was probably favored by TiO₂, which acted as a nucleant. The growth kinetics of α-cordierite crystals was fast, and the crystals seemed to grow by consuming glass directly from the growing interphase. The estimated amount of α-cordierite in the glass heated at 1160°C was 69.5 wt%, as determined using the Alegre method. The final microstructure consisted of an arrangement of well-shaped hexagonal prisms, with sizes <3 μm, immersed in a residual glassy phase. The feasibility to develop new glass-ceramic glazes using the present and previous works is considered.     

Influences of Zirconia and Silicon Nucleating Agents on the Devitrification of Li2O · Al2O3· 6SiO2 Glasses

The effects of Si and ZrO₂ dopants on the crystallization and phase transformation process in Li₂O · Al₂O₃· 6SiO₂ glasses were investigated using differential thermal analysis, X-ray powder diffractometry (XRD), and high-resolution transmission electron microscopy (TEM) interactively. Phase separation was observed in the studied glasses prior to substantial crystallization. Elemental Si (1 mol%) significantly aided in glass devitrification. Dropletlike phase-separated regions in the as-quenched or heat-treated glass devitrified at ∼760°C, which in turn provided sites for the heterogeneous nucleation and growth of β-quartz(ss) (solid solution), which transformed to β-spodumene(ss) at higher temperature. Low-temperature surface crystallization in these glasses occurred as low as 760°C. ZrO₂ has limited solubility in this glass system. Small ZrO₂ crystallites (·5 nm) in the as-quenched glass acted as sites for the heterogeneous nucleation and subsequent growth of large (<5 μm) β-quartz(ss) crystals in glasses containing 1.0 mol% or more ZrO₂. The transformation from β-quartz(ss) to β-spodumene(ss) was increasingly inhibited with ZrO₂ additions. The nucleating efficiency of Si was significantly greater than that of ZrO₂ in this glass system.     

Isothermal crystallization of pure and glass fiber reinforced poly(phenylene sulfide) composites

The isothermal crystallization of poly(phenylene sulfide) (PPS) and its glass fiber (GF) reinforced composite has been investigated by differential scanning calorimetry (DSC) and polarized optical microscope (POM) equipped with a hot stage. During the isothermal crystallization process of PPS the Avrami exponent value decreases with time, indicating the change of crystallization mechanism and presence of mixed growth mechanism (bidimensional and three‐dimensional growth of crystals). The presence of GF greatly accelerates the bulk crystallization rate of PPS and changes the crystalline morphology of PPS from the spherulites to transcrystallization. And the reason for development of transcrystallization is considered to be relevant with the compatibility of the interface between GF and PPS. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Non-Isothermal Crystallization of Bovine Milk Fat

The crystallization kinetics of milk fat were studied under non-isothermal and simulated adiabatic conditions using pulsed NMR spectroscopy. Isothermal experiments confirmed that when milk fat is shock cooled to below the α melting point it crystallizes in two steps due to the different crystallization kinetics of α and β′ modifications. In non-isothermal experiments, the fat samples were heated early during the plateau between steps to a temperature above the α melting point and β′ crystals formed more rapidly than in isothermal conditions. Fresh α crystals are believed to melt and form lamellar units containing triglyceride molecules with high degrees of isomorphism and these units can accelerate the nucleation and growth rates of β′ polymorph crystals. The crystallization behavior changed when the heating occurred late in the plateau and the α crystals are believed to have demixed, which allowed them to transform to β′ crystals directly in the solid state. Under simulated adiabatic conditions the rate of β′ crystallization was increased by a factor of 2–3 over the isothermal case. These findings were used to infer approaches to process difficult fat blends in scraped-surface heat exchanger plants.     

Melting behavior and isothermal crystallization kinetics of nylon 11/EVOH/dicumyl peroxide blends

Nylon 11/ethylene‐vinyl alcohol/dicumyl peroxide (DCP) blends were prepared using a single‐screw extruder. The melting behavior and isothermal crystallization kinetics were investigated using differential scanning calorimetry. The reorganization of nylon 11 crystals is strongly hindered owing to cocrosslinking phenomena. The analysis of the crystallization kinetics demonstrated that the Avrami equation well described the isothermal crystallization process of the primary stage. The spherulites growth kinetics parameters and fold surface free energy were also evaluated. The experimental results confirmed that the presence of DCP increased the crystallization rate. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Formation of Frozen α-Agl in Twin-Roller-Quenched Agl─Ag2 O─MxOy (MxOy= WO3, V2O5) Glasses at Ambient Temperature

Superionic conductor α-AgI, which is stable only above 147°C, was successfully frozen at ambient temperature in AgI─Ag₂O─M_xO_y (M_xO_y= WO₃, V₂O₅) glass matrices by a twin-roller-quenching technique. The system with WO₃, provided the larger composition regions where α-AgI was frozen at ambient temperature, compared to the system with V₂O₅. The matrix glasses with higher glass-transition temperatures had a stronger effect in depressing the α–β transformation of AgI. The α-AgI-frozen samples exhibited extremely large conductivities of 3 × 10⁻²-5 × 10⁻²S.cm⁻¹at 25°C.     

Kinetics of phase formation in jarosite glass-ceramic

The crystallisation behaviour of an iron-rich glass was studied by means of density measurements, Differential Thermal Analysis and X-ray Diffraction. The results highlighted that there is no typical nucleation process in which the number of nuclei is influenced by the thermal treatment and influence the crystallisation process. The kinetics of phase formation was investigated in isothermal and non-isothermal conditions; the Avrami parameter value, 1·5, is indicative of a three dimensional diffusion controlled growth of the pyroxene crystals on a fixed number of nuclei. The activation energy of crystal growth, obtained by the isothermal and non isothermal methods, resulted in being 377kJ mol⁻¹ and 298 kJ mol⁻¹, respectively. Considering the different temperature range, these values are in fair agreement and consistent with values reported by other authors. Using TEM-EDS analysis the high immiscibility of the initial glass was highlighted; the two liquid phases, one richer in Fe and the other in Si and Ca, promote the formation of magnetite and pyroxene during the thermal treatment, respectively.     

Crystallization kinetics and melting behaviour of microbial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)

Isothermal and non‐isothermal crystallization kinetics of microbial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐3HHx)] was investigated by differential scanning calorimetry (DSC) and ¹³C solid‐state nuclear magnetic resonance (NMR). Avrami analysis was performed to obtain the kinetic parameters of primary crystallization. The results showed that the Avrami equation was suitable for describing the isothermal and non‐isothermal crystallization processes of P(3HB‐3HHx). The equilibrium melting temperature of P(3HB‐3HHx) and its nucleation constant of crystal growth kinetics, which were obtained by using the Hoffman–Weeks equation and the Lauritzen–Hoffmann model, were, respectively, 121.8 °C and 2.87 × 10⁵ K² when using the empirical ‘universal’ values of U* = 1500 cal mol^?1. During the heating process, the melting behaviour of P(3HB‐3HHx) for both isothermal and non‐isothermal crystallization showed multiple melting peaks, which was the result of melting recrystallization. The lower melting peak resulted from the melting of crystals formed during the corresponding crystallization process, while the higher melting peak resulted from the recrystallization that took place during the heating process. Copyright © 2005 Society of Chemical Industry     

Crystallization behavior of polytetrafluoroethylene (PTFE)

For some polymers such as PTFE, the crystallization is so rapid that it is difficult to observe isothermal crystallization by differential scanning calorimetry (DSC). In this investigation, first, isothermal crystallization kinetics of PTFE was followed by DSC and the results were analyzed by the Avrami method, which showed that PTFE crystallizes one‐dimensionally from preexisting nuclei, presumably impurities. Furthermore, the crystallization activation energy, the equilibrium melting point, and the nucleation rate parameter K_g were calculated in the isothermal crystallization. Second, nonisothermal crystallization was also studied and the result was in accordance with the results of isothermal crystallization. Then, the Kissinger method was used to investigate the activation energy of PTFE in the nonisothermal crystallization. Third, the effect of glass fiber (used as filling) was investigated on crystallization of PTFE matrix. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 990–996, 2002     

Direct Observation of the Crystallization of Li2O-Al2O3-SiO2 Glasses Containing TiO2

The nucleation and crystallization of Li₂O-Al₂O₃-SiO₂ glasses containing TiO₂ were investigated using transmission electron microscopy of thin sections produced from bulk samples. Phase separation occurs during cooling from the melt, and on heating, a large number of titanium-aluminum crystals approximately 50 A in diameter are formed. These crystals are the heterogeneous nuclei for the crystallization of the remaining glass. Photomicrographs of various stages of crystallization show the development of the fine-grained glass-ceramic.     

Studies on the isothermal crystallization kinetics and crystal morphology of PTT/SGF composites

The kinetics of isothermal crystallization and crystal morphology of poly(trimethylene terephthalate)/short glass fibers (PTT/SGF) composites were investigated by using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). DSC data was analyzed by the Avrami equation and Hoffman‐Lauritzen theory. The results show that SGF plays a role as the nucleating agent, which largely accelerates the crystallization rate of PTT. SGF below 20% will increase the crystallinity of the composites but 30% SGF will decrease the crystallinity, which is also verified by the crystallinity results calculated from the wide‐angle x‐ray diffraction (WAXD) experiments. The crystal morphology of the composites exhibits so much microcrystallites because of the fast crystallization rate and the strong interaction between SGF and polymers, which is consistent with the results analysized by the Avrami theory. The nuclei exponent K_g is increased sharply as the SGF added into polymer, and SGF makes PTT easier to crystallize during isothermal crystallization process. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Effect of Chloride Incorporation on the Crystallization of Zirconium-Barium-lanthanum-Aluminum Fluoride Glass

One aspect of the influence of preparation procedure on the crystallization behavior of a zirconium-barium-lanthanum-aluminum fluoride glass was studied. The crystallization pattern of this glass may be affected by the chlorine concentration within it. In particular, when such glasses are heated at low temperatures, the α-BaZrF₆ crystalline phase forms only in those glasses which contain chloride.     

Crystallization of CaO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> glass prepared by float process

CaO–MgO–Al₂O₃–SiO₂ (CMAS) glass was prepared by float process. The effects of TiO₂ and heat-treatment on properties and crystallization behaviors of float glasses were investigated by atomic force microscope, differential scanning calorimeter, X-ray diffraction, electron probe microanalyzer, field emission scanning electron microscope and viscosity test. The results showed that CMAS parent glasses produced by float process had a high surface flatness (Ra is less than 80.1 ± 0.1 nm) and low tin penetration (14 μm). When the concentration of TiO₂ increased from 3.51 to 5.01 wt %, the glass transition temperature was decreased, and the crystallization temperature was shifted from 913 to 887°C using differential scanning calorimeter. Field emission scanning electron microscope images showed that phase separation was discovered in CMAS parent glass (containing 3.51 wt % TiO₂) treated at 670°C. Diopside as a major crystalline phase was precipitated in CMAS glass-ceramics nucleated at 700°C for 30 min and followed by crystallization at 910°C for 30 min.